CN103481584B

CN103481584B - Thin-black-layer-coametal metal sheet

Info

Publication number: CN103481584B
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: 2016-08-10
Anticipated expiration: 2033-06-05
Also published as: KR20130138684A; KR101500838B1; CN103481584A

Abstract

The Thin-black-layer-coametal metal sheet of the present invention is laminated with the first black layer of thickness 0.4～1.0 μm formed by water system black-colored resin composition at least one side of metallic plate, and on this first black layer, it is laminated with the second black layer of thickness 1.4～9 μm formed by solvent system blacking, wherein, water system black-colored resin composition contains the surface-treated carbon black being coated to surface with aqueous resin.Total coated film of the Thin-black-layer-coametal metal sheet of the present invention is the thinnest, and embodies good degree of blackness, without bad order.

Description

Thin-black-layer-coametal metal sheet

Technical field

The present invention relates to the Thin-black-layer-coametal metal sheet with good degree of blackness.

Background technology

In the past, as the bonnet of the slim TV of LCD TV and plasma television etc., use black plastic shell, closely Nian Lai, from giving the viewpoints such as electric conductivity (corresponding electromagnetic wave), the most gradually instead of with black coating film application to inner face side Steel plate (PCM: pre-coated metal).

In existing coated steel plate (PCM), in order to hide raw sheet, (plated steel sheet, hot-dip galvanized steel sheet, alloying are molten Melt galvanized steel plain sheet etc.) outward appearance and gloss and make black present, need the coating coating containing the black pigment such as white carbon black, and make it Thickness reaches (adhesion amount: about 12g/m about 10 μm²), and then as required at this black coating film layer (top coat: top coat (adhesion amount: about 5g/m about thickness 3 μm is set under layer)²) for giving priming coat (the プラ of processability, corrosion resistance イマ mono-U one ト).So in conventional PCM, generally the gross thickness of top coat and priming coat is set and be about 10～20 μm Thick.But, if the thickness of film is the thickest, then the usage amount of coating increases, the most elongated for the time of application and baking, therefore Manufacturing cost rises.Therefore, especially in recent years, along with intensifying of the competition in slim TV market, improve compression and reduce The requirement of manufacturing cost, wherein, especially requires the filming of film in PCM.

As the coated steel plate (PCM) turning to target with thin film, it is proposed that such as form primary coat on a face of steel plate (lower り) film also forms the painting the most eventually of the organic resin epithelium containing phosphorus flaky substance (upper り) film on this primary coat film The coated steel plate that total film thickness is below 10 μm (Japanese Unexamined Patent Publication 2008-55774).Additionally, also proposed a kind of coated steel plate, It possesses outermost layer film containing coloring pigment and containing coloring pigment and as the porous silica of rust resisting pigment Lower coating film, the thickness of outermost layer film is more than 2 μm, and the thickness of lower coating film is more than 2 μm, and the thickness of total film layer is 10 (Japanese Unexamined Patent Publication 2010-115902) below μm.

But, the coating thickness of usual PCM is the thinnest, and degree of blackness more reduces, and there is the outward appearance presenting dark brown color strength (b value is big) Or present the tendency of the outward appearance of greyish black color strength (L-value is big).In the coated steel plate of above-mentioned two prior art, although manage to pass through Improve degree of blackness containing modes such as phosphorus flaky substances, but present situation be not yet reach can be of great satisfaction degree of blackness (such as L-value is less than 20).

Therefore, the present inventor etc. proposes a kind of coated steel plate, even if also being able to body as the thickness of black coating film is less The now coated steel plate of good degree of blackness, it is black that this film steel plate has by the thickness formed with black combination about 0.3～1.5 μm Color epithelium, this black combination contains surface-treated carbon black (the Japanese Unexamined Patent Publication 2011-224972 being coated to surface with water-soluble resin Number).This coated steel plate is capable of the degree of blackness of the such excellent level of L-value less than 20, and coated film is the thinnest, is about 0.3～1.5 μm, therefore from the viewpoint of cutting down manufacturing cost, highly beneficial.But, on the other hand, in actual manufacture Time, owing to black epithelium is the thinnest, because producing the caused paint film defects such as the grit type pit of thus crawling and production line, hold Easily cause bad order, the design of coated steel plate can be damaged.The most in the prior art, by arranging on black epithelium Transparent epithelium, thus embody the characteristic such as corrosion resistance and resistance to marring, but if there is above-mentioned transparent epithelium, then can encourage coating , there is the tendency easily becoming more obvious in the paint film defects such as inequality, grit type pit.

Summary of the invention

The present invention completes in view of the foregoing, its object is to, it is provided that total coated film is the thinnest and embodies good black Colourity, Thin-black-layer-coametal metal sheet without bad order.

Can solve the problem that the Thin-black-layer-coametal metal sheet of the present invention of above-mentioned problem is laminated with at least one side of metallic plate First black layer of thickness 0.4～1.0 μm formed by water system black-colored resin composition, and be laminated with on this first black layer Second black layer of thickness 1.4～9 μm formed by solvent system blacking, above-mentioned water system black-colored resin composition contains with water It it is the surface-treated carbon black on resin-coated surface.

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

In a preferred embodiment of the invention, the degree of blackness (L-value) on above-mentioned first black layer surface is less than 25 and b values It is less than 3.

In the present invention, preferably: above-mentioned solvent system blacking contains resin particle, the particle diameter of this resin particle be 14 μm with Under, and the particle diameter of above-mentioned resin particle is more than t (μm) and 2t (μm) when the thickness of above-mentioned second black layer is set to t (μm) Below.

In a preferred embodiment of the invention, above-mentioned solvent system blacking contains the resin particle of below particle diameter 14 μm Son, the degree of blackness (L-value) on the second black layer surface being laminated on above-mentioned first black layer be less than 20 and b values be less than 1.5.

In the present invention, preferably: above-mentioned water system black-colored resin composition contains adhesive resin, and this adhesive resin comprises alkene Hydrocarbon-α, beta-unsaturated carboxylic acid copolymer, α, beta-unsaturated carboxylic acid polymer and selected from polymer containing oxazoline base and zirconium carbonate The cross-linking agent of ammonium, the content of above-mentioned cross-linking agent gathers relative to alkene-α, beta-unsaturated carboxylic acid copolymer and α, beta-unsaturated carboxylic acid Summation 100 mass parts of compound is 2～19 mass parts, and the containing ratio of above-mentioned adhesive resin is at water system black-colored resin composition All solids composition 100 mass % is 30～85 mass %.

In the present invention, preferably: above-mentioned water system black-colored resin composition possibly together with silica sol, this silica sol Containing ratio all solids composition 100 mass % in above-mentioned water system black-colored resin composition in be 5～30 mass %.

In the present invention, preferably: relative to above-mentioned surface-treated carbon black, above-mentioned adhesive resin and above-mentioned silica sol Solid constituent summation 100 mass parts, above-mentioned water system black-colored resin composition is possibly together with the silane coupler of 5～25 mass parts.

It addition, in this specification, " all solids composition in water system black-colored resin composition " refers to that above-mentioned surface processes The solid constituent summation of white carbon black, above-mentioned adhesive resin and above-mentioned silica sol.

In accordance with the invention it is possible to provide a kind of Thin-black-layer-coametal metal sheet, its metallic plate at least one side respectively with The thickness of regulation is laminated with the first black layer formed by water system black-colored resin composition and is formed by solvent system blacking Second black layer, above-mentioned water system black-colored resin composition contains the surface-treated carbon black being coated to surface with aqueous resin, is therefore Make that total coated film is the thinnest also can embody good degree of blackness, and the paint film defect such as crawling, grit type pit is also difficult to Become notable, there is good outward appearance.

Accompanying drawing explanation

Fig. 1 is in the Thin-black-layer-coametal metal sheet (using base treatment metallic plate EG) representing embodiment 1 and comparative example 1 The figure of relation of degree of blackness (L-value) of thickness and this black metal sheet of the second black layer.

Fig. 2 is in the Thin-black-layer-coametal metal sheet (using base treatment metallic plate GI) representing embodiment 1 and comparative example 1 The figure of relation of degree of blackness (L-value) of thickness and this black metal sheet of the second black layer.

Fig. 3 is in the Thin-black-layer-coametal metal sheet (using base treatment metallic plate EG) representing embodiment 1 and comparative example 1 The figure of relation of b value of thickness and this black metal sheet of the second black layer.

Fig. 4 is in the Thin-black-layer-coametal metal sheet (using base treatment metallic plate GI) representing embodiment 1 and comparative example 1 The figure of relation of b value of thickness and this black metal sheet of the second black layer.

Detailed description of the invention

The Thin-black-layer-coametal metal sheet (following, to be sometimes also referred to as " black metal sheet ") of the present invention is at metallic plate extremely Few one side is laminated with the first black layer formed by water system black-colored resin composition, and is laminated with by molten on this first black layer The second black layer that agent system blacking is formed, above-mentioned water system black-colored resin composition contains the table being coated to surface with aqueous resin Face treated carbon black.Hereinafter, the black metal sheet of the present invention is described in detail.

(metallic plate)

The metallic plate used as the present invention, as long as the metallic plate that can use as the raw sheet of pre-coated metal, It is not particularly limited.Such as, except non-plating cold-rolled steel sheet, hot-dip galvanized steel sheet (GI), alloy galvanized steel plate (GA), Beyond the steel plates such as plated steel sheet (EG), also can enumerate aluminium sheet and titanium plate etc..Wherein, preferred molten galvanized steel plain sheet (GI), plating Zinc steel plate (EG), aluminium sheet and titanium plate.

The preferably at least one side at above-mentioned metallic plate forms basal layer by base treatment in advance.If such as aftermentioned The metal sheet surface of side of formation the first black layer there is the chemical conversion skin membrane (basal layer) formed by base treatment, then Improve metallic plate and the adhesion of the first black layer.

As chemical conversion skin membrane (basal layer), organic coating layer, inorganic skin membrane, phosphate coating layer, chromic acid can be enumerated Salt skin membrane etc., wherein, preferably organic coating layer, inorganic skin membrane, phosphate coating layer.As organic coating layer, suitably select Select and use such as polyethylene-based resin, epoxy system resin, acrylic resin, polyurethane series resin, polyester based resin, fluorine system tree Fat and their mixture, copolymer, modified resin etc..Additionally, for the purpose of improving corrosion resistance, it is also possible to have at this Machine epithelium adds silica gel, silica sol etc.；Or for the purpose of improving the processability after film applies, it is also possible to trace Add various paraffin component；Or for the purpose of improving film adhesion, it is possible to add silane coupler.As inorganic skin membrane, Silicate skin membrane etc. can be enumerated.In addition it is also possible to add phosphoric acid and fluoride in this silicate skin membrane.

The adhesion amount of chemical conversion skin membrane (basal layer) does not has special provision, as long as such as organic coating layer and inorganic epithelium Layer, goes out from the viewpoint of corrosion resistance, is preferably calculated as 50mg/m with dry mass²Above.But, if it exceeds 150mg/m², the most resistance to Corrosive to improve effect saturated, and manufacturing cost rises.

As being formed with the metallic plate of basal layer and particularly preferred form, for example, will be containing aluminium dihydrogen phosphate, colloid Silicon dioxide and polyacrylic base treatment compositions (following, to be sometimes also referred to as " particular substrate treatment compositions ") coating On zinc-plated metallic plate and make its be dried obtained by metallic plate.If above-mentioned particular substrate treatment compositions is coated zinc-plated Metallic plate, then metal sheet surface is etched by the hydrion from aluminium dihydrogen phosphate, and by from the aluminum of aluminium dihydrogen phosphate Ion and the interaction of silica sol, it is possible to form the slightly solubility skin that the adhesion with aftermentioned first black layer is excellent Film, as a result of which it is, the epithelium adhesion of (after stretching/contraction distortion) improves after bending machining and extrusion process, it is possible to realize resistance to Corrosivity and the fissility of resistance to adhesive tape significantly improve.

In above-mentioned particular substrate treatment compositions, the content ratio of aluminium dihydrogen phosphate and silica sol is with solid constituent Than meter be preferably aluminium dihydrogen phosphate: silica sol (mass ratio)=30: 70～70: 30 (more preferably 35: 65～65: 35, enter One step preferably 45: 55～65: 35).If silica sol is more than aforementioned proportion, then makes film and reduce and be difficult to form substrate Layer, it is difficult to obtain corrosion resistance and the raising effect of the adhesion with whole coating, and then the adhesion also step-down to metallic plate, add It is likely to occur film after work to peel off.On the other hand, if silica sol is fewer than aforementioned proportion, then the ratio of aluminium dihydrogen phosphate Example increases, and does not reacts the ratio increase that the remaining aluminium dihydrogen phosphate of (etching) dissolves in water with metallic plate, is being coated with Producing corrosion under film, corrosion resistance reduces.

Preferably containing consolidating relative to aluminium dihydrogen phosphate and silica sol in above-mentioned particular substrate treatment compositions Body composition summation 100 mass parts is the polyacrylic acid of 0.1～5 mass parts (more than more preferably 0.2 mass parts, below 3 mass parts). Think that polyacrylic acid plays moderate control and implements the reaction (erosion of zinc-plated etc. metal sheet surface (zinc-plated) and aluminium dihydrogen phosphate Carve) effect, if less than above-mentioned scope, then etch and occur superfluously, therefore result is that corrosion resistance is likely to decrease, if Exceed above-mentioned scope, make etching insufficient the most on the contrary, it is impossible to be adequately formed and generated by aluminium dihydrogen phosphate and silica sol Slightly solubility epithelium, it is difficult to obtain the raising effect of adhesion and corrosion resistance.

Preferably possibly together with relative to aluminium dihydrogen phosphate and silica sol in above-mentioned particular substrate treatment compositions Solid constituent summation 100 mass parts is that the silane of 3～15 mass parts (more than more preferably 5 mass parts, below 12.5 mass parts) is even Connection agent.If silane coupler is less than above-mentioned scope, then to whole coating and the adhesion of metallic plate and the raising of corrosion resistance Effect has insufficient tendency, under harsher processing conditions, has the situation that epithelium is peeled off of causing, otherwise, even more than upper State scope, corrosion resistance and adhesion also it is possible to reduce.

(the first black layer)

First black layer of at least one side being laminated in above-mentioned metallic plate is formed by water system black-colored resin composition.

<surface-treated carbon black>

Water system black-colored resin composition is containing being coated to the surface-treated carbon black on surface using aqueous resin as black pigment Resin combination.When the common white carbon black not being coated to by aqueous resin on surface mixes with adhesive resin described later, because of pH The change of value and the intermiscibility of adhesive resin etc. and easily cause secondary coagulation, its result makes tinting strength, tinting power reduce, if with Aqueous resin is coated to the surface-treated carbon black on surface when mixing with adhesive resin, plays excellent dispersibility, it is difficult to occur two Secondary coagulation, the most as described later, even if the first black layer thickness formed with water system black-colored resin composition relatively thin also can be sent out Shoot sufficiently high degree of blackness.

It addition, in this specification, " being coated to the surface-treated carbon black on surface with aqueous resin " is not only with aqueous resin quilt Cover the form of white carbon black all surfaces, also include the form of a part for coating white carbon black.

As constituting the white carbon black of 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..As the aqueous resin on the surface of above-mentioned coating white carbon black, as long as white carbon black can be made to be difficult to The aqueous resin of secondary coagulation, then there is no particular limitation, can enumerate such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, water Soluble acrylic resin, polyacrylamide, polyvinylpyridine, polyacrylic acid etc..The amount (amount of coating) of aqueous resin relative to White carbon black 100 mass parts is preferably below more than 5 mass parts and 380 mass parts.Additionally, one can also be entered on surface-treated carbon black Step attaching surface activating agent.Thereby, it is possible to suppress the secondary coagulation of the surface-treated carbon black in adhesive resin further.As Above-mentioned surfactant, can enumerate known anion system, nonionic system, the surfactant of cation system.

As above-mentioned surface-treated carbon black, preferably by the ink droplet (prepared Chinese ink) of the high concentration used in such as calligraphy.Ink droplet For the aqueous dispersion containing surface-treated carbon black, such as, for make the oil of petroleum or coal measures in high-temperature gas the completeest The surface of the amorphous furnace black of the manufactures such as the oven process of full burning is coated to aqueous resin, is added as needed on the anti-of glycol system Freeze agent and preservative, carry out mixing and slurried, thus manufacture ink droplet.As ink droplet, it is possible to use the most commercially available prepared Chinese ink (such as Co., Ltd. Wu bamboo " super thick ink ink droplet BA-8 " etc.).It addition, surface-treated carbon black or its aqueous dispersion can also Make according to known method (such as Japanese Unexamined Patent Publication 7-188597 publication and Japanese Unexamined Patent Publication 6-234946 publication) Standby.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 mass % of water system black-colored resin composition, surface-treated carbon black (is using surface Be its solid constituent during the aqueous dispersion of treated carbon black) containing ratio preferably comprise more than 10 mass % (more preferably 20 matter Amount more than %), preferably comprise below 40 mass % (below more preferably 30 mass %).Containing ratio at surface-treated carbon black is less than During 10 mass %, L-value and the b value of the first black layer uprise, and its result makes the L of black metal sheet obtained by stacking the second black layer Value and b value also uprise, and in dark umber, have the tendency (with reference to Fig. 1～4) that can not embody abundant degree of blackness.On the other hand, on surface When the containing ratio of treated carbon black is more than 40 mass %, the resinous principle as binding agent contained in compositions reduces relatively, makes The adhesion step-down of the first black layer and the second black layer, or compositions becomes easy gelation and makes water system black resin group The aqueous stability of compound is likely to decrease.If the containing ratio of surface-treated carbon black is in above-mentioned scope, even if then surface processes White carbon black mix with adhesive resin be also difficult to occur secondary coagulation, it is possible to keep higher dispersion stabilization.

Water system black-colored resin composition usually contains for fixing surface in the first black layer formed by said composition The adhesive resin of treated carbon black.As adhesive resin, as long as the adhesive resin of surface-treated carbon black can be fixed, then There is no particular limitation for its kind, but, can the secondary coagulation of surface-treated carbon black in composite inhibiting, energy effectively Access the aspect of the aqueous stability of excellence, preferably polyethylene resin, polyurethane resin etc..Particularly preferably polyethylene tree Fat.Adhesive resin may be used alone, or two or more kinds may be used in combination.

Above-mentioned polyvinyl resin preferably by alkene-α, beta-unsaturated carboxylic acid copolymer (following, be sometimes referred to as that " alkene-acid is common Polymers "), α, beta-unsaturated carboxylic acid polymer (following, be sometimes referred to as " carboxylic acid polyalcohol ") and selected from the polymerization containing oxazoline base The cross-linking agent of thing and zirconium carbonate ammonium is constituted.Alkene-acid copolymer and carboxylic acid polyalcohol are without compromising on water system black-colored resin composition In the dispersion stabilization of surface-treated carbon black, make the compatibility with this white carbon black improve, and make the first black layer and metallic plate Adhesion improve.Additionally, be selected from cross-linking agent and alkene-acid copolymer and the carboxylic of the polymer containing oxazoline base and zirconium carbonate ammonium Acid polymer cross-links, and forms fine and close and stone black layer, therefore makes the resistance to marring of the second black layer improve.Especially carbonic acid The reactive height of zirconium ammonium, mobility when making film is the most excellent, and therefore the effect as cross-linking agent is bigger, has given play to wear-resisting sand rubber The effect that abrasivity is also excellent.

It addition, the what is called of the present invention " alkene-acid copolymer " refers to alkene and α, the copolymer of beta-unsaturated carboxylic acid, preferably Construction unit from alkene accounts for more than 50 mass % in the copolymer, and (that is, from α, the construction unit of beta-unsaturated carboxylic acid exists Below 50 mass %) copolymer.Additionally, so-called " carboxylic acid polyalcohol " refers to use α, beta-unsaturated carboxylic acid is that monomer gathers The polymer (also including copolymer) closed and obtain, is preferred from α, and the construction unit of beta-unsaturated carboxylic acid accounts for 90 in the polymer Carboxylic acid polyalcohol more than quality %.

Above-mentioned alkene-acid copolymer can be by making alkene and α, beta-unsaturated carboxylic acid copolymerization system by known method Make, it is also possible to commercially available.Alkene-acid copolymer can use 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, third Alkene etc., more preferably ethylene.For alkene-acid copolymer, olefin unit can be only from the alkene of a kind, it is also possible to 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 lift Go out the monocarboxylic acids such as such as acrylic acid, methacrylic acid .beta.-methylacrylic acid, iso-crotonic acid；The dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid Deng.Wherein, preferred acrylic acid.For alkene-acid copolymer, α, the construction unit of beta-unsaturated carboxylic acid can be only from 1 Plant α, beta-unsaturated carboxylic acid, it is also possible to from two or more α, beta-unsaturated carboxylic acid.

α in alkene-acid copolymer, beta-unsaturated carboxylic acid unit has the adhesion improving the first black layer with metallic plate Effect, in order to effectively play above-mentioned effect, the α in copolymer, beta-unsaturated carboxylic acid quantity of units be preferably 5 mass % with On, more than more preferably 10 mass %.On the other hand, the α in copolymer, the upper limit of beta-unsaturated carboxylic acid quantity of units the most above-mentioned that Sample is 50 mass %, from the viewpoint of corrosion resistance, below particularly preferably 30 mass %, more preferably 25 mass % with Under.

Above-mentioned alkene-acid copolymer can not to suppression surface-treated carbon black secondary coagulation etc. bring dysgenic In the range of there is the construction unit from other monomer.In alkene-acid copolymer, excellent from the construction unit amount of other monomer Electing below 10 mass % as, below more preferably 5 mass %, most preferred alkene-acid copolymer is only by alkene-and α, β-and no Alkene-acid copolymer that saturated carboxylic acid is constituted.As preferred alkene-acid copolymer, ethylene-acrylic acid copolymer can be enumerated.

The weight average molecular weight (Mw) of above-mentioned alkene-acid copolymer is preferably 1,000～10 ten thousand with polystyrene conversion, more excellent Elect 3,000～7 ten thousand as, more preferably 5,000～3 ten thousand.This Mw can utilize the GPC that polystyrene is used as standard to survey Fixed.

As above-mentioned carboxylic acid polyalcohol, one kind or two or more α can be enumerated, the homopolymer of beta-unsaturated carboxylic acid or copolymerization Thing or further copolymerization have the copolymer of other monomer (except alkene).Such carboxylic acid polyalcohol can be with known Method manufacture, it is also possible to commercially available.Carboxylic acid polyalcohol can use 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 above-mentioned alkene- The material that uses in the synthesis of acid copolymer and the α that illustrates, beta-unsaturated carboxylic acid all can use.Wherein, preferably acrylic acid and horse Come sour, more preferably maleic acid.

Carboxylic acid polyalcohol can be containing from α, and the construction unit of the monomer beyond beta-unsaturated carboxylic acid, from other monomer Construction unit amount be below 10 mass % in the polymer, below preferably 5 mass %, more preferably only by α, β-unsaturation The carboxylic acid polyalcohol that carboxylic acid is constituted.

As preferred carboxylic acid polyalcohol, such as polyacrylic acid, polymethylacrylic acid, acrylic acid-maleic acid can be enumerated common Polymers, poly etc., wherein, from the viewpoint of first black layer adhesion etc., more preferably poly.Poly Carboxyl amount many, therefore the first black layer improves further with the adhesion of metallic plate.

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

Alkene-acid copolymer in polyvinyl resin and carboxylic acid polyalcohol be preferably 1,000 containing ratio (mass ratio): 1～10: 1, more preferably 200: 1～20: 1, more preferably 100: 1～25: 1.If carboxylic acid polyalcohol containing ratio Time too low, sometimes cannot give full play to the effect combining alkene-acid copolymer with carboxylic acid polyalcohol, on the contrary, if carboxylic acid is polymerized Thing containing ratio surplus time, in compositions, alkene-acid copolymer and carboxylic acid polyalcohol occur to be separated, may uniform shape Become the first black layer.

The above-mentioned polymer containing oxazoline base has oxazoline base, and this oxazoline base is polymerized with alkene-acid copolymer, carboxylic acid The carboxyl that thing has crosslinks reaction, and thus resin is cross-linked to each other, and forms fine and close network structure.Thus first black layer Obdurability improves.

As the above-mentioned polymer containing oxazoline base, from improving the hardness of black layer and also the crisp of black layer can be improved The aspect of degree, preferably main chain comprises the polymer containing oxazoline base of styrene/acrylic, such as, commercially available product is preferably used Sino-Japan " EPOCROS (registered trade mark) " of this catalyst company.As " EPOCROS (registered trade mark) ", particularly preferred emulsion-type " EPOCROS (registered trade mark) K " series, as grade, has K-2010E (Tg:-50 DEG C), K-2020E (Tg:0 DEG C) and K- 2030E (Tg:50 DEG C).Wherein, set out at the aspect obtaining harder epithelium, most preferably " EPOCROS (registered trade mark) K- 2030E”。

For above-mentioned zirconium carbonate ammonium ((NH₄)₂[Zr(CO₃)₂(OH)₂]), when making film (film forming), carbon dioxide departs from ammonium, Become ZrO, the carboxyl of the most cross-linking aqueous adhesive resin or hydroxyl, it is possible to form epithelium.When this makes film (film forming) Reaction is able to maintain that mobility and utilizes the metal corsslinking of Zr to obtain high crosslink density (network structure), therefore forms tough skin Film.Therefore, if using zirconium carbonate ammonium, then the epithelium of composition the first black layer can be made to embody hardness and obdurability, it is possible to aobvious Write resistance to marring and the abrasion performance improving the epithelium constituting the second black layer.

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

Relative to the summation 100 mass parts (solid constituent) of alkene-acid copolymer and carboxylic acid polyalcohol, above-mentioned cross-linking agent (polymer and/or zirconium carbonate ammonium containing oxazoline base) preferably comprises more than 2 mass parts (more than more preferably 3 mass parts, further More than preferably 5 mass parts) and preferably 19 mass parts below (below more preferably 17 mass parts, further preferred 16 mass parts with Under).If the content of above-mentioned cross-linking agent is less than above-mentioned scope, then cross-linking reaction becomes insufficient, it is impossible to obtain formed skin The compactness of film, result makes the resistance to marring of the black metal sheet of gained be deteriorated sometimes.On the other hand, if above-mentioned cross-linking agent Content is more than above-mentioned scope, then the functional group's (carboxyl) making the first black layer have due to excessive cross-linking reaction reduces, and has Time can reduce with the adhesion of the second black layer and metallic plate.

In all solids composition 100 mass % of water system black-colored resin composition, the content of adhesive resin is preferably More than 30 mass % (more than more preferably 55 mass %) and below preferably 85 mass % (below more preferably 65 mass %).Viscous When the containing ratio of mixture resin is less than 30 mass %, the film of making of epithelium reduces, and may make the fixing change of surface-treated carbon black Obtain insufficient, or produce crawling and cause apparent problem.On the other hand, if the containing ratio of adhesive resin surpasses When crossing 85 mass %, the content of surface-treated carbon black reduces relatively, it is thus possible to cannot obtain sufficient degree of blackness.

Water system black-colored resin composition is preferably possibly together with silica sol.Thereby, it is possible to surface-treated carbon black is good Ground is fixed on the first black layer, and the corrosion resistance of the black metal sheet of gained and hardness can be made to improve.This its mechanism Details is still not clear, but is presumably due under corrosive environment, and silicon dioxide dissolves, dissolution, produces the cushioning effect of pH With passive state epithelium formation effect.And then, if containing silica sol, the most also confirmed for preventing water system black resin group The compound depressions when being coated with/being dried etc. are effectively.

As silica sol, there is no particular limitation, from the dispersibility water system black-colored resin composition and resistance to From the viewpoint of corrosivity raising effects etc., preferable particle size is the silica sol of 4～20nm, specifically, can enumerate grain The silica sol (commercially available product, " SNOWTEX (registered trade mark) XS " of Nissan Chemical company) in footpath 4～6nm, particle diameter 8～ The silica sol (commercially available product, " SNOWTEX (registered trade mark) S " of Nissan Chemical company) of 11nm, particle diameter 10～20nm Silica sol (commercially available product, " SNOWTEX (registered trade mark) 40 " of Nissan Chemical company) etc., wherein, particularly preferably " SNOWTEX (registered trade mark) XS ".

In all solids composition 100 mass % of water system black-colored resin composition, silica sol (solid constituent) Content be preferably below more than 5 mass % (more than more preferably 10 mass %) and preferably 30 mass % (more preferably 20 matter Amount below %).If the containing ratio of silica sol less than 5 mass %, the most sometimes cannot to confirm corrosion resistance, epithelium hard The raising effect of degree.On the other hand, if the containing ratio of silica sol is more than 30 mass %, then the stability of compositions becomes Difference, the most As time goes on thickening, also cannot obtain the effect improved further of corrosion resistance etc., the most not Profit.

Water system black-colored resin composition can contain silane coupler further.If containing silane coupler, then can Improve the adhesion of the first black layer and metallic plate.

As silane coupler, preferably there is at end the silane coupler of glycidoxy, such as γ-epoxy can be enumerated Propoxypropyl trimethoxy silane, γ-glycidoxypropyl diethoxy silane etc..Further preferably vinyl three (β- Methoxy ethoxy) silane.

The content of silane coupler is relative to above-mentioned surface-treated carbon black, above-mentioned adhesive resin and above-mentioned colloidal silica Solid constituent summation 100 mass parts of silicon is preferably more than 5 mass parts (more than more preferably 10 mass parts) and preferably 25 mass Below part (below more preferably 15 mass parts).Silane coupler content less than 5 mass parts time, sometimes cannot fully obtain by Add the effect that silane coupler is brought.On the other hand, if the content of silane coupler is more than 25 mass parts, then at black In metallic plate, a large amount of unreacted silane couplers of remaining, have the tendency that corrosion resistance reduces.

In water system black-colored resin composition can also do not damage in the range of effect of the present invention further Containing various additives.Such as, in the field of household appliances such as slim TV, complicated extrusion process etc. is implemented for black metal sheet Situation a lot, as the requirement performance to black metal sheet, it is desirable to processability.In this case, by water system black Resin combination adds the wax of water system, it is possible to give lubricity to the first black layer and realize the raising of processability.As water The wax of system, can enumerate " CHEMIPEARL (registered trade mark) W700 " of Mitsui Chemicals, Inc., " CHEMIPEARL (registered trade mark) W950 ", the polyethylene-based wax such as " CHEMIPEARL (registered trade mark) W900 ".

Water system black-colored resin composition can be prepared by mixing above-mentioned each composition with the ratio of regulation.Order by merging does not has There is particularly restriction, such as the most pre-when adhesive resin contains cross-linking agent (polymer or zirconium carbonate ammonium containing oxazoline base) First prepare the composition components beyond these cross-linking agent and add cross-linking agent wherein.

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

The thickness (dry film thickness) of the first black layer is more than 0.4 μm (more than preferably 0.5 μm, more than more preferably 0.6 μm) And 1.0 (below preferably 0.98 μm, below more preferably 0.9 μm) below μm.If the thickness of the first black layer is less than 0.4 μm, then The degree of blackness of the black metal sheet of the first black layer or even gained becomes insufficient, presents dark umber.On the other hand, if The thickness of one black layer is more than 1.0 μm, although then degree of blackness is excellent, it can be difficult to obtain the effect improved further of degree of blackness Really, on the other hand, application and the dry time spent are elongated so that manufacturing cost rises.If additionally, first black layer Thickness is blocked up, the most also cannot reach electric conductivity required when using in the field of household appliances such as slim TV.

The coating of water system black-colored resin composition when forming the first black layer, drying means have no particular limits, can Suitably to use known method.As the coating process of compositions, can enumerate such as stick coating method, curtain stream rubbing method, rolling method, Nebulization, spraying ring (spray ringer) method etc., wherein, from the viewpoint of cost etc., preferably stick coating method, rolling method, spray Mist is around-France.Additionally, as baking temperature, as long as the degree that black layer deteriorates will not be made because of heat, the most preferably 50 ～about 160 DEG C, more preferably about 70～140 DEG C.

First black layer has the degree of blackness of excellence, in the preferred configuration of the present invention, the black on the first black layer surface Degree (L-value) be less than 25 (preferably less than 24, further preferred less than 23) and b value be less than 3 (more preferably less than 2.6, further Preferably less than 2.1).It addition, in the present invention, L-value and b value are to utilize what the method for regulation in JISZ8722 recorded measured value Luminance index, can be measured by the method described in embodiment described later.Therefore, for the L* value that converts based on following formula and B* value, its preferred upper limit is also the scope that the higher limit from above-mentioned L-value and b value calculates.

L*=1.3632L-3.5904

B*=1.5744b-0.0380

(the second black layer)

Solvent system blacking is coated, is dried, toasts so that it is reaches the dry film thickness of regulation, thus can be with shape Become to be laminated in the second black layer on above-mentioned first black layer.By having above-mentioned second black layer, thus even with above-mentioned The thickness of the first black layer that water system black-colored resin composition is formed is as thin as above-mentioned scope, when it is formed by crawling, life Produce the grit type pit etc. of line and produce paint film defect, it is also possible to keep making black metal sheet to keep good outward appearance.

As solvent system blacking, have no particular limits, it is possible to use be used for the molten of black metal sheet all the time Agent system blacking.Solvent system blacking can be prepared by following known method, adds substrate the most in a solvent (such as melamine series is solid for resin (the such as macromolecule polyester resin etc. of molecular weight 10,000～about 20,000), firming agent Agent etc.) and rust resisting pigment as required (such as aluminum phosphate system rust resisting pigment, magnesium phosphate system rust resisting pigment, calcium silicates system prevent Rust pigment etc.), extender pigment etc., then add the white carbon black as coloring pigment and manufacture.Additionally, in commercially available product, can enumerate NIPPON FINE COATINGS company's system " FLC495BLACK ", " FLC6000BLACK ", " FLC6070BLACK ", " FLC6080BLACK ", " FLC6090BLACK ", " FLC6100BLACK ", BASF JAPAN company's system " HF1600BLACK " etc.. Solvent system blacking only can use a kind, it is also possible to and use two or more.It addition, from processability, resistance to marring, abrasion performance From the viewpoint of, the Tg of the matrix resin (such as polyester resin etc.) of solvent system blacking is preferably 15～30 DEG C.

Above-mentioned solvent system blacking preferably comprises resin particle.Thus become and there is higher degree of blackness and have good Embossed appearance and the black metal sheet of feel.If containing resin particle in the most transparent epithelium, then cannot embody good Concave-convex design.

Above-mentioned resin particle can be organic filler (such as acrylic acid pearl, styrene acrylic pearl, polyurethane pearl etc.), also Can be inorganic particulate (such as bead, silica beads etc.).Especially, from be difficult to solvent system blacking coagulation and From the standpoint of being readily available, preferably acrylic acid pearl.It addition, resin particle can only use a kind, it is also possible to and use two or more.

From the viewpoint of with the screening characteristics during coating process such as roll coater, the particle diameter of above-mentioned resin particle is preferably 14 μm Hereinafter, below more preferably 12 μm, more preferably below 10 μm.If the particle diameter of resin particle is more than 14 μm, then application Shi Keneng produces cut (Japanese: The じ draws I) etc..

Especially, when the thickness of the second black layer being set to t (μm), the particle diameter of resin particle be preferably more than t (μm) and 2t (μm) is below.If the film of the such as second layer is the thickness about 15 μm, then during the volatilization of the solvent in coating, moistening Producing the eddy current with volatilization under state in layer, resin particle moves to the surface of film, is consequently formed concavo-convex film, In the present invention, the thickness of the second black layer is relatively thin as described later, therefore cannot expect the generation of eddy current.If the second black layer The particle diameter of thickness and resin particle meet above-mentioned relation, even if then the thickness of the second black layer relatively thin also can embody good recessed Convex.

The thickness (dry film thickness) of the second black layer be more than 1.4 μm (more than preferably 1.5 μm, more than more preferably 1.6 μm, More than further preferred 2 μm, more than particularly preferred 3 μm, more than most preferably 4 μm) and preferably 9 μm below (below preferably 8 μm, Below more preferably 7 μm, below further preferred 6.5 μm, below particularly preferred 6 μm).If the thickness of the second black layer is less than 1.4 μm, then can be detrimental to outward appearance or make the degree of blackness of black metal sheet of gained become insufficient, and have abrasion, draw The weak tendency of toleration of wound.On the other hand, if the thickness of the second black layer is more than 9 μm, then application and being dried is spent Time is elongated, has and makes manufacturing cost increase or damage the tendency of bendability.It addition, contain resin at solvent system blacking During particle, the thickness (dry film thickness) of the second black layer is the thickness of the film formed by the solvent system blacking removing resin particle Degree, mensuration is the thickness of the part that there is not resin particle.

The coating of solvent system blacking when forming the second black layer, method dry, baking have no particular limits, Known method be may be appropriately used.As the coating process of coating, can enumerate as described in the formation of the first black layer Method, wherein, from the viewpoint of cost etc., preferably stick coating method, rolling method, spraying is around-France.Be dried, baking temperature is preferably Such as about 200～240 DEG C.

The black metal sheet of the present invention has the degree of blackness of excellence, in the preferred configuration of the present invention, the black of the present invention The degree of blackness (L-value) of metal sheet surface (the second black layer surface being laminated on the first black layer) is less than 20 (more preferably 19 Below, further preferred less than 18) and b value is less than 1.5 (more preferably less than 1.2, further preferred less than 1.0).It addition, this In invention, L-value and b value are the luminance index of the measured value measured by the method for regulation in JIS Z8722, can use reality described later The method described in example of executing measures.Therefore, for the L* value converted based on following formula and b* value, its preferred upper limit is also from upper State the scope that the higher limit of L-value and b value calculates.

L*=1.3632L-3.5904

B*=1.5744b-0.0380

Embodiment

Hereinafter, it is set forth in the present invention based on embodiment.But, following embodiment is not limited by the present invention, is not taking off Scope from objective aforementioned and described later carries out change and implements, and is integrally incorporated in the technical scope of the present invention.

First, below the evaluation methodology of employing in embodiment is illustrated.

(degree of blackness)

Use spectrophotometer (Japan's electricity color industry Zhu Shihui company's system " Spectrophotometer SQ2000 "), survey Determine material to be tested (be provided only with the metallic plate of the first black layer or there is the first black layer and the ferrous metal of the second black layer Plate) L-value, b value, utilize the L-value of gained, b value or based on following formula convert L* value obtained by this L-value, b value, b* value evaluate Degree of blackness.

L*=1.3632L-3.5904

B*=1.5744b-0.0380

In the present invention, for the first black layer, by L-value be less than 25 be set to qualified；For the first black layer and For two black layers (black metal sheet), L-value is that less than 20 (L* value is less than 24) are set to qualified.

(corrosion resistance (SST time))

Material to be tested (is provided only with to the metallic plate of the first black layer or has the first black layer and the second black layer Black metal sheet), implementing salt spraytest according to JIS Z2371, measuring until producing the time of 5% white rust (during SST Between), thus have rated corrosion resistance.

In the present invention, for the first black layer, by the SST time be within more than 72 hours, be set to qualified, black for first For chromatograph and the second black layer (black metal sheet), by the SST time be within more than 240 hours, be set to qualified.

(processability (T bending machining))

The material to be tested (black metal sheet) of 50 × 50mm size will be cut into, under room temperature (20 DEG C), make surface (second Black layer forms face) towards outside with vise folded bent gently, bending is to clamping same black at its bending section Till the limit of metallic plate (material to be tested), visually or with the magnifier of 10 times observe the folded bent portion after processing with or without splitting Stricture of vagina.Evaluation methodology is: the sheet number of the black metal sheet sandwiched is 0 and is set to 0T, and 1 is set to 1T, when specific surface cracks The sheet number of many 1 of sheet number is set to crackle critical (such as, 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 on sliding test device, on the surface (second of material to be tested (black metal sheet) Black layer forms side) apply load 16.5N, simultaneously with reciprocal 200 times of sliding distance about 26mm, utilize visualization parent metal Exposing of (base treatment metallic plate), it is evaluated according to following standard.

◎: the most unconfirmed expose to parent metal

Zero: confirm atomic little parent metal and expose

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

×: the length of the exposed division of parent metal is more than 2mm

(resistance to marring (pencil hardness))

For material to be tested (black metal sheet), according to JIS K5400 (1990), obtain second with pencil test machine Black layer surface does not produce the pencil hardness of scuffing.

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

Material to be tested (is provided only with the metallic plate of the first black layer or has the first black layer and the second black layer Black metal sheet) in boiling water, dipping, after 1 hour, is flowed out, by from film, the cosmetic variation that white carbon black is brought by visualization, It is evaluated according to following standard.

◎: outward appearance is unchanged

Zero: have pole minor variations

△: degree of blackness decreases (gloss reduction)

×: decolouring causes outward appearance inequality to occur

(embossed appearance)

For the surface (the second black layer forms side) of material to be tested (black metal sheet), according to following standard, according to mesh It is evaluated with feel depending on carrying out observing.

◎: presenting the black of distinctness and have the concave-convex sense of appropriateness, feel is the best

△ 1: although presenting the black of distinctness, but unconfirmed to concave-convex sense

△ 2: although presenting the black of distinctness, but concavo-convex excessive, and feel is poor

[embodiment 1, comparative example 1 ']

(making of base treatment metallic plate)

First, pure water about 952 mass parts adds acidoid silicon dioxide (Nissan Chemical company system " SNOWTEX (registered trade mark) O "；Solid constituent 20 mass %) 26.3 mass parts and aluminium dihydrogen phosphate (meter Shan chemical company system；Solid constituent 50 mass %) 19.5 mass parts, it is added to polyacrylic acid (Japan Chun Yao company system " JULIMAR (registered trade mark) AC-10- LP”；Solid constituent 100 mass %) 0.075 mass parts, then add silane coupler (chemical company of SHIN-ETSU HANTOTAI system " KBM403 "；Gu Body composition 100 mass %) 1.13 mass parts, preparation base treatment composition solution (solid component concentration is 1.7 mass %).

Then, at plated steel sheet (EG；Zn adhesion amount 20g/m²) or hot-dip galvanized steel sheet (GI；Zn adhesion amount 45g/m²) Surface and the back side, be 103mg/m according to dry mass²Mode utilize hand roller coating device coating gained base treatment group Polymer solution, is then dried 60 seconds at 120 DEG C, makes base treatment metallic plate.Hereinafter, plated steel sheet will be employed Base treatment metallic plate is set to base treatment metallic plate EG, using employ hot-dip galvanized steel sheet base treatment metallic plate as base Bottom reason metallic plate GI.

(formation of the first black layer)

In there is the autoclave of emulsifying device of band blender, thermometer, temperature controller (inner capacities 1.0L), add Ethylene-acrylic acid copolymer (Dow Chemical company's system " PRIMACOR (registered trade mark) 5990I ", from acrylic acid knot Structure unit: 20 mass %, melt index: 1300) 200.0 mass parts, poly aqueous solution (Nof Corp.'s system " NONPOL (registered trade mark) PMA-50W ", weight average molecular weight: about 1100 (polystyrene conversion), 50 mass % product) 8.0 mass Part, triethylamine 35.5 mass parts, 48%NaOH aqueous solution 6.9 mass parts (1.5 equivalent part), ready denier oil acid (broadcast mill chemical conversion Company's system " HARTALL FA3 ") 3.5 mass parts, ion exchange water 792.6 mass parts, seal, at 150 DEG C, 5 air pressure Lower high-speed stirred, after 3 hours, is cooled to 30 DEG C.Then, silane coupler (Momentive Performance is added Materials (former exabyte: GE Toshiba SILICONE) company's system " TSL8350 "；Solid constituent 100 mass %) 10.4 mass Part, 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 mass %, as adhesive resin precursor.

Then, prepared Chinese ink (Co., Ltd. Wu bamboo " super thick ink ink droplet BA-8 " as surface-treated carbon black；Solid constituent 13.5 mass %) 222 mass parts add pure water 423 mass parts while stirring, then, add as adhesive resin precursor After resin emulsion 285.0 mass parts obtained above, add silica sol (SNOWTEX (registered trade mark) XS, solid constituent 20 mass %) 50 mass parts, add silane coupler (chemical company of SHIN-ETSU HANTOTAI system " KBM403 "；Solid constituent 100 mass %) 12.5 mass parts and polymer (the Nippon Shokubai Co., Ltd's system " EPOCROS (registered trade mark) K-2030E " containing oxazoline base； Solid constituent 40 mass %) 7.5 mass parts, prepare water system black-colored resin composition.

The solid component concentration of this water system black-colored resin composition is 11.2 mass %, surface-treated carbon black (solid constituent) Containing ratio all solids composition (i.e. the consolidating of surface-treated carbon black, adhesive resin and silica sol of said composition Body composition summation (in below example too)) 100 mass % are 30 mass %, adhesive resin (resin emulsion and Polymer containing oxazoline base) containing ratio of (solid constituent) is in all solids composition 100 mass % of above-mentioned composition (wherein, the polymer containing oxazoline base is 3.0 matter in all solids composition 100 mass % of compositions to 60 mass % Amount %), the containing ratio of silica sol (solid constituent) is 10 in all solids composition 100 mass % of above-mentioned composition Weight %, in addition, relative to the solid constituent summation 100 of surface-treated carbon black, adhesive resin and silica sol Mass parts, containing the silane coupler of 12.5 mass parts.

On the surface of the base treatment metallic plate shown in table 1～4, rod is utilized to be coated with according to the dry film thickness shown in table 1～4 Assembling device is coated with the water system black-colored resin composition of above-mentioned gained, then, is dried 60 seconds at 160 DEG C, forms the first black gold Belong to layer.

(formation of the second black layer)

Solvent system blacking (NIPPON FINE COATINGS company's system " FLC495BLACK ") adds relative to Acrylic acid pearl (company's system of refining big day of the particle diameter that drying solid composition 100 mass parts is 2 mass parts about 2～12 μm of coating " ラ Block U ロ mono-Le "), add diluent, after viscosity being adjusted to about 50 seconds with Ford cup (Fordcup) No.4, above-mentioned The surface of the first black layer utilizes rod to be coated with painting device according to the dry film thickness shown in table 1～4 and is coated, then, at 230 DEG C It is dried 60 seconds, toasts, form the second black layer, obtain Thin-black-layer-coametal metal sheet.The thickness of the second black layer is The Thin-black-layer-coametal metal sheet that Thin-black-layer-coametal metal sheet is each embodiment of 1.42～4.55 μm, uncoated second black The Thin-black-layer-coametal metal sheet that Thin-black-layer-coametal metal sheet is comparative example 1 ' of layer (thickness 0 μm).It addition, the propylene added 1.2～1.5 times of the thickness that particle diameter is the second black layer of acid pearl.

By according to the thin film black application gold obtained so that upper type changes the first black layer and the thickness of the second black layer The genus L-value of plate, L* value, b value, b* value are shown in table 1～4.Table 1,3 is for using base treatment metallic plate EG as metal The situation of plate, table 2,4 is to use base treatment metallic plate GI as the situation of metallic plate.Additionally, Thin-black-layer-coametal metal sheet The thickness of the second black layer and the L-value of this black metal sheet or b value relation as shown in figures 1-4.

It addition, for the comparative example 1 ' that thickness is 0 μm of the second black layer in the Thin-black-layer-coametal metal sheet of gained Black coated metal plate, observed by visual film coated surface, outside results verification to crawling, grit type pit etc. See bad.But, for be formed the black coated metal plate of the embodiment of the second black layer carry out same observation time, the most really Recognize bad order.

[comparative example 1]

In the formation of the first black layer of embodiment 1, (KCC Corporation is public to use solvent system black primer Department (Korea S) system " BLACK PRIMER FP1817 ") replace water system black-colored resin composition, according to the desciccator diaphragm shown in table 1～4 Thickness is coated, and then, is dried 60 seconds at 230 DEG C, in addition, forms the first ferrous metal layer similarly to Example 1 With the second black layer, obtain the Thin-black-layer-coametal metal sheet compared.

By according to changing the thin film black compared obtained by the thickness of the first black layer and the second black layer with upper type The L-value of coated metal plate, L* value, b value, b* value are shown in table 1～4.Table 1,3 is made for using base treatment metallic plate EG For the situation of metallic plate, table 2,4 is to use base treatment metallic plate GI as the situation of metallic plate.Additionally, thin film black application The relation of the thickness of the second black layer of metallic plate and the L-value of this black metal sheet or b value is as shown in figures 1-4.

[table 1]

[table 2]

[table 3]

[table 4]

[embodiment 2]

(formation of the first black layer)

Use raw material (surface-treated carbon black, adhesive resin (resin emulsion and the base Han oxazoline same as in Example 1 Polymer), silica sol, silane coupler), change each usage amount in such a way, in addition, with embodiment 1 is prepared as water system black-colored resin composition.

That is, the usage amount of silica sol and silane coupler is fixed as (silica sol same as in Example 1 (solid constituent): all solids composition 100 mass % is 10 mass %, silane coupler: relative to all solids composition 100 Mass parts is 12.5 mass parts)；The usage amount of surface-treated carbon black is changed to the containing ratio of its solid constituent and reaches all solids Value shown in table 5 in composition 100 mass %；The use quantitative change of adhesive resin (resin emulsion and the polymer containing oxazoline base) The more containing ratio of its solid constituent (resin emulsion and the solid constituent summation of the polymer containing oxazoline base) reaches all Value shown in table 5 in solid constituent 100 mass %.It addition, resin emulsion and the polymer containing oxazoline base are fixed as each solid The quality ratio of composition reaches resin emulsion: containing polymer=95 of oxazoline base: 5.

The surface of the base treatment metallic plate EG obtained in embodiment 1, utilizes rod to be coated with according to the dry film thickness of about 0.7 μm Painting device is coated with water system black-colored resin composition obtained above, then, is dried 60 seconds at 160 DEG C, forms the first black Metal level.

(formation of the second black layer)

Solvent system blacking (NIPPON FINE COATINGS company system " and FLC495BLACK ") adds relative to The acrylic acid pearl of the particle diameter that drying solid composition 100 mass parts is 2 mass parts about 6 μm of coating, adds diluent, uses Ford cup After viscosity is adjusted about 50 seconds by No.4, rod is utilized to be coated with on the surface of above-mentioned first black layer according to the dry film thickness of about 4.0 μm Painting device is coated, and then, is dried 60 seconds at 230 DEG C, toasts, form the second black layer, obtain thin film black Coated metal plate.It addition, 1.5 times of the thickness that particle diameter is the second black layer of the acrylic acid pearl added.

Each for gained Thin-black-layer-coametal metal sheet will only be formed the L-value in the stage of the first black layer and b value, black first It is formed with the L-value of the black metal sheet of the second black layer and b value on chromatograph and processability is shown in Table 5.

[table 5]

[embodiment 3]

(formation of the first black layer)

Use raw material (surface-treated carbon black, adhesive resin (resin emulsion and the base Han oxazoline same as in Example 1 Polymer), silica sol, silane coupler), change each usage amount in such a way, in addition, with embodiment 1 is prepared as water system black-colored resin composition.Wherein, the polymer containing oxazoline base is changed to the thing shown in part table Matter.

That is, the usage amount of silane coupler is fixed as (silane coupler: become relative to all solids same as in Example 1 Dividing 100 mass parts is 12.5 mass parts)；The usage amount of silica sol is changed to the containing ratio of its solid constituent and reaches in group All solids composition 100 mass % of compound is 20 mass %；The usage amount of surface-treated carbon black is changed to its solid constituent Containing ratio be 20 mass % in all solids composition 100 mass % of compositions；Adhesive resin (resin emulsion and containing The polymer of oxazoline base) usage amount be changed to the containing ratio of its solid constituent and reach all solids composition 100 in compositions Quality % is 60 mass %；Containing ratio containing the solid constituent of the polymer of oxazoline base be changed to value shown in table 6 (in It is that the containing ratio of resin emulsion is " containing ratio of 60 mass %-polymer containing oxazoline base ").

(formation of the second black layer)

Solvent system blacking (NIPPON FINE COATINGS company's system " FLC495BLACK ") adds relative to The acrylic acid pearl of the particle diameter that drying solid composition 100 mass parts is 2 mass parts about 6 μm of coating, adds diluent, uses Ford cup After viscosity is adjusted about 50 seconds by No.4, rod is utilized to be coated with on the surface of above-mentioned first black layer according to the dry film thickness of about 4.0 μm Painting device is coated, and then, is dried 60 seconds at 230 DEG C, toasts, form the second black layer, obtain thin film black Coated metal plate.It addition, 1.5 times of the thickness that particle diameter is the second black layer of the acrylic acid pearl added.

Each Thin-black-layer-coametal metal sheet of gained will only be formed the corrosion resistance in the stage of the first black layer and water-fast Property, degree of blackness (L-value), corrosion resistance and the processability being formed with the black metal sheet of the second black layer on the first black layer are shown In table 6.

[table 6]

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

* 2: relative to the mass parts of resin emulsion 100 mass parts

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

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

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

[embodiment 4]

(formation of the first black layer)

Polymer containing oxazoline base is changed to zirconium carbonate ammonium (Japanese light metal (strain) system " BAYCOURT20 "；Solid Composition 20 mass %), in addition, use raw material (surface-treated carbon black, adhesive resin (resin breast same as in Example 1 Liquid), silica sol, silane coupler), and change each usage amount in such a way, in addition, with embodiment 1 with Sample ground preparation water system black-colored resin composition.

That is, the usage amount of silane coupler is fixed as (silane coupler: become relative to all solids same as in Example 1 Dividing 100 mass parts is 12.5 mass parts)；The usage amount of silica sol is changed to the containing ratio of its solid constituent and reaches in group All solids composition 100 mass % of compound is 20 mass %；The usage amount of surface-treated carbon black is changed to its solid constituent Containing ratio reach to be 20 mass % in all solids composition 100 mass % of compositions；Adhesive resin (resin emulsion and Zirconium carbonate ammonium) usage amount be changed to the containing ratio of its solid constituent and reach all solids composition 100 mass % in compositions In be 60 mass %；The containing ratio of the solid constituent of zirconium carbonate ammonium is changed to value shown in table 7 (then, the containing of resin emulsion Rate becomes " containing ratios of 60 mass %-zirconium carbonate ammoniums ").

(formation of the second black layer)

Solvent system blacking (NIPPON FINE COATINGS company's system " FLC6080BLACK ") adds relatively In the acrylic acid pearl of the particle diameter that drying solid composition 100 mass parts is 2 mass parts about 6 μm of coating, add diluent, use Ford After viscosity is adjusted about 50 seconds by cup No.4, on the surface of above-mentioned first black layer, the dry film thickness according to about 4.0 μm utilizes rod Painting painting device is coated, and then, is dried 60 seconds at 230 DEG C, toasts, form the second black layer, obtain thin film black Color coated metal plate.It addition, 1.5 times of the thickness that particle diameter is the second black layer of the acrylic acid pearl added.

Each Thin-black-layer-coametal metal sheet of gained will only be formed the corrosion resistance in the stage of the first black layer and water-fast Property, on the first black layer, it is formed with the degree of blackness (L-value) of the black metal sheet of the second black layer, corrosion resistance, processability, resistance to Frosted rubber abrasivity and resistance to marring are shown in Table 7.

[table 7]

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

* 2: relative to the mass parts of resin emulsion 100 mass parts

[embodiment 5, comparative example 5]

(formation of the first black layer)

(containing ratio of the solid constituent of zirconium carbonate ammonium is 5 to the water system black-colored resin composition obtained in use embodiment 4-4 Quality %), utilize rod to be coated with painting device and coated, according to the dry film thickness of about 0.7 μm, the bases obtained in embodiment 1 The surface of reason metallic plate EG, then, is dried 60 seconds at 160 DEG C, forms the first ferrous metal layer.

(formation of the second black layer)

Solvent system blacking (NIPPON FINE COATINGS company's system " FLC6080BLACK ") adds relatively In the acrylic acid pearl of the particle diameter that drying solid composition 100 mass parts is 2 mass parts about 6 μm of coating, add diluent, use Ford After viscosity is adjusted about 50 seconds by cup No.4, rod is utilized to be coated with painting device according to shown in table 8 on the surface of above-mentioned first black layer Dry film thickness be coated, then, 230 DEG C be dried 60 seconds, toast, form the second black layer, obtain thin film black Color coated metal plate.It addition, 0.6～3 times of the thickness that particle diameter is the second black layer of the acrylic acid pearl added.

Each Thin-black-layer-coametal metal sheet of gained (is formed with the ferrous metal of the second black layer on the first black layer Plate) degree of blackness (L-value), corrosion resistance, processability, wear-resisting sand rubber abrasivity and resistance to marring be shown in Table 8.

[table 8]

[embodiment 6]

(formation of the first black layer)

That is, the usage amount of silane coupler is fixed as (silane coupler: become relative to all solids same as in Example 1 Dividing 100 mass parts is 12.5 mass parts)；The usage amount of surface-treated carbon black is changed to the containing ratio of its solid constituent and reaches in group All solids composition 100 mass % of compound is 20 mass %；The usage amount of silica sol is changed to its solid constituent Containing ratio reach the value shown in table 9；The usage amount change of adhesive resin (resin emulsion and the polymer containing oxazoline base) Containing ratio for its solid constituent (resin emulsion and the solid constituent summation of the polymer containing oxazoline base) reaches shown in table 9 Value.It addition, the quality ratio that resin emulsion and the polymer containing oxazoline base are fixed as each solid constituent reaches resin emulsion: contain Polymer=95 of oxazoline base: 5.

(formation of the second black layer)

Each Thin-black-layer-coametal metal sheet of gained will only define the corrosion resistance in the stage of the first black layer and resistance to Aqueous, on the first black layer, it is formed with the degree of blackness (L-value) of the black metal sheet of the second black layer, corrosion resistance, processability And resistance to marring is shown in Table 9.

[table 9]

[embodiment 7]

(formation of the first black layer)

That is, the usage amount of silane coupler is changed to its content and reaches relative to all solids composition 100 mass parts to be table Amount shown in 10；The usage amount of silica sol is changed to the containing ratio of its solid constituent and reaches all solids in compositions Composition 100 mass % is 20 mass %；The usage amount of surface-treated carbon black is changed to the containing ratio of its solid constituent and reaches All solids composition 100 mass % of compositions is 20 mass %；Adhesive resin (resin emulsion and gathering containing oxazoline base Compound) usage amount be changed to the containing ratio of its solid constituent and reach in all solids composition 100 mass % of compositions be 60 mass %.It addition, the quality ratio that resin emulsion and the polymer containing oxazoline base are fixed as each solid constituent reaches resin Emulsion: containing polymer=95 of oxazoline base: 5.

(formation of the second black layer)

Each Thin-black-layer-coametal metal sheet of gained will only define the corrosion resistance in the stage of the first black layer and resistance to Aqueous, the first black layer is formed the corrosion resistance of the black metal sheet of the second black layer, processability and resistance to marring shows In table 10.

[table 10]

※ is relative to solid constituent summation 100 mass parts of surface-treated carbon black, adhesive resin and silica sol Mass parts

[embodiment 8]

(formation of the first black layer)

That is, the usage amount of silane coupler is fixed as (silane coupler: become relative to all solids same as in Example 1 Dividing 100 mass parts is 12.5 mass parts)；The usage amount of surface-treated carbon black is changed to the containing ratio of its solid constituent and reaches in group All solids composition 100 mass % of compound is 20 mass %；The usage amount of silica sol is changed to its solid constituent Containing ratio reach to be 20 mass % in all solids composition 100 mass % of compositions；Adhesive resin (resin emulsion and Polymer containing oxazoline base) usage amount be changed to its solid constituent (resin emulsion and the consolidating of polymer containing oxazoline base Body composition summation) containing ratio reach to be 60 mass % in all solids composition 100 mass % of compositions.It addition, resin Emulsion and be fixed as the quality ratio of each solid constituent containing the polymer of oxazoline base and reach resin emulsion: poly-containing oxazoline base Compound=95: 5.

(formation of the second black layer)

Solvent system blacking (NIPPON FINE COATINGS company's system " FLC495BLACK ") adds relative to The acrylic acid of particle diameter (scopes of about 2～14 μm) shown in the table 11 that drying solid composition 100 mass parts is 2 mass parts of coating Pearl, adds diluent, after viscosity being adjusted about 50 seconds with Ford cup No.4, utilizes rod to be coated with on the surface of above-mentioned first black layer Painting device is coated according to the dry film thickness (scopes of about 2.0～7.0 μm) of table 11, then, is dried 60 seconds at 230 DEG C Clock, toasts, and forms the second black layer, obtains Thin-black-layer-coametal metal sheet.

The evaluation of embossed appearance in each Thin-black-layer-coametal metal sheet of gained is shown in Table 11.

[table 11]

Claims

1. a Thin-black-layer-coametal metal sheet, it is laminated with by water system black-colored resin composition shape at least one side of metallic plate The first black layer of thickness 0.4～1.0 μm become, and be laminated with on described first black layer and formed by solvent system blacking The second black layer of thickness 1.4～9 μm,

Described water system black-colored resin composition contains the surface-treated carbon black being coated to surface with aqueous resin,

Further, described solvent system blacking contains the resin particle of below particle diameter 14 μm, at the film by described second black layer It is below more than t μm and 2t μm that thickness is set to the particle diameter of described resin particle during t μm, is laminated in second on described first black layer The degree of blackness on black layer surface i.e. L-value be less than 20 and b values be less than 1.5,

In all solids composition 100 mass % of described water system black-colored resin composition, described surface-treated carbon black is with solid The containing ratio of composition meter is 10～40 mass %.

Thin-black-layer-coametal metal sheet the most according to claim 1, wherein,

The degree of blackness i.e. L-value on described first black layer surface be less than 25 and b values be less than 3.

Thin-black-layer-coametal metal sheet the most according to claim 1 and 2, wherein,

Described water system black-colored resin composition contains adhesive resin, and described adhesive resin comprises alkene-α, β-unsaturation Polymers of carboxylic acid, α, beta-unsaturated carboxylic acid polymer, and selected from the polymer containing oxazoline base and the cross-linking agent of zirconium carbonate ammonium,

Relative to alkene-α, beta-unsaturated carboxylic acid copolymer and α, summation 100 mass parts of beta-unsaturated carboxylic acid polymer, The content of described cross-linking agent is 2～19 mass parts,

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

Thin-black-layer-coametal metal sheet the most according to claim 3, wherein,

Described water system black-colored resin composition is possibly together with silica sol, and the containing ratio of described silica sol is at described water It is that all solids composition 100 mass % in black-colored resin composition is 5～30 mass %.

Thin-black-layer-coametal metal sheet the most according to claim 4, wherein,

Solid constituent summation 100 relative to described surface-treated carbon black, described adhesive resin and described silica sol Mass parts, described water system black-colored resin composition is possibly together with the silane coupler of 5～25 mass parts.