CN1914358A - Electroplating solution composition for organic polymer-zinc alloy composite plating and plated metal material using such composition - Google Patents
Electroplating solution composition for organic polymer-zinc alloy composite plating and plated metal material using such composition Download PDFInfo
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- CN1914358A CN1914358A CN 200480041514 CN200480041514A CN1914358A CN 1914358 A CN1914358 A CN 1914358A CN 200480041514 CN200480041514 CN 200480041514 CN 200480041514 A CN200480041514 A CN 200480041514A CN 1914358 A CN1914358 A CN 1914358A
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Abstract
Disclosed is an electroplating solution composition which enables to obtain a plating with excellent corrosion resistance which exhibits excellent adhesion with a coating film without being subjected to a surface treatment. Such an electroplating solution composition for an organic polymer-zinc alloy composite plating is characterized by containing (A) 1-600 g/l of Zn ions, (B) 1-600 g/l of iron group element ions, (C) 0.1-200 g/l of a tungstic acid compound as W ions and (D) 0.5-500 g/l of a water-soluble or water-dispersible organic polymer compound having a number-average molecular weight of 1,000-1,000,000.
Description
Technical field
The present invention relates to have the organic polymer-zinc alloy composite plating solution composition that is used to form electroplating film of plating and two kinds of effects of surface treatment, and relate to by using said composition to electroplate the organic polymer-zinc alloy composite electroplating metal material that obtains.
Background technology
As the surface treatment of the zinc-base electroplating metal material that is used for automobile, household electrical appliance, material of construction etc., generally carried out with the processing of chromic salts with the processing of zinc phosphate, but the toxicity of chromium has been thought a problem.Processing with chromic salts has following problem: give out the smog of chromic salts in treatment step, sewage treatment equipment needs big cost, and chromic acid wash-out from chemical conversion film comes out.In addition, hexavalent chromium compound is by comprising that the many public organizations identification as the IARC (international Agency for Research onCancer Review) that represents is human carcinogenic substance and is the hypertoxicity material.
In addition, in using the processing of zinc phosphate, because using the rinsing of chromic acid after handling with zinc phosphate usually handles, with the problem of bringing chromium to handle, also have for the wastewater treatment of reaction accelerator, metal ion and analogue in the zinc phosphate treatment agent and the problems of treatment of mud, these owing to metal ion from the wash-out the metal to be processed.
In addition, strong request reduces the cost of coating line, therefore wishes to develop a kind of plated film, and it is excellent but need not surface treatment and excellent corrosion resistance for the binding property of filming.
For these purposes, developed water-soluble organic polymer added in the zinc-plated bath and when electroplating metal material with the method (for example, referring to patent documentation 1 and 2) of metal and organic polymer co-precipitation.
Yet, by only water-soluble organic polymer being added to the field that can't obtain enough erosion resistances in the general plating bath and be difficult to these methods are applied to the anti-heavy corrosion of needs for example in the automotive field.
Patent documentation 1:JP 1-177394A
Patent documentation 2:JP 7-56030B
Summary of the invention
The purpose of this invention is to provide the plating solution composition that can obtain plated film, this plated film need not also binding property excellence and the excellent corrosion resistance to filming of surface treatment.
As result for the broad research that addresses the above problem, the inventor has been found that, by iron family element ting ion and W ion are sneaked in the organic polymer-zinc alloy composite electroplating solution that contains Zn ion and water-soluble and/or water-dispersible organic polymer, can improve the erosion resistance of plated film significantly, and the inventor has finished the present invention.
Therefore, the present invention relates to the organic polymer-zinc alloy composite plating solution composition, it contains:
(A) 1 to 600g/l Zn ion,
(B) 1 to 600g/l iron family element ting ion,
(C) by the W ion count 0.1 to 200g/l based on the compound of wolframic acid and
(D) 0.5 to 500g/l have 1,000 to 1,000, the water-soluble or water-dispersible organic polymer compounds of 000 number-average molecular weight.
In addition, the present invention relates to the organic polymer-zinc alloy composite electroplating metal material, it can obtain by using above-mentioned organic polymer-zinc alloy composite plating solution composition acierage starting material.
In addition, the present invention relates to the steel plate of anti-fingerprint, wherein need not surface treatment and directly on the organic polymer-zinc alloy composite electroplating metal material, form organic resin film.
In addition, the present invention relates to lubricated steel sheet, wherein need not surface treatment and directly on above-mentioned organic polymer-zinc alloy composite electroplating metal material, form organic resin film with lubricating function.
Embodiment
Organic polymer-zinc alloy composite plating solution composition of the present invention (hereinafter to be referred as plating solution composition) contains Zn ion (A), iron family element ting ion (B), based on the compound (C) of wolframic acid and water-soluble or water-dispersible organic polymer compounds (D) as necessary component.
" Zn ion (A) "
Constituted the main ingredient of coating as the Zn ion of the component (A) of plating solution composition of the present invention.
The Zn ion is that the form with muriate, vitriol, fluorochemical, prussiate, oxide compound, organic acid salt, phosphoric acid salt or metal element is added in the plating bath.
" iron family element ting ion (B) "
This iron family element ting refers generally to nickel, cobalt or iron.Iron family element ting ion as the component (B) of plating solution composition of the present invention is selected from Ni ion, Co ion and Fe ion.Wherein, consider that from erosion resistance the Fe ion is preferred.
Iron family element ting ion (B) is that the form with muriate, vitriol, fluorochemical, prussiate, oxide compound, organic acid salt, phosphoric acid salt or metal element is added in the plating bath." based on the compound (C) of wolframic acid "
As the compound based on wolframic acid of the component (C) of plating solution composition of the present invention, it can be by significantly improving the erosion resistance of the coating that is obtained with organic polymer compounds (D) combination.
Example based on the compound (C) of wolframic acid comprises wolframic acid, tungstate, phospho-wolframic acid and Lin Wusuanyan.The example of this salt comprises ammonium salt, sylvite, calcium salt, sodium salt or the like.Especially, ammonium salt or sodium salt are preferred.Wherein, consider erosion resistance, ammonium tungstate, ammonium phosphowolframate, sodium wolframate and Tungstophosphoric acid, sodium salt are preferred.
" water-soluble or water-dispersible organic polymer compounds (D) "
As the water-soluble or water-dispersible organic polymer compounds of the component (D) of plating solution composition of the present invention, its be selected from even when mixing, remain with above-mentioned metal ion chemically stable those.By the organic polymer compounds is added in this plating bath, be improved significantly in the plated film and the binding property between the organic resin film that forms on this plated film that obtain by this plating bath, therefore under the sharp situation of carrying out the chemical conversion processing as zinc phosphate or chromic salt of plated film surface treatment of no use, also can obtain enough erosion resistances.
As organic polymer compounds (D), can use those with water-soluble performance or water-dispersible performance (the dispersive mode can be suspension or emulsion).As with the organic polymer compound dissolution, disperse or be emulsified in method in the water, can use common known method.Water-soluble or water-dispersible organic polymer compounds preferably has those compounds that are selected from least a hydrophilic radical in the group of being made up of non-ionic hydrophilic group, anionic hydrophilic group and cationic hydrophilic group as this.Specifically, can use contain can make the dissolving of this polymer compound independently or be dispersed in the water functional group (for example, at least a functional group in hydroxyl, carboxyl, amino (imido grpup) group, sulfonic group, phosphate group or the similar group) those, acidic resins as the situation of the resin that contains carboxyl under with amine compound such as thanomin or triethylamine, ammoniacal liquor; Alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide or part or all those polymer compounds or the like in basic resin neutralizes these functional groups under as the situation that contains amino resin with lipid acid such as acetate or lactic acid or mineral acid such as phosphoric acid.
The example of this type of organic polymer compounds (D) comprises Resins, epoxy, resol, acrylic resin, urethane resin, alkene-carboxylic acid resin, nylon resin, polyvinyl alcohol, the resin with polyalkylene oxide groups, polyoxyethylene glycol, Polyglycerine, carboxymethyl cellulose, Walocel MT 20.000PV, Natvosol or the like.
As above-mentioned Resins, epoxy, preferably use by amine being added to the obtainable cation epoxy resin of Resins, epoxy; Modified epoxy such as propenyl (acryl) modified resins and urethane modified resins; Or the like.The example of cation epoxy resin comprises epoxy compounds and uncle's monoamine or polyamines, secondary monoamine or polyamines, or the affixture of primary and secondary mixing polyamines (for example referring to US patent No.3984299); Epoxy compounds with have the secondary monoamine of ketoimine primary amino or an affixture of polyamines (for example, referring to US patent No.4017438); Epoxy compounds and etherification reaction product (for example, referring to JP 59-43013A) with oxy-compound of ketoimine primary amino; Or the like.
As above-mentioned epoxy compounds, number-average molecular weight that suitable is in 400 to 4,000 scopes, particularly in 800 to 2000 scopes and epoxy equivalent (weight) in 190 to 2,000 scopes, those in 400 to 1,000 scopes particularly.This type of epoxy compounds can for example react by polyphenolic substance and Epicholorohydrin and obtain.The example of this polyphenolic substance comprises two (4-hydroxyphenyl)-2,2-propane, 4,4-dihydroxy benaophenonel, two (4-hydroxyphenyl)-1,1-ethane, two (4-hydroxyphenyl)-1,1-Trimethylmethane, two (4-hydroxyl-tert-butyl-phenyl)-2,2-propane, two (2 hydroxy naphthalene base) methane, 1,5-dihydroxy naphthlene, two (2, the 4-dihydroxyphenyl) methane, four (4-hydroxyphenyl)-1,1,2,2-ethane, 4,4 '-dihydroxy-diphenyl sulfone, phenol novolak, cresols novolak or the like.
As resol, can use the water dissolution compound of making by polymer compound aptly, this polymer compound is by heating phenol component in the presence of catalytic reaction is sharp and formaldehyde carries out addition and condensation obtains.For above-mentioned phenol component, can use the phenolic compound or the four functional or polyfunctional phenolic compound of dual functional phenolic compound, trifunctional as starting raw material.Its example comprise neighbour-cresols as the bifunctional phenol compound, p-cresol, p-tert-butylphenol, right-ethylphenol, 2,3-xylenol and 2,5-xylenol; As the phenol of tri-functional phenols compound, meta-cresol ,-ethylphenol, 3, the 5-xylenol and-methoxyphenol; And as dihydroxyphenyl propane, the Bisphenol F of four sense phenolic compound.These phenolic compound can use separately or use as two or more the mixture in the middle of them.
The example of aforesaid propylene acid resin comprises monomeric homopolymer or the multipolymer that respectively has hydrophilic radical such as carboxyl, amino or hydroxyl, respectively has the monomer of hydrophilic radical and the multipolymer of other copolymerisable monomer.They are by letex polymerization, suspension polymerization or solution polymerization with if necessary by with gained resin neutralization or make it to become wetting ability or by the obtainable resin of this resin of modification.
Above-mentioned carboxylic monomeric example comprises vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, Ba Dousuan, methylene-succinic acid or the like.
Nitrogenous monomeric example comprises nitrogenous (methyl) alkyl acrylate as (methyl) vinylformic acid N, N-dimethyl aminoethyl ester, (methyl) vinylformic acid N, N-diethylamino ethyl ester and (methyl) vinylformic acid N-tertiary butyl amino-ethyl ester; Polymerisable acid amides such as acrylamide, Methacrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-dimethylaminopropyl (methyl) acrylamide and N, N-dimethyl aminoethyl (methyl) acrylamide; Aromatics nitrogen containing monomer such as 2-vinyl pyridine, l-vinyl-2-pyrrolidone and 4-vinylpridine; Allyl amine or the like.
The monomeric example of hydroxyl comprises the monoester compound of acrylic or methacrylic acid and polyvalent alcohol, as (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid hydroxypropyl ester, (methyl) vinylformic acid 2,3-dihydroxyl butyl ester, (methyl) vinylformic acid 4-hydroxybutyl ester and poly-(ethylene glycol) single (methyl) acrylate; Compound that is obtained to the above-mentioned monoester compound of acrylic or methacrylic acid and polyvalent alcohol by the 6-caprolactone ring-opening polymerization or the like.
Other monomeric example comprises (methyl) alkyl acrylate with 1 to 24 carbon atom, as (methyl) methyl acrylate, (methyl) vinylformic acid ethyl ester, (methyl) vinylformic acid n-propyl ester, (methyl) vinylformic acid isopropyl esters, (methyl) n-butylacrylate, (methyl) vinylformic acid isobutyl, (methyl) vinylformic acid tertiary butyl ester, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid n-octyl ester, (methyl) vinylformic acid Lauryl Ester, (methyl) tridecyl acrylate, (methyl) vinylformic acid stearyl and (methyl) vinylformic acid iso stearyl ester; Vinylbenzene, vinyl-acetic ester or the like.These compounds can use separately or use as two or more the mixture in the middle of them.In the present invention, " (methyl) acrylate " refers to acrylate or methacrylic ester.
As above-mentioned urethane resin, can suit to use by each urethane of forming by polyvalent alcohol such as polyester polyol or polyether polyol and vulcabond chain extension in the presence of the chainextender of low-molecular weight compound such as glycol or diamines with two or more active hydrogens, and obtained by stably being dispersed or dissolved in the water product those, and can (for example use known resin widely, referring to JP42-24192A, JP42-24194A, JP42-5118B, JP49-986B, JP49-33104B, JP50-15027B, and JP53-29175B).As the method that urethane resin stably is dispersed or dissolved in the water, for example can use following method.
(1) give wetting ability in side chain by ionic group such as hydroxyl, amino or carboxyl being incorporated into polyether polyols with reduced unsaturation or the end, and by self-emulsifying with polymer dispersed or be dissolved in method in the water.
(2) with end-capping reagent such as oxime, alcohol, phenol, mercaptan, amine or sodium bisulfite capping polyether polyols with reduced unsaturation or terminal isocyanate group group and use emulsifying agent and mechanical shear stress is dispersed in method in the water forcibly with the polyether polyols with reduced unsaturation that is closed completely.In addition, the polyether polyols with reduced unsaturation that will have a terminal isocyanate group mixes with water/emulsification profit/chainextender and uses mechanical shear stress to realize disperseing the method that increases with molecular weight simultaneously.
(3) use water-soluble polyol such as polyoxyethylene glycol as the polyvalent alcohol that is used for the main raw of urethane, the method that will disperse or dissolve as the urethane of aqurous ployurethane.
With regard to above-mentioned urethane resin, the above-mentioned method that disperses or dissolves is not limited to single method, can also use the mixture that is obtained by each method.
The example that is suitable for the synthetic vulcabond of above-mentioned urethane resin comprises aromatics, alicyclic and aliphatic diisocyanate, and comprise hexamethylene diisocyanate particularly, tetramethylene diisocyanate, 3,3 '-dimethoxy-4 ', 4 '-the biphenylene vulcabond, right-eylylene diisocyanate, between-eylylene diisocyanate, 1,3-(two isocyano methyl) pimelinketone, 1,4-(two isocyano methyl) pimelinketone, 4,4 '-two isocyano pimelinketone, 4,4 '-methylene-bis (cyclohexyl isocyanate), isophorone diisocyanate, 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, right-phenylene diisocyanate, '-diphenylmethane diisocyanate, between-phenylene diisocyanate, 2, the 4-naphthalene diisocyanate, 3,3 '-dimethyl-4,4 '-the biphenylene vulcabond, 4,4 '-the biphenylene vulcabond or the like.Wherein, particularly preferably be 2,4-toluene two and cyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
The example that is purchased product of above-mentioned urethane resin comprises HYDBAN HW-330, HW-340, HW-350 is (all by D ainippon Ink And Chemicals, Inc. make), SUPERFLEX 100,150, and F-3438D is (all by Dai-ichiKogyo Seiyakta Co., Ltd makes), or the like.
Above-mentioned polyvinyl alcohol resin preferably has 87% or the polyvinyl alcohol of higher saponification deg, particularly has 98% or the so-called fully saponified polyvinyl alcohol of higher saponification deg.In addition, its number-average molecular weight is aptly in 3,000 to 100,000 scopes.
As above-mentioned resin with polyoxyalkylene chain, resin with polyethylene oxide chain or polyoxytrimethylene chain can use aptly, and their example comprises polyoxyethylene glycol, polypropylene glycol, wherein this polyethylene oxide chain and this polyoxytrimethylene chain be with block polyoxyalkylene glycol of the form combination of block or the like.
As above-mentioned alkene-carboxylic acid resin, can use at least a water-dispersible or the water soluble resin that are selected from two types, be the multipolymer of alkene such as ethene or propylene and polymerisable unsaturated carboxylic acid, and by carrying out letex polymerization in the dispersion of polymerisable unsaturated compound being added to this multipolymer and further allowing this product carry out the crosslinked resin that obtains in the particle.
Above-mentioned multipolymer is alkene and one or both or the polytype polymerisable unsaturated carboxylic acid multipolymer as (methyl) vinylformic acid and toxilic acid.In this multipolymer, the content of suitable is this unsaturated carboxylic acid is in 3 to 60wt% scopes, and preferably in 5 to 40wt% scopes, this multipolymer can be by being dispersed in the water with the acidic group in the alkaline matter neutralized copolymer.
Consider and the binding property of organic resin film and the package stability of plating bath, use GPC (gel permeation chromatography) measuring method according to the number-average molecular weight that can be used for the water-soluble or water-dispersible organic polymer compounds (D) among the present invention of polystyrene conversion 1,000 to 1,000,000, particularly in 2,000 to 500,000 scopes.
In addition, preferably coordination agent is added in the plating bath so that be stabilized in metal ion in the plating bath.This coordination agent can be selected from by in the following group of forming: hydroxycarboxylate such as Citrate trianion, tartrate and gluconate, amino alcohol such as monoethanolamine, diethanolamine and trolamine, polyamines such as quadrol (EDA), diethylenetriamine and Triethylenetetramine (TETA), aminocarboxylate such as edetate and nitroacetic acid salt, polyvalent alcohol such as sorbyl alcohol and tetramethylolmethane, and their mixture.
In the present invention, the function of high corrosion resistance, coating binding property etc. can obtain as discontinuous particle sedimentary corrosion-inhibiting pigment and/or ceramic particle from electroplating solution by being used in combination.
As above-mentioned corrosion-inhibiting pigment, common known pigment can both use and their preferred example comprises phosphoric acid salt, molybdate, metaborate, silicate or the like.In addition, the example of ceramic particle comprises oxide compound such as Al
2O
3, SiO
2, TiO
2, ZrO
2, Y
2O
2, ThO
2, CeO
2And Fe
2O
3Carbide such as B
4C, SiC, WC, ZrC, TiC, graphite and fluorographite; Nitride such as BN, Si
3N
4And TiN; Boride such as Cr
3B
2And ZrB
2O silicate such as 2MgOSiO
2, MgOSiO
2, and ZrO
2SiO
2Deng particle.The combined amount of corrosion-inhibiting pigment and/or ceramic particle wishes to be based on the scope of every liter of plating bath 5 to 300g.In addition, this particle diameter is more little, and dispersion stabilization is excellent more.Therefore, it is preferred being of a size of 1 μ m or littler ultra-fine grain.In addition, wish the co-precipitation amount in the plating matrix is controlled to 1 to 30 weight %, particularly 1 to 10 weight % based on total precipitation capacity.When this co-precipitation amount after a little while, the effect of improving erosion resistance does not show, when it surpassed 30 weight %, plated film became fragile and can descend with the binding property of base mateiral, so this situation is problematic.
In order to improve erosion resistance, corrosion inhibition organic compound can further add in this plating bath.The example of preferred corrosion inhibition organic compound comprises alkynes, alkynol, amine or its salt, thio-compounds, aromatic carboxylic acid's compound or its salt and heterogeneous ring compound, or the like.
Wherein, this alkynes refers to contain the organic compound of carbon-to-carbon three key, and its example comprises pentyne, hexin, heptyne, octyne or the like.This alkynol refers to have the organic compound of one or more hydroxyls in alkynes, its example comprises propargyl alcohol, 1-hexin-3-alcohol, 1-heptyne-3-alcohol or the like.This amine refers to contain the organic compound of one or more nitrogen-atoms in molecule, it comprises any in aliphatics or the aromatic substance.The example of this type of amine comprises octylame, nonyl amine, decyl amine, lauryl amine, tridecyl amine, hexadecylamine or the like.This thio-compounds refers to contain the organic compound of one or more sulphur atoms in molecule, the example of this type of thio-compounds comprises decyl mercaptan, hexadecyl mercaptan, thiocarbamide or the like.This heterogeneous ring compound refers to contain atom except that carbon atom as the organic compound of ring atom in ring molecule, the example of this heterocyclic compounds comprises pyridine, benzothiazole, benzotriazole, quinoline, indoles or the like.In addition, the example of aromatic carboxylic acid's compound comprises phenylformic acid, Whitfield's ointment, toluic acid, naphthalene monocarboxylic acid or the like.For this amine or carboxylic acid cpd, might use their salt, and therefore can obtain equal effect.The salt that can use comprises: for amine, and acid salt such as vitriol and hydrochloride, for aromatic carboxylic acid's compound, metal-salt such as an alkali metal salt and zinc salt and ammonium salt.
The amount of adding the corrosion inhibition organic compound in the plating bath to is adjusted to ideally: be 0.1 to 10 weight % for alkynes or alkynol, for this amine or its salt 3 to 10 weight %, for thio-compounds 0.2 to 5 weight %, for being 1 to 10 weight % for the heterogeneous ring compound and being 3 to 8 weight % for aromatic carboxylic acid's compound or its salt.In addition, might in this plating bath, add the scaling loss coating that is generally used for improving under high current density or the additive of the throwing power under low current density.Its example comprises reaction product, polyethylene polyamine, other quaternary polyamines, urea, thiocarbamide, gelatin, polyvinyl alcohol, aldehyde of amine and epihalohydrin etc.
" plating solution composition "
Plating solution composition of the present invention contains Zn ion (A), iron family element ting ion (B), based on the compound (C) of wolframic acid and water-soluble or water-dispersible organic polymer compounds (D) as necessary component.The example of available plating bath comprises that (1) acid bath is as using the sulfate baths of zinc sulfate, use the muriate of zinc chloride to bathe, with the fluoroboric acid salt bath that uses zinc fluoroborate, (2) the neutral bath, wherein zinc chloride neutralizes with ammonia, Repone K or analogue, (3) alkaline bath is as the tetra-sodium salt bath that uses zinc pyrophosphate, comprise zincic acid salt bath of zinc and sodium hydroxide or the like.Consider film binding property and erosion resistance to coating, for for each components contents in this plating solution composition, suitable is such some compositions: it contains 1 to 600g/l, preferred 50 to 300g/l, more preferably 60 to 250g/l Zn ion (A), 1 to 600g/l, preferred 50 to 300g/l, more preferably 60 to 250g/l iron family element ting ion (B), 0.1 to 200g/l, preferred 5 to 150g/l, more preferably 10 to 100g/l the compound based on wolframic acid of pressing the W ionometer (C) and 0.5 is to 500g/l, preferred 10 to 300g/l, more preferably 20 to 200g/l as the water-soluble of solid matter or water-dispersible organic polymer compounds (D).
Can in plating solution composition of the present invention, add the coordination agent that is used for stable metal ion, be used for further improving erosion resistance can be as discontinuous particle from the sedimentary corrosion inhibition pigment of electroplating solution and/or ceramic particle, corrosion inhibition organic compound and analogue.In addition, in above-mentioned plating solution composition, might use additive, this additive is generally used for improving scaling loss coating or the throwing power under low current density under high current density, as pH regulator agent, pit inhibitor (pit inhibitor), antifogging agent, defoamer or the like.
By to electroplate with the similar mode of traditional method, via the co-precipitation of organic polymer compounds and metal, plating solution composition of the present invention can be formed in the plated film of aspect excellences such as the binding property of filming, erosion resistance.
As for galvanized condition, suitable is: for plating bath is the situation of sulfate baths, and pH is about 1 to 3, bathes about 30 to 80 ℃ of temperature; For plating bath is the situation that muriate is bathed, and pH is about 4 to 7, bathes about 10 to 50 ℃ of temperature; And be the situation of alkaline bath for plating bath, pH is 12 or higher, bathes about 10 to 50 ℃ of temperature, and the thickness of plated film is from 0.5 to 5 μ m approximately aptly in all cases.
" electroplating metal material "
Electroplating metal material of the present invention obtains by using above-mentioned plating solution composition plated metal starting material.Raw material metal comprises the ferruginous material of main bag, for example has been processed into the material that is used for automobile, household electrical appliance and material of construction of the shape of plate, pipe, joint, clamp, bolt, nut or the like.
This plating condition as mentioned above.In addition, advantage of the present invention can further strengthen by carry out aftertreatment with the acidic aqueous solution that contains the compound that is selected from least a element in the group of being made up of cobalt, nickel, titanium and zirconium after electroplating film forms.Be selected from by cobalt as containing, nickel, the compound of at least a element in the group that titanium and zirconium are formed, available example comprise oxide compound, oxyhydroxide, fluorochemical, coordination fluorochemical, muriate, nitrate, vitriol, carbonate of these metals or the like.Specifically, their preferred example comprises Xiao Suangu, Zircosol ZN, hydrofluorination titanium, hydrofluorination zirconium, hydrofluorination ammonium titanium and hydrofluorination ammonium zirconium.
The acidic aqueous solution that contains the compound of these metallic elements preferably has and drops on 1 to the pH that is lower than in 7, preferably from 3 to 6 the scope.This pH can utilize sour example hydrochloric acid, nitric acid, sulfuric acid and hydrofluoric acid, or alkali such as sodium hydroxide, potassium hydroxide and amine are regulated.In addition, as required, coordination agent, silicon oxide particle etc. can be added in the acidic aqueous solution.Addition 0.001 to the 5mol/ liter preferably that contains the compound of metallic element, preferred especially about 0.01 to 1mol/ liter.
Aftertreatment with acidic aqueous solution can be undertaken by allowing electroplating film contact with treatment soln, for example by with metallic substance at 20 to 80 ℃, soaked 5 seconds or the longer time preferred about 20 to 90 seconds in the treatment soln of preferred 30 to 60 ℃ bath temperature.
Because the above electroplating metal material that obtains is excellent on the binding property of filming, coating directly paint does not have on this material of special surface processing.In addition, even when it combines with the surface treatment agent of Chrome-free environmental response, it demonstrates excellent erosion resistance.
Under the situation of coating electroplating metal material of the present invention, coating is not particularly limited, any curing pattern such as drying at room temperature, thermofixation or active energy ray solidify and can both use, and the coating of the coating of any kind such as solvent based coating, water-borne coatings and powdered can use.Especially,, then generally on this plated film, apply galvanic deposit enamelled coating, inter coat and finishing coat in turn, then baking if plating solution composition of the present invention is applied on the automobile.
Because electroplating metal material of the present invention is excellent on erosion resistance, might directly on untreated tabular electroplating metal material, form organic resin film, therefore can be as the steel plate of anti-fingerprint.In addition, by giving lubricity for above-mentioned organic resin film, products obtained therefrom can be used as lubricated steel sheet.
The steel plate of anti-fingerprint has the steel plate of the thin organic resin film of formation thereon to get rusty during preventing before steel plate uses.The organic resin that forms organic resin film is not particularly limited.The example of appropriate resin comprises urethane resin, Resins, epoxy, acrylic resin, vibrin, resol, polyolefin resin, Synolac, melamine resin, polyvinyl butyral acetal (polybutyral) resin or the like.This organic resin can be the solvent type resin that is dissolved in the organic solvent, but as possible, dissolving or dispersion (suspending or emulsification) water-base resin, particularly emulsion resin in water is preferred.
In above-mentioned organic membrane, add silicon oxide particle so that improve the binding property and the erosion resistance of this mould.As silicon oxide particle, the water-dispersible colloided silica is suitable, but also can use fumed silica and pulverize silicon oxide.Can enumerate SNOWTEXN, SNOWTEX C, SNOWTEX O (all by Nissan ChemicalIndustries, Ltd. make) or the like as water-dispersible colloided silica and AEROSIL 200V, AEROSILR-811 (all by Nippon Aerosil Co., Ltd. makes) or the like as other silicon oxide particle.
The lubricated metal material is a steel plate of it having been given in advance lubricating quality; therefore the processing such as impact briquetting can be carried out not being coated with under the punching oil; thereby suppressed from the Chlorofluorocarbons of the unfavorable solvent of the position of global environmental protection as using the punching oil washing step after moulding and processing steel plate; 1; 1, the use of 1-trichloroethane.Usually, the lubricating function imparting agent is introduced in the steel plate that is used for anti-fingerprint or the organic resin film of analogous products, therefore forms lubricant film on steel plate.The lubricating function imparting agent is preferably given lubricated (frictional coefficient attenuating) function to this film but can be by the painted reagent of baking.The example of preferred lubricating function imparting agent comprises polyolefin-wax such as polyethylene and polypropylene; Fluorine-based wax such as tetrafluoroethylene resin (PTFE), daiflon, vinylidene fluoride resin, fluoroethylene resin, Tefzel resin and tetrafluoroethylene/hexafluoropropylene copolymer resin, or the like.They can use separately or use as two or more the mixture in the middle of them.
Thickness with organic resin film of anti-finger printing energy and oilness is about 0.5 to 5 μ m, can be the coloured film that contains dyestuff or pigment.In addition, because can omit surface treatment,, can shorten production process significantly and can improve operation efficiency so be incorporated into by the application step that will form organic resin film in the production line of electroplating steel plate.
If electroplating metal material of the present invention is carried out surface treatment, then this processing enough chromate-based surface treatment agent of energy or phosphate base surface treatment agent carry out.Because electroplating metal material of the present invention is excellent on erosion resistance, thus by with the surface treatment agent of Chrome-free environmental response such as zirconium radical surface treatment agent or the combination of titanium-based surface treatment agent, also demonstrated excellent erosion resistance.In order to reduce carrying capacity of environment, preferably the surface treatment agent with the Chrome-free environmental response makes up.
Metallic substance through coating can be used in common use in the application of the metallic substance of coating, as material of construction, household electrical appliance, automobile, fastening piece or the like, does not have special restriction.Apply undercoat and finishing coat method can according to use, the shape of the articles coated of wanting or the like selects aptly.For example, for the coating of moulded product, spraying, dipping, galvanic deposit or similar approach suit, for the coating of the metallic substance of template goods such as precoating, and suitable roller coat, curtain flow coat cloth or the similar approach used.
＜embodiment 〉
The present invention will illustrate with reference to the following example in more detail.In this respect, " part " and " % " that use below all provide with weight.
" the 1. manufacturing of the preparation of plating bath and electroplating metal material "
(embodiment 1 to 15 and Comparative Examples 1 to 3)
Each plating bath is to form according to the blending shown in the following Table 1 to obtain.
Cold rolled metal material (SPCC) with 0.8mm plate thickness carries out alkali degreasing and washes with water, uses each in the above-mentioned plating bath then, carries out plating under following condition.
The plating condition: plating is to have 1 to 30A/dm by use
2The direct current of current density carries out under the bath temperature of 30 to 60 ℃ of scopes.The thickness of plated film all is 3 μ m in all cases.Film thickness is measured by fluorescent X-ray analysis instrument SEA5200 (being made by SeikoInstruments Inc.).
Table 1
| Metal ion *1(g/L) | Organic resin *2(g/l) | Corrosion inhibitor 3* (g/l) | Electroplating steel plate No. | ||||||||||||
| Zn | Fe | CO | Ni | W | R1 | R2 | R3 | R4 | R5 | F1 | F2 | F3 | |||
| Embodiment | 1 | 82 | 79 | 10 | 20 | A1 | |||||||||
| 2 | 93 | 60 | 10 | 40 | A2 | ||||||||||
| 3 | 78 | 75 | 10 | 20 | A2 | ||||||||||
| 4 | 78 | 75 | 20 | 40 | A4 | ||||||||||
| 5 | 78 | 75 | 20 | 40 | A5 | ||||||||||
| 6 | 78 | 75 | 20 | 120 | A6 | ||||||||||
| 7 | 62 | 90 | 20 | 80 | A7 | ||||||||||
| 8 | 155 | 150 | 30 | 20 | A8 | ||||||||||
| 9 | 232 | 225 | 40 | 40 | A9 | ||||||||||
| 10 | 146 | 142 | 60 | 80 | A10 | ||||||||||
| 11 | 129 | 125 | 80 | 150 | A11 | ||||||||||
| 12 | 112 | 106 | 100 | 200 | A12 | ||||||||||
| 13 | 78 | 75 | 10 | 40 | 30 | A13 | |||||||||
| 14 | 78 | 75 | 20 | 40 | 20 | A14 | |||||||||
| 15 | 78 | 75 | 20 | 40 | 1 | A15 | |||||||||
| Comparative Examples | 1 | 90 | 80 | 20 | B1 | ||||||||||
| 2 | 170 | 20 | 40 | B2 | |||||||||||
| 3 | 170 | 20 | 40 | B3 |
*1: each metal ion in table 1 is provided by following compounds.
Zn：ZnSO
4·7H
2O
Fe：FeSO
4·7H
2O
Co：CoSO
4·7H
2O
Ni：NiSO
4·7H
2O
W：Na
2WO
4.2H
2O
*2: each organic resin in table 1 is those shown in below.
R1: sodium lignosulfonate, about 10,000 number-average molecular weight.
R2: the Na salt of the sulfonated products of novolac-type phenol resins, about 23,000 number-average molecular weight.
R3: the Na salt of the sulfonated products of novolac-type phenol resins, about 40,000 number-average molecular weight.
R4: the Na salt of the sulfonated products of poly-right-hydroxy styrenes, about 5,000 number-average molecular weight.
R5: the Na salt of the sulfonated products of bisphenol A type epoxy resin, about 7,000 number-average molecular weight.
*3: each corrosion inhibitor in table 1 is those shown in below.
F1:K-WHITE 840E is made condensation of aluminum phosphate by Tayca Corporation.
F2:SNOWTEX-0, by Nissan Chemical Industries, Ltd. makes, colloidal silica.
F3:3-amino-1,2, the 4-triazole.
" 2. coating system 1 "
(embodiment 16 to 30 and Comparative Examples 4 to 6)
Alkali degreasing is carried out on each surface of the electroplating metal material that obtains in the table 1 shown in above, washes with water, drains and dry.Thereafter, (by Kansai Paint Co., Ltd. makes, propenyl-melamine resin base coating with " MAGICRON 1000 white ", white) apply thereon so that build becomes 30 μ m, toast down at 160 ℃ then and obtained respectively to test coated panel in 20 minutes.
(Comparative Examples 7)
Also (has 20g/m to plate thickness with the steel plate that phosphoric acid salt (trade(brand)name: Palbond 3118, by Nihon Parkerizing Co., Ltd. makes) was handled with 0.8mm
2The SECC material of clad deposit amount: apply " MAGICRON1000white " JIS G-3313) (by Kansai Paint Co., Ltd. make, propenyl-melamine resin type coating, white), so that build becomes 30 μ m, and baking obtained the test coated panel in 20 minutes under 160 ℃.
The coated panel of respectively testing usefulness for obtaining in above embodiment and the Comparative Examples carries out various tests according to following test method.The results are shown in the following table 2.
(finishing coat binding property): after coated panel soaked 2 hours in about 98 ℃ boiling water with each test, its is taken out and it was at room temperature placed 2 hours, the coating surface that to test coated panel cuts with cutter then, thereby cause arriving along the longitudinal and laterally each 11 line of base metal, formed in view of the above and have 100 square blocks of 2mm with lattice.When cellophane tape closely being adhered to grid part and this adhesive tape moment peeled off, peel off area according to what following standard evaluation was filmed this moment.
5: do not observe peeling off of filming.
4: observe peeling off but peeling off area of filming and be lower than 10%.
3: peel off area from 10% to being lower than 25%.
2: peel off area from 25% to being lower than 50%.
1: peeling off area is 50% or higher.
(erosion resistance after the coating): cutting arrives the mark signature line of base metal on each test coated panel, according to JIS Z-2371 it is carried out salt-fog test and reaches 240 hours.Thereafter, should test coated panel washes with water also dry.Then, cellophane tape is closely adhered to mark signature line part, when adhesive tape moment is peeled off, measure from the maximum of mark signature line part peel off width (side, mm).
Table 2
| Electroplating steel plate No. | Test-results | |||
| The finishing coat binding property | Coating back erosion resistance (side, mm) | |||
| Embodiment | 16 | A1 | 5 | 3 |
| 17 | A2 | 5 | 2 | |
| 18 | A2 | 5 | 2 | |
| 19 | A4 | 5 | 2 | |
| 20 | A5 | 5 | 3 | |
| 21 | A6 | 5 | 2 | |
| 22 | A7 | 5 | 4 | |
| 23 | A8 | 5 | 4 | |
| 24 | A9 | 5 | 3 | |
| 25 | A10 | 5 | 2 | |
| 26 | A11 | 5 | 2 | |
| 27 | A12 | 5 | 2 | |
| 28 | A13 | 5 | 2 | |
| 29 | A14 | 5 | 2 | |
| 30 | A15 | 5 | 2 | |
| Comparative Examples | 4 | B1 | 2 | 5 |
| 5 | B2 | 4 | 7 | |
| 6 | B3 | 5 | 5 | |
| 7 | 4 | 7 | ||
" 3. coating system 2 "
(embodiment 31 to 45 and Comparative Examples 8 to 10)
Each of the electroplating metal material that obtains in the table 1 shown in above is carried out degreasing, washes with water, drains and dry.Thereafter, apply cationic electro-dipcoat paint " ELECRON GT-10 " (by Kansai Paint Co., Ltd. makes, the coating of epoxy polyester resin base) by the galvanic deposit coating, toasted 20 minutes down at 170 ℃ then, acquisition has the galvanic deposit-coated panel of the build of 20 μ m.Use atomizer that middle coating " AMILAC TP-65 gray " (by Kansai Paint Co., Ltd. makes, amino-alkyd resin base coating) is applied on the galvanic deposit coating surface so that build becomes 30 μ m, and 140 ℃ of bakings 20 minutes down.Thereafter, use atomizer to be coated with finishing coat " NEO AMILAC#6000white " (by Kansai Paint Co., Ltd. make amino-alkyd resin base coating) apply thereon so that build becomes 30 μ m, toast down at 140 ℃ then and obtained respectively to test coated panel in 20 minutes.
(Comparative Examples 11)
Also use phosphoric acid salt (trade(brand)name: Palbond 3020 by the galvanic deposit coating method to having the 0.8mm plate thickness, by Ninon Parkerizing Co., Ltd. manufacturing) alloyage hot-dip galvanized steel sheet (the SGCC F06 material of handling: JIS G-3302) apply cationic electro-dipcoat paint " ELECRON GT-10 " (by Kansai Paint Co., Ltd. make, epoxy polyester resin base coating), obtain to have the galvanic deposit coated panel of 20 μ m builds then 170 ℃ of following bakings 20 minutes.Use atomizer that middle coating " AMILAC TP-65gray " (by Kansai Paint Co., Ltd. makes, amino-alkyd resin base coating) is applied on the galvanic deposit coating surface so that build becomes 30 μ m, and 140 ℃ of bakings 20 minutes down.Thereafter, use atomizer with finishing coat " NEO AMILA C#6000white " (by Kansai Paint Co., Ltd. make amino-alkyd resin base coating) apply thereon so that build becomes 30 μ m, toast down at 140 ℃ then and obtained the test coated panel in 20 minutes.
Respectively test coated panel for what obtain in above embodiment and the Comparative Examples, carry out various tests according to following test method.The results are shown in the following table 3.
(scaling resistance): will test on the test specimen clamper that coated panel is fixed on gravel slabbing tester JA-400Model (by Suga Test Instruments Co., the slabbing testing apparatus that Ltd makes), and meet at right angles with respect to its gravel spout.Then, under-20 ℃, utilize 0.294MPs (3kgf/cm
2) pressurized air be sprayed on coating surface with the broken grouan that 50g has the No.7 particle diameter, the fragment that visual inspection produces on filming is also estimated according to following standard.
AA: the size of fragment is quite little, and only finishing coat is impaired.
A: the size of fragment is little, and only inter coat exposes.
B: the size of fragment is little, but the metallic substance of base metal exposes.
C: the size of fragment is quite big, and the metallic substance of base metal largely exposes.
(water-fast secondary bonding): after coated panel soaked 10 days in about 40 ℃ warm water with each test, cut the surface through coating of this test coated panel with cutter, thereby cause arriving along the longitudinal and laterally each 11 line of base metal, formed in view of the above and have 100 square blocks of 2mm with lattice.Cellophane tape is closely adhered to the grid part, and when this adhesive tape moment was peeled off, peeled off area according to what following standard evaluation was filmed this moment.
5: do not observe peeling off of filming.
4: observe peeling off but peeling off area of filming and be lower than 10%.
3: peel off area from 10% to being lower than 25%.
2: peel off area from 25% to being lower than 50%.
1: peeling off area is 50% or higher.
(erosion resistance): cutting arrives the mark signature line of base metal on the coated panel of each test usefulness, according to JIS Z-2371 it is carried out salt-fog test then and reaches 960 hours.Should test with coated panel washed and dry air thereafter.Then, estimate the getting rusty and swelling of general part, and cellophane tape closely adheres to mark signature line part according to following standard, measure when adhesive tape moment peels off from mark signature line maximum partly peel off width (side, mm).
A: do not observe rust and swollen generation on coating surface.
B: observe on coating surface rust and swollen and slightly produce.
C: observe on coating surface rust and swollen and obviously produce.
(resistance to salt water): cutting arrives the mark signature line of base metal on each test coated panel, then it is soaked 10 days down at 50 ℃ in 5% salt solution.Should test with coated panel washed and dry air thereafter.Then, estimate getting rusty of general part and swelling, and cellophane tape closely adhered on the mark signature line part according to following standard, when adhesive tape moment is peeled off, measure from the maximum of mark signature line part peel off width (side, mm).
A: do not observe rust and swollen generation on coating surface.
B: observe on coating surface rust and swollen and slightly produce.
C: observe on coating surface rust and swollen and obviously produce.
Table 3
| Electroplating film No. | Test-results | |||||||
| Anti-falling property of fragment | Water tolerance secondary binding property | Erosion resistance | Resistance to salt water | |||||
| General part | Maximum peel off width (side, mm) | General part | Maximum peel off width (side, mm) | |||||
| Embodiment | 31 | A1 | AA | 5 | A | 6 | A | 1 |
| 32 | A2 | AA | 5 | A | 4 | A | 1 | |
| 33 | A2 | AA | 5 | A | 4 | A | 1 | |
| 34 | A4 | AA | 5 | A | 4 | A | 0 | |
| 35 | A5 | AA | 5 | A | 3 | A | 0 | |
| 36 | A6 | AA | 5 | A | 3 | A | 0 | |
| 37 | A7 | AA | 5 | A | 5 | A | 2 | |
| 38 | A8 | AA | 5 | A | 6 | A | 3 | |
| 39 | A9 | AA | 5 | A | 3 | A | 0 | |
| 40 | A10 | AA | 5 | A | 3 | A | 1 | |
| 41 | A11 | AA | 5 | A | 2 | A | 0 | |
| 42 | A12 | AA | 5 | A | 2 | A | 1 | |
| 43 | A13 | AA | 5 | A | 2 | A | 0 | |
| 44 | A14 | AA | 5 | A | 2 | A | 0 | |
| 45 | A15 | AA | 5 | A | 2 | A | 0 | |
| Comparative Examples | 8 | B1 | A | 2 | A | 6 | A | 2 |
| 9 | B2 | C | 4 | A | 13 | A | 4 | |
| 10 | B3 | B | 5 | A | 10 | A | 3 | |
| 11 | C | 5 | A | 8 | A | 2 | ||
" 4. coating system 3 "
(embodiment 46 to 60 and Comparative Examples 12 to 14)
Alkali degreasing is carried out on each surface of the electroplating metal material that obtains in the table 1 shown in above, washes with water, drains and dry.Thereafter, utilize metering bar coater to apply colored 8000 priming paint of KP thereon (by Kansai Paint Co., Ltd. make, modified epoxy resin base coating) so that build becomes 5 μ m, making PMT (steel plate be up to temperature) become under 210 ℃ the condition 20 seconds of baking, film then with formation.Then, utilize metering bar coater on primer film, to apply the colored 1580white of KP (by Kansai Paint Co., Ltd. make, polyester resin-based coating) so that build becomes 15 μ m, make PMT become under 215 ℃ the condition baking 40 seconds then, thus produce have a last coating film respectively test coated panel.
(Comparative Examples 15)
Also use chromic salt (trade(brand)name: COSMER 500 at plate thickness with 0.8mm, by Kansai Paint Co., the Ltd manufacturing) hot-dip galvanized steel sheet (the SGCC Z25 material of handling: JIS G-3302), apply colored 8000 priming paint of KP (by Kansai Paint Co. by metering bar coater, Ltd. make, modified epoxy base coating), and make PMT become under 210 ℃ the condition 20 seconds of baking so that build becomes 5 μ m.Then, utilize metering bar coater on the priming paint film, to apply the colored 1580white of KP (by Kansai Paint Co., Ltd. make, polyester resin-based coating) so that build becomes 15 μ m, toast in that PMT is become under 215 ℃ the condition then, thus produce have a last coating film respectively test coated panel.
For each the test coating cladding plate that obtains in the foregoing description and the Comparative Examples, according to following test method, the test of the binding property of filming, erosion resistance and wet fastness.The results are shown in the following table 4.
(binding property of filming): cut the coating surface of this test coated panel with cutter, thereby cause arriving along the longitudinal and laterally each 11 line of base metal, formed in view of the above and have 100 square blocks of 1mm with lattice.When cellophane tape closely being adhered to grid part and this adhesive tape moment is peeled off, the extent of exfoliation that film according to following standard evaluation this moment.
5: do not observe peeling off of filming.
4: observe peeling off but peeling off area of filming and be lower than 10%.
3: peel off area from 10% to being lower than 25%.
2: peel off area from 25% to being lower than 50%.
1: peeling off area is 50% or higher.
(erosion resistance): will be cut into after the edge section and sealing backside of test coated panel of 70cm * 150cm size with last coating film, be arranged on test coated panel top the 4T folded part (carried out 180 ° of folded portions, coating surface externally and the spacing piece of four 0.8mm thickness get involved wherein) and in the mark signature line part of test coated panel bottom.According to JIS Z-2371 coated panel is carried out salt-fog test and reach 1000 hours.Then, according to following standard estimate the degree that produces at the white rust of 4T folded part, at the swelling width of mark signature line part with in the swelling generation degree of the general part part of cutting (not have to handle and).
＜general part 〉
AA: do not observe swollen and produce.
A: observe swollen and slightly produce.
B: observe swollen and obviously produce.
C: it is significant that swollen produces, and a part of filming is stripped from.
＜mark signature line part 〉
AA: be lower than 1mm from the surperficial swelling width of the list of mark signature line.
A: from the surperficial swelling width of the list of mark signature line from 1mm to being lower than 2mm.
B: from the surperficial swelling width of the list of mark signature line from 2mm to being lower than 5mm.
C: from the surperficial swelling width of the list of mark signature line greater than 5mm.
＜folded part 〉
AA: do not observe the generation of white rust.
A: observe the slight generation of white rust.
B: observe the obvious generation of white rust.
C: the generation of white rust is significant, and a part is filmed and peeled off.
(wet fastness): will be cut into 70cm * 150cm size and have after the edge section and sealing backside of test coated panel of last coating film, and test according to JIS K-5400 9.2.2.Temperature in the anti-moisture test instrument is that 50 ℃ and relative humidity are that test period is 1000 hours under 95 to 100% the condition.The swelling generation degree of filming on the test coated panel after test is estimated according to following standard.
AA: do not observe swollen and produce.
A: observe swollen and slightly produce.
B: observe swollen and obviously produce.
C: it is significant that swollen produces, and a part of filming is peeled off.
Table 4
| Electroplating film No. | Test-results | ||||||
| The binding property of filming | Erosion resistance | Wet fastness | |||||
| General part | Mark signature line part | Folded part | |||||
| Embodiment | 46 | A1 | 5 | AA | A | A | AA |
| 47 | A2 | 5 | AA | A | A | AA | |
| 48 | A2 | 5 | AA | A | A | AA | |
| 49 | A4 | 5 | AA | AA | A | AA | |
| 50 | A5 | 5 | AA | A | A | AA | |
| 51 | A6 | 5 | AA | A | A | AA | |
| 52 | A7 | 5 | AA | A | A | AA | |
| 53 | A8 | 5 | AA | A | A | AA | |
| 54 | A9 | 5 | AA | AA | A | AA | |
| 55 | A10 | 5 | AA | AA | A | AA | |
| 56 | A11 | 5 | AA | A | A | AA | |
| 57 | A12 | 5 | AA | A | A | AA | |
| 58 | A13 | 5 | AA | A | A | AA | |
| 59 | A14 | 5 | AA | A | A | AA | |
| 60 | A15 | 5 | AA | A | A | AA | |
| Comparative Examples | 12 | B1 | 2 | AA | B | B | B |
| 13 | B2 | 4 | AA | B | A | A | |
| 14 | B3 | 4 | AA | A | B | AA | |
| 15 | 4 | AA | A | B | AA | ||
" 5. coating system 4 "
(embodiment 61 to 75 and Comparative Examples 16 to 18)
Degreasing is carried out on each surface of the electroplating metal material that obtains in the table 1 shown in above, washes with water, drains and dry.To according to each basis in the organic resin coating composition C1 to C5 that at prescription following table 5 shown in (its formula rate be solid matter ratio) produced in combination table 6 shown in apply thereon, so that dry film weight become 0.8g/m thereafter,
2And make PMT become under 120 ℃ the condition 20 seconds of baking, respectively test coated panel to be manufactured on shown in the table 6.
The starting material of each note in table 5 are respectively following materials.
*1) NIKASOL RX-672A: by Nippon Carbide IndustriesCo., Inc. makes, the propenyl emulsion
*2) SUPERFLEX 150: by Dai-ichi Kogyo Seiyaku Co., Ltd. makes, polyurethane dispersions
*3) CHEMIPEARL S-650: by Mitsui Chemicals, Inc. makes, the ethene ionomer resin
*4) ADEKA BONTIGHTER HUX232: by Asahi Denka Co., Ltd. makes, carboxylic polyurethane dispersions
*5) EPIKOTE 1007: by Japan Epoxy Resins Co., Ltd. makes, Resins, epoxy
*6) DURANATE MF-80: by Asahi Kasei Corporation system, end-blocking (block) isocyanate resin
*7) SNOWTEX N: make colloided silica by Nissan Chemical Industries Ltd.
*8) AEROSIL R-811: by Nippon Aerosil Co., Ltd. makes, the fine powder silicon oxide
*9) CHEMIPEARL W-700: by Mitsui Chemicals, Inc. makes, a sub polyethylene prose style free from parallelism
*10) PTFE powder: teflon resin powder with particle diameter of 2 to 5 μ m
(Comparative Examples 19)
Have the 0.8mm plate thickness and using the steel plate of the electro-galvanizing of chromic salt (trade(brand)name: Cosmer 500, by Kansai Paint Co., Ltd. makes) processing (to have 20g/m
2The SECC material of electroplating deposition amount: JIS G 3313), be applied in the organic resin coating composition C1 shown in the table 5, so that dry film weight becomes 0.8g/m
2, and, make the test coated panel making PMT become under 120 ℃ the condition 20 seconds of baking.
Table 5
| Organic resin coating composition No. | |||||
| C1 | C2 | C3 | C4 | C5 | |
| NIKASOL RX-672A *1) | 75 | ||||
| SUPERFLEX 150 *2) | 75 | ||||
| CHEMIPEARL S-650 *3) | 75 | ||||
| ADEKA BONTIGHTER HUX232 *4) | 75 | ||||
| EPIKOTE 1007 *5) | 67.5 | ||||
| DURANATE MF-80 *6) | 7.5 | ||||
| SNOWTEX N *7) | 12.5 | 12.5 | 12.5 | 12.5 | |
| AEROSIL R-811 *8) | 12.5 | ||||
| CHEMIPEARL W-700 *9) | 12.5 | 12.5 | 12.5 | 12.5 | |
| The PTFE powder *10) | 12.5 | ||||
Respectively test coated panel for what in above embodiment and Comparative Examples, obtain, carry out various tests according to following test method.The results are shown in the following table 6.
(test method)
(anti-exposed corrodibility): will test after the edge section and sealing backside of coated panel, and according to JIS Z-2371 this coated panel be carried out salt-fog test and reach 360 hours.Then, estimate at the lip-deep rusting rate of treated film according to following standard.
A: white rust generation degree is lower than 5% of the area of filming.
B: the degree that white rust produces be film area 5% to being lower than 30%.
C: white rust generation degree be film area 30% or higher.
(finishing coat binding property): with " MAGICRON#1000 white " (by KansaiPaint Co., Ltd. make, propenyl-melamine resin base coating, white) be applied on the test coated panel so that build becomes 30 μ m, then at 150 ℃ of plates that toast 20 minutes acquisition coated face coatings down.After the plate of coated face coating soaked 2 hours in boiling water, it was at room temperature placed 2 hours, cut this coating surface with cutter then, thereby cause arriving along the longitudinal and laterally each 11 line of base metal, formed in view of the above and have 100 square blocks of 1mm with lattice.When cellophane tape closely being adhered to grid part and this adhesive tape moment peeled off, estimate the extent of exfoliation of finishing coat coated film according to following standard.
A: do not observe peeling off of coating film.
B: in 1 to 9 block, observe peeling off of coating film.
C: in 10 or more a plurality of block, observe peeling off of coating film.
(anti-finger printing): after the L value of filming, a value and the b value of using colour-difference meter " SM color computer MODELMODEL SM-5 " (by Suga Test Instruments Co., Ltd. makes) experiment with measuring plate, on filming, apply white vaseline.After wiping Vaseline, measure this L value, a value and b value once more with useless cloth.Then, calculate the aberration of Vaseline before and after applying, and under following standard the evaluation test plate.
A: Δ E is lower than 1.0
B: Δ E from 1.0 to being lower than 3.0
C: Δ E is from more than 3.0 or 3.0.
(oilness): by tensile testing machine at 50kg/cm
2The plate test coupon that stretches under surface pressure and the 100m/ minute rate of extension, and be determined at the dynamic friction coefficient of this moment, estimate oilness according to following standard.In this respect, this test is to having applied C3, and the system of C4 and C5 is carried out, and in this system the lubricating function imparting agent is added in each organic resin coating composition.
A: dynamic friction coefficient is lower than 0.15
B: dynamic friction coefficient from 0.15 to being lower than 0.30
C: dynamic friction coefficient is 0.30 or higher.
Table 6
| Electroplating film No. | Organic resin coating composition No. | Test-results | |||||
| Anti-exposed corrodibility | The finishing coat binding property | Anti-finger printing | Oilness | ||||
| Embodiment | 61 | A1 | C1 | A | A | A | - |
| 62 | A2 | C1 | A | A | A | - | |
| 63 | A2 | C2 | A | A | A | - | |
| 64 | A4 | C2 | A | A | A | - | |
| 65 | A5 | C3 | A | A | A | A | |
| 66 | A6 | C3 | A | A | A | A | |
| 67 | A7 | C3 | A | A | A | A | |
| 68 | A8 | C4 | A | A | A | A | |
| 69 | A9 | C4 | A | A | A | A | |
| 70 | A10 | C5 | A | A | A | A | |
| 71 | A11 | C5 | A | A | A | A | |
| 72 | A12 | C5 | A | A | A | A | |
| 73 | A13 | C2 | A | A | A | - | |
| 74 | A14 | C3 | A | A | A | A | |
| 75 | A15 | C5 | A | A | A | A | |
| Comparative Examples | 16 | B1 | C1 | B | C | A | - |
| 17 | B2 | C3 | B | A | A | A | |
| 18 | B3 | C5 | B | A | A | A | |
| 19 | C1 | A | B | A | - | ||
" 6. coating system 5 "
(embodiment 76 to 82)
The steel bolt carries out alkali degreasing and washes with water, then it is at room temperature soaked 30 seconds to carry out activation treatment in 1% sulphuric acid soln.By use batch-type cylinder electroplanting device, contain in the alkaline plating bath of predetermined metal ion table 7 shown in, corrosion inhibition pigment, corrosion inhibition organic compound and ceramic particle electroplate thereafter.The composition of film is regulated by change concentration ratio, current density and bath temperature of metal ion in plating bath, and coating film thickness is controlled by selecting electroplating time aptly.Then, aftertreatment is by it being immersed in the HNO that comprises 5g/l
3(NH with 15g/l
4)
2ZrF
6Acidic aqueous solution in carry out, produce the bolt that is for experiment thus.
(Comparative Examples 20)
The steel bolt carries out alkali degreasing and washes with water, then it is at room temperature soaked 30 seconds to carry out activation treatment in 1% sulphuric acid soln.Thereafter, electro-galvanizing (5 μ m) uses zincic acid salt bath (metallic zinc: 10g/l, sodium hydroxide: 120g/l) carry out.Then, at Yuken Industry Co., Ltd. makes contains chromic chromatedsolution: soaked 10 seconds down at 25 ℃ among the METASU CY-6, to carry out chromate treating, produce the bolt of contrast usefulness thus with it.The adhesion amount of chromate film is 5 to 6mg/dm
2
The erosion resistance of the gained bolt of using by following method evaluation test.Evaluation result is shown in table 7.
(erosion resistance): salt-fog test (SST) is carried out according to JIS Z2371, and erosion resistance was estimated by the needed time of generation of white rust 10% or red rust 5%.
Table 7
| Metal ion *4(g/L) | Organic resin *5 (g/l) | Corrosion inhibitor *6 | Erosion resistance | ||||||||||
| Zn | Fe | Co | Ni | W | R6 | R7 | F1 | F2 | F3 | White rust 10% | Red rust 5% | ||
| Embodiment | 76 | 78 | 75 | 20 | 20 | 168 | 480 | ||||||
| 77 | 93 | 60 | 10 | 20 | 120 | 504 | |||||||
| 78 | 93 | 60 | 10 | 20 | 120 | 480 | |||||||
| 79 | 93 | 60 | 10 | 20 | 120 | 600 | |||||||
| 80 | 78 | 75 | 20 | 20 | 30 | 240 | 720 | ||||||
| 81 | 78 | 75 | 20 | 20 | 20 | 240 | 720 | ||||||
| 82 | 78 | 75 | 20 | 20 | 1 | 168 | 680 | ||||||
| Comparative Examples 20 | 72 | 240 | |||||||||||
*4: each metal ion in table 7 is provided by following compounds.
Zn：ZnO
Fe：FeSO
4·7H
2O
Co：CoSO
4·7H
2O
Ni：NiSO
4·7H
2O
W：Na
2WO
4·2H
2O
*5: each organic resin in table 7 is those shown in below.
R6: polymine, about 3,000 number-average molecular weight.
R7: polyoxyethylene glycol, about 10,000 number-average molecular weight.
*6: each corrosion inhibitor in table 7 is those shown in below.
F1:K-WHITE 840E is made condensation of aluminum phosphate by Tayca Corporation.
F2:SNOWTEX-O, by Nissan Chemical Industries, Ltd. makes, colloidal silica
F3:3-amino-1,2, the 4-triazole.
Although the present invention at length and with reference to its specific embodiment is described, to those skilled in the art, it is evident that do not breaking away under the spirit and scope of the present invention, can carry out various variations and modification.
The application is that their content is introduced for your guidance herein based on Japanese patent application No 2003-410843 (application on December 9th, 2003) and 2004-149276 (application on May 19th, 2004).
＜industrial applicibility 〉
Because using the obtainable organic polymer-zinc alloy composite electroplating metal material of organic polymer-zinc alloy composite plating solution composition of the present invention is being excellent to the coating cohesive of filming thereon, therefore there be not surface treatment as obtaining enough coating adhesion and corrosion resistance with the chromate processing or in parkerized situation. Therefore, the noxious material that not only produces when surface treatment such as chromium waste liquid can be eliminated, and because the shortening of coating line, the in addition large advantage of cost.
Claims (13)
1. organic polymer-zinc alloy composite plating solution composition, it contains:
(A) 1 to 600g/l Zn ion,
(B) 1 to 600g/l iron family element ting ion,
(C) count 0.1 to 200g/l compound by the W ion based on wolframic acid, and
(D) 0.5 to 500g/l have 1,000 to 1,000, the water-soluble or water-dispersible organic polymer compounds of 000 number-average molecular weight.
2. organic polymer-zinc alloy composite plating solution composition according to claim 1, wherein, this iron family element ting ion (B) is the Fe ion.
3. organic polymer-zinc alloy composite plating solution composition according to claim 1 and 2 wherein, should be at least a compound that is selected from the group of being made up of wolframic acid, tungstate, phospho-wolframic acid and Lin Wusuanyan based on the compound (C) of wolframic acid.
4. according to any one described organic polymer-zinc alloy composite plating solution composition in the claim 1 to 3, wherein, this organic polymer compounds (D) has at least a hydrophilic radical that is selected from the group of being made up of non-ionic hydrophilic group, anionic hydrophilic group and cationic hydrophilic group.
5. according to any one described organic polymer-zinc alloy composite plating solution composition in the claim 1 to 4, wherein, this organic polymer compounds (D) has at least a hydrophilic radical that is selected from the group of being made up of hydroxyl, sulfonic group, phosphate, carboxyl, amino and ammonium group.
6. according to any one described organic polymer-zinc alloy composite plating solution composition in the claim 1 to 5, it further contains 5 to 300g/l corrosion inhibition pigment and/or ceramic particle.
7. organic polymer-zinc alloy composite plating solution composition according to claim 6, wherein, this corrosion inhibition pigment is to be selected from least a in the group of being made up of phosphoric acid salt, molybdate, metaborate and silicate.
8. organic polymer-zinc alloy composite plating solution composition according to claim 6, wherein, this ceramic particle is the particle that is selected from by at least a material in the following group of forming: Al
2O
3, SiO
2, TiO
2, ZrO
2, Y
2O
2, ThO
2, CeO
2, Fe
2O
3, B
4C, SiC, WC, ZrC, TiC, graphite, fluorographite, BN, Si
3N
4, TiN, Cr
3B
2, ZrB
2, 2MgOSiO
2, MgOSiO
2And ZrO
2SiO
2
9. according to any one described organic polymer-zinc alloy composite plating solution composition in the claim 1 to 8, it further contains 0.01 to 10g/l at least a organic compound in the group of being made up of alkynes, alkynol, amine or its salt, thio-compounds, aromatic carboxylic acid's compound or its salt and heterogeneous ring compound of being selected from.
10. organic polymer-zinc alloy composite electroplating metal material, it can come the plated metal starting material to obtain according to any one described organic polymer-zinc alloy composite plating solution composition in the claim 1 to 9 by using.
11. organic polymer-zinc alloy composite electroplating metal material according to claim 10, it contacts with the acidic aqueous solution that contains the compound that is selected from least a element in the group of being made up of cobalt, nickel, titanium and zirconium by the film that is formed by plating and obtains.
12. the steel plate of an anti-fingerprint wherein, is not having under the surface-treated situation, directly forms organic resin film on according to claim 10 or 11 described organic polymer-zinc alloy composite electroplating metal materials.
13. a lubricated steel sheet wherein, is not having under the surface-treated situation, directly forms organic resin film on according to claim 10 or 11 described organic polymer-zinc alloy composite electroplating metal materials.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003410843 | 2003-12-09 | ||
| JP410843/2003 | 2003-12-09 | ||
| JP149276/2004 | 2004-05-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1914358A true CN1914358A (en) | 2007-02-14 |
Family
ID=37722598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480041514 Pending CN1914358A (en) | 2003-12-09 | 2004-12-07 | Electroplating solution composition for organic polymer-zinc alloy composite plating and plated metal material using such composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1914358A (en) |
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| CN102648090A (en) * | 2009-12-07 | 2012-08-22 | 新日本制铁株式会社 | Chromate-free precoated steel sheet having excellent end-surface rust corrosion resistance |
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| JP2013151734A (en) * | 2011-12-26 | 2013-08-08 | Nippon Steel & Sumitomo Metal Corp | Electrogalvanized steel sheet for high image clarity coating substrate excellent in corrosion resistance after coating and enamel hair resistance, and method for producing the same |
| US10793956B2 (en) | 2015-08-29 | 2020-10-06 | Mitsubishi Materials Corporation | Additive for high-purity copper electrolytic refining and method of producing high-purity copper |
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| CN112424395A (en) * | 2018-07-05 | 2021-02-26 | 凯密特尔有限责任公司 | Method for treating metal surfaces with acidic aqueous compositions to improve corrosion resistance |
| CN110284163A (en) * | 2019-07-31 | 2019-09-27 | 广州三孚新材料科技股份有限公司 | Copper plating solution for solar cell and preparation method thereof |
| CN110284163B (en) * | 2019-07-31 | 2020-08-04 | 广州三孚新材料科技股份有限公司 | Copper plating solution for solar cell and preparation method thereof |
| CN114394596A (en) * | 2021-12-30 | 2022-04-26 | 铜陵日飞创客科技有限公司 | Special long-life bearing for high-power plowing plough |
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