WO2014000527A1 - Feuillard d'acier galvanisé présentant une bonne conductivité, une grande résistance à la corrosion et aux traces de doigt, et agent de traitement de surface et procédé de traitement - Google Patents

Feuillard d'acier galvanisé présentant une bonne conductivité, une grande résistance à la corrosion et aux traces de doigt, et agent de traitement de surface et procédé de traitement Download PDF

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Publication number
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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Prior art keywords
surface treatment
treatment agent
steel strip
galvanized steel
fingerprint
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PCT/CN2013/075783
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English (en)
Chinese (zh)
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/fr

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • 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
    • 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
    • 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
    • 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
    • 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

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.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

La présente invention concerne un feuillard d'acier galvanisé dont la surface est recouverte d'une composition de revêtement, un agent de traitement de surface pour feuillard d'acier galvanisé et un procédé de traitement de surface pour feuillard d'acier galvanisé. Ledit agent de traitement de surface comprend du polyuréthane et/ou une résine acrylique organique (A); un agent de pontage silane organique (Ba) contenant un ou plusieurs groupes fonctionnels amino, chaque groupe fonctionnel amino comportant au moins un hydrogène actif; un agent de pontage silane organique (Bb) contenant au moins un type de groupe fonctionnel époxy, le nombre de groupes fonctionnels époxy étant supérieur à un; un composé organophosphoré (C); un composé de type vanadium (D); un composé de type titane ou un composé de type titane contenant du fluor (E); et de la cire de polyéthylène. Le procédé de traitement de surface pour feuillard d'acier galvanisé comprend les étapes consistant à revêtir au moyen de l'agent de traitement de surface les deux surfaces d'un substrat galvanisé, la rugosité moyenne arithmétique Ra du substrat galvanisé pouvant varier de 0,4 à 1,2 µm et, de préférence, de 0,5 à 0,8 µm, et le nombre de crêtes RPc pouvant varier de 50 à 150 et, de préférence, de 60 à 100; et à chauffer et polymériser l'agent de traitement de surface, afin de former un film séché d'une épaisseur de 0,5 à 1,5 µm et, de préférence, un revêtement anti-traces de doigt d'une épaisseur de 0,7 à 1,0 µm, à la surface dudit substrat galvanisé.
PCT/CN2013/075783 2012-06-29 2013-05-17 Feuillard d'acier galvanisé présentant une bonne conductivité, une grande résistance à la corrosion et aux traces de doigt, et agent de traitement de surface et procédé de traitement WO2014000527A1 (fr)

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