JP2003033993A - Resin film laminated metal sheet, and container, construction material and outside plate for household equipment using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin film laminated metal sheet by which excellent binding properties and proper orientation to a metal sheet are made easily compatible without utilizing a binding agent, and to provide a container, a construction material and an outside plate for household equipment utilizing the resin film laminated metal sheet. SOLUTION: The respective faces of the metal sheet 26 and the thermoplastic resin film 28 to be joined layeredly in a vacuum tank are previously subjected to an activation treatment. After that, the respective activated faces of the metal sheet 26 and the thermoplastic resin film 28 are brought into contact and overlaid facing each other. Then, they are subjected to cold pressure-binding and joined layeredly to produce the resin film laminated metal sheet 20.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin film laminated metal plate obtained by laminating and joining a metal plate and a thermoplastic resin film without providing a metal plate with a surface treatment layer or an adhesive layer.
And a container, a building material, and an outer panel for home electric appliances using the resin film laminated metal sheet.

[0002]

2. Description of the Related Art Conventionally, a resin film-laminated metal plate obtained by laminating a thermoplastic resin film on a metal plate has been used for applications such as containers, building materials, and outer panels of home appliances. In these applications, processability of resin film laminated metal plate, adhesiveness of resin film to metal plate, permeation resistance of contents when processed into a container and filled with contents, outer panel for building materials and home appliances, etc. When applied, it is required to have excellent workability, weather resistance, and corrosion resistance. In order to keep these characteristics in good condition, considering the required characteristics, the resin film is laminated directly on the metal plate while adjusting the orientation of the resin film by using the heat-bonding method, or the orientation of the resin film is not affected, or is affected. In order to minimize the above, the resin film is laminated on the metal plate using an adhesive. In this way, when the resin film is directly heat-bonded to the metal plate or is bonded using an adhesive, in order to improve the adhesiveness with the resin film or the adhesive, the metal plate is subjected to chromate treatment or the like. Surface treatment is generally performed.

When the resin film is laminated on the metal plate by the thermal bonding method, the resin film is brought into contact with the metal plate heated above the melting point of the resin film so as to be overlapped with each other by using a pair of pressure rolls. Is pressed to bond. In the portion of the resin film that is in direct contact with the metal plate, the oriented crystal structure collapses due to heat from the metal plate to become amalphus, and adhesiveness is exhibited. On the other hand, in the portion of the resin film that is not in contact with the metal plate, heat from the metal plate is hard to be transmitted, and the degree of orientation collapsed due to heat before being laminated on the metal plate is reduced. In this way, since the adjustment of the adhesiveness and the orientation of the resin film to the metal plate are performed at the same time in the laminating step, the conditions for achieving both the suitable orientation and the good adhesiveness are extremely narrow, and the metal plate excellent in both properties is provided. Making it difficult to get.

When a resin film is laminated on a metal plate using an adhesive, the adhesive is applied to either the resin film or the metal plate in advance, and the two are abutted via this adhesive. The layers are superposed and pressed with a pair of pressure rolls for adhesion. In the case of using an adhesive, the orientation can be adjusted by heating the metal plate to a temperature inside or outside the melting point of the resin film, as in the case of using the heat bonding method. However, the method of laminating with an adhesive is unavoidable in terms of cost because it involves the use of an adhesive and the step of applying an adhesive.

[0005]

SUMMARY OF THE INVENTION In view of the above technical background, the present invention is a resin film which easily achieves both good adhesiveness to a metal plate and suitable orientation without using an adhesive. An object of the present invention is to provide a laminated metal plate, and a container, a building material, and an outer panel for a home electric appliance using the resin film laminated metal plate.

[0006]

The resin film-laminated metal plate of the present invention is a resin film-laminated metal plate obtained by laminating and joining a thermoplastic resin film on at least one side of a metal plate, and the metal plate is in a vacuum chamber. After activating the surfaces of the thermoplastic resin film and the thermoplastic resin film to be laminated and joined in advance, the metal plate and the thermoplastic resin film are brought into contact with each other so that their respective activation surfaces are opposed to each other, and then overlapped. A resin film laminated metal plate, which is characterized by being pressure-welded and laminated to each other, wherein activation treatment is performed by glow discharge in a low-pressure inert gas atmosphere, and the metal plate and the thermoplastic resin film are respectively Sputter etching the surfaces to be laminated and joined, and the metal plate is a steel plate, aluminum plate, aluminum alloy plate, magnesium plate, or magnesium alloy plate. Further, the steel sheet is any one of a tin-plated steel sheet, a tin alloy-plated steel sheet, a zinc-plated steel sheet, a zinc alloy-plated steel sheet, a nickel-plated steel sheet, a nickel alloy-plated steel sheet, and the thermoplastic resin film is polyester, polyolefin, The resin is a blend of polyamide, polyester and polyolefin. Further, the container, the building material, and the outer panel for home electric appliances of the present invention are all characterized by using any one of the above resin film laminated metal sheets.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the surfaces of a metal plate and a thermoplastic resin film to be laminated and joined are previously subjected to glow discharge in a low-pressure inert gas atmosphere in a vacuum chamber to perform sputter etching. After the treatment, the metal sheet and the thermoplastic resin film are abutted and overlapped so that the respective activation treated surfaces face each other, and then cold pressure welded to laminate and bond the resin film to the metal plate. It is a resin film laminated metal plate with excellent adhesiveness of
The orientation of the resin film can be easily adjusted by heat-treating separately after laminating in this way. This resin film laminated metal plate can be favorably applied to containers, building materials, and appliances for home appliances. Hereinafter, embodiments of the present invention will be described.

First, the metal plate used for the resin film-laminated metal plate of the present invention will be described. The metal plate is not particularly limited as long as it is a material capable of laminating and adhering resin films, but practically, it is a steel plate, tin-plated steel plate, tin-zinc, tin-lead, tin-bismuth, tin-copper. Tin alloy-plated steel sheet, zinc-plated steel sheet, zinc-nickel, zinc-aluminum, zinc-copper, zinc-cobalt-molybdenum and other zinc alloy-plated steel sheet, nickel-plated steel sheet,
A plated steel plate such as a nickel alloy plated steel plate of nickel-phosphorus, nickel-tin, nickel-copper, etc., a stainless steel plate, an aluminum plate, an aluminum alloy plate, a magnesium plate, a magnesium alloy plate or the like can be appropriately selected and used according to the application. The thickness of these metal plates is 0.1
It is preferably ˜1 mm.

Next, the resin film used in the resin film-laminated metal plate of the present invention will be described. The resin film is not particularly limited as long as it is a material that can be laminated and adhered to a metal plate, but in practice, a thermoplastic resin such as polyester, polyolefin, polyamide, or a resin obtained by blending polyester and polyolefin can be used. preferable.

As the polyester, polyethylene terephthalate, polybutylene terephthalate, ethylene terephthalate, butylene terephthalate, 1,
A polyester resin obtained by polymerizing at least one or more of 4-cyclohexanedimethyl terephthalate, ethylene isophthalate, butylene isophthalate, ethylene naphthalate, ethylene adipate and butylene adipate is preferable. A resin obtained by blending two or more of these polyester resins is also applicable. In particular, a polyester composed of ethylene isophthalate: 5 to 15 mol% and ethylene terephthalate 85 to 95 mol% has excellent processability, and after being laminated on a metal plate,
The resin film does not crack even when subjected to severe processing and is molded into a container, etc., and has excellent adhesiveness to a metal plate. Further, as polyesters other than the above, those using sebacic acid, trimellitic acid, azelaic acid or the like as the acid component of the ester unit, and propylene glycol, diethylene glycol, neopentyl glycol, pentaerythritol, etc. as the alcohol component of the ester unit are used. You can also apply what you had.

As the polyolefin, a resin composed of one or more 1-alkene copolymer resins having 2 to 8 carbon atoms can be mentioned. Examples of the 1-alkene copolymer resin having 2 to 8 carbon atoms include low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polybutene-1, polypentene-1, polyhexene-1, polyheptene-1, polyoctene. -1, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-hexene copolymer can be mentioned.

As the polyamide, 6 nylon, 11 nylon, 12 nylon, 66 nylon, 610 nylon,
Homopolymers such as 612 nylon, and copolymerized nylon composed of two or more of these homopolymers can be mentioned. Copolymerized nylon has lower melting point and mechanical strength than the homopolymer of the component, and flexibility and processability are improved. In particular, 6/66 copolymerized nylon obtained by polymerizing 6 nylon monomer: 10 to 90 mol% and 66 copolymerized nylon monomer: 90 to 10 mol% has excellent processability.

A resin obtained by blending any one or more of the above polyester resins with any one or more of the above polyolefins can also be used. The blend ratio of polyolefin resin to polyester resin is 3
It is preferably 0% by weight or less. When it exceeds 30% by weight, the transparency of the blended resin is reduced and the hardness is also reduced, so that the surface of the resin is easily scratched.

In the present invention, one of the above-mentioned thermoplastic resins is formed into a film having a thickness of 10 to 200 μm and laminated on a metal plate. As the resin film, resin pellets are heated and melted by a conventional method and extruded from the extruder,
Both an unstretched film used as a film as it is and a stretched oriented film in which crystals are oriented by extruding from an extruder and then stretching in a uniaxial or biaxial direction and heat setting can be applied.

Next, a method for producing the resin film-laminated metal plate of the present invention will be described. As shown in FIG. 1, the vacuum chamber 5
In 2, the long strip-shaped thermoplastic resin film 28 wound on the rewind reel 62 is activated by the activation processing device 70 while being unwound. Similarly,
Long strip metal plate 2 wound on the rewind reel 64
6 is activated by the activation processing device 80.

The activation process is carried out as follows. That is, the thermoplastic resin film 28 and the metal plate 26 loaded in the vacuum chamber 52 are brought into contact with one of the electrodes A, which is grounded, respectively, and 10 to 1 × 10 10 between the other electrode B, which is insulated and supported. Glow discharge is performed by applying an alternating current of 1 to 50 MHz in an extremely low pressure inert gas atmosphere of ^-3 Pa, preferably argon gas, and the heat of contact with the electrode A exposed in the plasma generated by the glow discharge. Sputter etching is performed so that each area of the plastic resin film 28 and the metal plate 26 is 1/3 or less of the area of the electrode B. The inert gas pressure is 1 x 10
^If it is less than ^-3 Pa, stable glow discharge is difficult to perform and high-speed etching is difficult, and if it exceeds 10 Pa, the activation treatment efficiency is lowered. If the applied alternating current is less than 1 MHz, it is difficult to maintain a stable glow discharge, and continuous etching is difficult. On the other hand, if it exceeds 50 MHz, oscillation is likely to occur and the power supply system is complicated, which is not preferable. Further, the area of the electrode A needs to be smaller than the area of the electrode B in order to perform the etching efficiently, and by setting the area to 1/3 or less, the etching can be performed with sufficient efficiency.

After that, the thermoplastic resin film 28 and the metal plate 26, which have been activated as described above, are brought into contact with each other so that the activated surfaces thereof face each other, and are overlapped with each other. Are cold-pressed and laminated to form a resin film laminated metal plate 20. At this time, the lamination joining can be performed at a low temperature and a low rolling rate, so that the thermoplastic resin film 28, the metal plate 26, and the resin film laminated metal sheet 20 that is laminated and joined have a structural change such as an orientation or breakage. It is possible to eliminate adverse effects. When the method of the present invention is used, where T is the temperature (° C.) of the thermoplastic resin film 28 and the metal plate 26 and R is the rolling ratio (%), 0 ° C. <T ≦ 120 ° C., 0.1% ≦ R
When ≦ 30%, a good pressed state can be obtained. If the temperature is lower than 0 ° C, a special refrigerating device is required, and if the temperature exceeds 120 ° C, depending on the resin, adverse effects such as melting may occur. 0.1%
If the rolling ratio is less than 30%, sufficient bonding strength cannot be obtained, and if it exceeds 30%, adverse effects such as breakage occur. Preferably,
0 ° C. <T ≦ 50 ° C. and 0.1% ≦ R ≦ 3%.

As described above, the thermoplastic resin film 2
The resin film laminated metal plate 20 is formed by laminating and bonding 8 and the metal plate 26, and is wound up by the winding roll 66. In this way, the resin film laminated metal plate 20 is manufactured. Although FIG. 1 shows the case where the thermoplastic resin film 28 is laminated on one side of the metal plate 26 (the upper side of the metal plate 26 in FIG. 1), the other side of the metal plate 26 is activated by an electrode A and an electrode. B is additionally provided after the first activation processing step, and further on the other surface side of the metal plate 26 (the lower side of the metal plate 26 in FIG. 1), the rewind reel 62, the electrode A,
It is also possible to obtain the double-sided resin film laminated metal plate by providing the electrode B and the electrode B, activating the both surfaces of the metal plate 26, and then laminating the thermoplastic resin film 28 on each of the activated both surfaces. .

The resin film-laminated metal plate 20 manufactured in this manner may be subjected to a heat treatment for the purpose of adjusting the orientation of the resin film and removing or reducing the residual stress of the metal plate, if necessary. For example, by heating in an oven to uniformly adjust the orientation of the entire resin film, or by contacting a cooling means such as a cooling roll to the resin film to cool the resin film surface, using an induction heating method to remove only the metal plate. It is also possible to heat the resin film, while leaving the orientation of the outermost surface of the resin film, to eliminate the orientation of the resin layer in contact with the metal plate, and the temperature of the cooling roll in contact with the resin film and the conditions of induction heating as appropriate. By selecting it, it is also possible to form a continuous orientation gradient in the thickness direction of the resin film.

When the thickness or hardness of the thermoplastic resin film or the metal plate is not suitable for manufacturing using a roll,
When laminating a resin film on a relatively small-sized cut plate-shaped metal plate, batch processing can be used. In the vacuum chamber, a plurality of thermoplastic resin films or metal plates that had been cut into a predetermined size were loaded and conveyed to the activation processing section, and the surfaces to be processed at appropriate positions such as vertical or horizontal were placed facing or juxtaposed to each other. If the device part that holds the thermoplastic resin film or metal plate also serves as a pressure welding device, it is installed or held in place and clamped to fix it. In the case where the device portion holding the plastic resin film or the metal plate does not also serve as the pressure contact device, it is achieved by transporting it to a pressure contact device such as a press device for pressure contact.

[0021]

EXAMPLES The present invention will be described in detail below with reference to examples. (Example 1) Using a metal plate and a thermoplastic resin film shown in Table 1 in a vacuum chamber, each laminated surface was sputter-etched and activated under the conditions shown in Table 2, and each activation treatment was performed. The surfaces were brought into contact with each other, and pressure was applied under the conditions shown in Table 2 using a pair of pressure rolls for lamination to prepare a resin film laminated metal plate. Among the metal plates in Table 1, Sample No. 10 is the alloy No. 1050 shown in JIS H 4000, and Sample No. 11 is the JIS H 40.
Alloy No. 3004 shown in 00 to sample No. 13
Then, alloy number M shown in JIS H 4201
P1 was used respectively. As shown in Table 3, some of the resin film-laminated metal plates were then subjected to heat treatment using an induction heating method to adjust the orientation of the resin film. The degree of orientation (plane orientation coefficient) of the resin film of the resin film-laminated metal plate thus obtained is the formula for determining the plane orientation coefficient by measuring the refractive index in the plane direction and the thickness direction using an Abbe refractometer. I asked more. Regarding the surface orientation coefficient of the outermost surface (free surface) of the resin film and the surface in contact with the metal plate, a part of the resin film laminated metal plate is cut out, and the metal plate is dissolved and removed with an acid on both surfaces of the film. It was determined by measuring the refractive index in the plane direction and the thickness direction. Table 3 shows the measurement results of the orientation coefficient.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3]

[Evaluation of Adhesiveness] Ten test pieces each having a width of 10 mm and a length of 100 mm were cut out from the resin film laminated metal plates of sample Nos. 1 to 13 shown in Tables 1 and 2, and the resin film surface was formed at one end thereof. Forced peeling at the interface with the metal plate, T
Peel test pieces were prepared, T-peel strength was measured using a Tensilon tensile tester, the average value of 10 test pieces was obtained, and the quality of the adhesiveness was judged according to the following criteria. In the evaluation, the following ○ and ◎ were passed. ⊚: T peel strength ≧ 20 N / 10 mm ○: T peel strength ≧ 12 N / 10 mm and <20 N /
10 mm Δ: T peel strength ≧ 8 N / 10 mm and <12 N / 1
0 mm x: T peel strength <8 N / 10 mm These results are shown in Table 3.

Example 2 Sample No. 1 shown in Tables 1 and 2
After punching the resin film-laminated metal plate of No. 3 into a blank having a diameter of 160 mm, a can bottom having a diameter of 100 mm was drawn, and then a re-drawing process was performed to obtain a can bottom having a diameter of 80 mm. Further, this re-drawing can was ironed at the same time as the styling process to obtain a drawn and ironed can having a can bottom diameter of 65 mm. Next, the upper part of the can was trimmed using a known method and subjected to neck-in processing and flange processing, but peeling and cracking of the resin film did not occur, and it was suitable for use as a beverage container.

Example 3 Sample No. 3 shown in Tables 1 and 2
The resin film-laminated metal plate of 1 was molded into the body of an 18 L square can, the seam was electrically welded, and the seam on the inner surface side was corrected using a powder coating made of a thermoplastic resin. The canopy material and the ground material made of the same resin film laminated metal plate were double-wound around this body to make an 18 L square can.
No peeling or cracking of the resin film was observed in the bent portion or the wound portion, and this resin film-laminated metal plate could be suitably applied as an 18 L square can.

Example 4 Sample No. 6 shown in Tables 1 and 2
The resin film laminated metal plate of is cut out into a size of 46 cm × 126 cm, the 3 cm × 3 cm portions are cut out at the four corners, and then four laps are bent at a width of 3 cm by 90 °, and the vertical length is 40 c.
Although it was formed into a box shape of m × width: 120 cm × height: 3 cm, peeling or cracking of the resin film was not observed in the bent portion. In addition, the DuPont impact test specified in JIS K 5400 (size of impact part: diameter 0.
Impact resistance was evaluated at 5 inches, weight: 1 kg, height: 50 cm), but no cracks were found in the resin film, and this resin film laminated metal plate should be suitably applied as an indoor partition plate. I was able to.

Example 5 Same as sample No. 7 shown in Table 1.
One Zn-Co-Mo plated steel sheet with polyester
The paint was applied and baked. On the other hand, the trials shown in Tables 1 and 2
Polyethylene film that is the same as the resin film used for material number 7
White pigment TiO on the rephthalate pellets _Two20 weight
% Of the pellets, the resin powder of sample No. 7 was used.
A resin film was prepared under the same conditions as Rum. This white
A polyethylene terephthalate film was designated as sample number 7.
Under the same conditions, the uncoated side of the single-sided coated steel sheet
Layered and then resin film laminated metal of sample number 7 in Table 1
The heat treatment was applied under the same conditions as in the plate. Got
90 degree bending processing was applied to the white resin film laminated metal plate.
However, no peeling or cracking of the resin film was observed,
Also, the Erichsen overhanging process of overhanging height 5mm
Although it was carried out, peeling and cracking of the resin film were confirmed
Can be suitably applied as the outer panel of the refrigerator door.
did it.

(Example 6) The same resin film laminated metal plate as sample No. 10 shown in Table 1 was processed under the processing conditions of a total drawing ratio: 3.2 and a total ironing ratio: 35%, a diameter of 10 mm and a height of 2
Formed into a 2mm cylindrical condenser container,
No peeling or cracking of the resin film was observed, and the resin film was suitable for use as a capacitor container.

[0031]

As described above, in the resin film-laminated metal plate of the present invention, the surfaces where the metal plate and the thermoplastic resin film are laminated and bonded are previously glowed in a vacuum chamber in a low pressure inert gas atmosphere. A resin film made by discharging and performing sputter etching, then abutting them so that the activation surfaces of the metal plate and the thermoplastic resin film face each other, and then cold-pressing and laminating. There is a laminated metal plate, and the adhesiveness of the resin film to the metal plate is excellent. In addition, since it is not necessary to heat the resin film above the melting point or to use an adhesive in the bonding step, it is possible to heat-treat again only for adjusting the orientation degree of the resin film after laminating. It can be easily adjusted. Further, since no adhesive is used, it is cost effective. Therefore, the resin film-laminated metal plate of the present invention can be favorably applied to applications such as containers, building materials, and household appliances.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a laminating apparatus for a resin film laminated metal plate used in the present invention.

[Explanation of symbols]

20 Resin film laminated metal plate 26 Metal plate 28 Thermoplastic resin film 52 vacuum chamber 60 pressure welding unit 62 Rewind reel 64 rewind reel 66 winding roll 70 Activation processing device 72 electrode roll 74 electrodes 80 Activation processor 82 electrode roll 84 electrodes A electrode A (for thermoplastic resin film or metal plate) B electrode B (counter electrode)

Continued front page    F-term (reference) 4F100 AB01A AB03A AB09A AB10A                       AB16A AB18A AB21A AB31A                       AK01B AK01C AK03B AK03C                       AK41B AK41C AK46B AK46C                       AL05B AL05C BA02 BA03                       BA06 BA07 BA10A BA10B                       BA10C EC011 EH661 EH71A                       EJ591 EJ601 EJ641 GB07                       GB16 GB48 JB16B JB16C                       JL11

Claims (9)

[Claims] 1. A resin film-laminated metal plate obtained by laminating and bonding a thermoplastic resin film to at least one surface of a metal plate, wherein the respective surfaces of the metal plate and the thermoplastic resin film to be laminated and bonded are arranged in a vacuum chamber. After pre-activation treatment, the activation treatment surfaces of the metal plate and the thermoplastic resin film are abutted and overlapped so as to face each other, and then cold-pressed and laminated and joined. Resin film laminated metal plate. 2. The activation treatment is characterized in that glow discharge is performed in a low-pressure inert gas atmosphere, and the surfaces of the metal plate and the thermoplastic resin film to be laminated and joined are subjected to sputter etching treatment. The resin film-laminated metal plate according to claim 1. 3. The resin film laminated metal plate according to claim 1, wherein the metal plate is a steel plate. 4. The resin film laminated metal sheet according to claim 3, wherein the steel sheet is a tin-plated steel sheet, a tin alloy-plated steel sheet, a zinc-plated steel sheet, a zinc alloy-plated steel sheet, a nickel-plated steel sheet, or a nickel-alloy plated steel sheet. 5. The resin film-laminated metal plate according to claim 1, wherein the metal plate is an aluminum plate, an aluminum alloy plate, a magnesium plate, or a magnesium alloy plate. 6. The resin film-laminated metal plate according to claim 1, wherein the thermoplastic resin film is polyester, polyolefin, polyamide, or a resin obtained by blending polyester and polyolefin. 7. A container using the resin film-laminated metal plate according to claim 1. 8. A building material using the resin film-laminated metal plate according to claim 1. 9. An outer panel for a home electric appliance, which uses the resin film-laminated metal plate according to claim 1.