JPH04143395A - New shutter and material therefor - Google Patents

Abstract

PURPOSE:To improve the weathering resistance, durability and designability by constituting at least a shutter surface with a metal sheet mainly covered by a fluororesin containing film. CONSTITUTION:The surface of an aluminum plate is roughened by means of sandblasting and then it is subjected to electrolytic etching in an aqueous solution of sodium chloride, forming a rough surface. Next, the aluminum plate is heated and an ethylene-tetrafluoroethylene copolymer film is fused to the rough surface together with the aluminum plate, forming a fluororesin laminated aluminum plate. Then, a metal sheet 2 and a fluororesin film 1 thermally fused and heated are pressurized with a silicon roll. Successively, the resin laminated aluminum plate formed is cut off and a shutter slat is formed by a roll forming machine, thus a shutter is manufactured.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel shutter and materials used therein. More specifically, the present invention relates to a novel shutter and materials used therefor. Regarding new shutters and materials used for them.

[Conventional technology] Shutters are used to protect buildings,
They are installed at the entrances and exits of shops, warehouses, car floors, factories, etc., and are generally left open when people are inside the building. Therefore, it is usually not visible to the people using the building. For this reason, shutters are often achromatic or achromatic, such as black, gray, or white, and there is little consideration given to the design, other than the store name or company name mark written on the surface. In addition, repairs tend to be neglected, and while the functions are being satisfied, they are often not cleaned, and even if there is dust, discoloration of the paint, blisters, rust, etc., they are left unattended. In some cases, there was also graffiti.

However, in recent years, the appearance of street shadows has become a hot topic, and the exterior walls of buildings themselves have come to have a variety of colors, so it has become desirable to have shutters that match the exterior walls.

In addition, in the case of shops, a variety of products can be seen even after closing hours on holidays, so it has become possible to think of ways to increase advertising effectiveness by using shutters that match the show windows. Furthermore, there is a demand for being able to remove dirt and graffiti by washing windows and exterior walls when cleaning them. On the other hand, since factories are exposed to a variety of atmospheres, there was a desire for products with high corrosion resistance. These various problems could not be solved with shutters made from conventionally used coated steel plates or stainless steel.

Therefore, there has been a strong desire for a new shutter that is rich in design, durable, weather resistant, and has excellent cleaning properties.

[Problems to be Solved by the Present Invention] The purpose of the present invention is to solve the above-mentioned problems that the prior art had, and to provide a novel shutter that was completely unknown in the past and a method for using it. It provides materials.

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems, and is characterized in that at least the surface layer of the shutter is mainly made of a fluorine-containing resin film and the substrate is made of metal. The present invention provides a new shutter that achieves this. The configuration of the present invention will be explained in more detail below.

The "fluorine-containing resin" as used in the present invention is not particularly regulated as long as it is a thermoplastic resin that contains a fluorine atom in the molecular structure of the resin, but generally, the molecular structure of the resin is Tetrafluoroethylene resins having four fluorine atoms in them, trifluoroethylene resins, nifluoroethylene resins, fluoroethylene resins, copolymers of these resins, and mixtures. . Here, the tetrafluoroethylene resin specifically includes, for example, tetrafluoroethylene resin (PTFE), tetrafluoroethylene/perfluoroalkoxyethylene copolymer (PFA), and tetrafluoroethylene/hexafluoroethylene copolymer (PFA). PFAS
ETFE is preferred, especially ETFE. In addition, the above-mentioned trifluoroethylene resin specifically includes, for example, trifluorochloride ethylene resin (PCTFE) and trifluorochloride ethylene/ethylene copolymer (ECTFE), among which PCTEFE is preferable. Specifically, the difluoroethylene-based and -fluoroethylene-based resins are, for example, vinylidene fluoride resin (PVDF) and vinyl fluoride resin (PVC).

In addition, it goes without saying that the fluorine-containing resin film used for the surface of the present invention must be free from damage such as pinholes, and as long as it completely covers the metal plate serving as the substrate, the film must be free from damage such as pinholes. Although the thickness may be any value, it is generally 5 to 200 microns, preferably 20 to 100 microns.

These fluorine-containing resin films can be produced by conventional methods, such as hot melt extrusion, casting, etc., and if necessary, pigments, Dyes can be blended for coloring, or inorganic fillers such as glass powder, glass beads, glass fibers, aluminum oxide, talc, mica, silica, etc. can be blended to improve strength. It is also possible to print desired designs.

Furthermore, the "metal plate" as used in the present invention is not particularly limited and can be any metal plate, but generally, for example, it is an iron-based, aluminum-based, copper-based metal plate, etc. Of these, iron-based and aluminum-based metal plates are preferred.

The iron-based metal plate may be any metal plate whose composition mainly contains iron, and specifically,
Examples include cold-rolled steel sheets, galvanized steel sheets, zinc alloy-plated steel sheets, aluminum-plated steel sheets, copper-plated steel sheets, stainless steel sheets, phosphate-treated steel sheets, and aluminum-zinc alloy-plated steel sheets. Among them, galvanized steel sheets, zinc alloy-plated steel sheets, etc. Preferred are steel plates, aluminum plated lead steel plates, aluminum-zinc alloy plated steel plates, and stainless steel plates.

Further, as the aluminum-based metal plate, any metal plate may be used as long as the metal plate mainly contains aluminum metal in its composition, but generally, for example,
It is an aluminum plate described in pages 13 to 22 of "Aluminum Handbook (2nd edition)" published by the Light Metals Association of Japan on September 30, 2007, and specifically, pure aluminum, (AI
-Cu) system, (AI-Mn) system, (At-5i) system, (
At-Mg) system, (AI-Mg-5i) system and (Al-
There are Zn-Mg) type plates, among which pure aluminum type, (AI-Mn) type and (AI-Mg) type plates are preferable.

Although the thickness of the metal plate in the present invention is not particularly limited, it is generally, for example, 0.2 to 3 m/m, preferably 0.4 to 2 m/m.

Next, the fluorine-containing resin film, which will become the front surface, and the metal plate, which will become the substrate, need to be joined, and the joining methods include a method using an adhesive and a method of heat fusing. Examples of the adhesive include polyester adhesives, modified epoxy adhesives, epoxy nylon adhesives, and silicone phenol nitrile adhesives.

It is also possible to use an adhesive.

In addition, films can be bonded by heat fusion welding by conventional methods, but generally, for example, a pretreatment step, a heating step, a film lamination step, a pressurizing step,
It can be obtained through processes such as a reheating process and a cooling process. The above steps will be explained below.

(1) Pretreatment Step This step is a step that is carried out as necessary to coat the metal plate and the fluorine-containing resin film more strongly.

■ Pre-treatment process of metal plates The purpose of pre-treatment of metal plates is to remove oily substances that adhere to the surface.
Cleaning and removing foreign substances, oxide films, etc., exposing bare metal to the surface by polishing, etc., surface plating,
Apply surface treatment such as acid treatment, and if necessary,
Add roughness to the surface, etc.

a. Surface cleaning is not particularly limited, and conventional cleaning methods used for specific metals may be used. For example, as a degreasing method,
Degrease and clean using organic solvents, alkaline aqueous solutions, surfactants, etc.

b. Surface polishing The surface can be polished to expose the bare metal on the surface, for example, by mechanical and chemical polishing.

C.Surface Treatment If necessary, chemical conversion treatments such as plating treatment, coating treatment for installing a metal oxide film layer, and antirust treatment can be performed on the surface covered with the film. For example, specific examples of chemical conversion treatments for iron-based metals include phosphate treatment with zinc phosphate, calcium phosphate, etc., and chromate treatment with reactive chromate, coating type chromate, and the like.

d) Surface Roughening The surface can be roughened by a surface roughening method using physical means such as brushing, sandblasting, and shotblasting, or by a surface roughening method using a chemical or electrochemical etching method or a combination thereof.

■ Film pre-treatment process Removing oily matter, foreign matter, etc. adhering to the film surface, applying an oxide film etc. by corona discharge treatment, chemical treatment, etc., and using various surface treatment agents. For example, treatments such as coating aminosilane, vinylsilane, mercaptosilane, etc. can be performed.

(2) Heating process This is a process in which the pretreated metal plate is heat treated in the air or in an atmosphere substantially free of oxygen. In the present invention, the latter is particularly preferable in the case of iron-based metal plates, and is also necessary. In this step, the film is also heat-treated at the same time.

■Heating atmosphere The above-mentioned “substantially oxygen-free atmosphere” means:
There is no particular restriction as long as the atmosphere can heat the metal plates and films that have undergone the pretreatment process while substantially maintaining their surface conditions, but specifically, the atmosphere may have an oxygen content of 1% or less preferable.

To create this heating atmosphere, it can be filled with an inert gas or heated in a vacuum state. Any type of inert gas may be used, but generally nitrogen gas, argon gas, neon gas, helium gas, etc. are preferred, with nitrogen gas and argon gas being preferred, and nitrogen gas being particularly preferred.

Further, the vacuum state is 5 Torr or less, preferably I
Torr or less, more preferably 0. It is less than I Torr.

■Heating temperature The optimum heating temperature is determined depending on the type of fluororesin film and metal plate to be coated, but in general, the softening point temperature (mp) of the fluororesin film
As mentioned above, it is desirable that the temperature is preferably (mp + 30) °C or higher, more preferably (mp + 50) °C or higher, and lower than the thermal decomposition temperature. Specifically, in the case of a fluororesin film, the temperature is For ethylene copolymers, generally 280-400℃, ethylene-
In tetrafluoroethylene copolymers, generally 26
0 to 370°C, generally 220 to 350°C for ethylene-chlorotrifluoroethylene copolymers, and 250 to 300°C for polyvinylidene fluoride.

■ Heating time Heating time varies depending on the heating method and is not something that should be specified in particular.It must be the time required for at least the surface of the metal plate to reach the heating temperature, and may be adjusted as appropriate depending on the type and thickness of the metal plate. It is determined.

(3) Lamination step This step is a step of covering a heated metal plate with a fluorine-containing resin film by lamination and pressing.

■ Lamination atmosphere The lamination atmosphere is not particularly limited, but in the case of iron-based materials, at least a film is laminated on a heated metal plate.
It is desirable that the atmosphere is substantially free of oxygen until it is placed, and the atmosphere is preferably similar to that in the previous step (2).

■ A film laminated and placed on a press-heated metal plate, for example,
This is a process of continuously pressing with a book roll or the like to strongly coat the material. Here, the roll in contact with the film is preferably a roll that does not adhere to the film, such as a rubber roll or a metal roll, and the pressing force is 5 to 30 kg/cnr, preferably 10 to 20 kg/cnr.

(4) Reheating process This step is a reheating step that is performed as necessary to further strengthen the fusion force between the metal plate and the film of the film-coated metal plate obtained in the previous step.

(2) Heating Atmosphere The heating atmosphere is not particularly limited, and may be in the air, but is preferably an atmosphere similar to that in the previous step (2).

■ Heating temperature The optimum heating temperature is determined as appropriate depending on the type of fluororesin film and metal plate to be coated, but generally it is higher than the softening point temperature (mp) of the fluororesin film, preferably (mp+20)℃ or higher, more preferably (mp+30)℃ or higher and lower than the thermal decomposition temperature. Specifically, in the case of a fluororesin film, tetrafluoroethylene/perfluoroalkoxyethylene For copolymer, it is generally 280 to 400°C, for ethylene-tetrafluoroethylene copolymer, it is generally 260 to 360°C, and for ethylene-chlorotrifluoroethylene copolymer, it is generally 220 to 350°C. °C and 200 to 250 °C for polyvinylidene fluoride.

■ Heating time Heating time is not something that should be specified in particular; it must be at least the time required for the metal plate to reach a certain temperature and until sufficient fusing strength is achieved, and should be determined as appropriate depending on the type of film metal plate. generally for 1 to 20 minutes.

(5) Cooling process This process is a process of cooling the reheated film-laminated metal plate to room temperature, and can be cooled using, for example, an air cooling fan, water, or the like.

The film-laminated metal plate of the present invention obtained through the above steps exhibits strong adhesive strength between the metal plate and the fluorine-containing resin film, and has excellent durability.

The process of processing the bonded body of metal and fluorine-containing resin film obtained through the above steps into a shutter involves conventional processes such as a cutting process, a pressing process, a roll forming process, and further processing as necessary. , bonding process, etc.

The forming process for the fluororesin film laminated metal plate involves cutting it into the desired shape (cutting process) by shearing, cutting (milling, sawing), etc., then bending, drawing, etc. to create a shutter. After forming into a slat for use, joining processing (joining process) can be performed as necessary by methods such as welding (arc welding, plasma welding, electron beam welding), brazing, soldering, riveting and adhesion.

As the printing layer, it is preferable to provide the printing layer described in Japanese Patent Application No. 1-73899 and Japanese Patent Application No. 1-139155. For example, the printing layer in Japanese Patent Application No. 1-73899 is a fluororesin layer heat-sealed to the metal surface, and the uppermost layer is made of a fluororesin composition with a thixotropic index (TI value) of 2 to 8. The printing layer is formed by printing using the ink of
A preferred embodiment of the printed layer in No. 73899 is a printed layer in which a fluororesin film having a printed layer is heat-sealed to a metal surface with the printed layer inside.

The shutter of the present invention obtained in this way has a smooth continuous uniform layer of fluorine-containing resin on its surface without any pinholes, so it not only has excellent weather resistance but also has excellent durability and remains beautiful forever. The design is extremely excellent because it can maintain a smooth surface and at the same time print or draw on film or metal.

In addition, due to its non-wetting properties, not only is there less contamination, but also adhered dirt can be cleaned extremely easily. Furthermore, graffiti and other mischief done on the surface can be removed. The surface can also be used as a temporary advertising solution. For example, it becomes possible to paste advertisements or draw designs.

As mentioned above, it can be seen that the shutter obtained by the present invention is a shutter with novel and excellent performance that meets modern demands.

The present invention will be explained in more detail below with reference to Examples, but it goes without saying that the present invention is not limited only to the Examples.

Example 1 First, an aluminum plate of A3004 P-H34 (thickness 1.0°) specified in JISH4000 was used as an aluminum base material, and the surface of the aluminum plate was subjected to sandblasting treatment (using 80 meshes of reduced iron powder, pneumatic treatment). After roughening Ra (center line average roughness) to 1.8 μm under a pressure of 3b/c+v), it was electrolytically etched in a 4% sodium chloride aqueous solution at a current density of 3.3 A/dr to have an Ra of 3.5 μm. A rough surface was formed.

This aluminum plate was heated to a temperature of 350°C, and a 50 μm thick ethylenetetrafluoroethylene copolymer film (melt flow index 3) was formed on the rough surface.
0+a37 seconds) were thermally fused to obtain a fluororesin laminated aluminum plate having the same shape as shown in FIG.

The heat fusion bonding is performed by bonding the heated metal plate and the film using a silicon roll with a diameter of 103 mm at a pressure of 15 y/cm.
The experiment was conducted under 3 conditions.

A shutter is manufactured using the resin laminated aluminum plate formed as described above. First, the resin laminated aluminum plate has a width of 100 mm and a length of 1000 mm. The slats for the shutter were cut into the shape shown in Figure 1 using a roll forming machine and attached to the shutter.

Example 2 The surface of the fluorine film in Example 1 in contact with metal was activated by corona treatment to a wetting index of 42 dyn/am. Next, polyvinylidene fluoride was dissolved in dimethylacetamide and screen printing was performed on the active surface of the above film using an ink mixed with the application material to produce a printed film.

Next, a fluororesin film-coated aluminum plate was obtained in the same manner as in Example 1 so that the printed surface of this printed film was in contact with metal, and a shutter was manufactured.

Example 3 Screen printing was performed on an aluminum plate that had been pretreated in the same manner as in Example 1 using the ink prepared in Example 2 to obtain a printed aluminum plate. A fluorine film was heat-sealed to the printed surface of this printed aluminum plate in the same manner as in Example 1 to obtain a fluororesin film-covered [full minilamb board], and a shutter was produced.

Example 4 Commercially available phosphate-treated electrical galvanized steel sheet (Nippon Steel:
Bonded steel plate EGC1 thickness 0.6m/m) was treated with an alkaline degreaser (Nippon Barcalizing, Fine Cleaner 3).
The surface was washed with water for 3 minutes at 60° C. (using 01), and then washed with water and dried. This steel plate was placed in a nitrogen-substituted heating furnace with an oxygen concentration of 0.1% and heat-treated at 350°C for 6 minutes. 50μ titanium oxide 8
A white ethylenetetrafluoroethylene resin film containing parts by weight was heat-sealed at 7 kg/c and a pressure of 2. Further, this heat-sealed steel sheet was reheated at 325° C. for 7 minutes in an oxygen atmosphere, and cooled by being left indoors to obtain an ethylenetetrafluoroethylene resin film-coated steel sheet.

A shutter was manufactured using the obtained coated steel plate.

Example 5 In Example 1, the ethylenetetrafluoroethylene film was replaced with vinylidene fluoride film.

Example 6 In Example 1, the ethylenetetrafluoroethylene film was replaced with a vinyl fluoride film.

Example 7 A shutter was produced in the same manner as in Example 4 except that a SUS-304 (plate thickness Q, 6 m10) film was used instead of the steel plate and the printed film obtained in Example 2 was replaced.

Example 8 Commercially available phosphate-treated electrical galvanized steel sheet (Nippon Steel:
bonded steel plate EGC, thickness 0.6m/m) with an alkaline degreaser (Nippon Vercalizing, Fine Cleaner 3).
01) for 3 minutes at 60°C, then washed with water and dried. This steel plate and a white ethylenetetrafluoroethylene resin film with a thickness of 50μ containing 8 parts by weight of titanium oxide were treated with corona discharge to have a wettability index of 42 dynes/■, which was manufactured by Sony Bond 5C209 (manufactured by Sony Chemical ■). It was pasted using The amount of adhesive applied is dry 20g/
After applying nl adhesive, it was heated for 150 x 3 minutes to complete the adhesion. A shutter was produced using this fluorine film coated plate.

Example 9 The following acrylic adhesive was applied to the printed surface of the printing film obtained in Example 2 to a dry thickness of 40μ, dried, and degreased. SUS-304 (plate thickness: 0.6 m to 7 m)
I pasted it on. Using the obtained fluororesin-coated plate, a shiyayata- was produced.

(Acrylic adhesive) An adhesive containing 100 parts by weight of Niracera PE-121, 1.4 parts by weight of Seasolve 704, and 0.7 parts by weight of Tinuvin 622 LD was used.

Example 10 In Example 8, a slutter for a shutter was produced by laminating a steel plate and a fluororesin film cut into the following predetermined sizes.

Width Length Steel plate: 100 x 1000 m/m Film: 140 x 1000 m/m The excess portion of the film was folded back as shown in Figure 2.

The performance of the shutter obtained in the above example was evaluated and the results are shown in Table 1 below.

Table 1 (Evaluation method) 1. Processability: No color change such as whiteness in embossed parts or folded parts, and no change in appearance such as lifting or wrinkles was rated O.

2. Durability J I
Using WS type sunshine carbon (manufactured by Gas Test Instruments) shown in SA1415, an accelerated rough road test was conducted for 5000 hours, and the appearance was compared with the preserved test pieces. A case where the appearance was almost the same as that of the preserved test piece was marked as ○, and a case where there was a change was marked as ×.

3. Corrosion resistance As a corrosion resistance mock test, a cylindrical container with a diameter of 53 and a depth of 23 was made using the remaining flat plates from which the shutters were prototyped on each side, and 3 cc of aqua regia was poured inside and left at 70°C to change the container. The presence or absence of was observed. Those with no change were designated as O.

46 Cleanability Method A Graffiti was written on the shutter surface using magic ink.
After that, it was wiped off using ethanol.

Those that could be easily and completely wiped off were marked as ○.

Method B: The prototype shutter slutter was left outside for a month and the dirt was wiped with a dry rag. Those from which the dust and dirt could be easily wiped off were designated as O.

5. Removal of stickers Method A high-quality paper was pasted on the shutter using a vinyl acetate solvent-based adhesive, and after drying, the high-quality paper was peeled off.

Those that were not adhered were rated O.

Method B: The high-quality paper was fixed to the shutter with cellophane tape, and after one month, the cellophane tape was peeled off.

Those that peeled off cleanly were rated as ○.

6. Design Printed designs with clear colors and designs were rated O.

As is clear from Table 1 above, the shutter obtained by the present invention has excellent cleanability, durability, and corrosion resistance, and is rich in design, and the shutter surface can be used as a kind of temporary advertising medium. It is clear that this is an extremely excellent product.

[Brief explanation of drawings]

FIG. 1 shows a cross section of the slutter for shutters of the present invention, including: 1... Fluororesin layer, 2... Metal plate, 3-...14.511I/II. 4...67.0m/m. 5... 13.1m/m. FIG. 2 is a sample diagram of how the film was attached to the metal plate in Example 10. ■... Fluororesin film, 2... Adhesive, 3... Metal plate. Ward 1 Figure-2

Claims (1)

[Scope of Claims] 1. A shutter characterized in that at least the surface of the shutter is mainly made of a metal plate coated with a fluorine-containing resin film. 2. The novel shutter according to claim 1, wherein the fluororesin film has a printed layer. 3. The novel shutter according to claim 1, wherein the fluorine-containing resin is a tetrafluorinated resin. 4. The novel shutter according to claim 3, wherein the tetrafluorinated resin is a tetrafluoroethylene-ethylene copolymer (ETFE). 5. The novel shutter according to claim 1, wherein the fluororesin is a difluoride resin. 6. The novel shutter according to claim 1, wherein the fluorinated resin is a monofluorinated resin. 7. The novel shutter according to claim 1, wherein the film has a thickness of 5 to 200 μm. 8. The novel shutter according to claim 1, wherein the metal of the metal plate is an aluminum metal plate. 9. The novel shutter according to claim 1, wherein the metal of the metal plate is an iron-based metal plate. 10. Claims 1 and 7, wherein the metal plate has a thickness of 0.2 to 3.0 m/m.
and the novel shutter described in any of Item 8. 11. A material used for a shutter, characterized in that at least the surface of the shutter is a metal plate coated mainly with a fluorine-containing resin film.