WO2014000527A1 - 良导电、高耐蚀耐指纹镀锌钢带及表面处理剂、处理方法 - Google Patents

良导电、高耐蚀耐指纹镀锌钢带及表面处理剂、处理方法 Download PDF

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WO2014000527A1
WO2014000527A1 PCT/CN2013/075783 CN2013075783W WO2014000527A1 WO 2014000527 A1 WO2014000527 A1 WO 2014000527A1 CN 2013075783 W CN2013075783 W CN 2013075783W WO 2014000527 A1 WO2014000527 A1 WO 2014000527A1
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surface treatment
treatment agent
steel strip
galvanized steel
fingerprint
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PCT/CN2013/075783
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English (en)
French (fr)
Inventor
张剑萍
陈�光
戴毅刚
朱岚
赵艳亮
黄胜标
陈卓人
牟战旗
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宝山钢铁股份有限公司
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Publication of WO2014000527A1 publication Critical patent/WO2014000527A1/zh

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment 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
    • B05D3/02Pretreatment 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
    • B05D3/0254After-treatment
    • B05D3/0263After-treatment with IR heaters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00Processes for applying liquids or other fluent materials
    • B05D1/28Processes 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08Homopolymers or copolymers of acrylic acid esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • C09D5/082Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084Inorganic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00Compositions for coatings
    • C08G2150/90Compositions for anticorrosive coatings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/10Metal compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds

Definitions

  • the invention relates to a galvanized steel strip and a surface treatment technology thereof, in particular to a good conductive, high corrosion resistance and fingerprint resistant galvanized steel strip, a surface treatment agent and a treatment method, which can meet the previous non-chromate coating technology and is difficult to realize. At the same time, it satisfies the characteristics of excellent electrical conductivity and high corrosion resistance, and has the heat resistance, heat resistance, fingerprint resistance, weldability, paintability and resistance to processing blackening of general non-chromate coatings. All performance. Background technique
  • Galvanized steel strip is one of the most widely used metal products in the world and is widely used in home appliances, construction and automotive.
  • many types of chromium-free and fingerprint-resistant galvanized steel strips with different characteristics have been developed.
  • Chinese Patent Publication No. CN101435078A discloses a chromium-free resin composition having both good corrosion resistance, alkali resistance, processability, electrical conductivity and chemical resistance, and a method for treating a galvanized steel strip using the composition.
  • the composition is composed of a polyurethane resin, an organic oxide of Ti and Zr, an inorganic salt, and a water-based solvent, but the galvanized steel strip treated by such a composition has corrosion resistance and electrical conductivity and other useful properties, However, the examples show that the conductivity is only ⁇ (surface resistance) or less, and the corrosion resistance (in a neutral salt spray test) is 96 hours. Such performance is not sufficient in industries where electrical conductivity and corrosion resistance are required to be higher, such as office automation appliances such as copiers and facsimile machines.
  • U.S. Patent No. 2005/0058843 A1 provides a method for treating a galvanized steel sheet with an aqueous composition obtained by mixing two kinds of silanes such as vinyl silane and aminosilane, and has certain moist heat resistance and corrosion resistance (with a neutral salt). Fog tester), but the treatment method is to soak the steel sheet in the above aqueous composition and dry for 5 minutes. Such a method cannot achieve continuous treatment of the galvanized steel strip.
  • Chinese Patent Publication No. CN101228294A provides a non-chromate surface-treated metal material having both corrosion resistance, heat resistance, fingerprint resistance, electrical conductivity, paintability, and resistance to processing blackening, in a metal material.
  • the surface of the water-based metal surface treatment agent is coated and dried to form a composite film containing various components, but the conductivity provided by the patent only guarantees the interlayer resistance value, and does not involve the surface resistance value of particular interest to the home appliance industry.
  • Chinese Patent Publication No. CN 101688309A provides an aqueous surface for galvanized steel sheets Chemical and galvanized steel sheets, by processing GI and GA surfaces, can achieve good electrical conductivity and high corrosion resistance, as well as coating and alkali resistance, but the technical route adopted is inorganic salt as coating. In the film-forming skeleton, only a part of the organic acrylic resin is mixed in the coating layer, and such a coating structure is difficult to ensure excellent fingerprint resistance.
  • Chinese Patent Publication No. CN 1887449A provides a surface treatment agent for galvanized steel sheets having excellent alkali resistance and solvent resistance, and is treated by an aqueous treatment agent composed of polyurethane, silane, specific inorganic salt and a small amount of auxiliary agents.
  • the galvanized steel sheet can obtain a chromium-free and fingerprint-resistant steel strip which is excellent in alkali resistance, solvent resistance, corrosion resistance, fingerprint resistance, paintability and resistance to processing blackening, but the patent cannot guarantee that the coating has The above properties have good surface conductivity while film thickness conditions.
  • various chrome-free surface treatment technologies that are currently available are difficult to integrate chrome-free fingerprint-resistant galvanized steel strips that meet the needs of high-end home appliance users with comprehensive performances such as good electrical conductivity, high corrosion resistance, and fingerprint resistance. Summary of the invention
  • the object of the invention is a good conductive, high corrosion-resistant and fingerprint-resistant galvanized steel strip, a surface treatment agent and a treatment method, and has excellent comprehensive properties such as electrical conductivity (grounding property), corrosion resistance, weldability and processing. Applicable to home appliances and office supplies, etc., the electrical products are in line with the relevant international standards for electromagnetic wave leakage testing.
  • a good conductive, high corrosion and fingerprint resistant galvanized steel strip, the surface of which is covered with a fingerprint resistant film, the film composition comprising:
  • the arithmetic mean roughness of the galvanized substrate has a Ra value of 0.4 ⁇ 1.2 ⁇ , and the peak number RPc is between 50 and 150.
  • the treatment agent for the good conductive, high corrosion resistant and fingerprint resistant galvanized steel strip of the invention is an aqueous solution, the solid content of which is 10-20% by weight, and the weight percentage of each component in the solid fraction is : Polyurethane and/or acrylic organic resin (A), 40 ⁇ 60% ; organosilane coupling agent (Ba), containing more than one amino functional group, at least one active amino group; organic silane coupling agent (Bb), Containing at least one epoxy functional group, the number of epoxy functional groups is more than one; the weight ratio of (Ba) I (Bb) is from 0.3 to 0.5; the above organic resin (A) and organosilane coupling agent ((Ba) + The weight ratio of (Bb) ) is 1 ⁇ 0 ⁇ 2 ⁇ 0; (Ba) + (Bb), the content in the solid part is 38 ⁇ 53% ; the organophosphorus compound (C), the phosphorus element accounts for the total solids The weight percentage is 0.01 ⁇ 0.1%; the vanadium
  • the polyurethane and/or acrylic organic resin (A) has a glass transition temperature of 30 to 80 ° C and is water-soluble or water-dispersible.
  • the polyurethane resin is a polymer of a polyalcohol and a polyisocyanate
  • the polyalcohol is a polyester polyglycol, a polyether polyglycol, a polycarbonate polyglycol, and an N,N-dimethylaminodihydroxy group.
  • a polyalcohol of an amino group such as methyl propane; a polyalcohol containing a polyethylene oxide chain similar to polyethylene glycol; and a polyisocyanate is an aliphatic poly diisocyanate or an aromatic poly diisocyanate.
  • the acrylic resin is ruthenium, osmium-dimethylaminopropyl acrylate, ⁇ -methylaminoethyl methacrylate monomer, polyethylene glycol methacrylate, hydroxyethyl methacrylate monomer, acrylic acid A copolymerized acrylic resin of a monomer and a styrene, acrylonitrile or vinyl acetate monomer.
  • the polyurethane and/or acrylic organic resin ( ⁇ ) has an average molecular weight in the range of 1,000 to 1,000,000, preferably in the range of 2,000 to 500,000.
  • the phosphonic acid containing a hydroxyl group in the organophosphorus compound (C) is hydroxyethylidene diphosphonic acid or hydroxyethylidene diphosphonic acid; and the phosphonic acid containing a carboxylic acid group is a phosphonohydroxyacetic acid.
  • the vanadium compound (D) includes a sulfate, a fluoride salt or an oxide.
  • the titanium compound (E) is a titanium compound containing at least four fluorine atoms.
  • the polyethylene wax (F) is obtained by an ethylene polymerization method or a polyethylene wax produced as a thermal decomposition product of polyethylene, and has a carboxyl group and a hydroxyl functional group in its structure.
  • the polyethylene wax (F) has a molecular weight in the range of 1000 to 10,000 and an average particle diameter of 0.1 to 1 ⁇ 6 ⁇ m.
  • the surface treatment method of the good conductive, high corrosion resistance and fingerprint resistant galvanized steel strip according to the invention adopts a two-roll or three-roll roll coater to coat the above-mentioned aqueous treatment agent with a solid content percentage of 10-20% by weight Covering both sides of the galvanized substrate, the galvanized substrate has an arithmetic mean roughness Ra of 0.4 to 1.2 ⁇ m, preferably 0.5 to 0.8, and a peak number of RPc of 50 to 150, preferably 60 to 100; using hot air or infrared induction heated and cured, the plate temperature is controlled to 80 ⁇ 140 ° C, preferably 100 ⁇ 120 ° C; 0.5 ⁇ 1.5 ⁇ form a dry film thickness of the zinc-plated substrate surface after cooling, preferably 0.7 ⁇ 1.0 ⁇ fingerprint resistant film.
  • the galvanized metal material which can be used in the present invention is not particularly limited and may include a pure zinc plating layer or a zinc-based alloy plating layer.
  • the pure zinc-coated steel strip it may be an electrogalvanized steel strip or a steel strip such as an electrogalvanized nickel alloy, hot-dip galvanized or hot-dip aluminized zinc.
  • the surface physical profile such as roughness of the galvanized steel strip is mainly achieved by controlling the surface topography of the substrate before plating, and the surface profile is mainly transmitted after galvanizing.
  • the surface roughness of the substrate is controlled by the roll surface roughness of each of the front and rear rack rolls, and then the electroplating of the strip is completed in the continuous galvanizing unit.
  • the surface profile of the galvanized substrate is controlled to have an arithmetic mean roughness Ra of 0.4 to 1.2 ⁇ m and a number of peaks (depending on the intersection lines C1 and C2, per centimeter (or per inch) exceeding the upper intersection line C1 and less than the lower intersection line C2.
  • the number of contours) RPc value between 50 and 120 (according to the definition of GB3505-1983, the same below), the preferred range is between Ra value 0.5 ⁇ 0.8, RPc value 60 ⁇ 100.
  • the organic thin coating layer having a dry film thickness of 0.5 to 1.5 ⁇ m and having excellent corrosion resistance and electrical conductivity
  • the aqueous treatment applied to the surface thereof The agent will not form a uniform coating film on the surface of the steel strip, resulting in uneven corrosion resistance on the surface of the steel strip.
  • the film at the trough will be thicker and the coating will be relatively thin at the peak.
  • the uneven thickness will cause the coating at the peak to fail prematurely in the corrosive environment. See Figure 1, which shows the surface roughness of the galvanized substrate is too large, 1 is the galvanized base.
  • the surface profile of the material, 2 is the contour of the coating surface.
  • the coating on the surface of the steel strip will be relatively continuous and dense.
  • the insulating properties of the organic coating may increase the surface resistance and affect the conductivity, especially when the surface resistance is less than ⁇ . ⁇ and distribution.
  • Fig. 2 which shows the surface roughness of the galvanized substrate is too small
  • 1 is the surface profile of the galvanized substrate
  • 2 is the surface profile of the coating.
  • the control of the surface profile and film thickness of the substrate should be within a correspondingly balanced range.
  • the invention is used for the surface treatment agent of the excellent conductive, high corrosion-resistant chromium-free fingerprint-resistant galvanized steel strip:
  • the organic resin portion ( ⁇ ) refers to acrylic acid and/or polyurethane having a glass transition temperature Tg of 30 to 80 ° C. If the Tg is less than 30 ° C, the overall hardness of the organic composite film is insufficient, which may cause deterioration in abrasion resistance and press formability. However, if Tg > 80 ° C, the overall hardness of the organic composite film becomes too high and becomes brittle, and the film is easily destroyed during processing.
  • the polyurethane and/or acrylic organic resin is water-soluble or water-dispersible, that is, the resin has an ionic functional group as a hydrophilic group, and/or a non-ionic functional group can be dissolved in water or form a self-emulsifying sol. Alternatively, it may be made water-soluble by using a surfactant or may be forcedly dispersed into an aqueous resin.
  • the polyurethane resin is a polymer of a polyalcohol and a polyisocyanate
  • the polyalcohol is a polyester polyglycol, a polyether polyglycol, a polycarbonate polyglycol, and a N,N-dimethylamino dimethylol group.
  • a polyalcohol of an amino group such as propane or a polyalcohol having a polyethylene oxide chain similar to polyethylene glycol; and the polyisocyanate is an aliphatic polydiisocyanate or an aromatic polyisocyanate.
  • the acrylic resin is ruthenium, osmium-dimethylaminopropyl acrylate, ⁇ -methylaminoethyl methacrylate monomer, polyethylene glycol methacrylate, hydroxyethyl methacrylate monomer, acrylic acid A copolymerized acrylic resin of a monomer and a styrene, acrylonitrile or vinyl acetate monomer.
  • the above aqueous resin has an average molecular weight in the range of 1,000 to 1,000,000, preferably in the range of 2,000 to 500,000.
  • the above-mentioned resin has a molecular weight of less than 1,000, and the film formation property of the film may be poor, and when the molecular weight exceeds 1,000,000, the surface treatment composition may be unstable.
  • the organosilane coupling agent (Ba) used in the treating agent of the present invention contains at least one active hydrogen-containing amino group as a reactive functional group per molecule.
  • the configuration is not particularly limited.
  • a composition similar to N-(2-aminoethyl) 3-aminopropylmethyldimethoxysilane or 3-aminopropyltriethoxysilane can be used.
  • the organosilane coupling agent (Bb) used in the present invention contains at least one epoxy group as a reactive functional group per molecule, and is not particularly limited in structure. example For example, 3-glycidoxypropyltrimethoxysilane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane and the like can be used.
  • the weight ratio of the organosilane compound (Ba) to (Bb) (Ba) / (BbM is preferably in the range of 0.3 - 0.5. If less than 0.3, that is, the organosilane compound (Ba) is less When the organic composite film has poor adhesion to the galvanized steel sheet, peeling of the film may occur during press forming. If it is more than 0.5, that is, when the amount of the organosilane compound (Bb) is large, the corrosion resistance may be deteriorated.
  • the weight ratio (A) / ((Ba) + (Bb)) of the total amount of the organosilane compound to the resin ( ⁇ ) is preferably between 1.0 and 2.0. If it is less than 1.0, that is, the amount of resin is small, the solvent resistance and coating adhesion of the coating are deteriorated. If the weight ratio is higher than 2.0, that is, when the resin is large, corrosion resistance, workability, and Performance such as conductivity is lowered.
  • the phosphonic acid containing a hydroxyl group in the organophosphorus compound (C) in the treating agent of the present invention is hydroxyethylidene diphosphonic acid or hydroxyethylidene diphosphonic acid; and the phosphonic acid containing a carboxylic acid group is a phosphonohydroxyglycolic acid.
  • the organophosphorus compound (C) in the aqueous treatment agent is an organic compound containing a C-P bond, and the phosphorus atom can be in a valence state, which has a high inhibitory effect on corrosion of the metal.
  • Specific examples thereof include a hydroxyl group-containing phosphonic acid such as hydroxyethylidene diphosphonic acid or hydroxyethylidene diphosphonic acid, and a carboxylic acid group-containing phosphonic acid such as phosphonohydroxyacetic acid, and salts thereof.
  • the weight percentage of the C component (in terms of phosphorus) in the total solid content is preferably 0.01 to 0.1%. When the weight percentage is less than 0.01%, the effect of addition is not satisfactory, the corrosion resistance is lowered, and especially the corrosion resistance after alkali washing is insufficient; when the weight percentage exceeds 0.1%, the system stability of the treating agent is affected.
  • the vanadium compound (D) in the aqueous treatment agent is water-soluble and oxidizing, and has an inhibitory effect on corrosion of the galvanized steel sheet.
  • the vanadium compound D the vanadium ion has a good valence state of 2+, 3+, 4+, and 5+, and thus does not limit the source of the vanadium element.
  • Specific examples may be sulfates, fluoride salts and oxides. These compounds may be anhydrous or hydrated.
  • the total weight percent of the vanadium-containing compound is 0.1 to 1.0% by weight, preferably 0.2 to 0.5%.
  • the weight percentage is less than 0.2%, the oxidation of vanadium has a poor passivation effect on the galvanized surface, and the corrosion resistance is not improved; if the weight percentage is higher than 1%, the stability of the treatment agent is deteriorated. Moreover, the surface of the coating is easily yellowed and the heat resistance is lowered.
  • the titanium compound (E) involved in the aqueous treatment agent contains a titanium compound having at least four fluorine atoms. Its function is to etch the galvanized surface oxide film to improve the adhesion of the film.
  • This titanium The compound (E) is 0.1 to 3% by weight in terms of Ti in the organic film. When it is less than 0.1%, the effect of addition cannot be achieved, resulting in deterioration of film adhesion and corrosion resistance. If it exceeds 3%, the film composition is stably reduced, and it may also cause a decrease in the surface quality of the galvanized steel sheet.
  • a polyethylene wax (F) is added to the aqueous treatment agent, and a polyethylene wax produced by an ethylene polymerization method or a thermal decomposition product of polyethylene is obtained by an oxidation method, and has a functional group such as a carboxyl group or a hydroxyl group.
  • the molecular weight is in the range of 1000 to 10,000.
  • the polyethylene wax of the present invention has an average particle diameter of 0.1 to 1.6 ⁇ m.
  • the content of the polyethylene wax (F) in the film is 1 to 3 % by weight, and the content of the polyethylene wax (F) in the film is preferably 1.5 to 2.5%. If the content is less than 1%, sufficient abrasion resistance cannot be obtained. If the content exceeds 3%, it may cause deterioration in properties such as corrosion resistance, solvent resistance, and paintability.
  • the surface treatment method of the galvanized steel strip of the invention is to apply the above aqueous treatment agent to both sides of the strip by a two-roll or three-roll roll coater, to control the proper solid content and viscosity of the treatment agent, and to adjust the roll coating process.
  • Parameters such as liquid roller/coating roller speed ratio and coating roller pressure to obtain a suitable film thickness, controlled by a curing oven (hot air or infrared induction heating), curing at 80 to 140 ° C, rapid cooling (water cooling or air cooling) After drying, the film is formed, and finally the strip is crimped into a steel coil.
  • the sheet temperature (PMT) for heat curing after coating is 80 to 140 ° C, preferably 100 to 120 ° C.
  • PMT is lower than 80 °C, the moisture volatilization in the wet film does not affect the curing effect, and it is unfavorable for corrosion resistance and solvent resistance.
  • PMT is higher than 140 °C, the cooling of the strip before crimping is insufficient, and the energy consumption is not conducive to Cost Control.
  • the aqueous treating agent of the present invention forms a fingerprint-resistant coating of 0.5 to 1.5 ⁇ m (dry film) on a galvanized surface, preferably 0.7 to 1.0 ⁇ m.
  • the film thickness is less than 0.5 ⁇ , and the galvanized surface is difficult to be completely covered by the anti-fingerprint coating. No matter whether the galvanized surface roughness is too large or too small, although it can have excellent conductivity, it has corrosion resistance and alkali resistance. The performance such as fingerprint resistance is lowered. If the film thickness exceeds 1.5 ⁇ m, the conductivity is lowered, and the uniformity of the entire strip surface is deteriorated even if the surface roughness of the galvanized substrate is at an upper limit of about 1.2 ⁇ m. Moreover, as the film thickness increases, the processing cost per unit area increases, and the coating adhesion is also affected.
  • the galvanized steel strip of the invention has excellent electrical conductivity and corrosion resistance, and the surface resistance of the steel sheet can reach ⁇ . ⁇ or less, the surface white rust area of the neutral salt spray test is less than 5%, and the steel has excellent fingerprint resistance. Characteristics such as sex, paintability, weldability, wear resistance, etc., suitable for use in areas such as electronic equipment with harsh grounding, such as copiers, printers, etc. DRAWINGS
  • Fig. 1 and Fig. 2 are schematic views showing the surface profile formed by coating the surface treatment of the two steel strips with a coating agent. detailed description
  • the substrate of the embodiment of the present invention is exemplified by an electrogalvanized or hot-dip galvanized steel sheet.
  • Table 1 shows the ingredients of the examples of the present invention.
  • Table 2 shows the performance of the present invention.
  • Table 3, Table 4, and Table 5 are specific materials corresponding to the examples of the present invention.
  • White rust rate is 5% or more but less than 10%
  • White rust rate is 10% or more but less than 30%
  • the sample was subjected to the Eriksson test (the cup height was 7 mm), it was subjected to the neutral salt spray test standard of JIS Z2371 for 72 hours, and the white rust formation state of the processed portion (the cup-shaped portion) was observed.
  • White rust in the cup-shaped mutant is greater than 10% but less than 30%
  • a 4-probe surface contact impedance measurement method is used. The principle is shown in Figure 1. When current flows through probe A and probe D, a potential difference (V) between probe B and probe C is generated. It is detected, and thus the resistance V/I is the measured surface impedance value.
  • the conductivity of the material is characterized by a 9 point (uniform distribution) surface contact resistance value in an area of 300 ⁇ 300 mm2.
  • the arithmetic mean value of the 9-point surface contact resistance is less than 0.05 ⁇ , and the single point value shall not be greater than 0.05 ⁇ ;
  • The arithmetic mean value of the 9-point surface contact resistance is greater than 0.05 ⁇ but less than ⁇ . ⁇ , and the single point value shall not be greater than ⁇ . ⁇ ;
  • The arithmetic mean value of the 9-point surface contact resistance is greater than ⁇ . ⁇ but less than ⁇ . ⁇ , and the single point value shall not be greater than ⁇ . ⁇ ;
  • 9-point surface contact impedance arithmetic mean is greater than ⁇ . ⁇ ;
  • SEIKO ADVANCE on the surface of the clean sample to control the dry film thickness of 10 ⁇ 3 microns; coat the melamine alkyd resin coating with a bar or other means (no limit), to control the dry film thickness of 20 ⁇ 5 microns;
  • the above two prepared coating samples were subjected to the following adhesion test after being allowed to stand at room temperature for 24 hours.
  • the prepared coating sample plate is placed in boiling water, and more than half of the sample must be immersed in boiling water; kept boiled for 30 minutes, taken out, and left at room temperature for 2 hours;
  • Adhesion is 100/100 90/100 or more
  • the coating has swelling, and the color difference AE*>5.0.
  • the results of the examples show that the galvanized surface treatment product of the invention has excellent electrical conductivity and corrosion resistance, and at the same time satisfies fingerprint resistance, abrasion resistance, paintability and Comprehensive performance such as processing.

Abstract

一种表面覆有皮膜组合物的镀锌钢带、镀锌钢带的表面处理剂以及镀锌钢带的表面处理方法,其中表面处理剂包含:聚氨酯和/或丙烯酸有机树脂(A),含有一个以上氨基官能团、氨基官能团的活性氢至少为一个的有机硅烷偶联剂(Ba)和含有至少一种环氧基官能团、环氧基官能团数一个以上的有机硅烷偶联剂(Bb),有机磷化合物(C),钒化合物(D),钛化合物或含氟钛化合物(E),和聚乙烯蜡。镀锌钢带的表面处理方法是将表面处理剂涂覆到镀锌基材两面,该镀锌基材轮廓算术平均粗糙度Ra值0.4~1.2μm,优选0.5~0.8、波峰数RPc值50〜150之间,优选60〜100;加热固化,在镀锌基材表面形成干膜膜厚0.5〜1.5μm、优选0.7〜1.0μm的耐指纹皮膜。

Description

良导电、 高耐蚀耐指纹镀锌钢带及表面处理剂、 处理方法 技术领域
本发明涉及镀锌钢带及其表面处理技术, 特别涉及一种良导电、 高耐 蚀耐指纹镀锌钢带及表面处理剂、 处理方法, 可以满足以往的非铬酸盐涂 层技术难以实现的同时满足优良导电性和高耐蚀的特性, 并具备了一般非 铬酸盐涂层所具有的耐湿热性、 耐热性、 耐指纹性、 焊接性、 涂装性和抗 加工黑变性等全部性能。 背景技术
镀锌钢带是世界上应用最为广泛的金属制品之一, 广泛应用于家电、 建筑和汽车领域。 为了进一歩提高镀锌钢带的耐蚀性, 开发出了许多种具 有不同特性的无铬耐指纹镀锌钢带。中国专利公开号 CN101435078A公开 了一种同时具有良好耐腐蚀性、 耐碱性、 加工性和导电性和耐化学性的无 铬树脂组成物及用此组成物对镀锌钢带进行处理的方法, 其组成物由聚氨 酯树脂、 Ti及 Zr的有机氧化物、 无机盐及以水为主的溶剂, 但是由这样 的组成物处理的镀锌钢带尽管具有耐蚀性和导电性及其他有用特性, 但是 实施例显示其导电性仅达到 ΙιηΩ (表面电阻) 以下、 耐蚀性(以中性盐雾 试验计) 为 96 小时。 这样的性能在对导电性和耐蚀性要求更高的行业, 如复印机、 传真机等办公自动化电器等领域是不够的。
美国专利 US 2005/0058843 A1提供了一种用乙烯基硅烷、氨基硅烷等 两种硅烷混合后的水性组成物处理镀锌钢板的方法, 具有一定的耐湿热性 能和耐蚀性 (以中性盐雾试验计) , 但是其处理方法是将钢板浸泡在上述 水性组成物中并干燥 5分钟, 这样的方法无法实现镀锌钢带的连续处理。
中国专利公开号 CN101228294A 提供了一种同时具备耐蚀性、 耐热 性、 耐指纹性、 导电性、 涂装性以及抗加工黑变性的非铬酸盐表面处理金 属材, 其方法是在金属材表面涂布并干燥水系金属表面处理剂而形成含有 各种成份的复合皮膜, 但是该专利提供的导电性仅保证了层间阻抗值, 未 涉及家电行业特别关注的表面电阻值。
中国专利公开号 CN 101688309A提供了一种镀锌钢板用水性表面处 理液及镀锌钢板, 通过处理 GI和 GA表面可以使钢板同时获得良导电和 高耐蚀性, 同时具有涂装性和耐碱性, 但是由于其采用的技术路线是无机 盐作为涂层的成膜骨架, 涂层中仅混合了部分的有机丙烯酸树脂, 这样的 涂层结构难以保证优异的耐指纹性能。
中国专利公开号 CN 1887449A提供一种具有优异耐碱性和耐溶剂性 的用于镀锌钢板的表面处理剂, 通过将聚氨酯、 硅烷、 特定的无机盐及少 量助剂等组成的水性处理剂处理镀锌钢板可以获得一个耐碱性、 耐溶剂 性、 耐蚀性、 耐指纹性、 涂装性、 抗加工黑变性都很优异的无铬耐指纹钢 带, 但是该专利无法保证涂层在具有上述性能的膜厚条件下同时具有良好 的表面导电性能。 综上所述, 目前已有的各种无铬表面处理技术都难以综 合良导电、 高耐蚀、 耐指纹等综合性能都满足高端家电用户需求的无铬耐 指纹镀锌钢带。 发明内容
本发明的目的是一种良导电、 高耐蚀耐指纹镀锌钢带及表面处理剂、 处理方法, 其导电性 (接地性) 、 耐蚀性、 焊接性和加工等各项综合性能 优良, 适用于家电和办公用品等领域, 所成电气制品符合电磁波泄露测试 的相关国际标准。
为达到上述目的, 本发明的技术方案是:
良导电、 高耐蚀耐指纹镀锌钢带, 其表面覆盖一层耐指纹皮膜, 该皮 膜组成物包含:
a) 聚氨酯和 /或丙烯酸有机树脂 (A) , 所占重量百分比为 40〜60% ; b) 含有一个以上氨基官能团、 氨基官能团的活性氢至少为一个的有机 硅烷偶联剂 (Ba) 和含有至少一种环氧基官能团、 环氧基官能团数 一个以上的有机硅烷偶联剂(Bb ), ( Ba) I ( Bb )的重量比在 0.3〜 0.5; 上述有机树脂 (A) 与有机硅烷偶联剂 ( (Ba) + ( Bb ) ) 的 重量比为 1.0〜2.0; 有机硅烷偶联剂所占重量百分比为 38〜53% ; c) 有机磷化合物, 以磷元素计所占重量百分比为 0.01〜0.1 %;
d) 钒化合物 (D ) , 以钒元素计所占重量百分比为 0.1〜1.0%; e) 钛化合物或含氟钛化合物 (E ) , 以钛元素量计所占重量百分比为 0.1— 3.0%;
f) 聚乙烯蜡, 占皮膜含量 1〜3%。
进一歩, 镀锌基材轮廓算术平均粗糙度 Ra值 0.4~1.2μιη、波峰数 RPc 值 50〜150之间。
本发明用于所述的良导电、 高耐蚀耐指纹镀锌钢带的处理剂, 为水性 溶液, 其固体份含量的重量百分比为 10〜20%, 固体份中各组分的重量百 分比为: 聚氨酯和 /或丙烯酸有机树脂 (A) , 40〜60%; 有机硅烷偶联剂 (Ba) , 含有一个以上氨基官能团, 氨基官能团的活性氢至少为一个; 有 机硅烷偶联剂 (Bb) , 含有至少一种环氧基官能团, 环氧基官能团数一个 以上; (Ba) I (Bb) 的重量比在 0.3〜0.5; 上述有机树脂 (A) 与有机硅 烷偶联剂 ( (Ba) + (Bb) ) 的重量比为 1·0〜2·0; (Ba) + (Bb) , 在 固体份中的含量为 38〜53%; 有机磷化合物 (C) , 以磷元素占固体份总 量为计的重量百分比, 0.01〜0.1%; 钒化合物 (D) , 以钒元素占固体份 总量计的重量百分比, 0.1〜1.0%; 钛化合物或含氟钛化合物 (E) , 以钛 元素占固体份总量计的重量百分比, 0.1〜3.0%; 聚乙烯蜡 (F) , 占固体 份总量的重量百分比, 1〜3%。
进一歩, 所述的聚氨酯和 /或丙烯酸有机树脂 (A) 的玻璃化转化温度 为 30〜80°C, 且具备水溶性或者水分散性。
又, 所述的聚氨酯树脂为聚醇与聚异氰酸酯的聚合物, 聚醇为聚脂聚 二醇、 聚醚聚二醇、 聚碳酸酯聚二醇、 含有 N, N-二甲胺基二羟甲基丙烷 等氨基的聚醇、 含有类似于聚乙二醇那样的聚环氧乙烷链的聚醇; 聚异氰 酸酯为脂肪族聚二异氰酸酯、 芳香族聚二异氰酸酯。
所述的丙烯酸树脂为, Ν,Ν-二甲氨基丙基丙烯酸酯, Ν-甲氨基乙基丙 烯酸甲酯单体、 聚乙二醇甲基丙烯酸酯, 甲基丙烯酸羟乙酯单体, 丙烯酸 单体与苯乙烯、 丙烯腈、 醋酸乙烯酯单体的共聚丙烯酸树脂。
所述的聚氨酯和 /或丙烯酸有机树脂 (Α) 的平均分子量在 1,000〜 1,000,000范围内, 优选在 2,000〜500,000范围内。
再有, 所述的有机磷化合物 (C) 中含有羟基的膦酸为羟基乙叉二膦 酸、 羟基亚乙基二膦酸; 含有羧酸基的膦酸为膦酰基羟基乙酸。
所述的钒化合物 (D)包括硫酸盐、 氟化物盐或氧化物。 所述的钛化合物 (E), 至少含有 4个以上氟原子的钛化合物。
另外, 所述的聚乙烯蜡 (F), 是由乙烯聚合法或者作为聚乙烯的热分解 物生成的聚乙烯蜡经过氧化法获得, 其结构上含有羧基、 羟基官能团。
所述的聚乙烯蜡 (F)的分子量在 1000〜10000 范围内, 平均粒径在 0· 1〜 1 ·6μηι。
本发明所述的良导电、 高耐蚀耐指纹镀锌钢带的表面处理方法, 采用 两辊或三辊辊涂机,将上述固含量重量百分比为 10〜20%的水性处理剂一 歩法涂覆到镀锌基材两面, 该镀锌基材轮廓算术平均粗糙度 Ra 值 0.4~1.2μιη, 优选 0.5~0.8、 波峰数 RPc值 50〜 150之间, 优选 60〜100; 采用热风或红外感应加热固化, 板温控制为 80〜140°C, 优选是 100〜120 °C ; 冷却后在镀锌基材表面形成干膜膜厚 0.5〜1.5μιη、 优选 0.7〜1.0μιη 的耐指纹皮膜。
在本发明镀锌钢带设计中:
在本发明中可使用的镀锌金属材料, 没有特别限定, 可以包括纯锌镀 层或锌基合金镀层。 作为纯锌镀层钢带, 可以是电镀锌钢带, 也可以是电 镀锌镍合金、 热镀锌、 热镀铝锌等钢带。
本发明中镀锌钢带的表面物理轮廓如粗糙度等的实现主要是控制镀 前基材的表面形貌,镀锌后表面轮廓主要是传递。在冷轧带钢经过轧机时, 通过前后机架各轧辊的辊面粗糙度来控制基材的粗糙度等表面形貌, 然后 在连续镀锌机组完成对带钢的电镀锌。
镀锌基材表面轮廓,控制其算术平均粗糙度 Ra值 0.4~1.2μιη、波峰数 (取决于交线 C1和 C2, 每厘米 (或每英寸) 超出上交线 C1和小于下交 线 C2的轮廓的数目) RPc值 50〜120之间 (依据 GB3505— 1983的定义, 以下同) , 优选的范围是在 Ra值 0.5~0.8、 RPc值 60〜100之间。
对于本发明干膜厚度为 0.5〜1.5μιη, 同时要求具备优良耐蚀性和导电 性的有机薄涂层而言, 当镀锌层的表面粗糙度过大时, 涂覆在其表面的水 性处理剂将无法在钢带表面形成厚度均匀的涂层干膜, 从而导致了钢带表 面耐蚀性的不均匀, 波谷处的膜会较厚而在波峰处涂层会相对较薄, 这种 膜厚不均匀的现象会导致波峰处的涂层在腐蚀环境中的防护性能过早地 失效, 参见图 1, 其所示为镀锌基材表面粗糙度过大的情况, 1 为镀锌基 材表面轮廓, 2为涂层表面轮廓。 粗糙度过小时, 涂层在钢带表面的覆盖 会相对连续而且致密, 有机涂层的绝缘属性则有可能使表面电阻增大而影 响导电性,尤其在对表面电阻小于 Ο. ΙιηΩ且分布性和均匀性有严格要求的 情况下, 参见图 2, 其所示为镀锌基材表面粗糙度过小的情况, 1 为镀锌 基材表面轮廓, 2为涂层表面轮廓。
因此基材的表面轮廓和膜厚的控制应该处于相互对应的平衡范围内。 本发明用于优良导电、 高耐蚀无铬耐指纹镀锌钢带的表面处理剂中: 有机树脂部分 (Α) 是指玻璃化转化温度 Tg为 30〜80°C的丙烯酸和 / 或聚氨酯, 如果 Tg<30°C, 有机复合皮膜的整体硬度不足, 有可能导致 耐磨耗性、 冲压加工性等下降。 但如果 Tg〉80°C, 有机复合皮膜的整体 硬度过高而变脆, 加工时皮膜容易被破坏。
所述的聚氨酯和 /或丙烯酸有机树脂具备水溶性或者水分散性, 也就 是, 这些树脂具备作为亲水基的离子型官能团, 以及 /或者非离子型官能 团能溶解于水中或者形成自我乳化溶胶, 或者使用表面活性剂使其水溶性 化、 或者通过强制分散成为水性树脂。
所述的聚氨酯树脂为聚醇与聚异氰酸酯的聚合物, 聚醇为聚脂聚二 醇、 聚醚聚二醇、 聚碳酸酯聚二醇、 含有 N, N-二甲胺基二羟甲基丙烷等 氨基的聚醇、 含有类似于聚乙二醇那样的聚环氧乙烷链的聚醇; 聚异氰酸 酯为脂肪族聚二异氰酸酯、 芳香族聚二异氰酸酯。
所述的丙烯酸树脂为, Ν,Ν-二甲氨基丙基丙烯酸酯, Ν-甲氨基乙基丙 烯酸甲酯单体、 聚乙二醇甲基丙烯酸酯, 甲基丙烯酸羟乙酯单体, 丙烯酸 单体与苯乙烯、 丙烯腈、 醋酸乙烯酯单体的共聚丙烯酸树脂。
上述的水性树脂的平均分子量在 1,000〜 1,000,000 范围内, 优选在 2,000〜500,000范围内。上述树脂的分子量低于 1,000, 皮膜的成膜性可能 较差, 而分子量超过 1,000,000时可能会导致表面处理组成物的不稳定。
本发明处理剂中使用的有机硅烷偶合剂 (Ba), 每个分子中至少含有一 个作为反应性官能团的含有活性氢的氨基。 构造没有特别的限定, 举例而 言: N- ( 2-氨乙基) 3-氨丙基甲基二甲氧基硅烷、 3-氨丙基三乙氧基硅烷 类似的组成物都可以使用。 本发明中使用的有机硅烷偶合剂 (Bb), 每个分 子中至少含有一个作为反应性官能团的环氧基, 构造上无特别的限定。 例 如: 3-环氧丙氧基丙基三甲氧基硅烷、 2- ( 3、 4环氧环己基) 乙基三甲氧 基硅烷等类似的组成物都可以使用。
在有机复合皮膜中, 有机硅烷化合物 (Ba)和 (Bb)的重量比 (Ba)/(BbM尤 选在 0.3-0.5的范围内。 如果低于 0.3, 也就是有机硅烷化合物 (Ba)较少时, 有机复合皮膜对镀锌钢板的附着性差, 有可能在冲压成型时出现皮膜剥 落。 如果大于 0.5, 也就是有机硅烷化合物 (Bb)量较多时, 可能导致耐腐 蚀性变差。 另外, 在有机复合皮膜中, 有机硅烷化合物的总量 «Βί + :» 与树脂 (Α)的的重量比 (A)/((Ba)+(Bb))优选在 1·0〜2·0之间。 如果低于 1.0, 也就是说树脂量少, 涂层耐溶剂性和涂装附着性变差, 如果这个重量比高 于 2.0, 也就是说树脂较多时, 有可能导致耐腐蚀性、 加工性、 导电性等 性能的降低。
本发明处理剂中所述的有机磷化合物 (C ) 中含有羟基的膦酸为羟基 乙叉二膦酸、 羟基亚乙基二膦酸; 含有羧酸基的膦酸为膦酰基羟基乙酸。
水性处理剂中的有机磷化合物 (C ) , 由于属于含有 C-P结合键的有 机化合物, 磷原子可呈的价态不限, 对金属的腐蚀具有较高的抑制作用。 具体的例子为, 羟基乙叉二膦酸、 羟基亚乙基二膦酸等含有羟基的膦酸, 以及膦酰基羟基乙酸等含有羧酸基的膦酸、以及其盐类等。另外 C组分(以 磷计)在总固体含量所占的重量百分比优选为 0.01〜0.1%。 重量百分比低 于 0.01%时, 添加效果不理想, 耐蚀性下降, 尤其是碱洗后耐蚀性不足; 重量百分比超过 0.1%, 则处理剂的体系稳定性受到影响。
水性处理剂中的钒化合物 (D), 因为是水溶性同时具有氧化性、 对电 镀锌钢板具有腐蚀的抑制作用。作为钒化合物 D,钒离子的价态有 2+、 3+、 4+、 以及 5+等均具有良好的效果, 因此并未限定钒元素的来源。 具体的 可以是硫酸盐、 氟化物盐和氧化物。 这些化合物可以是无水化合物, 也可 以是水合物。 含钒化合物在总固含量总所占重量百分比为 0.1〜1.0%, 优 选在 0.2〜0.5%范围。 如果重量百分比低于 0.2%, 钒的氧化性对镀锌表面 侵蚀后产生的钝化效果不良, 耐蚀性得不到提高; 如果重量百分比高于 1%, 处理剂的稳定性会变差, 且涂层表面易黄变, 耐热性会下降。
水性处理剂中涉及的钛化合物 (E),至少含有 4个以上氟原子的钛化合 物。 其作用为对镀锌表面氧化膜进行刻蚀, 以提高皮膜的附着性。 这种钛 化合物 (E)以 Ti计在有机皮膜中的重量百分比为 0.1〜3%。 低于 0.1%, 不 能达到添加效果, 导致皮膜附着性、 耐蚀性下降。 如果超过 3%、 皮膜组 成物的稳定下降, 同时也可能导致镀锌钢板表面品质的下降。
水性处理剂中还添加了聚乙烯蜡 (F),是由乙烯聚合法或者作为聚乙烯 的热分解物生成的聚乙烯蜡经过氧化法获得, 其结构上含有羧基、 羟基等 官能团。 一般其分子量在 1000〜10000范围内。 本发明的聚乙烯蜡的平均 粒径在 0.1〜1.6μιη。 另外, 聚乙烯蜡 (F)在皮膜中的含量在 1〜3重量%, 聚乙烯蜡 (F)在皮膜中含量优选在 1.5〜2.5%。 如果含量低于 1%, 不能获 得充分的耐磨损性。 如果含量超过 3%, 有可能导致耐蚀性、 耐溶剂性、 涂装性等性能的下降。
本发明镀锌钢带的表面处理方法是利用两辊或三辊辊涂机将上述水 性处理剂以一歩法方式涂覆到带钢两面, 控制处理剂合适的固含量和粘 度, 调整辊涂工艺参数如带液辊 /涂覆辊速比和涂覆辊压力来得到合适膜 厚, 经固化炉 (热风或红外感应加热)控制 ΡΜΤ为 80〜140°C固化, 快速 冷却 (水冷或风冷) 后干燥成膜, 最后带钢卷曲成钢卷。 涂覆后加热固化 的板温 (PMT) 为 80〜140°C, 优选是 100〜120°C。 PMT低于 80°C, 湿 膜中水分挥发不尽影响固化效果, 对耐蚀性、 耐溶剂等性能不利; PMT 高于 140°C, 卷曲前带钢冷却不充分, 且能耗增加不利于成本控制。
本发明用水性处理剂在镀锌表面成膜为 0.5〜1.5μιη (干膜)的耐指纹 涂层, 优选是 0.7〜1.0μιη。 膜厚不到 0.5μιη, 镀锌表面很难完全被耐指纹 涂层覆盖保护, 无论镀锌表面粗糙度偏大或偏小, 虽然可以有优良的导电 性, 但耐蚀性、 耐碱性、 耐指纹性等表现都会下降; 如果膜厚超过 1.5μιη, 导电性会下降, 整个带钢表面的导电均匀性会变差, 即使镀锌基材表面粗 糙度处于 1.2μιη左右的上限水平。而且随膜厚增加单位面积的处理成本上 升, 涂装密着性也会受到影响。
本发明的有益效果
本发明镀锌钢带具有优良导电性和耐蚀性, 钢板的表面电阻可达 Ο. ΙιηΩ以下, 中性盐雾试验 120h表面白锈面积小于 5%, 同时该钢待还具 备优良的耐指纹性、 涂装性、 焊接性、 耐磨等加工等特性, 适用于对接地 性苛刻的电子设备等领域, 如复印机、 打印机等办公自动化设备。 附图说明
图 1、 图 2为两种钢带表面形貌上涂覆处理剂成膜后形成的表面轮廓 的示意图。 具体实施方式
下面结合实施例对本发明做进一歩说明。
本发明实施例基材以电镀锌、 热镀锌钢板为例。 表 1所示为本发明实 施例成分。 表 2所示为本发明性能。 表 3、 表 4、 表 5为本发明实施例所 对应的具体物质。
其中, 性能评价试验如下:
1、 平板耐蚀性
根据 JIS Z2371 中性盐雾试验 (SST ) 进行 120 小时, 试样尺寸 75x l50mm, 观察板面白锈率。
<评价标准> 白锈率小于 5%
o : 白锈率 5%以上但小于 10%
Δ : 白锈率 10%以上但小于 30%
X . 白锈率 30%以上
2、 加工部位耐蚀性
试样进行埃里克森试验 (杯突高度 7mm) 后, 按照 JIS Z2371中性盐 雾试验标准进行 72小时, 观察加工部位 (杯突变形部分) 白锈生成状况。
<评价标准> 杯突变形部位白锈小于 10%
o : 杯突变形部位白锈大于 10%但小于 30%
Δ : 杯突变形部位白锈大于 30%但小于 50%
X: 杯突变形部位白锈大于 50%
3、 导电性
采用一种 4探针式表面接触阻抗的测定方法, 其原理如图 1 所示, 当 电流流过探针 A和探针 D时, 探针 B与探针 C之间产生电势差 (V) 被 检测出来, 由此电阻 V/I即为测定的表面阻抗值。
以 300 <300mm2面积内 9点(均匀分布)表面接触阻抗值来表征材料 的导电性。
<评价标准> 9点表面接触阻抗算术平均值小于 0.05ιηΩ, 且单点 值不得大于 0.05ιηΩ;
ο : 9 点表面接触阻抗算术平均值大于 0.05ιηΩ 但小于 Ο. ΙιηΩ, 且单点值不得大于 Ο. ΙιηΩ;
Δ : 9 点表面接触阻抗算术平均值大于 Ο. ΙιηΩ 但小于 Ι.ΟιηΩ, 且单点值不得大于 Ι.ΟιηΩ;
: 9点表面接触阻抗算术平均值大于 Ι.ΟιηΩ;
4、 涂装附着性
用丝网印刷或棒涂方式涂覆油墨 (推荐牌号日本精工油墨 # 1300
SEIKO ADVANCE) 于洁净的试样表面, 以控制干膜厚度 10±3微米; 用棒涂或其他方式涂覆三聚氰胺醇酸树脂涂料 (牌号不限) , 以控制 干膜厚度 20±5微米;
上述两种制成的涂层样板在室温放置 24小时后进行如下密着性测试。 将制备好的涂层样板放入沸水中, 试样一半以上必须浸入沸水; 保持煮沸 30分钟后取出, 在室温放置 2小时;
择试样在沸水浸泡部位, 用漆膜划格仪在划 1mm间隔的百格; 在网格上贴上透明胶带, 用手指或夹具按压至完全密合, 然后拉住胶 带一端垂直于试样表面瞬间撕开, 剥离后观察密着性 (密着性=未被剥离 的方格数 /100) 。
<评价标准> 密着性为 100/100 90/100以上
Figure imgf000011_0001
5、 耐溶剂性 常温下, 试样在有机溶剂如异丙醇、 乙醇、 丁酮、 二氯甲烷、 正己烷、 甲苯、 挥发油等中浸泡 168小时后, 观察涂层表面是否有溶胀, 并测定前 后色差 (ΔΕ*值) 。
<评价标准> 涂层无溶胀, 且色差 AE*<1.0
o : 涂层无溶胀, 且色差 AE*>1.(HS<3.0
Δ : 涂层无溶胀, 且色差 AE*>3.(HS<5.0
: 涂层有溶胀, 且色差 AE*>5.0 从实施例结果表明, 本发明镀锌表面处理产品兼具优良的导电性和耐 蚀性, 同时满足耐指纹性、 耐磨性、 涂装性和加工等综合性能。
表 1
Figure imgf000013_0001
Figure imgf000014_0001
表 2
Figure imgf000015_0001
Figure imgf000016_0001
表 3树脂类型
Figure imgf000017_0001
表 4有机硅烷偶联剂
Figure imgf000017_0002
e2 钛酸四丁酯

Claims

权 利 要 求 书
1. 良导电、 高耐蚀耐指纹镀锌钢带, 其特征是: 其表面覆盖一层耐指纹 皮膜, 该皮膜组成物包含:
a) 聚氨酯和 /或丙烯酸有机树脂 (A) , 所占重量百分比为 40〜60%; b) 含有一个以上氨基官能团、氨基官能团的活性氢至少为一个的有机 硅烷偶联剂(Ba)和含有至少一种环氧基官能团、 环氧基官能团数 一个以上的有机硅烷偶联剂(Bb), (Ba) I (Bb)的重量比在 0.3〜 0.5; 上述有机树脂 (A) 与有机硅烷偶联剂 ( (Ba) + (Bb) ) 的 重量比为 1.0〜2.0; 有机硅烷偶联剂所占重量百分比为 38〜53%; c) 有机磷化合物 (C) , 以磷元素计所占重量百分比为 0.01〜0.1%; d) 钒化合物 (D) , 以钒元素计所占重量百分比为 0.1〜1.0%; e) 钛化合物或含氟钛化合物 (E) , 以钛元素量计所占重量百分比为 0.1— 3.0%;
f) 聚乙烯蜡, 占皮膜含量 1〜3%。
2. 如权利要求 1所述的良导电、 高耐蚀耐指纹镀锌钢带, 其特征是, 镀 锌基材轮廓算术平均粗糙度 Ra值 0.4~1.2μιη、 波峰数 RPc值 50〜150 之间。
3. 用于权利要求 1所述的良导电、高耐蚀耐指纹镀锌钢带的表面处理剂, 为水性溶液, 其固体份含量的重量百分比为 10〜20%, 固体份中各组 分的重量百分比为: 聚氨酯和 /或丙烯酸有机树脂 (A) , 40〜60%; 有机硅烷偶联剂 (Ba) , 含有一个以上氨基官能团, 氨基官能团的活 性氢至少为一个; 有机硅烷偶联剂 (Bb) , 含有至少一种环氧基官能 团, 环氧基官能团数一个以上; (Ba) I (Bb) 的重量比在 0.3〜0.5; 上述有机树脂 (A) 与有机硅烷偶联剂 ( (Ba) + (Bb) ) 的重量比 为 1.0〜2.0; (Ba) + (Bb) , 在固体份中的含量为 38〜53%; 有机磷 化合物(C), 以磷元素占固体份总量为计的重量百分比, 0.01〜0.1%; 钒化合物 (D) , 以钒元素占固体份总量计的重量百分比, 0.1〜1.0%; 钛化合物或含氟钛化合物(E) , 以钛元素占固体份总量计的重量百分 比, 0.1-3.0%; 聚乙烯蜡(F) , 占固体份总量的重量百分比, 1〜3%。
4. 如权利要求 3所述的表面处理剂, 其特征是, 所述的聚氨酯和 /或丙烯 酸有机树脂 (A) 的玻璃化转化温度为 30〜80°C, 且具备水溶性或者 水分散性。
5. 如权利要求 3所述的表面处理剂, 其特征是, 所述的聚氨酯树脂为聚 醇与聚异氰酸酯的聚合物, 聚醇为聚脂聚二醇、 聚醚聚二醇、 聚碳酸 酯聚二醇、 含有 N, N-二甲胺基二羟甲基丙烷等氨基的聚醇、 含有类 似于聚乙二醇那样的聚环氧乙烷链的聚醇; 聚异氰酸酯为脂肪族聚二 异氰酸酯、 芳香族聚二异氰酸酯。
6. 如权利要求 3所述的表面处理剂, 其特征是, 所述的丙烯酸树脂为, Ν,Ν-二甲氨基丙基丙烯酸酯, Ν-甲氨基乙基丙烯酸甲酯单体、 聚乙二 醇甲基丙烯酸酯, 甲基丙烯酸羟乙酯单体, 丙烯酸单体与苯乙烯、 丙 烯腈、 醋酸乙烯酯单体的共聚丙烯酸树脂。
7. 如权利要求 3所述的表面处理剂, 其特征是, 所述的聚氨酯和 /或丙烯 酸有机树脂 (Α) 的平均分子量在 1,000〜 1,000,000 范围内, 优选在 2,000〜500,000范围内。
8. 如权利要求 3所述的表面处理剂,其特征是,所述的有机磷化合物(C ) 中含有羟基的膦酸为羟基乙叉二膦酸、 羟基亚乙基二膦酸; 含有羧酸 基的膦酸为膦酰基羟基乙酸。
9. 如权利要求 3所述的表面处理剂, 其特征是, 所述的钒化合物 (D)包括 硫酸盐、 氟化物盐或氧化物。
10.如权利要求 3所述的表面处理剂, 其特征是, 所述的钛化合物 (Ε), 至 少含有 4个以上氟原子的钛化合物。
11.如权利要求 3所述的表面处理剂, 其特征是, 所述的聚乙烯蜡 (F), 是 由乙烯聚合法或者作为聚乙烯的热分解物生成的聚乙烯蜡经过氧化法 获得, 其结构上含有羧基、 羟基官能团。
12.如权利要求 3或 1 1所述的表面处理剂,其特征是,所述的聚乙烯蜡 (F) 的分子量在 1000〜10000范围内, 平均粒径在 0.1〜1.6μιη。
13.如权利要求 1所述的良导电、高耐蚀耐指纹镀锌钢带的表面处理方法, 其特征是, 采用两辊或三辊辊涂机, 将上述固体份含量重量百分比为
10〜20%的表面处理剂一歩法涂覆到镀锌基材两面, 该镀锌基材轮廓 算术平均粗糙度 Ra值 0.4~1.2μιη, 优选 0.5~0.8、 波峰数 RPc值 50〜
150之间, 优选 60〜100; 采用热风或红外感应加热固化, 板温控制为 80〜140°C, 优选是 100〜120°C ; 冷却后在镀锌基材表面形成干月 厚 0.5〜1.5μιη、 优选 0.7〜1.0μιη的耐指纹皮膜。
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