JP2000094577A - Weather-resistant resin-coated metal plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin-coated metal plate mainly used outdoor, and having excellent weather resistance and processability. SOLUTION: In the resin-coated metal plate comprising a colored acrylic resin film 13 and a transparent resin film 14 sequentially laminated and integrated on a metal plate of a base material 11 via an adhesive 12; the film 14 is formed of a blended composition of a polyvinylidene fluoride resin and an acrylic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a weather-resistant resin-coated metal sheet. More specifically, the present invention relates to a weather-resistant resin-coated metal plate mainly used outdoors and having good weather resistance and workability.

[0002]

2. Description of the Related Art Conventionally, a purpose of imparting a design property to a resin-coated metal plate used for outdoor use, in particular, a resin-coated metal plate coated with a vinyl chloride resin (hereinafter sometimes abbreviated as "PVC"). In general, a printed pattern is generally formed by printing a pattern on a vinyl chloride resin film layer and laminating a transparent acrylic resin film on the printed surface of the pattern. Was. However, the resin-coated metal sheet coated with the coating layer having such a configuration has a defect mainly in weather resistance and workability, so when used, its use is limited to a narrow range, and in a wide range. It is currently used. In the case of a PVC-coated metal plate having an acrylic resin film laminated on the surface, a transparent acrylic resin film forming a surface layer has an ultraviolet ray for the purpose of protecting the printing surface and the PVC resin layer from ultraviolet rays when used outdoors. The one to which the absorbent was added was used.

[0003] Acrylic resins themselves have good weather resistance, and are excellent in transparency and bending whitening resistance (they are hardly whitened when bent). This is because they have advantages such as being able to be laminated and integrated by the fusion method, and are often used for surface coating of a vinyl chloride resin-coated metal plate. The acrylic resin used for the surface coating of the resin-coated metal plate is generally referred to as a flexible acrylic resin or a soft acrylic resin. It is a copolymer resin obtained by graft polymerization of an acrylate resin. The copolymerization method and the constitution of the coating layer are described in JP-A-48-36947, JP-A-53-64228 and JP-A-53-64228. 57-1
No. 46652 has been proposed.

[0004] Such a PVC-coated metal sheet whose surface is covered with an acrylic resin film exhibits relatively good formability, but the flexible PVC layer has a smaller thickness than the acrylic resin film. The reason for this is that the deformation stress applied to the acrylic resin film at the time of bending is alleviated. Generally, the thickness of the transparent acrylic resin film covering the surface is about 30 to 50 μ, while the thickness of the PVC layer is about 120 to 250 μ.

[0005]

However, in the above-described layer structure of the coating resin layer, the ultraviolet ray shielding property of the transparent acrylic resin film of the surface layer is not sufficient.
The current situation is that the VC layer is gradually deteriorated by ultraviolet rays as the outdoor use period elapses, and the expected good weather resistance is not obtained. For example, a desorption hydrochloric acid reaction occurs due to the deterioration of the vinyl chloride resin itself, and hydrochloric acid corrodes the surface of the base metal to cause peeling, or a deteriorated product of an additive such as a plasticizer deteriorates the adhesive layer. Or cause peeling.

[0006] In order to improve the weather resistance of the resin-coated metal plate having the above-mentioned layer constitution, (i) the thickness of the transparent acrylic resin film of the surface layer is increased, or (ii) the PVC layer which is severely degraded. , And the like.
However, this causes the thickness of the transparent acrylic resin film and the thickness of the PVC layer to be close to each other, resulting in reduced workability.

Further, in order to increase the flexibility of the transparent acrylic resin film itself and prevent a decrease in workability, (a) a method of increasing the amount of a crosslinked elastic material component, (b) copolymerization of methyl methacrylate in a matrix phase A method of decreasing the ratio and increasing the copolymerization ratio of an acrylate resin having a glass transition point lower than room temperature, such as butyl acrylate, may be considered. However, the method (a) has a limit in improving the tensile elongation at break which directly leads to improvement in workability, and it is known that the weather resistance is also reduced. In addition, not only is the surface stain resistance reduced, but also the weather resistance is further reduced as compared with the above method (a), so that it is not suitable for a coating protective film. As described above, a PVC-coated metal plate coated with a transparent acrylic resin film, which has good workability and excellent weather resistance, has not been proposed.

On the other hand, a polyvinylidene fluoride resin (hereinafter, referred to as a polyvinylidene fluoride resin) is used as a PVC coating film of a PVC coated metal plate.
A transparent film made of a blend composition of “PVdF” and an acrylic resin (hereinafter sometimes abbreviated as “blend film”) is commercially available. Since the crystalline resin PVdF and the acrylic resin are mutually compatible with each other, the blend film is transparent, and the tensile elongation at break consists only of PVdF due to the effect of inhibiting the crystallization of PVdF. This is significantly improved as compared with a film or a coating film made of only an acrylic resin. Further, a two-layer laminated film is formed by a co-extrusion molding method, and its surface layer is formed of PVd.
A layer having a relatively large amount of F, and therefore having good weather resistance and stain resistance, and a back layer adhered to the PVC being a layer having a relatively large amount of an acrylic resin and having excellent heat-fusibility with PVC. Is also commercially available and is suitably used as a coating protective film on PVC.

As described above, the PVC resin-coated metal plate on which the blended film of the PVdF and the acrylic resin is laminated is made of only the acrylic resin because the tensile elongation at break of the blended film is improved. Although it has better processability than that obtained by laminating a film, the weather resistance is not much different from that obtained by laminating a film composed of only an acrylic resin. this is,
As in the case of a film made of only an acrylic resin, if the thickness is about 30 to 50 μm, the ultraviolet ray shielding property is not sufficient, and the added ultraviolet ray absorber gradually forms on the PVC layer over time. By shifting, the effect as an ultraviolet cut film is attenuated.
This is because the VC layer is also deteriorated by ultraviolet rays.

[0010] In a film made of only an acrylic resin, the acrylic resin is gradually deteriorated with the passage of time under the influence of the degradation product of the PVC layer. In the case of a film of a blend of PVdF and an acrylic resin, the weather resistance of the film itself is extremely good, so that the film is not affected by the degradation products of the PVC layer. The presence of a good blended film prevents dissipation and accumulates at the interface between the PVC layer and the blended film, which results in the blended film peeling off from the surface of the degraded PVC layer and consequently having poor weather resistance May be given.

Further, the degradation products of the PVC layer and the degradation products of PVdF accumulated at the interface may be significantly discolored. As described above, the resin-coated metal plate having the layer structure in which the blended film is laminated on the PVC layer also has a satisfactory weather resistance due to the limit of the protection effect by the organic ultraviolet absorber and the imbalance of the weather resistance of the upper and lower films. At present, it has not been obtained.

The present invention has been made in view of the above-mentioned situation in the technical field to which a resin-coated metal plate belongs, and is mainly used outdoors and has excellent weather resistance and workability. As a result of intensive studies for the purpose of providing a board, a transparent acrylic resin film composed of a blend composition of a polyvinylidene fluoride resin and an acrylic resin is sequentially laminated and integrated on a metal plate with a colored acrylic resin film Found that the above objectives could be solved at once,
The present invention has been completed.

[0013]

In order to solve the above-mentioned problems, the present invention provides a method of forming a colored acrylic resin film (A) and a transparent resin film (B) on a base metal plate via an adhesive layer. Wherein the transparent resin film (B) is a film composed of a blend composition of a polyvinylidene fluoride resin and an acrylic resin. A resin-coated metal plate is provided.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
A weather-resistant resin-coated metal plate according to the present invention uses a metal plate as a substrate. As the metal plate, a steel plate generally used as a base material of a resin-coated metal plate is referred to, specifically, a hot-dip galvanized steel plate, an electro-galvanized steel plate, an aluminum / zinc composite plated steel plate, an aluminum-plated steel plate, Examples include a stainless steel plate and an aluminum alloy plate. There is no particular limitation on the thickness, heat treatment conditions, plating thickness, and the like of these metal plates, and the surface treatment of the metal plate may be performed by a phosphate treatment, a chromate treatment, or the like.

A resin is laminated on the metal plate of the substrate via an adhesive layer. Adhesives that can be used include acrylic adhesives, urethane adhesives, acrylic / urethane adhesives, epoxy adhesives, phenolic adhesives, amide adhesives, acid-modified olefin adhesives, and vinyl acetate adhesives Agents, polyester-based adhesives, copolyester-based adhesives, copolyamide-based adhesives, and mixtures thereof. The adhesive is not limited to those exemplified.

The method of applying the adhesive on the metal plate is not particularly limited. The viscosity is adjusted so that the adhesive is easily applied by adding an organic solvent to the adhesive, and the adhesive is applied by a roll coating method, a bar coating method, a gravure coating method, or the like. Can be applied. The coated surface is preferably dried by a hot air oven, an infrared heating oven, or the like, to scatter the organic solvent. The thickness of the adhesive layer after drying is preferably selected in the range of 1 to 10 μm.
Depending on the type of the adhesive, a method of applying and baking on a metal plate can also be used. As an example, a method in which an adhesive dissolved in a solvent is continuously applied by a roll coating method while unwinding a steel sheet wound in a roll shape, and then introduced into a drying furnace installed in-line, and then to a baking furnace Can be.

The weather-resistant resin-coated metal sheet according to the present invention is obtained by coating a colored acrylic resin film (A) (hereinafter simply referred to as “film (A)” or “intermediate layer”) on the metal sheet via an adhesive layer. Is sometimes laminated). As the acrylic resin used for forming the film (A), those generally called a flexible acrylic resin or a soft acrylic resin may be mentioned. These are all based on a crosslinked acrylic rubber elastic component as a core and
It is made of a copolymer resin obtained by graft polymerization of an acrylate resin. The crosslinked elastic component is mainly composed of an acrylate resin having a glass transition temperature lower than 0 ° C. such as butyl acrylate, and has a crosslinked structure by copolymerizing a small amount of ethylene glycol / dimethacrylate or the like. .

The monomers grafted to the crosslinked elastic body and forming the matrix phase of the acrylic resin include methyl methacrylate as a main component, butyl acrylate, and other (meth) acrylate compounds. Details of the method for polymerizing the flexible acrylic resin or the soft acrylic resin and the constitution of the matrix phase are described in JP-A-48-36947 and JP-A-53-636.
No. 4228, JP-A-57-146652 and the like.

Since the colored acrylic resin film (A) is colored by adding an inorganic pigment, it is more resistant to acryl resin than a conventional acrylic resin used for surface coating of a PVC resin coated metal plate. There is no need to be excellent in bending whitening property, transparency and the like, and therefore, it is not necessary to complicate the structure of the matrix phase. Further, since the surface of the film (A) is covered with a transparent film (B) having good weather resistance (hereinafter, sometimes simply referred to as “film (B)” or “surface layer”), a conventional PVC resin is used. Film (A) compared to acrylic resin used for surface coating of coated metal plate
It is not necessary to have excellent weather resistance, and therefore, the copolymerization ratio of methyl methacrylate in the matrix layer is reduced,
By increasing the ratio of (meth) acrylate resin such as butyl acrylate with low glass transition temperature,
It may be more flexible.

Since the weather-resistant resin-coated metal sheet according to the present invention does not include a vinyl chloride resin layer unlike the conventional resin-coated metal sheet, the resin component itself may be discolored due to the formation of the polyene structure or may be added in a large amount. Deterioration of additives such as plasticizers does not occur, and there is no risk of discoloration etc. due to accumulation at the interface between the vinyl chloride resin layer and the transparent acrylic resin layer. The desorbed hydrochloric acid due to the deterioration of the resin white body does not corrode and cause peeling of the surface of the base metal, and a deteriorated product of an additive such as a plasticizer does not deteriorate the adhesive layer and cause peeling. .

The film (A) is colored. The reason for coloring the film (A) is to improve the ultraviolet shielding property of the film (A), enhance the design, and improve the coloration of the printed layer formed on the surface. Colorants used for this purpose are preferably inorganic pigments, titanium oxide, calcium carbonate, white ones such as barium sulfate,
Alternatively, a pigment having a color tone of an inorganic composite oxide is used. Among the white pigments, the difference in the refractive index from the acrylic resin is large, and therefore, a titanium oxide having a large light-shielding effect, particularly rutile-type titanium oxide, is preferable, but since this titanium oxide and the like also have a strong photocatalytic action, It is preferable to use a completely surface-treated resin so as not to promote the deterioration of the acrylic resin.

Immediately after the outdoor use of the weather-resistant resin-coated metal sheet according to the present invention is started, the effect of shielding ultraviolet rays by the surface blend film containing the ultraviolet absorbent is great. As the period elapses, the shielding effect of the organic ultraviolet absorber gradually decreases due to dissipation from the surface, decomposition in the base resin, transfer to the film (A) layer, and the like. At that time, in order to prevent the adhesive layer between the substrate and the metal plate from being directly deteriorated by ultraviolet rays, it is important to shield the film (A) from ultraviolet rays with inorganic pigments.

Further, a colored acrylic resin film (A)
In addition to the above colorants, ultraviolet absorbers, light stabilizers,
Various resin additives generally added for the purpose of improving the weather resistance of the resin, such as a radical scavenger and an antioxidant, can be blended.

The film (A) has a tensile elongation at break at room temperature, measured in accordance with JIS K7127, of MD (extrusion direction of film) -TD (direction perpendicular to the extrusion direction of film) of 150. % To 500%. Tensile breaking elongation is 150
%, The formability of the finally obtained resin-coated metal sheet when post-processed by roll forming or press molding is not sufficient, and when the tensile elongation at break exceeds 500%, the glass of the matrix layer The transition temperature is too low, and the handleability of the raw material resin and the handleability after forming the film are deteriorated, so that the resin cannot be put to practical use.

The film (A) has a thickness of 25 to 250 μm.
It is preferable to select in the range of m. When the thickness is less than 25 μm, the handleability as a film is reduced,
Even if a large amount of the inorganic pigment is added, it is not preferable because sufficient ultraviolet shielding property cannot be exhibited. If the thickness exceeds 250 μm, it is not practical in terms of cost.

The weather-resistant resin-coated metal plate according to the present invention is formed by sequentially laminating and integrating a transparent resin film (B) on the film (A) layer. The film (B) is composed of a blend film of a polyvinylidene fluoride resin (PVdF) and an acrylic resin. Polyvinylidene fluoride resin is a homopolymer of vinylidene fluoride,
Or, a copolymer resin mainly composed of vinylidene fluoride and another copolymerizable monomer, which is compatible with an acrylic resin. By combining the two resins that are mutually compatible, the blend film can also be made transparent.

Acrylic resins that can be blended with PVdF include polymethyl methacrylate (PMMA) homopolymer and impact-resistant PMMA, in addition to the above-mentioned flexible acrylic resin for forming the film (A). Among these acrylic resins, PMMA homopolymer has the best weather resistance, but the blend ratio that can give flexibility to a blend film with PVdF resin {same as the transparent resin film (B)} is given. It is limited to a narrow range, and from that viewpoint, it is preferable to use a flexible acrylic resin having a certain degree of tensile elongation at break. As the flexible acrylic resin, a resin having good weather resistance in which 90% by weight or more of the composition of the matrix phase is methyl methacrylate is preferable.

From the viewpoint of forming the surface layer of the resin-coated metal plate, the ratio of PVdF is preferably high, while from the viewpoint of lamination and integration with the film (A), the ratio of acrylic resin is preferably high. preferable. Also, from the viewpoint of protection of the underlayer, it is preferable that the blend ratio of the acrylic resin having excellent compatibility with the ultraviolet absorber is high. The blend ratio is preferably selected in the range of 10 to 90 parts by weight of a polyvinylidene fluoride resin and 90 to 10 parts by weight of an acrylic resin.

The film (B) comprising the blend may have a multilayer structure instead of a single layer. Denka DX-14, which is commercially available as a film having a multilayer structure, can be suitably used.

The thickness of the film (B) is from 20 μm to 10 μm.
It is preferable to select in the range of 0 μm. When the thickness is less than 20 μm, it is difficult to impart an effective ultraviolet shielding property to the film (B). When the thickness is more than 100 μm, the use of a large amount of expensive PVdF-based resin increases the cost. Is also not preferred. As in the case of the film (A), the blend film of the PVdF-based resin and the acrylic-based resin {the transparent resin film (B)} has a tensile elongation at room temperature of 15 in each direction of MD-TD.
Those having 0% or more are preferable from the viewpoint of moldability.

The film (A) and the film (B) are sequentially integrated with a metal plate as a base material. The method of manufacturing the film is to manufacture the film (A) and the film (B) separately. Then, a method in which both films are laminated may be used, or a method in which both films are laminated at once by a co-extrusion molding method may be used. Further, the above-mentioned multi-layered film including at least the film layer (BB1) and the film layer (BB2) can also be manufactured by a method of separately manufacturing and laminating both films, or a co-extrusion method.

When the resin coating layer is formed on the surface of the metal plate, stones are formed between the film (A) and the film (B).
A pattern printing layer such as a grain pattern or an abstract pattern may be provided. As a method of providing the printing layer, a generally used printing method can be used. For example, a method of performing multicolor printing on a colored film (A) using an acrylic resin-based binder ink with a gravure coater, and laminating and integrating the film (B) on the printed surface. Although it can be mentioned, it is not limited to the exemplified method. The thickness of the printing layer is in a general range of 1 to 10 μm, and the printing may be partial printing or full printing depending on the pattern.

In the weather-resistant resin-coated metal sheet according to the present invention, the film (B) forming the outermost surface layer has an intermediate layer (the film (A) layer and the printed layer (C)) that is protected from ultraviolet deterioration. An ultraviolet absorber is blended for protection. As the ultraviolet absorber, any of a benzotriazole type, a benzophenone type, a triazine type and the like can be used without any particular limitation. The amount of these UV absorbers added is
For 100 parts by weight of the base resin forming the film,
It is preferable to select in the range of 0.5 to 6.0 times. 0.
If it is less than the five-fold maximum, effective ultraviolet shielding properties cannot be obtained at a practical thickness, and even if it is more than 6.0 parts by weight, migration to the colored acrylic resin film will not be visible. As a result, the effect of increasing the amount cannot be obtained,
Neither is preferred.

The acrylic resin constituting the film (B) may be copolymerized with a so-called reactive ultraviolet absorber to impart ultraviolet shielding properties. As an example of a reactive UV absorber, a product name "RU
VA-93 "(manufactured by Otsuka Chemical Co., Ltd.).
As an example of copolymerizing a reactive ultraviolet absorber, in the process of producing a flexible acrylic resin, when a (meth) acrylate resin is graft-polymerized to a core of a crosslinked acrylic rubber elastic component, A method of adding an appropriate amount of the above-mentioned reaction type ultraviolet absorber to the raw material monomer is exemplified. As another example, a so-called polymer type UV absorber obtained by previously copolymerizing the reactive UV absorber with a (meth) acrylate-based resin is added to the base resin during the production of the transparent resin film, and the mixture is melt-kneaded. Can be mentioned.

The procedure for producing the weather-resistant resin-coated metal sheet according to the present invention is not particularly limited, but generally, a pattern printing layer such as a grain, a grain, or an abstract pattern is formed on the surface of the film (A). (C) is provided first. The subsequent procedure is not particularly limited, but the film (B) is laminated and integrated on the print layer of the film (A), and the film (A) of the laminated and integrated film is coated with an adhesive and baked on a metal plate surface. The procedure for laminating the layers is generally used.

Hereinafter, the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following description unless it exceeds the gist.

FIG. 1 is a sectional view of an example of a weather-resistant resin-coated metal plate according to the present invention, FIG. 2 is a sectional view of another embodiment, and FIG. 3 is a sectional view of still another embodiment. Show. FIG.
Is an example in which there is no adhesive layer between the colored acrylic resin film 13 and the blended film 14. FIG.
Is an example in which an adhesive layer is provided between the colored acrylic resin film 23 and the blended film 24. FIG. 3 shows an example in which a printing layer 37 is provided between the colored acrylic resin film 33 and the blended film 34, and the blended film is further composed of two layers, a BB1 layer and a BB2 layer.

[Examples] The present invention will be described below based on examples and comparative examples. [Examples 1 to 3, Comparative Examples 1 to 7] Example 1
The colored acrylic resin film (A) ("intermediate layer") and the transparent resin film (B) ("surface layer") used in Examples 3 and Comparative Examples 1 to 7 are as follows. is there. The tensile elongation of the following film (A) in the MD (direction of extrusion of the film) and TD (direction perpendicular to the direction of extrusion of the film) is JIS K7127.
Is an average value of n = 5 measured in accordance with The physical properties of the base resin of the film (A) are as shown in Table 1.

[0039]

[Table 1]

1. Acrylic resin film (A) (colored film disposed on metal plate side-intermediate layer) A1: Commercially available transparent flexible acrylic pellet A
HALS 944LD manufactured by Ciba-Geigy and AO-50 (antioxidant) manufactured by Asahi Denka Co., Ltd.
0.2 parts by weight (hereinafter, parts by weight means 100 parts by weight of the base resin) and 15 parts by weight of titanium oxide are blended with each other, and the mixture is melt-kneaded by an extruder to obtain a film. The thickness is 100 μm. The tensile elongation of this film is MD = 451
%, TD = 469%.

A2: A commercially available transparent flexible acrylic pellet C was added to the same type of HAL as in the film of A1.
S, an antioxidant and titanium oxide were blended in the same amounts, and formed into a film by an extruder.
00 μm. The tensile elongation of this film is MD
= 153%, TD = 159%.

A3: A commercially available transparent flexible acrylic pellet D was added to the same type of HAL as in the film of A1.
S, an antioxidant and titanium oxide were blended in the same amounts, and formed into a film by an extruder.
00 μm. The tensile elongation of this film is MD
= 293%, TD = 315%.

A4: A commercially available transparent flexible acrylic pellet B was added to the same HAL as in the film of A1.
S, an antioxidant and titanium oxide were blended in the same amounts, and formed into a film by an extruder.
00 μm. The tensile elongation of this film is MD
= 46%, TD = 52%.

A5: Polyvinyl chloride having an average degree of polymerization of 1050, 35 parts by weight of dioctyl phthalate, 2 parts by weight of epoxidized soybean oil, and a total of 7 parts by weight of a lead-based stabilizer and a Ba-Zn-based stabilizer , 8 parts by weight of titanium oxide were blended and kneaded with a heating roll having a diameter of 8 inches to a thickness of 2 parts.
A film of 00 μm was obtained. The tensile elongation of this film is MD = 310%, TD = 332%.

A6: 40 parts by weight of a crosslinked elastomer component obtained by polymerizing 36 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, and 0.4 parts by weight of triethylene glycol dimethacrylate by an emulsion polymerization method were added to butyl acrylate. Graft copolymerization of 21 parts by weight and 39 parts by weight of methyl methacrylate (a total of 60 parts by weight of both) yielded particles of a flexible acrylic resin. However, the fluidity during heat molding was extremely poor, and a thin film was formed by extrusion molding. Was difficult to obtain. Then, the content of the crosslinked elastic body was reduced to 30 parts by weight and formed into a film by an extrusion molding method to obtain a film having a thickness of 100 μm. The tensile elongation at break of this film at normal temperature is TD = 532%, MD =
590, but the Tg of the matrix was about 20 ° C.
It was judged that the film having a thickness of 100 μ was extremely difficult to handle and was not practical for practical use due to severe surface stickiness at room temperature and lack of rigidity of the film. From this result, the upper limit of the tensile elongation at break of the colored acrylic resin film (A) at room temperature was set to 500%
And

2. Transparent resin film (B) (film laminated on intermediate layer-surface layer) B1: UV absorber is blended, thickness is 40 μm, P
A two-layer film obtained by laminating a film in which VdF and an acrylic resin are mixed in a weight ratio of 70:30 and a film in which VdF and an acrylic resin are mixed in a ratio of 30:70 ｛Denka DX-14 film, manufactured by Denki Kagaku Kogyo KK ). The tensile elongation of this film is MD = 214% and TD = 227%.

B2: A commercially available PVdF pellet and a transparent flexible acrylic resin pellet are mixed at a weight ratio of 70:30, and a benzotriazole-based ultraviolet absorber (Asahi Denka Kabushiki Kaisha) is used as an ultraviolet absorber. Industrial company, LA
-31) was blended in 2 parts by weight and kneaded with a twin-screw extruder to obtain pellets. The pellet was formed into a 50 μm thick blend film by a single screw extruder equipped with a T die.
The tensile elongation of this film is MD = 235%, TD
= 252%.

B3: A commercially available transparent flexible acrylic pellet D is blended with the same amount of the same type of ultraviolet absorber as in the film of B2 and formed into a film by an extruder, and has a thickness of 50 μm. The tensile elongation of this film is MD = 316%, TD = 335%.

B4: A commercially available transparent flexible acrylic pellet B was blended with the same amount of the same type of ultraviolet absorber as in the film of B2 and formed into a film by an extruder, and the thickness was 50 μm. The tensile elongation of this film is MD = 101% and TD = 89%.

B5: Transparent flexible acrylic pellet B in which the same amount of the same type of UV absorber as in the commercially available PV2F film and the commercially available B2 film is blended.
Are subjected to co-extrusion in a feed block method, and PV
Transparent flexible acrylic pellet B with dF layer thickness of 10 μm
A two-layer film having a layer thickness of 40 μm was obtained. The tensile elongation of this film is MD = 97% and TD = 113%.

3. Manufacture of resin-coated metal plate A thickness of 450 μm, a thin film of an acrylic adhesive having a thickness of 5 μm after drying is baked at 210 ° C. on one surface of a hot-dip galvanized steel sheet treated with phosphoric acid,
The various acrylic resin films (A) and the various transparent resin films (B) described above were combined and laminated as described in Table 2 below, and were laminated on the adhesive layer of the steel sheet. Laminated. Metal plate, acrylic resin film (A)
The three layers MD and TD of the transparent resin film (B) and the transparent resin film (B) were laminated so as to match each other. In Example 2, an acrylic adhesive (Polyment NK) was applied to one surface of the transparent resin film (B).
-380) (thickness after drying was 3 μm), and after drying, was laminated on the surface of the acrylic resin film (A) by a dry lamination method.

[0052]

[Table 2]

4. Evaluation test of workability of resin-coated metal sheet Regarding the resin-coated metal sheet created by the above procedure, JIS Z
-2248 There are three types of bending method, push bending method, V bending method and impact contact bending method specified in "Metallic Material Bending Test Method", and the evaluation test results are shown in Table-3. After completion of the test, the coating resin layer at the bent portion was visually observed. If no cracks, cracks or peeling were observed, ○ indicates that no cracks or cracks of 20% or less of the width of the bent portion were observed,
Cracks and cracks were observed in 20% or more of the width of the bent portion, and those which were worse than those of Δ were indicated by x, and those of n = 3 were described.

(1) In the pressing and bending method, a 4φ round bar is first arranged inside with the resin-coated side of the resin-coated metal plate facing outward, and preliminary rounding is performed along the surface of the round bar. This is a method in which one is placed on the surface of a lower die on a resin-coated metal plate that has been preliminarily bent, and the other is brought into close contact with the upper die of a screw bending test device and pressed to be bent 180 °. Was performed at a temperature of 23 ° C.

(2) In the V-bending method, the surface of the metal block is
A V-shaped groove with an angle θ = 90 ° is engraved, and a resin-coated metal plate is placed on the V-shaped groove of the metal block with the coated resin surface facing down, and the angle of the tip from the upper side Is a method in which a resin-coated metal plate is pushed into a V-shaped groove of a metal block using a jig having a 90 ° angle.
Temperature.

(3) In the impact contact bending method, as in the push bending method, first, a 4φ round bar was arranged inside, and was preliminarily bent along the surface of the round bar and preliminarily bent. One is placed on the surface of a lower mold on a resin-coated metal plate, and the upper mold of 5 kg is dropped on the other surface from a height of 35 cm. The test was performed at a temperature of 23 ° C.

[0057]

[Table 3]

The following is clear from Table-3. (1) Examples 1, 2, and 4, and Comparative Examples 2 and 3 satisfy all of the workability of the evaluation items. (2) In Comparative Example 2, a surface film conforming to the claims of the present invention was used, and a soft PVC sheet was used in place of the colored acrylic resin film (A). Is a film using an acrylic resin A in both layers (A). (3) In Example 3, the moldability was slightly worse than these,
The same level as Comparative Example 5 of the layer configuration composed of the conventional transparent acrylic resin film and the colored PVC film, or slightly lower than this. However, PVC is used for other intermediate layers.
Shows much better moldability as compared with Comparative Example 1, Comparative Example 4, and Comparative Example 6, which do not use the same.

5. Evaluation of Weathering Resistance of Resin-Coated Metal Sheet The resin-coated metal sheets of Examples and Comparative Examples were subjected to a weather resistance acceleration test using a weather meter. The weather meter used was “Sunshine Weather Meter” manufactured by Suga Test Instruments Co., Ltd., and the black panel temperature was 63 ° C.
3,000 hours and 6,000 hours under the conditions described above, the appearance change was visually observed, the color difference change was confirmed with a color difference meter, and the presence or absence of peeling of the coating resin was visually observed. Table 4 shows the evaluation results.

[0060]

[Table 4]

6. Comprehensive Evaluation of Resin-Coated Metal Plate The comprehensive evaluation results of Examples 1 to 3 and Comparative Examples 1 to 7 are shown in Table-5. In Table 5, ○ means good, × means bad,
Δ means intermediate between ○ and ×, and-means not evaluated.

[0062]

[Table 5]

From Tables 4 and 5, the following is clear. (1) In Examples 1, 2, 4, and Comparative Examples 1 and 4, the coating resin layer had very little discoloration, no peeling occurred, and no noticeable change in appearance. . From the viewpoint of weather resistance, it can be said that each of these has much better performance than the configuration in which a vinyl chloride resin film is disposed in the layer on the metal plate side. However, from the viewpoint of workability, those of Comparative Examples 1 and 4 are inferior,
The embodiment is equivalent to the configuration using a vinyl chloride resin film for the layer (intermediate layer) on the metal plate side. (2) In Comparative Examples 2 and 5 in which the vinyl chloride resin film was laminated on the intermediate layer, the discoloration was severe, and the wrinkles observed in Comparative Example 2 were a colored acrylic resin film (A ) And the transparent resin film (B) are reduced, and the transparent resin fill (B) of the surface layer is partially lifted.

(3) In Comparative Example 3, the same acrylic resin used for the colored acrylic resin film (A) layer was formed into a film without adding a pigment, and used as a surface layer. In this case, the discoloration is slightly severe and the surface gloss is reduced as compared with the surface layers of other acrylic resin films and blend films. The main cause of discoloration is the accumulation of contaminants from the outside on the rough surface due to deterioration.This is not discoloration due to deterioration of the resin itself, but acrylic resin with increased flexibility to ensure moldability. It shows that when used as a surface layer directly in contact with the atmosphere, the weather resistance and the stain resistance are poor. (4) Comparative Example 4 using an acrylic resin film for the intermediate layer and an acrylic resin film for the surface layer,
No cracks due to weather resistance deterioration are observed in the surface layer, but the workability is poor.

(5) A vinyl chloride resin film for the intermediate layer,
In the case of Comparative Example 5 in which an acrylic resin film was used for the surface layer, cracks that could be visually confirmed were generated in the surface layer, but the acrylic resin in the surface layer was deteriorated due to the deterioration generated in the vinyl chloride resin film in the intermediate layer. It is considered that the resin film deteriorated. (6) Comparative Example 7 in which a blended film of a PVdF-based resin and an acrylic-based resin is directly laminated on the surface of a metal plate,
Although the film itself is not deteriorated at all, the adhesive force between the film and the base metal is sharply reduced, and the film can be easily peeled off by hand. It is considered that although an ultraviolet absorber was added to the film, the ultraviolet light shielding property was not sufficient and the adhesive layer was deteriorated.

[0066]

The present invention has been described in detail above, and has the following particularly advantageous effects, and its industrial utility value is extremely large. 1. The weather-resistant resin-coated metal sheet according to the present invention exhibits much better weather resistance than a conventional vinyl chloride resin-coated metal sheet whose surface is coated with a transparent acrylic resin film. 2. The weather-resistant resin-coated metal plate according to the present invention exhibits the same excellent workability as a conventional vinyl chloride-based resin-coated metal plate whose surface is covered with a transparent acrylic resin film. 3. The weather-resistant resin-coated metal plate according to the present invention, when a printed pattern layer is formed between the colored acrylic resin film (A) and the transparent resin film (B) on the surface,
The printed surface is sharp and beautiful, and is suitable as a resin-coated metal plate to be used outdoors.

[Brief description of the drawings]

FIG. 1 is a partially enlarged sectional view of an example of a weather-resistant resin-coated metal plate according to the present invention.

FIG. 2 is a partially enlarged cross-sectional view of another example of the weather-resistant resin-coated metal sheet according to the present invention.

FIG. 3 is a partially enlarged cross-sectional view of still another example of the weather-resistant resin-coated metal sheet according to the present invention.

[Explanation of symbols]

 11, 21, 31: Base metal plate 12, 22, 26, 32: Adhesive layer 13, 23, 33: Colored acrylic resin film 14, 24: Blend film 34: Two layers of BB1 and BB2 Film 37: Printing layer

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 8, 1999 (1999.6.8)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 2

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claim 3

[Correction method] Change

[Correction contents]

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0002

[Correction method] Change

[Correction contents]

[0002]

2. Description of the Related Art Conventionally, a purpose of imparting a design property to a resin-coated metal plate used for outdoor use, in particular, a resin-coated metal plate coated with a vinyl chloride resin (hereinafter sometimes abbreviated as "PVC"). In general, a printed pattern is generally formed by printing a pattern on a vinyl chloride resin film layer and laminating a transparent acrylic resin film on the printed surface of the pattern. Was. However, the resin-coated metal sheet coated with the coating layer having such a configuration has a defect mainly in weather resistance and workability, so when used, its use is limited to a narrow range, and in a wide range. At present, it has not been used. In the case of a PVC-coated metal plate having an acrylic resin film laminated on the surface, a transparent acrylic resin film forming a surface layer has an ultraviolet ray for the purpose of protecting the printing surface and the PVC resin layer from ultraviolet rays when used outdoors. The one to which the absorbent was added was used.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction contents]

[0004] Such a PVC-coated metal sheet whose surface is covered with an acrylic resin film exhibits relatively good formability, but the flexible PVC layer has a smaller thickness than the acrylic resin film. The reason for this is that the deformation stress applied to the acrylic resin film at the time of bending is alleviated. Generally, the thickness of the PVC layer is about 120 to 250 μm , while the thickness of the transparent acrylic resin film covering the surface is about 30 to 50 μm .

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

Further, in order to increase the flexibility of the transparent acrylic resin film itself and prevent a decrease in workability, (a) a method of increasing the amount of a crosslinked elastic material component, (b) copolymerization of methyl methacrylate in a matrix phase A method of decreasing the ratio and increasing the copolymerization ratio of an acrylate resin having a glass transition point (Tg) such as butyl acrylate lower than room temperature may be considered. However, the method (a) has a limit in improving the tensile elongation at break which directly leads to improvement in workability, and it is known that the weather resistance is also reduced.
The method (b) not only reduces the contamination resistance of the surface but also further reduces the weather resistance compared to the method (a),
Not suitable for protective coating film. As described above, a PVC-coated metal plate coated with a transparent acrylic resin film, which has good workability and excellent weather resistance, has not been proposed.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

On the other hand, a polyvinylidene fluoride resin (hereinafter, referred to as a polyvinylidene fluoride resin) is used as a PVC coating film of a PVC coated metal plate.
A transparent film made of a blend composition of “PVdF” and an acrylic resin (hereinafter sometimes abbreviated as “blend film”) is commercially available. Since the crystalline resin PVdF and the acrylic resin have excellent compatibility with each other, the blend film is transparent and has a tensile effect due to the effect of inhibiting the crystallization of PVdF.
Film elongation at break is made from only PVdF Ri, or,
Compared to a film made of only acrylic resin,
It will be greatly improved. Further, a two-layer laminated film is formed by a co-extrusion molding method, and the surface layer is a layer having a relatively large amount of PVdF, and thus a layer having good weather resistance and stain resistance,
A backside layer bonded to PVC is also commercially available as a layer having a relatively large amount of an acrylic resin and excellent in heat-fusibility with PVC, and is suitably used as a protective coating film on PVC.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

As described above, the PVC resin-coated metal plate on which the blended film of the PVdF and the acrylic resin is laminated is made of only the acrylic resin because the tensile elongation at break of the blended film is improved. Although it has better processability than that obtained by laminating a film, the weather resistance is not much different from that obtained by laminating a film composed of only an acrylic resin. this is,
As in the case of a film made of only an acrylic resin, if the thickness is about 30 to 50 μm , the ultraviolet shielding property is not sufficient, and the added ultraviolet absorber gradually decreases with the passage of time. In this case, the effect as an ultraviolet ray cut film is attenuated, so that the PVC layer is eventually deteriorated by ultraviolet rays.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

[0011] In addition, deterioration students of the stored PVC layer at the interface
The product may discolor significantly. Thus, PV
Regarding the resin-coated metal plate having a layer structure in which the blended film is laminated on the C layer, also from the limit of the protection effect by the organic ultraviolet absorber and the imbalance of the weather resistance of the upper and lower films,
At present, satisfactory weather resistance has not always been obtained.

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
A weather-resistant resin-coated metal plate according to the present invention uses a metal plate as a substrate. As the metal plate, a plate generally used as a base material of a resin-coated metal plate is referred to, specifically, a hot-dip galvanized steel plate, an electro-galvanized steel plate, an aluminum / zinc composite plated steel plate, an aluminum-plated steel plate, Examples include a stainless steel plate and an aluminum alloy plate. There is no particular limitation on the thickness, heat treatment conditions, plating thickness, and the like of these metal plates, and the surface treatment of the metal plate may be performed by a phosphate treatment, a chromate treatment, or the like.

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction contents]

The weather-resistant resin-coated metal sheet according to the present invention is obtained by coating a colored acrylic resin film (A) (hereinafter simply referred to as “film (A)” or “intermediate layer”) on the metal sheet via an adhesive layer. Is sometimes laminated). As the acrylic resin used for forming the film (A), those generally called a flexible acrylic resin or a soft acrylic resin may be mentioned. These are all based on a crosslinked acrylic rubber elastic component as a core and
It is made of a copolymer resin obtained by graft polymerization of an acrylate resin. The crosslinked elastic component is mainly composed of an acrylate resin having a glass transition point lower than 0 ° C., such as butyl acrylate, and has a crosslinked structure by copolymerizing a small amount of ethylene glycol, dimethacrylate, or the like. .

[Procedure amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

Since the colored acrylic resin film (A) is colored by adding an inorganic pigment, it is more resistant to acryl resin than a conventional acrylic resin used for surface coating of a PVC resin coated metal plate. There is no need to be excellent in bending whitening property, transparency and the like, and therefore, it is not necessary to complicate the structure of the matrix phase. Further, since the surface of the film (A) is covered with a transparent film (B) having good weather resistance (hereinafter, sometimes simply referred to as “film (B)” or “surface layer”), a conventional PVC resin is used. Film (A) compared to acrylic resin used for surface coating of coated metal plate
It is not necessary that the weather resistance itself be excellent.
Tsu lowered copolymerization ratio of methyl methacrylate box phase, low glass transition point, for example by increasing the proportion of such (meth) acrylate resin of butyl acrylate may be one with enhanced more flexibility.

[Procedure amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

Since the weather-resistant resin-coated metal sheet according to the present invention does not include a vinyl chloride resin layer unlike the conventional resin-coated metal sheet, the resin component itself may be discolored due to the formation of the polyene structure or may be added in a large amount. Deterioration of additives such as plasticizers does not occur, and there is no risk of discoloration etc. due to accumulation at the interface between the vinyl chloride resin layer and the transparent acrylic resin layer. The desorbed hydrochloric acid due to deterioration of the resin itself does not corrode the surface of the base metal and cause peeling, and a deteriorated product of an additive such as a plasticizer does not deteriorate the adhesive layer to cause peeling.

[Procedure amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction contents]

The film (A) has a tensile elongation at break at room temperature, measured in accordance with JIS K7127, of 150 (MD (film extrusion direction) -TD (direction perpendicular to the film extrusion direction)). It needs to be in the range of ~ 500%. 150% elongation at break
If it is less than 5, the formability of the finally obtained resin-coated metal sheet after forming by roll forming or press molding is not sufficient, and if the tensile elongation at break exceeds 500%, the glass transition of the matrix phase The points are too low,
Both the handleability of the raw material resin and the handleability after forming the film are deteriorated and cannot be put to practical use.

[Procedure amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0025

[Correction method] Change

[Correction contents]

The film (A) has a thickness of 25 to 250 μm.
It is preferable to select in the range of m. When the thickness is less than 25 μm, the handleability as a film is reduced,
Can not exhibit sufficient UV-shielding property even when added in large amounts of inorganic pigments is not preferable, also, the thickness of 250 [mu] m
Beyond is not realistic in terms of cost.

[Procedure amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0027

[Correction method] Change

[Correction contents]

Acrylic resins that can be blended with PVdF include polymethyl methacrylate (PMMA) homopolymer and impact-resistant PMMA, in addition to the above-mentioned flexible acrylic resin for forming the film (A). Among these acrylic resins, PMMA homopolymer has the best weather resistance, but the blend ratio that can give flexibility to a blend film with PVdF resin {same as the transparent resin film (B)} is given. It is limited to a narrow range, and from that viewpoint, it is preferable to use a flexible acrylic resin having a certain degree of tensile elongation at break. The flexible acrylic resin, more than 90% by weight of the composition of the Matrigel Tsu box phase, is favorable for weatherability and Mechirumetakuri les over preparative preferred.

[Procedure amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction contents]

From the viewpoint of forming the surface layer of the resin-coated metal plate, the ratio of PVdF is preferably high, while from the viewpoint of lamination and integration with the film (A), the ratio of acrylic resin is preferably high. preferable. Also, from the viewpoint of protection of the underlayer, it is preferable that the blend ratio of the acrylic resin having excellent compatibility with the ultraviolet absorber is high. The blend ratio is preferably selected in the range of 10 to 90 parts by weight of a polyvinylidene fluoride resin and 90 to 10 parts by weight of an acrylic resin.

[Procedure amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0030

[Correction method] Change

[Correction contents]

The thickness of the film (B) is 20 to 100 μm.
It is preferable to select in the range of m. When the thickness is less than 20 μm, it is difficult to impart an effective ultraviolet shielding property to the film (B). When the thickness is more than 100 μm , the cost is increased by using a large amount of expensive PVdF-based resin, Neither is preferred. As in the case of the film (A), the blend film of the PVdF-based resin and the acrylic-based resin {the transparent resin film (B)} has a tensile elongation at room temperature of 15 in each direction of MD-TD.
Those having 0% or more are preferable from the viewpoint of moldability.

[Procedure amendment 18]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction contents]

In the weather-resistant resin-coated metal sheet according to the present invention, the film (B) forming the outermost surface layer has an intermediate layer (the film (A) layer and the printed layer (C)) that is protected from ultraviolet deterioration. An ultraviolet absorber is blended for protection. As the ultraviolet absorber, any of a benzotriazole type, a benzophenone type, a triazine type and the like can be used without any particular limitation. The amount of these UV absorbers added is
For 100 parts by weight of the base resin forming the film,
It is preferable to select in the range of 0.5 to 6.0 parts by weight . 0.
If the amount is less than 5 parts by weight , an effective ultraviolet shielding property cannot be obtained in a practical thickness. As a result, the effect of increasing the amount cannot be obtained,
Neither is preferred.

[Procedure amendment 19]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction contents]

[Examples] The present invention will be described below based on examples and comparative examples. [Examples 1 to 3, Comparative Examples 1 to 7] Example 1
The colored acrylic resin film (A) ("intermediate layer") and the transparent resin film (B) ("surface layer") used in Examples 3 and Comparative Examples 1 to 7 are as follows. is there. The tensile elongation of the following film (A) in MD (direction of extrusion of the film) and TD (direction perpendicular to the direction of extrusion of the film) is an average value of n = 5 measured in accordance with JIS K7127. is there. The physical properties of the base resin of the film (A) are as shown in Table 1.

[Procedure amendment 20]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction contents]

[0039]

[Table 1]

[Procedure amendment 21]

[Document name to be amended] Statement

[Correction target item name] 0045

[Correction method] Change

[Correction contents]

A6: 40 parts by weight of a crosslinked elastomer component obtained by polymerizing 36 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, and 0.4 parts by weight of triethylene glycol dimethacrylate by an emulsion polymerization method were added to butyl acrylate. Graft copolymerization of 21 parts by weight and 39 parts by weight of methyl methacrylate (a total of 60 parts by weight of both) yielded particles of a flexible acrylic resin. However, the fluidity during heat molding was extremely poor, and a thin film was formed by extrusion molding. Was difficult to obtain. Then, the content of the crosslinked elastic body was reduced to 30 parts by weight and formed into a film by an extrusion molding method to obtain a film having a thickness of 100 μm. The tensile elongation at break of this film at normal temperature is: MD = 590%, TD =
532% , but the Tg of the matrix phase was about 2
It was determined that the film having a thickness of 100 μm was extremely difficult to handle because it was 0 ° C., the surface was very sticky at room temperature, and the film had no rigidity. From these results, the upper limit of the tensile elongation at break of the colored acrylic resin film (A) at room temperature was 500
%.

[Procedure amendment 22]

[Document name to be amended] Statement

[Correction target item name] 0057

[Correction method] Change

[Correction contents]

[0057]

[Table 3]

[Procedure amendment 23]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

[Correction contents]

[0062]

[Table 5]

[Procedure amendment 24]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction contents]

From Tables 4 and 5, the following is clear. (1) In Examples 1, 2, 4, and Comparative Examples 1 and 4, the coating resin layer had very little discoloration, no peeling occurred, and no noticeable change in appearance. . From the viewpoint of weather resistance, it can be said that each of these has much better performance than the configuration in which a vinyl chloride resin film is disposed in the layer on the metal plate side. However, from the viewpoint of workability, those of Comparative Examples 1 and 4 are inferior,
The embodiment is equivalent to the configuration using a vinyl chloride resin film for the layer (intermediate layer) on the metal plate side. (2) In Comparative Examples 2 and 5 in which the vinyl chloride resin film was laminated on the intermediate layer, the discoloration was severe, and the wrinkles observed in Comparative Example 2 were a colored acrylic resin film (A ) and the adhesive force is reduced between the transparent resin film (B), the partial lifting due to generated in the transparent resin film of the surface layer (B).

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) B32B 27/30 B32B 27/30 D C08L 27/16 C08L 27/16 33/06 33/06 F term (reference) 4F100 AA21 AB01A AB03 AK19C AK19D AK25B AK25C AK25D AL05C AL05D AT00A BA02 BA03 BA04 BA05 BA07 BA10A BA10C BA10D EC18 GB90 HB31E JK08B JL09 JL10B JN01C JN01D YY00B YY00C YY00D4J002BD142

Claims (4)

[Claims] 1. A resin-coated metal plate in which a colored acrylic resin film (A) and a transparent resin film (B) are sequentially laminated and integrated on a base metal plate via an adhesive layer. A weather-resistant resin-coated metal plate, wherein the transparent resin film (B) is a film composed of a blend composition of a polyvinylidene fluoride resin and an acrylic resin. 2. The colored acrylic resin film (A) has a tensile elongation at break measured in accordance with JIS K7127 of 150 in both the MD and TD directions.
The weather-resistant resin-coated metal sheet according to claim 1, wherein the metal sheet has a range of about 500%. 3. A transparent resin film (B) comprising 10 to 40 parts by weight of a polyvinylidene fluoride resin and an acrylic resin 9
0 to 60 parts by weight of the film layer comprising the blend composition (B
B1) and at least two layers of a film layer (BB2) composed of a blend composition of 60 to 90 parts by weight of a polyvinylidene fluoride resin and 40 to 10 parts by weight of an acrylic resin. Item 3. A weather-resistant resin-coated metal sheet according to item 2. 4. A printing layer (C) provided between a colored acrylic resin film (A) and a transparent resin film (B). 4. The weather-resistant resin-coated metal plate according to claim 1.