CN102746778B - Galvanizing steel strip with good conductivity, high corrosion resistance and fingerprint resistance, surface treatment agent and treatment method - Google Patents
Galvanizing steel strip with good conductivity, high corrosion resistance and fingerprint resistance, surface treatment agent and treatment method Download PDFInfo
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- CN102746778B CN102746778B CN201210223570.8A CN201210223570A CN102746778B CN 102746778 B CN102746778 B CN 102746778B CN 201210223570 A CN201210223570 A CN 201210223570A CN 102746778 B CN102746778 B CN 102746778B
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
- B05D3/0263—After-treatment with IR heaters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C08G2150/00—Compositions for coatings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/32—Phosphorus-containing compounds
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Abstract
Provided is a galvanizing steel strip with good conductivity, high corrosion resistance and fingerprint resistance, a surface treatment agent and a treatment method. The galvanizing steel strip is covered with a fingerprint-resistant film, wherein the film composition comprises: polyurethane and/or acrylic organic resin (A), with the weight percentage thereof being 40% to 60%; an organic silane coupling agent (Ba) containing one or more amino function groups which has at least one active hydrogen, and an organic silane coupling agent (Bb) containing at least one epoxy function group the number of which is more than one, with the weight ratio of Ba to Bb being from 0.3 to 0.5 and the weight percentage of the organic silane coupling agent being 38% to 53%; organo phosphorous compounds (C), with the weight percentage of phosphorus element being 0.01% to 0.1%; vanadium compounds (D), with the weight percentage of vanadium element being 0. 1% to 1.0%; titanium compounds or fluorine-containing titanium compounds (E), with the weight percentage of titanium element being 0. 1% to 3.0%; and polyethylene wax, with the weight percentage thereof being 1% to 3% of the film.
Description
Technical field
The present invention relates to Galvanized Steel Strip and process for treating surface thereof, be particularly related to a kind of good conduction, the high anti-corrosion Galvanized Steel Strip of resistance to fingerprint and surface treatment agent, treatment process, can meet and when non-chromate coatings technology is in the past difficult to realize, meet good electric conductivity and high anti-corrosion characteristic, and possess the over-all propertiess such as humidity resistance, thermotolerance, anti-finger printing, weldability, coating and anti-processing blackening that general non-chromate coatings has.
Background technology
Galvanized Steel Strip is one of metal products being most widely used in the world, is widely used in household electrical appliances, building and automotive field.In order further to improve the solidity to corrosion of Galvanized Steel Strip, developed the chromium-free fingerprint-resistant Galvanized Steel Strip that many kinds have different qualities.China Patent Publication No. CN101435078A discloses a kind of good corrosion resistance that simultaneously has, alkali resistance, processibility and electroconductibility and chemical-resistant non-chrome resin composition and the method for Galvanized Steel Strip being processed with this constituent, its constituent is by urethane resin, the organic oxygen compound of Ti and Zr, inorganic salt and the solvent of water as master of take, although but the Galvanized Steel Strip of being processed by such constituent has solidity to corrosion and electroconductibility and other useful property, but embodiment shows its electroconductibility and only reaches below 1m Ω (surface resistivity), solidity to corrosion (take neutral salt spray test) is 96 hours.Such performance is electroconductibility and solidity to corrosion are required to higher industry, if the fields such as office automation electrical equipment such as duplicating machine, facsimile recorder are inadequate.
US Patent No. 2005/0058843A1 provides a kind of method of processing steel plate galvanized with the aqueous compositions after two kinds of silane mixture such as vinyl silanes, aminosilane, there is certain wet-hot aging performance and solidity to corrosion (in neutral salt spray test), but its treatment process is that steel plate is immersed in above-mentioned aqueous compositions and is dried 5 minutes, and such method cannot realize the continuous processing of Galvanized Steel Strip.
China Patent Publication No. CN101228294A provides a kind of non-chromate surface-treated metal material that simultaneously possesses solidity to corrosion, thermotolerance, anti-finger printing, electroconductibility, coating and anti-processing blackening, its method is to form at the also dry water-based metal-surface-treating agent of metal material surface coated the composite film that contains various compositions, but the electroconductibility that this patent provides has only guaranteed layer impedance value, do not relate to the sheet resistance value of household electric appliances special concern.
China Patent Publication No. CN 101688309A provides a kind of steel plate galvanized use surface treatment liquid and steel plate galvanized, by processing GI and GA surface, can make steel plate obtain good conduction and high anti-corrosion simultaneously, there is coating and alkali resistance simultaneously, but because its technological line adopting is that inorganic salt are as the film forming skeleton of coating, the organic crylic acid resin that has only mixed part in coating, such coating structure is difficult to guarantee excellent anti-finger printing energy.
China Patent Publication No. CN 1887449A provides a kind of surface treatment agent for steel plate galvanized with excellent alkali resistance and solvent resistance, by the aqueous treatment agent processing steel plate galvanized of composition such as urethane, silane, specific inorganic salt and a small amount of auxiliary agent being obtained to all very excellent chromium-free fingerprint-resistant steel bands of an alkali resistance, solvent resistance, solidity to corrosion, anti-finger printing, coating, anti-processing blackening, but cannot guaranteeing coating, this patent under the thickness condition of above-mentioned performance, there is good surface conduction performance having simultaneously.The over-all propertieies such as in sum, existing various Chrome-free process for treating surface are all difficult to comprehensive good conduction at present, height is anti-corrosion, resistance to fingerprint all meet the chromium-free fingerprint-resistant Galvanized Steel Strip of high-end household electrical appliances customer need.
Summary of the invention
The object of the invention is a kind of good conduction, the high anti-corrosion Galvanized Steel Strip of resistance to fingerprint and surface treatment agent, treatment process, every high comprehensive performances such as its electroconductibility (ground connection property), solidity to corrosion, weldability and processing, be applicable to the fields such as household electrical appliances and office appliance, become electric product to meet the relevant international standard of electromagnetic wave leakage test.
For achieving the above object, technical scheme of the present invention is:
Good conduction, the high anti-corrosion Galvanized Steel Strip of resistance to fingerprint, its surface coverage one deck epithelium of resistance to fingerprint, this epithelium constituent comprises:
A) urethane and/or vinylformic acid organic resin (A), shared weight percent is 40～60%;
B) active hydrogen that contains an above amido functional group, amido functional group is at least the organo silane coupling agent (Ba) of and contains at least one epoxy functionality, the more than one organo silane coupling agent of epoxy functionality number (Bb), and (Ba)/weight ratio (Bb) is 0.3～0.5; The weight ratio of above-mentioned organic resin (A) and organo silane coupling agent ((Ba)+(Bb)) is 1.0～2.0; The shared weight percent of organo silane coupling agent is 38～53%;
C) organo phosphorous compounds, the shared weight percent of the phosphoric of take is 0.01～0.1%;
D) vanadium compound (D), the shared weight percent of the v element of take is 0.1～1.0%;
E) titanium compound or fluorine-containing titanium compound (E), the shared weight percent of titanium elements amount of take is 0.1～3.0%;
F) polyethylene wax, accounts for epithelium content 1～3%.
Further, zinc-plated substrate profile arithmetic average roughness Ra value 0.4 ~ 1.2 μ m, crest are counted between RPc value 50～150.
The present invention is for the treatment agent of described good conduction, the high anti-corrosion Galvanized Steel Strip of resistance to fingerprint, for aqueous solution, the weight percent of its amount of solid content is 10～20%, and in solid part, the weight percent of each component is: urethane and/or vinylformic acid organic resin (A), 40～60%; Organo silane coupling agent (Ba), contains an above amido functional group, and the active hydrogen of amido functional group is at least one; Organo silane coupling agent (Bb), contains at least one epoxy functionality, and epoxy functionality number is more than one; (Ba)/weight ratio (Bb) is 0.3～0.5; The weight ratio of above-mentioned organic resin (A) and organo silane coupling agent ((Ba)+(Bb)) is 1.0～2.0; (Ba)+(Bb), the content in solid part is 38～53%; Organo phosphorous compounds (C), the phosphoric of take account for solid part total amount as weight percent, 0.01～0.1%; Vanadium compound (D), accounts for the weight percent of solid part total amount, 0.1～1.0% in v element; Titanium compound or fluorine-containing titanium compound (E), account for the weight percent of solid part total amount, 0.1～3.0% in titanium elements; Polyethylene wax (F), accounts for the weight percent of solid part total amount, 1～3%.
Further, the glass transition temperature of described urethane and/or vinylformic acid organic resin (A) is 30～80 ℃, and possesses water-soluble or water dispersible.
Again, described urethane resin is the polymkeric substance of polyalcohols and polymeric polyisocyanate, polyalcohols is polyester polyglycol, polyethers polyglycol, polycarbonate polyglycol, contains N, the polyalcohols of the amino such as N dimethylamine base dihydroxy methylpropane, contains the polyalcohols that is similar to the such polyethylene oxide chain of polyoxyethylene glycol; Polymeric polyisocyanate is aliphatic poly vulcabond, fragrant adoption vulcabond.
Described acrylic resin is, N, N-dimethylamino-propyl acrylate, N-methylamino-ethylacrylic acid methylmethacrylate monomer, polyethylene glycol methacrylate-styrene polymer, hydroxyethyl methylacrylate monomer, the co-polypropylene acid resin of Acrylic Acid Monomer and vinylbenzene, vinyl cyanide, Vinyl Acetate Monomer.
The molecular-weight average of described urethane and/or vinylformic acid organic resin (A) is 1,000～1, in 000,000 scope, preferably 2,000～500, in 000 scope.
Have, the phosphonic acids that contains hydroxyl in described organo phosphorous compounds (C) is 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, hydroxy ethylene diphosphonic acid again; The phosphonic acids that contains carboxylic acid group is phosphono oxyacetic acid.
Described vanadium compound (D) comprises vitriol, fluoride salt or oxide compound.
Described titanium compound (E), at least contains 4 titanium compounds of fluorine atoms above.
In addition, described polyethylene wax (F), is to be obtained through oxidation style by vinyl polymerization method or the polyethylene wax that generates as poly pyrolysate, contains carboxyl, hydroxy functional group in its structure.
The molecular weight of described polyethylene wax (F) is in 1000～10000 scopes, and median size is at 0.1～1.6 μ m.
The surface treatment method of good conduction of the present invention, the high anti-corrosion Galvanized Steel Strip of resistance to fingerprint, adopt two rollers or three roller roller coating machines, the aqueous treatment agent single stage method that is 10～20% by above-mentioned solid content weight percent is coated to zinc-plated base material two sides, this zinc-plated substrate profile arithmetic average roughness Ra value 0.4 ~ 1.2 μ m, preferably 0.5 ~ 0.8, crest counts between RPc value 50～150, preferably 60～100; Adopt hot blast or infrared induction to be heating and curing, plate temperature control is made as 80～140 ℃, preferably 100～120 ℃; After cooling, at zinc-plated substrate surface, form dry film thickness 0.5～1.5 μ m, the preferred epithelium of resistance to fingerprint of 0.7～1.0 μ m.
In Galvanized Steel Strip design of the present invention:
Spendable galvanized metal material, is not particularly limited in the present invention, can comprise pure zinc coating or zinc base alloy coating.As pure zinc coating steel band, can be electro-galvanizing steel band, can be also the steel bands such as electroplated zinc nickel alloy, pot galvanize, hot-dip aluminizing zinc.
In the present invention the surface physics profile of Galvanized Steel Strip as the realization of roughness etc. be mainly the surface topography of controlling base material before plating, zinc-plated rear surface profile is mainly to transmit.When cold rolled strip process milling train, by the roll surface roughness of front and back each roll of frame, control the surface topographies such as roughness of base material, then at continuous zinc coating unit, complete the electro-galvanizing with steel.
Zinc-plated substrate surface profile, control its arithmetic average roughness Ra value 0.4 ~ 1.2 μ m, crest number (depends on intersection C1 and C2, every centimetre (or per inch) exceeds intersection C1 and is less than the number of the profile of lower intersection C2) between RPc value 50～120 (according to the definition of GB3505-1983, as follows), preferred scope is between Ra value 0.5 ~ 0.8, RPc value 60～100.
For build of the present invention, be 0.5～1.5 μ m, require to possess organic shallow layer of excellent corrosion resistance and electroconductibility simultaneously, when the surfaceness of zinc coating is excessive, be coated in its surperficial aqueous treatment agent and cannot form in steel strip surface the coating dry film of even thickness, thereby caused steel strip surface corrosion proof inhomogeneous, the film at trough place can be compared with thick and can be relatively thin in crest place coating, the barrier propterty of the coating that the phenomenon of this membrane thickness unevenness can cause crest place in corrosive environment lost efficacy prematurely, referring to Fig. 1, it is depicted as the excessive situation of zinc-plated substrate surface roughness, 1 is zinc-plated substrate surface profile, 2 is coatingsurface profile.When roughness is too small, coating is relatively continuous and fine and close in the covering meeting of steel strip surface, the insulation attribute of organic coating likely makes surface resistivity increase and affects electroconductibility, especially in the situation that effects on surface resistance is less than 0.1m Ω and distributivity and homogeneity and has strict demand, referring to Fig. 2, it is depicted as the too small situation of zinc-plated substrate surface roughness, and 1 is zinc-plated substrate surface profile, and 2 is coatingsurface profile.
Therefore the surface profile of base material and the control of thickness should the range of balance in mutual correspondence in.
The present invention is used for the surface treatment agent of good conduction, high anti-corrosion chromium-free fingerprint-resistant Galvanized Steel Strip:
Organic resin part (A) refers to that glass transition temperature Tg is vinylformic acid and/or the urethane of 30～80 ℃, if 30 ℃ of Tg <, the integral hardness of organic composite film is not enough, likely causes the declines such as wear resistant, punch process.If but 80 ℃ of Tg >, the integral hardness of organic composite film is too high and become fragile, and adds man-hour epithelium easily destroyed.
Described urethane and/or vinylformic acid organic resin possess water-soluble or water dispersible, namely, these resins possess the ionic functional group as hydrophilic group, and/or non-ionic type functional group can be dissolved in the water or form self-emulsification colloidal sol, or use tensio-active agent to make its water-solubleization or become water-base resin by Forced Dispersion.
Described urethane resin is the polymkeric substance of polyalcohols and polymeric polyisocyanate, polyalcohols is polyester polyglycol, polyethers polyglycol, polycarbonate polyglycol, contains N, the polyalcohols of the amino such as N dimethylamine base dihydroxy methylpropane, contains the polyalcohols that is similar to the such polyethylene oxide chain of polyoxyethylene glycol; Polymeric polyisocyanate is aliphatic poly vulcabond, fragrant adoption vulcabond.
Described acrylic resin is, N, N-dimethylamino-propyl acrylate, N-methylamino-ethylacrylic acid methylmethacrylate monomer, polyethylene glycol methacrylate-styrene polymer, hydroxyethyl methylacrylate monomer, the co-polypropylene acid resin of Acrylic Acid Monomer and vinylbenzene, vinyl cyanide, Vinyl Acetate Monomer.
The molecular-weight average of above-mentioned water-base resin is 1,000～1, in 000,000 scope, preferably 2,000～500, in 000 scope.The molecular weight of above-mentioned resin is lower than 1,000, and the film-forming properties of epithelium may be poor, and molecular weight is over causing the unstable of surface treatment constituent at 1,000,000 o'clock.
The organosilane coupler (Ba) using in treatment agent of the present invention, at least contains one as the amino that contains active hydrogen of reactive functional groups in each molecule.There is no particular limitation for structure, for example: N-(2-aminoethyl) 3-aminopropyl methyl dimethoxysilane, the similar constituent of 3-aminopropyl triethoxysilane can be used.The organosilane coupler (Bb) using in the present invention, at least contains one as the epoxy group(ing) of reactive functional groups in each molecule, textural nothing limits especially.Such as 3-glycidoxypropyltrime,hoxysilane, 2-(3,4 epoxycyclohexyls) ethyl trimethoxy silane etc. similarly constituent can use.
In organic composite film, organic silane compound (Ba) and weight ratio (Bb) (Ba)/(Bb) preferably in the scope of 0.3-0.5.If lower than 0.3, when namely organic silane compound (Ba) is less, organic composite film is poor to the tack of steel plate galvanized, likely when impact briquetting, occurs that epithelium peels off.If be greater than 0.5, namely organic silane compound (Bb) is measured when more, may cause erosion resistance variation.In addition, in organic composite film, the total amount of organic silane compound ((Ba)+(Bb)) and resin (A) weight ratio (A)/((Ba)+(Bb)) preferably between 1.0～2.0.If lower than 1.0, that is to say that amount of resin is few, coating solvent resistance and painting adhesion variation, if this weight ratio higher than 2.0, that is to say when resin is more, likely cause the reduction of the performances such as erosion resistance, processibility, electroconductibility.
The phosphonic acids that contains hydroxyl in organo phosphorous compounds described in treatment agent of the present invention (C) is 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, hydroxy ethylene diphosphonic acid; The phosphonic acids that contains carboxylic acid group is phosphono oxyacetic acid.
Organo phosphorous compounds in aqueous treatment agent (C), owing to belonging to the organic compound that contains C-P associative key, the valence state that phosphorus atom can be is not limit, and corrosion of metal is had to higher restraining effect.Concrete example is, the phosphonic acids that 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, hydroxy ethylene diphosphonic acid etc. contains hydroxyl, and the phosphonic acids that contains carboxylic acid group such as phosphono oxyacetic acid and its esters etc.C component (in phosphorus) is preferably 0.01～0.1% at the shared weight percent of total solids level in addition.Weight percent is lower than 0.01% time, and additive effect is undesirable, and solidity to corrosion declines, and especially after alkali cleaning, solidity to corrosion is not enough; Weight percent surpasses 0.1%, and the system stability for the treatment of agent is affected.
Vanadium compound in aqueous treatment agent (D), because be the water-soluble restraining effect that has oxidisability, electrogalvanizing steel plate is had to corrosion simultaneously.As vanadium compound D, the valence state of vanadium ion has 2+, 3+, 4+ and 5+ etc. all to have good effect, does not therefore limit the source of v element.Concrete can be vitriol, fluoride salt and oxide compound.These compounds can be anhydrous compounds, can be also hydrates.Vanadium-containing compound is 0.1～1.0% at the total shared weight percent of total solid content, preferably in 0.2～0.5% scope.If weight percent is lower than 0.2%, the passivation effect that the oxidisability of vanadium produces after galvanizing surface is corroded is bad, and solidity to corrosion can not get improving; If weight percent is higher than 1%, the stability for the treatment of agent is understood variation, and the easy xanthochromia of coatingsurface, and thermotolerance can decline.
The titanium compound relating in aqueous treatment agent (E), at least contains 4 titanium compounds of fluorine atoms above.It act as galvanizing surface oxide film is carried out to etching, to improve the tack of epithelium.It is 0.1～3% that this titanium compound (E) be take the weight percent of Ti in organic coating.Lower than 0.1%, can not reach additive effect, cause epithelium tack, solidity to corrosion to decline.If surpass 3%, the stable decline of epithelium constituent, also may cause the decline of galvanized steel sheet surface quality simultaneously.
In aqueous treatment agent, also having added polyethylene wax (F), is to be obtained through oxidation style by vinyl polymerization method or the polyethylene wax that generates as poly pyrolysate, contains the functional groups such as carboxyl, hydroxyl in its structure.General its molecular weight is in 1000～10000 scopes.The median size of polyethylene wax of the present invention is at 0.1～1.6 μ m.In addition, the content of polyethylene wax (F) in epithelium is in 1～3 % by weight, polyethylene wax (F) in epithelium content preferably 1.5～2.5%.If content, lower than 1%, can not obtain sufficient wearability.If content surpasses 3%, likely cause the decline of the performances such as solidity to corrosion, solvent resistance, coating.
The surface treatment method of Galvanized Steel Strip of the present invention is to utilize two rollers or three roller roller coating machines that above-mentioned aqueous treatment agent is coated to band steel two sides in single stage method mode, control suitable solid content and the viscosity for the treatment of agent, adjust roller coating technology parameter and obtain suitable thickness as roller with liquid/coating roller speed ratio and coating roller pressure, through curing oven (hot blast or infrared induction heating), control PMT is 80～140 ℃ and solidifies, drying and forming-film after cooling (water-cooled or air-cooled), is finally with steel to be curled into coil of strip fast.Applying the curing plate temperature (PMT) of post-heating is 80～140 ℃, preferably 100～120 ℃.PMT is lower than 80 ℃, and in wet film, moisture evaporation affects solidification effect not to the utmost, unfavorable to performances such as solidity to corrosion, resistance to solvents; PMT is higher than 140 ℃, and curling front band steel is cooling insufficient, and energy consumption increase is unfavorable for cost control.
Use treatment agent of the present invention is 0.5～1.5 μ m(dry film in galvanizing surface film forming) resistance to fingerprint coating, 0.7～1.0m preferably.Thickness is less than 0.5m, and galvanizing surface is difficult to completely by the covering protection of resistance to fingerprint coating, and no matter galvanizing surface roughness is bigger than normal or less than normal, although can there be good electroconductibility, the performances such as solidity to corrosion, alkali resistance, anti-finger printing all can decline; If thickness surpasses 1.5m, electroconductibility can decline, and the conduction homogeneity meeting variation of whole belt steel surface, even the upper limit level of zinc-plated substrate surface roughness in 1.2m left and right.And rise with the processing cost of thickness increase unit surface, application adherence also can be affected.
Beneficial effect of the present invention
Galvanized Steel Strip of the present invention has good electric conductivity and solidity to corrosion, the surface resistivity of steel plate can reach below 0.1m Ω, neutral salt spray test 120h surface white rust area is less than 5%, simultaneously this steel treat also possess good anti-finger printing, coating, weldability, the characteristics such as processing such as wear-resisting, be applicable to the fields such as electronics to ground connection property harshness, as business automation equipments such as duplicating machine, printers.
Accompanying drawing explanation
Fig. 1, Fig. 2 are the schematic diagram of the surface profile that forms after coating processing agent film forming on two kinds of steel strip surface patterns.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
It is example that embodiment of the present invention base material be take electro-galvanizing, hot-dip galvanizing sheet steel.Table 1 is depicted as embodiment of the present invention composition.Table 2 is depicted as performance of the present invention.Table 3, table 4, table 5 are the corresponding concrete material of the embodiment of the present invention.
Wherein, benchmark test is as follows:
1, dull and stereotyped solidity to corrosion
According to JIS Z2371 neutral salt spray test (SST), carry out 120 hours specimen size 75 * 150mm, access panel colourless rust rate.
< judgement criteria > ◎: white rust rate is less than 5%
Zero: white rust rate is more than 5% but be less than 10%
△: white rust rate is more than 10% but be less than 30%
*: white rust rate is more than 30%
2, working position solidity to corrosion
Sample carries out, after Erichsen test (cupping height 7mm), according to JIS Z2371 neutral salt spray test standard, carrying out 72 hours, observes working position (cupping crushed element) white rust generating state.
< judgement criteria > ◎: cupping deformation place white rust is less than 10%
Zero: cupping deformation place white rust is greater than 10% but be less than 30%
△: cupping deformation place white rust is greater than 30% but be less than 50%
*: cupping deformation place white rust is greater than 50%
3, electroconductibility
Adopt a kind of measuring method of 4 probe-type Surface Contact impedances, its principle as shown in Figure 1, when electric current flows through probe A and probe D, produces potential difference (V) and is detected between probe B and probe C, and resistance V/I is the surface impedance value of mensuration thus.
With 9 point (being uniformly distributed) Surface Contact resistance values in 300 * 300mm2 area, carry out the electroconductibility of exosyndrome material.
< judgement criteria > ◎: 9 Surface Contact impedance arithmetical av are less than 0.05m Ω, and One-Point-Value must not be greater than 0.05m Ω;
Zero: 9 Surface Contact impedance arithmetical av is greater than 0.05m Ω but is less than 0.1m Ω, and One-Point-Value must not be greater than 0.1m Ω;
△: 9 Surface Contact impedance arithmetical av are greater than 0.1m Ω but are less than 1.0m Ω, and One-Point-Value must not be greater than 1.0m Ω;
*: 9 Surface Contact impedance arithmetical av are greater than 1.0m Ω;
4, painting adhesion
With silk screen printing or excellent painting mode coating printing ink (recommending trade mark NSK ink #1300SEIKO ADVANCE) in clean specimen surface, to control 10 ± 3 microns of builds;
With rod painting or other modes, apply trimeric cyanamide phthalic resin coating (trade mark is not limit), to control 20 ± 5 microns of builds;
Above-mentioned two kinds of coating models of making carry out following adherence test after room temperature is placed 24 hours.
The coating model preparing is put into boiling water, and sample is over half must immerse boiling water;
Keep boiling after 30 minutes and take out, in room temperature, place 2 hours;
Select sample and soak position at boiling water, hundred lattice with paint film lattice drawing instrument at stroke 1mm interval;
On grid, stick scotch tape, with finger or fixture, be pressed into completely closely sealedly, then hold adhesive tape one end and tear perpendicular to specimen surface moment, peel off rear observation adherence (adherence=be not stripped from number of squares/100).
< judgement criteria > ◎: adherence is 100/100
Zero: adherence is more than 95/100
△: adherence is below 95 but more than 90/100
*: adherence is below 90/100
5, solvent resistance
Under normal temperature, sample soaks after 168 hours in as Virahol, ethanol, butanone, methylene dichloride, normal hexane, toluene, volatilization wet goods at organic solvent, and whether observe coatingsurface has swelling, and aberration (△ E* value) before and after measuring.
< judgement criteria > ◎: coating is without swelling, and aberration △ E*<1.0
Zero: coating is without swelling, and aberration △ E*>1.0 but <3.0
△: coating is without swelling, and aberration △ E*>3.0 but <5.0
*: coating has swelling, and aberration △ E*>5.0
From embodiment result, show, galvanizing surface treating product of the present invention has good electroconductibility and solidity to corrosion concurrently, meets the over-all propertieies such as anti-finger printing, wear resistance, coating and processing simultaneously.
Table 1
Table 2
Table 3 resinous type
Table 4 organo silane coupling agent
| b1 | 3-TSL 8330 |
| b2 | APTES |
| b3 | 3-glycidoxypropyltrime,hoxysilane |
| b4 | 3-glycidoxy propyl group methyl dimethoxysilane |
Other compounds of table 5
| c1 | 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid |
| c2 | Hydroxy ethylene diphosphonic acid |
| c3 | Phosphoric acid |
| c4 | Ammonium di-hydrogen phosphate |
| d1 | Ammonium meta-vanadate |
| d2 | Vanadium Pentoxide in FLAKES |
| d3 | Oxalic acid vanadyl |
| e1 | Ammonium titanium fluoride |
| e2 | Tetrabutyl titanate |
Claims (13)
1. good conduction, the high anti-corrosion Galvanized Steel Strip of resistance to fingerprint, is characterized in that: its surface coverage one deck epithelium of resistance to fingerprint, and this epithelium constituent comprises:
A) urethane and/or vinylformic acid organic resin (A), shared weight percent is 40～60%; The glass transition temperature of described urethane and/or vinylformic acid organic resin (A) is 30～80 ℃, and possesses water-soluble or water dispersible;
B) active hydrogen that contains an above amido functional group, amido functional group is at least the organo silane coupling agent (Ba) of and contains at least one epoxy functionality, the more than one organo silane coupling agent of epoxy functionality number (Bb), and (Ba)/weight ratio (Bb) is 0.3～0.5; The weight ratio of above-mentioned organic resin (A) and organo silane coupling agent ((Ba)+(Bb)) is 1.0～2.0; The shared weight percent of organo silane coupling agent is 38～53%;
C) organo phosphorous compounds (C), the shared weight percent of the phosphoric of take is 0.01～0.1%;
D) vanadium compound (D), the shared weight percent of the v element of take is 0.1～1.0%;
E) titanium compound or fluorine-containing titanium compound (E), the shared weight percent of titanium elements amount of take is 0.1～3.0%;
F) polyethylene wax, accounts for epithelium content 1～3%;
Wherein, Galvanized Steel Strip profile arithmetic average roughness Ra value 0.4～1.2 μ m, crest are counted between RPc value 50～150.
2. for the surface treatment agent of good conduction claimed in claim 1, the high anti-corrosion Galvanized Steel Strip of resistance to fingerprint, for aqueous solution, the weight percent of its amount of solid content is 10～20%, in solid part, the weight percent of each component is: urethane and/or vinylformic acid organic resin (A), 40～60%; Organo silane coupling agent (Ba), contains an above amido functional group, and the active hydrogen of amido functional group is at least one; Organo silane coupling agent (Bb), contains at least one epoxy functionality, and epoxy functionality number is more than one; (Ba)/weight ratio (Bb) is 0.3～0.5; The weight ratio of above-mentioned organic resin (A) and organo silane coupling agent ((Ba)+(Bb)) is 1.0～2.0; (Ba)+(Bb), the content in solid part is 38～53%; Organo phosphorous compounds (C), the phosphoric of take account for solid part total amount as weight percent, 0.01～0.1%; Vanadium compound (D), accounts for the weight percent of solid part total amount, 0.1～1.0% in v element; Titanium compound or fluorine-containing titanium compound (E), account for the weight percent of solid part total amount, 0.1～3.0% in titanium elements; Polyethylene wax (F), accounts for the weight percent of solid part total amount, 1～3%; Wherein, the glass transition temperature of described urethane and/or vinylformic acid organic resin (A) is 30～80 ℃, and possesses water-soluble or water dispersible; Galvanized Steel Strip profile arithmetic average roughness Ra value 0.4～1.2 μ m, crest are counted between RPc value 50～150.
3. surface treatment agent as claimed in claim 2, it is characterized in that, described urethane resin is the polymkeric substance of polyalcohols and polymeric polyisocyanate, polyalcohols is polyester polyglycol, polyethers polyglycol, polycarbonate polyglycol, contains N, the polyalcohols of N dimethylamine base dihydroxy methylpropane amino, contains one or more in the polyalcohols that is similar to the such polyethylene oxide chain of polyoxyethylene glycol; Polymeric polyisocyanate is aliphatic poly vulcabond or fragrant adoption vulcabond.
4. surface treatment agent as claimed in claim 2, it is characterized in that, described acrylic resin is, N, the acrylic resin that one or more copolymerization in one or more in N-dimethylamino-propyl acrylate, N-methylamino-ethylacrylic acid methylmethacrylate monomer, polyethylene glycol methacrylate-styrene polymer, hydroxyethyl methylacrylate monomer, Acrylic Acid Monomer and vinylbenzene, vinyl cyanide or Vinyl Acetate Monomer form.
5. surface treatment agent as claimed in claim 2, is characterized in that, the molecular-weight average of described urethane and/or vinylformic acid organic resin (A) is 1,000～1, in 000,000 scope.
6. surface treatment agent as claimed in claim 2, is characterized in that, the molecular-weight average of described urethane and/or vinylformic acid organic resin (A) is 2,000～500, in 000 scope.
7. surface treatment agent as claimed in claim 2, is characterized in that, the phosphonic acids that contains hydroxyl in described organo phosphorous compounds (C) is 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid or hydroxy ethylene diphosphonic acid; The phosphonic acids that contains carboxylic acid group is phosphono oxyacetic acid.
8. surface treatment agent as claimed in claim 2, is characterized in that, described vanadium compound (D) comprises vitriol, fluoride salt or oxide compound.
9. surface treatment agent as claimed in claim 2, is characterized in that, described titanium compound (E) at least contains 4 titanium compounds of fluorine atoms above.
10. surface treatment agent as claimed in claim 2, it is characterized in that, described polyethylene wax (F), is to be obtained through oxidation style by vinyl polymerization method or the polyethylene wax that generates as poly pyrolysate, contains carboxyl or hydroxy functional group in its structure.
11. surface treatment agents as described in claim 2 or 10, is characterized in that, the molecular weight of described polyethylene wax (F) is in 1000～10000 scopes, and median size is at 0.1～1.6 μ m.
The surface treatment method of 12. 1 kinds of good conductions, the high anti-corrosion Galvanized Steel Strip of resistance to fingerprint, it is characterized in that, adopt two rollers or three roller roller coating machines, the surface treatment agent single stage method that is 10～20% by the amount of solid content weight percent described in claim 2 is coated to Galvanized Steel Strip two sides, and this Galvanized Steel Strip profile arithmetic average roughness Ra value 0.4～1.2 μ m, crest are counted between RPc value 50～150; Adopt hot blast or infrared induction to be heating and curing, plate temperature control is made as 80～140 ℃; After cooling, on Galvanized Steel Strip surface, form the epithelium of resistance to fingerprint of dry film thickness 0.5～1.5 μ m.
The surface treatment method of 13. good conductions as claimed in claim 12, the high anti-corrosion Galvanized Steel Strip of resistance to fingerprint, is characterized in that described Galvanized Steel Strip profile arithmetic average roughness Ra value 0.5～0.8; Crest is counted RPc value 60～100; Adopt hot blast or infrared induction to be heating and curing, plate temperature control is made as 100～120 ℃; After cooling, on Galvanized Steel Strip surface, form the epithelium of resistance to fingerprint of dry film thickness 0.7～1.0 μ m.
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| CN201210223570.8A CN102746778B (en) | 2012-06-29 | 2012-06-29 | Galvanizing steel strip with good conductivity, high corrosion resistance and fingerprint resistance, surface treatment agent and treatment method |
| PCT/CN2013/075783 WO2014000527A1 (en) | 2012-06-29 | 2013-05-17 | Galvanized steel strip with good conductivity, high corrosion resistance and fingerprint resistance, and surface treatment agent and treatment method |
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| CN102746778B (en) * | 2012-06-29 | 2014-12-03 | 宝山钢铁股份有限公司 | Galvanizing steel strip with good conductivity, high corrosion resistance and fingerprint resistance, surface treatment agent and treatment method |
| CN103254755B (en) * | 2013-05-27 | 2016-01-27 | 宝山钢铁股份有限公司 | There is hot-dip aluminizing zincium steel plate of excellent weather resistance, solidity to corrosion and alkali resistance and preparation method thereof and surface treatment agent |
| CN103387764B (en) * | 2013-08-08 | 2014-11-05 | 句容骏成电子有限公司 | Surface screen printing ink and application thereof |
| EP2876140A1 (en) * | 2013-11-25 | 2015-05-27 | Eczacibasi Yapi Gerecleri Sanayi Ve Ticaret Anonim Sirketi | An anti-fingerprint coating composition and a method for applying this coating composition to surfaces |
| CN105463436B (en) * | 2015-07-27 | 2018-03-09 | 宝山钢铁股份有限公司 | A kind of manufacture method for the environmentally friendly surface conditioning agent of galvanized steel plain sheet, galvanized steel plain sheet and galvanized steel plain sheet |
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| CN105779984A (en) * | 2016-04-20 | 2016-07-20 | 南京科润工业介质股份有限公司 | Chromate-free passivation agent for aluminum alloy |
| CN105937031B (en) * | 2016-06-29 | 2018-10-30 | 周少霞 | A kind of preparation method of heat zinc coating plate passivating solution |
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| CN109943841A (en) * | 2019-05-08 | 2019-06-28 | 兴化市华成镀锌管件有限公司 | A kind of galvanized steel plain sheet resistance and fingerprint resistance inorganic agent and preparation method thereof |
| CN112301342B (en) * | 2020-07-02 | 2021-12-21 | 上海兴赛尔表面材料有限公司 | Chromium-free passivation composition for aluminum-plated zinc plate and manufacturing and using method thereof |
| CN111849286B (en) * | 2020-07-30 | 2021-11-05 | 辽宁宝瑞科技有限公司 | Bacteriostatic fingerprint-resistant coating agent, and preparation method and application thereof |
| CN115109991A (en) * | 2021-03-21 | 2022-09-27 | 上海梅山钢铁股份有限公司 | High-adhesion aluminum-zinc-plated steel plate for building foaming and manufacturing method thereof |
| WO2022248488A1 (en) * | 2021-05-27 | 2022-12-01 | Chemetall Gmbh | Non-cr passivating composition and article treated by the same |
| CN117082793B (en) * | 2023-10-11 | 2024-03-12 | 荣耀终端有限公司 | Shell, manufacturing method thereof and electronic equipment |
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