Printed decorative metal plate and method for manufacturing the same

Abstract

To provide a printed decorative metal plate that can be improved in corrosion resistance and processability at low cost, and a method for manufacturing the same.SOLUTION: Provided is a printed decorative metal plate 10 including: a metal plate 11; a ground layer 12 provided on one of surfaces of the metal plate 11; a substrate layer 13 provided on the ground layer 12; a pattern layer 14 provided on the substrate layer 13; and a surface protection layer 15 provided on the pattern layer 14. The substrate layer 13 contains pigments in polyester resin and melamine resin and contains at least one of epoxy resin and acrylic resin or contains a corrosion inhibitor. The metal plate 11 is a galvanized steel sheet and has formed on its surface layer a chemical conversion coating film layer 17A made of zircon hydrofluoric acid. The chemical conversion coating film layer 17A is provided on the metal plate 11 within a range of more than or equal to 50 mg / m2 and less than or equal to 150 mg / m2.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a printed decorative metal sheet used for entrance doors of dwellings such as detached houses, condominiums, and apartments, and a method for manufacturing the same. [Background technology]

[0002] Printed decorative metal sheets, which are made by attaching a resin sheet with a printed design to a metal plate, are used for entrance doors of detached houses, condominiums, apartments, and other residential buildings. In homes using printed decorative metal sheets for their entrance doors, if the homes are built in salt-damaged areas, such as near the coast, the printed decorative metal sheets are prone to corrosion and deterioration. Therefore, for printed decorative metal sheets used for entrance doors of homes built in salt-damaged areas, it has been considered to use stainless steel for the metal plate, to protect both sides of the metal plate with a resin sheet, or to thicken the resin layer adhered to the surface of the metal plate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-090002 Summary of the Invention [Problem to be solved by the invention]

[0004] However, using stainless steel or laminating a resin sheet for protection in printed decorative metal sheets increases costs, making them difficult to implement. Also, increasing the thickness of the resin layer adhered to the surface of the metal sheet reduces flexibility, which may lead to a decrease in processability.

[0005] In view of the above, an object of the present invention is to provide a printed decorative metal sheet that can improve corrosion resistance and processability while being low in cost, and a method for manufacturing the same. [Means for solving the problem]

[0006] In order to solve the above-mentioned problems, the printed decorative metal sheet according to the present invention is a printed decorative metal sheet comprising a metal sheet, a base layer provided on one side of the metal sheet, a base layer provided on the base layer, a picture layer provided on the base layer, and a surface protective layer provided on the picture layer, wherein the base layer contains a pigment in a polyester-based resin and a melamine-based resin, and further contains at least one of an epoxy-based resin and an acrylic-based resin, or contains a rust inhibitor, and the metal sheet is a zinc-plated steel sheet, and a chemical conversion coating layer made of zirconia hydrofluoric acid is formed on at least one side of the metal sheet, and the chemical conversion coating layer is formed on the metal sheet in a concentration of 50 mg / m 2 More than 150mg / m 2 It is characterized in that it is provided within the following range.

[0007] Furthermore, in the printed decorative metal sheet according to the present invention, it is preferable that the thickness of the chemical conversion coating layer is 0.05 μm or more and 0.2 μm or less.

[0008] Furthermore, it is preferable that the printed decorative metal plate of the present invention, in the above-mentioned printed decorative metal plate, has a chemical conversion coating layer formed on the other side of the metal plate, and a back surface protective layer provided on the chemical conversion coating layer on the other side of the metal plate.

[0009] Further, the printed decorative metal sheet according to the present invention is the printed decorative metal sheet described above, wherein the base layer is formed on the metal sheet at a thickness of 9.5 g / m 2 More than 18g / m 2 It is preferable that the range is set as follows:

[0010] Furthermore, in the printed decorative metal sheet according to the present invention, it is preferable that the underlayer in the above-mentioned printed decorative metal sheet contains a pigment and an organic additive in a polyester resin.

[0011] Furthermore, in the printed decorative metal sheet according to the present invention, it is preferable that the base layer further contains a rust inhibitor.

[0012] On the other hand, in order to solve the above-mentioned problems, the method for producing a printed decorative metal sheet according to the present invention includes a chemical conversion coating layer forming step of applying a chemical conversion treatment solution to at least one surface of a metal sheet made of a zinc-plated steel sheet to perform a chemical conversion treatment, thereby forming a chemical conversion coating layer on at least one surface of the metal sheet, a base layer forming step of providing a base layer on the chemical conversion coating layer on one surface of the metal sheet, a base layer forming step of providing a substrate layer on the base layer, a picture layer forming step of providing a picture layer on the substrate layer, and a surface protective layer forming step of providing a surface protective layer on the picture layer, wherein the chemical conversion coating layer forming step is performed by using a chemical conversion treatment solution containing fluorozirconic acid in an amount of 0.1 mass % or more and 1 mass % or less relative to the total mass of the chemical conversion treatment solution, and applying a chemical conversion treatment solution to at least one surface of the metal sheet in an amount of 50 mg / m 2 More than 150mg / m 2 The chemical conversion treatment liquid is applied to at least one surface of the metal plate so as to be within the following range, and the base layer forming step is characterized in that the base layer is formed by incorporating a pigment into a polyester-based resin and a melamine-based resin, and further incorporating at least one of an epoxy-based resin and an acrylic-based resin, or incorporating a rust inhibitor.

[0013] Furthermore, in the method for manufacturing a printed decorative metal plate according to the present invention, in the method for manufacturing a printed decorative metal plate described above, the chemical conversion coating layer formation process is a process for forming the chemical conversion coating layer on one side and the other side of the metal plate, and it is preferable that a back side protective layer formation process is further carried out in which a back side protective layer is provided on the chemical conversion coating layer on the other side of the metal plate. [Effects of the Invention]

[0014] In the printed decorative metal sheet according to the present invention, the substrate layer contains a pigment in a polyester resin and a melamine resin, and further contains at least one of an epoxy resin and an acrylic resin, or contains a rust inhibitor, the metal sheet is a zinc-plated steel sheet, and a chemical conversion coating layer made of fluorozirconic acid is formed on at least one surface of the metal sheet, and the chemical conversion coating layer is formed on the metal sheet in a concentration of 50 mg / m 2 More than 150mg / m 2 Since the content is within the following range, it is possible to improve corrosion resistance and workability while keeping costs low.

[0015] Furthermore, in the method for producing a printed decorative metal sheet according to the present invention, the chemical conversion coating layer forming step is carried out by distributing the solid components of the chemical conversion treatment solution on at least one surface of the metal sheet to 50 mg / m 2 of the chemical conversion treatment solution, and the chemical conversion treatment solution contains 0.1 mass % or more and 1 mass % or less of zirconic acid based on the total mass of the chemical conversion treatment solution. 2 More than 150mg / m 2 This is a process of applying a chemical conversion treatment liquid to at least one surface of a metal plate so as to set within the following range, and the base layer formation process is a process of forming a base layer by incorporating a pigment into a polyester-based resin and a melamine-based resin, and further incorporating at least one of an epoxy-based resin and an acrylic-based resin, or incorporating a rust inhibitor, so that the printed decorative metal plate of the present invention described above can be reliably manufactured. [Brief explanation of the drawings]

[0016] [Figure 1] 1 is a cross-sectional view showing a schematic structure of a main embodiment of a printed decorative metal plate according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0017] The present invention will be described below with reference to the drawings, with reference to the preferred embodiments of the printed decorative metal sheet and the manufacturing method thereof. Note that the present invention is not limited to the following embodiments described with reference to the drawings, and various technical matters described in each embodiment may be appropriately combined as needed.

[0018] [Main embodiment] A main embodiment of the printed decorative metal sheet and the method for manufacturing the same according to the present invention will be described with reference to FIG.

[0019] <Printed decorative metal sheet> As shown in FIG. 1, a resin underlayer 12 is provided on one surface (the upper surface in FIG. 1) of a metal plate 11 made of a zinc-plated steel plate. A resin base layer 13 is provided on the underlayer 12. A design layer 14 printed with ink is provided on the base layer 13. A resin surface protective layer 15 is provided on the design layer 14. Furthermore, a resin back surface protective layer 16 is provided on the other surface (the lower surface in FIG. 1) of the metal plate 11.

[0020] Chemical conversion coating layers 17A and 17B made of zirconic acid are formed between the metal plate 11 and the base layer 12 and between the metal plate 11 and the back surface protective layer 16, i.e., on both the surface layers of one side and the other side of the metal plate 11, respectively.

[0021] <Metal plate 11> The metal plate 11 is a plate that serves as the base of the printed decorative metal plate 10. The metal plate 11 is made of a galvanized steel plate. Examples of galvanized steel plates include hot-dip galvanized steel plates (unalloyed and alloyed), hot-dip zinc-5% aluminum alloy plated steel plates (Zn-Al system), hot-dip 55% aluminum-zinc alloy plated steel plates (Al-Zn system), hot-dip zinc-aluminum-magnesium alloy plated steel plates (Zn-Al-Mg system), and electrogalvanized steel plates, with hot-dip galvanized steel plates being preferred.

[0022] The hot-dip galvanized steel sheet is a steel sheet in which the surface is plated with zinc by immersing the steel sheet in molten zinc, which can improve adhesion to adjacent layers and corrosion resistance. The metal sheet 11 preferably has a thickness of 0.25 mm or more and 1 mm or less.

[0023] <Base layer 12> The underlayer 12 is a layer for improving the adhesion between the metal sheet 11 and the base layer 13 and for improving corrosion resistance. The underlayer 12 is a polyester resin containing a pigment and an organic additive, and preferably contains a rust inhibitor, which can further improve corrosion resistance. The underlayer 12 is formed on the metal sheet 11 in a thickness of 9.5 g / m. 2 More than 18g / m 2 It is preferable that the underlayer 12 has a thickness of 1 μm or more and 10 μm or less, since this can reliably improve corrosion resistance. Furthermore, it is preferable that the underlayer 12 has a thickness of 1 μm or more and 10 μm or less. Such underlayer 12 can also be provided by baking and drying at a temperature of 200° C. or more.

[0024] <Base material layer 13> The substrate layer 13 is the base layer among the resin layers, and is capable of imparting a base color to the pattern layer 14. The substrate layer 13 contains a base color pigment in a polyester resin and a melamine resin, and further contains at least one of an epoxy resin and an acrylic resin, or a rust inhibitor, thereby improving corrosion resistance. The thickness of the substrate layer 13 is preferably 10 μm or more and 30 μm or less.

[0025] <Picture layer 14> The design layer 14 is a layer for imparting design with a design. The design layer 14 is formed using printing ink or paint, etc., which is obtained by dissolving or dispersing a colorant such as a dye or pigment together with a suitable binder resin in a suitable dilution solvent. The printing ink or paint, etc., is applied by various printing methods, such as gravure printing, offset printing, or inkjet printing, or various coating methods, such as gravure coating or roll coating.

[0026] Known binder resins can be used as the binder resin. For example, thermosetting resins such as polyester resins, urethane resins, epoxy resins, melamine resins, alkyd resins, phenolic resins, and acrylic resins, which are used in the underlayer 12, can be used. Known pigments can be used. For example, titanium oxide, zinc oxide, carbon black, iron / composite oxides, iron oxide, organic pigments, metallic pigments, pearl pigments, and the like can be used. Of these, iron / composite oxides are used as heat-shielding pigments.

[0027] The pattern is not particularly limited, and examples thereof include wood grain, stone grain, fabric grain, abstract patterns, geometric patterns, letters, symbols, solid colors, and combinations of two or more of these. The pattern layer 14 typically has a thickness of 0.1 μm or more and 0.2 μm or less. When inkjet printing is used, the thickness of the pattern layer 14 will be greater than the above range.

[0028] In addition, when a wood grain pattern is applied to the pattern layer 14, it is also possible to further enhance the design by providing a matte duct printing layer printed with a matte duct pattern between the pattern layer 14 and the surface protection layer 15.

[0029] <Surface protective layer 15> The surface protective layer 15 is a transparent layer that provides weather resistance, bending workability, scratch resistance, and cleanability. The surface protective layer 15 is a polyester resin containing inorganic and organic additives, and may further contain resin beads, silica, etc. to further enhance design, or may further contain weathering agents such as ultraviolet absorbers and light stabilizers to further improve weather resistance. The surface protective layer 15 preferably has a thickness of 10 μm or more and 15 μm or less.

[0030] <Back surface protective layer 16> The back surface protective layer 16 is a layer for protecting the other surface (the lower surface in FIG. 1 ) of the metal plate 11, i.e., the back surface. The back surface protective layer 16 is made of an epoxy resin or polyester resin containing inorganic or organic additives, and preferably further contains a rust inhibitor, which can further enhance corrosion resistance. The back surface protective layer 16 preferably has a thickness of 2 μm or more and 10 μm or less.

[0031] <Chemical coating layer 17A, 17B> The chemical conversion coating layers 17A and 17B are layers for enhancing the corrosion resistance of the metal sheet (hot-dip galvanized steel sheet) 11. The chemical conversion coating layers 17A and 17B contain Zr so as to exhibit sufficient corrosion resistance and sufficient adhesion to the base layer 13.

[0032] The chemical conversion coating layers 17A and 17B have a concentration of 50 mg / m 2 per unit area on the metal plate 11. 2 More than 150mg / m 2 The following limits are set: 50 mg / m 2 If the content is less than 150 mg / m, the corrosion resistance cannot be fully exhibited. 2 If the temperature exceeds this range, unevenness will occur, which will easily cause a decrease in various functions.

[0033] Furthermore, the thickness of the chemical conversion coating layers 17A, 17B is preferably 0.05 μm or more and 0.2 μm or less. If the thickness is less than 0.05 μm, it is difficult to fully exhibit corrosion resistance, which is undesirable, and if the thickness is more than 0.2 μm, it is likely to cause a decrease in adhesion to the base layer 13, which is undesirable.

[0034] In this way, the chemical conversion coating layers 17A and 17B are chromate-free coatings (non-chromate coatings) formed by a chromate-free treatment (non-chromate treatment) that does not contain hexavalent chromium, taking environmental impact into consideration.

[0035] <Method for manufacturing printed decorative metal sheet 10> A method for manufacturing the printed decorative metal board 10 according to this embodiment as described above will now be described.

[0036] First, a metal sheet 11 of the desired size is prepared from a hot-dip galvanized steel sheet. Then, fluorozirconic acid, fluorotitanic acid, or ammonium titanium fluoride is added to water and mixed to prepare a chemical conversion treatment solution. The chemical conversion treatment solution is prepared so that it contains fluorozirconic acid in a range of 0.1% by mass to 1% by mass relative to the total mass.

[0037] After the chemical conversion treatment solution is prepared in this manner, the chemical conversion treatment solution is applied to one side of the metal sheet 11 for chemical conversion treatment. At this time, the solid content of the chemical conversion treatment solution is 50 mg / m 2 More than 150mg / m 2 The chemical conversion treatment liquid is applied to one surface of the metal sheet 11 so as to be laid out on the metal sheet 11 within the following range. The chemical conversion treatment liquid is also applied to the other surface of the metal sheet 11 in the same manner as on the one surface, to perform chemical treatment. As a result, chemical conversion coating layers 17A, 17B made of zirconic hydrofluoric acid and having a thickness of 0.05 μm to 0.2 μm are formed on the surface layers of both surfaces of the metal sheet 11, respectively, containing Zr so as to exhibit sufficient corrosion resistance and sufficient adhesion to the base layer 13 (this is the chemical conversion coating layer forming step).

[0038] Next, the above-mentioned material of the back surface protection layer 16 is applied to the chemical conversion coating layer 17B on the other side of the metal plate 11 and dried and solidified to form the back surface protection layer 16 having a thickness of 2 μm or more and 10 μm or less (hereinafter referred to as the back surface protection layer formation process).

[0039] Next, the above-mentioned material of the base layer 12 was applied to the chemical conversion coating layer 17A on one side of the metal plate 11 in a solid content of 9.5 g / m 2 More than 18g / m 2 The amount of the coating is as follows: the coating is applied, dried, and solidified to form the underlayer 12 having a thickness of 1 μm or more and 10 μm or less (this is the underlayer forming step).

[0040] Then, the above-mentioned material of the base layer 13 is applied onto the underlayer 12 and dried and solidified to form the base layer 13 having a thickness of 10 μm or more and 30 μm or less (this is the base layer forming step).

[0041] Furthermore, the material for the design layer 14 is printed on the base layer 13 and dried and solidified to form the design layer 14 having a thickness of 0.1 μm or more and 0.2 μm or less (design layer forming step).

[0042] Finally, the above-mentioned material for the surface protection layer 15 is applied onto the design layer 14 and dried and solidified to form the surface protection layer 15 having a thickness of 10 μm or more and 15 μm or less (surface protection layer forming step).

[0043] By providing the layers 12 to 17A, 17B on the metal plate 11 in this manner, the printed decorative metal plate 10 according to this embodiment can be manufactured.

[0044] Effects of this embodiment In the printed decorative metal sheet 10 according to this embodiment, the base layer 13 contains a pigment in a polyester resin and a melamine resin, and further contains at least one of an epoxy resin and an acrylic resin, or contains a rust inhibitor. The metal sheet 11 is a hot-dip galvanized steel sheet, and the chemical conversion coating layers 17A and 17B made of fluorinated zirconia are formed on the metal sheet 11 at a concentration of 50 mg / m. 2 More than 150mg / m 2 Since the content is within the following range, it is possible to improve corrosion resistance and workability while keeping costs low.

[0045] Furthermore, since the thickness of the chemical conversion coating layers 17A and 17B is 0.05 μm or more and 0.2 μm or less, it is possible to reliably improve corrosion resistance and workability while keeping costs low.

[0046] On the other hand, in the method for producing the printed decorative metal sheet 10 according to this embodiment, the chemical conversion coating layer forming step of forming the chemical conversion coating layers 17A, 17B by applying a chemical conversion treatment solution to the surface layers of both sides of the metal sheet 11 made of a hot-dip galvanized steel sheet and carrying out chemical conversion treatment is performed by applying a chemical conversion treatment solution containing 0.1 mass % or more and 1 mass % or less of zirconic acid to the surface layers of both sides of the metal sheet 11 at a solid component concentration of 50 mg / m 2 More than 150mg / m 2 This is a process of applying a chemical conversion treatment liquid so as to provide a coating within the following range, and the base layer formation process is a process of forming the base layer 13 by incorporating a pigment into a polyester-based resin and a melamine-based resin, and further incorporating at least one of an epoxy-based resin and an acrylic-based resin, or incorporating a rust inhibitor, so that the printed decorative metal plate 10 of this embodiment can be easily manufactured.

[0047] [Other embodiments] In the above-described embodiment, the printed decorative metal sheet 10 is described as having chemical conversion coating layers 17A, 17B on both sides of the metal sheet 11. However, the present invention is not limited to this. As another embodiment, depending on the environment in which it is used, for example, it is also possible to omit the chemical conversion coating layer 17B on the other side of the metal sheet 11 and provide a chemical conversion coating layer 17A only on one side of the metal sheet 11.

[0048] In the above-described embodiment, the printed decorative metal sheet 10 is described as having a back surface protective layer 16 on the other side of the metal sheet 11, but the present invention is not limited to this. As another embodiment, for example, depending on the conditions of use, it is also possible to use a printed decorative metal sheet in which the back surface protective layer 16 is omitted. [Example]

[0049] Examples of the printed decorative metal sheet and the manufacturing method thereof according to the present invention are specifically described below. Note that the present invention is not limited to the following examples, and various technical matters described in each example may be appropriately combined as needed.

[0050] [Preparation of test specimens and comparison specimens] <Test specimen 1> 《Metal plate》 A hot-dip galvanized steel sheet (SGC440, Z12) having a thickness of 0.4 mm conforming to the Japanese Industrial Standard "JIS G3302" was prepared as the metal sheet 11.

[0051] 《Chemical coating layer formation process》 A chemical conversion treatment solution was obtained by adding these active ingredients to water and stirring them so that the total mass of the solution was 20 mass% fluorozirconium hydrochloride (FZA), 0.5 mass% fluorotitanic acid, and 0.5 mass% ammonium titanium fluoride.

[0052] The solid component of the obtained chemical conversion treatment solution was 85 mg / m on one side of the metal plate 11. 2 After the chemical conversion treatment liquid was applied to one side of the metal plate 11 so as to become a uniform layer, and dried and solidified, the chemical conversion treatment liquid was similarly applied to the other side of the metal plate 11, and dried and solidified. As a result, chemical conversion coating layers 17A and 17B (thickness: 0.09 μm) were formed on the surfaces of both sides of the metal plate 11.

[0053] 《Back side protective layer formation process》 The epoxy resin and inorganic additives were mixed uniformly so that the ratio was 49 mass % and 51 mass %, and the mixture was applied to the chemical conversion coating layer 17B on the other side of the metal plate 11, and then heated to 200°C or higher to bake, dry, and solidify the mixture. As a result, a back surface protective layer 16 (thickness: 7 μm) was formed on the chemical conversion coating layer 17B on the other side of the metal plate 11.

[0054] 《Base layer formation process》 The polyester resin, pigment, and organic additive were mixed uniformly to a concentration of 57% by mass, 42% by mass, and 1% by mass, respectively, and applied to the chemical conversion coating layer 17A on one side of the metal plate 11 at a solid content of 10 g / m 2 After coating so as to form the above coating, the coating was heated at 200° C. or higher to bake, dry, and solidify the coating. As a result, an underlayer 12 (thickness: 8 μm) was formed on the chemical conversion coating layer 17A on one side of the metal plate 11.

[0055] 《Base material layer formation process》 These are uniformly mixed so that the polyester resin is 45% by mass, the melamine resin is 15% by mass, and the pigment is 40% by mass. Then, epoxy resin and acrylic resin are further added and mixed uniformly, and a solid content of 20 g / m is formed on the underlayer 12. 2 After coating so as to form the above, the mixture was heated at 200° C. or higher, baked, dried and solidified, thereby forming a base layer 13 (thickness: 13 μm) on the underlayer 12.

[0056] <<Pattern layer formation process>> A commonly used printing ink was printed on the base layer 13 to form a pattern layer 14 (thickness: 2 to 3 μm) on the base layer 13.

[0057] 《Surface protective layer formation process》 These were uniformly mixed so that the polyester resin was 84% ​​by mass, the inorganic additives were 9% by mass, and the organic additives were 7% by mass, and then coated on the pattern layer 14. After that, the mixture was heated at 200°C or higher to bake, dry, and solidify the pattern layer 14. This formed a surface protection layer 15 (thickness: 10 μm) on the pattern layer 14. In this way, a specimen 1 of the printed decorative metal sheet 10 was obtained.

[0058] <Test specimen 2> In the undercoat layer formation process, the solid content is 13.8 g / m 2 Specimen 2 of the printed decorative metal sheet 10 was obtained by fabricating it in the same manner as specimen 1, except that the base layer 12 (thickness: 11 μm) was formed by coating in such a manner that the thickness of the base layer 12 was 11 μm.

[0059] <Test specimen 3> In the chemical conversion coating layer forming step, the solid component of the chemical conversion treatment solution is 140 mg / m on the metal plate 11. 2 Specimen 3 of printed decorative metal plate 10 was obtained by preparing it in the same manner as specimen 1, except that the chemical conversion treatment liquid was applied to metal plate 11 so that it became as shown, and then dried and solidified to form chemical conversion coating layers 17A, 17B of 0.18 μm thickness on both surface layers of metal plate 11.

[0060] <Test piece 4> In the undercoat layer formation process, the solid content is 13.8 g / m 2 Specimen 4 of the printed decorative metal sheet 10 was obtained by fabricating it in the same manner as specimen 3, except that the base layer 12 (thickness: 11 μm) was formed by coating it so that the thickness of the base layer 12 was 11 μm.

[0061] <Comparative body 1> In the undercoat layer formation process, the solid content is 1.5 g / m 2 A comparative sample 1 of the printed decorative metal sheet 10 was obtained by fabricating the sample in the same manner as the test sample 1, except that the base layer 12 (thickness: 1.2 μm) was formed by coating the sample so that the thickness of the test sample 10 was 1.2 μm.

[0062] <Comparative body 2> In the undercoat layer formation process, the solid content is 1.5 g / m 2 A comparative sample 2 of the printed decorative metal sheet 10 was obtained by fabricating the sample in the same manner as the test sample 3, except that the base layer 12 (thickness: 1.2 μm) was formed by coating the sample so that the thickness of the test sample 3 was 1.2 μm.

[0063] <Comparative body 3> In the chemical conversion coating layer forming step, the solid component of the chemical conversion treatment solution is 35 mg / m on the metal plate 11. 2 A comparison specimen 3 of the printed decorative metal plate 10 was obtained by preparing it in the same manner as test specimen 2, except that the chemical conversion treatment liquid was applied to the metal plate 11 so that it became as shown in FIG. 1, dried and solidified, and chemical conversion coating layers 17A and 17B having a thickness of 0.04 μm were formed on both surfaces of the metal plate 11.

[0064] <Comparative body 4> In the chemical conversion coating layer forming step, the solid component of the chemical conversion treatment solution is 170 mg / m on the metal plate 11. 2 A comparison specimen 4 of the printed decorative metal plate 10 was obtained by preparing it in the same manner as test specimen 4, except that the chemical conversion treatment liquid was applied to the metal plate 11 so that it became as shown in FIG. 1, dried and solidified, and chemical conversion coating layers 17A and 17B having a thickness of 0.22 μm were formed on both surfaces of the metal plate 11.

[0065] [Exam Contents] <Bending test> 180-degree bending test The test was conducted in accordance with the Japanese Industrial Standard "JIS Z2248." Specifically, a bending test was conducted in which test specimens 1 to 4 and comparison specimens 1 to 4 were folded 180 degrees under normal temperature (25°C ± 5°C) and low temperature (0°C ± 2°C) environments, a method also known as hemming. Two types of 180-degree bending tests were conducted: 0T bending (tight bending), in which the specimens are tightly fitted together without any gaps when bent, and 1T bending, in which the specimens are bent with a minimum bending radius of 0.5t relative to the plate thickness t.

[0066] <90 degree bending test> Similarly to the above, a bending test was performed in which test specimens 1 to 4 and comparative specimens 1 to 4 were folded back by 90 degrees in a room temperature environment (25°C ± 5°C). The 90-degree bending test involved bending at a bending radius R of 1 mm.

[0067] Evaluation Method The bending portions of the test specimens 1 to 4 and the comparative specimens 1 to 4 that had undergone the bending test were visually evaluated directly and with a magnifying glass (magnification: 10 times), and then the adhesive peeling was evaluated using cellophane tape. The results are shown in Tables 1 and 2.

[0068] In the visual evaluations in Tables 1 and 2, "○" indicates that no peeling, cracking, whitening, etc. occurred, "△" indicates that peeling, cracking, whitening, etc. were observed at a level that was not problematic, and "×" indicates that peeling, cracking, whitening, etc. occurred, with "○" and "△" being rated as passing. In addition, in the adhesive peeling evaluations in Tables 1 and 2, "○" indicates that no peeling occurred, "△" indicates that slight peeling was observed, and "×" indicates that peeling occurred, with "○" and "△" being rated as passing. Furthermore, samples that passed all bending test evaluation results were deemed to have excellent processability and were marked with "○", and all other samples were marked with "×".

[0069] <Impact resistance test> The test was conducted in accordance with the Japanese Industrial Standard "JIS K5600 5-3." Specifically, a DuPont-type testing machine was used to drop a weight (500±1 g) from a specified height (50 cm) onto impact dies (radius: 6.35±0.03 mm (1 / 4 inch)) made of test specimens 1 to 4 and comparison specimens 1 to 4. The impact resistance was evaluated by directly visually inspecting the surface of the dies and by checking the adhesive peeling with cellophane tape. The results are shown in Tables 1 and 2.

[0070] In Tables 1 and 2, "○" indicates that there was no visual abnormality in the surface condition and no adhesive peeling occurred, and "×" indicates that there was a visual abnormality in the surface condition or adhesive peeling occurred, and "○" was considered to be a pass.

[0071] <Adhesion test> After forming 1 mm square grid-shaped cuts on the surfaces of test specimens 1 to 4 and comparative specimens 1 to 4, adhesive peeling was performed using cellophane tape to evaluate adhesion. The results are shown in Tables 1 and 2. In Tables 1 and 2, "○" indicates that no peeling occurred, "×" indicates that peeling occurred, and "○" indicates that the specimen passed.

[0072] <Boiling water resistance test> Test specimens 1 to 4 and comparative specimens 1 to 4 were placed in water and boiled. After 5 hours, they were removed from the water, and the surface condition was directly and visually inspected. Then, adhesive peeling was confirmed using cellophane tape (secondary adhesion) to evaluate boiling water resistance. The results are shown in Tables 1 and 2.

[0073] In the visual inspections in Tables 1 and 2, "○" indicates that no shrinkage, peeling, discoloration, etc. occurred, and "×" indicates that shrinkage, peeling, discoloration, etc. occurred, with "○" being a pass. In addition, in the secondary adhesion in Tables 1 and 2, "○" indicates that no peeling occurred, and "×" indicates that peeling occurred, with "○" being a pass.

[0074] <Neutral salt spray resistance test> The test was conducted in accordance with Japanese Industrial Standard "JIS K5600 7-1." Specifically, the edges of test specimens 1 to 4 and comparative specimens 1 to 4 were sealed, cross-cut slits were made on the surfaces, and the surfaces were sprayed with a 5% NaCl aqueous solution. After leaving the specimens in a temperature environment of 0°C ± 2°C for 750 hours, the surface condition was evaluated. The results are shown in Tables 1 and 2. In Tables 1 and 2, "○" indicates that no blisters exceeding 2 mm in size occurred, "×" indicates that blisters exceeding 2 mm in size occurred, and "○" indicates that the specimens passed.

[0075] [Test Results] The results of the above tests are shown in Tables 1 and 2.

[0076] [Table 1]

[0077] [Table 2]

[0078] As can be seen from Table 2, comparative examples 1 and 2 (undercoat layer coating amount: 1.5 mg / m 2 In a 180-degree 0T bending test at low temperature, slight deterioration was observed when viewed with a magnifying glass, but there were no particular problems and the evaluation result for workability was passed. However, in the neutral salt spray resistance test, blisters exceeding 2 mm in size occurred and the product failed.

[0079] In addition, comparative sample 3 (amount of chemical conversion treatment solution applied: 35 mg / m 2 In the 180° 0T bending test at low temperature, slight deterioration was observed when viewed with a magnifying glass, and slight peeling was observed when adhesive peeling evaluation using cellophane tape, but there were no particular problems and the evaluation result for processability was passed. However, in the neutral salt spray resistance test, blisters exceeding 2 mm in maximum size were formed, just like comparative samples 1 and 2, and the test failed.

[0080] On the other hand, comparative sample 4 (amount of chemical conversion treatment solution applied: 170 mg / m 2 ) did not produce blisters exceeding 2mm in size in the neutral salt spray resistance test, but in the 180-degree bending test, not only was slight deterioration and peeling observed under many conditions, but clear deterioration and peeling were also observed in the 0T bending test at low temperatures, so the workability evaluation result was unsuccessful.

[0081] In contrast, as can be seen from Table 1, specimens 1 to 4 showed slight deterioration when viewed with a magnifying glass in the 180-degree bending test at low temperature, and slight peeling was observed in the adhesive peeling evaluation using cellophane tape, but there were no particular problems and the processability evaluation results were pass. Furthermore, in the neutral salt spray resistance test, no blisters exceeding 2 mm in size were formed, and the specimens also passed.

[0082] Therefore, it was confirmed that the printed decorative metal sheet and the manufacturing method thereof according to the present invention can improve corrosion resistance and processability while being low cost. [Industrial Applicability]

[0083] The printed decorative metal sheet and its manufacturing method according to the present invention can improve corrosion resistance and processability while being low cost, and therefore can be used extremely beneficially in various industries, including the construction industry. [Explanation of symbols]

[0084] 10 Printed decorative metal plate 11 Metal plate 12 Base layer 13 Base material layer 14 Picture layer 15 Surface protective layer 16 Back protective layer 17A,17B Conversion coating layer

Claims

1. A metal plate; a base layer provided on one surface of the metal plate; a substrate layer provided on the underlayer; A pattern layer provided on the base layer; a surface protection layer provided on the pattern layer; A printed decorative metal sheet comprising: the substrate layer contains a pigment in a polyester resin and a melamine resin, and further contains at least one of an epoxy resin and an acrylic resin, or contains a rust inhibitor; the metal plate is a galvanized steel plate, and a chemical conversion coating layer made of fluorozirconic acid is formed on at least one surface of the metal plate; The chemical conversion coating layer is formed on the metal plate at a thickness of 50 mg / m ２ 150mg / m or more ２ It is set within the following range: A printed decorative metal sheet characterized by:

2. The chemical conversion coating layer has a thickness of 0.05 μm or more and 0.2 μm or less. The printed decorative metal sheet according to claim 1 .

3. The chemical conversion coating layer is formed on the other surface of the metal plate, and a back surface protection layer is provided on the chemical conversion coating layer on the other surface of the metal plate. The printed decorative metal sheet according to claim 1 .

4. The underlayer is formed on the metal plate at a thickness of 9.5 g / m ２ 18g / m or more ２ It is set within the following range: The printed decorative metal sheet according to any one of claims 1 to 3.

5. The underlayer contains a polyester resin, a pigment, and an organic additive. The printed decorative metal sheet according to any one of claims 1 to 3.

6. The underlayer further contains a rust inhibitor.

6. The printed decorative metal sheet according to claim 5.

7. a chemical conversion coating layer forming step of applying a chemical conversion treatment solution to at least one surface of a metal sheet made of a zinc-plated steel sheet to perform chemical treatment, thereby forming a chemical conversion coating layer on at least one surface of the metal sheet; a base layer forming step of providing a base layer on the chemical conversion coating layer on one surface of the metal plate; a base layer forming step of providing a base layer on the underlayer; a pattern layer forming step of providing a pattern layer on the base layer; a surface protection layer forming step of providing a surface protection layer on the pattern layer; A method for manufacturing a printed decorative metal sheet, The chemical conversion coating layer forming step is a step in which the chemical conversion treatment solution contains fluorozirconic acid in an amount of 0.1 mass % or more and 1 mass % or less relative to the total mass of the chemical conversion treatment solution, and the solid components of the chemical conversion treatment solution are applied to at least one surface of the metal plate in an amount of 50 mg / m ２ 150mg / m or more ２ a step of applying the chemical conversion treatment solution to at least one surface of the metal plate so as to provide a surface area within the following range: The base layer forming step is a step of forming the base layer by incorporating a pigment into a polyester resin and a melamine resin, and further incorporating at least one of an epoxy resin and an acrylic resin, or incorporating a rust inhibitor. A method for manufacturing a printed decorative metal sheet.

8. the chemical conversion coating layer forming step is a step of forming the chemical conversion coating layer on one surface and the other surface of the metal plate, Furthermore, a back surface protective layer forming step is performed in which a back surface protective layer is provided on the chemical conversion coating layer on the other side of the metal plate. The method for manufacturing a printed decorative metal sheet according to claim 7.

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