TW201206694A - Black metal plate - Google Patents

Abstract

Disclosed is a black metal sheet exhibiting high jetness which conceals the colour and gloss of a metal sheet, even if the film thickness of the black coating film (black layer) used to coat the surface of the metal sheet is thin, specifically, even if the amount of the black coating film (black layer) deposited is 0.28-1.5g/m (film thickness: approx. 0.26-1.42 μ m). The black metal sheet has a metal sheet, and a black layer formed on at least one surface of the metal sheet. The black layer is configured from a 100 parts per mass black composition comprising 20-73 parts per mass of a binder resin, and 22-60 parts per mass of a surface-treated carbon black, the surface of which is coated with a water-soluble resin. The black layer is characterised in having a dry mass of 0.28-1.5g/m2 and the jetness (L* value) of the surface being at most 24.

Description

201206694 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a black metal plate having a good blackness. [Prior Art] In recent years, the back cover of a thin-type TV such as a liquid crystal television or a plasma TV has been coated with a black coating film from the viewpoint of cost reduction and electric conductivity to the inner surface side (electromagnetic wave countermeasure). The situation in which steel plates (PCM: pre-coated metal) replace black plastics is gradually increasing. However, in the conventional PCM, in order to shield the appearance or gloss of the original plate (electroplated galvanized steel sheet, hot-dip galvanized steel sheet, alloyed hot-dip galvanized steel sheet, etc.) from black, it is necessary to make the adhesion amount to about 12 g/m 2 (film). The coating of carbon black as a black pigment is applied in a manner of about ΙΟμηη), and has a problem in that it takes a lot of time for coating and sintering. Therefore, from the viewpoint of rationalization of the coating operation and resource saving, it is expected to achieve thin film formation of a black coating film (black layer). A PCM having a thin film thickness of a plurality of black coating films (black layers) has been disclosed so far. For example, the applicant disclosed in Patent Document 1 that an original plate having a blackness (L値) of 56 or less is formed. A black metal film having a film thickness of 0.4 to 3 μm is a characteristic black metal plate. However, in the black metal plate described in Patent Document 1, the blackness (L値) minimum 値 is 30.1 Å, and sufficient blackness may not be exhibited. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2001-9966 [Draft of the Invention] 201206694 (Problem to be Solved by the Invention) The present invention has been made in view of the above various circumstances, and an object of the present invention is to provide a metal sheet even if it is coated. The film thickness of the black coating film (black layer) on the surface is thin, specifically, even if the adhesion amount of the black coating film (black layer) is 〇.2 8~1.58/1112 (film thickness: about 〇.2 6~1.42) 4111), it is also possible to exhibit a high blackness which shields the color tone or gloss of the metal plate, and a black metal plate which is excellent in adhesion between the metal plate and the black coating film (black layer). (Means for Solving the Problem) The ferrous metal plate of the present invention which solves the above-mentioned problems, characterized in that it has a metal plate and a black layer formed on at least one side of the metal plate; the black layer is composed of a black component The black composition comprises, in an amount of 100 parts by mass, 22 to 60 parts by mass of the surface-treated carbon black coated with the water-soluble resin, and 20 to 73 parts by mass of the binder resin; and drying of the black layer The mass is 0.2 8 to 1.5 g/m 2 ; the blackness (L*値) of the surface of the black layer is 24 or less. In the present specification, the term "surface-treated carbon black coated with a water-soluble resin" is not only a form in which the entire surface of the carbon black is coated with a water-soluble resin, but also a portion covered with a water-soluble resin. Type. In addition, L*値 is a 明亮 which is converted by the following formula 1 from the brightness index L値 measured by the method defined in JIS Z8 72 2 . In the present invention, the binder resin is a polyethylene resin and/or a polyurethane resin, and is preferably in a preferred embodiment. Specifically, preferably, the polyethylene resin is composed of an olefin-α, θ-unsaturated carboxylic acid copolymer, α,

S -6- 201206694 composed of a cold-unsaturated carboxylic acid polymer and a oxazoline group-containing polymer; with respect to olefin-α, an @-unsaturated carboxylic acid copolymer and an α-unsaturated carboxylic acid polymer A total of 100 parts by mass of the oxazoline group-containing polymer is contained in an amount of 2 to 8 parts by mass. Further, preferably, the polyurethane resin is a carboxyl group-containing polyurethane resin, and the urethane prepolymer is subjected to a chain extension reaction by a chain extender. The urethane prepolymer is composed of at least one polyisocyanate component selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, and dicyclohexylmethane diisocyanate, and 1,4-cyclohexane. A polyol component of dimethanol, a polyether polyol, and a polyol having a carboxyl group. Further, the black composition is prepared by adding the binder resin to an aqueous solution containing carbon black and the water-soluble resin, and further containing colloidal ceria 5 to 20 in 100 parts by mass of the black composition. The quality is also a preferred embodiment. In addition, the metal plate further has a bottom layer formed by an underlayer treatment on at least one side, and the bottom layer is composed of an underlayer containing aluminum diphosphate, colloidal cerium oxide and polyacrylic acid to dry the substrate. The formation of a mass of 12 to U7 mg/m2 is also a preferred embodiment. Preferably, in the underlying treatment composition, the content ratio of aluminum diphosphate to colloidal cerium oxide is aluminum diphosphate: colloidal cerium oxide (mass ratio) = 3 5 : 6 5 to 6 5 : 3 5, Further, it is contained in an amount of 1.0 part by mass based on 100 parts by mass of the total of aluminum phosphate and colloidal cerium oxide. Further, in the above-mentioned underlayer treatment composition, 100 parts by mass of the total amount of aluminum phosphate and colloidal silica sand is added, and 3 to 15 parts by mass of the decane coupling agent is also included. 201206694 In addition, on the aforementioned black layer Further, the bright surface layer has a dry mass of 1 to 4 g/m 2 , and the blackness (L*値) of the surface of the bright surface layer is 24 or less, which is also a preferred embodiment. A glossy resin composition for forming the above-mentioned bright surface layer, preferably i) a polymer polyester having a weight average molecular weight of 10,000 to 25,000 and 1835 to 75° (:, oxindole 511^1 <; 011/§ or more) Resin, ii) contains: a polymer polyester resin having a weight average molecular weight of 10,000 to 2 5,000 and a Tg of 35 to 7.5 ° C, and a low molecular weight polyester having a weight average molecular weight of 1,500 to 2,500 and TglO to 45 ° C. a resin, a mixed resin of an average hydroxy hydrazine of 25 mgKOH/g or more, which is a mixture of a polymer polyester resin: a low molecular weight polyester resin (mass ratio) = 8:2 to 6:4, iii) contains a weight A polyester urethane resin having an average molecular weight of 30,000 to 40,000, Tg-3 to 23 ° C, or less than 10 mg KOH/g of oxindole, or iv) containing: a weight average molecular weight of 30,000 to 40,000, Tg-3 to 23 art Polyester urethane resin, low molecular weight polyester resin with weight average molecular weight 1,500 00~2,500, Tg 10~45 °C, polyester urethane resin: low molecular weight Polyester resin (mass ratio) = 2: A mixed resin having an average oxindole of 25 mgKOH/g or more in a ratio of 8 to 4:6. In addition, in the case of 100 parts by mass of the above-mentioned glossy resin composition, further comprising 2 to 10 parts by mass of the polyethylene wax, and 100 parts by mass of the above-mentioned glossy resin composition, further containing 5 to 20 parts by mass of the rust preventive agent, For the preferred embodiment. Effect of the invention:

S -8 - 201206694 In the present invention, the surface-treated carbon black coated with a water-soluble resin is used as a black pigment, and when carbon black having a surface not covered with a water-soluble resin is used as a black pigment. When the black pigment is mixed with the binder resin, it exhibits better dispersibility and is less likely to cause secondary aggregation. Therefore, a black layer formed by using the black composition composed of the surface-treated carbon black and the binder resin can exhibit high blackness, and as a result, even if the black composition is applied to the metal plate The amount of control is low (thin film thickness of the thin black layer), and a black metal plate having better blackness can also be obtained. And the rationalization and resource saving of the coating operation can be achieved. Therefore, according to the present invention, it is possible to provide a black film (black layer) having a surface of a metal plate which is thinner, and can exhibit a high blackness which shields the color tone or gloss of the metal plate, and the metal plate and the black film are coated. A black metal plate with good adhesion to the film (black layer). [Embodiment] The ferrous metal plate of the present invention has a metal plate and a black layer formed on at least one side of the metal plate; the black layer is composed of a black composition, and the black composition is 1 The 00 parts by mass includes: 22 to 60 parts by mass of the surface-treated carbon black coated with the water-soluble resin, and 20 to 73 parts by mass of the binder resin; and the dry quality of the black layer is 〇-28 to 1.5 g. /m2; The blackness (LMil) of the surface of the black layer is 24 or less. The ferrous metal plate of the present invention will be described in detail below. (Metal plate)

S-9 - 201206694 The metal plate used in the present invention is not particularly limited as long as it is used as an original plate of a pre-coated metal. For example, a non-electroplated cold-rolled steel sheet, a hot-dip galvanized steel sheet (GI), an alloyed hot-dip galvanized steel sheet (GA), an electric ore fresh steel sheet (EG), or the like may be used, and there are also a nameplate and a plate. Among these, a hot-dip galvanized steel sheet (GI), an electrogalvanized steel sheet (EG), an aluminum plate, and a titanium plate are preferable. Preferably, the metal plate has a bottom layer formed by at least one surface treatment on at least one side. For example, when the chemical conversion coating layer formed by the underlayer treatment is provided on the surface of the metal plate, the adhesion between the metal plate and the black layer can be improved. Examples of the chemical conversion coating layer (bottom layer) include a chromate coating layer, an organic coating layer, an inorganic coating layer, and a phosphate coating layer. Among them, the chromate coating layer may be a reactive chromate coating layer or a coating type chromate coating layer, and in particular, in the case of a coating type chromate coating, in order to further improve corrosion resistance, it may be added. Phosphoric acid, colloidal cerium oxide, organic resin. Further, the organic film layer can be appropriately selected, for example, a polyethylene resin, an epoxy resin, an acrylic resin, an urethane resin, a polyester resin, a fluorine resin, and the like, A copolymer, a modified resin, or the like is used. For the purpose of further improving the corrosion resistance, silicone rubber, colloidal cerium oxide, or the like may be added to the organic film, and various wax components may be added in a trace amount for the purpose of improving the workability after the formation of the coating film, or For the purpose of improving the adhesion of the coating film, a decane coupling agent may be added. Examples of the inorganic coating layer include a niobate coating layer and the like. Phosphoric acid or fluoride may be further added to the niobate coating layer. There is no special regulation on the amount of the chromate coating layer, and the corrosion resistance is observed.

S -10- 201206694 point, preferably 5 mg / m 2 or more. However, when it exceeds 300 mg/m2, the improvement effect of corrosion resistance is saturated, and the manufacturing cost is increased. The reason why the amount of adhesion between the organic film layer and the inorganic film layer is the same as that of the above-described chromate film layer is preferably 5 g/m2 or more and 20 g/m2 or less. In particular, the primer layer is preferably a composition comprising an underlayer containing aluminum diphosphate, colloidal cerium oxide and polyacrylic acid so as to have a dry mass of 12 to 117 mg/m 2 (more preferably 20 mg/m 2 or more and 80 mg/m 2 or less). More preferably, it is formed by a method of 40 mg/m2 or more and 80 mg/m2 or less. When the specific underlayer treatment composition is applied to a galvanized metal sheet, the surface of the metal sheet can be etched by hydrogen ions from aluminum diphosphate, and by aluminum ions from the aluminum phosphate and colloidal cerium oxide. By interaction, it is possible to form a poorly soluble film which is excellent in adhesion to an overcoat layer such as a black layer or an inner surface water-based bright surface layer described later, and as a result, a film which is improved in bending or molding (elongation and shrinkage deformation) can be obtained. Adhesion, which greatly improves corrosion resistance or tape peel resistance. When the amount of adhesion of the underlayer formed by the specific underlayer treatment composition is less than 12 mg/m 2 in terms of dry mass, it is difficult to uniformly cover the surface of the metal sheet by the poorly soluble film, and it is difficult to sufficiently exhibit corrosion resistance or overcoating. The adhesion enhancement effect of the layer, on the other hand, when the amount exceeds 117 mg/m2, although the corrosion resistance is improved, the amount of residual aluminum phosphate which is not reacted (etched) with the surface of the metal plate is increased, and The amount of colloidal cerium oxide which does not contribute to the adhesion is also increased, resulting in a decrease in the adhesion of the adhesion to the overcoat layer or a decrease in the adhesion of the underlayer to the metal sheet. According to this adhesion amount, the film thickness of the underlayer is usually 0.007 to 〇.〇7μηι. In the specific underlayer treatment composition, the content ratio of aluminum diphosphate to colloidal dioxide-11 - 201206694 , is preferably aluminum phosphate: colloidal cerium oxide (mass ratio) = 3 5 : 65 to 65 : 3 5 (extra is 40/50~60/50). When the colloidal ceria is more than the above ratio, the film forming property is lowered to make it difficult to form the underlayer, and it is difficult to obtain the corrosion resistance or the adhesion with the overcoat layer, and the adhesion to the metal plate is also lowered. After processing, there will be doubts about peeling off the film. On the other hand, when the colloidal cerium oxide is less than the aforementioned ratio, the ratio of aluminum diphosphate increases, so that the ratio of the residual aluminum phosphate dissolved in water which is not reacted (etched) with the metal plate increases, and the uranium is produced under the coating film. It may cause a decrease in corrosion resistance. In the specific underlayer treatment composition, it is preferable to contain 0.2 to 1.0 part by mass of polyacrylic acid (particularly 0.4 part by mass or more and 0.8 part by mass or less) based on 100 parts by mass of the total of the aluminum phosphate and the colloidal cerium oxide. The polyacrylic acid can be regarded as having a function of appropriately controlling the reaction (etching) of the surface of the (galvanized) metal plate to which zinc plating or the like is applied, and if it is less than 0.2 parts by mass, excessive etching is caused, and as a result, corrosion resistance is lowered. When the amount is more than 1 part by mass, the etching is insufficient, and the poorly soluble film produced by the aluminum diphosphate and the colloidal cerium oxide cannot be sufficiently formed, and it is difficult to obtain the adhesion and the corrosion resistance. . In the specific underlayer treatment composition, it is preferable to further contain 3 to 15 parts by mass of the decane coupling agent (particularly 5 parts by mass or more and 12.5 parts by mass or less) based on 100 parts by mass of the total of the aluminum phosphate and the colloidal cerium oxide. ). When the decane coupling agent is less than 3 parts by mass, the effect of improving the adhesion or corrosion resistance of the upper coating layer and the metal sheet tends to be insufficient, and under more severe processing conditions, the film may be peeled off. Even if it exceeds 15 mass - 12 - 201206694 parts, there is still doubt that corrosion resistance or adhesion is reduced. (Surface-treated carbon black) In the present invention, the black pigment constituting the ochre composition is replaced with carbon black (surface-treated carbon black) whose surface is coated with a water-soluble resin instead of the carbon black (surface) used in the past. The carbon black not covered with the water-soluble resin may be referred to as "untreated carbon black" in the following, and is characterized by the use of untreated carbon black in order to fully exhibit the obtained black metal plate. The blackness (achieving L*値24 or less) must increase the film thickness of the black layer (increasing the adhesion amount) (Fig. 2). In contrast, when the surface-treated carbon black is used, even the film of the black layer is thinned. Thick (reduced adhesion), a black metal plate with better blackness (Fig. 1) can also be obtained. When the surface-treated carbon black is used in place of the untreated carbon black, the details of the mechanism for exerting the above effects are still unknown, but can be considered as follows. In other words, when the untreated carbon black is mixed with the binder resin to prepare a black composition, secondary aggregation is likely to occur due to a change in pH or compatibility with a binder resin, and the color of the black composition is caused. The force is reduced. Therefore, in order to obtain a black metal plate having a sufficient degree of blackness, it is necessary to increase the film thickness of the black layer (increasing the adhesion amount). On the other hand, the surface-treated carbon black does not easily cause secondary aggregation even when mixed with the binder resin, so that the black composition can maintain high coloring power. Therefore, even if the film thickness of the black layer is thinned (the amount of adhesion is reduced), a black metal plate having a good blackness can be obtained. The carbon black constituting the surface-treated carbon black is not particularly limited, and examples thereof include soot, loose smoke, commercially available carbon black for coloring, and carbon for rubber 201206694 black. These carbon blacks can be produced by a direct fire incineration method, a core incineration method, a tank method, a furnace method, an acetylene method, or the like. Specifically, MA-7, MA-100, #970, #2200, #2600 (above, manufactured by Mitsubishi Chemical Corporation), Specia 1 Β 1 ack-5, Specia 1 Β 1 ack·1 00, Cο 1 〇r BIack-S170, Printex 140V (above is Degussa Japan Co., Ltd.), Neo Spectra Mark 1, Neo Spectra Mark 5 (above, Columbian Carbon Japan Co., Ltd.), etc. Acidic carbon black; #5, #40,#960,#2300 (The above is manufactured by Mitsubishi Chemical Corporation), Printex 90, Printex G, Printex 45, Printex L (above, Degussa Japan Co., Ltd.) 'RAVEN 420 ' RAVEN H20 POWDER (above Alkaline carbon black such as Columbian Carbon Japan Co., Ltd.). These carbon blacks may be used singly or in combination of two or more. The water-soluble resin that covers the surface of the carbon black is not particularly limited as long as it does not cause secondary aggregation of the carbon black in the binder resin, and examples thereof include gelatin, polyvinyl alcohol, and polyvinylpyrrolidone. , water-soluble acrylic acid, acrylamide, vinyl pyridine, polyvinyl acid and the like. These water-soluble resins may be used singly or in combination of two or more. The content of the water-soluble resin is preferably 5 parts by mass or more and 380 parts by mass or less based on 100 parts by mass of the carbon black. When the content of the water-soluble resin is less than 5 parts by mass, the binder resin may not be sufficiently inhibited. Secondary coagulation of surface treated carbon black. Further, when the content of the water-soluble resin exceeds 380 parts by mass, the viscosity of the black composition using the surface-treated carbon black may increase, and the handleability may be deteriorated.

-14 - 201206694 The surface-treated carbon black used in the present invention may further contain a surfactant. Thereby, secondary aggregation of the surface-treated carbon black in the binder resin can be further suppressed. The surfactant may be a generally known anionic or nonionic 'cationic surfactant. The content of the surfactant may be 0.5 to 130 parts by mass of the surface-treated carbon black with respect to 100 parts by mass of the carbon black, and the content of the black component is 22 parts by mass or more (preferably 25 mass). More preferably, it is 30 parts by mass or more, and 60 parts by mass or less (preferably 50 parts by mass or less). The surface-treated carbon black used in the present invention is less likely to cause secondary aggregation even when it is mixed with the binder resin. Therefore, even if the content is 22 parts by mass or more, the dispersion has high dispersion stability and can be obtained. A higher black component of coloring power. As a result, even if the amount of adhesion of the black composition (thickness of the thin black layer) is reduced, a black metal plate having a good blackness can be obtained. When the surface-treated carbon black is less than 22 parts by mass, the obtained black metal The b値 of the plate is higher (more than 1) (Fig. 3), and it is dark brown. It may not be possible to form the blackness (L*値) to be 24 or less (Fig. 4). In addition, when the content exceeds 60 parts by mass, b値 is lower (1 or less) (Fig. 3)', although a black layer (Fig. 4) having a blackness (L*値) of 24 or less can be formed 'but due to black composition The amount of binder resin in the material is reduced. It may be difficult to keep the surface treated carbon black in the black layer. Further, the 'black composition' becomes easily colloidal, which may lower the liquid stability of the black composition. -15- £201206694 (Binder Resin) The adhesive resin used in the present invention is for fixing the surface-treated carbon black in a black layer, and contains 20 parts by mass in 100 parts by mass of the black composition. The above (particularly preferably 35 parts by mass or more) and 73 parts by mass or less (especially preferably 70 parts by mass or less, more preferably 60 parts by mass or less). When the content of the binder resin is less than 20 parts by mass, the film forming property of the black layer is deteriorated, and the surface-treated carbon black may be insufficiently fixed. Further, the damage resistance of the ferrous metal plate is deteriorated, and the damage is marked, which may cause problems in appearance. When the content of the binder resin exceeds 73 parts by mass, a black metal sheet having a desired blackness (L*値24 or less) may not be obtained due to a decrease in the content of the surface-treated carbon black. The binder resin used in the present invention is not particularly limited as long as the surface-treated carbon black can be fixed in the black layer, but is preferably a polyethylene resin and/or a polyamine group. The acid ester resin is a main component. According to the study of the present inventors, the black composition obtained by using the binder resin can effectively suppress secondary aggregation of the surface-treated carbon black and has good liquid stability. Specifically, 45 parts by mass of the surface-treated carbon black, 45 parts by mass of a polyethylene resin, a polyurethane resin, an epoxy resin or an acrylic resin as a binder resin, and a colloidal cerium oxide 10 parts by mass of the mixture was mixed to prepare a black composition (details as described in the examples), and this was applied to a plated steel plate and dried to have a dry adhesion amount of 0.5 g/m 2 . Black metal plate with blackness L*値24 or less. On the other hand, in the black composition using the acrylic resin or the epoxy resin as the binder tree 201206694, a tendency to increase the viscosity was observed as time passed. On the other hand, in the black composition obtained by using a polyurethane resin or a polyethylene resin, no tendency to increase the viscosity was observed, and good liquid stability was exhibited. Further, when the particle size distribution (secondary particle diameter) of each black composition is measured, when an acrylic resin or an epoxy resin is used as the binder resin, the volume average particle diameters are 13.5 0111 and 14.350 〇1, respectively. The particle size is significantly increased. On the other hand, when a polyurethane resin or a polyethylene resin was used, the volume average particle diameter was 2.82 μm and 4.46 μm, respectively, and no significant increase in the secondary particle diameter was observed. Therefore, the stability of the black composition over time can be considered to be greatly affected by the type of the binder resin. &lt;Polyethylene Resin&gt; The polyethylene resin used as the binder resin is preferably an olefin-α, a non-unsaturated carboxylic acid copolymer (hereinafter sometimes referred to as an "olefin-acid copolymer"), α, A /3-unsaturated carboxylic acid polymer (hereinafter sometimes referred to as "carboxylic acid polymer") and a oxazoline group-containing polymer. The olefin-acid copolymer and the carboxylic acid polymer do not impair the dispersion stability of the surface-treated carbon black in the black composition, and are excellent in compatibility with the carbon black. Further, since the oxazoline group-containing polymer can be crosslinked with the olefin-acid copolymer and the carboxylic acid polymer to form a dense and extremely hard black layer, it is possible to suppress the surface of the black layer from being wetted by water or the like. In the case where the surface-treated carbon black in the black layer is eluted (decolored), the damage resistance of the surface of the ferrous metal sheet can also be improved. The "olefin-acid copolymer" in the present invention is a copolymer of an olefin and an α,0 - not -17 - 201206694 saturated carboxylic acid, and the constituent unit derived from the olefin is 50% by mass or more in the copolymer (that is, from The constituent unit of the α,/3-unsaturated carboxylic acid is 50% by mass or less. Further, the "carboxylic acid polymer" is a polymer (including a copolymer) obtained by polymerizing an α,/3-unsaturated carboxylic acid as a monomer, and a constituent unit derived from an α,A-unsaturated carboxylic acid is The amount of the polymer is 90% by mass or more. <<Olefin-acid copolymer>> The olefin-acid copolymer used in the present invention can be produced by copolymerizing an olefin and an unsaturated carboxylic acid by a known method, and a commercially available product can also be used. In the present invention, one type or two or more types of olefin-acid copolymers can be used. The olefin which can be used for the production of the olefin-acid copolymer is not particularly limited, and is preferably ethylene, propylene or the like, and particularly preferably ethylene. As the olefin-acid copolymer, any one of olefin-forming units derived from only one type of olefin or two or more types of olefins can be used. The α,/3-unsaturated carboxylic acid which can be used for the production of the olefin-acid copolymer is not particularly limited, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and isocrotonic acid; maleic acid; And dicarboxylic acids such as fumaric acid and itaconic acid. Among these, acrylic acid is preferred. An olefin-acid copolymer, which can be used as an α,3-3-unsaturated carboxylic acid constituent unit derived from only one α,β-unsaturated carboxylic acid or from two or more kinds of α,lu-unsaturated carboxylic acids Any of the olefin-acid copolymers used in the present invention, in the absence of inhibition

S -18- 201206694 Within the range of adverse effects such as secondary aggregation of surface-treated carbon black, it may have constituent units derived from other monomers. In the olefin-acid copolymer, the constituent unit amount from the other monomer is preferably 10% by mass or less, and particularly preferably 5 Å. Hereinafter, the most preferred olefin-acid copolymer is composed of only an olefin and an α, 10,000-unsaturated carboxylic acid. A preferred olefin-acid copolymer' can be exemplified by a bi-acrylic acid copolymer. The unsaturated carboxylic acid in the olefin-acid copolymer is used for improving the adhesion between the black layer and the metal plate, and the amount of α, 、 unsaturated decanoic acid in the copolymer is preferably 5% by mass or more. Good is 1% by mass or more. However, when the amount of the unsaturated carboxylic acid is excessive, there is a concern that the corrosion resistance is lowered. In the copolymer, the amount of the cerium-unsaturated citric acid is preferably 30% by mass or less, and particularly preferably 25% by mass or less. The weight average molecular weight (Mw) of the olefin-acid copolymer used in the present invention is preferably from 1, 〇〇〇 to 1,000,000, particularly preferably from 3,000 to 70,000, more preferably 5,000, in terms of polystyrene. ~30,000. The Mw can be measured by GPC using polystyrene as a standard. <<Carboxylic Acid Polymer>> The carboxylic acid polymer used in the present invention may, for example, be a monomer or a copolymer using one or more kinds of unsaturated carboxylic acids, or may be further copolymerized with other monomers. Copolymer. Such a carboxylic acid polymer can be produced by a known method, and a commercially available product can also be used. In the present invention, one type or two or more types of carboxylic acid polymers can be used. The unsaturated carboxylic acid which can be used for the production of the carboxylic acid polymer is not particularly limited to -19 to 201206694, and an unsaturated carboxylic acid which can be exemplified for the synthesis of the above olefin-acid copolymer can be used. Among them, acrylic acid and maleic acid are preferred, and maleic acid is preferred. The carboxylic acid polymer may contain a constituent unit derived from a monomer other than the unsaturated carboxylic acid, but the constituent unit amount derived from the other monomer is 1% by mass or less, preferably 5% by mass or less, particularly preferably 5% by mass or less. It is preferably a carboxylic acid polymer composed only of an α, a non-unsaturated carboxylic acid. Preferred examples of the carboxylic acid polymer include polyacrylic acid, polymethacrylic acid, acrylic acid-maleic acid copolymer, polymaleic acid, etc., among which, in terms of black layer adhesion, etc., it is particularly preferable. For polymaleic acid. Polymaleic acid, because of the large amount of carboxyl groups, can enhance the adhesion between the black layer and the metal plate. The Mw of the carboxylic acid polymer used in the present invention is preferably from 50,000 to 30,000 in terms of polystyrene, particularly preferably from 00 to 10,000, more preferably from 900 to 3,000 'preferably from 1,000 to 2,000. . The Mw can be measured by GPC using polystyrene as a standard. The content ratio (mass ratio) of the olefin-acid copolymer to the carboxylic acid polymer in the polyethylene resin is 1,000:1 to 10:1, preferably 200:1 to 20:1', particularly preferably 1〇. 〇: 1~2 5: 1. When the content of the carboxylic acid polymer is too low, the effect of combining the olefin-acid copolymer and the carboxylic acid polymer cannot be sufficiently exhibited. Conversely, when the content of the carboxylic acid polymer is excessive, the olefin-acid is in the black composition. The copolymer and the carboxylic acid polymer are phase separated, and there is a concern that a uniform black layer cannot be formed. "Oxazolinyl-containing polymer"

S -20- 201206694 The polyethylene resin used in the present invention, the oxazoline group in the oxazoline group-containing polymer, can be crosslinked with the carboxyl group of the above olefin-acid copolymer or carboxylic acid polymer The reaction allows the resins to crosslink with each other to form a compact mesh structure. Thereby, the strength of the black layer can be improved. The oxazoline group-containing polymer used in the present invention is preferably "Epocros C registered trademark" manufactured by Nippon Shokubai Co., Ltd., which is a styrene/acrylic acid. This is because the extremely hard black layer can be formed and the brittleness of the black layer is improved. Specially available in the "Epocros (registered trademark) K" series in the form of emulsions, grades K-2010E (Tg: -50 °C), K-2020E (Tg: 0 °C) and K-20 3 0E (Tg: 50 ° C). In order to obtain a hard film, the best is Epocros K-2030E. The oxazoline group-containing polymer is preferably contained in an amount of 2 parts by mass or more (particularly 4 parts by mass or more) based on 100 parts by mass (solid content) of the total of the olefin-acid copolymer and the carboxylic acid polymer. It is below the mass part (especially preferably 6 parts by mass or less). When the amount of the oxazoline group-containing polymer is less than 2 parts by mass, the crosslinking reaction is insufficient, the tightness of the black layer is not obtained, and the corrosion resistance is deteriorated, and the surface-treated carbon black may not be fixed in the black layer. Further, the hardness of the black layer cannot be sufficiently obtained, and the damage resistance may be deteriorated. On the other hand, when the oxazoline group-containing polymer exceeds 8 parts by mass, the functional group (carboxyl group) of the black layer is reduced due to excessive crosslinking reaction, and the surface-treated carbon black cannot be fixed to black. In the layer, the adhesion of the black layer to the metal plate may be lowered. &lt;Polyurethane resin&gt; -21 - 201206694 In addition to the above polyethylene resin, a polyurethane resin which is suitable as a binder, and a carboxyl group-containing polyurethane, And the urethane prepolymer is chain extended by a chain extender, the urethane prepolymer is selected from the group consisting of toluene diester, diphenylmethane diisocyanate and dicyclohexyl At least one polyisocyanate component of the group consisting of methane diisocyanate and a polyol containing 1,4-alkanediethanol, a polyether polyol, and a polyol having a carboxyl group. According to this configuration, even in the formation of the black layer, a black metal plate excellent in corrosion resistance and scratch resistance can be obtained without adding an agent. The urethane resin can be produced by a known method (for example, 曰本 2005-200757). "Polyisocyanate component" The polyisocyanate component used in the polyurethane resin must contain a solvent selected from the group consisting of toluene diisocyanate (TDI), diphenylmethane diester (MDI) and dicyclohexane methane diisocyanate (hydrogenation). MDI) is a group of at least one polyisocyanate. By using the polyisocyanate component, a black metal plate excellent in corrosion resistance can be obtained. In addition to the above-mentioned essential isocyanate component, the polyisocyanate may be used insofar as the corrosion resistance is not lowered, but the content of the polyisocyanate component is 70% by mass or more of the total polyisocyanate component. When the content of the cyanate component is less than 70% by mass, the corrosion resistance is lowered. The polyisocyanate other than the above-mentioned necessary polyisocyanate component may be a tetramethylene diisocyanate, a hexamethylene diisocyanate or a hexa-ester ester tree long anti-isocyanide ring-bonded component. The aggregation of the group of acid esters is preferably

S -22- 201206694 Methane diisocyanate, isophorone diisocyanate, xylene diisocyanate, phenylene diisocyanate, and the like. These polyisocyanate components may be used singly or in combination of two or more. <<Polyol component>> The polyol component used in the polyurethane resin preferably contains all three kinds of plural components of 1,4-cyclohexanedimethanol, a polyether polyol, and a polyol having a carboxyl group. More preferably, the alcohol component is composed of all three kinds of diols. Thereby, a black metal plate excellent in corrosion resistance and slidability can be obtained. In particular, the use of 1,4-cyclohexanedimethanol as a polyol component improves the rust-preventing effect of the polyurethane resin. The polyether polyol is not particularly limited as long as it has at least two or more hydroxyl groups in the molecular chain and the main skeleton is composed of alkylene oxide units, and examples thereof include polyoxyethylene glycol (sometimes) Just called "polyethylene glycol"), polyoxypropylene glycol (sometimes called "polypropylene glycol"), polyoxybutylene butane (sometimes called "polybutadiene diol" or "poly" Ether diol"), and a commercially available product can also be used. Among the above polyether polyols, polyoxypropylene glycol or polybutylene ether glycol is preferred. As the polyether polyol, a commercially available product having an average molecular weight of, for example, about 400 to 4,000 is preferably used. When the average molecular weight is less than 400, the black layer is too hard, and when it exceeds 4,000, it becomes too soft. The average molecular weight can be determined by measuring 〇H値 (oxindole). In the present invention, the (mass ratio) of the aforementioned 1,4-cyclohexanedimethanol and the polyether polyol is 1,4-cyclohexanedimethanol: polyether polyol = 1: 1 to 1 -23- 201206694: 19, also a better type. The rust-preventing effect of the resulting polyurethane resin can be further improved by using a certain ratio of 1,4-cyclohexanedimethanol having a rust-preventing effect. The polyol having a carboxyl group used in the present invention is not particularly limited as long as it has at least one or more carboxyl groups and at least two or more hydroxyl groups, and examples thereof include dimethylolpropionic acid and dihydroxyl. Methyl butyric acid, dihydroxypropionic acid, dihydroxysuccinic acid, and the like. In addition to the above-described necessary polyol component, other polyol components may be used insofar as the corrosion resistance is not lowered, but the content of the polyol component is preferably 70% by mass or more of all the polyol components. . When the content of the essential polyol component is less than 70% by mass, the corrosion resistance tends to be lowered. The polyol other than the above-mentioned essential polyol component is not particularly limited as long as it has a plurality of hydroxyl groups, and examples thereof include a low molecular weight polyol or a high molecular weight polyol. The low molecular weight polyol is a polyol having an average molecular weight of about 500 or less, and the high molecular weight polyol is a polyol having an average molecular weight of more than about 500. "urethane prepolymer" urethane prepolymer (specifically, a carboxyl group-containing isocyanate terminal urethane prepolymer having a relatively low molecular weight), which can be used as described above The polyisocyanate component and the polyol component are obtained by mixing an isocyanate group by an excess ratio of NCO/OH. The temperature of the synthetic urethane prepolymer is not particularly limited, but is preferably 50 to 200 °C. When the urethane prepolymer is produced, the viscosity is adjusted and improved.

S -24 - 201206694 From the viewpoint of the emulsification dispersibility of the prepolymer, it is also preferable to use a solvent. The solvent is preferably a solvent which is inactive with respect to the isocyanate group and has a relatively high hydrophilicity, and examples thereof include N-methylpyrrolidone, acetone, ethyl acetate, methyl ethyl ketone, and N. N-dimethylformamide or the like is preferably N-methylpyrrolidone. After completion of the reaction of the polyisocyanate component with the polyol component, the resulting urethane prepolymer is preferably neutralized with a base and emulsified and dispersed in water. The neutralizing agent is not particularly limited, and ammonia, a tertiary amine such as triethylamine or triethanolamine, or a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide can be used, and triethylamine is preferably used. <<Carboxyl group-containing polyurethane resin>> The carboxyl group-containing polyurethane resin used in the present invention can be emulsified and dispersed in the above urethane prepolymer, and can be chained in water. The extender is obtained by chain extension reaction. The chain extension reaction can be suitably carried out before the emulsification dispersion, at the same time as the emulsification dispersion, or after the emulsification dispersion, depending on the reactivity of the chain extender to be used. The chain extender used in the present invention is not particularly limited, and examples thereof include aliphatic polyamines such as ethylenediamine, propylenediamine, and hexamethylenediamine; toluenediamine, xylenediamine, and diamine. An aromatic polyamine such as diphenylmethane; an alicyclic polyamine such as diaminocyclohexanemethane, piperazine or isophorone diamine; anthracene, bismuth succinate, diammonium adipate Anthraquinones such as dithizone. Among these, ethylenediamine and/or hydrazine are preferred. The carboxyl group-containing polyurethane resin used in the present invention has an acid hydrate of -25 to 201206694, preferably 10 mgKOH/g or more and 60 mgKOH/g or less. When the acid mash is less than 10 mgKOH/g, the stability of the aqueous dispersion of the polyurethane resin may be lowered. When the acid strontium exceeds 60 m gKOH/g, the corrosion resistance of the obtained ferrous metal plate tends to decrease. The determination of acid bismuth is based on JIS-K0 0 7 0. (Black composition) The black composition used in the present invention can be obtained by mixing the surface-treated carbon black and the binder resin at the above specific ratio. For example, an aqueous solution of surface-treated carbon black (an aqueous solution containing carbon black and a water-soluble resin) may be mixed with a binder resin to prepare. The aqueous solution of the surface-treated carbon black can be prepared by a known method (for example, JP-A-7-188597 or JP-A-6-234446), and a commercially available product (for example, ink can be used). Wuzhu Co., Ltd. made "Super Ink Drops BA-8"). Here, in the case of using the above aqueous solution, it is preferred to use an aqueous solution having a volume average particle diameter (particle diameter after secondary aggregation) of the surface-treated carbon black in an aqueous solution of not more than 100 nm. By using the aqueous solution to modulate the black composition, even if it is a film, the gloss and color tone of the surface of the metal plate can be shielded, and a black layer exhibiting a deep blackness can be formed. In order to further obtain a deep black appearance, it is preferred to use an aqueous solution having a volume average particle diameter of 700 nm or less, more preferably an aqueous solution of 50 On or less. In the conventionally known aqueous solution of carbon black, the volume average particle diameter may reach 4400 nm. The black metal plate of the present invention is dried using the above black composition.

S -26- 201206694 The dry mass is 〇.28g/m2 or more and 1.5g/m2 or less. The black layer is formed on one side or both sides of the metal plate. In particular, when the black metal plate of the present invention is used as a back cover for a thin television, a black layer can be formed only on one side (outer side) of the metal plate. When the adhesion amount of the black layer is less than 0.28 g/m2, the blackness (L*値) of the black metal plate may exceed 24', which may appear dark brown. When the adhesion amount of the black layer exceeds Ug/m2, the blackness (L* 値) of the black metal plate is 24 or less, but the conductivity required in the field of home appliances such as a thin television may not be achieved. In addition, there is also a problem that the blackness improvement effect disappears, and the coating and sintering take more time, resulting in an increase in manufacturing cost. Considering the conductivity and manufacturing cost of the ferrous metal plate, the adhesion amount of the black layer is preferably 〇.35g/m2 or more (more preferably 0.5g/m2 or more), and 1 _0g/m2 or less (especially 〇.75g). /m2 or less) The method and conditions for forming the black layer using the above black composition are not particularly limited, and the black composition can be applied to one side or both sides of the metal plate by a known coating method. Heat and dry. Examples of the coating method of the black composition include a bar coating method, a trickle coating method, a roll coating method, a spray method, and a ring spray method. Among them, from the viewpoint of cost and the like, it is preferred. It is a stick coating method, a roll coating method, or a ring spray method. Further, the heating and drying conditions 'the heating and drying temperature can be exemplified by 50 to 160. (:, preferably 7〇~l4〇C. When the heating and drying temperature is passed, the black layer is deteriorated, so it is not preferable &lt;colloidal cerium oxide&gt; The black composition used in the present invention is preferably Further, it contains a rubber -27-201206694 state cerium oxide. With this configuration, the surface-treated carbon ruthenium can be well fixed to the black layer, and in addition, the corrosion resistance or hardness of the ferrous metal plate can be improved. It is still unclear, but it is presumed that in a corrosive environment, it causes a pH buffering effect or a passive film formation due to the dissolution and dissolution of cerium oxide. Furthermore, it is also observed that the black composition is coated and dried. The colloidal cerium oxide to be used is not particularly limited, and the surface area average particle diameter is preferably 4 to 20 nm from the viewpoints of dispersibility or corrosion-improving effect in the black composition. The colloidal cerium oxide, specifically, a colloidal cerium oxide (Snowtex XS) having a surface area average particle diameter of 4 to 6 nm, a colloidal cerium oxide (Snowtex S) having a surface area average particle diameter of 8 to ll nm, and an average surface area of the surface area 1 0~20m colloidal two The content of the colloidal cerium oxide is preferably 5 parts by mass or more (particularly 7 parts by mass or more) in 100 parts by mass of the black composition. 20 parts by mass or less (especially preferably 15 parts by mass or less). When the content of the colloidal cerium oxide is less than 5 parts by mass, the surface-treated carbon black may not be well fixed to the black layer. Corrosion resistance or hardness improvement of the film. When the content of colloidal cerium oxide exceeds 20 parts by mass, the corrosion resistance may be lowered, and the stability of the black composition may be deteriorated, and the adhesion may be viscous over time. Further, the surface-treated carbon black may not be well fixed to the black layer. &lt;Chane coupling agent&gt; In the present invention, a decane coupling agent may be added to the black composition.

S -28- 201206694 Adds a decane coupling agent to improve the tamper resistance of ferrous metal sheets. Further, the adhesion between the obtained black layer and the metal plate or the bright surface layer described later can be improved. The decane coupling agent is preferably a decane coupling agent having a glycidoxy group at the terminal, and examples thereof include r-glycidoxypropyltrimethoxy decane and r-glycidoxypropylmethyldiethoxylate. Decane, ethylene tris(methoxyethoxy)decane, and the like. The amount of the decane coupling agent to be added is preferably 1 part by mass or more (particularly 2 parts by mass or more) and 17 parts by mass or less (particularly preferably 15 parts by mass or less) based on 100 parts by mass of the black composition. When the amount added is less than 1 part by mass, the effect of adding a decane coupling agent may not be sufficiently obtained. Further, when the content of the decane coupling agent exceeds 17 parts by mass, the amount of the decane coupling agent which is not useful for the reaction is large, and conversely, the corrosion resistance is lowered. &lt;Wax&gt; A wax may be further added to the black composition used in the present invention. In the field of home appliances such as thin televisions, complicated embossing of ferrous metal sheets is often performed. At this time, the properties required for the inner surface of the ferrous metal sheet are required to have workability in addition to the aforementioned conductivity and corrosion resistance. By adding a water-based wax to the black composition, lubricity can be imparted to the black layer to improve workability. Examples of the wax of the water system include polyethylene waxes such as "Chemipearl W700", "Chemipearl W950", and "Chemipearl W900" manufactured by Mitsui Chemicals. The amount of the wax to be added is preferably 1 to 10 parts by mass (particularly preferably 3 to 7 parts by mass) based on 100 parts by mass of the black composition. When the amount of the wax added was less than 1 part by mass, no effect of addition was observed -29-201206694. When more than ί mass parts of wax is added, the effect of reducing the dynamic friction coefficient is also saturated. (Glossy Layer) The ferrous metal plate of the present invention has a glossy finish on the black layer. According to this configuration, the ferrous metal sheet of the present invention can improve the scratch resistance, the workability, and the corrosion resistance, and the blackness (LM straight) also tends to be improved (Figs. 4 and 6). Further, as the amount of adhesion of the bright surface layer increases, the glossiness is increased, and a black metal plate having a black appearance with a black finish can be obtained (Fig. 7). The amount of adhesion of the bright surface layer is preferably lg/m2 or more (particularly 1.5 g/m2 or more, more preferably 2 g/m2 or more), and 4 g/m2 or less (particularly 3.5 g/m2 or less). More preferably, it is 3 g/m2 or less). When the amount of adhesion to the bright surface layer is less than 1 g/m2, the effect of improving damage resistance, workability, and corrosion resistance cannot be obtained. Further, when the amount of adhesion exceeds 4 g/m2, the effect of improving corrosion resistance and scratch resistance can be observed, but the workability is lowered. For example, peeling of the black layer tends to occur during press molding. Further, when the adhesion amount of the bright surface layer is 3 g/m2 or more, the blackness (L*値) and the glossiness (G60) are largely changed (Fig. 7). The glossy resin composition constituting the glossy layer preferably contains a weight average molecular weight of 10,000 to 25,000 (particularly 15,000 to 25,000), Tg 35 to 75 ° C, and hydroxyindole 5 mgKOH/g or more (particularly 6 mgKOH/g). The above polymer polyester resin. By using the high molecular weight polyester resin to form a bright surface layer, a black metal plate excellent in workability and damage resistance can be obtained.

S -30- 201206694 When the weight average molecular weight of the polymer polyester resin is less than 10,000, the flexibility and workability of the ferrous metal sheet are deteriorated due to insufficient flexibility and toughness of the bright surface layer. Further, when the weight average molecular weight exceeds 25,000, the flexibility and the toughness are excellent. However, as the functional group which reacts with the crosslinking agent is reduced, the tightness of the bright surface layer is insufficient, and the corrosion resistance may be deteriorated. When the Tg of the high molecular polyester resin is less than 35 ° C, sufficient bright surface hardness cannot be obtained, and the scratch resistance may be lowered or the peeling of the bright surface layer may occur during the press working. Further, when the Tg exceeds 75 ° C, the bright surface layer becomes too hard, and cracks may occur when the bright surface layer is formed to lower the corrosion resistance. Further, since the bright surface layer becomes brittle, peeling of the bright surface layer may occur due to the impact during processing. Examples of the polymer polyester resin include "Arakyd 7021", "KA-21 12", "KA-2049E (above, Arakawa Chemical Industry Co., Ltd.), rVyi〇n28ss", and "Vyi〇n29xs" (above: Toyo "Super Beckolite M-6805-40", "Super Beckolite M-680 1 -30 j", "Beckolite M-620 1 40-IM" (manufactured by DIC Corporation), etc. In order to further improve the scratch resistance, workability, and corrosion resistance of the ferrous metal sheet obtained by using the polymer polyester resin, a crosslinking agent may be added to the gloss resin composition. "Cymel 303", "Cymel 370", "Cymel 325" (above, Nihon Cytec Industries), "Sumimar M-40WT" (manufactured by Sumitomo Chemical Industries, Ltd.), "Super Beekamine L-1" 05-6〇" (The above is a DIC company) and other methylated melamine resin; " -31 - 201206694

"Super Beckamine L- 145-60", "Super Beckamine L-117-60", "Super Beckamine L-125-60" (above DIC), etc.; "Beckering melamine resin"; "Super Beckamine TD" Butyl benzoguanamine resin such as "Super Beckamine 15-594" (manufactured by DIC Corporation). These crosslinking agents may be used singly or in combination of two or more. For the acid-curing catalyst for the crosslinking agent, the product of the company "Production: KING INDUSTRIES, INC", "NACURE 5225", "NACURE 3 52 5", and "Beckamine P-198" manufactured by DIC Corporation, etc. . In order to further improve the corrosion resistance of the ferrous metal sheet and increase the crosslinking density, a polymer having a weight average molecular weight of 1 〇, 〇〇〇 2 2 5,000 (particularly 1 5,000 to 25,000) and Tg 35 to 75 ° C can be polymerized. Ester resin, low molecular weight polyester resin with weight average molecular weight 1,50 0~2,500, TglO~45 5t, high molecular weight polyester resin: low molecular weight polyester resin (mass ratio) = 8 : 2~ The mixing ratio of 6:4 is mixed to form a glossy resin composition. In many cases, the polymer polyester resin is oxonium 10 mgKOH/g or less, and the crosslinking point (functional group) is small when the crosslinking agent is added, so that the crosslinking reaction is not sufficiently performed, and the bright surface layer cannot be made compact. . Therefore, a low molecular weight polyester resin having a large oxindole is added to promote a crosslinking reaction with a crosslinking agent, whereby a dense bright surface layer can be formed to remarkably improve corrosion resistance, chemical resistance, and the like. In other words, by blending the polymer polyester resin and the low molecular weight polyester resin with the above mixing ratio, the processability or damage resistance of the polymer polyester resin can be exhibited, and the low molecular polyester system can be obtained. The compacting of the bright surface layer by the crosslinking reaction between the resin and the crosslinking agent reveals corrosion resistance or chemical resistance, etc.

The average oxanthene of S-32-201206694 is preferably 25 mgKOH/g or more. The low molecular weight polyester resin is preferably "Beckolite 46-118", "Beckolite M-6405 - 50", "Becko1 ite Μ - 6402 - 50", etc. The weight molecular weight of the above polyester resin (weight average) Molecular weight), using tetrahydrofuran as a dissolving solution, two column columns ("KF-804L j" manufactured by Shodex) were connected in series, and gel permeation was carried out under the conditions of a column temperature of 40 ° C and a flow rate of 1.0 m 1 /min. The chromatograph (GPC) was measured by "JASCO Corporation, Intelligent HPLC" and converted to polystyrene. Hydroxyl hydrazine can be obtained in accordance with JIS K0070. When a commercially available polyester resin is used, the nominal enthalpy can be used within the above range. The glossy resin composition constituting the glossy surface layer preferably contains a polyesteramine having a weight average molecular weight of 30,000 to 40,000 and a butyl 8-3 to 23° (: 'hydroxyxanthene 1〇11^1^011/£ or less) A urethane resin. The polyester urethane resin has a hydrolysis resistance (water resistance) because it has an aromatic polyester as a basic skeleton. Further, since it has a urethane bond, High oxindole and strontium sulphate result in improved adhesion to the black layer and improved reactivity with the crosslinking agent (hardener) to form a tough film. The average weight of the polyester urethane resin When the molecular weight is less than 30,000, the flexibility, toughness, and water resistance of the bright surface layer may not be obtained. When the weight average molecular weight exceeds 40,000, the fluidity of the resin may be deteriorated, and a uniform smooth film may not be obtained. When the Tg of the polyester urethane resin is less than -3 ° C, the hardness of the bright surface coating film is lowered, and there is a concern that the workability or the damage resistance is deteriorated. Further, when the T g exceeds 23 ° C, it is bright. The hardness of the top coat increases and the softness decreases. It may be -33-201206694 When the same 'hydroxyl oxime exceeds 1 〇 mgKOH/g', the functional group of the resin increases, resulting in an increase in the crosslinking point, which lowers the flexibility of the bright surface layer coating, which may deteriorate the workability. The ester resin is preferably 乂71〇111111-83 00: weight average molecular weight 30,000, D = 2 3° (:, oxindole 3 to 4 mgKOH/g, "Vylon UR-23 00: weight average molecular weight 32,000, Tg = 18 ° C, oxindole 2 to 4 mg KOH / g", "Vylon UR-3210: weight average molecular weight 40,000, D = § = -3 ° (:, oxindole 2 to 3 mg KOH / g", "Vylon UR -3 500 : weight average molecular weight 40,00, Tg = 10 ° C, hydroxy hydrazine l 〇 mg KOH / g" (above, manufactured by Toyobo Co., Ltd.), etc. Further, a glossy resin composition constituting a glossy surface layer And preferably comprising: a polyester urethane resin having a weight average molecular weight of 30,000 to 40,000 and a Tg-3 to 23 ° C, and a low molecular weight molecular weight of 1,500 to 2,500, and a low molecular weight of TglO to 45 ° C Polyester resin, average hydroxy group mixed with polyester urethane resin: low molecular weight polyester resin (mass ratio) = 2: 8 to 4: 6 A mixed resin of 25 mg KOH/g or more. When the mixed resin is used, the effect of the polyester urethane resin (the water resistance is good and the adhesion to the enamel layer is high) can be sufficiently exhibited to form a strong coating. Films, etc., and reducing the amount of polyester urethane resin which is more expensive than usual polyester resins, are advantageous in terms of cost. When the polyester urethane resin is less than the aforementioned mixing ratio' The water resistance is significantly degraded. When immersed in boiling water for a few hours, the water will penetrate into the interface between the black layer and the bright surface coating layer, and the adhesion of the interface will be reduced. After the immersion drying, the interface will be peeled off and spotted. white

S -34- 201206694 Unequal doubts. When the polyester urethane resin is more than the aforementioned mixing ratio, the performance improvement effect (water resistance, etc.) which can be matched with high cost cannot be obtained. &lt;Polyethylene Wax&gt; In the present invention, it is preferred to contain 2 to 10 parts by mass of the polyethylene wax in the above-mentioned 100 parts by mass of the glossy resin composition (solid content). With this configuration, the polyethylene crucible can function as a lubricant, and imparts scratch resistance or workability to the obtained black metal sheet. When the content of the polyethylene wax is less than 2 parts by mass, the effect of adding wax is not obtained. Further, even if the content of the polyethylene ruthenium exceeds 10 parts by mass, the effect of lowering the friction coefficient by the addition of ruthenium cannot be improved, and the corrosion resistance may be lowered. More preferably 4 to 6 parts by mass. Examples of the polyethylene wax include a solvent-dispersed wax, and specific examples thereof include HIGH FLAT X-20P-2 manufactured by Gifu Shellac Co., Ltd. dispersed in xylene or HIGH FLAT Τ-20Ρ-2» dispersed in toluene. In the present invention, it is preferable to contain 5 parts by mass or more (particularly 7 parts by mass or more) and 20 parts by mass or less of the rust preventive agent in 100 parts by mass of the bright surface resin composition (solid content). Good for 15 parts by weight or less). When the amount of the rust inhibitor added is less than 5 parts by mass, the rust-preventing effect such as corrosion resistance cannot be obtained. Further, when the amount of the rust inhibitor added exceeds 20 parts by mass, aggregation or segregation tends to occur in the glossy resin composition, or the appearance is poor due to a decrease in gloss (production of matting). Further, a precipitate or the like is generated in the glossy resin composition to lower the stability. The gloss of the ferrous metal plate can be controlled by the type of the rust preventive agent and the addition of -35 - 201206694, and the blackness can be maintained while the addition is added, and the matte appearance can be obtained. Specific examples of the rust inhibitor include those selected from the group consisting of calcium ion-exchanged dioxygen solvent-based colloidal cerium oxide and aluminum tripolyphosphate. For the calcium ion-exchanged cerium oxide, "Sylomask 52 Sylomask 55" manufactured by Fuji Chemicals Co., Ltd., r Sylysia 5 3 0", and r Sylysia 71C solvent-based colloidal cerium oxide can be cited as Nissan Chemical Co., Ltd. XBAST" , "MIBK-ST" and so on. "G-WHITE G105", "K G110", "K-WHITE #105", and "K-WHITE G73 0" manufactured by Tayca Co., Ltd. using the above-mentioned bright resin composition to form The method for the bright surface layer is not particularly limited, and a method for applying a bright surface resin to a surface of a black layer and/or a metal plate by a generally known method can be applied. Use the same method as when forming a black layer. Further, under heating and drying conditions, the heating and drying temperature is shown to be 200 to 230 ° C (heat drying time: about 1 to 2 minutes). When the ferrous metal plate of the present invention is provided only on one side of the metal plate, it may have a bright surface layer on the inner surface (i.e., the surface having one side of the black layer). In the present specification, the inner layer is particularly referred to as an "inner glossy layer" to distinguish it from the above-mentioned bright surface layer. By setting the inner surface bright layer, it is possible to further improve the etching property and the like. The amount of adhesion of the inner surface of the bright surface layer is preferably 丨 concentration in terms of dry mass, and 矽, i group to S ί 1 y s i a ′′ ' Γ 丨 等. The system is listed as -WHITE, etc. and the conditional grease is dry. The degree of use can be as bright as the black layer of the black layer. The resistance is 0 _ 2 g/m2 -36- 201206694 or more (more preferably 0.5 g/ M2 or more), 2.5 g/m2 or less (especially preferably 2.0 g/m2 or less). When the amount of the inner surface bright layer is less than g2 g/m2, it is difficult to apply uniformly to the metal sheet, and it is difficult to obtain On the other hand, when the adhesion amount of the inner surface bright surface layer exceeds 2.5 g/m 2 , the conductivity is lowered or the peeling amount of the resin film is increased during the molding process, causing adhesion of the peeling film. In the case of the accumulation of the mold, there is a concern that the problem of the molding is hindered. The inner surface is coated with an ethylene-unsaturated carboxylic acid copolymer as disclosed in Japanese Laid-Open Patent Publication No. 2005-246953 (including The neutralized state is formed as an emulsion composition of a main component, and the emulsion composition contains: a carboxyl group of 1 mol to 0.2 to 0.8 mol per mol of the ethylene-unsaturated carboxylic acid copolymer ( 20~80 mol%) of the amine below the boiling point i〇〇t, and relative The carboxyl group 1 molar of the ethylene-unsaturated carboxylic acid copolymer is a monovalent metal compound equivalent to 0.02 to 0.4 mol (2 to 40 mol%), and the solid content relative to the resin composition is 1 0 0 % by mass, a crosslinking agent having 0 or 5 to 2% by mass of a functional group having two or more reactive groups capable of reacting with a carboxyl group, and substantially containing no amine or ammonia having a boiling point exceeding 1 ° C. Further In the emulsion composition, cerium oxide particles (colloidal cerium oxide, etc.), a wax, a diluent solvent, an anti-dipping agent, a flattening agent, an antifoaming agent, a penetrating agent, an emulsifier, and the like may be appropriately added. Membrane auxiliary, coloring pigment, tackifier, decane coupling agent, other resin (for example, carboxylic acid polymer, etc.), etc. (black metal plate) The ferrous metal plate of the present invention is made of surface-treated carbon black as -37 - 201206694 is a black pigment, so it is easy to obtain a black metal plate with a blackness (L*値) of 24 or less. The black metal plate of the present invention has a blackness (L*値) in a form having no bright surface layer. Preferably, it is 23 or less, and particularly preferably 22 or less. [Examples] The present invention is not limited to the scope of the invention, and is intended to be included within the scope of the invention. The evaluation method and the criterion for the determination (single particle size of the carbon black) The carbon black aqueous solution was suction-filtered with a filter of 0.2 μm, and was subjected to a stage-injection scanning electron microscope FE-SEM (SU-70, manufactured by Hitachi, Ltd.). ") to observe the filtration residue. (Volume average particle diameter of carbon black in an aqueous solution) An aqueous solution of carbon black was measured by a laser diffraction/scattering method using a Microtrac FRA9220 (manufactured by Leeds &amp; Northrup Co., Ltd.). (Volume average particle diameter of carbon black in the black composition) The measurement was carried out in the same manner as in the measurement method of the volume average particle diameter of carbon black in the above aqueous solution. 38 - 201206694 (blackness) Using a spectrophotometer ("Spectro Color Meter SQ2000" manufactured by Nippon Denshoku Industries Co., Ltd.), the measurement of the black metal plate and the black metal plate with the glossy surface layer L, a, b値, and converted to L *値 according to the following formula 1. In the present invention, those having L * 値 of 24 or less (L 値: 20 or less) are acceptable. L* = l .3632L-3.5904 · · · Equation 1 In addition, the blackness (blackness) of the ferrous metal plate and the ferrous metal plate with the glossy finish was judged by visual judgment and evaluated on the following basis. ◎: Black 〇 with a deep degree: black △: tea black X: brown (gloss) was measured and determined at an angle of 60° (G60) using "Gloss Meter VG2000" manufactured by Nippon Denshoku Industries Co., Ltd. Glossiness (G値) of ferrous metal plate and black metal plate with glossy finish. (Black layer peeling test) According to JIS K5 60 0-5-6 (1999), the surface of the black metal plate -39-201206694 was cut into a checkerboard shape (lmmxlmm, 100 mesh) by a cutting knife to Eichsen (Erichsen) Tester) After extruding 6 mm (Ehrlich: 6 mm), an adhesive tape ("CT4 05AP-24" manufactured by Nichiban Co., Ltd.) was attached, and the tape was peeled off to carry out a tape peeling test to observe the peeling state of carbon black and below Benchmark to evaluate. ◎: The residual ratio of the black layer is 100%. 〇: The residual ratio of the black layer is less than 100% and is 90% or more. Δ: The residual ratio of the black layer is less than 90% and is 80% or more. X: The residual ratio of the black layer is not up to 80% (carbon black dissolution test) After immersing a black metal plate or a black metal plate with a glossy finish in boiling water for 1 hour, visually observe the carbon black from a black metal plate or a black metal plate with a glossy finish The appearance change (water resistance) caused by the dissolution is evaluated on the basis of the following criteria. ◎: No change in appearance 〇: Very little change △: There is a decrease in blackness (loss of gloss) X: Uneven appearance due to discoloration (SST time) According to JIS Z2371, black metal plate or black with a glossy finish The metal plate was subjected to a salt spray test, and the time (corrosion resistance) until white rust was generated was measured. In the present invention, when the ferrous metal plate is used, the above time is 48.

S -40- 201206694 hrs When the black metal plate with a glossy finish is attached, the above time is 1 20 hours. (SST cycle test) According to JIS Z2 371 'A salt water spray (spray time 8 hours) was applied to a black metal plate with a bright finish layer, and then stopped for 16 hours, thereby performing a salt spray test for 1 cycle and calculating white The number of cycles (corrosion resistance) up to 5% of rust. In the present invention, those of 4 cycles or more are acceptable. ◎ : 6 cycles or more 〇: 4 cycles or more and less than 6 cycles △ : 2 cycles or more and less than 4 cycles X : less than 2 cycles (inside conductivity) With the terminal of the tester, it is measured with bright The inner surface of the black metal plate of the surface layer (the black metal plate on the side of the bright surface layer is not formed), and the resistance 値 is gently slid, and the inside of the black metal plate with the bright surface layer is evaluated on the following basis. Surface conductivity. ◎: less than 100 Ω 〇: 100 Ω or more and less than 200 Ω △ : 200 Ω or more and less than 500 Ω X : 5 0 0 Ω or more (pencil hardness) -41 - 201206694 According to JIS Κ-5 400 (1 990 ), on a black metal plate or a black metal plate with a bright surface layer, scratch the surface of the black layer or the bright surface layer with a pencil scratching tester, and obtain a pencil hardness that does not cause damage (surface damage resistance) Sex). (Τbending workability) The black metal plate with a glossy finish of 50x50mm will be cut, and the surface (the surface of the bright surface layer) will be gently bent outward at room temperature (20 ° C) with pliers. The same metal plate was clamped on the curved portion and bent to the threshold, and a crack was observed on the bent portion after the processing by visual observation or a magnifying glass. The evaluation method is based on the number of sheets of the black metal plate with the bright surface layer being sandwiched, which is 0T for the scorpion, 1T for the one piece, and the first piece of the number of cracks on the surface as the crack. Limit (for example, when 1T is cracked, 2T is used as the crack limit) ^ (0°CT bending workability) Cool the black metal plate with a glossy finish cut to 0 0x50 mm to 0 °C The surface (bright surface forming surface) was bent outward at 〇 ° C, and other evaluations were performed in the same manner as the above-described T bending workability. (Whitening resistance) Using a 80-ton crank molding apparatus ("NCL-80TS" manufactured by Aida Engineering Co., Ltd.), a single molding test was performed on a ferrous metal plate or a ferrous metal plate with a bright surface layer under the following conditions. -42- 201206694 Mold: Cylindrical mold size: blank diameter ΙΙΟιηιηφ, punch outer diameter 50.64 ιηηιφ, mold inner diameter: 5 1.64mm, punch R: 5mm, mold R: 3mm, clearance ±0mm processing speed: 40spm Platen pressure: lkg/cm2 On the curved portion and the sliding surface of the molded article, the change in the black appearance (whitening resistance) caused by the peeling due to the elongation or impact of the black layer or the bright layer is visually observed. Column reference to evaluate the deep drawing processability of ferrous metal sheets or ferrous metal sheets with glossy finishes. ◎: Very good 〇: Good △: Poor X: Very poor (adhesive tape resistance) The same as the above-mentioned whitening resistance, a single molding test was performed on a ferrous metal plate or a ferrous metal plate with a glossy finish. Adhesive tape ("#95 10" manufactured by Sliontec Co., Ltd.) was attached to the sliding portion (side surface portion of the cylinder) of the obtained molded product, and the tape was peeled off to carry out a tape peeling test, and the film was visually observed at this time. The peeling state is evaluated by the following criteria. ◎: Very good (no film peeling) 〇: Good (very little film peeling) △: Poor (with film peeling) -43- 201206694 x: Very poor (almost (completely peeling) (dynamic friction coefficient) The surface of the black metal plate with a bright surface layer (gloss surface formation surface) under the following conditions using a HEIDON surface measurement tester (TYPE; 14DR) manufactured by Shinto Scientific Co., Ltd. In the above, the SUS ball is pressed while being pressed with a constant load, and the coefficient of dynamic friction is calculated. Test load: 500g Sliding speed: l〇〇mm/min Sliding distance: 4 0 mm Test times: 3 times at room temperature (evaluated by the average 値 of 3 times) Sliding casting: SUS ball l〇mm0 (appearance appearance) ) Visually observe and tap with your fingers to confirm if there is a “roughness” and evaluate it on the following basis. ◎: smooth and no rough feeling 〇: smooth but slightly rough feeling △: matt and rough feeling X: large rough feeling (weather resistance) According to JIS K 5400, under the following conditions, a bright surface layer is attached The black metal plate is subjected to a solar carbon weathering test. -44- 201206694

Environmental conditions: 63±3°C Irradiation time: 150 hours 18 minutes/120 minutes continuous shower (rainfall) Visually observe the appearance of the black metal plate with a glossy finish before and after the solar carbon weathering test, and below The baseline is used to assess the change. ◎: No change in appearance 〇: only slight change △: change in hue and gloss X: uneven change in hue and gloss Hereinafter, the preparation of each raw material used in the experimental example and evaluation of its physical properties will be described. (Single particle size of surface-treated carbon black and untreated carbon black) The surface-treated carbon black aqueous solution used in the experimental example was measured ("Ultra-dense ink drop BA-8" manufactured by Kuretakes Co., Ltd. And untreated carbon black (Tokai Carbon Co., Ltd. "Self-dispersive carbon black Aqua-Black 162" has a single particle size of about 150 nm and 100 nm. (Surface treated carbon black in an aqueous solution, untreated The volume average particle diameter of the carbon black) The volume average particle diameter of the surface-treated carbon black aqueous solution (BA-8) and the untreated carbon black (Aqua-Black 162) used in the experimental examples were determined, respectively. It is 430 nm, 4400 nm. As described above, the surface-treated carbon black and the untreated carbon black have a particle size almost the same as that of the single-45-201206694, but the surface-treated carbon black in the aqueous solution is untreated. Compared with carbon black, the volume average particle size is remarkably small, so it is known that surface-treated carbon black is less likely to cause secondary aggregation in water. (Surface treated carbon black, untreated carbon black in black composition) Volume average particle size) in ink (B A-8) 45 parts by mass (converted to surface-treated carbon black), polyethylene resin ("Chemipearl S100" manufactured by Mitsui Chemicals Co., Ltd.), and polyurethane resin (Adeka Bontighter HUX541 manufactured by Adeka Co., Ltd.) ), epoxy resin ("KA-1 826YA" manufactured by Arakawa Chemical Industries Co., Ltd.), or 45 parts by mass of acrylic resin ("Rikabond ES-21" manufactured by Central Chemical Industry Co., Ltd.) (converted to resin solid content) as a binder 10 parts by mass of a resin and colloidal cerium oxide ("Snowtex XS" manufactured by Nissan Chemical Co., Ltd.) to prepare a black composition having a solid concentration of 10%. The particle size distribution (secondary particle diameter) of the obtained black composition was measured. When an acrylic resin or an epoxy resin is used as the binder resin, the volume average particle diameter is 13.0 5 μm and 14.3 5 μm, respectively, and the secondary particle diameter is remarkably increased. In contrast, polyethylene resin or polyamine is used. In the case of the urethane resin, the volume average particle diameter is 2.82 μm and 4.46 μm, respectively. As can be seen from the above, the binder resin used in the present invention is a polyethylene resin or Secondary aggregation point of the resin by urethane, carbon black can be hindered by the view of the surface treatment is preferred.

S-46-201206694 (Preparation of binder resin (polyethylene resin) precursor) An ethylene-acrylic acid copolymer ("Primacor (registered trademark) 59901" manufactured by Dow Chemical Co., Ltd., which is an olefin-acid copolymer, is composed of acrylic acid. Unit: 20% by mass, mass average molecular weight (Mw): 20,000, melt index: 1300, acid hydrazine: 150) 200.0 parts by mass, polymaleic acid aqueous solution as a carboxylic acid polymer (Nonpol (registered trademark) ) PMA-50W", Mw: about 11 〇〇 (in terms of polystyrene), 5% by mass of 8.0 parts by mass, and 35.5 parts by mass of triethylamine (0.63 equivalent to the carboxyl group of the ethylene-acrylic acid copolymer), 6 parts by mass of a 48% NaO hydrazine aqueous solution (0.15 equivalent to the carboxyl group of the ethylene-acrylic acid copolymer), 3.5 parts by mass of pine oil fatty acid ("Hartall FA3" manufactured by Harima Chemicals Co., Ltd.), and 792.6 parts by mass of ion-exchanged water were added. In an autoclave equipped with an emulsifier equipped with a stirrer, a thermometer, and a temperature controller, and sealed, stir at high speed for 15 hours at 15 (TC and 5 atm), then cool to 3 (TC. Then add a decyl coupling agent of a glycidoxy group ("TSL 8350" manufactured by GE Toshiba Silicone Co., Ltd., γ-glycidoxypropyltrimethoxy decane), 10.4 parts by mass, containing carbon dioxins Imine compound (Carbodilite (registered trademark) SV-02, manufactured by Nisshinbo Co., Ltd.), polycarbodiimide, Mw: 2,700, solid content 40% by mass) 31.2 parts by mass, ion-exchanged water 72.8 parts by mass, stirring 1 An aqueous dispersion (emulsion) of a precursor of a binder resin (polyethylene resin) was prepared in a minute (the solid content concentration was about 20% by mass, measured in accordance with JIS K683 3). Hereinafter, the emulsion may be referred to as " Adhesive Resin (a) Precursor. -47- 201206694 (Preparation of Binder Resin (Polyurethane Resin) Precursor) Polytetramethylene Ether Glycol as a Polyol Component Chemical Industry Co., Ltd., average molecular weight 1 000 ) 60 parts by mass; 14 parts by mass of 1,4_ cyclohexanedimethanol and 20 parts by mass of dimethylolpropionic acid, put into a mixer, thermometer, temperature controller It In the synthesis apparatus, 30.0 parts by mass of N-methylpyrrolidone as a reaction solvent is added, and 104 parts by mass of toluene diisocyanate (hereinafter sometimes referred to as "TDI") as an isocyanate component is charged, and the temperature is raised to 80 to 85 °. C was reacted for 5 hours to obtain a urethane prepolymer. The resulting prepolymer had an NCO content of 8.9%. Further, 16 parts by mass of triethylamine was added for neutralization, and a mixed aqueous solution of ethylenediamine and 16 parts by mass of water and 480 parts by mass of water was added thereto, and emulsification was carried out at 50 ° C for 4 hours to produce a chain extension reaction. An aqueous dispersion (emulsion) of the polyurethane resin (solid concentration: 29.1%, acid sulphate 4 1.4) was obtained. Hereinafter, the emulsion may be referred to as "adhesive resin (b)". Experimental Example 1-1 to 1-10: Production of a ferrous metal plate (modulation of a black composition) Ink as a surface-treated carbon black ("Ultra-rich ink drop BA-8" manufactured by Kawatake Co., Ltd.) 44.4 to 133.3 parts by mass, while adding 138.2 to 107.8 parts by mass of pure water, and then adding 99.8 to 42.8 parts by mass of the binder resin (a) precursor, and adding colloidal cerium oxide (Snowtex manufactured by Nissan Chemical Co., Ltd.) (registered trademark) XS", solid concentration 20%) 15 parts by mass, finally added as a oxazoline group-containing polymer

S -48- 201206694

Epocros (registered trademark) K-2030E (manufactured by Nippon Shokubai Co., Ltd.) was prepared in an amount of 2·6 to 1.1 parts by mass, and 300 parts by mass of a black composition (solid content concentration of 10% by mass) was prepared, and the black composition was prepared. 1 part by mass contains 20 to 60 parts by mass of the surface-treated carbon black, 30 to 70 parts by mass of the binder resin (a), and 1 part by mass of the colloidal cerium oxide. The polymer containing the oxazolin group is added in an amount of 5 parts by mass based on 100 parts by mass of the total of the ethylene-acrylic acid copolymer and the polymaleic acid. (Production of ferrous metal plate) The prepared black composition was applied to an electrogalvanized steel sheet having a thickness of 0.5 mm by means of a bar coating apparatus so that the dry mass became 0.5 g/m 2 (EG; Zn adhesion) Amount of 20 g/m2), hot-dip galvanized steel sheet (GI; Zn adhesion amount 60 g/m2), titanium (Ti) plate, aluminum (A1) plate on one side, dried at a drying temperature of 120 ° C for 60 seconds Make a black metal plate. Experimental Example 1-1 1 to 1-20: Production of a black metal plate with a bright surface layer (modulation of the glossy resin composition 1)

In the case of a polymer polyester resin ("KA-2112" manufactured by Arakawa Chemical Co., Ltd., weight average molecular weight 23,000, and 45.3 parts by mass), a crosslinking agent (Nihon Cytec Industries, Inc.) was added while stirring. Cymel 3 03") 3.4 parts by mass and 2.5 parts by mass of an acid-hardening catalyst ("NACURE 5 225" manufactured by Kusu Chemical Co., Ltd.), followed by addition of 5.1 parts by mass of polyethylene wax ("X-20P-2" manufactured by Gifu Shellac Co., Ltd.) 1.0 parts by mass of aluminum dihydrogen tripolyphosphate ("K-WHITE -49-201206694 G105" manufactured by Tayca Co., Ltd.) and scalar ion-exchanged silica sand ("Sylomask 52" manufactured by Fuji Silysia Chemicals Co., Ltd.) was added as a rust inhibitor. 1.0 parts by mass, and diluted and stirred with 144.2 parts by mass of a diluent ("N Thinner 450" manufactured by Nippon Paint Co., Ltd.). The obtained solvent-based glossy resin composition 1 was obtained from a polymer polyester resin of 68% by mass. And the crosslinking agent is 17% by mass, the rust inhibitor is 5% by mass of aluminum dihydrogen phosphate, the calcium ion exchanged cerium oxide is 5% by mass, and the polyethylene ruthenium is 5 mass%, and the outer layer is acid hardened. Catalyst 2.6 quality (Preparation of a black metal plate with a glossy finish) The solvent-based glossy resin composition 1 was applied to Experimental Example 1 by means of a bar coating apparatus so that the dry mass was 2 g/m2. A black metal plate with a glossy finish is produced on the black layer surface of the black metal plate obtained in 1 to 1 _ 1 0. (Evaluation results of ferrous metal plate and black metal plate with glossy finish) The evaluation results of the board and the black metal plate with the glossy finish are shown in Table 1.

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驺SSSSSS;=:;SS -51 - 201206694 Comparison of Experimental Examples 1-1 to 1-8 with Experimental Examples 1-9 to 1-10, and Experimental Examples 1-11 to 1-18 and Experimental Example 1 In the comparison of -19 to 1-20, it was found that when the content of the surface-treated carbon black was 25 to 60% by mass, a black metal plate having a good blackness (L*値24 or less) was obtained. Further, when the content of the surface-treated carbon black exceeds 60% by mass, it is known that the adhesion between the black layer and the metal layer may be deteriorated. Experimental Example 1 - 1 In the black metal plate with a glossy finish, the carbon black was sufficiently prevented from being eluted from the black layer. Fig. 3 to Fig. 6 show the relationship between the carbon black concentration when EG is used as a metal plate and b値 and L*値 of the ferrous metal plate. From the comparison between Fig. 4 and Fig. 6, it can be seen that the black metal plate with the bright surface layer has a tendency to increase the blackness (L-値 is lowered). Experimental Example 2-1 to 2-10: ferrous metal Preparation of the plate (modulation of the black composition) In 259.3 parts by mass of the ink (BA-8), 422.6 parts by mass of pure water was added while stirring, and then 261.3 parts by mass of the binder resin (a) precursor was added, and then the colloidal state was added. Ceria (Nippon Chemical Co., Ltd. (Snowtex (registered trademark) XS) 50 parts by mass, and finally added Epocros (registered trademark) K-203 0E 6.9 parts by mass, otherwise, the same as Experimental Example 1-1, Further, 1 part by mass of the black composition (solid content concentration: 1% by mass) was prepared. The black composition contained 3 parts by mass of the surface-treated carbon black and the binder resin. (a) 5 5 parts by mass, colloidal cerium oxide 1 〇 parts by mass -52- 201206694 (manufactured of ferrous metal plate) by hand roll coating device so that the dry mass becomes 0.2 5~1·7 g/ In the form of m2, the prepared black composition is applied to an electrogalvanized steel having a thickness of 0.5 mm. Two sides of (EG; Zn adhesion amount: 20 g/m2) were dried at a drying temperature of 120 ° C for 60 seconds to prepare a black metal plate. Experimental Example 2-11 to 2-15: Production of a black metal plate (black composition) Preparation of the material) The same procedure as in Experimental Example 2-1 was carried out except that the ink (BA-8) was replaced by a self-dispersing carbon black (manufactured by Tokai Carbon Co., Ltd., Aqua-Black 162). 1 part by mass of the black composition (solid content concentration: 1% by mass), the black composition: 1 part by mass of the self-dispersion type carbon black, 35 parts by mass, and the binder resin (a) 55 parts by mass 10 parts by mass of colloidal cerium oxide. (Preparation of ferrous metal plate) The black composition prepared in Experimental Example 2-11 was replaced with the black composition prepared in Experimental Example 2-11 so that the black composition was made. A black metal plate was produced in the same manner as in Experimental Example 2-1 except that the dry mass was 0.30 to 1.80 g/m 2 . Experimental Example 2-1 6 to 2-30: Bright Production of a black metal plate on the surface layer (modulation of the glossy resin composition 2) in a polymer polyester resin (Arakawa) Chemical Industry Co., Ltd. "Arakyd-53-201206694 7012", weight average molecular weight 25,000, Ding 850 乞) 38.9 parts by mass, adding 3.4 parts by mass of a crosslinking agent (Cymel 303) and an acid curing catalyst (NACURE 5225) while stirring 2.0 parts by mass, followed by adding 5.1 parts by mass of polyethylene wax (X-20P-2), adding 2.0 parts by mass of aluminum trihydrogen phosphate (K-WHITE G105) as a rust preventive agent, and using a thinner (N Thinner) 450) 1 50.7 parts by mass was diluted and stirred to prepare: 80% by mass of the polymer polyester resin, 17% by mass of the crosslinking agent, 2.6% by mass of the acid curing catalyst, and 10% by mass of the rust inhibitor. And a solvent-based glossy resin composition 2 of 5 mass% of polyethylene wax. (Preparation of a black metal plate with a bright surface layer) The solvent-based glossy resin composition 2 was applied to Experimental Example 2-1 to 2 by a bar coating apparatus so that the dry mass was 2 g/m 2 . -1 single sheet of ferrous metal sheet obtained in 5, and made a black metal plate with a glossy finish (black metal plate, evaluation result of black metal plate with bright surface layer), black metal plate and bright The evaluation results of the black metal plate of the surface layer are shown in Table 2.

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0S s οε ςε sss -55- 201206694 Comparison of Experimental Examples 2-1 to 2-8 with Experimental Examples 2-11 to 2-15, and Experimental Examples 2-16 to 2-23 and Experimental Examples 2-26 to 2 In the comparison of -30, it was found that by using the surface-treated carbon black as a black pigment, a black metal plate having good blackness or corrosion resistance can be obtained as compared with the case of using untreated carbon black. This is considered to be that the untreated carbon black causes secondary aggregation in the black composition, and the surface of the black layer becomes thick and becomes porous. Further, it is known that by using the surface-treated carbon black as a black pigment, It also suppresses the peeling of carbon black from the black layer. In particular, in the ferrous metal plate (experimental examples 2-1 to 2-8, experimental examples 2-16 to 2-23) of the present invention (with bright surface layer), no dissolution of carbon black from the black layer was observed at all. . When surface-treated carbon black was used (Experimental Examples 2-1 to 2-10), and when untreated carbon black was used (Experimental Examples 2-11 to 2-15), the amount of black layer adhesion and the black metal plate L * The relationship between 値 is shown in Figures 1 and 2. From Fig. 1, it can be seen that when surface-treated carbon black is used, a black metal plate having a black layer adhesion amount of about 0.3 g/m2 and a blackness (L*値) of 24 or less can be obtained, with the amount of adhesion. The increase of L-値 is reduced, and when the adhesion amount is about 0.5 g/m2 or more, L*値 is almost stable. On the other hand, in the second drawing, it can be seen that when the untreated carbon black is used, a black metal plate having a black layer adhesion amount of about 0.3 g/m 2 and a blackness (L*値) of 24 or less cannot be obtained. , L*値 has a large degree of change, and it is impossible to obtain a stable blackness. Experimental Example 3-1 to 3-9: Production of ferrous metal plate (modulation of black composition) Using Epocros (registered trademark) K-2030E (A), Epocros

S-56 - 201206694 (registered trademark) K-2020E (B), Epocros (registered trademark) K-2010E (C) (all made by Nippon Shokubai Co., Ltd., styrene/acrylic resin) as adhesive resin (a) an oxazoline group-containing polymer of the composition, and an oxazoline group-containing group is added in an amount of 1 to 1 part by mass based on 100 parts by mass based on the total of the ethylene-acrylic acid copolymer and the polymaleic acid. In the same manner as in Experimental Example 1-1, the polymer was prepared to contain 35 parts by mass of the surface-treated carbon black and 5 parts by mass of the binder resin (a) in 100 parts by mass of the black composition. , a black component of colloidal cerium oxide in an amount of 1 part by mass. (Production of ferrous metal plate) The prepared black composition was applied to an electrogalvanized steel sheet having a thickness of 55 mm by a manual roll coating apparatus so that the dry mass became 〇·5 g/m 2 ( EG; Ζιι adhesion amount of 20 g/m2) on both sides, drying at a drying temperature of 120 ° C for 60 seconds to produce a black metal plate. The evaluation results of the obtained ferrous metal plate are shown in Table 3. [Table 3] Experimental Example: Darkness of oxazoline group-containing copolymer (visual) Black layer peeling test carbon black solution. Test SST time surface content rate (%) 3-1 A 2 〇〇48 3-2 A 4 ◎ @ @ 72 3-3 A 5 @ © ◎ 72 3-4 A 6 ◎ © ◎ 72 3-5 A 8 © © © 72 3-6 B 5 @ @ 0 72 3-7 C 5 @ 〇0 48 3-8 A 1 © △ X &lt; 24 3-9 A 10 ◎ △ △ 48 From Experimental Examples 3-1 to 3-7 and Experimental Example 3 In the comparison of 8 to 3-9, it can be seen that -57-201206694 when a polyethylene resin is used as the binder resin, the content of the oxazoline group-containing copolymer in the resin is set to 2 to 8 mass. °/〇' can be used to fix the surface-treated carbon black in the black layer. In addition, a black metal plate with good corrosion resistance can be obtained. Experimental Examples 4-1 to 4-11: Fabrication of black metal plates (black composition) Modulation)

Snowtex XS (A; surface area average particle size 4 to 6 nm), Snowtex 40 (B: surface area average particle diameter 10 to 20 nm), and Snowtex S (C; surface area average particle diameter 8 to 11 nm) (all manufactured by Nissan Chemical Co., Ltd.) Any one of them as colloidal cerium oxide, and the content of 100 parts by mass of the black composition is set to: 35 parts by mass of surface-treated carbon black, 50 to 75 parts by mass of binder resin (a), and glue The black composition was prepared in the same manner as in Experimental Example 1-1 except that the cerium oxide was not more than 25 parts by mass. The surface area average particle diameter of the colloidal ceria means that when the surface area average particle diameter is l~l〇nm, it is determined by the Sears method, and when it is 10 to l〇〇nm, it is determined by the BET method. It is the nominal 値 described in the manufacturer's manual. (Production of ferrous metal plate) The black composition prepared was applied to a plated galvanized steel sheet having a thickness of 55 mm by a manual roll coating device so that the dry mass was 〇5 g/m 2 (EG). ; Both sides of the Zn adhesion amount of 20 g/m 2 ) were dried at a drying temperature of 120 ° C for 60 seconds to prepare a black metal plate. The evaluation results of the obtained ferrous metal sheets are shown in Table 4.

S -58- 201206694

[Table 4] Experimental example Colloidal cerium oxide black depth (visual) Black layer peeling test carbon black solution. Test SST time pencil hardness _ Content rate w 4-1 A 5 @ ο Ο 48 8 4-2 A 7 © © 48 HB 4-3 A 10 13 ◎ 72 HB 4-4 A 15 @ © ◎ 72 HB 4-5 A 20 © ο Ο 48 F 4-6 B 10 ◎ © 48 HB 4-7 C 10 “® r ο ο 72 HB 4-8 A 0 "Δ X &lt;24 28 4-9 A 4 @ ο △ &lt;24 B 4-10 A 22 ◎ △ A 48 Book 4-11 A 25 厶XX &lt;24 F From In the comparison of Experimental Examples 4-1 to 4-7 with Experimental Examples 4-8 to 4, it was found that uranium resistance can be obtained by containing colloidal cerium oxide in an amount of 5 to 20% by mass in the black composition. And a black metal plate excellent in damage resistance. Further, the surface-treated carbon black can be well fixed in the black layer. Experimental Example 5-1 to 5-7: Production of a black metal plate (modulation of a black composition) The binder resin (b) was replaced with the binder resin (a) precursor 'other than the other except the same as Experimental Example 2-1, and the surface-treated carbon black was contained in 100 parts by mass of the black composition. 35 parts by mass, binder resin ( b) 5 parts by mass of a black component of a colloidal cerium oxide of 1 part by mass. Further, a decane coupling agent ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts by mass of the black composition. 17 parts by mass. The prepared black composition (containing a decane coupling agent) was applied to an electrogalvanized steel sheet having a thickness of 0.5 mm by a manual roll coating apparatus to a dry mass of 0.5 g/m 2 to -59 to 201206694. EG; Zn adhesion amount: 20 g/m2), both sides were dried at a drying temperature of 120 ° C for 60 seconds to produce a black metal plate. Experimental Example 5·8 to 5-14: a black metal plate with a bright surface layer Production (Preparation of Glossy Resin Composition 3) Polymer Polyester Resin (Vylon 29XS, manufactured by Toyobo Co., Ltd.); Weight average molecular weight 2 0,0 0 0 to 2 5, 0 0 0, Tg = 72 15 parts by mass of a cross-linking agent ("Sumimar M-40WT" manufactured by Sumitomo Chemical Co., Ltd.) and a rust preventive agent (manufactured by Nissan Chemical Industries, Ltd.) were added to 60 parts by mass of 〇C and 値6.5 mg KOH/g. XBA-ST": solvent-based colloidal cerium oxide) 10 parts by mass, followed by adding 5 parts by mass of polyethylene wax (X-20P-2), and then diluted with 10 parts by mass of diluent (N Thinner 450) The mixture was stirred to contain 68% by mass of a polymer polyester resin, 17% by mass of a crosslinking agent, and a rust inhibitor 10 % Amount, polyethylene wax, and 5 mass% of solvent-based glossy resin composition 3 (parts by mass solid concentration of 10%). (Preparation of a black metal plate with a bright surface layer) The solvent-based glossy resin composition 3 was applied to Experimental Examples 5-1 to 5 by a bar coating apparatus so that the dry mass was 2 g/m 2 . On one side of the ferrous metal plate obtained in -7, a black metal plate with a glossy finish was produced. The evaluation results of the obtained black metal plate with a glossy finish are shown in Table 5.

S -60- 201206694

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SI @&gt; @ ◎ s ◎ @ © ◎ ◎ ◎ ◎ ◎ oo 00 Ϊ & & & α ◎ ◎ ◎ ◎ ◎ ◎ ◎ @ ◎ @ ο ◎ ◎ in © ν @ ◎ 201206694 From the fifth table It has been found that even if the binder resin (b) (polyurethane resin) is used instead of the binder resin (a) (polyethylene resin), the adhesion between the black layer and the metal layer can be obtained. A black metal plate in which carbon black is not easily dissolved and corrosion resistance is also good. Further, it was found that the corrosion resistance of the ferrous metal plate can be improved by adding a decane coupling agent to the black composition. Experimental Example 6-1 to 6·9: Production of a black metal plate with a bright surface layer (modulation of a black composition) A black composition was prepared in the same manner as in Experimental Example 2-1. (Production of ferrous metal plate) The prepared black composition was applied to an electrogalvanized steel sheet having a thickness of 0.5 mm by means of a manual roll coating apparatus so that the dry mass became 0.5 g/m 2 (EG; Zn) The both sides of the adhesion amount of 20 g/m2) were dried at a drying temperature of 120 ° C for 60 seconds to prepare a black metal plate. (Preparation of a black metal plate with a bright finish layer) The solvent-based bright surface prepared in Experimental Example 2 - 6 was obtained by a bar coating apparatus so that the dry mass became 0.5 to 5 g/m 2 . The resin composition 2 was applied to one side of the ferrous metal plate obtained in Experimental Examples 6-1 to 6-9, and a black metal plate with a glossy surface layer obtained by producing a black metal plate with a bright surface layer was prepared. The evaluation results are shown in Table 6.

S -62- 201206694

I Table 6] Experiment. Example Bright surface attachment wing (g/mO blackness (L* 値) Gloss (G60) SST Time SST Cycle pencil hardness τ Bending workability White resistance. 6-1 1.0 23.7 1Β. 0 120 〇Η 1Τ 〇6-2 1.5 23.5 18.0 144 2Η 1Τ ◎ 6-3 2.0 23.6 1Θ.1 168 © 2Η 0Τ ◎ 6-4 2.5 22.5 24.3 168 © 2Η 0Τ ◎ 6-5 3·0 21.4 30. S 192 2Η 0Τ @ 6-6 3.5 Γ 18.6 47.7 192 © 2Η 1Τ 〇6·7 4,0 18.2 53.5 .216 ◎ 2Η 2Τ 0 6-8 0.5 24.4 17.8 "72 △ ΗΒ 4Τ X 6-9 5.0 17.9 . 57.4 240 @ 2Η 3Τ X From the comparison of Experimental Examples 6 -1 to 6 - 7 and Experimental Examples 6 - 8 to 6 - 9, it can be seen that the adhesion amount of the bright surface layer is set to 1 to 4 g/m 2 . Corrosion resistance, damage resistance, and good workability of the black metal plate. Fig. 7 shows the influence of the amount of the bright surface layer on the blackness (L * 値) and gloss of the ferrous metal plate. When the vicinity of 3 g/m2, the blackness and gloss are greatly changed. Experimental Example 7-1~7-33: Fabrication of a black metal plate with a bright finish (manufacture of a black metal plate) Pair of black composition 1A black metal plate was produced in the same manner as in Experimental Example 5-1 except that 7 parts by mass of a decane coupling agent ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.) was added in an amount of 〇〇. Preparation) The following polymer polyester resin, polyester urethane resin, or low molecular weight polyester resin (A~E; manufactured by Arakawa Chemical Industries, Ltd., -63-201206694 F~I, Ο; Other than the experimental example 5-8, except that it was manufactured by Toyobo Co., Ltd., J~Μ, P~Q; DIC Co., Ltd.), and the content of the polyester resin was 6.8 % by mass. A solvent-based glossy resin composition 4 having a crosslinking agent of 17% by mass, a rust inhibitor 1% by mass, and a polyethylene wax of 5% by mass. A: Arakyd 7012, weight average molecular weight 25,000, Tg50 ° C, oxindole 7.5 8: 〖Insert-2112, weight average molecular weight 23,000, D = 70 ° (:, oxindole 7.0 C: KA-2049E, weight average molecular weight 22,000, Tg 70 ° C, 値 7.0 0: 〖8-20598, weight average molecular weight 22,000, Dingke 70° (:, 値 4.0 E: Arakyd 7036, weight average molecular weight 26,000 , Tg20 ° C, oxindole 1 2.5 F : Vylon 29XS ' Weight average molecular weight 20,000~25,000, Tg = 72 ° C, oxindole 6.5 G : Vylon 28SS, weight average molecular weight 15, 〇〇〇 ~ 20,000, Tg = 6 8 °C, oxindole 6.5 11: 乂丫1〇11〇 〖59€8, weight average molecular weight 5,000~8,000, Tg=15°C, oxonium 17.0 1:¥丫1〇11〇1(:13€8, Weight average molecular weight 5,000~8,000, Tg=l 5°C, oxindole 20.5 J : Super Beckolite M-680 1 -30, weight average molecular weight

S -64 - 201206694 1 5,000 ' Tg72〇C, oxindole 1 0·0 K : Beckolite 46-118, weight average molecular weight 1,500 °, Τ g 2 0 °C, oxindole 1 2 0 L : BeckoliteM- 6405-50, weight average molecular weight 2,500, Tg42 ° C, oxindole 120 M : Beckolite M-6402-50, weight average molecular weight 2,500, TglO ° C, oxindole 120 Ο : Vylon UR-3500, weight average molecular weight 4 0,0 0 0, T g = 1 0 °C, oxindole 1 ο P : Super Beckolite M-6805-40 ' Weight average molecular weight 15,000, Tg35 ° C, oxindole 10 Q : Beckolite M-620 1 -40 -IM, weight average molecular weight 10,000, Tg41 t, oxindole 30 (manufacture of a black metal plate with a bright finish layer) The solvent system was prepared by a bar coating device so that the dry mass became 2 g/m 2 The results of the evaluation of the black metal plate with the glossy finish obtained by applying the glossy resin composition 4 to one side of the above-mentioned ferrous metal plate to produce a black metal plate with a glossy finish are shown in Table 7. . -65- 201206694 [Table 7] Experimental example Polyester (urethane) resin SST Time SST Cyclic scale mm τ Bending processability Whitening resistance Molecular urethane): Mix ratio of low molecular weight (mass ratio) ) 値 値 mg / KOH 高 跛 跛 ) 7-1 7-1 A 7.5 168 © 2Η οτ © . 7-2 B — 7 168 ◎ 2Η οτ ◎ 7-3 C a 7 168 ◎ Η οτ ο 7 -4 F 6.5 168 ◎ 3Η ΊΤ ◎ 7-5 G - 6.5 168 © Η ΟΤ ◎ 7-6 J — 10 168 ◎ Η ΟΤ 0 7-7 A (80) κ (20) 30.0 168 2Η οτ ◎ 7- 8 A (70) κ (30) 41.3 192 ◎ 2Η οτ © 7-9 A (60) κ (40) 52.5 192 ◎ Η οτ ο 7-10 A (7 0) L (30) 41.3 168 ◎ 2Η οτ © 7-11 A (70) Μ (30) 41.3 192 @ Η οτ ◎ 7-12 B (70) Κ (30) 40.9 168 ◎ 2Η οτ © 7-13 C (70) Κ (30) 40.9 168 ◎ 2Η οτ @ 7-14 F (70) Κ (30) 40.6 192 ◎ 3Η οτ ◎ 7-15 F (80) Κ (20) 29.2 168 ◎ 2Η οτ ο 7-16 F (70) L (30) 40.6 168 © 2Η 1Τ ◎ 7-17 F (70) Μ (30) 40.6 192 © 2Η οτ ® 7-18 Q (7 0) Κ (30) 40.6 168 ◎ 2Η 07 ο 7-19 J (70) (30) 43.0 168 ◎ 2Η 1Τ ο 7-20 D —. 4.0 96 Δ F 3Τ X 7-21 D (80) κ (20) 27.2 144 .ο Η 2Τ Λ 7-22 E a 12.5 168 ο Η 1Τ Δ 7-23 H 17.5 120 厶F 3Τ X 7-24 1 —' 20.5 144 △ F 3Τ Δ 7-25 0 10.0 168 © 3Η οτ ◎ 7-26 o (30) κ (70) 65.0 192 ◎ 2Η οτ ◎ 7 -27 o (30) L (7 0) 65.0 192 © 2Η οτ ◎ 7-2B O (30) Μ (7 0) 65.0 192 Γ ◎ 3Η 1Τ ◎ 7-29 P (7 0) L (3 0) 65.0 168 ◎ 2Η οτ ◎ 7-30 P (70). Μ (30) 65.0 168 ◎ 2Η οτ ◎ 7-31 J (70) L (3 0) 65.0 168 ◎ 2Η οτ ◎ 7-32 J (7 0) Μ (30) 65.0 192 @ 2Η οτ ◎ 7-33 Q (70) L (3 0) 75.0 192 ◎ Η 2Τ 0 From Experimental Examples 7-1 to 7-19 and Experimental Examples 7-25 to 7-33, and experiments In the comparison of the examples 7-2 0 to 7-24, it was found that a black metal sheet excellent in corrosion resistance and workability can be obtained by using the polyester resin specified in the present invention as a glossy resin composition. Experimental Examples 8-1 to 8-8: Production of a black metal plate with a bright surface layer -66-201206694 (Production of a black metal plate) A black metal plate was produced in the same manner as in Experimental Example 6-1. (Preparation of the bright resin composition 2 (a)) The content of the polyethylene wax is 12% by mass, and the resin of the polymer polyester resin and the crosslinking agent is mixed at a ratio of 80:20. The solvent-based glossy resin composition 2 (a) was prepared in the same manner as in Experimental Example 2-16 except that 75.4% to 86.4% by mass. (Production of a black metal plate with a bright finish layer) The solvent-based glossy resin composition 2 (a) is applied to the above-mentioned ferrous metal by a bar coating apparatus so that the dry mass is 2 g/m 2 . One side of the board, and a black metal plate with a glossy finish is made. The evaluation results of the obtained ferrous metal plate with a glossy finish are shown in Table 8. [Table 8] Experimental Example Wax Replenishment %) SST Time SST Cycle Pencil Hardness τ Bending Processability Whitening Resistance Dynamic Friction Coefficient 8-1 2 168 Η 1Τ 〇0.161 8-2 4 168 © 2Η 0Τ ◎ 0.153 8-3 5 168 © 2Η 0Τ 0.150 8-4 6 168 © 2Η 0Τ 0.150 8-5 8 168 @ 2Η 0Τ 0.149 8-6 10 168 © 2Η ΟΤ @ 0.14β 8-7 t 168 © Η 1 2Τ 厶0.182 8-8 12 144 〇2Η ΟΤ @ 0.150 From the comparison of Experimental Examples 8 -1 to 8 - 6 and Experimental Example 8 - 7 to 8 _ 8 'It is known that 2 to 10% by mass of polyethylene wax is contained in the glossy resin composition. 'A black metal plate with good corrosion resistance and damage resistance and low friction coefficient is obtained. -67- 201206694 The plate is made of gold and black.} Attached: 9-plate 1~6-9-gold case of the system 12, black color C is in phase with the plate black gold 2 A substance c into a group of rust grease anti-trees under the surface with C to make the company limited to have a share of 0 ^ week C ff y spoon a Γ F is the design rate of the company has a public division There are a number of shares in the company S company limited to share the stock industry β β C • 1 m - E production C 3 2 曰 2%, and will mix polymer polyester resin at a ratio of 80: 20. The solvent-based glossy resin composition 2 (b) was prepared in the same manner as in Experimental Example 2-6 except that the resin material of the crosslinking agent was 70.4 to 89.4% by mass. A: aluminum dihydrogen phosphate K-WHITE G105, particle size 2.3 μιη Β: aluminum dihydrogen phosphate K-WHITE G7 3 0, particle size 2.3 μιη C: calcium ion exchange ceria Sylomask 62-Ca6%, Particle size 2.8 μηι D: Calcium ion exchange ceria Sylomask 5 3 0, particle size 2.7μηι Ε : Calcium ion exchange ceria Sylomask 710, particle size 2.8μηι F: colloidal ceria XBA-ST, 10~20nm (Preparation of a black metal plate with a bright finish layer) The solvent-based glossy resin composition 2 (b) is applied to the ferrous metal by a bar coating device so that the dry mass is 2 g/m 2 . One side of the board, and a black metal plate with a glossy finish is made. The result of the evaluation of the s-68-201206694 ferrous metal plate with a bright finish is shown in Table 9. [Table 9]

Greedy rust inhibitor SST time SST cycle T bending processability whitening coating appearance mm concentration (% by mass) 9-1 A 5 120 @ 1T @ @ 9-2 A 7 1β8 ◎ OT &amp; @ 9-3 A 10 168 @ ΟΤ _ ◎ @ 9-4 A 15 168 ◎ οτ @ © 9,5 A 20 168 © 2Τ 0 ο 9-6 B 10 168 @ ΟΤ ® @ 9-7 C 10 144 o ΟΤ ◎ ◎ 9- 8 D 10 144 o 1Τ © ο 9-9 E 10 144 o 1Τ ◎ ο 9-10 F 10 144 &amp; οτ © 9-11 A 3 96 X οτ @ © 9-12 A 22 120 A 4Τ XX From the experimental example 9-1 to 9-10, in comparison with Experimental Examples 9-11 to 9-12, it was found that corrosion resistance and workability were obtained by containing 5 to 20% by mass of the rust preventive agent in the glossy resin composition. And the appearance of the black metal plate. Experimental Examples 10-1 to 10-10: Preparation of a black metal plate with an inner bright surface layer and a black metal plate with a bright inner surface layer (modulation of the underlying treatment composition) in acidic colloidal oxidation 555 parts by mass of pure aluminum phosphate (manufactured by Mishan Chemical Co., Ltd.) and pure water, compared with acidic colloidal ceria and aluminum phosphate, in 55 parts by mass of "Snowtex (registered trademark)" manufactured by Nissan Chemical Co., Ltd.) In a total amount of 0.5 parts by mass, a polyacrylic acid (Jurymer AC-10-LP, manufactured by Nippon Pure Chemical Industries, Ltd.) was added in an amount of 7.5 parts by mass, and then 7.5 parts by mass of a decane coupling agent ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.) was added. The composition of the underlying treatment composition -69- 201206694 (Preparation of the underlying treated metal sheet) The prepared underlying treatment composition is applied to the plating by means of a manual roll coating apparatus to adhere to 120~120 mg/m2 on a dry mass basis. The inner surface of the galvanized steel sheet (EG; Zn adhesion amount: 20 g/m2) was dried at a drying temperature of 120 ° C for 60 seconds to prepare a bottom treated metal sheet. (Modulation of black composition) As a surface treated Carbon Black Ink (Wu Zhu 55.6 parts by mass of the "Ultra-Concentrated Ink Drops BA-8" manufactured by Seiko Co., Ltd., while adding 3 5 7.4 parts by mass of pure water, followed by the addition of 71.3 parts by mass of the binder resin (a) precursor. 12.5 parts by mass of colloidal cerium oxide (manufactured by Nissan Chemical Co., Ltd., Snowtex (registered trademark) XS), 1.3 parts by mass of a decane coupling agent, and Epocros (registered trademark) K- as a oxazoline group-containing polymer were added. 2030E parts by mass, and 500 parts by mass of a black composition (solid content concentration: 5% by mass) was prepared, and the black composition contained 30 parts by mass of the surface-treated carbon black and the binder resin in 100 parts by mass of the black composition. (a) 60 parts by mass, 10 parts by mass of colloidal cerium oxide, and 5 parts by mass of decane coupling agent (outer layer) (Formation of black layer) by means of a bar coating device so that the dry mass becomes 1 g/m2 Applying the prepared black composition to one side (surface) of the underlying treated metal sheet, and drying at a drying temperature of 160 ° C for 60 seconds to produce a black layer.

S-70-201206694 (Preparation of inner surface water-based glossy resin composition) First, an emulsion (emulsion) of an ethylene-unsaturated carboxylic acid copolymer and a carboxylic acid polymer is prepared. In other words, an ethylene-acrylic acid copolymer ("Primacor (registered trademark) 59901" manufactured by Dow Chemical Co., Ltd.; constituent unit derived from acrylic acid: 20% by mass, mass average molecular weight (Mw): 20 , 〇〇〇, melt index: 1300, strontium: 150) 200.0 parts by mass, a polymaleic acid aqueous solution as a carboxylic acid polymer (Nonpol (registered trademark) PMA-50W, manufactured by Nippon Oil Co., Ltd., Mw: about 1 100 (polystyrene-converted), 5% by mass of 8.0 parts by mass, 35.5 parts by mass of triethylamine (0.63 equivalent to carboxyl group of ethylene-acrylic acid copolymer), and 6.9 parts by mass of 48% aqueous NaOH solution (relative to ethylene) - the carboxyl group of the acrylic copolymer is 0.15 equivalent), 3.5 parts by mass of pine oil fatty acid ("1^^11? person 3" manufactured by Harima (13^11^〇&amp; 13 company), and 79.2 parts by mass of ion-exchanged water, It was added to an autoclave equipped with an emulsification apparatus equipped with a stirrer, a thermometer, and a temperature controller, and sealed, and stirred at a high speed at 150 ° C and 5 atm for 3 hours, and then cooled to 30 ° C. Then, a propylene oxide-containing oxide was added. Base deforestation coupling agent (Momentive Perf Ormance Materials (old company name: GE Toshiba Silicone) company "TSL 8350": r-glycidoxypropyl trimethoxane) 4 parts by mass, carbodiimide (Mw: 2,700, solid content 40% by mass) 31.2 parts by mass, 72.8 parts by mass of ion-exchanged water, and stirred for 10 minutes to prepare an emulsion (emulsion) of the ethylene-unsaturated carboxylic acid copolymer and the carboxylic acid polymer (solid content concentration of about 20% by mass, according to JIS K683 3 Then, in the obtained emulsion, colloidal cerium oxide (a) having a surface area average particle diameter of -71 - 201206694 4 to 6 nm (nominal 値) was sequentially added (Snowtex (registered trademark) )XS": solid content concentration: 20% by mass) and colloidal cerium oxide (b) having a surface area average particle diameter of 10 to 2 Onm (nominal 値) (Snowtex (registered trademark) 40" manufactured by Nissan Chemical Co., Ltd.; After the mixture was sufficiently mixed, a decane coupling agent containing a glycidoxy group ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.: solid content concentration: 1% by mass) was added, followed by addition as a metavanadate Sodium metavanadate (emerging chemistry "Sodium metavanadate" manufactured by the company; solid concentration of about 66% by mass. Then epoxy resin modified with acrylic acid (Modepics (registered trademark) 302" manufactured by Arakawa Chemical Industries Co., Ltd.: solid concentration of 33.5 mass %)) The mixture was added to prepare a water-based glossy resin composition on the inner surface. In the preparation of the water-based glossy resin composition on the inner surface, the mixing amount (or mixing ratio) of each component, colloidal cerium oxide (a): colloidal cerium oxide (b) (mass ratio) = 5 0 : 50, inorganic component: resin component (the total solid content of the above emulsion and the epoxy resin modified by epoxy resin) (mass ratio) = 30: 70 to 95: 5, acrylic modified epoxy resin 5 parts by mass of the total solid content of the above-mentioned emulsion is 5 parts by mass (5% by mass in the resin component), and the total amount of the decane coupling agent containing a glycidoxy group is 100 parts by mass based on the total of the inorganic component and the resin component. 10 parts by mass of the metavanadate is 1 part by mass based on 100 parts by mass of the total of the inorganic component and the resin component. (The production of a black metal plate with a glossy inner surface (formation of the inner surface water-based glossy layer))

S-72-201206694 The inner surface water-based glossy resin composition is applied to the inner surface of the underlying treated metal sheet on which the black layer is formed by a bar coating apparatus so that the dry mass becomes 〇5 g/m2. (The bottom layer treated surface without black layer), dried at a drying temperature of 170 ° C for 60 seconds to form an inner surface water-based bright surface layer, and a black metal plate with an inner surface bright surface layer (the surface has a black layer) , the metal plate with a bright finish on the inside). (Preparation of solvent-based glossy resin composition 5 for the surface) to polyester urethane resin (Vylon UR-3 500, manufactured by Toyobo Co., Ltd.): weight average molecular weight 40,000, Tg = 10 °C, Hydroxylhydrazine 10 mgKOH/g 'solid content concentration: 40% by mass> To a mass of 76 parts by mass, 200 parts by weight of a diluent ("N Thinner 450" manufactured by Nippon Paint Co., Ltd.) was added, and the mixture was diluted and stirred, and then a crosslinking agent (manufactured by DIC Corporation) was added. "Super Beckolite TD-126": butylated benzoguanamine resin; weight average molecular weight of 600, solid content of 60%) 12.7 parts by mass, stirring and dissolving. Then, a solution of 4.6 parts by mass of an acid hardening catalyst ("NACURE 5225" manufactured by Kawamoto Chemical Co., Ltd.) dissolved in 86.6 parts by mass of a diluent was added, and a matting agent ("MIBK Silica Slurry" manufactured by Fuji Silysia Co., Ltd.; solid type) was sequentially added thereto. The concentration of 8% by mass) was 10 parts by mass, and 10.2 parts by mass of polyethylene wax (Zhehua 31^113 &lt;: "-20?-2" manufactured by the company). The obtained solvent-based glossy resin composition 5 was composed of 76% by mass of a matrix resin, 19% by mass of a crosslinking agent, and 5% by mass of a polyethylene wax, and the outer layer was an acid-hardening catalyst of 4.6% by mass, and matting was used. Agent (Silica) 2% by mass. -73- 201206694 (Preparation of a black metal plate with a bright finish on the surface (formation of a solvent-based bright surface layer)) With a bar coating device, the dry mass is 3 g/m2. The solvent-based glossy resin composition 5 was applied to the surface (the surface having the black layer) of the black metal plate with the inner surface bright layer, and dried at a drying temperature of 230 ° C for 60 seconds. A black metal plate with a glossy finish on the inside of the watch (a metal plate with a bright finish on the inside of the watch) is attached. (Evaluation results of a black metal plate with a bright inner surface and a black metal plate with a bright inner surface) A black metal plate with a glossy inner surface and a glossy finish on the inside The evaluation results of the ferrous metal plate are shown in Table 10. [Table.1 0]..

S Experimental Example Bottom Treatment Adhesion (mg/m2) Black metal with internal lightness 1 i layer with black metal plate with bright surface inside surface y Evaluation surface SST Time SST Cyclic conductivity SST Time SST Cycle 0 〇CT Bending workability Weather resistance Tape peeling resistance 10-1 12 Table 96 0 .— 168 ◎ 1T 〇10-2 20 Table 96 〇192 ◎ 0T 〇10-3 40 Table 120 ◎ 216 @ OT ◎ ◎ 101-4 60 Table 144 © 240 ◎ OT ◎ ◎ 10-5 80 Table 144 ◎ A 240 ◎ ; 0T ◎ ◎ 10—6 100 Table 144 © A / 264 ◎ 1T ◎ ◎ 10-7 117 Table 144 ◎ I. 264 ◎ 2T 〇〇10-8 .120 Table 144 〇—264 ◎ 3T 〇△ 10—9 8 Table 72 Δ —· 16B ◎ 2T Δ 〇10—10 0 Table 72 Δ I. 168 ◎ 3T Δ A 10-3 40 〇◎一一一———. 10-4 Γ 60 Within 120 0 ◎ — — _ 1 10—5 80 Within 120 〇 ◎ — — _ 10—6 100 Within 120 0 〇 — — —. 10—10 0 Within 48 Δ ◎ — — — '—* — 10—8 .120 Within 120 Δ △ — — — . — — — — — — — — — — — — — — — — — — — — — — Black shiny surface of the metal plate in layers with the table and the inner surface of the metal plate surface bright black layers produced (primer treatment composition modulation) Experimental Example in the same manner to prepare a composition for a primer treatment 〇_ 1. (Production of the underlying treated metal sheet) The prepared underlayer treatment composition was applied to the hot-dip galvanized steel sheet (GI; Zn adhesion amount by means of a manual roll coating apparatus to adhere 0 to 120 mg/m2 on a dry mass basis) 45 g/m2 ) of the inner surface of the watch, dried at a drying temperature of 12 (TC for 60 seconds to produce a bottom treated metal plate. (Preparation of a black metal plate with a bright inner layer) In the same manner as in Experimental Example 10-1, a black metal plate with an inner glossy surface layer was produced. (The production of a black metal plate with a bright surface layer on the inside of the watch) In the same manner as in Experimental Example 10-1, a black metal plate with a bright surface layer on the inside of the watch (a black metal plate with an inner glossy surface layer, attached with a table) was prepared. Evaluation results of the black metal plate on the inner surface of the bright surface) The evaluation results of the black metal plate with the inner surface finish and the black metal plate with the bright surface on the inside are shown in Table 11. -75- 201206694 [Table 1 1] Experimental example bottom layer treatment adhesion (mg/m2) The black metal plate on the surface is covered with a black metal plate on the surface of the surface. Evaluation surface SST Time SST Cyclic conductivity SST Time SST cycle (TCT bending force workability. Weather resistance tape peeling 11-1 12 Table 120 ◎ 192 ◎ .2T ◎ 〇 11-2 40 Table 120 @ — 216 © 1T ◎ 11-3 60 Table 144 ◎ _ 240 ◎ 1T ◎ ◎ 11—4 80 Table 168 ◎ One· 264 1T ◎ ◎ 11 A 5 100 168 168 — 288 @ 2T @ 〇11-6 :117 Table 168 ◎. A 28B ◎ 3T © △ 11-7 120 Table 168 ◎ — 288 ◎ 4T ◎ Δ 11 -8 8 . Table 96 〇 — 192 ◎ 2T 〇 〇11—9 0 Table 96 〇.II _ · 192 ◎ 4T 〇 △ 11-2 40 144 〇〇 — — one — one. 11 one 3 60 168 〇〇 — one —... —&quot; 11-4 80 168 ◎ 0 — 1 — 11-5 100 144 ◎ Δ 一 一 — 一 11-9 0 内 72 Δ 〇 — ' 一 . — _ 11 — 7 120 144 〇 Δ — —* — • — - Experimental Examples 12-1 to 12-8: Fabrication of a black metal plate with a glossy inner surface and a black metal plate with a glossy finish on the inside (bottom layer) For the preparation of the chemical composition, ～70 parts by mass of aluminum phosphate (manufactured by Mishan Chemical Co., Ltd.) is added to the acid colloidal cerium oxide ("Snowtex (registered trademark) 〇" manufactured by Nissan Chemical Co., Ltd.). Pure water, 0.5 parts by mass of a total of acrylic colloidal cerium oxide and aluminum phosphite, added with polyacrylic acid (Jurymer AC-10-LP, manufactured by Nippon Pure Chemical Co., Ltd.), and then a decane coupling agent ( The bottom layer treatment composition was prepared by 7.5 parts by mass of "KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.). (Preparation of the underlying treated metal sheet) By means of a manual roll coating device, 60 mg/m2 of -76- is adhered to the dry mass meter.

S 201206694 Method 'Apply the prepared underlayer treatment composition to the inner surface of an electrogalvanized steel sheet (EG; Zn adhesion amount: 20 g/m2), and dried at a drying temperature of 120 ° C for 60 seconds to prepare an underlayer treatment. Metal plate. (Production of a black metal plate with an inner surface smoothing layer) A black metal with an inner surface bright surface layer was produced in the same manner as in Experimental Example 10-1 except that the metal sheet obtained by the above-mentioned underlayer treatment was used. board. (Production of a black metal plate with a bright surface layer on the inside of the table) The same as in Experimental Example 10-1 except that the underlying surface treated metal plate was used, and the surface bright surface layer was prepared. Black metal plate (evaluated with a black metal plate with a bright inner surface and a black metal plate with a bright inner surface). A black metal plate with a bright inner surface and a bright inner surface. The evaluation results of the ferrous metal plate of the surface layer are shown in Table 12. ° 77- 201206694 Ιήΐ2] The mixing ratio of the acidic colloidal cerium oxide to the aluminum phosphate (mass) is attached. The metal plate is attached with a black metal plate on the surface of the surface. SST Time SST Cycle SST Time SST Cycle 0°CT Bending processability Weather resistance Tape peeling resistance Two-bait 矽 Phosphoric acid 12-1 35 65 72 〇166 0 1T 〇 ◎ 12—2 40 60 96 〇192 © 1T ◎ ◎ 12-3 45 55 120 ◎ 240 ◎ 0T ◎ ◎ 12—4 50 50 144 ◎ 240 ◎ 0T ◎ ◎ 12—5 55 45 144 ◎ 240 ◎ 0T © ◎ 12-6 60 40 144 〇240 〇1T ◎ ◎ 12—7 65 3S 120 Δ 14 4 〇4T 〇A 12-8 70 30 48 A 120 △ 5T Δ △ Experimental Example 13-1~13-8: Black metal plate with a bright inner surface and ferrous metal with a glossy finish on the inside Preparation of the board (modulation of the underlying treatment composition) 45 parts by mass of aluminum phosphate (manufactured by Miyama Chemical Co., Ltd.) was added to 55 parts by mass of acidic colloidal cerium oxide (Snowtex (registered trademark) 曰 manufactured by Seiko Chemical Co., Ltd.). And 1 part by mass of the total of the acidic colloidal cerium oxide and the aluminum phosphite, and added polyacrylic acid (Jurymer AC-10-LP, manufactured by Nippon Pure Chemical Co., Ltd.) in an amount of 0 to 1.2 parts by mass, and then added 7.5 parts by mass of a decane coupling agent ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared to prepare a primer composition. (Preparation of a metal sheet for underlayer treatment) A method of attaching 60 mg/m2 to a dry mass by a manual roll coating device The prepared underlayer treatment composition was applied onto the inner surface of an electrogalvanized steel sheet (EG; Zn adhesion amount: 20 g/m2), and dried at a drying temperature of 120 ° C for 60 seconds to prepare a bottom-treated metal sheet.

-78-201206694 (Manufacturing of a black metal plate with a bright inner layer) The same as the experimental example 10-1 except that the metal sheet obtained by the above-mentioned bottom layer was used, the inner surface was produced. Layer of black metal plate. (Production of a black metal plate with a bright surface layer on the inside of the table) The same as in Experimental Example 10-1 except that the underlying surface treated metal plate was used, and the surface bright surface layer was prepared. Black metal plate (evaluated with a black metal plate with a bright inner surface and a black metal plate with a bright inner surface). A black metal plate with a bright inner surface and a bright inner surface. The evaluation results of the ferrous metal plate of the top layer are shown in Table 13. [Table 13] Experimental Example Polyacrylic Acid Addition A black δ 龛 surface layer with internal enamel is a black metal plate (mass part) with a surface finish on the surface. SST Time SST Cycle SST Time SST Cycle (TCT Bending) Processability Weather resistance Tape peeling resistance 13-1 0.2 96 0 168 ◎ 1T ◎ 13-2 0.4 96 〇192 ◎ στ ◎ ◎ 13-3 0.5 144 @ 240 ◎ οτ ◎ ◎ 13-4 0.5 144 © 240 ◎ 0Τ ◎ ◎ 13-5 αβ 144 ◎ Z40 ◎ 0Τ ◎ © 13—6 1.0 144 ◎ 240 ◎ 2Τ © 〇13-7 0 72 A 168 IT @ | ◎ 13—8 1.2 144 ◎ 144 4T ◎ Δ Experimental example: with Manufacture of a black metal plate with a glossy finish and a black metal plate with a bright finish on the surface -79-201206694 (Preparation of the underlying treatment composition) in acidic colloidal cerium oxide (Snowtex (made by Nissan Chemical Co., Ltd.) 45 parts by mass of aluminum phosphite (manufactured by Mishan Chemical Co., Ltd.) and pure water, and 100 parts by mass of the total of the acidic colloidal cerium oxide and aluminum phosphite, and polyacrylic acid is added to 55 parts by mass. "Jurymer AC-10-LP" made by Nippon Pure Chemical Co., Ltd. 5 parts by mass, and then 0 to 17 parts by mass of a decane coupling agent ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.) was added to prepare an underlayer treatment composition. (Preparation of a bottom-treated metal sheet) By a manual roll coating device, The dry mass meter was attached to a method of 60 mg/m2, and the prepared underlayer treatment composition was applied to the inner surface of an electrogalvanized steel sheet (EG; Zn adhesion amount: 20 g/m2), and dried at a drying temperature of 120 ° C. The bottom layer of the metal sheet was produced in the second. (Production of the black metal sheet with the inner surface smooth layer) The same procedure as in the experimental example 10-1 was carried out except that the metal sheet having the inner surface of the bright surface layer was used. A black metal plate with a bright inner surface. (Manufacturing of a black metal plate with a bright finish on the inside of the watch) Using the underlayer treated metal plate obtained above, except that 'others are the same as Experimental Example 10-1. A black metal plate with a glossy finish on the inside of the watch 201206694 (a black metal plate with a glossy inner surface and a black metal plate with a glossy finish on the inside) is produced. Layer of black metal plate with inner surface The evaluation results of the black metal plate of the surface layer are shown in Table 14. [Table 1 4] Experimental Example Addition amount of decane coupling agent (mass parts) Black metal plate with a bright inner surface is attached with a bright surface inside the surface Layer black metal plate SST time SST cycle SST time SST cycle OtT bending workability weather resistance tape peeling resistance 14 1 1 3.0 120 ◎ 192 ◎ 1T 〇 14-2 5,0 144 ◎ 240 ◎ 0T ◎ ◎ 14-3 7.5 144 ◎ 240 ◎ 0T ◎ 14-4 10.0 144 ◎ 240 ◎ 0T ◎ ◎ 14 to 5 12 5 144 © 240 ◎ 0T ◎ 14-6 15.0 120 ◎ 240 ◎ 1T. ◎ ◎ 14-7 0 72 A 168 ◎ 3T 〇 △ 14-8 17.0 Camel 144 〇 3T 〇 △ Experimental Example 15-1 to 15-10: Preparation of a black metal plate with a bright surface layer (modulation of the underlying treatment composition) in acidic colloidal cerium oxide (Nissan) 45 parts by mass of aluminum diphosphate (manufactured by Mishan Chemical Co., Ltd.) and pure water were added to 55 parts by mass of "Snowtex (registered trademark)" manufactured by Chemical Co., Ltd., and the total amount of acidic colloidal cerium oxide and aluminum phosphate was 1 〇. 〇Minutes, add polyacrylic acid (Jury, manufactured by Nippon Pure Chemical Co., Ltd.) 0.5 parts by mass of mer AC-10-LP, and then 7.5 parts by mass of a decane coupling agent ("1 &lt;: 81^403" manufactured by Shin-Etsu Chemical Co., Ltd.) was added to prepare a primer composition. (Production of the underlying treated metal plate) The prepared underlying treatment composition was applied to an electrogalvanized steel sheet (EG; Zn by a manual roll coating apparatus to adhere to a dry mass meter of -80 - 201206694 mode of 60 mg/m2). The inner surface of the surface having an adhesion amount of 20 g/m2 was dried at a drying temperature of 120 ° C for 60 seconds to prepare a bottom treated metal sheet. (Preparation of solvent-based glossy resin composition 6) The following polymer polyester resin, polyester urethane resin, or low molecular weight polyester resin (all of which are in the preparation of glossy resin composition 4) are used. The resin used was replaced by a polyester urethane resin (Vylon UR-3500), and other methods of the solvent-based glossy resin composition 5 of the surface of Experimental Example 10-1 were used. The solvent-based glossy resin composition 6 was prepared in the same manner. G : Vylon 28SS, weight average molecular weight 1 5,000~20,000, D = § = 68 乞, hydroxy 値 6.5 J : Super Beckolite M-68 0 1 - 3 0, weight average molecular weight 1 5,000, Tg 72 ° C, oxindole 1 0 · 0 K: Beckolite 46-118, weight average molecular weight 1,500, Tg20 t, oxindole 1 2 0 L : Beckolite M-6405-50, weight average molecular weight 2, '500, Tg 42 ° C, oxonium 120 M : Beckolite M -6402-50, weight average molecular weight 2,5 00, Tgl0 °C, oxindole 120 〇: 乂丫1〇111; 11-3500 'weight average molecular weight 40,000, butan = 10 °C, oxonium 10 P: Super Beckolite M-6805 -40, weight average molecular weight

S -82- 201206694 1 5,000 ' Tg3 5 °C , oxindole 1 0 Q : Super Beckolite M-680 1 -3 0, weight average molecular weight 15,000, Tg72 ° C, oxonium 10 (black metal with bright finish) Production of a board) A ferrous metal with a glossy finish was produced in the same manner as in Experimental Example 1〇-1 except that the metal sheet obtained by the above treatment was used and the gloss resin composition 6 obtained above was used. board. The evaluation results of the black metal plate with the glossy finish are shown in Table 15. [Table 1 5] Experimental Example Polyester (urethane) resin SST Time SST Cycle 0°CT Bending processability Weather resistance Tape peeling 髙 Molecule (urethane): Mix ratio of low molecular weight (quality ) 値 値 / mg/KOH polymer (urethane) low molecular weight: 15-1 〇 a 10 240 @ 0T 15-2 Ο (3 0) K (70) 65 240 ◎ 0T ◎ ◎ 15-3 0 (3 0). U (70) 65 216 © 0T ◎ 15-4 0 (3 0) Μ (70) 65 216 1T ◎ ◎ 15-5 P (70) L (3 0) 65 216 ◎ 1T ◎ @ 15 -6 P C70) Μ (3 0) 65 216 1T ◎ @ 15-7 J C70) L (30) 65 192 2T © @ 15-8 J (7 0) Μ (30) 65 240 © 2T © ◎ 75- 9 0(7 0) L (30) 75 216 © 2T ◎ © t5-10 Q A 6.5 264 ◎ 2T © © [Simplified illustration] Figure 1 shows the black layer formed by surface-treated carbon black. A graph showing the relationship between the amount of adhesion and the blackness (L*値) of a black metal plate. Fig. 2 is a view showing the relationship between the adhesion amount of the black layer formed using the untreated carbon black and the blackness (L*値) of the black metal plate. Fig. 3 shows the surface treated carbon black concentration and black. A diagram of the relationship of b 値 (yellow) of a metal plate. -83- 201206694 Section 4® shows the relationship between the surface treated carbon black concentration and the blackness (L*値) of the ferrous metal plate. The stomach 5 diagram shows a graph of the relationship between the carbon black concentration and the b値 (yellowing) of the surface treated black metal plate. Fig. 6 is a view showing the relationship between the surface-treated carbon black concentration and the blackness (L*値) of the black metal plate provided with the glossy surface layer. Fig. 7 is a graph showing the relationship between the amount of bright surface layer adhesion and the glossiness and blackness of a black metal plate.

S -84-

Claims (1)

201206694 VII. Patent application garden: 1. A ferrous metal plate characterized by: a metal plate and a black layer formed on at least one side of the metal plate; the black layer is composed of a black composition, The black composition comprises, in an amount of 100 parts by mass, 22 to 60 parts by mass of the surface-treated carbon black coated with the water-soluble resin, and 20 to 73 parts by mass of the binder resin; and the dry quality of the black layer is 0.28. ~1.5 g/m2 ; The blackness (L*値) of the surface of the black layer is 24 or less. 2. The ferrous metal sheet of claim 1, wherein the binder resin is a polyethylene resin and/or a polyurethane resin. 3. The ferrous metal sheet of claim 2, wherein the polyethylene resin is an olefin-«, /3-unsaturated carboxylic acid copolymer, an unsaturated carboxylic acid polymer, and an oxazoline group-containing polymerization. The composition of the olefin-α-, 3-unsaturated carboxylic acid copolymer and the α, unsaturated carboxylic acid polymer in a total amount of 1 part by mass, containing the aforementioned oxazoline group-containing polychain amine to The polyblack is derived from the benzene, and the second group of alcohols. The former is in the middle and the group is formed in the middle, and the ester is in the second structure, and the fat is acidified into the alkane. The saplings of the saplings are the vinegar and the vinegar is the genus of the genus M-chain benzoic acid 1' color black base cyanide has more black amine into the polyether containing the polyether from the dihydric alcohol item 3 of the selected alkane to the 1J base group.. A, more than the circumference Carboxyl is pre-existing. Fan-containing ester is a ring-based compound. It is an acid-based diacetate. If you have a special fat, you can use it. Please use a tree-based polyester cyanine. Please use 8 «sedylamine pre-acids and 2 as vinegar. Cyanol, alcohol, etc. 4. Alkyl acid, I. 5, a long base, a second, a polyamine, an alkylene oxide, and a small ether -85 - 201206694. The color composition is obtained by adding the above binder resin to carbon black and the foregoing. It is prepared in an aqueous solution of a water-soluble resin. 6. The ferrous metal sheet according to claim 1, wherein the black component comprises 100 to 20 parts by mass of the colloidal cerium oxide. 7. The ferrous metal sheet according to claim 1, wherein the metal sheet further comprises at least one side of a bottom layer formed by an underlayer treatment, wherein the bottom layer is composed of aluminum phosphite, colloidal dioxide. The composition of the underlying layer of polyacrylic acid is formed in such a manner that the dry mass is 12 to 117 mg/m 2 . 8. The ferrous metal sheet according to item 7 of the patent application, wherein the underlying treatment composition is aluminum phosphate The content ratio with colloidal cerium oxide is aluminum phosphate: colloidal cerium oxide (mass ratio) = 3 5 : 6 5 to 65 : 3 5 , and is relative to the total of aluminum phosphate and colloidal cerium oxide 1 The mass part contains 0.2 to 1.0 part by mass of polyacrylic acid. 9. The ferrous metal sheet according to item 7 of the patent application, wherein the bottom treatment composition further comprises a decane coupling agent 3 to 15 with respect to 1 〇〇 by mass of the total of the aluminum phosphate and the colloidal cerium oxide. Parts by mass. 10. The ferrous metal plate according to claim 1, wherein the black layer further has a bright surface layer, the dry surface has a dry mass of 1 to 4 g/m 2 , and the blackness of the surface of the bright surface layer (L) *値) is 24 or less. 1 1. A ferrous metal plate according to claim 10, wherein the glossy resin composition forming the bright surface layer has a weight average molecular weight of 10,000 to 25,000 and a Tg of 35 to 75. (:, high score of hydroxyindole 5 mgKOH/g or more S-86-201206694 sub-polyester resin. 1 2. A ferrous metal plate as claimed in item 10 of the patent application, wherein the bright surface resin composition of the above-mentioned bright surface layer is formed The product contains a polymer polyester resin having a weight average molecular weight of 10,000 to 25,000 and a Tg of 35 to 75 t, and a low molecular weight polyester resin having a weight average molecular weight of 1,500 to 2,500 and TglO to 45 ° C. Polymer polyester resin: low molecular weight polyester resin (mass ratio) = 8 : Mixed ratio of average oxindole 25 mg KOH / g or more mixed in a ratio of 2 to 6 : 4 . a black metal plate of the item 10, wherein the bright surface resin composition forming the bright surface layer comprises a polyester having a weight average molecular weight of 30,000 to 40,000, a Tg-3 to 23 ° C, or a hydroxyindole of 1 〇 mgKOH/g or less A urethane resin. The ferrous metal sheet according to claim 10, wherein the glossy resin composition forming the bright surface layer comprises: a weight average molecular weight of 30,000 to 40,000, Tg-3 to 23 °C polyester urethane tree, with weight average molecules 1500~2,500, TglO~45°C low molecular polyester resin, mixed with polyester urethane resin: low molecular weight polyester resin (mass ratio) = 2: 8~4 : 6 A mixed resin having an average hydroxy hydrazine of 25 mg KOH/g or more. 15. The ferrous metal plate according to claim 11, wherein the above-mentioned glossy resin composition further contains polyethylene wax 2 to 10 parts by mass. The ferrous metal sheet according to any one of the items 11 to 15, wherein the above-mentioned glossy resin composition 100 parts by mass further contains -87-201206694 rust inhibitor 5 to 20 mass. S -88-