TW201345708A - Colored resin-coated metal sheet - Google Patents

Abstract

The present invention provides a colored resin-coated metal sheet exhibiting excellent design quality of the combination of metal hue and colored resin and can produce thin film resin to color the chromium-free plain sheet even in a high-speed production line. The colored resin-coated metal sheet is a chromium-free metal sheet having colored resin layer of 0.3 ~ 2.2 <mu>m thickness at least on a single surface. The colored resin layer contains one or more than two kinds of pigments. If x is set to be 60 DEG specular gloss measured on the colored resin layer and y is set to be the average reflection rate at 500~600 nm, then x and y satisfy the following formula (1) and (2): (1) y >=-0.19x+23.0, (2) y >`= 10.

Description

Colored resin coated metal plate

The present invention relates to a colored resin coated metal plate for a frame for an automobile or a household electrical product or an exterior plate or a building material such as a built-in/outer part, a steel furniture, etc., in detail A color-coded resin-coated metal sheet that is designed to be concealed by the original color and is a combination of pigmented rain and metallic color.

Zinc-coated steel sheets have been widely used in automobiles, electrical products, building materials, and the like. However, in the state in which the zinc-based plated metal sheet is insufficient in corrosion resistance and adhesion to the coating material, it is subjected to chromium-free treatment or phosphate treatment, and when high corrosion resistance is required, these formations are formed. A resin film is provided on the treatment layer. On the other hand, from the viewpoint of the beauty of the appearance or the degree of completion of the product, the uppermost resin film is required to have a color tone and high designability required by the user. In the case of coloring a resin, although an inorganic pigment or an organic pigment is generally used, it is usually premised on concealing the original sheet. In order to conceal the original sheet and obtain a beautiful appearance, a coating film having an adhesion amount of 10 g/m ² or more is usually required, and since the cost of the coating material and the long sintering step are required, the manufacturing cost becomes high.

Therefore, it is attempted to color with a translucent resin film without concealing the original sheet. For example, Japanese Laid-Open Patent Publication No. Hei 9-122578 discloses a colored resin-coated metal sheet in which a resin coating film containing a coloring pigment is formed on an original plate after chromate treatment. However, at present, chromium-free is the mainstream, and the technique described in the above patent publication cannot be directly applied to a chromium-free metal plate.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a high-performance colored resin-coated metal which exhibits a high-chromatographic original plate which can be produced by a film-form resin which can be produced by a high-speed production line and which exhibits a combination of a metallic color and a colored resin. board.

The colored resin-coated metal sheet according to the first aspect of the invention is a chromium-free metal sheet having a colored resin layer having a thickness of at least 0.3 to 2.2 μm on one surface, and the colored resin layer contains one or two or more kinds of pigments, and the colored resin is used. When the 60° specular gloss measured on the layer side is x and the average reflectance of 500 to 600 nm is y, the following formulas (1) and (2) are satisfied.

The colored resin layer preferably contains one or more pigment dispersants selected from the group consisting of water-soluble acrylic resins, water-soluble styrene acrylic resins, and nonionic surfactants, and may also contain a polyamine-based thixotropic agent. .

The colored resin-coated metal sheet according to the first aspect of the invention preferably satisfies the following formula (3).

The colored resin layer contains a yellow pigment, and the yellow pigment is preferably any one of a benzimidazolone type, a quinoxaline type, and an isoindolinone type.

The average reflectance of the chromium-free metal plate before forming the colored resin layer at 500 to 600 nm is preferably 50% or more.

The colored resin-coated metal sheet according to the second aspect of the invention is a chromium-free metal sheet having a colored resin layer having a thickness of at least 0.3 to 2.2 μm on one surface, and the colored resin layer contains one or two or more kinds of 0.5 to 17.5% by mass. A pigment, and a water-soluble styrene acrylic resin and/or a nonionic surfactant as a pigment dispersant in an amount of 0.05 to 6.2% by mass.

The colored resin layer is a preferred embodiment of the present invention in which one or more organic pigments are contained.

The colored resin-coated metal sheet according to the third aspect of the invention is a chromium-free metal sheet having a colored resin layer having a thickness of at least 0.3 to 2.2 μm on one side, and the colored resin layer contains one or more pigments and 0.03~ 3.8 mass% of a polyamine-based thixotropic agent. Here, regarding the above pigments, the use of black pigment alone is excluded from the scope of the present invention.

In the first to third inventions, the colored resin-coated metal plate having the transparent coating film on the colored resin layer is also included. In this case, the thickness of the transparent coating film is preferably 0.4 to 4.5 μm.

According to the first aspect of the invention, it is possible to provide a colored resin-coated metal sheet having a film-like resin and a metallic color tone obtained by coloring a chromium-free original sheet and a color-receiving resin, which exhibits high designability at a low cost. In addition, the top layer The colored resin-coated metal plate having a clear coating film is a metal plate excellent in abrasion resistance and tape peeling resistance.

According to the second aspect of the invention, since the dispersibility of the pigment is improved, a film having no color unevenness can be formed, and a colored resin-coated metal sheet exhibiting high design properties can be provided at low cost. Further, the colored resin-coated metal sheet having the transparent coating film in the uppermost layer is a metal plate excellent in abrasion resistance and tape peeling resistance.

According to the third aspect of the invention, since the movement of the pigment before the coating film is dried can be suppressed, a film having no color unevenness can be formed, and the colored resin-coated metal sheet exhibiting high design can be provided at low cost. Further, the colored resin-coated metal sheet having the transparent coating film in the uppermost layer is a metal plate excellent in abrasion resistance and tape peeling resistance.

As described above, the colored resin-coated metal sheets of the first to third inventions can be applied to various applications such as home electric appliances, building materials, and automobile parts.

Fig. 1 is a graph showing the relationship between the 60° specular gloss of a colored resin-coated metal sheet and the average reflectance at 500 to 600 nm.

Fig. 2 is an explanatory view for explaining a state in which a pigment is moved.

Fig. 3 is a photograph of a substitute image of a stain and a normal product.

"Formation of the invention" <First invention>

In order to solve the above problems, the inventors of the present invention conducted coloring coating with a translucent film resin, and examined the appearance of the obtained colored resin-coated metal sheet. As a result, it was found that foreign matter adhered to the original plate, irregularities on the surface, flaws, and the like greatly affected the appearance after coating, and it was easy to cause poor appearance. In addition, the defect is not only due to the presence of flaws, but also because the colored resin is hard to enter the concave portion of the crucible. Therefore, the colored resin is retained around the crucible, and the appearance is concave (approximately 2 mm in diameter). At the time of thick film coating, pits can be filled, and appearance defects are not caused. However, when the film is applied, the appearance of a pit-like shape remains poor, which is a problem. Therefore, attention has been paid to the light absorption of the pigment and the relative visibility of the human eye, and the criteria for making the appearance of the pit-shaped appearance unclear have been examined. Therefore, the first invention (hereinafter referred to as the present invention) is attained.

Relative visibility refers to the intensity of the brightness of light of each wavelength perceived by the human eye as a numerical value. In a bright place, the human eye has a strong tendency to experience light of 500 to 600 nm with a peak wavelength of 555 nm. Therefore, in the present invention, the 60° specular gloss x of the colored resin-coated metal sheet and the average reflectance y of 500 to 600 nm are measured, and the following formulas (1) and (2) are derived from the relationship between the two. Figure 1 is a graph showing the relationship between 60° specular gloss and average reflectance from 500 to 600 nm.

If y is larger than the right side of the above formula (1), the absorption of light by the pigment can be suppressed, and the human eye feels bright, the average reflectance of 500 to 600 nm is large, and the 60° specular gloss is also high, so that the pit is in the shape of a pit. The appearance of the poor area becomes almost inconspicuous.

In order to exhibit the metallic color tone of the original plate, if y is 10 or more and the average reflectance y is less than 10, the type of the pigment (for example, red, blue, blue-violet, red-purple, etc.) may conceal the original plate, so it cannot be said that the metal has been exhibited. Highly designed tones.

The above 60° specular gloss and an average reflectance of 500 to 600 nm were measured from the side of the colored resin layer. The 60° specular gloss of the measuring instrument can be measured by a gloss meter (for example, the gloss meter “VG-2000” manufactured by Nippon Denshoku Industries Co., Ltd.), and the average reflectance can be measured by a spectrophotometer (for example, a photometric color spectrometer manufactured by Nippon Denshoku Industries Co., Ltd.). SQ-2000") measurement. The average reflectance at 500 to 600 nm was measured at a wavelength of 10 nm at intervals (measured number: 11), and (total reflectance per wavelength) / (measured number 11) = average reflectance.

The 60° specular gloss refers to a gloss value of an incident angle of 60° and a reflection angle of 60° with respect to a surface perpendicular to the surface of the sample after coating. The details are described in JIS K 5600-4-7.

In Fig. 1, it is more preferable to satisfy the region of the following formula (3).

In this region, the pit-like appearance is not conspicuous, and a colored resin-coated metal plate having more excellent design properties is formed.

Hereinafter, the constituent material of the colored resin-coated metal sheet of the present invention will be described.

[Original board]

The original plate of the colored resin coated metal plate of the present invention is a cold rolled steel plate, a molten pure zinc plated steel sheet (GI), or an alloyed molten Zn-Fe plated steel sheet (GA), and an alloyed molten Zn-5% Al plating. Steel plate (GF), electroplated pure zinc plate (EG), electroplated Zn-Ni steel plate, aluminum plate, titanium plate, galvanized steel plate, etc., are chromium-free steel plates.

In the prior art, it is preferred to carry out a chemical conversion treatment in the form of a phosphoric acid aqueous solution containing colloidal cerium oxide and an aluminum phosphate compound as described in JP-A-2005-264312. When an acidic aqueous liquid containing colloidal cerium oxide and an aluminum phosphate compound is used as a chemical conversion treatment liquid, the surface of the zinc-based plating layer is etched by the acidic aqueous liquid, and the surface of the zinc-based plating layer is formed. The aluminum phosphate is also a reaction layer of a main body of AlPO ₄ or Al ₂ (HPO ₄ ) _{3 which} is poorly soluble (not easily soluble in water or an alkaline aqueous solution). The cerium oxide particles are deposited in the reaction layer to be incorporated, thereby integrating the aluminum phosphate with the cerium oxide microparticles. Further, a dense reaction layer is formed between the zinc-based plating layer which is roughened by etching, and the combination with the resin coating film formed on the reaction layer becomes dense and strong. Further, when the acidic aqueous solution contains a water-soluble resin such as polyacrylic acid, the sedimentation state of the cerium oxide fine particles in the obtained reaction layer can be made stronger.

The average reflectance of the original plate system of 500 to 600 nm is preferably 50% or more. When an original plate having a large reflectance is used, the reflectance after forming a translucent colored resin layer that does not conceal the original plate is also increased, and the pit-like appearance defect is not conspicuous. The thickness of the original plate is not particularly limited, but is preferably about 0.3 to 1 mm.

[Pigment Dispersant]

In the present invention, the dispersibility of the pigment is also one of the important factors for improving the reflectance of the colored resin-coated metal sheet and reducing the appearance of the pit-like appearance. It is preferred to add a pigment dispersant to the resin composition for forming a colored resin layer. . A preferred pigment dispersant is one or more selected from the group consisting of water-soluble acrylic resins, water-soluble styrene acrylic resins, and nonionic surfactants. When such a film is used, a pigment dispersing agent remains in the colored coating film.

The water-soluble acrylic resin or the water-soluble styrene acrylic resin preferably has an acid value of about 50 to 300. Specifically, the water-soluble acrylic resin is an alkali-base complex of a copolymer of an unsaturated carboxylic acid such as (meth)acrylic acid and a copolymer of (meth)acrylate or the like in an amount of 50% by mass or less. The water-soluble styrene acrylic resin is an alkali-base complex of a copolymer of styrene and/or methyl styrene of 50 to 95% by mass and a copolymer of (meth)acrylic acid or maleic acid. Other copolymerizable monomers include, for example, a monomer having a sulfonic acid group, and a (meth)acrylate or the like can be used even in the water-soluble styrene acrylic resin. The number average molecular weight of these resins is preferably from about 2,500 to about 15,000.

Nonionic surfactants are commercially available from various manufacturers and can be used as long as they are nonionic.

In the water-soluble acrylic resin, the water-soluble styrene acrylic resin, and the nonionic surfactant, those having a benzene ring or a naphthalene ring structure are preferred, which means that the water-soluble styrene acrylic resin preferably has a benzene ring or a naphthalene ring. A nonionic surfactant of a ring structure.

Since the pigment dispersant is added to the pigment in advance in many cases, the resin composition can be contained in the composition by using the pigment described later. There are pigment dispersants. It is preferred to use a pigment dispersant in a coloring resin layer in an amount of 0.05 to 6.2% by mass. If it is too large, corrosion resistance and chemical resistance may fall, and if it is too small, the dispersibility of a pigment may deteriorate.

Thixotropic agent

The coating material for the film coating (the resin composition for forming a colored resin layer) has a low solid content concentration, and therefore is applied to a subsequent coating film on the metal plate, and the coating film contains the film before it is completely dried. The resin component and the pigment move in the coating film, and as described above, a state of gradation as shown in Fig. 2 is formed. Therefore, in the present invention, a thixotropic agent is added to the resin composition for forming a colored resin layer. In particular, polyamido-based thixotropic agents are effective for inhibiting pigment movement. Although the reason is not clear, polyamine is a polymer obtained by bonding a plurality of monomers by a guanamine bond, and is adsorbed on a pigment by hydrogen bonding, and the steric hindrance of the polymer after adsorption improves the dispersion of the pigment. Stability; since the mesh structure is formed in the coating film by the hydrogen bond between the molecular chains of the polyamide molecules, the movement and segregation of the pigment can be prevented. The polyamine-based thixotropic agent was added so that the viscosity of the resin composition for forming a colored resin layer was measured by Ford Cup #4 to be about 10 to 20 seconds. It is used in the range of 0.03 to 3.8% by mass in terms of solid content. When it is less than 0.03 mass%, the suppression of the movement of the pigment becomes insufficient, and the occurrence of the color unevenness cannot be solved. When the amount is more than 3.8 mass%, the viscosity of the resin composition composition becomes too high, and the coating property is deteriorated, which is not preferable.

The polyamine-based thixotropic agent used in the present invention is obtained by reacting a dicarboxylic acid with a diamine, and is not particularly limited as long as it is a polyamine. Water coating The polyamine-based thixotropic agent for the material is obtained from, for example, the DISPARLON (registered trademark) AQ series, from Nanben Chemical Co., Ltd., and the like.

In the AQ series, polyamine which is represented by the following chemical formula is used as a main component, and the molecular weight of the polyamine is 3,000 or less. In the chemical formula, R and R' are an alkyl group.

[Colored Resin Layer Forming Aqueous Polyurethane Resin]

In the colored resin-coated metal sheet of the present invention, a metal plate having a colored resin layer formed on one surface or both surfaces of the original sheet is used, and as the base resin, an aqueous polyurethane resin is preferably used. The water-based polyurethane resin is preferably a carboxyl group-containing polyurethane resin having an acid value of 10 to 60 mgKOH/g as described in JP-A-2005-199673. The carboxyl group-containing polyurethane resin is an aqueous dispersion of a polyurethane resin which must be synthesized using a polyol having a carboxyl group. As the raw material, a polyol component such as 1,4-cyclohexanedimethanol, a polytetramethylene glycol having an average molecular weight of about 400 to 4000, a polyol having a carboxyl group such as dihydroxymethylpropionic acid, or the like, and toluene diisocyanate can be used. An isocyanate component such as diphenylmethane diisocyanate or dicyclohexylmethane diisocyanate. The chain extender is preferably a polyamine such as ethylenediamine.

The aqueous solution of the carboxyl group-containing polyurethane resin used in the present invention can be produced by a known method, for example, an amine group containing a carboxyl group. The carboxyl group of the formate prepolymer is neutralized by using an alkali base, and is subjected to emulsion dispersion in an aqueous medium to cause a chain extension reaction; and the carboxyl group-containing polyurethane resin is high in the presence of an emulsifier A method in which the shearing force is emulsified and dispersed to cause a chain extension reaction.

First, a carboxyl group-containing isocyanate-terminated urethane prepolymer having a relatively low molecular weight is produced by using the above-mentioned polyisocyanate and the above-mentioned polyol in such a manner that the isocyanate group is excessive in an NCO/OH ratio. The temperature of the synthetic urethane prepolymer is not particularly limited, but it can be synthesized at a temperature of 50 to 200 °C.

After completion of the reaction of the urethane prepolymer, the obtained carboxyl group-containing isocyanate-terminated urethane prepolymer is neutralized with a base and can be emulsified and dispersed in water. The intermediate 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.

After the carboxyl group-containing isocyanate group-terminated urethane prepolymer is emulsified and dispersed, a chain extension reaction can be carried out in water using a chain extender such as a polyamine. The reactivity of the chain extension reaction in the chain extension reaction is appropriately carried out before the emulsification dispersion, at the same time as the emulsification dispersion, or after the emulsification and dispersion.

[Colored Resin Layer Forming Aqueous Polyurethane Resin Composition]

In forming the coloring coating film, it is preferred to use the cerium oxide particles together with the above aqueous polyurethane resin as a composition. The cerium oxide particles are preferably about 10 to 30% by mass in 100% by mass of the composition. The cerium oxide particles are preferably colloidal dioxide having a surface area average particle diameter of 10 to 20 nm. Oh, this colloidal cerium oxide can be obtained from Nissan Chemical Industries Co., Ltd. as SNOWTEX (registered trademark) 40.

Further, the aqueous polyurethane resin composition may contain a wax. Industrially preferred are polyethylene wax, polypropylene wax, modified wax, copolymerized wax with ethylene or propylene, vinyl copolymer wax, oxides thereof, and carboxyl group-derived derivatives, or the like. Paraffin wax, carnauba wax, etc. The wax is preferably about 0.5 to 20% by mass in 100% by mass of the composition of the composition.

In order to crosslink the aqueous polyurethane resin, a crosslinking agent may be added. From the viewpoint of reactivity, an epoxy crosslinking agent such as sorbitol polyglycidyl ether, (poly) glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether is preferred. And polyglycidyl ethers such as neopentyl glycol diglycidyl ether and (poly)ethylene glycol diglycidyl ether or polyglycidylamines. As such an epoxy-based crosslinking agent, for example, EPICLON (registered trademark) CR75, CR5L, and the like manufactured by DIC Corporation can be obtained. The crosslinking agent is preferably about 5 to 20 parts by mass based on 100 parts by mass of the resin.

[Colored resin layer forming aqueous polyethylene resin composition]

In the colored resin-coated metal sheet of the present invention, an aqueous polyethylene resin composition can be used as the resin composition for the substrate. As the aqueous polyethylene resin, for example, 60 to 80 parts by mass of the inorganic component composed of a plurality of colloidal cerium oxides having different surface area average particle diameters as described in JP-A-2011-92837 and olefin-α,β- are preferably used. A resin composed of an unsaturated carboxylic acid copolymer, an α,β-unsaturated carboxylic acid polymer, and an acrylic modified epoxy resin 20 to 40 parts by mass, and further containing 5 to 15 parts by mass of a decane coupling agent containing a glycidoxy group and 0.5 to 3 parts by mass of metavanadate with respect to 100 parts by mass of the total of the inorganic component and the resin component. .

The colloidal cerium oxide is preferably a colloidal cerium oxide having a surface area average particle diameter of 4 to 6 nm and a colloidal cerium oxide having a surface area of 10 to 20 nm. The former is, for example, "SNOWTEX" (registered trademark of Nissan Chemical Industries, Ltd.). XS", the latter is, for example, the above-mentioned "SNOWTEX (registered trademark) 40". The mixing ratio of the two is not particularly limited, and is preferably the same amount.

The olefin-α,β-unsaturated carboxylic acid copolymer refers to a copolymer of an olefin and an α,β-unsaturated carboxylic acid, and the constituent unit derived from an olefin such as ethylene or propylene is 50% by mass or more in the copolymer (ie, The constituent unit of the α,β-unsaturated carboxylic acid such as (meth)acrylic acid is 50% by mass or less. Particularly preferred is an ethylene-acrylic acid copolymer. The "α,β-unsaturated carboxylic acid" also includes an "α,β-unsaturated carboxylic acid salt" in which a part of the carboxyl group is neutralized with a neutralizing agent.

The α,β-unsaturated carboxylic acid polymer refers to a polymer obtained by using an α,β-unsaturated carboxylic acid as a monomer (also including a copolymer), and a constituent unit derived from an α,β-unsaturated carboxylic acid is in a polymer. The amount is 90% by mass or more. Particularly good for polymaleic acid.

The mixing ratio of the olefin-α,β-unsaturated carboxylic acid copolymer to the α,β-unsaturated carboxylic acid polymer is preferably from about 100:1 to about 100:5.

The acrylic modified epoxy resin preferably uses an aqueous dispersion, and the aqueous acrylic modified epoxy resin is commercially available, for example, the Arakawa Chemical Industry can be obtained. "MODEPICS (registered trademark) 301", "MODEPICS (registered trademark) 302", "MODEPICS (registered trademark) 303", "MODEPICS (registered trademark) 304", etc., manufactured by the company. The acrylic modified epoxy resin is preferably from about 2% by mass to about 15% by mass based on 100% by mass of the resin component.

A decane coupling agent having a glycidoxy group, for example, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, vinyltri(β-) Methoxyethoxy) decane, and the like.

The metavanadate is, for example, sodium metavanadate (NaVO ₃ ), ammonium metavanadate (NH ₄ VO ₃ ), potassium metavanadate (KVO ₃ ) or the like.

The aqueous polyethylene resin composition may contain a compound containing a carbodiimide group. Commercially available carbodiimide-containing compounds, such as N,N-dicyclohexylcarbodiimide, N,N-diisopropylcarbodiimide, etc., polycarbodiimide manufactured by Nisshinbo Co., Ltd. "CARBODILITE (registered trademark)" series of a polymer having a plurality of carbodiimide groups in one molecule. As the "CARBODILITE (registered trademark)" level, there are water-soluble "SV-02", "V-02", "V-02-L2", "V-04", or latex type "E-01". , "E-02" and so on.

The amount of the compound containing a carbodiimide group is set in accordance with the amount of the olefin-α,β-unsaturated carboxylic acid copolymer and the α,β-unsaturated carboxylic acid polymer to be crosslinked. The total amount is preferably from 0.5 to 20 parts by mass based on 100 parts by mass of the total.

〔pigment〕

Examples of the types of pigments used for coloring each of the following colors include reddish red: insoluble azo (naphthol and anilide) or organic dyes such as soluble azo, iron oxide red, and cadmium red. Inorganic non-based pigments such as red and lead dan; yellow: insoluble azo (naphthol and anilide), soluble azo, quinacridone, benzimidazolone, quinoxaline, and heterogeneous Organic pigments such as indanone and chrome yellow, cadmium yellow, nickel titanium titanium yellow, yellow dan, bismuth chromate, etc.; green: organic phthalocyanine pigment; blue blue: organic phthalocyanine It is a pigment.

Organic pigments such as dioxin-based pigments; inorganic pigments such as Prussian blue, ultramarine blue, cobalt blue, and emerald green; orange: organic pigments such as benzoxazolone and pyrazolone; black: aniline black, nigro An inorganic pigment such as octane or the like, an inorganic pigment such as carbon black or iron black; or an inorganic pigment such as titanium oxide, calcium carbonate, zinc oxide, barium sulfate, zinc lanthanum or lead white. In the above-mentioned coloring pigment, two or more kinds of coloring pigments having different colors or different coloring pigments can be colored in a suitable blending ratio to obtain a gray color, a brown color, a purple color, a reddish purple color, and a blue purple color. Orange, gold, etc. The desired color. Among the yellow pigments, the benzoimidazolone type, the quinoxaline type, and the isohexanone have a tendency to exhibit a yellow color change after the weather resistance test is promoted, and thus can be used as a preferable pigment.

Among the pigments which are commercially available as a disperse pigment, for example, "AF BLACK E-2B" (manufactured by Dairi Seiki Co., Ltd.) composed of black: carbon black and water-soluble acrylic resin, carbon black and "SA BLACK DY-6" (made by Yuki Co., Ltd.) composed of water-soluble styrene acrylic resin, carbon black and nonionic surfactant "PSM BLACK 12578" (made by Yuki Co., Ltd.); white: "AF WHITE E-3D" made of titanium oxide and water-soluble acrylic resin (manufactured by Dairi Seiki Co., Ltd.), titanium oxide and water-soluble styrene acrylic acid "GP WHITE NF-3769" (manufactured by Yuki Co., Ltd.) made of a resin, "GP WHITE 13600" (manufactured by Yuki Co., Ltd.) composed of titanium oxide and a nonionic surfactant, and blue: anthocyanin "AF BLUE E-2B" (made by Daisei Seiki Co., Ltd.), anthocyanin-based pigment and water-soluble styrene-acrylic resin SABLUE DY-12 which is composed of a pigment and a water-soluble acrylic resin. "PSM BLUE HB" (made by Yuki Co., Ltd.) composed of anthocyanin-based pigments and nonionic surfactants, and "AF YELLOW" consisting of a diazo dye and a water-soluble acrylic resin. "SA YELLOW RS" (manufactured by Daiwa Seiki Co., Ltd.), diazo dye and nonionic surfactant, which are composed of E-12" (made by Daisei Seiki Co., Ltd.), diazo dye and water-soluble styrene acrylic resin "PSM YELLOW RS" composed of the agent "AF YELLOW E-26" (manufactured by Dairi Seiki Co., Ltd.), a benzimidazolone-based dye and a water-soluble acrylic resin composed of a benzimidazolone-based dye and a water-soluble acrylic resin, "NAF1012" "SA YELLOW GLN-K" (made by Yuki Co., Ltd.), benzimidazolone-based dye and water-soluble benzene, which are composed of YELLOW" (made by Daisei Seiki Co., Ltd.), a diazo dye and a water-soluble styrene acrylic resin. "SA YELLOW 13755" (manufactured by Yuki Co., Ltd.) composed of ethylene acrylic resin, "SA" composed of quinoxaline-based dye and water-soluble styrene acrylic resin "PSM YELLOW 10G" (manufactured by Yuki Co., Ltd.), heteroisoindanone dye and nonionic system composed of YELLOW A1559" (made by Yuki Co., Ltd.), diazo dye and nonionic surfactant "PSM YELLOW 12298" (manufactured by Yuki Co., Ltd.) and green: "AF GREEN E-1" (manufactured by Dairi Seiki Co., Ltd.), which is composed of a surfactant, and a water-soluble acrylic resin. "SA GREEN DY-4" (made by Yuki Co., Ltd.) composed of anthocyanin-based pigment and water-soluble styrene acrylic resin, red purple: quinacridone-based dye and water-soluble acrylic resin "PSM PINK KR" (made by Yuki Co., Ltd.) composed of RED E-17 (made by Daisei Seiki Co., Ltd.), quinacridone-based pigment and nonionic surfactant, blue-violet: dioxazine "SA Blue Violet #800" (manufactured by Yuki Co., Ltd.) composed of a pigment and a water-soluble styrene acrylic resin.

In order to satisfy the above formulas (1) and (2), and it is preferable to satisfy the formula (3), it is necessary to adjust the addition amount in accordance with the film thickness of the colored resin layer. When the film thickness is, for example, 3 μm or less, the amount of the pigment added increases, and the average reflectance of 500 to 600 nm becomes lower. Further, in order to effectively utilize the metallic color tone of the original sheet for design, it is necessary to suppress the amount of addition of the pigment having a large hiding power. Therefore, the upper limit of the content of the pigment is preferably about 20% by mass.

[Thickness of Colored Resin Layer]

In the present invention, the film thickness of the colored resin layer is set to 0.3 to 2.2 μm. If it is thinner than 0.3 μm, the effect of coloring or design is not exhibited. If exceeded At 2.2 μm, it is contrary to the object of the present invention which seeks to make a film which is cost-effective, and thus is not preferable.

[Resin Composition for Forming Colored Resin Layer and Coating Method Thereof]

In order to prepare the composition for forming a colored resin layer used in the present invention, it is sufficient to mix the components. It is preferred to emulsify the components together or separately emulsified as needed, and to mix them as an aqueous dispersion.

The method of applying the above resin composition to the original plate is not particularly limited, and a bar coating method, a roll coating method, a spray method, a curtain type flat coating method, or the like can be employed. After coating, it is preferably dried by heating at about 80 to 130 °C.

[transparent coating film]

The colored resin-coated metal sheet of the present invention can have a clear coating film on the colored resin layer. The material of the transparent coating film is not particularly limited, and examples thereof include a polyester resin, an acrylic resin, a polyurethane resin, a polyolefin resin, a fluorine resin, an anthrone resin, an epoxy resin, and these resins. a mixture or a modified resin or the like. When considering hardness, abrasion resistance, tape peeling resistance, etc., it is preferable that it is an organic solvent soluble (amorphous) polyester resin. The organic solvent-soluble polyester resin is preferably a "VYLON (registered trademark)" series manufactured by Toyobo Co., Ltd. from the viewpoint of obtaining a wide variety of resins.

The polyester resin can be crosslinked with a melamine resin or the like. Examples of the melamine resin include the "SUMIMAL (registered trademark)" series manufactured by Sumitomo Chemical Co., Ltd. and the "CYMEL (registered trademark)" series manufactured by Cytec Corporation. Crosslinker consideration The hardness, the abrasion resistance, the tape peeling resistance, and the like are preferably 5 to 30 parts by mass based on 100 parts by mass of the resin. The coating method can be the same as described above. Further, since the film thickness of the clear coating film has little influence on the reflectance, it is not particularly limited, but is preferably about 0.4 to 4.5 μm.

<Second invention>

The present inventors conducted coloring coating with a translucent film resin, and examined the appearance of the obtained colored resin-coated metal sheet. As a result, it was found that although it is a film, the color spots are conspicuous, the color spots are affected by the pigment dispersibility, and when the dispersibility of the pigment is poor, aggregates are formed, and the appearance defects caused by stains or "seeding" become conspicuous. . Therefore, the inventors of the present invention have reviewed the dispersing agent capable of improving the dispersibility of the pigment, and have completed the second invention.

Hereinafter, a constituent material of the colored resin-coated metal sheet of the second invention (hereinafter referred to as the present invention) will be described.

[Original board]

The same as the first invention described above.

[Pigment Dispersant]

In the present invention, the dispersibility of the pigment is one of important factors for improving the appearance defect caused by the stain or the protrusion, and the resin composition for forming the resin layer in the present invention contains the water-soluble styrene acrylic resin and / or non An ionic surfactant is used as a pigment dispersant. Therefore, a pigment dispersing agent remains in the colored coating film.

Usually, the pigment exhibits an excellent color tone when the particle diameter is 0.1 to 0.5 μm, but the water-soluble styrene acrylic resin and the nonionic surfactant are adsorbed on the surface of the pigment, and the dispersibility is improved by the repulsive force. The present inventors have found that a water-soluble styrene acrylic resin is more excellent in pigment dispersibility than a simple water-soluble acrylic resin. This is because the styrene acrylic resin has a benzene ring, so the steric hindrance of the benzene ring increases the repulsive force at the time of dispersion. Further, the resin layer of the present invention is composed of a water-based resin as described later, and the affinity for the water-based resin is superior to that of other surfactants, and thus exhibits good dispersibility. As in the case of the water-soluble styrene acrylic resin, a surfactant having a benzene ring or a naphthalene structure is more preferable among the nonionic surfactants. Since these pigment dispersants are excellent in dispersibility, they have the advantage of being used in a small amount which does not adversely affect corrosion resistance and chemical resistance.

The acid value of the water-soluble styrene acrylic resin is preferably about 50 to 300. Specifically, the water-soluble styrene acrylic resin is an alkali neutralized product of a copolymer of 50 to 95% by mass of styrene and/or methylstyrene and (meth)acrylic acid or maleic acid. Examples of the other copolymerizable monomer include a sulfonic acid group-containing monomer or the like, or a (meth) acrylate. The number average molecular weight is preferably from about 2,500 to about 15,000.

Nonionic surfactants are commercially available from various manufacturers and can be used as long as they are nonionic.

In most cases, the pigment dispersant is added to the pigment in advance, so A pigment dispersing agent can be contained in the resin composition by using the pigment described later. It is preferred to use a pigment dispersant in an amount of 0.05 to 6.2% by mass in the colored resin layer. If it is too large, corrosion resistance and chemical resistance may fall, and if it is too small, the effect of the improvement of dispersibility may not be favorable. In the present invention, the index for evaluating the uniformity of coating is a 60° specular gloss. The details are shown in the examples.

[Colored Resin Layer Forming Aqueous Polyurethane Resin]

The same as the first invention described above.

[Colored Resin Layer Forming Aqueous Polyurethane Resin Composition]

The same as the first invention described above.

[Colored resin layer forming aqueous polyethylene resin composition]

The same as the first invention described above.

〔pigment〕

Examples of the type of the pigment include the same pigments as those described for the pigment used in the first invention.

Among the above pigments, organic pigments are preferred. The inorganic pigment has an adsorption site having an acidic and basic property on the surface, adsorbs an alkaline substance in an acidic portion, and adsorbs an acidic substance in an alkaline portion. In addition, the inorganic pigment has a high specific gravity and is likely to settle in a low-viscosity paint. When the production time elapses for a long period of time, the color tone at the beginning is different from the color tone at the end. The hue will become unstable.

On the other hand, the surface of the organic pigment is substantially non-polar, and in order to minimize the interface between the pigment particles, the natural energy of the action is added to the intermolecular force, and the dispersant is easily collected and adsorbed on the surface of the pigment. Therefore, the organic pigment It is easier to exert the dispersing effect of the dispersing agent. Therefore, it is preferred to use an organic pigment as the pigment. Only an organic pigment may be used, or one or more organic pigments may be used in combination with one or more inorganic pigments.

The pigment is preferably from 0.5 to 17.5% by mass in the colored resin layer. If the amount is too small, the color development may be insufficient. If the original plate is concealed, the metallic color tone may not be effectively exhibited, and the "protrusion" due to the aggregate may be easily formed, which is not preferable.

The disperse pigment which is commercially available as a disperse pigment together with the pigment dispersant is the same as the disperse pigment described in the disperse pigment used in the first invention.

[Thickness of Colored Resin Layer]

The same as the first invention described above.

[Resin Composition for Forming Colored Resin Layer and Coating Method Thereof]

The same as the first invention described above.

[transparent coating film]

It is the same as the first invention described above.

<Third invention>

The present inventors conducted coloring coating using a translucent film resin, and examined the appearance of the obtained colored resin-coated metal sheet. As a result, it was found that although it was a film, the color spots were remarkable. When the evaluation is carried out in more detail, it is clear that the reason for the color unevenness is that the pigment particles are not aggregated until the water in the coating film is dried until the water is dried in the coating film. In the coating film, a portion having a rich pigment concentration and a light portion are formed, and in this state, it is directly dried to cause a stain. Fig. 2 is an explanatory view showing a state in which the pigment is moved. Fig. 3 is a photograph showing a stain and a normal photograph taken using a digital camera.

Although the reason for the pigment formation group shown in Fig. 2 cannot be determined, since the film is formed, the composition for the colored resin layer has a low solid content, and therefore the pigment is easily moved. Review the addition of a flat flattening agent that adjusts the surface tension, but flattening can't prevent stains. It is presumed that the flattening agent mainly lowers the surface tension of the surface of the coating film, and only functions to make the film thickness uniform. Therefore, the movement of the pigment inside the coating film cannot be suppressed.

In the third invention (hereinafter referred to as the present invention), the movement of the pigment inside the coating film before drying is successfully suppressed by using a polyamine-based thixotropic agent. The constituent materials of the colored resin-coated metal sheets of the present invention will be described below.

[Original board]

The same as the first invention described above.

Thixotropic agent

The same as the first invention described above.

When a black pigment is used alone, the light absorbability is high, and even if a thixotropic agent is blended, the color of the color is noticeable, and although the effects of the present invention can be confirmed, practically, an appearance without problems can be obtained.

[Pigment Dispersant]

In the present invention, a pigment dispersant may be added to the resin composition for forming a colored resin layer. A suitable pigment dispersant is the same as the pigment dispersant exemplified in the above first invention.

[Colored Resin Layer Forming Aqueous Polyurethane Resin]

The same as the first invention described above.

[Colored Resin Layer Forming Aqueous Polyurethane Resin Composition]

The same as the first invention described above.

[Colored resin layer forming aqueous polyethylene resin composition]

The same as the first invention described above.

〔pigment〕

The same as the first invention described above.

These commercially available pigments need to be adjusted in accordance with the film thickness of the colored resin layer. A film having a film thickness of, for example, 3 μm or less is intended to effectively exhibit metallic color. When designing the adjustment, the premise is that the original board is not concealed. When such a translucent coating film is formed, the color spots are remarkable as compared with the case where the metal plate is completely concealed by the thick film. Therefore, the upper limit of the content of the pigment is preferably about 20% by mass.

[Thickness of Colored Resin Layer]

The same as the first invention described above.

[Resin Composition for Forming Colored Resin Layer and Coating Method Thereof]

The same as the first invention described above.

[transparent coating film]

The same as the first invention described above.

[Examples]

In the following, the first to third inventions are further described in detail by way of examples. However, the first to third inventions are not limited to the following embodiments, and modifications are also included in the scope of the invention without departing from the scope of the first to third inventions. In the present invention. Hereinafter, "part" means "parts by mass", and "%" means "mass%". In addition, the evaluation method used in the examples will also be described.

<Example 1>

The embodiment of the first invention described above is as follows.

[Evaluation method] (a) Whether there is a pit-like appearance

The colored resin forming surface of the coated sample (50 × 120 mm) was photographed with a digital camera, and the obtained photograph was visually observed on a computer. The number of pits in the range of 30 × 30 mm was counted and evaluated based on the following criteria.

☆: no pits, ◎: less than 5, ○: 5 or more and less than 10, △: 10 or more and less than 30, ×: 30 or more

(b) 60° specular gloss

The colored resin forming surface of the coated sample (50 × 120 mm) was measured using a gloss meter "VG-2000" manufactured by Nippon Denshoku Industries Co., Ltd.

(c) Average reflectance from 500 to 600 nm

The colored resin-forming surface of the coated sample (50 × 120 mm) was measured using a simultaneous photometry spectrophotometer "SQ-2000" manufactured by Nippon Denshoku Industries Co., Ltd. The average reflectance at 500 to 600 nm was measured at a wavelength of 10 nm intervals (measurement number: 11), and was set to (total reflectance per wavelength) / (measurement number 11) = average reflectance.

(d) About formula (1)~(3)

From the 60° specular gloss and the average reflectance of 500 to 600 nm, it is evaluated whether or not the following formulas (1) to (3) are satisfied. The case of satisfaction is set to ○, and the case of not satisfied is set to ×.

(e) Abrasion resistance

A coated sample (50×100 mm) in which a 2 coat of a clear coating film was laminated on a colored resin layer was used, and an eraser (manufactured by Okawa Plastics Co., Ltd.) was used as a target material by a HEIDON test machine to have a load of 16.1±0.05 N. The surface of the sample was wiped at a speed of 25.4 mm and a round-trip/2 seconds, and the number of times until the texture of the original plate was observed (the number of abrasions) was measured.

(f) Processing section adhesion

A coating sample (50×50 mm) in which a 2 coat of a transparent coating film was laminated on a colored resin layer was used, and 2T bending was performed at a normal temperature (that is, bending was performed in a state where two sheets of the same thickness were sandwiched). The cellophane tape was attached to the bent portion to perform a peeling test. ○ Evaluation was no peeling, Δ was evaluated as a peeling area of 50% or less, and × was evaluated as a peeling area exceeding 50%.

[Original board]

The five original plates shown in Table 1 were used. The original plate is subjected to a chromium-free chemical conversion treatment. The treatment liquid was mixed with polyacrylic acid (reagent, average molecular weight: 25,000), aluminum dihydrogen phosphate (manufactured by Nippon Chemical Industry Co., Ltd., solid content: 50% by mass), and colloidal cerium oxide (SNOWTEX (registered trademark) manufactured by Nissan Chemical Co., Ltd.; ST -O), an acidic aqueous liquid of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.; KBM-403; 100% solid content). The compounding ratio of each component was 4.4% of polyacrylic acid, 57.8% of aluminum dihydrogen phosphate, 31.1% of colloidal cerium oxide, and 6.7% of decane coupling agent in terms of solid content. The treatment liquid was sprayed on the original plate after alkali degreasing using a sprayer, and the excess solution was removed using a Wringer roll, and then washed with a spray pressure of 100 kPa for 5 seconds, and dried at 40 ° C on various steel plates and Al plates. Assume A chrome-free layer is placed.

〔pigment〕

Pigments of various colors shown in Table 2 were used (with a dispersant added).

Preparation Example 1-1 (Preparation of aqueous solution of carboxyl group-containing polyurethane resin and preparation of resin composition for forming a polyurethane-based colored resin layer)

In a synthesis apparatus equipped with a stirrer, a thermometer, and a temperature controller, 60 parts of polytetramethylene ether glycol (average molecular weight: 1000; manufactured by Hodogaya Chemical Co., Ltd.) as a polyol component, 1,4-cyclohexane Dimethyl 14 parts of alcohol and 20 parts of dimethylolpropionic acid were added, and 30 parts of N-methylpyrrolidone as a reaction solvent was further added. 104 parts of toluene diisocyanate which is an isocyanate component was put, and it heated up to 80-85 degreeC, and it was set as reaction for 5 hours. The resulting prepolymer had an NCO content of 8.9%. Further, 16 parts of triethylamine was added for neutralization, and a mixed aqueous solution of 16 parts of ethylenediamine and 480 parts of water was added, followed by emulsification at 50 ° C for 4 hours, and a chain extension reaction was carried out to obtain an aqueous solution of a polyurethane resin ( The nonvolatile resin component was 29.1% and the acid value was 41.4).

The aqueous solution of the carboxyl group-containing polyurethane resin obtained above, colloidal cerium oxide (ST-40 manufactured by Nissan Chemical Industries, Inc.: particle size: 10 to 20 nm), and epoxy-based crosslinking agent (manufactured by DIC Corporation: EPICLON) (registered trademark) CR75), polyethylene wax particles (manufactured by Mitsui Chemicals Co., Ltd.: CHEMIPEARL (registered trademark) W-700, average particle diameter: 1 μm, softening point: 132 ° C), various pigments, polyamine-based thixotropic agents (Nanben) Manufactured by Chemicals Co., Ltd.: DISPARLON (registered trademark) AQ-607 for water-based paints, a resin composition for forming a polyurethane-based colored resin layer is prepared.

The mixing ratio of each component is 58.5 to 73.5 parts of a carboxyl group-containing polyurethane resin, 20 parts of colloidal cerium oxide, 2 parts of an epoxy crosslinking agent, and 3.5 parts of polyethylene wax particles, in terms of solid content. The polyamine-based thixotropic agent is 0 or 1.0 part, and each pigment (including a dispersing agent) is 1 to 15 parts. The variable portion of the thixotropic agent and the pigment was formulated in such a manner that the amount of the resin was changed and the total amount was 100 parts.

Preparation Example 1-2 (Preparation of aqueous polyethylene resin and polyethylene system) Preparation of resin composition for forming a color resin layer)

An ethylene-acrylic acid copolymer (available from Dow Chemical Co., Ltd.: PRIMACOR (registered trademark) 5990I) was added to an autoclave equipped with an emulsification apparatus equipped with a stirrer, a thermometer, and a temperature controller. Acrylic acid unit: 20% by mass, Mw: 20000, MI: 1300, acid value: 150) 200.0 parts, polymaleic acid aqueous solution as α,β-unsaturated carboxylic acid polymer (Nippon Oil Co., Ltd.: NONPOL (registered) Trademark) PMA-50W, Mw: 8.0 parts of about 1100 (in terms of polystyrene), 50% by mass), 35.5 parts of triethylamine (0.63 equivalent to carboxyl group of ethylene-acrylic acid copolymer), and 6.9 parts of 48% NaOH aqueous solution (0.15 equivalents based on the carboxyl group of the ethylene-acrylic acid copolymer), 3.5 parts of tall oil fatty acid (HARTALL FA3 manufactured by Ignition Co., Ltd.), 792.6 parts of ion-exchanged water, and sealed, and high-speed at 150 ° C and 5 atm. Stir for 3 hours and then cool to 30 °C.

Next, a decane coupling agent containing a glycidoxy group (manufactured by Momentive Performance Materials (formerly known as GE Toshiba SILICONE): TSL 8350, γ-glycidoxypropyltrimethoxydecane) was added in an amount of 10.4 parts, and carbonization was added. The diimine-based compound (manufactured by Nisshinbo Co., Ltd.: CARBODILITE (registered trademark) SV-02, polycarbodiimide, Mw: 2700, solid content 40%) 31.2 parts, ion-exchanged water 72.8 parts, stirred for 10 minutes, prepared An emulsion (latex) of an ethylene-acrylic acid copolymer and a polymaleic acid (solid content concentration of about 20%, measured in accordance with JIS K6833).

Colloidal cerium oxide (A) (manufactured by Nissan Chemical Industries, Ltd.: ST-XS (solid content concentration: 20%)) and surface area average particle diameter 10 are sequentially added to the above-mentioned emulsion in an average surface area of 4 to 6 nm (nominal value). ~20nm (nominal value) colloidal cerium oxide (B) (manufactured by Nissan Chemical Industries, Ltd.: ST-40 (solid content concentration: 40%)), after thorough mixing, a decane coupling agent containing a glycidoxy group (Xin Yue) Chemical Industry Co., Ltd.: KBM403 (solid content concentration: 100%), followed by sodium metavanadate (manufactured by Emerging Chemical Industry Co., Ltd., sodium metavanadate (solid content concentration: about 66%)). Further, an acrylic resin-modified epoxy resin (MODEPICS (registered trademark) 302 (solid content concentration: 33.5%)) was added to the mixture to prepare a polyethylene resin composition. The mixing ratio of each component is in terms of solid content, ethylene-acrylic acid copolymer and polymaleic acid 25.7%, acrylic modified epoxy resin 1.3%, colloidal cerium oxide (A) 31.5%, colloidal cerium oxide (B) 31.5%, decane coupling agent 9.0%, sodium metavanadate 1.0%.

Polyethylene wax (made by Mitsui Chemical Co., Ltd.: CHEMIPEARL (registered trademark) W-900, average particle diameter: 0.6 μm, softening point: 132 ° C), the above various pigments, and the above-mentioned polyamine-based thixotropic reaction were mixed with the polyethylene resin composition. (DISPARLONAQ-607), a resin composition for forming a polyethylene-based colored resin layer was prepared.

The blending ratio of each component is 89.5 to 95.0 parts of polyethylene resin composition, 3.5 parts of polyethylene wax particles, 0 or 1.0 parts of polyamine-based thixotropic agent, and 1.5 to 6 parts of various pigments (including dispersion) in terms of solid content. Agent). The variable part of the thixotropic agent and pigment is used to change the amount of resin, and the total amount becomes 100. The method of allocation.

Experimental Example 1-1

The resin composition for forming a polyurethane-based resin layer and a polyethylene-based colored resin layer was adjusted to have a solid concentration of 10 to 18%, and stirred at 700 rpm for 10 minutes using a dispersing mixer, and then in the above five types (EG1, EG2). The surface of the original plate of GI, GL, and AL) is coated by a roll coater, and dried by heating at a plate temperature of 90 to 100 ° C to obtain a film having a film thickness of 0.5 to 2.0 μm and a polyethylene formed with a polyurethane. A metal plate is coated with a colored resin of a resin film having a thickness of 0.3 to 1.3 μm. The evaluation results are shown in Tables 3 to 18.

Experimental example 1-2

In the resin composition for forming a polyurethane-based colored resin layer, 71.3 parts of a carboxyl group-containing polyurethane resin, 20 parts of colloidal cerium oxide, 2 parts of an epoxy crosslinking agent, and polyethylene wax are used. 3.5 parts, 0.2 parts of polyamine-based thixotropic agent, 2 kinds of pigments (SA GREEN DY-4: 2.1 parts, SA blue-purple #800: 0.9 parts), a total of 3 parts, adjusted to a solid concentration of 10 ~18%, stirred at 700 rpm for 10 minutes using a dispersing mixer.

Further, a coating material for a clear coating film was prepared. Organic solvent-soluble polyester resin (manufactured by Toyobo Co., Ltd.: VYLON (registered trademark) 29), melamine crosslinking agent (Sumitomo Chemical Co., Ltd.: SUMIMAL (registered trademark) M-40ST, solid content 80%) Mixing with (dry) 100:20, using a mixed solvent of xylene/cyclohexanone (mass ratio 1:1) as a diluent solvent, diluting to a solid concentration of 5 to 20%, and stirring at 3000 rpm using a dispersing mixer 5 minutes.

The resin composition for forming a polyurethane-based colored resin layer was applied onto the surface of the EG1 and GI original sheets by a roll coater, and dried by heating at a sheet temperature of 90 to 100 ° C to form a colored resin layer having a thickness of 1.2 μm. The film thickness of the coating material for coating a clear coating film was 0.3 to 5.3 μm by a bar coater, and the film was sintered at a plate temperature of 220 ° C for 60 seconds to obtain a 2-coat colored resin-coated metal plate. The evaluation results of the two-coat colored resin-coated metal sheets are shown in Table 19.

Experimental Example 1-3

Among the pigments shown in Table 2, for SA BLACK DY-6 (black), GP WHITE 13600 (white), SA BLUE DY-12 (blue), SA YELLOW RS (yellow), PSM PINK KR (red purple), SA GREEN DY-4 (green), SA blue violet #800 (blue-violet), the resin composition for forming a polyurethane-based colored resin layer prepared in the above Preparation Example 1-1, and Preparation Example 1-2 The prepared resin composition for forming a polyethylene colored resin layer was subjected to a weather resistance test. The original plate, the thixotropic agent concentration, the pigment concentration, and the film thickness are shown in Table 20.

The weather resistance test was carried out in accordance with JIS K 5600 7-8, using a simultaneous photometry spectrophotometer "SQ-2000" manufactured by Nippon Denshoku Industries Co., Ltd., and irradiated with a sunlight weather tester (Sunshine Weather Meter) for 100 hours ( The L value, the a value, and the b value before and after the absence of rain are determined by the following equation: ΔE (color difference).

When ΔE is 2 or less, it is evaluated as ○, and when it exceeds 2, it is evaluated as Δ. The results are shown in Table 20.

As is clear from Table 20, carbon black and titanium oxide which are inorganic pigments need not be said, and the anthocyanin type, quinacridone type, and dioxin type which are an organic pigment also have excellent weather resistance, and it is practical. The level of the problem. However, the diazo-based yellow pigment is remarkably discolored and has poor weather resistance. The determination that each pigment has faded can also be performed by confirming the increase in the blue b value, the increase in the green a value, the decrease in the reddish purple a value, and the increase in the bluish purple b value.

Experimental Example 1-4

The weather resistance test was performed in the same manner as in Experimental Example 1-3 on the seven yellow pigments shown in Table 21. The original plate, the thixotropic agent concentration, the pigment concentration, and the film thickness are shown in Table 22. In the same manner as in Experimental Example 1-3, it was evaluated whether or not ΔE was 2 or less, and a change in b value indicating a change in yellowness was also obtained. When b'-b was zero or more, it was recorded as ○, and when it was not zero, it was recorded as Δ. The overall evaluation system ΔE and b'-b are both ○, and one of them or both of them are Δ. The results are shown in Table 22.

From the results of Table 22, it was confirmed that the three kinds of yellow pigments of the benzimidazolone type, the quinoxaline type, and the isoindolinone type are excellent in weather resistance regardless of the type of the original plate, the resin, and the pigment dispersant.

Moreover, these three yellow pigments showed a specificity in which the yellowness after the test was increased and the yellowness of the resin coating film was enhanced.

Experimental Example 1-5

In the same manner as in Experimental Example 1-1, it was evaluated whether or not the above-described seven yellow pigments satisfy the formulae (1) to (3), and whether or not there is a pit-like appearance defect. The results are shown in Table 23 to Table 28.

<Example 2>

The embodiment of the second invention described above is as follows.

[Evaluation method] (1) gloss retention rate

For the original resin (50 × 120 mm) and the colored resin forming surface of the coated sample (50 × 120 mm), a gloss meter "VG-2000" manufactured by Nippon Denshoku Industries Co., Ltd. was used, and the respective 60° specular gloss was measured. The gloss retention ratio (%) was determined according to the following formula.

Gloss retention (%) = 100 × 60° specular gloss value of the coated sample / gloss value of the original plate

The gloss retention was 35% or more and was evaluated as ◎, 20% or more and less than 35% were evaluated as ○, and less than 20% was evaluated as ×.

(2) Wear resistance

The same as the foregoing embodiment 1.

(3) Processing part adhesion

The same as the foregoing embodiment 1.

[Original board]

The five original plates shown in Table 29 were used. The original plate was subjected to a chromium-free chemical conversion treatment. As the treatment liquid, polyacrylic acid (reagent, average molecular weight: 25,000), aluminum dihydrogen phosphate (manufactured by Nippon Chemical Industry Co., Ltd., solid content: 50% by mass), and colloidal cerium oxide (SNOWTEX (registered trademark) manufactured by Nissan Chemical Co., Ltd.) were used. ST-O), decane coupling agent (Shin-Etsu Acidic aqueous solution made by Chemical Industry Co., Ltd.; KBM-403; solid content 100%). The blending ratio of each component was 4.4% of polyacrylic acid, 57.8% of aluminum dihydrogen phosphate, 31.1% of colloidal cerium oxide, and 6.7% of decane coupling agent in terms of solid content. This treatment liquid was blown to the original plate after alkali degreasing using a sprayer, and the excess solution was removed by a dewatering roll, and then washed with a spray pressure of 100 kPa for 5 seconds, dried at 40 ° C, and a chromium-free treatment layer was set on various steel sheets and Al plates. .

〔pigment〕

Pigments of various colors shown in Table 30 were used (dispersant added). A water-soluble acrylic resin was used as a dispersing agent as a comparative example.

Preparation Example 2-1 (Preparation of aqueous solution of carboxyl group-containing polyurethane resin and preparation of resin composition for forming a polyurethane resin layer)

In a synthesis apparatus equipped with a stirrer, a thermometer, and a temperature controller, 60 parts of polytetramethylene ether glycol (average molecular weight: 1000; manufactured by Hodogaya Chemical Co., Ltd.) as a polyol component, 1,4-cyclohexane 14 parts of dimethanol and 20 parts of dimethylolpropionic acid were added, and 30 parts of N-methylpyrrolidone as a reaction solvent was further added. 104 parts of toluene diisocyanate which is an isocyanate component was put, and it heated up to 80-85 degreeC, and it was set as reaction for 5 hours. The resulting prepolymer had an NCO content of 8.9%. Further, 16 parts of triethylamine was added for neutralization, and a mixed aqueous solution of 16 parts of ethylenediamine and 480 parts of water was added, and the mixture was emulsified at 50 ° C for 4 hours while carrying out a chain extension reaction to obtain an aqueous solution of a polyurethane resin (not The volatile resin component was 29.1% and the acid value was 41.4).

The aqueous solution of the carboxyl group-containing polyurethane resin obtained above, colloidal cerium oxide (ST-40 manufactured by Nissan Chemical Industries, Inc.: particle size: 10 to 20 nm), and epoxy-based crosslinking agent (manufactured by DIC Corporation: EPICLON) (registered trademark) CR75), polyethylene wax particles (manufactured by Mitsui Chemicals, Inc.: CHEMIPEARL (registered trademark) W-700, average particle diameter: 1 μm, softening point: 132 ° C), various pigments described above, and polyurethane-based system A resin composition for forming a colored resin layer.

The blending ratio of each component is 57.5 to 73.5 parts of a carboxyl group-containing polyurethane resin, 20 parts of colloidal cerium oxide, 2 parts of an epoxy crosslinking agent, 3.5 parts of polyethylene wax particles, and various kinds of components. Pigment (including points Powder) 1 to 17 parts of the way to mix. The variable portion of the pigment was formulated in such a manner that the amount of the resin was changed and the total amount was 100 parts.

Preparation Example 2-2 (Preparation of Aqueous Polyethylene Resin and Preparation of Resin Composition for Forming Polyethylene Colored Resin Layer)

An ethylene-acrylic acid copolymer (PRIMACOR (registered trademark) 5990I, which is an olefin-α,β-unsaturated carboxylic acid copolymer, was added to an autoclave having an emulsification apparatus including a stirrer, a thermometer, and a temperature controller. Acrylic acid unit: 20% by mass, Mw: 20000, MI: 1300, acid value: 150) 200.0 parts, polymaleic acid aqueous solution as α,β-unsaturated carboxylic acid polymer (Nippon Oil Co., Ltd.: NONPOL (registered trademark) PMA-50W, Mw: about 1100 (in terms of polystyrene), 8.0 parts by mass of 8.0 parts, 35.5 parts of triethylamine (0.63 equivalents based on the carboxyl group of the ethylene-acrylic acid copolymer), and 6.9 parts of a 48% aqueous NaOH solution ( 3.5 parts of a tall oil fatty acid (HARTALL FA3 manufactured by Soy Chemical Co., Ltd.) and 792.6 parts of ion-exchanged water were sealed and sealed at 150 ° C and 5 atm. 3 hours, then cooled to 30 °C.

Next, a decane coupling agent containing a glycidoxy group (manufactured by Momentive Performance Materials (formerly known as GE Toshiba SILICONE): TSL 8350, γ-glycidoxypropyltrimethoxydecane) 10.4 parts was added, and carbonized carbon was added. The imine group compound (manufactured by Nisshinbo Co., Ltd.: CARBODILITE (registered trademark) SV-02, polycarbodiimide, Mw: 2700, solid content 40%) 31.2 parts, 72.8 parts of ion-exchanged water, stirred for 10 minutes to prepare ethylene - Acrylic copolymer and polymaleic acid Emulsion (latex) (solid content concentration about 20%, measured based on JIS K6833).

A colloidal cerium oxide (A) having a surface area average particle diameter of 4 to 6 nm (nominal value) is sequentially added to the above emulsion (ST-XS (solid content concentration: 20%) manufactured by Nissan Chemical Industries, Ltd.) and a surface area average particle diameter of 10 ~20nm (nominal value) colloidal cerium oxide (B) (manufactured by Nissan Chemical Industries, Ltd.: ST-40 (solid content concentration: 40%)), after thorough mixing, a decane coupling agent containing a glycidoxy group (Xin Yue) Chemical Industry Co., Ltd.: KBM403 (solid content concentration: 100%)), followed by sodium metavanadate (manufactured by Emerging Chemical Industry Co., Ltd., sodium metavanadate (solid content concentration: about 66%)). Further, an acrylic modified epoxy resin (MODEPICS (registered trademark) 302 (solid content concentration: 33.5%)) was added to the mixture to prepare a polyethylene resin composition. The blending ratio of each component is in terms of solid content, ethylene-acrylic acid copolymer and polymaleic acid 25.7%, acrylic modified epoxy resin 1.3%, colloidal cerium oxide (A) 31.5%, colloidal cerium oxide (B) 31.5%, decane coupling agent 9.0%, sodium metavanadate 1.0%.

The polyethylene resin composition was mixed with a polyethylene wax (manufactured by Mitsui Chemicals, Inc.: CHEMIPEARL (registered trademark) W-900, an average particle diameter of 0.6 μm, and a softening point of 132 ° C), and various pigments described above to prepare a polyethylene-based colored resin layer. A resin composition for formation.

The blending ratio of each component is adjusted in terms of solid content, such as 89.5 to 95.0 parts of a polyethylene resin composition, 3.5 parts of polyethylene wax particles, and 1.5 to 7 parts of various pigments (including a dispersing agent). The variable part of the pigment is changed The amount of the resin was changed, and the total amount was 100 parts.

Experimental example 2-1

The resin composition for forming a polyurethane-based resin layer and a polyethylene-based colored resin layer was adjusted to have a solid concentration of 10 to 18%, and the mixture was stirred at 700 rpm for 10 minutes using a dispersing mixer, and then applied to the above by using a roll coater. The surface of the original plate of five kinds (EG1, GI, GL, SUS, AL) is heated and dried at a plate temperature of 90 to 100 ° C to obtain a film thickness of 0.5 to 2.0 μm and polyethylene 0.3 to 1.3 μm. The colored resin of the resin film is coated with a metal plate. The evaluation results are shown in Tables 31 to 46. In Tables 31 to 46, the pigment concentration is calculated based on the coating formulation, and the content of the pigment dispersant is calculated as the difference between the solid component concentration and the pigment concentration.

As can be seen from the respective tables, when the metal plate is coated with a colored resin using a water-soluble styrene acrylic resin or a nonionic surfactant as a dispersing agent, the gloss retention rate of the original plate is higher, and coating is performed. The uniformity is more excellent. In particular, the system containing an organic pigment has a higher gloss retention ratio than the inorganic pigment. In addition, in black, white, blue and green, even when the dispersant content is small, it can be seen that the water-soluble styrene acrylic resin and the nonionic surfactant have more excellent dispersion than the water-soluble acrylic resin. Sexual tendency.

The relationship between gloss retention and coating uniformity can be as described below. Pigments having poor dispersibility are agglomerated, and aggregates are mixed into the coating film. Large particle size The agglomerate becomes an uneven portion of the colored coating film, and the light is scattered as compared with the uniform colored coating film, and the 60° specular gloss value is lowered.

Experimental Example 2-2

In the resin composition for forming a polyurethane-based colored resin layer, 71.5 parts of a carboxyl group-containing polyurethane resin, 20 parts of colloidal cerium oxide, 2 parts of an epoxy crosslinking agent, and polyethylene wax are used. 3.5 parts and 2 kinds of pigments (SA GREEN DY-4: 2.1 parts, SA blue-purple #800: 0.9 parts) were mixed in a total of 3 parts, adjusted to a solid concentration of 10 to 18%, using a dispersing mixer Stir at 700 rpm for 10 minutes.

Further, a coating material for a clear coating film was prepared. The organic solvent-soluble polyester resin (VYLON (registered trademark) 29 manufactured by Toyobo Co., Ltd.) and the melamine crosslinking agent (Sumitomo Chemical Co., Ltd.: SUMIMAL (registered trademark) M- are mixed in a mass ratio (dry type) of 100:20. 40ST, solid content 80%), using a mixed solvent of xylene/cyclohexanone (mass ratio 1:1) as a diluent solvent, diluting the solid content concentration to 5 to 20%, and using a dispersing mixer at 3000 rpm Stir for 5 minutes.

The resin composition for forming a polyurethane-based colored resin layer was applied onto the surface of the EG and GI original sheets by a roll coater, and dried by heating at a sheet temperature of 90 to 100 ° C to form a colored resin layer having a thickness of 1.2 μm. The coating material for a clear coating film was applied by a bar coater to a thickness of 0.3 to 5.3 μm, and baked at a plate temperature of 220 ° C for 60 seconds to obtain a 2-coat colored resin-coated metal plate. The evaluation results of the two-coat colored resin-coated metal sheets are shown in Table 47.

<Example 3>

The embodiment of the third invention described above is shown below.

[Evaluation method] (1) Appearance

The appearance of the coated sample (100 mm × 100 mm) was evaluated by visual observation on the following basis.

☆: no color spots, ◎: only slightly stained, ○: some light spots, △: light spots on the whole face, ×: whole face spots

(2) Wear resistance

The same as the foregoing embodiment 1.

(3) Processing part adhesion

The same as the foregoing embodiment 1.

[Original board]

The same as the foregoing embodiment 1.

〔pigment〕

Pigments of various colors shown in Table 48 (containing a dispersant) were used.

Preparation Example 3-1 (Preparation of aqueous solution of carboxyl group-containing polyurethane resin and preparation of resin composition for forming a polyurethane-based colored resin layer)

In a synthesis apparatus equipped with a stirrer, a thermometer, and a temperature controller, 60 parts of polytetramethylene ether glycol (average molecular weight: 1000; manufactured by Hodogaya Chemical Co., Ltd.) as a polyol component, 1,4-cyclohexane 14 parts of dimethanol and 20 parts of dimethylolpropionic acid were added, and 30 parts of N-methylpyrrolidone as a reaction solvent was further added. 104 parts of toluene diisocyanate which is an isocyanate component was charged, and the temperature was raised to 80 to 85 ° C, and the reaction was carried out for 5 hours. The resulting prepolymer had an NCO content of 8.9%. Further, 16 parts of triethylamine was added for neutralization, and a mixed aqueous solution of 16 parts of ethylenediamine and 480 parts of water was added, and the mixture was emulsified at 50 ° C for 4 hours, and a chain extension reaction was carried out to obtain an aqueous solution of a polyurethane resin ( The nonvolatile resin component was 29.1% and the acid value was 41.4).

The aqueous solution of the carboxyl group-containing polyurethane resin obtained above, colloidal cerium oxide (ST-40 manufactured by Nissan Chemical Industries, Ltd.: particle size: 10 to 20 nm), and epoxy-based crosslinking agent (manufactured by DIC Corporation: EPICLON) (registered trademark) CR75), polyethylene wax particles (manufactured by Mitsui Chemicals Co., Ltd.: CHEMIPEARL (registered trademark) W-700, average particle diameter: 1 μm, softening point: 132 ° C), various pigments and anthrone-based flat agents (Nanmoto Chemical Co., Ltd.) System: DISPARLON (registered trademark) LS-900 for water-based paints, ketone-based flattening agent (made by Nanben Chemical Co., Ltd.: DISPARLON (registered trademark) AQ-7120 for water-based paints), and polyamine-based thixotropic agent (Nanmoto Chemicals) Company system: for water coating DISPARLON (registered trademark) AQ-607), a resin composition for forming a polyurethane-based colored resin layer is prepared.

The mixing ratio of each component is 58.5 to 72.5 parts of a carboxyl group-containing polyurethane resin, 20 parts of colloidal cerium oxide, 2 parts of an epoxy crosslinking agent, and 3.5 parts of polyethylene wax particles, in terms of solid content. The fluorenone-based or acrylone-based flattening agent or the polyamine-based thixotropic agent was blended in an amount of from 1 part to 15 parts of various pigments (including a dispersing agent), and the total amount was 100 parts.

Preparation Example 3-2 (Preparation of Aqueous Polyethylene Resin and Preparation of Resin Composition for Forming Polyethylene Colored Resin Layer)

An ethylene-acrylic acid copolymer (PRIMACOR (registered trademark) 5990I, which is an olefin-α,β-unsaturated carboxylic acid copolymer, was added to an autoclave having an emulsification apparatus including a stirrer, a thermometer, and a temperature controller. Acrylic acid unit: 20% by mass, Mw: 20000, MI: 1300, acid value: 150) 200.0 parts, polymaleic acid aqueous solution as α,β-unsaturated carboxylic acid polymer (Nippon Oil Co., Ltd.: NONPOL (registered trademark) PMA-50W, Mw: about 1100 (in terms of polystyrene), 8.0 parts by mass of 8.0 parts, 35.5 parts of triethylamine (0.63 equivalents based on the carboxyl group of the ethylene-acrylic acid copolymer), and 6.9 parts of a 48% aqueous NaOH solution ( 3.5 parts of a tall oil fatty acid (HARTALL FA3), and 792.6 parts of ion-exchanged water were sealed with respect to the carboxyl group of the ethylene-acrylic acid copolymer, and sealed at a high speed at 150 ° C and 5 atm. Hours, then cool to 30 °C.

Then add a decane coupling agent containing a glycidoxy group (Momentive Performance Materials (formerly known as: GE Toshiba SILICONE) Company: TSL8350, γ-glycidoxypropyltrimethoxydecane) 10.4 parts, a compound containing a carbodiimide group (manufactured by Nisshinbo Co., Ltd.: CARBODILITE (registered trademark) SV-02, polycarbodiimide, Mw: 2700, solid content 40%) 31.2 parts, 72.8 parts of ion-exchanged water, and stirred for 10 minutes to prepare an emulsion of ethylene-acrylic acid copolymer and polymaleic acid (latex) (solid content concentration about 20%, based on JIS K6833 Perform the measurement).

A colloidal cerium oxide (A) having a surface area average particle diameter of 4 to 6 nm (nominal value) was sequentially added to the above emulsion (ST-XS (solid content concentration: 20%) manufactured by Nissan Chemical Industries, Ltd.) and a surface area average particle diameter of 10 ~20nm (nominal value) colloidal cerium oxide (B) (manufactured by Nissan Chemical Industries, Ltd.: ST-40 (solid content concentration: 40%)), after thorough mixing, a decane coupling agent containing a glycidoxy group (Xin Yue) Chemical Industry Co., Ltd.: KBM403 (solid content concentration: 100%), and sodium metavanadate (manufactured by Emerging Chemical Industry Co., Ltd., sodium metavanadate (solid content concentration: about 66%)). An acrylic resin-modified epoxy resin (MODEPICS (registered trademark) 302 (solid content concentration: 33.5%)) was added to the mixture to prepare a polyethylene resin composition. The compounding ratio of each component is 25.7% of ethylene-acrylic acid copolymer and polymaleic acid, 1.3% of acrylic acid modified epoxy resin, 31.5% of colloidal cerium oxide (A), and colloidal cerium oxide (in terms of solid content). B) 31.5%, decane coupling agent 9.0%, sodium metavanadate 1.0%.

Polyethylene wax (made by Mitsui Chemicals Co., Ltd.: CHEMIPEARL (registered trademark) W-900, average particle size) 0.6 μm, softening point 132 ° C), the above various pigments, the above-mentioned anthrone-based flat agent (LS-900), an acrylic fluorene-based flattening agent (AQ-7120) or a polyamine-based thixotropic agent (AQ-607), A resin composition for forming a polyethylene-based colored resin layer was prepared.

The mixing ratio of each component is 89.5 to 94 parts of a polyethylene resin composition, 3.5 parts of a polyethylene wax particle, an anthrone or an acetonone-based flat modifier or a polyamine-based thixotropic agent in terms of a solid content. It is formulated in a manner of 1.5 to 6 parts of various pigments (including a dispersing agent), and the total amount is 100 parts.

Experimental example 3-1

The resin composition for forming a polyurethane-based resin layer and a polyethylene-based colored resin layer was adjusted to have a solid concentration of 10 to 18%, and the mixture was stirred at 700 rpm for 10 minutes in a dispersing mixer, and then coated on the above by a roll coater. The surface of the original plate of five kinds (EG1, EG2, GI, GL, and AL) is dried by heating at a plate temperature of 90 to 100 ° C to obtain a film thickness of 0.5 to 2.0 μm formed of polyurethane and a film thickness of polyethylene. A metal plate is coated on the colored resin of the resin film of 0.3 to 1.3 μm. The evaluation results are shown in Tables 49 to 72.

Experimental Example 3-2

In the resin composition for forming a polyurethane-based colored resin layer, 71.3 parts of a carboxyl group-containing polyurethane resin, 20 parts of colloidal cerium oxide, 2 parts of an epoxy crosslinking agent, and polyethylene wax are used. 3.5 parts, 0.2 parts of polyamine-based thixotropic agent, and 2 kinds of pigments (SA GREEN DY-4: 2.1 parts, SA blue-purple #800: 0.9 parts) were adjusted to a solid concentration in a total of 3 parts. 10~18%, stirred for 10 minutes at 700 rpm using a dispersing mixer.

Further, a coating material for a clear coating film was prepared. The organic solvent-soluble polyester resin (VYLON (registered trademark) 29 manufactured by Toyobo Co., Ltd.) and the melamine crosslinking agent (Sumitomo Chemical Co., Ltd.: SUMIMAL (registered trademark) M- are mixed in a mass ratio (dry type) of 100:20. 40ST, solid content 80%), using a mixed solvent of xylene/cyclohexanone (quality ratio 1:1) as a diluent solvent, diluting with a solid concentration of 5 to 20%, and stirring at 3000 rpm using a dispersing mixer 5 minutes.

The resin composition for forming a polyurethane-based colored resin layer is applied onto the surface of the EG1 and GI original sheets by a roll coater, and dried by heating at a sheet temperature of 90 to 100 ° C to form a colored resin layer having a thickness of 1.2 μm. The coating material for a clear coating film was applied by a bar coater to a thickness of 0.3 to 5.3 μm, and baked at a plate temperature of 220 ° C for 60 seconds to obtain a 2-coat colored resin-coated metal plate. The evaluation results of the two-coat colored resin-coated metal sheets are shown in Table 73.

<Example 4>

The implementation of all the conditions satisfying the first to third inventions is as follows. A part of the sample of Example 1 was prepared in such a manner as to satisfy the conditions of the second and third inventions. For each sample, the gloss retention ratio of the evaluation index of the second invention, the appearance (the presence or absence of color spots) as the evaluation index of the third invention, and the presence or absence of the pit-like appearance defect as the evaluation index of the first invention are respectively Evaluation was carried out in the same manner and on the same basis as in Examples 2, 3 and 1. The results are shown in Tables 74 to 79.

[Industrial Availability]

According to the first to third aspects of the present invention, it is possible to provide a colored resin-coated metal sheet which exhibits high design properties by combining a metallic color tone and a colored resin obtained by coloring a chromium-free original sheet with a film-form resin at a low cost. Further, the colored resin-coated metal sheet having the transparent coating film in the uppermost layer is a metal plate excellent in abrasion resistance and tape peeling resistance.

Therefore, the colored resin-coated metal sheets of the first to third inventions can be used in various applications such as home electric appliances, building materials, and automobile parts.

Claims (11)

A colored resin-coated metal plate which is a chromium-free metal plate having a colored resin layer having a thickness of at least 0.3 to 2.2 μm on one side, wherein the colored resin layer contains one or more pigments, and the colored resin layer When the 60° specular gloss measured on the side is x, and the average reflectance of 500 to 600 nm is y, the following formulas (1) and (2) are satisfied: The colored resin-coated metal sheet according to the first aspect of the invention, wherein the colored resin layer contains one or more pigment dispersions selected from the group consisting of water-soluble acrylic resins, water-soluble styrene acrylic resins, and nonionic surfactants. Agent. A colored resin-coated metal sheet according to the first aspect of the invention, wherein the colored resin layer contains a polyamine-based thixotropic agent. The colored resin-coated metal sheet according to any one of claims 1 to 3, wherein the following formula (3) is further satisfied: The colored resin-coated metal sheet according to any one of claims 1 to 3, wherein the colored resin layer contains a yellow pigment, which is a benzimidazolone type, a quinoxaline type, an isoindolinone Any of the systems. The colored resin-coated metal sheet according to any one of claims 1 to 3, wherein the chromium-free metal sheet before forming the colored resin layer has an average reflectance of 50% or more at 500 to 600 nm. A colored resin-coated metal plate which is a chromium-free metal plate having a colored resin layer having a thickness of at least 0.3 to 2.2 μm on one side, wherein the colored resin layer contains 0.5 to 17.5% by mass of one or more pigments. And at least one of 0.05 to 6.2% by mass of a water-soluble styrene acrylic resin and a nonionic surfactant as a pigment dispersant. A colored resin-coated metal sheet according to claim 7, wherein the colored resin layer contains one or more organic pigments. A colored resin-coated metal plate which is a chromium-free metal plate having a colored resin layer having a thickness of 0.3 to 2.2 μm on one side, wherein the colored resin layer contains one or more pigments, but does not include separate use. Black pigment and 0.03 to 3.8% by mass of polyamido-based thixotropic agent. The colored resin-coated metal sheet according to any one of claims 1, 7 and 9, wherein the colored resin layer has a clear coating film thereon. A colored resin-coated metal plate according to claim 10, wherein the transparent coating film has a film thickness of 0.4 to 4.5 μm.