CN103481584A

CN103481584A - Thin-black-layer-coated metal sheet

Info

Publication number: CN103481584A
Application number: CN201310220558.6A
Authority: CN
Inventors: 中元忠繁; 江口彻; 山本佳代
Original assignee: Kobe Steel Ltd
Current assignee: Kobe Steel Ltd
Priority date: 2012-06-11
Filing date: 2013-06-05
Publication date: 2014-01-01
Anticipated expiration: 2033-06-05
Also published as: KR101500838B1; CN103481584B; KR20130138684A

Abstract

The invention provides a thin-black-layer-coated metal sheet. A first black layer having 0.4 to 1.0 micrometer thickness and formed by water black resin composition is laminated on at least one side of the metal board and a second black layer having 1.4 to 9 micrometers thickness and formed by solvent black coating is laminated on the first black layer, wherein the water black resin composition contains surface processing carbon black covered with water resin. The thin-black-layer-coated metal sheet has a very thin integral coating film and has a good black degree and no appearance defects.

Description

Film black coated metal plate

Technical field

The present invention relates to have the film black coated metal plate of good degree of blackness.

Background technology

In the past, as the bonnet of the slim TV of LCD TV and plasma television etc., use the black plastic shell, in recent years, from inner face side being given to the viewpoint such as electric conductivity (corresponding electromagnetic wave), gradually instead of the (PCM: pre-matel coated) of the steel plate with the black coating film application.

In existing coated steel plate (PCM), for the outward appearance of hiding raw sheet (plated steel sheet, hot-dip galvanized steel sheet, alloy galvanized steel plate etc.) and gloss, black is presented, need to be coated with the coating that contains the black pigments such as carbon black, and make its thickness reach 10 μ m left and right (adhesion amounts: about 12g/m ²), and then as required at this black coating film layer (top coat: thickness 3 μ m left and right (adhesion amounts: about 5g/m are set top coat layer) ²) priming coat (プライマ mono-コ mono-ト for giving processability, corrosion resistance

).Like this in PCM in the past, usually the gross thickness of top coat and priming coat is set as to approximately 10～20 μ m are thick.But, if the thickness of filming is very thick, the use amount of coating increases, for the time of application and baking also elongated, so manufacturing cost rises.Therefore, especially in recent years, along with intensifying of the competition in slim TV market, improve the requirement of compression and reduction manufacturing cost, wherein, especially require the filming of filming in PCM.

As the coated steel plate (PCM) that turns to target with film, having proposed for example on a face of steel plate, to form the organic resin epithelium total film thickness that whole painting the (upper Tu り) filmed that primary coat (lower Tu り) is filmed and formation contains the phosphorus flaky substance on this primary coat is filmed is the coated steel plate (No. 2008-55774, TOHKEMY) below 10 μ m.In addition, a kind of coated steel plate has also been proposed, it possesses the outermost layer that contains coloring pigment and films and contain coloring pigment and as the lower coating film of the porous silica of rust resisting pigment, the thickness that outermost layer is filmed is more than 2 μ m, the thickness of lower coating film is more than 2 μ m, and the thickness of total film layer is 10 μ m following (No. 2010-115902, TOHKEMYs).

But the coating thickness of PCM is thinner usually, degree of blackness more reduces, and existence presents the outward appearance of pitchy strong (the b value is large) or presents the tendency of the outward appearance of grey black strong (the L value is large).In the coated steel plate of above-mentioned two prior aries, although manage to improve degree of blackness by containing the modes such as phosphorus flaky substance, present situation is not yet to be able to degree of blackness of great satisfaction (for example the L value is below 20).

Therefore, the inventor etc. have proposed a kind of coated steel plate, even the less coated steel plate that also can embody good degree of blackness of thickness as black coating film, this steel plate of filming has by the about black epithelium of 0.3～1.5 μ m of the thickness formed with black combination, and this black combination contains with the surface-treated carbon black on water-soluble resin coating surface (No. 2011-224972, TOHKEMY).This coated steel plate can be realized the degree of blackness of L value so excellent level below 20, and coated film is very thin, is about 0.3～1.5 μ m, therefore from cutting down the viewpoint of manufacturing cost, highly beneficial.But on the other hand, when actual manufacture, because the black epithelium is too thin, the paint film defect because of due to grit type pit of producing crawling and production line thus etc., easily cause bad order, can diminish the design of coated steel plate.Especially in the prior art, by transparent epithelium is set on the black epithelium, thereby embody the characteristics such as corrosion resistance and resistance to marring, if but have above-mentioned transparent epithelium, can encourage the paint film defects such as crawling, grit type pit, have the tendency that easily becomes more obvious.

Summary of the invention

The present invention In view of the foregoing completes, and its purpose is, provide total coated film very thin and embody good degree of blackness, without the film black coated metal plate of bad order.

The film black coated metal plate of the present invention that can solve above-mentioned problem is laminated with the first black layer of thickness 0.4～1.0 μ m formed by the water system black-colored resin composition at least one face of metallic plate, and to be laminated with on this first black layer by solvent be the second black layer of thickness 1.4～9 μ m that form of blacking, above-mentioned water system black-colored resin composition contains the surface-treated carbon black with aqueous resin coating surface.

In the present invention, in all solids composition 100 quality % of above-mentioned water system black-colored resin composition, the containing ratio of above-mentioned surface-treated carbon black (solid constituent) is preferably 10～40 quality %.

In the preferred embodiment of the present invention, the degree of blackness on above-mentioned the first black layer surface (L value) is below 25 and the b value is below 3.

In the present invention, preferably: above-mentioned solvent is that blacking contains resin particle, the particle diameter of this resin particle is below 14 μ m, and the particle diameter of above-mentioned resin particle is more than t (μ m) and below 2t (μ m) when the thickness by above-mentioned the second black layer is made as t (μ m).

In the preferred embodiment of the present invention, above-mentioned solvent is that blacking contains the following resin particle of particle diameter 14 μ m, and the degree of blackness (L value) that is laminated in the second black layer surface on above-mentioned the first black layer is below 20 and the b value is below 1.5.

In the present invention, preferably: above-mentioned water system black-colored resin composition contains adhesive resin, this adhesive resin comprises alkene-α, the beta-unsaturated carboxylic acid copolymer, α, beta-unsaturated carboxylic acid polymer and be selected from the polymer of Han oxazolinyl and the crosslinking agent of zirconium carbonate ammonium, the content of above-mentioned crosslinking agent is with respect to alkene-α, beta-unsaturated carboxylic acid copolymer and α, summation 100 mass parts of beta-unsaturated carboxylic acid polymer are 2～19 mass parts, the containing ratio of above-mentioned adhesive resin is 30～85 quality % in all solids composition 100 quality % of water system black-colored resin composition.

In the present invention, preferably: above-mentioned water system black-colored resin composition also contains cataloid, in all solids composition 100 quality % of the containing ratio of this cataloid in above-mentioned water system black-colored resin composition, is 5～30 quality %.

In the present invention, preferably: with respect to solid constituent summation 100 mass parts of above-mentioned surface-treated carbon black, above-mentioned adhesive resin and above-mentioned cataloid, above-mentioned water system black-colored resin composition also contains the silane coupler of 5～25 mass parts.

In addition, in this specification, " all solids composition in the water system black-colored resin composition " refers to the solid constituent summation of above-mentioned surface-treated carbon black, above-mentioned adhesive resin and above-mentioned cataloid.

According to the present invention, a kind of film black coated metal plate can be provided, its at least one side at metallic plate is laminated with the thickness of stipulating the first black layer formed by the water system black-colored resin composition respectively and is the second black layer that blacking forms by solvent, above-mentioned water system black-colored resin composition contains the surface-treated carbon black with aqueous resin coating surface, also can embody good degree of blackness even therefore always coated film is very thin, and the paint film defects such as crawling, grit type pit also are difficult to become significantly, have good outward appearance.

The accompanying drawing explanation

Fig. 1 means the figure of relation of the degree of blackness (L value) of the thickness of the second black layer in the film black coated metal plate (use base treatment metallic plate EG) of embodiment 1 and comparative example 1 and this ferrous metal plate.

Fig. 2 means the figure of relation of the degree of blackness (L value) of the thickness of the second black layer in the film black coated metal plate (use base treatment metallic plate GI) of embodiment 1 and comparative example 1 and this ferrous metal plate.

Fig. 3 means the figure of relation of the b value of the thickness of the second black layer in the film black coated metal plate (use base treatment metallic plate EG) of embodiment 1 and comparative example 1 and this ferrous metal plate.

Fig. 4 means the figure of relation of the b value of the thickness of the second black layer in the film black coated metal plate (use base treatment metallic plate GI) of embodiment 1 and comparative example 1 and this ferrous metal plate.

The specific embodiment

Film black coated metal plate of the present invention (below, sometimes also referred to as " ferrous metal plate ") be laminated with at least one face of metallic plate the first black layer formed by the water system black-colored resin composition, and to be laminated with by solvent on this first black layer be the second black layer that blacking forms, above-mentioned water system black-colored resin composition contains the surface-treated carbon black with aqueous resin coating surface.Below, ferrous metal plate of the present invention is described in detail.

(metallic plate)

The metallic plate used as the present invention, so long as the metallic plate that can use as pre-metal-coated raw sheet gets final product, be not particularly limited.For example, except the steel plates such as non-plating cold-rolled steel sheet, hot-dip galvanized steel sheet (GI), alloy galvanized steel plate (GA), plated steel sheet (EG), also can enumerate aluminium sheet and titanium plate etc.Wherein, preferred molten galvanized steel plain sheet (GI), plated steel sheet (EG), aluminium sheet and titanium plate.

Preferably at least one side at above-mentioned metallic plate forms basalis by base treatment in advance.If for example the metal sheet surface in a side of formation the first black layer described later has by the formed skin membrane (basalis) that changes into of base treatment, improve the adhesion of metallic plate and the first black layer.

As changing into skin membrane (basalis), can enumerate organic coating layer, inorganic skin membrane, phosphate coating layer, chromate skin membrane etc., wherein, preferred organic skin membrane, inorganic skin membrane, phosphate coating layer.As the organic coating layer, suitable choice for use such as polyethylene-based resin, epoxy are that resin, acrylic resin, polyurethane series resin, polyester based resin, fluorine resin and their mixture, copolymer, modified resin etc. get final product.In addition, the raising corrosion resistance of take is purpose, also can in this organic coating, add silica gel, cataloid etc.; The processability that the raising of perhaps take is filmed after applying is purpose, also can the various paraffin compositions of indium addition; Or take raising and film adhesion as purpose, also can add silane coupler.As inorganic skin membrane, can enumerate silicate skin membrane etc.In addition, also can in this silicate skin membrane, add phosphoric acid and fluoride.

The adhesion amount that changes into skin membrane (basalis) does not have special provision, for example, so long as organic coating layer and inorganic skin membrane go out from the viewpoint of corrosion resistance, preferably with dry mass, counts 50mg/m ²above.But, if surpass 150mg/m ², corrosion resistance to improve effect saturated, and manufacturing cost rises.

As the metallic plate that is formed with basalis and particularly preferred form, for example for will contain aluminium dihydrogen phosphate, cataloid and polyacrylic base treatment composition (below, sometimes also referred to as " particular substrate treatment compositions ") coat on zinc-plated metallic plate and make its dry and metallic plate.If above-mentioned particular substrate treatment compositions is coated to zinc-plated metallic plate, metal sheet surface is by the hydrogen ion etching from aluminium dihydrogen phosphate, and the interaction by aluminium ion and cataloid from aluminium dihydrogen phosphate, can form the slightly solubility epithelium with the adhesion excellence of aftermentioned the first black layer, consequently, after bending machining and extrusion process, the epithelium adhesion of (after stretching/contraction distortion) improves, and can realize that corrosion resistance and anti-tape stripping significantly improve.

In above-mentioned particular substrate treatment compositions, aluminium dihydrogen phosphate and cataloid be preferably aluminium dihydrogen phosphate containing proportional in the solid constituent ratio: cataloid (mass ratio)=30: 70～70: 30 (more preferably 35: 65～65: 35, further preferably 45: 55～65: 35).If cataloid is more than aforementioned proportion, make the film reduction and be difficult to form basalis, be difficult to obtain corrosion resistance and with the raising effect of the adhesion of whole coating, and then, to the adhesion of metallic plate also step-down, after processing, likely film and peel off.On the other hand, if cataloid is fewer than aforementioned proportion, the ratio of aluminium dihydrogen phosphate increases, and therefore sometimes with metallic plate, react the ratio increase that the remaining aluminium dihydrogen phosphate of (etching) dissolves in water, in the lower generation corrosion of filming, corrosion resistance reduces.

Preferably in above-mentioned particular substrate treatment compositions, contain solid constituent summation 100 mass parts with respect to aluminium dihydrogen phosphate and cataloid and be the polyacrylic acid of 0.1～5 mass parts (more preferably more than 0.2 mass parts, below 3 mass parts).Think that polyacrylic acid plays the effect of reacting (etching) that moderate control has been implemented the metal sheet surface of zinc-plated grade (zinc-plated) and aluminium dihydrogen phosphate, if lower than above-mentioned scope, etching occurs superfluously, therefore result is that corrosion resistance likely reduces, if surpass above-mentioned scope, make on the contrary etching insufficient, can't form fully the slightly solubility epithelium generated by aluminium dihydrogen phosphate and cataloid, be difficult to obtain the raising effect of adhesion and corrosion resistance.

Preferably in above-mentioned particular substrate treatment compositions, also contain solid constituent summation 100 mass parts with respect to aluminium dihydrogen phosphate and cataloid and be the silane coupler of 3～15 mass parts (more preferably more than 5 mass parts, below 12.5 mass parts).If silane coupler is lower than above-mentioned scope, the adhesion of whole coating and metallic plate and the raising effect of corrosion resistance are had to inadequate tendency, under harsher processing conditions, the situation that epithelium is peeled off of causing is arranged, otherwise, even surpass above-mentioned scope, corrosion resistance and adhesion also still likely reduce.

(the first black layer)

At least the first black layer of one side that is laminated in above-mentioned metallic plate is formed by the water system black-colored resin composition.

<surface-treated carbon black >

The water system black-colored resin composition is to contain to using the surface-treated carbon black on aqueous resin coating surface as the resin combination of black pigment.While not mixed with adhesive resin described later by the common carbon black of aqueous resin coating on surface, because of the variation of pH value, with the intermiscibility of adhesive resin etc., easily cause the secondary aggegation, its result reduces tinting strength, tinting power, if when the surface-treated carbon black with aqueous resin coating surface mixes with adhesive resin, bring into play excellent dispersiveness, be difficult to occur the secondary aggegation, therefore as described later, also can give play to sufficiently high degree of blackness even the first black layer thickness formed with the water system black-colored resin composition is thinner.

In addition, in this specification, " with the surface-treated carbon black on aqueous resin coating surface " is not only the form with aqueous resin coating carbon black all surfaces, also comprises the form of the part of coating carbon black.

As the carbon black that forms surface-treated carbon black, there is no particular limitation, can enumerate such as oil smoke, pine soot, commercially available color black, rubber grade carbon black etc.Aqueous resin as the surface of above-mentioned coating carbon black, so long as can make carbon black be difficult to the aqueous resin of secondary aggegation, there is no particular limitation, can enumerate such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, water soluble acrylic resin, polyacrylamide, polyvinylpyridine, polyacrylic acid etc.More than the amount of aqueous resin (amount of coating) is preferably 5 mass parts with respect to carbon black 100 mass parts and below 380 mass parts.In addition, also further attaching surface activating agent on surface-treated carbon black.Thus, can further suppress the secondary aggegation of the surface-treated carbon black in adhesive resin.As above-mentioned surfactant, can enumerate the surfactant that known anion is, nonionic is, cation is.

As above-mentioned surface-treated carbon black, preferably utilize the ink droplet (prepared Chinese ink) of the high concentration of using in calligraphy for example.Ink droplet is the aqueous dispersion that contains surface-treated carbon black, for example, coating is carried out with aqueous resin in surface for the amorphous furnace black of the manufacture such as unburnt oven process in high-temperature gas of the oil with making petroleum or coal measures, add as required antifreezing agent and the anticorrisive agent of glycol system, mix and slurry, manufacture thus ink droplet.As ink droplet, can use such as commercially available prepared Chinese ink (such as Wu of Co., Ltd. bamboo " super thick ink ink droplet BA-8 " etc.).In addition, surface-treated carbon black or its aqueous dispersion also can for example, be prepared according to known method (Japanese kokai publication hei 7-188597 communique and Japanese kokai publication hei 6-234946 communique).Surface-treated carbon black (or its aqueous dispersion) may be used alone, or two or more kinds may be used in combination.

In all solids composition 100 quality % of water system black-colored resin composition, the containing ratio of surface-treated carbon black (being its solid constituent when using the aqueous dispersion of surface-treated carbon black) preferably contains 10 quality % above (more preferably more than 20 quality %), preferably contains 40 quality % following (more preferably below 30 quality %).At the containing ratio of surface-treated carbon black during lower than 10 quality %, L value and the b value of the first black layer uprise, its result make stacked the second black layer and L value and the b value of ferrous metal plate also uprise, be dark umber, the tendency (with reference to Fig. 1～4) that can not embody abundant degree of blackness is arranged.On the other hand, when the containing ratio of surface-treated carbon black surpasses 40 quality %, the resinous principle as adhesive contained in composition reduces relatively, make the adhesion step-down of the first black layer and the second black layer, or composition becomes easy gelation and the aqueous stability of water system black-colored resin composition is likely reduced.If the containing ratio of surface-treated carbon black is in above-mentioned scope, even surface-treated carbon black mixes and also is difficult to occur the secondary aggegation with adhesive resin, can keep higher dispersion stabilization.

The water system black-colored resin composition is usually containing the adhesive resin that is useful on fixed surface treated carbon black in the first black layer formed by said composition.As adhesive resin, so long as adhesive resin that can the fixed surface treated carbon black, there is no particular limitation for its kind, but, the secondary aggegation of the surface-treated carbon black in composite inhibiting effectively, can access excellent aqueous stability aspect, preferably polyethylene resin, polyurethane resin etc.Be particularly preferably polyvinyl resin.Adhesive resin may be used alone, or two or more kinds may be used in combination.

Above-mentioned polyvinyl resin is preferably by alkene-α, the beta-unsaturated carboxylic acid copolymer (below, be sometimes referred to as " alkene-acid copolymer "), α, beta-unsaturated carboxylic acid polymer (below, be sometimes referred to as " carboxylic acid polyalcohol ") and be selected from the polymer of Han oxazolinyl and the crosslinking agent of zirconium carbonate ammonium forms.Alkene-acid copolymer and carboxylic acid polyalcohol can not damage the dispersion stabilization of the surface-treated carbon black in the water system black-colored resin composition, make to improve with the compatibility of this carbon black, and the adhesion of the first black layer and metallic plate is improved.In addition, be selected from the crosslinking agent of the polymer of Han oxazolinyl and zirconium carbonate ammonium and alkene-acid copolymer and carboxylic acid polyalcohol crosslinked, form fine and close and stone black layer, therefore make the resistance to marring of the second black layer improve.Especially the reactivity of zirconium carbonate ammonium is high, and the mobility while making film is also excellent, therefore larger as the effect of crosslinking agent, has given play to the also effect of excellence of wear-resisting sand rubber abrasivity.

In addition, what is called of the present invention " alkene-acid copolymer " refers to alkene and α, and (the copolymer of beta-unsaturated carboxylic acid preferably accounts for more than 50 quality % from the construction unit of alkene in copolymer, from α, the construction unit of beta-unsaturated carboxylic acid is below 50 quality %) copolymer.In addition, so-called " carboxylic acid polyalcohol " refers to and uses α, beta-unsaturated carboxylic acid is the polymer (also comprising copolymer) that monomer carries out polymerization and obtains, and preferably from α, the construction unit of beta-unsaturated carboxylic acid accounts for the carboxylic acid polyalcohol more than 90 quality % in polymer.

Above-mentioned alkene-acid copolymer can make alkene and α by the method with known, the beta-unsaturated carboxylic acid copolymerization is manufactured, and also can commercially availablely buy.Alkene-acid copolymer can be used one kind or two or more.

As the alkene that can use in the manufacture of alkene-acid copolymer, there is no particular limitation, optimal ethylene, propylene etc., more preferably ethene.For alkene-acid copolymer, olefin unit can be only from the alkene of a kind, also can be from alkene of more than two kinds.

The α that can use in the manufacture of alkene-acid copolymer, also there is no particular limitation for beta-unsaturated carboxylic acid, can enumerate monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, iso-crotonic acid; The dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid etc.Wherein, preferred acrylic acid.For alkene-acid copolymer, α, the construction unit of beta-unsaturated carboxylic acid can be only from a kind of α, and beta-unsaturated carboxylic acid also can be from two or more α, beta-unsaturated carboxylic acid.

α in alkene-acid copolymer, the beta-unsaturated carboxylic acid unit has the effect of the adhesion that improves the first black layer and metallic plate, in order effectively to bring into play above-mentioned effect, the α in copolymer, more than the beta-unsaturated carboxylic acid quantity of units is preferably 5 quality %, more preferably more than 10 quality %.On the other hand, the α in copolymer, the upper limit of beta-unsaturated carboxylic acid quantity of units is 50 quality % as described above, from the viewpoint of corrosion resistance, is particularly preferably below 30 quality %, more preferably below 25 quality %.

Above-mentioned alkene-acid copolymer can not bring in dysgenic scope and have the construction unit from other monomer the secondary aggegation that suppresses surface-treated carbon black etc.In alkene-acid copolymer, from the construction unit amount of other monomer, be preferably below 10 quality %, more preferably below 5 quality %, most preferred alkene-acid copolymer is for only by alkene-and α, alkene-acid copolymer that beta-unsaturated carboxylic acid forms.As preferred alkene-acid copolymer, can enumerate ethylene-acrylic acid copolymer.

The weight average molecular weight of above-mentioned alkene-acid copolymer (Mw) is preferably 1,000～100,000 with polystyrene conversion, and more preferably 3,000～70,000, more preferably 5,000～30,000.This Mw can utilize the GPC as standard by polystyrene to measure.

As above-mentioned carboxylic acid polyalcohol, can enumerate one kind or two or more α, the homopolymers of beta-unsaturated carboxylic acid or copolymer or the copolymer that further copolymerization has other monomer (except alkene) to form.Such carboxylic acid polyalcohol can be manufactured by known method, also can commercially availablely buy.Carboxylic acid polyalcohol can be used one kind or two or more.

As the α that can use in the manufacture of carboxylic acid polyalcohol, beta-unsaturated carboxylic acid, as can be at the material of use in above-mentioned alkene-acid copolymer synthetic and illustrative α, beta-unsaturated carboxylic acid all can be used.Wherein, preferred acrylic acid and maleic acid, more preferably maleic acid.

Carboxylic acid polyalcohol can contain from α, the construction unit of the monomer beyond beta-unsaturated carboxylic acid is below 10 quality % from the construction unit amount of other monomer in polymer, is preferably below 5 quality %, more preferably only by α, the carboxylic acid polyalcohol that beta-unsaturated carboxylic acid forms.

As preferred carboxylic acid polyalcohol, can enumerate such as polyacrylic acid, polymethylacrylic acid, acrylic acid-maleic acid, poly etc., wherein, from the viewpoint of first black layer adhesion etc., more preferably poly.The carboxyl amount of poly is many, and therefore the adhesion of the first black layer and metallic plate further improves.

The weight average molecular weight of above-mentioned carboxylic acid polyalcohol (Mw) is preferably 500～30,000 in polystyrene conversion, and more preferably 800～10,000, more preferably 900～3,000, most preferably be 1,000～2,000.This Mw can utilize the GPC as standard by polystyrene to be measured.

The ratio (mass ratio) that contains of the alkene-acid copolymer in polyvinyl resin and carboxylic acid polyalcohol is preferably 1,000: 1～10: 1, and more preferably 200: 1～20: 1, more preferably 100: 1～25: 1.If carboxylic acid polyalcohol contain ratio when too low, sometimes can't give full play to the effect of combination alkene-acid copolymer and carboxylic acid polyalcohol, on the contrary, if carboxylic acid polyalcohol contain ratio when superfluous, in composition, alkene-acid copolymer and carboxylic acid polyalcohol are separated, and possibly can't evenly form the first black layer.

Polymer Ju You oxazolinyl Gai oxazolinyl of ， of above-mentioned Han oxazolinyl and the carboxyl generation cross-linking reaction that alkene-acid copolymer, carboxylic acid polyalcohol have, resin is cross-linked to each other thus, forms fine and close network structure.The obdurability of the first black layer improves thus.

Polymer as above-mentioned Han oxazolinyl, from the hardness that improves black layer and the aspect that can improve the brittleness of black layer, the polymer that preferably main chain comprises styrene/acrylic Han oxazolinyl, for example preferably used " EPOCROS (registration mark) " of Japanese catalyst company system in commercially available product.As " EPOCROS (registration mark) ", " EPOCROS (registration mark) K " series of emulsion-type particularly preferably, as grade, K-2010E (Tg:-50 ℃), K-2020E (Tg:0 ℃) and K-2030E (Tg:50 ℃) are arranged.Wherein, obtain harder epithelium aspect set out, most preferably " EPOCROS (registration mark) K-2030E ".

For above-mentioned zirconium carbonate ammonium ((NH ₄) ₂[Zr (CO ₃) ₂(OH) ₂]), when making film (film forming), carbon dioxide and ammonium break away from, and become ZrO, and the carboxyl of cross-linking aqueous adhesive resin or hydroxyl, can form epithelium thereon.Reaction when this makes film (film forming) can maintain mobility and utilize the metal corsslinking of Zr to obtain high crosslink density (network structure), therefore forms tough epithelium.Therefore, if use zirconium carbonate ammonium, can make the epithelium that forms the first black layer embody hardness and obdurability, can significantly improve resistance to marring and the abrasion performance of the epithelium that forms the second black layer.

As the commercially available product of above-mentioned zirconium carbonate ammonium, can preferably use " BAYCOURT20 " of Japanese light metal (strain) system.

With respect to summation 100 mass parts (solid constituent) of alkene-acid copolymer and carboxylic acid polyalcohol, polymer and/or the zirconium carbonate ammonium of above-mentioned crosslinking agent (Han oxazolinyl) preferably contain 2 mass parts above (more preferably 3 mass parts above, further preferably more than 5 mass parts) and be preferably 19 mass parts following (more preferably 17 mass parts are following, further preferably 16 mass parts are following).If the content of above-mentioned crosslinking agent is less than above-mentioned scope, cross-linking reaction becomes insufficient, can't obtain the compactness of formed epithelium, and result makes the resistance to marring variation of the ferrous metal plate of gained sometimes.On the other hand, if the content of above-mentioned crosslinking agent more than above-mentioned scope, the functional group's (carboxyl) who the first black layer is had due to excessive cross-linking reaction reduces, and sometimes with the adhesion of the second black layer and metallic plate, can reduce.

In all solids composition 100 quality % of water system black-colored resin composition, the content of adhesive resin is preferably 30 quality % above (more preferably more than 55 quality %) and is preferably 85 quality % following (more preferably 65 quality % are following).At the containing ratio of adhesive resin during lower than 30 quality %, epithelium make the film reduction, what may make surface-treated carbon black fixedly becomes insufficient, or produces crawling and cause apparent problem.On the other hand, if, when the containing ratio of adhesive resin surpasses 85 quality %, the content of surface-treated carbon black reduces relatively, therefore possibly can't obtain sufficient degree of blackness.

The water system black-colored resin composition preferably also contains cataloid.Thus, surface-treated carbon black can be fixed in to the first black layer well, and can make corrosion resistance and the hardness of the ferrous metal plate of gained improve.The details of this its mechanism is still not clear, but infers it is due under corrosive environment, and silica dissolves, stripping, the cushioning effect and the passive state epithelium formation effect that produce pH.And then, if contain cataloid, also confirm for preventing that the depression of water system black-colored resin composition when the coating/dry etc. is effectively.

As cataloid, there is no particular limitation, viewpoint from the dispersiveness the water system black-colored resin composition and corrosion resistance raising effect etc., the cataloid that preferable particle size is 4～20nm, particularly, can enumerate the cataloid (commercially available product of particle diameter 4～6nm, " SNOWTEX (registration mark) XS " of daily output chemical company system), cataloid (the commercially available product of particle diameter 8～11nm, " SNOWTEX (registration mark) S " of daily output chemical company system), cataloid (the commercially available product of particle diameter 10～20nm, " SNOWTEX (registration mark) 40 " of daily output chemical company system) etc., wherein, particularly preferably " SNOWTEX (registration mark) XS ".

In all solids composition 100 quality % of water system black-colored resin composition, the content of cataloid (solid constituent) is preferably 5 quality % above (more preferably more than 10 quality %) and is preferably 30 quality % following (more preferably 20 quality % are following).If the containing ratio of cataloid, lower than 5 quality %, can't confirm the raising effect of corrosion resistance, epithelium hardness sometimes.On the other hand, if the containing ratio of cataloid surpasses 30 quality %, the bad stability of composition, sometimes As time goes on and thickening, also can't obtain the effect of the further raising of corrosion resistance etc., unfavorable economically.

The water system black-colored resin composition can further contain silane coupler.If contain silane coupler, can improve the adhesion of the first black layer and metallic plate.

As silane coupler, preferably there is endways the silane coupler of glycidoxy, can enumerate such as γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyldiethoxysilane etc.Preferred vinyl three ('beta '-methoxy ethyoxyl) silane also.

The content of silane coupler be preferably 5 mass parts with respect to solid constituent summation 100 mass parts of above-mentioned surface-treated carbon black, above-mentioned adhesive resin and above-mentioned cataloid more than (more preferably more than 10 mass parts) and be preferably 25 mass parts following (more preferably 15 mass parts are following).During lower than 5 mass parts, sometimes can't fully obtain the effect of bringing by adding silane coupler at the content of silane coupler.On the other hand, if the content of silane coupler surpasses 25 mass parts, remaining a large amount of unreacted silane couplers in the ferrous metal plate, the tendency that has corrosion resistance to reduce.

Can also in the scope of not damaging effect of the present invention, further contain as required various additives in the water system black-colored resin composition.For example, in the field of household appliances such as slim TV, complicated extrusion process etc. of situation implement to(for) the ferrous metal plate is a lot, as the performance that requires to the ferrous metal plate, requires processability.In such cases, by add the wax of water system in the water system black-colored resin composition, can give lubricity and realize the raising of processability the first black layer.As the wax of water system, can enumerate the polyethylene-based wax such as " CHEMIPEARL (registration mark) W700 ", " CHEMIPEARL (registration mark) W950 ", " CHEMIPEARL (registration mark) W900 " of Mitsui Chemicals, Inc. system.

The water system black-colored resin composition can mix above-mentioned each by the ratio with regulation and become to assign to prepare.Order by merging has no particular limits, and preference is as contained polymer or the zirconium carbonate ammonium of crosslinking agent (Han oxazolinyl at adhesive resin) time composition components beyond previously prepared these crosslinking agents add therein crosslinking agent.

One or both sides at above-mentioned metallic plate are coated with above-mentioned water system black-colored resin composition and make its drying, to reach the dry film thickness of regulation, can form thus the first black layer of the present invention.

The thickness of the first black layer (dry film thickness) is 0.4 μ m above (preferably 0.5 μ m above, more preferably more than 0.6 μ m) and 1.0 μ m following (preferably 0.98 μ m is following, more preferably 0.9 μ m is following).If the thickness of the first black layer is lower than 0.4 μ m, the degree of blackness of the ferrous metal plate of the first black layer and even gained becomes insufficient, presents dark umber.On the other hand, if the thickness of the first black layer surpasses 1.0 μ m, although degree of blackness excellence, the effect that is difficult to obtain the further raising of degree of blackness, on the other hand, application and the dry time spent are elongated, make the manufacturing cost rising.In addition, if the thickness of the first black layer is blocked up, sometimes also can't reach desired electric conductivity while using in the field of household appliances such as slim TV.

Coating, the drying means of the water system black-colored resin composition while forming the first black layer have no particular limits, and can suitably adopt known method.As the coating process of composition, can enumerate such as excellent painting method, curtain stream rubbing method, rolling method, spray-on process, spraying ring (spray ringer) method etc., wherein, from the viewpoint of cost etc., preferred excellent painting method, rolling method, spraying are around-France.In addition, as baking temperature, for example, so long as can, because heat gets final product the deteriorated degree of black layer, not be preferably 50～160 ℃ of left and right, more preferably 70～140 ℃ of left and right.

The first black layer has excellent degree of blackness, in preferred configuration of the present invention, the degree of blackness on the first black layer surface (L value) is that (preferably below 24, further preferably below 23) and b value are (more preferably below 2.6, further preferably below 2.1) below 3 below 25.In addition, in the present invention, L value and b value be utilize the method stipulated in JISZ8722 to record the luminance index of measured value, can be measured by the described method of embodiment described later.Therefore, for the L* value and the b* value that convert based on following formula, its preferred upper limit is also the scope of calculating from the higher limit of above-mentioned L value and b value.

L＊＝1.3632L-3.5904

b＊＝1.5744b-0.0380

(the second black layer)

Be that blacking is coated with, dry, baking by solvent, make its dry film thickness that reaches regulation, can form thus the second black layer be laminated on above-mentioned the first black layer.By thering is above-mentioned the second black layer, thereby even the thickness of the first black layer that utilizes above-mentioned water system black-colored resin composition to form is as thin as above-mentioned scope, when it forms by the grit type pit of crawling, production line etc. and the generation paint film defect also can keep making the ferrous metal plate keep good outward appearance.

Be blacking as solvent, have no particular limits, can use all the time the solvent for the ferrous metal plate is blacking.Solvent is can prepare by following known method by blacking, (for example molecular weight 10 for example in solvent, to add matrix resin, 000～20, the macromolecule polyester resin of 000 left and right etc.), curing agent (such as melamine series curing agent etc.) and rust resisting pigment (being that rust resisting pigment, magnesium phosphate are that rust resisting pigment, calcium silicates are rust resisting pigment etc. such as aluminum phosphate) as required, extender pigment etc., then add as the carbon black of coloring pigment and manufacture.In addition, in commercially available product, can enumerate NIPPON FINE COATINGS company's system " FLC495BLACK ", " FLC6000BLACK ", " FLC6070BLACK ", " FLC6080BLACK ", " FLC6090BLACK ", " FLC6100BLACK ", BASF JAPAN company system " HF1600BLACK " etc.Solvent is that blacking can only be used a kind, and also two or more kinds may be used.In addition, from the viewpoint of processability, resistance to marring, abrasion performance, solvent is that the Tg of the matrix resin (such as mylar etc.) of blacking is preferably 15～30 ℃.

Above-mentioned solvent is that blacking preferably contains resin particle.Become thus the ferrous metal plate that there is higher degree of blackness and there is good concavo-convex outward appearance and feel.If for example in transparent epithelium, containing resin particle, can't embody good concave-convex design.

Above-mentioned resin particle can be organic filler (such as acrylic acid pearl, styrene acrylic pearl, polyurethane pearl etc.), can be also inorganic particulate (such as bead, silica beads etc.).Especially, from solvent, be blacking, be difficult to aggegation and easily obtain aspect consider, preferred acrylic acid pearl.In addition, resin particle can only be used a kind, and also two or more kinds may be used.

The viewpoint of the screening characteristics from coating process such as roll coaters the time, the particle diameter of above-mentioned resin particle is preferably below 14 μ m, more preferably below 12 μ m, more preferably below 10 μ m.If the particle diameter of resin particle surpasses 14 μ m, may produce cut (Japanese: The じ draws I) etc. during application.

Especially, when the thickness by the second black layer is made as t (μ m), more than the particle diameter of resin particle is preferably t (μ m) and below 2t (μ m).If for example filming of the second layer is the thickness of 15 μ m left and right, during the solvent evaporates in coating, produce the eddy current of following volatilization in layer under moisture state, resin particle moves to the surface of filming, form thus concavo-convex filming, the thickness of the second black layer is thinner as described later in the present invention, therefore can't expect the generation of eddy current.If the thickness of the second black layer and the particle diameter of resin particle meet above-mentioned relation, though the thickness of the second black layer thinner also can embody good concavo-convex.

The thickness of the second black layer (dry film thickness) be 1.4 μ m above (preferably 1.5 μ m above, more preferably 1.6 μ m above, further preferably 2 μ m above, particularly preferably 3 μ m above, most preferably more than 4 μ m) and be preferably 9 μ m following (preferably 8 μ m are following, more preferably 7 μ m are following, further preferably 6.5 μ m are following, particularly preferably 6 μ m are following).If the thickness of the second black layer, lower than 1.4 μ m, can be detrimental to outward appearance or make the degree of blackness of the ferrous metal plate of gained become insufficient, and have the tendency a little less than the tolerance of abrasion, scuffing.On the other hand, if the thickness of the second black layer surpasses 9 μ m, application and the dry time spent elongated, have the manufacturing cost of making to rise or diminish the tendency of bendability.In addition, at solvent, be blacking while containing resin particle, the serve as reasons solvent of removing resin particle of the thickness of the second black layer (dry film thickness) is the thickness of the film that forms of blacking, mensuration be the thickness that does not have the part of resin particle.

Solvent while forming the second black layer is that coating, the drying of blacking, the method for baking have no particular limits, and can suitably adopt known method.As the coating process of coating, can enumerate the method as described in the formation of the first black layer, wherein, from the viewpoint of cost etc., preferred excellent painting method, rolling method, spraying are around-France.Dry, baking temperature is preferably for example 200～240 ℃ of left and right.

Ferrous metal plate of the present invention has excellent degree of blackness, in preferred configuration of the present invention, the degree of blackness (L value) on ferrous metal plate of the present invention surface (being laminated in the second black layer surface on the first black layer) is that (more preferably below 19, further preferably below 18) and b value are (more preferably below 1.2, further preferably below 1.0) below 1.5 below 20.In addition, in the present invention, L value and b value are with the luminance index of the measured value of the method mensuration of stipulating in JIS Z8722, can measure by the described method of embodiment described later.Therefore, for the L* value and the b* value that convert based on following formula, its preferred upper limit is also the scope of calculating from the higher limit of above-mentioned L value and b value.

L＊＝1.3632L-3.5904

b＊＝1.5744b-0.0380

Embodiment

Below, at length set forth the present invention based on embodiment.But following embodiment is not limited by the present invention, in the scope that does not break away from aforementioned and aim described later, changes enforcement, all is included in technical scope of the present invention.

At first, below, the evaluation method adopted in embodiment is described.

(degree of blackness)

Use spectrophotometer (Japanese electric look industry strain formula meeting company's system " Spectrophotometer SQ2000 "), measure L value, b value for examination material (only be provided with the metallic plate of the first black layer or there is the first black layer and the ferrous metal plate of the second black layer), utilize the L value, b value of gained or convert this L value, b value and the L* value, the b* value evaluation degree of blackness that obtain based on following formula.

L＊＝1.3632L-3.5904

b＊＝1.5744b-0.0380

In the present invention, for the first black layer, by the L value be below 25, be made as qualified; For the first black layer and the second black layer (ferrous metal plate), the L value is that (the L* value is below 24) below 20 is made as qualified.

(corrosion resistance (SST time))

For supplying examination material (only be provided with the metallic plate of the first black layer or there is the first black layer and the ferrous metal plate of the second black layer), implement salt spraytest according to JIS Z2371, measure until produce the time (SST time) of 5% white rust, estimated thus corrosion resistance.

In the present invention, for the first black layer, by the SST time be more than 72 hours, be made as qualified, for the first black layer and the second black layer (ferrous metal plate), by the SST time be more than 240 hours, be made as qualified.

(processability (T bending machining))

To cut into the confession examination material (ferrous metal plate) of 50 * 50mm size, under room temperature (20 ℃), make surface (the second black layer forms face) folding crooked gently with vise toward the outer side, be bent to till its bend can be clamped the limit of same ferrous metal plate (for the examination material), folding bend visual or that observe after processing with the magnifying glass of 10 times has flawless.Evaluation method is: the sheet number of the ferrous metal plate sandwiched is 0 and is made as 0T, and 1 is made as 1T, and the sheet number that sheet number when specific surface cracks is many 1 is made as crackle critical (for example,, when 1T has crackle to produce, 2T is that crackle is critical).

(wear-resisting sand rubber abrasivity)

The sand rubber of diameter 6mm is fixed in to the sliding test device, on the surface for examination material (ferrous metal plate), (the second black layer forms side) applies load 16.5N, while reciprocal 200 times with the about 26mm of sliding distance, utilize exposing of visualization parent metal (base treatment metallic plate), estimated according to following standard.

◎: fully unconfirmedly expose to parent metal

Zero: confirm atomic little parent metal and expose

△: the length of the exposed division of parent metal is in 2mm

*: the length of the exposed division of parent metal surpasses 2mm

(resistance to marring (pencil hardness))

For for examination material (ferrous metal plate), according to JIS K5400 (1990), obtain the second black layer surface with the pencil test machine and do not produce the pencil hardness of scuffing.

(resistance to water (carbon black flows out test))

After will flooding 1 hour in boiling water for examination material (only be provided with the metallic plate of the first black layer or there is the first black layer and the ferrous metal plate of the second black layer), by visualization, by from filming, flowing out the cosmetic variation that carbon black brings, according to following standard, estimated.

◎: outward appearance is unchanged

Zero: atomic little variation is arranged

△: degree of blackness decrease (gloss reducing)

*: decolouring causes the uneven generation of outward appearance

(concavo-convex outward appearance)

For the surface for examination material (ferrous metal plate) (the second black layer forms side), according to following standard, according to visual the observation with feel, estimated.

◎: present distinct black and have appropriate concave-convex sense, feel is also good

△ 1: although present distinct black, unconfirmed to concave-convex sense

△ 2: although present distinct black, concavo-convex excessive, feel is poor

[embodiment 1, comparative example 1 ']

(making of base treatment metallic plate)

At first, approximately in 952 mass parts, add acidoid silica (daily output chemical company's system " SNOWTEX (registration mark) O " at pure water; Solid constituent 20 quality %) 26.3 mass parts and aluminium dihydrogen phosphate (rice mountain chemical company system; Solid constituent 50 quality %) 19.5 mass parts, add polyacrylic acid (Japanese pure medicine company's system " JULIMAR (registration mark) AC-10-LP " wherein; Solid constituent 100 quality %) 0.075 mass parts, then add silane coupler (chemical company of SHIN-ETSU HANTOTAI system " KBM403 "; Solid constituent 100 quality %) 1.13 mass parts, preparation base treatment composition solution (solid component concentration is 1.7 quality %).

Then, at plated steel sheet (EG; Zn adhesion amount 20g/m ²) or hot-dip galvanized steel sheet (GI; Zn adhesion amount 45g/m ²) surface and the back side, according to dry mass, be 103mg/m ²mode utilize the base treatment composition solution of hand roller coating device coating gained, then dry 60 seconds under 120 ℃, make the base treatment metallic plate.Below, the base treatment metallic plate that has used plated steel sheet is made as to base treatment metallic plate EG, will use the base treatment metallic plate of hot-dip galvanized steel sheet as base treatment metallic plate GI.

(formation of the first black layer)

The preparation of<water system black-colored resin composition >

There is the band mixer, thermometer, in the autoclave of the emulsifying device of temperature controller (inner capacities 1.0L), add ethylene-acrylic acid copolymer (Dow Chemical company system " PRIMACOR (registration mark) 5990I ", from acrylic acid construction unit: 20 quality %, melt index: 1300) 200.0 mass parts, the poly aqueous solution (Nof Corp.'s system " NONPOL (registration mark) PMA-50W ", weight average molecular weight: about 1100 (polystyrene conversion), 50 quality % product) 8.0 mass parts, triethylamine 35.5 mass parts, the 48%NaOH aqueous solution 6.9 mass parts (1.5 equivalent part), ready denier oil acid (broadcast mill and change into company's system " HARTALL FA3 ") 3.5 mass parts, ion exchange water 792.6 mass parts, sealed, at 150 ℃, under 5 air pressure, high-speed stirred is after 3 hours, be cooled to 30 ℃.Then, add silane coupler (Momentive Performance Materials (former exabyte: the SILICONE of GE Toshiba) company's system " TSL8350 "; Solid constituent 100 quality %) 10.4 mass parts, poly-carbodiimide (Nisshinbo company system " SV-02 ") 31.2 mass parts, ion exchange water 72.8 mass parts, stir 10 minutes, obtain the resin emulsion that solid constituent is 20 quality %, using it as the adhesive resin precursor.

Then, (the Wu of Co., Ltd. bamboo " super thick ink ink droplet BA-8 " of the prepared Chinese ink as surface-treated carbon black; Solid constituent 13.5 quality %) add while stirring pure water 423 mass parts in 222 mass parts, then, after adding resin emulsion obtained above 285.0 mass parts as the adhesive resin precursor, add cataloid (SNOWTEX (registration mark) XS, solid constituent 20 quality %) 50 mass parts, then add silane coupler (chemical company of SHIN-ETSU HANTOTAI system " KBM403 "; Solid constituent 100 quality %) 12.5 mass parts are with the polymer of Han oxazolinyl (Nippon Shokubai Co., Ltd's system " EPOCROS (registration mark) K-2030E "; Solid constituent 40 quality %) 7.5 mass parts, preparation water system black-colored resin composition.

The solid component concentration of this water system black-colored resin composition is 11.2 quality %, the containing ratio of surface-treated carbon black (solid constituent) (is surface-treated carbon black at all solids composition of said composition, the solid constituent summation of adhesive resin and cataloid (in following embodiment too)) in 100 quality %, be 30 quality %, the containing ratio of adhesive resin (resin emulsion is with the polymer of Han oxazolinyl) (solid constituent) in all solids composition 100 quality % of above-mentioned composition, be 60 quality % (wherein, the polymer of Han oxazolinyl is 3.0 quality % in all solids composition 100 quality % of composition), the containing ratio of cataloid (solid constituent) is 10 % by weight in all solids composition 100 quality % of above-mentioned composition, in addition, with respect to surface-treated carbon black, solid constituent summation 100 mass parts of adhesive resin and cataloid, the silane coupler that contains 12.5 mass parts.

The application of<water system black-colored resin composition >

On the surface of the base treatment metallic plate shown in table 1～4, be coated with according to the dry film thickness utilization shown in table 1～4 rod the water system black-colored resin composition that painting device is coated with above-mentioned gained, then, 160 ℃ of 60 seconds of drying, form the first ferrous metal layer.

(formation of the second black layer)

At solvent, be to add the approximately acrylic acid pearl of 2～12 μ m (the company's system " ラ Block コロ mono-Le " of refining large day) of particle diameter that drying solid composition 100 mass parts with respect to coating are 2 mass parts in blacking (NIPPON FINE COATINGS company's system " FLC495BLACK "), add diluent, after being adjusted into about 50 seconds with Ford cup (Fordcup) No.4 by viscosity, being coated with painting device on the surface of above-mentioned the first black layer according to the rod of the dry film thickness utilization shown in table 1～4 is coated with, then, 230 ℃ of 60 seconds of drying, toasted, form the second black layer, obtain film black coated metal plate.The film black coated metal plate that the film black coated metal plate that the thickness of the second black layer is 1.42～4.55 μ m is each embodiment, the film black coated metal plate that the film black coated metal plate of uncoated the second black layer (thickness 0 μ m) is comparative example 1 '.In addition, 1.2～1.5 times of the thickness that the particle diameter of the acrylic acid pearl of interpolation is the second black layer.

L value, L* value, b value, the b* value of the film black coated metal plate that will obtain according to the thickness that changes the first black layer and the second black layer with upper type are shown in table 1～4.Table 1,3 is for using the situation of base treatment metallic plate EG as metallic plate, and table 2,4 is for being used the situation of base treatment metallic plate GI as metallic plate.In addition, the relation of the L value of the thickness of the second black layer of film black coated metal plate and this ferrous metal plate or b value is as shown in Fig. 1～4.

In addition, the black coated metal plate of the comparative example 1 ' that is 0 μ m for the thickness of the second black layer in the film black coated metal plate of gained, observe by visual film coated surface, and results verification is to bad orders such as crawling, grit type pits.But, while for the black coated metal plate of the embodiment that is formed with the second black layer, carrying out same observation, unconfirmed to bad order.

[comparative example 1]

In the formation of the first black layer of embodiment 1, using solvent is that black primer (KCC Corporation company (Korea S) system " BLACK PRIMER FP1817 ") replaces the water system black-colored resin composition, according to the dry film thickness shown in table 1～4, be coated with, then, 230 ℃ of 60 seconds of drying, in addition, form similarly to Example 1 the first ferrous metal layer and the second black layer, obtain the relatively film black coated metal plate of use.

L value, L* value, b value, the b* value of the film black coated metal plate of the relatively use that will obtain according to the thickness that changes the first black layer and the second black layer with upper type are shown in table 1～4.Table 1,3 is for using the situation of base treatment metallic plate EG as metallic plate, and table 2,4 is for being used the situation of base treatment metallic plate GI as metallic plate.In addition, the relation of the L value of the thickness of the second black layer of film black coated metal plate and this ferrous metal plate or b value is as shown in Fig. 1～4.

[table 1]

[table 2]

[table 3]

[table 4]

[embodiment 2]

(formation of the first black layer)

The preparation of<water system black-colored resin composition >

Use the raw material identical with embodiment 1 (surface-treated carbon black, adhesive resin (resin emulsion is with the polymer of Han oxazolinyl), cataloid, silane coupler), change in such a way each use amount, in addition, prepare similarly to Example 1 the water system black-colored resin composition.

That is, the use amount of cataloid and silane coupler is fixed as identical with embodiment 1 (cataloid (solid constituent): be 10 quality %, silane coupler in all solids composition 100 quality %: be 12.5 mass parts with respect to all solids composition 100 mass parts); The containing ratio that the use amount of surface-treated carbon black changes to its solid constituent reaches the value shown in table 5 in all solids composition 100 quality %; The containing ratio that the use amount of adhesive resin (resin emulsion is with the polymer of Han oxazolinyl) changes to its solid constituent (resin emulsion is with the solid constituent summation of the polymer of Han oxazolinyl) reaches the value shown in table 5 in all solids composition 100 quality %.In addition, resin emulsion is with the polymer of Han oxazolinyl is fixed as the polymer that the quality ratio of each solid constituent reaches resin emulsion ∶ Han oxazolinyl=95: 5.

The application of<water system black-colored resin composition >

The surface of the base treatment metallic plate EG obtained in embodiment 1, be coated with painting device according to the dry film thickness utilization rod of about 0.7 μ m and be coated with water system black-colored resin composition obtained above, then, 160 ℃ of 60 seconds of drying, forms the first ferrous metal layer.

(formation of the second black layer)

At solvent, be that (NIPPON FINE COATINGS company system " is added the approximately acrylic acid pearl of 6 μ m of particle diameter that drying solid composition 100 mass parts with respect to coating are 2 mass parts to blacking in FLC495BLACK "), add diluent, after with Ford cup No.4, viscosity being adjusted to about 50 seconds, being coated with painting device on the surface of above-mentioned the first black layer according to the about dry film thickness utilization rod of 4.0 μ m is coated with, then, 230 ℃ of 60 seconds of drying, toasted, form the second black layer, obtain film black coated metal plate.In addition, 1.5 times of the thickness that the particle diameter of the acrylic acid pearl of interpolation is the second black layer.

By only forming L value and the b value in the stage of the first black layer, the L value of ferrous metal plate that is formed with the second black layer on the first black layer and b value and processability in each film black coated metal plate of gained, be shown in Table 5.

[table 5]

[embodiment 3]

(formation of the first black layer)

The preparation of<water system black-colored resin composition >

Use the raw material identical with embodiment 1 (surface-treated carbon black, adhesive resin (resin emulsion is with the polymer of Han oxazolinyl), cataloid, silane coupler), change in such a way each use amount, in addition, prepare similarly to Example 1 the water system black-colored resin composition.Wherein the polymer of ， Han oxazolinyl changes to the material shown in the part table.

That is, the use amount of silane coupler is fixed as identical with embodiment 1 (silane coupler: be 12.5 mass parts with respect to all solids composition 100 mass parts); It is 20 quality % that the containing ratio that the use amount of cataloid changes to its solid constituent reaches in all solids composition 100 quality % of composition; The containing ratio that the use amount of surface-treated carbon black changes to its solid constituent is 20 quality % in all solids composition 100 quality % of composition; It is 60 quality % that the containing ratio that the use amount of adhesive resin (resin emulsion is with the polymer of Han oxazolinyl) changes to its solid constituent reaches in all solids composition 100 quality % of composition; The containing ratio of the solid constituent of the polymer of Han oxazolinyl changes to the value shown in table 6 (so the containing ratio of resin emulsion is " containing ratio of the polymer of 60 quality %-Han oxazolinyls ").

The application of<water system black-colored resin composition >

(formation of the second black layer)

At solvent, be to add the approximately acrylic acid pearl of 6 μ m of particle diameter that drying solid composition 100 mass parts with respect to coating are 2 mass parts in blacking (NIPPON FINE COATINGS company's system " FLC495BLACK "), add diluent, after with Ford cup No.4, viscosity being adjusted to about 50 seconds, being coated with painting device on the surface of above-mentioned the first black layer according to the about dry film thickness utilization rod of 4.0 μ m is coated with, then, 230 ℃ of 60 seconds of drying, toasted, form the second black layer, obtain film black coated metal plate.In addition, 1.5 times of the thickness that the particle diameter of the acrylic acid pearl of interpolation is the second black layer.

By only forming corrosion resistance and the resistance to water in the stage of the first black layer in each film black coated metal plate of gained, degree of blackness (L value), corrosion resistance and the processability that is formed with the ferrous metal plate of the second black layer on the first black layer is shown in Table 6.

[table 6]

* 1: shared ratio in all solids composition 100 quality % of composition

* 2: with respect to the mass parts of resin emulsion 100 mass parts

A:EPOCROS " K-2030E " (Japanese catalyst company system, styrene/acrylic are resin)

B:EPOCROS " K-2020E " (Japanese catalyst company system, styrene/acrylic are resin)

C:EPOCROS " K-2010E " (Japanese catalyst company system, styrene/acrylic are resin)

[embodiment 4]

(formation of the first black layer)

The preparation of<water system black-colored resin composition >

The polymer of Han oxazolinyl is changed to zirconium carbonate ammonium (Japanese light metal (strain) system " BAYCOURT20 "; Solid constituent 20 quality %), in addition, use the raw material identical with embodiment 1 (surface-treated carbon black, adhesive resin (resin emulsion), cataloid, silane coupler), and change in such a way each use amount, in addition, prepare similarly to Example 1 the water system black-colored resin composition.

That is, the use amount of silane coupler is fixed as identical with embodiment 1 (silane coupler: be 12.5 mass parts with respect to all solids composition 100 mass parts); It is 20 quality % that the containing ratio that the use amount of cataloid changes to its solid constituent reaches in all solids composition 100 quality % of composition; It is 20 quality % that the containing ratio that the use amount of surface-treated carbon black changes to its solid constituent reaches in all solids composition 100 quality % of composition; It is 60 quality % that the containing ratio that the use amount of adhesive resin (resin emulsion and zirconium carbonate ammonium) changes to its solid constituent reaches in all solids composition 100 quality % of composition; The containing ratio of the solid constituent of zirconium carbonate ammonium changes to the value shown in table 7 (so the containing ratio of resin emulsion becomes " containing ratios of 60 quality %-zirconium carbonate ammoniums ").

The application of<water system black-colored resin composition >

(formation of the second black layer)

At solvent, be to add the approximately acrylic acid pearl of 6 μ m of particle diameter that drying solid composition 100 mass parts with respect to coating are 2 mass parts in blacking (NIPPON FINE COATINGS company's system " FLC6080BLACK "), add diluent, after with Ford cup No.4, viscosity being adjusted to about 50 seconds, being coated with painting device on the surface of above-mentioned the first black layer according to the about dry film thickness utilization rod of 4.0 μ m is coated with, then, 230 ℃ of 60 seconds of drying, toasted, form the second black layer, obtain film black coated metal plate.In addition, 1.5 times of the thickness that the particle diameter of the acrylic acid pearl of interpolation is the second black layer.

By only forming corrosion resistance and the resistance to water in the stage of the first black layer in each film black coated metal plate of gained, degree of blackness (L value), corrosion resistance, processability, wear-resisting sand rubber abrasivity and the resistance to marring that is formed with the ferrous metal plate of the second black layer on the first black layer is shown in Table 7.

[table 7]

* 1: shared ratio in all solids composition 100 quality % of composition

* 2: with respect to the mass parts of resin emulsion 100 mass parts

[embodiment 5, comparative example 5]

(formation of the first black layer)

Use the water system black-colored resin composition (containing ratio of the solid constituent of zirconium carbonate ammonium is 5 quality %) obtained in embodiment 4-4, utilize rod to be coated with painting device, according to the about dry film thickness of 0.7 μ m, it is coated to the surface of the base treatment metallic plate EG obtained in embodiment 1, then, 160 ℃ of 60 seconds of drying, form the first ferrous metal layer.

(formation of the second black layer)

At solvent, be to add the approximately acrylic acid pearl of 6 μ m of particle diameter that drying solid composition 100 mass parts with respect to coating are 2 mass parts in blacking (NIPPON FINE COATINGS company's system " FLC6080BLACK "), add diluent, after with Ford cup No.4, viscosity being adjusted to about 50 seconds, on the surface of above-mentioned the first black layer, utilizing rod to be coated with painting device is coated with according to the dry film thickness shown in table 8, then, 230 ℃ of 60 seconds of drying, toasted, form the second black layer, obtain film black coated metal plate.In addition, 0.6～3 times of the thickness that the particle diameter of the acrylic acid pearl of interpolation is the second black layer.

Degree of blackness (L value), corrosion resistance, processability, wear-resisting sand rubber abrasivity and the resistance to marring of each film black coated metal plate (being formed with the ferrous metal plate of the second black layer on the first black layer) of gained are shown in Table 8.

[table 8]

[embodiment 6]

(formation of the first black layer)

The preparation of<water system black-colored resin composition >

That is, the use amount of silane coupler is fixed as identical with embodiment 1 (silane coupler: be 12.5 mass parts with respect to all solids composition 100 mass parts); It is 20 quality % that the containing ratio that the use amount of surface-treated carbon black changes to its solid constituent reaches in all solids composition 100 quality % of composition; The containing ratio that the use amount of cataloid changes to its solid constituent reaches the value shown in table 9; The containing ratio that the use amount of adhesive resin (resin emulsion is with the polymer of Han oxazolinyl) changes to its solid constituent (resin emulsion is with the solid constituent summation of the polymer of Han oxazolinyl) reaches the value shown in table 9.In addition, resin emulsion is with the polymer of Han oxazolinyl is fixed as the polymer that the quality ratio of each solid constituent reaches resin emulsion ∶ Han oxazolinyl=95: 5.

The application of<water system black-colored resin composition >

(formation of the second black layer)

By only having formed corrosion resistance and the resistance to water in the stage of the first black layer in each film black coated metal plate of gained, degree of blackness (L value), corrosion resistance, processability and the resistance to marring that is formed with the ferrous metal plate of the second black layer on the first black layer is shown in Table 9.

[table 9]

[embodiment 7]

(formation of the first black layer)

The preparation of<water system black-colored resin composition >

That is, the use amount of silane coupler changes to its content to reach with respect to all solids composition 100 mass parts is the amount shown in table 10; It is 20 quality % that the containing ratio that the use amount of cataloid changes to its solid constituent reaches in all solids composition 100 quality % of composition; It is 20 quality % that the containing ratio that the use amount of surface-treated carbon black changes to its solid constituent reaches in all solids composition 100 quality % of composition; It is 60 quality % that the containing ratio that the use amount of adhesive resin (resin emulsion is with the polymer of Han oxazolinyl) changes to its solid constituent reaches in all solids composition 100 quality % of composition.In addition, resin emulsion is with the polymer of Han oxazolinyl is fixed as the polymer that the quality ratio of each solid constituent reaches resin emulsion ∶ Han oxazolinyl=95: 5.

The application of<water system black-colored resin composition >

(formation of the second black layer)

By only having formed corrosion resistance and the resistance to water in the stage of the first black layer in each film black coated metal plate of gained, corrosion resistance, processability and the resistance to marring that is formed with the ferrous metal plate of the second black layer on the first black layer is shown in Table 10.

[table 10]

※ is with respect to the mass parts of solid constituent summation 100 mass parts of surface-treated carbon black, adhesive resin and cataloid

[embodiment 8]

(formation of the first black layer)

The preparation of<water system black-colored resin composition >

That is, the use amount of silane coupler is fixed as identical with embodiment 1 (silane coupler: be 12.5 mass parts with respect to all solids composition 100 mass parts); It is 20 quality % that the containing ratio that the use amount of surface-treated carbon black changes to its solid constituent reaches in all solids composition 100 quality % of composition; It is 20 quality % that the containing ratio that the use amount of cataloid changes to its solid constituent reaches in all solids composition 100 quality % of composition; It is 60 quality % that the containing ratio that the use amount of adhesive resin (resin emulsion is with the polymer of Han oxazolinyl) changes to its solid constituent (resin emulsion is with the solid constituent summation of the polymer of Han oxazolinyl) reaches in all solids composition 100 quality % of composition.In addition, resin emulsion is with the polymer of Han oxazolinyl is fixed as the polymer that the quality ratio of each solid constituent reaches resin emulsion ∶ Han oxazolinyl=95: 5.

The application of<water system black-colored resin composition >

(formation of the second black layer)

At solvent, it is the acrylic acid pearl of adding particle diameter (the approximately scope of 2～14 μ m) shown in the table 11 that drying solid composition 100 mass parts with respect to coating are 2 mass parts in blacking (NIPPON FINE COATINGS company's system " FLC495BLACK "), add diluent, after with Ford cup No.4, viscosity being adjusted to about 50 seconds, on the surface of above-mentioned the first black layer, utilize rod painting painting device to be coated with according to the dry film thickness (the approximately scope of 2.0～7.0 μ m) of table 11, then, 230 ℃ of 60 seconds of drying, toasted, form the second black layer, obtain film black coated metal plate.

The evaluation of concavo-convex outward appearance in each film black coated metal plate of gained is shown in Table 11.

[table 11]

Claims

1. a film black coated metal plate, its at least one face at metallic plate is laminated with the first black layer of thickness 0.4～1.0 μ m formed by the water system black-colored resin composition, and on described the first black layer, to be laminated with by solvent be the second black layer of thickness 1.4～9 μ m that form of blacking

Described water system black-colored resin composition has contained with the aqueous resin coating surperficial surface-treated carbon black.

2. film black coated metal plate according to claim 1, wherein,

In all solids composition 100 quality % of described water system black-colored resin composition, it is 10～40 quality % that described surface-treated carbon black be take the containing ratio of solid component meter.

3. film black coated metal plate according to claim 1, wherein,

The degree of blackness on described the first black layer surface is that the L value is below 25 and the b value is below 3.

4. film black coated metal plate according to claim 1, wherein,

Described solvent is that blacking contains resin particle, and the particle diameter of described resin particle is below 14 μ m, and the particle diameter of described resin particle is more than t μ m and below 2t μ m when the thickness by described the second black layer is made as t μ m.

5. film black coated metal plate according to claim 1, wherein,

Described solvent is that blacking contains the following resin particle of particle diameter 14 μ m, and the degree of blackness that is laminated in the second black layer surface on described the first black layer is that the L value is below 20 and the b value is below 1.5.

6. according to the described film black of any one in claim 1～5 coated metal plate, wherein,

Described water system black-colored resin composition contains adhesive resin, and described adhesive resin comprises alkene-α, beta-unsaturated carboxylic acid copolymer, α, and beta-unsaturated carboxylic acid polymer and be selected from the polymer of Han oxazolinyl and the crosslinking agent of zirconium carbonate ammonium,

With respect to alkene-α, beta-unsaturated carboxylic acid copolymer and α, summation 100 mass parts of beta-unsaturated carboxylic acid polymer, the content of described crosslinking agent is 2～19 mass parts,

The containing ratio of described adhesive resin is 30～85 quality % in all solids composition 100 quality % of water system black-colored resin composition.

7. film black coated metal plate according to claim 1, wherein,

Described water system black-colored resin composition also contains cataloid, in all solids composition 100 quality % of the containing ratio of described cataloid in described water system black-colored resin composition, is 5～30 quality %.

8. film black coated metal plate according to claim 7, wherein, with respect to solid constituent summation 100 mass parts of described surface-treated carbon black, described adhesive resin and described cataloid, described water system black-colored resin composition also contains the silane coupler of 5～25 mass parts.