CN102746778A - 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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- CN102746778A CN102746778A CN2012102235708A CN201210223570A CN102746778A CN 102746778 A CN102746778 A CN 102746778A CN 2012102235708 A CN2012102235708 A CN 2012102235708A CN 201210223570 A CN201210223570 A CN 201210223570A CN 102746778 A CN102746778 A CN 102746778A
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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
- 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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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- 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
- 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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- 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
- 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
- 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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/90—Compositions for anticorrosive coatings
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- C—CHEMISTRY; METALLURGY
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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 anti-fingerprint the and surface treatment agent, treatment process; Can satisfy and satisfy good electric conductivity and high anti-corrosion characteristic when in the past non-chromate coatings technology is difficult to realize, and possess over-all propertiess such as the humidity resistance that general non-chromate coatings had, thermotolerance, anti-finger printing, weldableness, coating and anti-processing blackening.
Background technology
Galvanized Steel Strip is to use one of metal products the most widely 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.Chinese patent publication number CN101435078A discloses a kind of method that has good corrosion resistance, alkali resistance, processibility and electroconductibility and chemical-resistant non-chrome resin composition simultaneously and with this constituent Galvanized Steel Strip is handled; Its constituent is main solvent by the organic oxygen compound of urethane resin, Ti and Zr, inorganic salt and with water; Although but the Galvanized Steel Strip of being handled by such constituent has solidity to corrosion and electroconductibility and other useful property, embodiment shows that its electroconductibility only reaches below the 1m Ω (surface resistivity), solidity to corrosion (in neutral salt spray test) is 96 hours.Such performance is not enough in that electroconductibility and solidity to corrosion are required higher industry like fields such as office automation electrical equipment such as duplicating machine, facsimile recorders.
U.S. Pat 2005/0058843A1 provides a kind of method of handling steel plate galvanized with the aqueous compositions after two kinds of silane mixture such as vinyl silanes, aminosilane; Have 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 the above-mentioned aqueous compositions and dry 5 minutes, and such method can't realize the continuous processing of Galvanized Steel Strip.
Chinese patent publication number CN101228294A provides a kind of non-chromate surface-treated metal material that possesses solidity to corrosion, thermotolerance, anti-finger printing, electroconductibility, coating and anti-processing blackening simultaneously; Its method is to form the composite film that contains various compositions at metal material surface coated and dry water-based metal-surface-treating agent; But the electroconductibility that this patent provides has only guaranteed the layer impedance value, does not relate to the sheet resistance value of household electric appliances special concern.
Chinese patent publication number CN 101688309A provide a kind of steel plate galvanized use surface treatment liquid and steel plate galvanized; Can make steel plate obtain good conduction and high anti-corrosion simultaneously through handling GI and GA surface; Have coating and alkali resistance simultaneously; But because its technological line that adopts is the film forming skeletons of inorganic salt as coating, only mixed the organic crylic acid resin of part in the coating, such coating structure is difficult to guarantee excellent anti-finger printing ability.
Chinese patent publication number CN 1887449A provides a kind of surface treatment agent that is used for steel plate galvanized with excellent alkali resistance and solvent resistance; Can obtain an alkali resistance, solvent resistance, solidity to corrosion, anti-finger printing, coating, all very excellent chromium-free fingerprint-resistant steel band of anti-processing blackening through the aqueous treatment agent of compositions such as urethane, silane, specific inorganic salt and little auxiliary is handled steel plate galvanized, have the surface of good conductivity simultaneously having under the thickness condition of above-mentioned performance but this patent can't guarantee coating.In sum, at present existing various Chrome-free process for treating surface all are difficult to the chromium-free fingerprint-resistant Galvanized Steel Strip that over-all propertieies such as comprehensive good conduction, high anti-corrosion, anti-fingerprint all satisfy high-end household electrical appliances customer need.
Summary of the invention
The objective of the invention is a kind of good conduction, the high anti-corrosion Galvanized Steel Strip of anti-fingerprint the and surface treatment agent, treatment process; Each item high comprehensive performances such as its electroconductibility (ground connection property), solidity to corrosion, weldableness and processing; Be applicable to fields such as household electrical appliances and office appliance, become electric product to meet the relevant international standard that hertzian wave is revealed test.
For achieving the above object, technical scheme of the present invention is:
Good conduction, the high anti-corrosion Galvanized Steel Strip of anti-the fingerprint, its surface coverage one deck epithelium of anti-the 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 one organo silane coupling agent (Ba) and contains at least a epoxy functionality, the more than one organo silane coupling agent of epoxy functionality number (Bb), and weight ratio (Ba)/(Bb) is 0.3～0.5; Above-mentioned organic resin (A) is 1.0～2.0 with the weight ratio of organo silane coupling agent ((Ba)+(Bb)); The shared weight percent of organo silane coupling agent is 38～53%;
C) organo phosphorous compounds is 0.01～0.1% in the shared weight percent of phosphoric;
D) vanadium compound (D) is 0.1～1.0% in the shared weight percent of v element;
E) titanium compound or fluorine-containing titanium compound (E) are 0.1～3.0% in the shared weight percent of titanium elements amount;
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 the RPc value 50～150.
The present invention is used for the treatment agent of described good conduction, the high anti-corrosion Galvanized Steel Strip of anti-the fingerprint; Be aqueous solution; The weight percent of its amount of solid content is 10～20%, and the weight percent of each component is in the solid: 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 a epoxy functionality, and epoxy functionality is several more than one; (Ba)/(Bb) weight ratio is 0.3～0.5; Above-mentioned organic resin (A) is 1.0～2.0 with the weight ratio of organo silane coupling agent ((Ba)+(Bb)); (Ba)+(Bb), the content in solid is 38～53%; Organo phosphorous compounds (C) accounts for the weight percent that the solid total amount is, 0.01～0.1% in phosphoric; Vanadium compound (D) accounts for the weight percent of solid total amount in v element, 0.1～1.0%; Titanium compound or fluorine-containing titanium compound (E) account for the weight percent of solid total amount in titanium elements, 0.1～3.0%; Polyethylene wax (F) accounts for the weight percent of solid 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 amino such as TMSDMA 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 vinyl resin does; N, N-dimethylamino-propyl propenoate, N-methylamino-ethylacrylic acid methylmethacrylate monomer, polyethylene glycol methacrylate-styrene polymer; The Rocryl 400 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 the described organo phosphorous compounds (C) is HEDP, hydroxy ethylene diphosphonic acid again; The phosphonic acids that contains the carboxylic acid group is the phosphono oxyacetic acid.
Described vanadium compound (D) comprises vitriol, fluoride salt or oxide compound.
Described titanium compound (E) contains the titanium compound of 4 above fluorine atoms at least.
In addition, described polyethylene wax (F) is to obtain through oxidation style by the vinyl polymerization method or as the polyethylene wax that poly pyrolysate generates, and contains carboxyl, hydroxy functional group on 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 anti-the fingerprint; Adopt two rollers or three roller roller coating machines; With above-mentioned solid content weight percent is that 10～20% aqueous treatment agent single stage method 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, preferred 0.5 ~ 0.8, crest counts between the RPc value 50～150 preferred 60～100; Adopt hot blast or infrared induction to be heating and curing, the plate temperature control is made as 80～140 ℃, preferably 100～120 ℃; The cooling back forms the epithelium of anti-fingerprint of dry film thickness 0.5～1.5 μ m, preferred 0.7～1.0 μ m at zinc-plated substrate surface.
In Galvanized Steel Strip design of the present invention:
Spendable in the present invention galvanized metal material, not special the qualification can comprise pure zinc coating or zinc base alloy coating.As pure zinc coating steel band, can be the electro-galvanizing steel band, also can be steel bands such as electroplated zinc nickel alloy, pot galvanize, hot-dip aluminizing zinc.
The realization of the surface physics profile of Galvanized Steel Strip such as roughness etc. mainly is the surface topography of base material before the control plating among the present invention, and zinc-plated back surface profile mainly is to transmit.When the milling train, control the surface topographies such as roughness of base material at cold rolled strip, accomplish electro-galvanizing at the continuous zinc coating unit then the band steel through the roll surface roughness of front and back each roll of frame.
Zinc-plated substrate surface profile; Control its arithmetic average roughness Ra value 0.4 ~ 1.2 μ m, the crest number (depends on intersection C1 and C2; Every centimetre (or per inch) exceed intersection C1 and less than the following number of the profile of intersection C2) between the RPc value 50～120 (according to the definition of GB3505-1983; As follows), preferred range is between Ra value 0.5 ~ 0.8, RPc value 60～100.
For build of the present invention is 0.5～1.5 μ m, requires to possess organic shallow layer of good solidity to corrosion and electroconductibility simultaneously, when the surfaceness of zinc coating is excessive; Be coated in its surperficial aqueous treatment agent and can't form the uniform coating dry film of thickness in steel strip surface; Thereby caused steel strip surface corrosion proof inhomogeneous, the film at trough place can be thicker and coating can be thinner relatively at the crest place, and the phenomenon of this membrane thickness unevenness can cause the barrier propterty of coating in corrosive environment at crest place to lose efficacy prematurely; Referring to Fig. 1; It is depicted as the excessive situation of zinc-plated substrate surface roughness, and 1 is zinc-plated substrate surface profile, and 2 is the coatingsurface profile.When roughness is too small; Coating is continuous relatively and fine and close in the covering meeting of steel strip surface, and the insulation attribute of organic coating then might make surface resistivity increase and influence electroconductibility, especially surface resistivity is being had under the situation of strict demand less than 0.1m Ω and distributivity and homogeneity; 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 the coatingsurface profile.
Therefore the surface profile of base material and the control of thickness should be in the range of balance of mutual correspondence.
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) is meant that glass transition temperature Tg is 30～80 ℃ vinylformic acid and/or a urethane, if Tg＜30 ℃, the integral hardness of organic composite film is not enough, might cause declines such as wear resistant, punch process property.If but Tg＞80 ℃, the integral hardness of organic composite film is too high and become fragile, and adds the man-hour epithelium and is destroyed easily.
Described urethane and/or vinylformic acid organic resin possess water-soluble or water dispersible; Just; 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, perhaps use tensio-active agent make its water-solubleization, or through forcing to disperse to become water-base resin.
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 amino such as TMSDMA 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 vinyl resin does; N, N-dimethylamino-propyl propenoate, N-methylamino-ethylacrylic acid methylmethacrylate monomer, polyethylene glycol methacrylate-styrene polymer; The Rocryl 400 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 maybe be relatively poor, and molecular weight surpasses the instability that may cause the surface treatment constituent at 1,000,000 o'clock.
The organosilane coupler (Ba) that uses in the treatment agent of the present invention contains the amino that contains active hydrogen as reactive functional groups at least in each molecule.Structure does not have special qualification, and for example: N-(2-aminoethyl) 3-aminopropyl methyl dimethoxysilane, the similar constituent of 3-aminopropyl triethoxysilane can use.The organosilane coupler (Bb) that uses among the present invention contains an epoxy group(ing) as reactive functional groups at least in each molecule, textural no special qualification.For example: 3-glycidoxypropyltrime,hoxysilane, 2-(3,4 epoxycyclohexyl) ethyl trimethoxy silane etc. similarly constituent can use.
In organic composite film, organic silane compound (Ba) and weight ratio (Bb) (Ba)/(Bb) are preferably in the scope of 0.3-0.5.If be lower than 0.3, just organic silane compound (Ba) more after a little while, organic composite film is poor to the tack of steel plate galvanized, might when impact briquetting, epithelium occur and peel off.If greater than 0.5, just organic silane compound (Bb) amount possibly cause the erosion resistance variation more for a long time.In addition, in organic composite film, total amount of organic silane compound ((Ba)+(Bb)) and resin (A) weight ratio (A)/((Ba)+(Bb)) preferably between 1.0～2.0.If be 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 is higher than 2.0, that is to say resin more for a long time, might cause the reduction of performances such as erosion resistance, processibility, electroconductibility.
The phosphonic acids that contains hydroxyl in the organo phosphorous compounds described in the treatment agent of the present invention (C) is HEDP, hydroxy ethylene diphosphonic acid; The phosphonic acids that contains the carboxylic acid group is the phosphono oxyacetic acid.
Organo phosphorous compounds in the aqueous treatment agent (C), owing to belong to the organic cpds that contains the C-P associative key, the valence state that phosphorus atom can be is not limit, and corrosion of metal is had higher restraining effect.Concrete example does, HEDP, hydroxy ethylene diphosphonic acid etc. contains the phosphonic acids of hydroxyl, and phosphono oxyacetic acid etc. contains phosphonic acids and its esters of carboxylic acid group 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 at 0.01% o'clock, and additive effect is undesirable, and solidity to corrosion descends, and especially solidity to corrosion is not enough after the alkali cleaning; Weight percent surpasses 0.1%, and then the system stability of treatment agent is affected.
Vanadium compound in the aqueous treatment agent (D) water-solublely has oxidisability simultaneously, electrogalvanizing steel plate is had the corrosive restraining effect because be.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, also can be 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 oxidisability of vanadium is bad to the passivation effect that galvanizing surface corrodes the back generation, and solidity to corrosion can not get improving; If weight percent is higher than 1%, the stability of treatment agent meeting variation, and the easy xanthochromia of coatingsurface, thermotolerance can descend.
The titanium compound that relates in the aqueous treatment agent (E) contains the titanium compound of 4 above fluorine atoms at least.It act as the galvanizing surface sull is carried out etching, to improve the tack of epithelium.This titanium compound (E) is 0.1～3% in the weight percent of Ti in organic epithelium.Be lower than 0.1%, can not reach additive effect, cause epithelium tack, solidity to corrosion to descend.If surpass 3%, the stable decline of epithelium constituent, also possibly cause the decline of galvanized steel sheet surface quality simultaneously.
Also having added polyethylene wax (F) in the aqueous treatment agent, is to obtain through oxidation style by the vinyl polymerization method or as the polyethylene wax that poly pyrolysate generates, and contains functional groups such as carboxyl, hydroxyl on 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 at 1～3 weight %, polyethylene wax (F) in epithelium content preferably 1.5～2.5%.If content is lower than 1%, can not obtain sufficient wearability.If content surpasses 3%, might cause performance decrease 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 with the single stage method mode; Suitable solid content and the viscosity of control treatment agent; Adjustment roller coating technology parameter such as roller with liquid/coating roller speed ratio and coating roller pressure obtain suitable thickness; Control PMT is 80～140 ℃ of curing through curing oven (hot blast or infrared induction heating), and cooling (water-cooled or air-cooled) after drying film forming is with steel to be curled into coil of strip at last fast.Applying post-heating solidified plate temperature (PMT) is 80～140 ℃, preferably 100～120 ℃.PMT is lower than 80 ℃, and moisture evaporation influences solidification effect not to the utmost in the wet film, and is unfavorable to performances such as solidity to corrosion, anti-solvents; PMT is higher than 140 ℃, be with the steel cooling insufficient before curling, and the energy consumption increase is unfavorable for cost control.
Use treatment agent of the present invention is the anti-fingerprint coating of 0.5～1.5 μ m (dry film), preferably 0.7～1.0m in the galvanizing surface film forming.Thickness is less than 0.5m, and galvanizing surface is difficult to fully by anti-fingerprint coating covering protection, and no matter the galvanizing surface roughness is bigger than normal or less than normal, though good electroconductibility can be arranged, performances such as solidity to corrosion, alkali resistance, anti-finger printing all can descend; If thickness surpasses 1.5m, electroconductibility can descend, and the conduction homogeneity meeting variation of whole belt steel surface is even zinc-plated substrate surface roughness is in the upper limit level about 1.2m.And rise with the processing cost that thickness increases unit surface, the 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 the 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, weldableness, characteristics such as processing such as wear-resisting, be applicable to the fields such as electronics harsh, like business automation equipments such as duplicating machine, stamping machines to ground connection property.
Description of drawings
Fig. 1, Fig. 2 are the synoptic diagram of the surface profile that forms after the coating processing agent film forming on two kinds of steel strip surface patterns.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
Embodiment of the invention base material is an example with electro-galvanizing, hot-dip galvanizing sheet steel.Table 1 is depicted as embodiment of the invention composition.Table 2 is depicted as performance of the present invention.Table 3, table 4, table 5 are the pairing concrete material of the embodiment of the invention.
Wherein, benchmark test is following:
1, dull and stereotyped solidity to corrosion
Carried out 120 hours specimen size 75 * 150mm, access panel colourless rust rate according to JIS Z2371 neutral salt spray test (SST).
< judgement criteria>◎: the white rust rate is less than 5%
Zero: the white rust rate is more than 5% but less than 10%
△: the white rust rate is more than 10% but less than 30%
*: the white rust rate is more than 30%
2, working position solidity to corrosion
Sample carried out 72 hours according to JIS Z2371 neutral salt spray test standard after carrying out Erichsen test (cupping height 7mm), observed 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 less than 30%
△: cupping deformation place white rust is greater than 30% but less than 50%
*: cupping deformation place white rust is greater than 50%
3, electroconductibility
Adopt the measuring method of a kind of 4 probe-types surface contact impedance, its principle is as shown in Figure 1, when electric current flows through probe A and probe D, produces potential difference (V) between probe B and the probe C and is detected, and resistance V/I is the surface impedance value of mensuration thus.
The electroconductibility of coming exosyndrome material with the surperficial contact impedance value of 9 points (uniform distribution) in 300 * 300mm2 area.
< judgement criteria>◎: 9 surperficial contact impedance arithmetical av are less than 0.05m Ω, and the single-point value must not be greater than 0.05m Ω;
Zero: 9 surperficial contact impedance arithmetical av is greater than 0.05m Ω but less than 0.1m Ω, and the single-point value must not be greater than 0.1m Ω;
△: 9 surperficial contact impedance arithmetical av are greater than 0.1m Ω but less than 1.0m Ω, and the single-point value must not be greater than 1.0m Ω;
*: 9 surperficial contact impedance arithmetical av are greater than 1.0m Ω;
4, painting adhesion
Be coated with mode with silk screen printing or rod and apply printing ink (recommending trade mark NSK printing ink #1300SEIKO ADVANCE) in the specimen surface of cleaning, with 10 ± 3 microns of control builds;
Be coated with or other modes apply trimeric cyanamide phthalic resin coating (trade mark is not limit) with rod, with 20 ± 5 microns of control builds;
Above-mentioned two kinds of coating models of processing carry out following adherence test after room temperature is placed 24 hours.
The coating model for preparing is put into boiling water, and sample is over half must to immerse boiling water;
Keep boiling after 30 minutes and take out, placed 2 hours in room temperature;
Select sample and soak the position, draw the lattice appearance with paint film and drawing 1mm hundred lattice at interval at boiling water;
On grid, stick scotch tape, be pressed into complete driving fit, hold adhesive tape one end then and tear, peel off the back and observe adherence (adherence=be not stripped from number of squares/100) perpendicular to specimen surface moment with finger or anchor clamps.
< 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 the normal temperature, sample soaked in organic solvent such as Virahol, ethanol, butanone, methylene dichloride, normal hexane, toluene, volatilization wet goods after 168 hours, and whether observe coatingsurface has swelling, and aberration (△ E* value) before and after measuring.
< judgement criteria>◎: coating does not have swelling, and aberration △ E* < 1.0
Zero: coating does not have swelling, and aberration △ E*>1.0 but < 3.0
△: coating does not have swelling, and aberration △ E*>3.0 but < 5.0
*: coating has swelling, and aberration △ E*>5.0
Show that from embodiment result galvanizing surface treating product of the present invention has good electroconductibility and solidity to corrosion concurrently, satisfies 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 | The 3-TSL 8330 |
| b2 | The 3-aminopropyltriethoxywerene werene |
| b3 | The 3-glycidoxypropyltrime,hoxysilane |
| b4 | 3-glycidoxy propyl group methyl dimethoxysilane |
Other compounds of table 5
| c1 | HEDP |
| c2 | Hydroxy ethylene diphosphonic acid |
| c3 | Phosphoric acid |
| c4 | Ammonium di-hydrogen phosphate |
| d1 | Ammonium meta-vanadate |
| d2 | Vanadium Pentoxide in FLAKES |
| d3 | The oxalic acid vanadyl |
| e1 | Ammonium titanium fluoride |
| e2 | Tetrabutyl titanate |
Claims (13)
1. good conduction, the high anti-corrosion Galvanized Steel Strip of anti-the fingerprint is characterized in that: its surface coverage one deck epithelium of anti-the fingerprint, and 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 one organo silane coupling agent (Ba) and contains at least a epoxy functionality, the more than one organo silane coupling agent of epoxy functionality number (Bb), and weight ratio (Ba)/(Bb) is 0.3～0.5; Above-mentioned organic resin (A) is 1.0～2.0 with the weight ratio of organo silane coupling agent ((Ba)+(Bb)); The shared weight percent of organo silane coupling agent is 38～53%;
C) organo phosphorous compounds (C) is 0.01～0.1% in the shared weight percent of phosphoric;
D) vanadium compound (D) is 0.1～1.0% in the shared weight percent of v element;
E) titanium compound or fluorine-containing titanium compound (E) are 0.1～3.0% in the shared weight percent of titanium elements amount;
F) polyethylene wax accounts for epithelium content 1～3%.
2. good conduction as claimed in claim 1, the high anti-corrosion Galvanized Steel Strip of anti-the fingerprint is characterized in that zinc-plated substrate profile arithmetic average roughness Ra value 0.4 ~ 1.2 μ m, crest are counted between the RPc value 50～150.
3. the surface treatment agent that is used for the described good conduction of claim 1, the high anti-corrosion Galvanized Steel Strip of anti-the fingerprint; Be aqueous solution; The weight percent of its amount of solid content is 10～20%, and the weight percent of each component is in the solid: 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 a epoxy functionality, and epoxy functionality is several more than one; (Ba)/(Bb) weight ratio is 0.3～0.5; Above-mentioned organic resin (A) is 1.0～2.0 with the weight ratio of organo silane coupling agent ((Ba)+(Bb)); (Ba)+(Bb), the content in solid is 38～53%; Organo phosphorous compounds (C) accounts for the weight percent that the solid total amount is, 0.01～0.1% in phosphoric; Vanadium compound (D) accounts for the weight percent of solid total amount in v element, 0.1～1.0%; Titanium compound or fluorine-containing titanium compound (E) account for the weight percent of solid total amount in titanium elements, 0.1～3.0%; Polyethylene wax (F) accounts for the weight percent of solid total amount, 1～3%.
4. surface treatment agent as claimed in claim 3 is characterized in that, the glass transition temperature of described urethane and/or vinylformic acid organic resin (A) is 30～80 ℃, and possesses water-soluble or water dispersible.
5. surface treatment agent as claimed in claim 3; 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 amino such as TMSDMA 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.
6. surface treatment agent as claimed in claim 3; It is characterized in that described vinyl resin is N; N-dimethylamino-propyl propenoate; N-methylamino-ethylacrylic acid methylmethacrylate monomer, polyethylene glycol methacrylate-styrene polymer, Rocryl 400 monomer, the co-polypropylene acid resin of Acrylic Acid Monomer and vinylbenzene, vinyl cyanide, Vinyl Acetate Monomer.
7. surface treatment agent as claimed in claim 3 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, preferably 2,000～500, in 000 scope.
8. surface treatment agent as claimed in claim 3 is characterized in that, the phosphonic acids that contains hydroxyl in the described organo phosphorous compounds (C) is HEDP, hydroxy ethylene diphosphonic acid; The phosphonic acids that contains the carboxylic acid group is the phosphono oxyacetic acid.
9. surface treatment agent as claimed in claim 3 is characterized in that, described vanadium compound (D) comprises vitriol, fluoride salt or oxide compound.
10. surface treatment agent as claimed in claim 3 is characterized in that, described titanium compound (E) contains the titanium compound of 4 above fluorine atoms at least.
11. surface treatment agent as claimed in claim 3 is characterized in that, described polyethylene wax (F) is to obtain through oxidation style by the vinyl polymerization method or as the polyethylene wax that poly pyrolysate generates, and contains carboxyl, hydroxy functional group on its structure.
12., it is characterized in that the molecular weight of described polyethylene wax (F) is in 1000～10000 scopes like claim 3 or 11 described surface treatment agents, median size is at 0.1～1.6 μ m.
13. the surface treatment method of good conduction as claimed in claim 1, the high anti-corrosion Galvanized Steel Strip of anti-the fingerprint; It is characterized in that; Adopting two rollers or three roller roller coating machines, is that 10～20% surface treatment agent single stage method 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 with above-mentioned amount of solid content weight percent; Preferred 0.5 ~ 0.8, crest counts between the RPc value 50～150 preferred 60～100; Adopt hot blast or infrared induction to be heating and curing, the plate temperature control is made as 80～140 ℃, preferably 100～120 ℃; The cooling back forms the epithelium of anti-fingerprint of dry film thickness 0.5～1.5 μ m, preferred 0.7～1.0 μ m at zinc-plated substrate surface.
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| Application Number | Priority Date | Filing Date | Title |
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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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| 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 |
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| WO2014000527A1 (en) | 2014-01-03 |
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