JPH04142928A - Novel antifouling panel - Google Patents

Abstract

PURPOSE:To prevent new scribbling or sticking of bills, by using a fluororesin layer as a main constituent on at least one side of a panel. CONSTITUTION:A 'fluorine-containing resin' is not particularly limited but may be any thermoplastic resin that contains a fluorine atom in the molecular structural formula thereof. The fluorine-containing resin may be a tetrafluoroethylene resin having four fluorine atoms in the molecular structural formula thereof, and further may be a trifluoroethylene resin, a difluoroethylene resin, a monofluoroethylene resin, a copolymer of these resins, a mixture thereof, or the like. A fluorine-containing resin layer used on one side of a panel is preferably a free of damages such as pinholes. The thickness of the fluorine- containing resin layer may have any value, provided that the layer covers wholly the surface of a metallic plate used as a substrate. Generally, the thickness is 5-200mum, preferably 20-100mum. The thickness of the metallic plate is not particularly limited; generally, the thickness is, for example, 0.05-3mm, preferably 0.1-2mm.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel antifouling panel and materials used therein, and more particularly to a novel antifouling panel having a fluororesin coating layer.

[Prior art]

Graffiti and various types of posters have been placed on conventional utility poles, station buildings, platforms, theaters, underpasses, various structures in bridge parks, isolation walls at construction sites, and 3° public toilets, which are not only degrading their aesthetic appearance. Over time, there are many cases where the color changes to brownish brown due to rain or sunlight, or parts of it are torn off, resulting in an extremely unsightly condition. Also, it is not easy to remove for cleaning, which is a problem. To prevent these problems, the only solution is to wrap uneven panels around utility poles to prevent stickers from forming. Under these circumstances, there was a strong demand for panels that could not be pasted or that could be peeled off very easily, and that could not be marked with graffiti or that could be easily erased.

[Problem to be solved by the invention]

The purpose of the present invention is to solve the above-mentioned problems that the prior art had, and at the same time, provide a novel antifouling property that is completely unknown in the past and also has decorative properties by applying patterns and colors. It provides panels.

[Means for solving problems]

The present invention has been made to solve the above-mentioned problems, and provides a novel panel capable of preventing graffiti and pasting, characterized in that at least one side of the panel is made of metal mainly consisting of a fluororesin layer. It is something.

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, difluoroethylene resins, -fluoroethylene resins, copolymers of these resins, and mixtures, etc. be.

Here, the tetrafluoroethylene resin specifically refers to, for example, tetrafluoroethylene resin (PTFE), tetrafluoroethylene/perfluoroalkoxyethylene copolymer (PFA),
), tetrafluoroethylene/hexafluoropropylene/perfluoroalkoxyethylene copolymer (EPE), and tetrafluoroethylene/ethylene copolymer (ETFE), among which ETFE is preferred. In addition, the above-mentioned trifluoroethylene resin specifically includes, for example, trifluorochloroethylene resin (PCTFE) and trifluorochloride ethylene/ethylene copolymer (ECTFE), among which PC
TFE is preferred. Specifically, the difluoroethylene-based and -fluoroethylene-based resins include, for example, vinylidene fluoride resin (PVDF) and vinyl fluoride resin (PVDF).
F).

In addition, the fluororesin layer used on one side of the present invention is preferably a film without damage such as pinholes, and if it completely covers the metal plate serving as the substrate, the layer thickness is Any number is fine, but generally 5 to 2
00μ, preferably 20 to 100μ.

These fluororesin films can be produced by conventional methods, such as hot-melt extrusion, casting, etc., and if necessary, pigments, dyes, etc. Blend and color,
Inorganic fillers such as glass powder, glass peas, and glass fibers, aluminum oxide, talc, mica, and silica can be added to improve strength and the like. 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 composition mainly contains aluminum metal, 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, (AI-8i) system, (A
I-Mg) system, (AI-Mg-8i) system and (
There are AI-Zn-Mg) type plates, among which pure aluminum type, (Δl-Mn) type and (Al-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, 0.05 to 3 m/m, preferably 0.1 to 2 m/m.

Next, the fluorine-containing resin film and the metal plate serving as the substrate must be bonded together, and there are two methods for bonding, such as using an adhesive and heat-fusion bonding. is preferred.

Films can be bonded by heat-melting and bonding using conventional methods, but generally, for example,
It can be obtained through processes such as a pretreatment process, a heating process, film lamination, a pressurizing process, a reheating process, and a cooling process. Below, the first step will be explained.

(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.

Surface polishing The bare metal can be exposed on the surface by surface polishing, such as mechanical and chemical polishing.

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.

69 Surface Roughening The surface can be roughened by a surface roughening method using physical means such as brushing, sandblasting, shot blasting, etc., 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, straw material treatment, etc., and using various surface treatment agents. For example, treatments such as coating aminosilane, vinylsilane, mercaptosilane, etc. can be performed.

(2) Heat treatment of the pre-treated metal plate in the air or in an atmosphere substantially free of oxygen] The latter is particularly preferred in the case of iron-based materials in the present invention; This is a step in which the film is also heat-treated at the same time, if necessary.

■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, and nitrogen gas and argon gas are particularly preferred, with nitrogen gas being particularly preferred.

In addition, the vacuum state is 5 Torr or less, preferably I
Torr or less, more preferably 01 Torr or less.

■ Heating temperature The optimum heating temperature is determined as appropriate depending on the type of fluororesin film and metal plate to be coated, but in general, the softening point temperature of the fluororesin film (mp
) or more, preferably (mp +30) 'C or more, more preferably (mp +50) 'C or more'2, and below the thermal decomposition temperature. Specifically, in the case of a fluororesin film, 4 For fluorinated ethylene/perfluoroalkoxyethylene copolymers, generally 280 to 40
0°C, generally 260-370°C for ethylene-tetrafluoroethylene copolymers, and generally 220-370°C for ethylene-chlorotrifluoroethylene copolymers.
50℃, and 250 to 300 for polyvinylidene fluoride.
°C etc.

■ 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 restricted, but in the case of iron-based materials, it must be an atmosphere that is substantially free of oxygen, at least until the film is laminated and placed on the heated metal plate. It is desirable that the atmosphere be similar to that of the previous step (2).

(2) This is a step in which the film laminated and placed on a press-heated metal plate is continuously pressed, for example, with two rolls, to coat it with a strong coating. Here, the roll in contact with the film is preferably a roll that does not stick to the film, such as a rubber roll or a metal roll, and the pressing force is 5 to 30 kg/cm2,
Preferably it is 10-20 kg/cm2.

(4) Reheating process This process is a reheating process 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 process.

(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 depending on the type of fluororesin film and metal plate to be coated, but in general, it is determined by the softening point temperature (mp) of the fluororesin film.
Above, preferably Cmp +20)'C or higher, more preferably (mp +30)'C or higher, and lower than the thermal decomposition temperature. Specifically, in the case of a fluororesin film, tetrafluoroethylene, For perfluoroalkoxyethylene copolymers, the temperature is generally 280 to 400°C.
, in the ethylene-tetrafluoroethylene copolymer,
Generally 260-360°C, for ethylene-chloro I/lifluoroethylene copolymer, generally 220-35°C.
0°C and 200-250°C for polyvinylidene fluoride
etc.

■ Heating time The heating time does not have to be specified in particular; it must be at least the time it takes for the metal plate to reach a predetermined temperature and for the welding force to be sufficiently developed. It is determined, but - 1 to 20 minutes for boat fishing.

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

The film-coated 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 converting the bonded product of metal and fluorine-containing resin film obtained through the above process into an antifouling panel involves conventional processes such as a cutting process, a pressing process, and, if necessary, a bonding process. There are processes etc.

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 two most layers have a thixotropic index (TI value).
is a printed layer printed using an ink made of a fluororesin composition of 2 to 8, and the printed layer of Japanese Patent Application No. 1-73899 has a printed layer on a metal surface. A preferred embodiment includes a printed layer in which a fluororesin film is heat-sealed with the printed layer on the inside.

The thus obtained stain-resistant panel of the present invention has a resin layer that is a smooth continuous uniform layer made of a fluorine-containing resin film with no pinholes. If you cover it with paper, there is no suitable adhesive, so it cannot be pasted, or at best it is only temporarily fixed with an adhesive material, so it is very easy to peel off. Also, when it comes to graffiti, there is no suitable binder, and most of the time it doesn't remain on the resin, or even if it does, it can be easily removed with a rag. Also, even if the adhesive sticks firmly, such as a magic marker, it can be easily wiped off with a detergent solution or alcohol. In addition, this panel can easily remove mold, algae, and the droppings of birds such as pigeons in areas exposed to high humidity outdoors near the ground. Furthermore, since it has very good weather resistance, it is possible to apply beautiful colored designs to objects outdoors and maintain its beauty for a long time, so that public places can be kept comfortable.

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 A3004P-H34 (thickness 1 mm) specified in JISH4000 was used as an aluminum base material, and the surface of the aluminum plate was sandblasted (reduced iron powder 80 mesh was used, pneumatic pressure 3
kg/cm2), Ra (center line average roughness)
After roughening the surface to 18 μm, electrolytic etching was performed in a 4% sodium chloride aqueous solution at a current density of 3.3 A/drff to form a rough surface with Ra of 3.5 μm.

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 m 37 seconds) were thermally fused to obtain a fluororesin laminated aluminum plate having the same shape as shown in FIG.

The above-mentioned thermal fusion bonding is performed by applying a pressure of 15 k to the heated metal plate and the above-mentioned film using a silicone roll with a diameter of 10 cm.
The test was conducted under the condition of g/cm.

An antifouling panel for utility poles was produced using the resin laminated aluminum plate formed as described above.

Example 2 The surface of the fluorine film in Example 1 that was in contact with metal was activated by corona treatment to a wetting index of 42 dyn/cm. Next, polyvinylidene fluoride was dissolved in dimethylacetamide and an ink mixed with a pigment was used to perform screen printing on the active surface of the above film to prepare a printed film.

Next, an aluminum plate coated with a fluororesin film 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 an antifouling panel suitable for a wainscot panel for an underground passage was produced.

Example 3 Commercially available phosphate-treated electrogalvanized steel sheet (Nippon Steel:
bonded steel plate EGC, thickness 0.6m/m) with an alkaline degreaser (Nippon Parkerizing Co., Ltd., Fine Cleaner 3).
The surface was washed with water and dried under conditions of 608C for 3 minutes. This steel plate was placed in a nitrogen-substituted heating furnace with an oxygen concentration of 01% and heat treated at 350°C for 6 minutes, and then heated to a thickness of 50 μm using a pair of silicon rolls also placed in a nitrogen atmosphere with the same oxygen concentration. 7kg/cm2 of ethylenetetrafluoroethylene resin film
It was heat fused at a pressure of . Further, this heat-sealed steel sheet was reheated at 325° C. for 7 minutes in a nitrogen atmosphere, and cooled by being left indoors to obtain an ethylenetetrafluoroethylene resin film-coated steel sheet. Protective panels for platform pillars were made using the obtained coated steel plates.

Example 4 In Example 3, an ethylenetetrofluoroethylene film was replaced with a vinylidene fluoride film. The heating temperature is 27
The temperature was 0°C.

Example 5 A vinyl fluoride resin film was used in place of the ethylenetetrafluoroethylene film of Example 3. Heating temperature is 2
The temperature was 20°C.

The performance evaluation of each panel obtained in the examples is shown in the table below.
Shown in 1.

(Evaluation method) 1. Antifouling property A A commercially available water-based paint was applied to each side panel and allowed to dry. When peeled off by hand after drying, those that could be easily peeled off were rated as ○.

B. Magic ink was applied to each side panel, dried, and then wiped off with ethyl alcohol. Those that could be easily wiped off were rated as ○.

C6 The panels made in each example were rubbed with pigeon droppings, dried, and then wiped with Miscellaneous 1. Those that could be easily wiped off were rated as ○.

D Paper was attached to the panels made on each side with a vinyl acetate resin emulsion adhesive.

Those that fell off with drying or fell off with a slight force were marked as ○.

E Attach commercially available adhesive labels to the panels made on each side 1
It peeled off after several months. A case where the label was peeled off cleanly was rated as ○.

2. Corrosion Resistance A cylindrical container with a diameter of 5 cm and a depth of 2 cm was prepared using the remaining flat plates from which the panels were prototyped on each side, and 3 cc of aqua regia was poured into the container and left at 70°C to observe any changes. If there was no abnormality for 3 days, it was marked as ○.

3. Weather resistance Using the remaining flat plates from which panels were prototyped on each side, JIS A
Using WS type Sunshine Carbon (manufactured by Suga Test Instruments) shown in No. 1415-1977, an accelerated exposure test was conducted for 5000 hours, and its appearance was compared with a preserved test piece. A case where the appearance is almost the same as that of the preserved test piece is marked as ○, and a case where there is a change is marked as ×.

4 Appearance A rating of O was given when the printed design was clearly visible.

From Table 1 above, it is clear that the antifouling panel having the fluororesin-coated metal layer according to the present invention has extremely excellent antifouling performance, excellent durability and weather resistance, and has an excellent design.

Claims (1)

[Scope of Claims] 1. A novel antifouling panel made of metal, characterized in that at least the outer surface mainly consists of a fluororesin-containing coating layer. 2. The novel antifouling panel according to claim 1, wherein the fluororesin-containing coating layer is a fluororesin film. 3. The antifouling panel according to claim 2, wherein the fluororesin film has a printed layer. 4. The novel antifouling panel according to claim 2, wherein the fluororesin is a tetrafluoride resin. 5. The novel antifouling panel according to claim 3, wherein the tetrafluorocarbon resin is an ethylene-tetrafluoroethylene copolymer. 6. The novel antifouling panel according to claim 2, wherein the fluororesin is a difluororesin. 7. The novel antifouling panel according to claim 2, wherein the fluororesin is a monofluororesin. 8. The novel antifouling panel according to claim 1, wherein the fluororesin coating has a thickness of 5 to 200 μm. 9. The novel antifouling panel according to claim 1, wherein the metal is an aluminum-based metal. 10. The novel antifouling panel according to claim 1, wherein the metal is an iron-based metal. 11. The novel antifouling panel according to claim 1, paragraphs 6 and 7, wherein the metal is plate-shaped with a thickness of 0.05 to 3 mm/m.