WO2010072152A1 - 一种镀锌钢板表面处理剂和一种镀锌钢板及其制备方法 - Google Patents

一种镀锌钢板表面处理剂和一种镀锌钢板及其制备方法 Download PDF

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WO2010072152A1
WO2010072152A1 PCT/CN2009/075903 CN2009075903W WO2010072152A1 WO 2010072152 A1 WO2010072152 A1 WO 2010072152A1 CN 2009075903 W CN2009075903 W CN 2009075903W WO 2010072152 A1 WO2010072152 A1 WO 2010072152A1
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Prior art keywords
surface treatment
treatment agent
galvanized steel
steel sheet
agent according
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PCT/CN2009/075903
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English (en)
French (fr)
Inventor
万军军
张曦霖
米戈尔·凯文
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汉高（中国）投资有限公司
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Application filed by 汉高（中国）投资有限公司 filed Critical 汉高（中国）投资有限公司
Priority to EP09834105.0A priority Critical patent/EP2383370B1/en
Priority to MX2011006887A priority patent/MX2011006887A/es
Priority to CA2748285A priority patent/CA2748285C/en
Priority to AU2009329626A priority patent/AU2009329626B2/en
Priority to BRPI0923695-3A priority patent/BRPI0923695B1/pt
Publication of WO2010072152A1 publication Critical patent/WO2010072152A1/zh
Priority to US13/169,568 priority patent/US8906990B2/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • 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
    • 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
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31529—Next to metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31605—Next to free metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the invention relates to a galvanized steel sheet surface treatment agent and a preparation method thereof, and a galvanized steel sheet and a preparation method thereof.
  • a layer of metallic zinc is usually applied to the surface of the steel sheet.
  • This zinc-coated steel sheet is called a galvanized steel sheet.
  • Chromate has been used in industry since the 1930s and was once the most widely used process for surface treatment of galvanized steel. Chromate provides short-term rust and corrosion protection by an aqueous solution of chromic acid, chromium salts and inorganic acids that produces a thin conversion layer on the metal surface, and a chemical reaction between the metal and the solution causes the metal to dissolve. And form a protective film containing complex chromium and metal compounds.
  • the method has the advantages of simple process, low cost and good corrosion resistance.
  • chromium-containing compounds in the coating film, especially hexavalent chromium are seriously harmful to the human body and the environment.
  • chromium-free organic or inorganic surface treatment technologies have been developed in recent years, such as inorganic chemical conversion film systems containing metal molybdenum, vanadium or zirconium, aqueous polymer dispersions, silica systems and polymerization. Aqueous dispersion, a silicate system, and the like.
  • the surface treatment process of introducing silicon-containing organic-inorganic nano-hybrid materials into galvanized sheets is one of the research hotspots.
  • Silicon germanium has been used as a treatment agent for corrosion protection of metal surfaces for a long time, such as: US Patent No. 20030049486A1, US20050058843A1 and ⁇ 1153089B1 by introducing a silicon germanium composition containing vinyl silicon germanium and a germanium group.
  • Treatment of the surface of a metal mainly zinc
  • US6955728B1 by treating zinc with a treatment agent containing acyloxysilane s surface.
  • CN 1887449A and CN 1887451A use a composition of silicon germanium, a water-soluble polymer and a vanadium-containing compound as a surface treatment agent for a galvanized steel sheet to impart alkali resistance and solvent resistance to the surface of the steel sheet.
  • these surface treatment agents are not ideal for corrosion prevention or contain toxic heavy metal elements. Therefore, it is urgent to seek a galvanized steel sheet surface treatment agent which has the same excellent corrosion resistance and environmental protection requirements. Summary of the invention
  • the technical problem to be solved by the invention is to overcome the defects that the existing galvanized steel sheet surface treatment agent has an anticorrosive effect, contains toxic heavy metals, and provides a galvanized coating with various excellent properties and no toxic heavy metal elements.
  • the galvanized steel sheet surface treatment agent of the present invention comprises: A, an epoxy group-containing silicon germanium derivative, B, a mercapto group-containing silicon germanium derivative, C, a nonoxysilane derivative, and D, the following three One or more of the following: aqueous cationic polymer dispersion, nonionic polymeric aqueous dispersion, and water soluble polymer.
  • the epoxy group-containing silicon germanium derivative refers to a silicon germanium compound having at least one epoxy group in its molecular structure, preferably a compound represented by formula I, and most preferably glycidyl ether One or more of methyl dimethicone, glycidyl ether propyl trimethoxysilane and glycidyl ether ethyl triacetyl silicon germanium, said epoxy group-containing silicon germanium derivative
  • the content of the substance is preferably from 20 to 45%, more preferably from 20 to 35%, most preferably from 20 to 25%; the percentage is the percentage of the total mass of the mass of A, B, C and D.
  • Y is a fluorenylene group of C r C 6 ;
  • R is a -C 6 fluorenyl group;
  • X is dC 4 decyloxy or C 2 -C 4 acyloxy;
  • n is 0 or 1.
  • the fluorenyl-containing silicon germanium derivative refers to silicon having at least one mercapto group in its molecular structure.
  • the quinone compound is preferably a compound of the formula II and/or formula III, preferably methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, 1 , 2-di-triethoxysilylacetyl.
  • the content of the fluorenyl group-containing silicon germanium derivative is preferably 15 to 45%, more preferably 15 to 35%, most preferably 15 to 25% ; the percentage is the mass of A, B, C. And the percentage of total mass of D.
  • R and Z are independently C r C 6 fluorenyl; M is C r C 6 fluorenylene; X is -C 4 decyloxy or C 2 -C 4 acyloxy; n is 0 or 1.
  • the bismuth silicon germanium derivative refers to a silicon germanium compound having at least one decyloxy group in its molecular structure, preferably a compound represented by formula IV, preferably tetramethoxysilane, tetra One or more of ethoxylated silicon germanium and tetrapropoxy silicon germanium.
  • the content of the nonoxysilane derivative is preferably 5 to 30%, more preferably 5 to 20%, most preferably 5 to 10%; and the percentage thereof is A, B, C and The percentage of total mass of D.
  • the aqueous cationic polymer dispersion is preferably one or more of a cationic polyurethane aqueous dispersion, a cationic acrylate aqueous dispersion, a cationic epoxide aqueous dispersion, and a cationic alkyd aqueous dispersion.
  • the nonionic polymer aqueous dispersion is preferably one or more of a nonionic polyurethane aqueous dispersion, a nonionic acrylate aqueous dispersion, a nonionic epoxy aqueous dispersion, and a nonionic alkyd water dispersion body weight.
  • the water-soluble polymer is preferably one or more of water-soluble polyethylene glycol, water-soluble polyacrylamide, water-soluble polyurethane, and water-soluble polyacrylic acid.
  • the molecular weight of the cationic polymer aqueous dispersion, the nonionic polymer aqueous dispersion or the water-soluble polymer has no influence on the application effect of the surface treatment agent of the present invention, and the existing various molecular weight cationic polymer water dispersion can be selected. Used as a bulk, nonionic polymer aqueous dispersion or water soluble polymer.
  • the content of the component D is preferably from 30 to 60%, more preferably from 30 to 50%, most preferably 30 to 40%; the percentage is the percentage of its mass to the total mass of A, B, C and D.
  • an acidic compound and/or water may also be added to the reactants.
  • the acidic compound is preferably an organic acid or an inorganic acid.
  • the inorganic acid is preferably hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, fluorotitanic acid, fluorozirconic acid, fluorosilicic acid or hydrofluoric acid; and the organic acid is preferably acetic acid or hydroxysulfonic acid.
  • the content of the acidic compound is preferably from 5 to 35%, more preferably from 5 to 20%, most preferably from 5 to 10%, based on the total mass of the four components A, B, C and D.
  • the content of the water is preferably from 50 to 200%, more preferably from 100 to 200%, most preferably from 150 to 200%, based on the total mass of the four components of the foregoing, B, C and D.
  • the galvanized steel sheet surface treating agent of the present invention is a uniform translucent material having a pH of usually 2 to 7.
  • the pH adjuster can also be used to adjust the pH to a suitable value.
  • the invention further relates to a process for the preparation of the composition of the invention:
  • the above ingredients can be obtained by uniformly mixing the above ingredients.
  • the mixing temperature and time can be conventional conditions in the art, and the preferred conditions are: the mixing temperature is preferably 5 to 70 ° C, usually at a natural room temperature; the mixing time is preferably 0.5 to 8 hours, More preferably 1 to 3 hours.
  • the mixing is carried out under stirring to make it homogeneously mixed.
  • the present invention further relates to a galvanized steel sheet having a surface coated with a galvanized steel sheet surface treatment agent of the present invention.
  • the amount of the galvanized steel sheet surface treatment agent of the present invention coated on the surface of the galvanized steel sheet is preferably 0.5 to 2 mg/m 2 .
  • the galvanized steel sheet may be various types of galvanized steel sheets in the art, such as an electrogalvanized steel sheet or a hot-dip galvanized steel sheet.
  • the present invention further relates to a method for producing a galvanized steel sheet according to which the surface treatment agent for galvanized steel sheets of the present invention is coated on a galvanized steel sheet at a film forming temperature of 60 to 120 °C.
  • the reagents and starting materials used in the present invention are commercially available.
  • the positive effect of the present invention is that: the galvanized steel sheet surface treatment agent of the present invention does not contain toxic heavy metal elements, and has excellent corrosion resistance, alkali resistance, solvent resistance, high temperature resistance, electrical conductivity, and recoating. Sex.
  • the components of the galvanized steel sheet surface treatment agent of Examples 1 to 12 are, in order, A, an epoxy group-containing silicon germanium derivative, B, a mercapto group-containing silicon germanium derivative, C, a nonoxysilane derivative. And D, one or more of the following: a cationic polymer aqueous dispersion, a nonionic polymer aqueous dispersion, and a water soluble polymer. The content of each component is shown in Table 1.
  • a cationic acrylate aqueous dispersion, water, the above components are uniformly mixed according to the ratio of Table 1 at 20 ° C, and the pH is adjusted to 5 by a pH adjuster (KOH 7 ⁇ liquid or nitric acid), and galvanized can be obtained after 2 hours.
  • a pH adjuster KOH 7 ⁇ liquid or nitric acid
  • 0(CH2)2CH3 a nonionic aqueous epoxy dispersion, nitric acid, water.
  • the above ingredients were uniformly mixed at a ratio of 25 ° C in Table 1, and the pH was adjusted to 2 by a pH adjuster (KOH sputum or nitric acid) for 0.5 hours to obtain a galvanized steel sheet surface treatment agent.
  • a pH adjuster KOH sputum or nitric acid
  • the above ingredients were uniformly mixed at a ratio of 50 ° C in Table 1, and the pH was adjusted to 4 by a pH adjuster (KOH 7j ⁇ liquid or nitric acid), and a galvanized steel sheet surface treatment agent was obtained after 2 hours.
  • a pH adjuster KOH 7j ⁇ liquid or nitric acid
  • OCH2CH3 a nonionic alkyd aqueous dispersion, fluorotitanate, water.
  • the above ingredients were uniformly mixed at a ratio of 15 ° C in Table 1, and the pH was adjusted to 3 with a pH adjuster (KOH ⁇ liquid or nitric acid) for 1.5 hours to obtain a galvanized steel sheet surface treatment agent.
  • a pH adjuster KOH ⁇ liquid or nitric acid
  • OCH2CH3 water soluble polyethylene glycol, fluorozirconic acid, water.
  • the above components were uniformly mixed at a ratio of 70 ° C in Table 1, and the pH was adjusted to pH 6 or 2 hours with a pH adjuster (KOH 7j ⁇ liquid or nitric acid) to obtain a galvanized steel sheet surface treatment agent.
  • a pH adjuster KOH 7j ⁇ liquid or nitric acid
  • Fluoric acid water
  • the above ingredients are uniformly mixed at a ratio of 25 ° C according to Table 1, and the pH is adjusted to 3 by a pH adjuster (KOH ⁇ liquid or nitric acid), and a galvanized steel sheet surface treatment agent can be obtained after 1 hour.
  • a pH adjuster KOH ⁇ liquid or nitric acid
  • the above ingredients were uniformly mixed at a ratio of 25 ° C in Table 1, and the pH was adjusted to 4 with a pH adjuster (KOH aqueous solution or hydrochloric acid) for 3 hours to obtain a galvanized steel sheet surface treatment agent.
  • a pH adjuster KOH aqueous solution or hydrochloric acid
  • the commercially available galvanized steel sheet is impregnated or sprayed with Henkel Ridoline 1559 weak alkaline degreasing cleaning agent: 10 ⁇ 20%; temperature: room temperature; cleaning time: 1 ⁇ 2 minutes). Rinse the cleaned galvanized steel sheet with tap water. The residual moisture on the surface of the galvanized steel sheet is squeezed out for use.
  • the surface treatment agent prepared in Example 11 was uniformly applied to the surface of the treated steel sheet by a coater. The coating amount was 1.5 mg/m 2 and the film formation temperature was 90 °C.
  • the commercially available galvanized steel sheet is impregnated or sprayed with Henkel Ridoline 1559 weak alkaline degreasing cleaning agent: 10 ⁇ 20%; temperature: room temperature; cleaning time: 1 ⁇ 2 minutes). Rinse the cleaned galvanized steel sheet with tap water. The residual moisture on the surface of the galvanized steel sheet is blown dry for use.
  • the surface treatment agent prepared in Example 12 was uniformly applied to the surface of the treated steel sheet by a coater. The coating amount was 2 mg/m 2 and the film formation temperature was 120 °C. Effect embodiment
  • Substrate Commercially available galvanized steel sheet (without pretreatment or oil treatment only)
  • Coating The comparative surface treatment agents 1 to 4 obtained by the following formulation and the surface treatment agent of the present invention were uniformly applied to the surface of the treated steel sheet by a coating bar or a coater. The following percentages are percentages by mass.
  • Corrosion resistance Corrosion area is measured according to ASTM B117-03, a standard method of the American Society for Materials.
  • the galvanized steel sheet surface treating agent of the present invention has excellent corrosion resistance, solvent resistance, high temperature resistance, electrical conductivity, and recoatability as compared with the comparative surface treating agents 1 to 4.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Wood Science & Technology (AREA)
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  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Description

一种镀锌钢板表面处理剂和一种镀锌钢板及其制备方法 技术领域
本发明涉及一种镀锌钢板表面处理剂及其制备方法， 和一种镀锌钢板及 其制备方法。 背景技术
为防止钢板表面遭受腐蚀， 延长其使用寿命， 通常在钢板表面涂覆一层 金属锌。 这种涂锌的钢板称为镀锌钢板。
对于刚刚制得的镀锌钢板， 有时需要立即对其作 "镀后表面处理"， 为后 续成型或涂敷涂料等工艺作表面准备， 同时也为后续操作、 储存和运输过程 中为镀锌钢板提供短期保护。 目前， 许多表面处理工艺已应用于工业中， 如 磷化、 铬酸盐化、 涂油以及它们的变种和组合。
铬酸盐化从上世纪 30年代开始应用于工业界， 一度成为镀锌钢板后表 面处理使用最广泛的工艺。铬酸盐化可提供短期防锈和防蚀保护，其过程为， 铬酸、 铬盐和无机酸的水溶液在金属表面上产生薄的转化层， 金属与溶液之 间的化学反应引起金属溶解， 并形成含有复杂的铬和金属化合物的保护膜。 该方法的工艺简单， 成本低， 抗蚀性能好。 但是涂膜中的含铬化合物， 特别 是六价铬元素， 对人体及环境都有严重危害。
为了寻求对环境友好的工艺，近年来多种无铬有机或无机表面处理技术 得到发展， 如含金属钼、 钒或锆的无机化学转化膜体系、 聚合物水分散体一 二氧化硅体系和聚合物水分散体一硅酸盐体系等等。
目前，将含硅有机一无机纳米杂化材料引入到镀锌板的表面处理工艺是 研究的热点之一。硅垸被用来作为金属表面的防腐蚀的处理剂的研究由来已 久，如： U.S. Patent No. 20030049486A1 , US20050058843A1与 ΕΡ 1153089B1 通过引入一种含有乙烯基硅垸与含有垸基的硅垸组合物处理金属 （主要是 锌）的表面， US6955728B1则通过用一种含有酰氧基硅垸的处理剂来处理锌 的表面。 CN 1887449A与 CN 1887451A则将硅垸、 水溶性聚合物以及含钒 化合物的组合物作为镀锌钢板的表面处理剂， 使钢板表面有耐碱性和耐溶剂 性。 但这些表面处理剂或者防腐蚀效果不理想， 或者含有有毒重金属元素， 因此， 亟待寻求具有同样优异的防腐蚀性能和更加符合环保要求的镀锌钢板 表面处理剂。 发明内容
本发明所要解决的技术问题是为了克服现有的镀锌钢板表面处理剂防 腐蚀效果不理想， 含有有毒重金属的缺陷， 而提供一种具有各种优异性能、 且不含有毒重金属元素的镀锌钢板表面处理剂及其制备方法， 以及一种涂覆 该表面处理剂的镀锌钢板及其制备方法。
本发明的镀锌钢板表面处理剂含有： A、 含环氧基的硅垸衍生物， B、 含垸基的硅垸衍生物， C、 垸氧基硅垸衍生物， 以及 D、 下述三种中的一种 或多种： 阳离子聚合物水分散体、 非离子聚合物水分散体和水溶性聚合物。
成分 A: 所述的含环氧基的硅垸衍生物是指分子结构中含至少一个环氧 基的硅垸类化合物， 较佳的为如式 I所示的化合物， 最优选缩水甘油醚丙基 甲基二甲氧基硅垸、缩水甘油醚丙基三甲氧基硅垸和缩水甘油醚乙基三乙酰 基硅垸中的一种或多种， 所述的含环氧基的硅垸衍生物的含量较佳的为 20-45%, 更佳的为 20〜35%， 最佳的为 20〜25%； 百分比为其质量占 A、 B、 C和 D总质量的百分比。
Figure imgf000003_0001
式 I
其中， Y为 CrC6的亚垸基； R为 -C6垸基； X为 d-C4垸氧基或 C2-C4酰 氧基； n为 0或 1。
成分 B: 所述的含垸基的硅垸衍生物指分子结构中含至少一个垸基的硅 垸类化合物， 较佳的为如式 II和 /或式 III所示的化合物， 优选甲基三甲氧基 硅垸、二甲基二甲氧基硅垸、 甲基三乙氧基硅垸、 1,2-二-三乙氧基硅基乙垸。 所述的含垸基的硅垸衍生物的含量较佳的为 15〜45%，更佳的为 15〜35%，最 佳的为 15〜25%; 百分比为其质量占 A、 B、 C和 D总质量的百分比。
Z— SiX3-n X3-n—— Si— (M)2— Si— X3-n 式 II 式 III
其中， R和 Z独立的为 CrC6垸基； M为 CrC6亚垸基； X为 -C4垸氧基 或 C2-C4酰氧基； n为 0或 1。
成分 C: 所述的垸氧基硅垸衍生物是指分子结构中含至少一个垸氧基的 硅垸类化合物， 较佳的如式 IV所示的化合物， 优选四甲氧基硅垸、 四乙氧基 硅垸和四丙氧基硅垸中的一种或多种。所述的垸氧基硅垸衍生物的含量较佳 的为 5〜30%， 更佳的为 5〜20%， 最佳的为 5〜10%； 百分比为其质量占 A、 B、 C和 D总质量的百分比。
HnSiX4-n 其中， X为 d-C4垸氧基； n为 0或 1。
成分 D: 所述的阳离子聚合物水分散体较佳的为阳离子聚氨酯水分散 体、 阳离子丙烯酸酯水分散体、 阳离子环氧水分散体和阳离子醇酸水分散体 中的一种或多种。所述的非离子聚合物水分散体较佳的为非离子聚氨酯水分 散体、 非离子丙烯酸酯水分散体、 非离子环氧水分散体和非离子醇酸水分散 体重的一种或多种。 所述的水溶性聚合物较佳的为水溶性聚乙二醇、 水溶性 聚丙烯酰胺、 水溶性聚氨酯和水溶性聚丙烯酸中的一种或多种。
所述的阳离子聚合物水分散体、非离子聚合物水分散体或水溶性聚合物 的分子量对本发明的表面处理剂的应用效果没有影响，可选用现有的各种分 子量的阳离子聚合物水分散体、 非离子聚合物水分散体或水溶性聚合物使 用。
所述的成分 D的含量较佳的为 30〜60%， 更佳的为 30〜50%， 最佳的为 30〜40%; 百分比为其质量占 A、 B、 C和 D总质量的百分比。
本发明中， 在反应物中还可加入酸性化合物和 /或水。
其中， 所述的酸性化合物较佳的为有机酸或无机酸。 所述的无机酸较佳 的为盐酸、 硫酸、 硝酸、 磷酸、 氟钛酸、 氟锆酸、 氟硅酸或氢氟酸； 所述的 有机酸较佳的为醋酸或羟基磺酸。 所述的酸性化合物的含量较佳的为前述 A、 B、 C和 D四种成分总质量的 5〜35%，更佳的为 5〜20%，最佳的为 5〜10%。
其中， 所述的水的含量较佳的为前述 、 B、 C和 D四种成分总质量的 50-200%, 更佳的为 100〜200%， 最佳的为 150〜200%。
本发明的镀锌钢板表面处理剂为均一的半透明状物质， 其 pH值一般为 2〜7。 也可使用 pH调节剂调节 pH至合适值。
本发明还涉及本发明的组合物的制备方法： 将上述各成分均匀混合， 即 可制得。 混合的温度和时间可为本领域常规条件， 优选条件为： 混合的温度 较佳的为 5〜70°C， 通常在自然室温下进行即可； 混合的时间较佳的为 0.5〜8 小时， 更佳的为 1〜3小时。 较佳的， 在搅拌条件下进行混合使其混合均匀。
本发明还进一歩的涉及一种镀锌钢板， 其表面涂覆了本发明的镀锌钢板 表面处理剂。该镀锌钢板表面涂覆的本发明的镀锌钢板表面处理剂的量较佳 的为 0.5〜2mg/m2。本发明中，所述的镀锌钢板可为本领域各种类型的镀锌钢 板， 如电镀锌钢板或热镀锌钢板等。
本发明进一歩的涉及所述的镀锌钢板的制备方法，其本发明的镀锌钢板 表面处理剂涂覆镀锌钢板上， 成膜温度为 60〜120°C。
本发明所用试剂及原料均市售可得。
本发明的积极进歩效果在于： 本发明的镀锌钢板表面处理剂不含有毒重 金属元素， 且具有优异的抗腐蚀性、 耐碱性、 耐溶剂性、 耐高温性、 导电性 以及再涂装性。
具体实施方式 下面通过实施例的方式进一歩说明本发明，但并不因此将本发明限制在 所述的实施例范围之中。
实施例 1〜12的镀锌钢板表面处理剂配方中各组分依次为 A、 含环氧基 的硅垸衍生物， B、 含垸基的硅垸衍生物， C、 垸氧基硅垸衍生物， 以及 D、 下述三种中的一种或多种： 阳离子聚合物水分散体、 非离子聚合物水分散体 和水溶性聚合物。 各组分的含量如表 1所示。
实施例 1
OCH3 ?C0CH3
^ ^^O- CH2_Si— OCH3 CH3OCO— Si— CH2CH3
O OCH3 OCOCH3
CH3O-
Figure imgf000006_0001
将上述成分按表 1中配比 5°C下均匀混合， 用 pH调节剂 （KOH水溶 或硝酸） 调节 pH至 7， 8小时后即可制得热镀锌钢板表面处理剂。
实施例 1
CH3 OCOCH3
,0-(CH2)3-Si— OCH3 CH3OCO-S1— CH3
0 OCH3 OCOCH3
CH3O-
Figure imgf000006_0002
将上述成分按表 1中配比 10°C下均匀混合， 用 pH调节剂 （ 011水 液或硝酸） 调节 pH至 6， 3小时后即可制得镀锌钢板表面处理剂。
实施例 3 OCH3 OCH3
,0-(CH2)6-Si— OCH3 CH3(CH2)5-Si— OCH3
O OCH3 OCH3
OCH3
H-Si— CH3
OCH3
阳离子丙烯酸酯水分散体， 水 将上述成分按表 1中配比 20°C下均匀混合， 用 pH调节剂 （KOH 7\ 液或硝酸） 调节 pH至 5， 2小时后即可制得镀锌钢板表面处理剂。
实施例 4
OCH2CH2CH3 OCH3 OCH3
,0-CH2-Si— OCH2CH2CH3 CH3O-S1— (CH2)2— Si— 0CH3
O OCH2CH2CH3 OCH3 OCH3
OCH3
CH3O-S1— OCH3
OCH3
阳离子环氧水分散体， 硫酸， 水( 将上述成分按表 1中配比 40°C下均匀混合， 用 pH调节剂 （KOH氺 液或硝酸） 调节 pH至 3， 1小时后即可制得镀锌钢板表面处理剂。
实施例 5
OCH3 OCH3
,0-(CH2)3-Si— OCH3 CH3CH2— Si— OCH3
O OCH3 OCH3
0(CH2)2CH3
CH3(CH2)20-Si— 0(CH2)2CH3
0(CH2)2CH3 ， 非离子环氧水分散体， 硝酸， 水。 将上述成分按表 1中配比 25°C下均匀混合， 用 pH调节剂 （KOH氺 液或硝酸） 调节 pH至 2， 0.5小时后即可制得镀锌钢板表面处理剂。 OCH3 OCH3
,0-(CH2)6-Si— OCH3 CH3(CH2)5-Si— OCH3
O OCH3 OCH3
Figure imgf000008_0001
磷酸， 水。
将上述成分按表 1中配比 50°C下均匀混合， 用 pH调节剂 （KOH 7j< 液或硝酸） 调节 pH至 4， 2小时后即可制得镀锌钢板表面处理剂。
实施例 7
OCH3 OCH3 OCH3
^^^0-CH2-Si— OCH3 CH3O-S1— (CH2)2-Si— 0CH3
O OCH3 OCH3 OCH3
OCH2CH3
CH3CH20-Si— OCH2CH3
OCH2CH3 ， 非离子醇酸水分散体， 氟钛酸， 水。
将上述成分按表 1中配比 15°C下均匀混合， 用 pH调节剂 （KOH氺 液或硝酸） 调节 pH至 3， 1.5小时后即可制得镀锌钢板表面处理剂。
实施例 8 CH3
Figure imgf000008_0002
OCH2CH3
CH3CH20-Si— OCH2CH3
OCH2CH3 ， 水溶性聚乙二醇， 氟锆酸， 水。
将上述成分按表 1中配比 70°C下均匀混合， 用 pH调节剂 （KOH 7j< 液或硝酸） 调节 pH至 6， 2小时后即可制得镀锌钢板表面处理剂。
实施例 9 CH3 CH3 CH3
,0-(CH2)3-Si— OCH3 CH3OCO-S1— (CH2)2-Si— OCOCH3
O OCH3 OCH2CH3 OCOCH3
OCH3
H-Si— CH3
0CH3 ， 水溶性聚丙烯酰胺， 氟硅酸， 水。 将上述成分按表 1中配比 60°C下均匀混合， 用 pH调节剂 （KOH 7j< 液或硝酸） 调节 pH至 5， 2小时后即可制得镀锌钢板表面处理剂。
实施例 10
CH3 OCH3
,0-(CH2)3-Si— OCH3 CH3— Si— CH2CH3
O OCH3 OCH3
OCH3
H-Si— CH3
OCH3
氟酸， 水 将上述成分按表 1中配比 25°C下均匀混合， 用 pH调节剂 （KOH氺 液或硝酸） 调节 pH至 3， 1小时后即可制得镀锌钢板表面处理剂。
实施例 11
CH3 OCH3
I I
,0-(CH2)3-Si— OCH2CH3 CH3(CH2)5— Si— OCH3
O OCH2CH3 OCH3
CH3CH20-
Figure imgf000009_0001
将上述成分按表 1中配比 30°C下均匀混合， 用 pH调节剂 （KOH 7j< 液或硝酸） 调节 pH至 4， 3小时后即可制得镀锌钢板表面处理剂。
实施例 12 OCOCH3 CH3 CH3
,0-(CH2)3-Si— OCOCH3 CH3O-S1— (CH2)2-Si— 0CH3
O OCOCH3 OCH3 OCH3
OCH3
CH3O-S1— OCH3
0CH3 ， 非离子丙烯酸酯水分散体， 羟基磺酸， 水
将上述成分按表 1中配比 25°C下均匀混合， 用 pH调节剂 （KOH水溶 液或盐酸） 调节 pH至 4， 3小时后即可制得镀锌钢板表面处理剂。
表 1 实施例 1~12各组分含量
Figure imgf000010_0001
实施例 13
将市售镀锌钢板用汉高 Ridoline 1559弱碱性脱脂清洗剂浸渍或喷淋处 理浓度： 10〜20%； 温度： 室温； 清洗时间： 1〜2分钟）。 用自来水对清洗过 的镀锌钢板漂洗。对镀锌钢板表面残留水份空气吹干备用。 用涂敷机将实施 例 10 制得的表面处理剂均匀涂敷在已处理过的钢板表面。 涂覆量为 0.5mg/m2, 成膜温度为 60°C。
实施例 14
将市售镀锌钢板用汉高 Ridoline 1559弱碱性脱脂清洗剂浸渍或喷淋处 理浓度： 10〜20%； 温度： 室温； 清洗时间： 1〜2分钟）。 用自来水对清洗过 的镀锌钢板漂洗。对镀锌钢板表面残留水份空气挤干备用。 用涂敷机将实施 例 11 制得的表面处理剂均匀涂敷在已处理过的钢板表面。 涂覆量为 1.5mg/m2, 成膜温度为 90°C。
实施例 15
将市售镀锌钢板用汉高 Ridoline 1559弱碱性脱脂清洗剂浸渍或喷淋处 理浓度： 10〜20%； 温度： 室温； 清洗时间： 1〜2分钟）。 用自来水对清洗过 的镀锌钢板漂洗。对镀锌钢板表面残留水份空气吹干备用。 用涂敷机将实施 例 12制得的表面处理剂均匀涂敷在已处理过的钢板表面。涂覆量为 2mg/m2， 成膜温度为 120°C。 效果实施例
一、 基材： 市售镀锌钢板 （未经前处理， 或者仅涂油处理）
二、 基材清洗：
1.用汉高 Ridoline 1559 弱碱性脱脂清洗剂浸渍或喷淋处理。 （浓度： 10〜20%wt); 温度： 室温； 清洗时间： 1〜2分钟。）
2.用自来水对清洗过的镀锌钢板漂洗。
3.对镀锌钢板表面残留水份空气吹干或挤干备用。
三、涂敷： 用涂敷线棒或涂敷机将由下表配方制得的对比表面处理剂 1〜4以 及本发明的表面处理剂分别均匀涂敷在已处理过的钢板表面。下述百分比为 质量百分比。
Figure imgf000012_0001
将上述反应物质混合均匀后，在 25°C条件下搅拌 30分钟后得到均一物质。 四、 固化： 钢板峰值温度（Peak Metal Temperature, PMT)控制在 80〜120°C), 干膜膜厚为 0.5〜2mg/m2。
五、 测试：
( 1 ) 耐腐蚀性： 根据美国材料学会标准方法 ASTM B117-03 , 测腐蚀 面积。
(2)耐碱性： 汉高 Ridoline 336、 50°C， 浸没 2分钟， 水洗后目测板面。
(3 )耐溶剂性： 用棉球蘸 80%酒精 /丁酮（MEK), 负重约 1公斤在样 板表面来回擦 30次， 测定擦试前后的 ΔΕ值。
(4) 导电性： 依照 IBM标准， 使用三菱 Loresta MP-T360电导仪， 并采用 BSP探头进行测试样板的导电性。
( 5 ) 耐高温性： 将样板放入 220°C烘箱中烘烤 20分钟后取出， 测定
Figure imgf000013_0001
如上表所示： 与对比表面处理剂 1〜4相比， 本发明的镀锌钢板表面处 理剂具有优异的抗腐蚀性、 耐溶剂性、 耐高温性、 导电性以及再涂装性。

Claims

权利要求
1、 一种镀锌钢板表面处理剂， 其特征在于其含有： A、 含环氧基的硅垸 衍生物， B、 含垸基的硅垸衍生物， C、 垸氧基硅垸衍生物， 以及 D、 下述 三种中的一种或多种： 阳离子聚合物水分散体、 非离子聚合物水分散体和水 溶性聚合物。
2、 如权利要求 1所述的表面处理剂， 其特征在于： 所述的含环氧基的 硅垸衍生物为如式 I所示的化合物；
Figure imgf000014_0001
式 I
其中， Y为 CrC6的亚垸基； R为 -C6垸基； X为 d-C4垸氧基或 C2-C4酰 氧基； n为 0或 1。
3、 如权利要求 1所述的表面处理剂， 其特征在于： 所述的含环氧基的 硅垸衍生物为缩水甘油醚丙基甲基二甲氧基硅垸、缩水甘油醚丙基三甲氧基 硅垸和缩水甘油醚乙基三乙酰基硅垸中的一种或多种。
4、 如权利要求 1所述的表面处理剂， 其特征在于： 所述的含环氧基的 硅垸衍生物的含量为 20〜45%； 百分比为其质量占 A、 B、 C和 D总质量的 百分比。
5、 如权利要求 1所述的表面处理剂， 其特征在于： 所述的含垸基的硅 垸衍生物为如式 Π和 /或式 III所示的化合物；
Z— SiX3-n X3-n— Si— (M)2— Si— X3-n 式 II 式 III
其中， R和 Z独立的为 CrC6垸基； M为 CrC6亚垸基； X为 CrC4垸氧基 或 C2-C4酰氧基； n为 0或 1。
6、 如权利要求 1所述的表面处理剂， 其特征在于： 所述的含垸基的硅 垸衍生物为甲基三甲氧基硅垸、 二甲基二甲氧基硅垸、 甲基三乙氧基硅垸和 1,2-二-三乙氧基硅基乙垸中的一种或多种。
7、 如权利要求 1所述的表面处理剂， 其特征在于： 所述的含垸基的硅 垸衍生物的含量为 15〜45%； 百分比为其质量占 A、 B、 C和 D总质量的百 分比。
8、 如权利要求 1所述的表面处理剂， 其特征在于： 所述的垸氧基硅垸 衍生物为如式 IV所示的化合物；
HnSiX4-n 式 JY 其中， X为 CrC4垸氧基； n为 0或 1。
9、 如权利要求 1所述的表面处理剂， 其特征在于： 所述的垸氧基硅垸 衍生物为四甲氧基硅垸、 四乙氧基硅垸和四丙氧基硅垸中的一种或多种。
10、 如权利要求 1所述的表面处理剂， 其特征在于： 所述的垸氧基硅垸 衍生物的含量为 5〜30%； 百分比为其质量占 A、 B、 C和 D总质量的百分比。
11、 如权利要求 1所述的表面处理剂， 其特征在于：
所述的阳离子聚合物水分散体为阳离子聚氨酯水分散体、阳离子丙烯酸 酯水分散体、 阳离子环氧水分散体和阳离子醇酸水分散体中的一种或多种； 所述的非离子聚合物水分散体为非离子聚氨酯水分散体、非离子丙烯酸 酯水分散体、 非离子环氧水分散体和非离子醇酸水分散体中的一种或多种； 所述的水溶性聚合物为水溶性聚乙二醇、 水溶性聚丙烯酰胺、 水溶性聚 氨酯和水溶性聚丙烯酸中的一种或多种。
12、如权利要求 1所述的表面处理剂， 其特征在于： 所述的 D的含量为 30〜60%； 百分比为其质量占 A、 B、 C和 D总质量的百分比。
13、 如权利要求 1所述的表面处理剂， 其特征在于： 所述的表面处理剂 还含有入酸性化合物和 /或水。
14、 如权利要求 13所述的表面处理剂， 其特征在于： 所述的酸性化合 物含量为 、 B、 C和 D四种成分总质量的 5〜35%； 所述的水的含量为 A、 B、 C和 D四种成分总质量的 50〜200%。
15、 如权利要求 13所述的表面处理剂， 其特征在于： 所述的酸性化合 物为盐酸、 硫酸、 硝酸、 磷酸、 氟钛酸、 氟锆酸、 氟硅酸、 氢氟酸、 醋酸和 羟基磺酸中的一种或多种。
16、 如权利要求 1所述的表面处理剂， 其特征在于： 所述的表面处理剂 的 pH值为 2〜7。
17、 如权利要求 1〜16任一项所述的表面处理剂的制备方法， 其特征在 于其包括如下歩骤： 5〜70°C下， 将所述的各成分均匀混合 0.5〜8小时， 即可 制得。
18、 一种镀锌钢板， 其特征在于： 其表面涂覆了如权利要求 1〜16任一 项所述的镀锌钢板表面处理剂。
19、 如权利要求 18所述的镀锌钢板， 其特征在于： 所述的镀锌钢板表 面涂覆的镀锌钢板表面处理剂的量为 0.5〜2mg/m2。
20、 如权利要求 18所述的镀锌钢板的制备方法， 其特征在于： 将如权 利要求 1〜16任一项所述的镀锌钢板表面处理剂涂覆镀锌钢板上， 成膜温度 为 60〜120°C。
PCT/CN2009/075903 2008-12-26 2009-12-23 一种镀锌钢板表面处理剂和一种镀锌钢板及其制备方法 WO2010072152A1 (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101249782B1 (ko) * 2011-03-04 2013-04-03 대주나노솔라주식회사 열경화형 침지코팅 조성물
CN111205403A (zh) * 2020-01-13 2020-05-29 东南大学 一种用于核酸快速提取的聚丙烯酰胺微球及其制备方法和应用

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102220577B (zh) * 2011-06-29 2013-09-04 安徽工业大学 一种用于镀锌板彩涂预处理的有机无机复合水性表面处理液
CN103360822B (zh) * 2012-03-31 2016-02-03 攀钢集团攀枝花钢铁研究院有限公司 一种金属防护涂料及其用途和热镀金属材料
CN103360829B (zh) * 2012-03-31 2015-10-28 攀钢集团攀枝花钢铁研究院有限公司 一种金属防护涂料及其用途和热镀金属材料
CN103360840B (zh) * 2012-03-31 2015-10-28 攀钢集团攀枝花钢铁研究院有限公司 一种金属防护涂料及其用途和热镀金属材料
CN103360838B (zh) * 2012-03-31 2015-10-28 攀钢集团攀枝花钢铁研究院有限公司 一种金属防护涂料及其用途和热镀金属材料
CN102943259B (zh) * 2012-09-24 2014-06-18 中国海洋石油总公司 一种用于镀锌系列钢板的水系无铬表面处理液
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JP6318248B2 (ja) * 2013-08-06 2018-04-25 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ 金属表面予備処理のための被覆組成物、その製造およびその使用
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5292549A (en) * 1992-10-23 1994-03-08 Armco Inc. Metallic coated steel having a siloxane film providing temporary corrosion protection and method therefor
CN1299401A (zh) * 1998-03-12 2001-06-13 日本帕卡濑精株式会社 用于金属材料的表面处理组合物和表面处理方法
US20030049486A1 (en) 1999-07-19 2003-03-13 Wim J. Van Ooij Silane coatings for metal
CN1814860A (zh) * 2005-02-02 2006-08-09 日本帕卡濑精株式会社 金属材料表面处理用组合物和处理方法
CN1887451A (zh) 2005-06-27 2007-01-03 宝山钢铁股份有限公司 具有优异耐碱性和耐溶剂性的镀锌钢板
CN1887449A (zh) 2005-06-27 2007-01-03 宝山钢铁股份有限公司 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
EP1153089B1 (en) 1999-02-05 2007-03-28 Chemetall Plc Method of treating metals using vinyl silanes and multi-silyl-functional silanes in admixture
CN101228294A (zh) * 2005-07-22 2008-07-23 新日本制铁株式会社 耐蚀性、耐热性、耐指纹性、导电性、涂装性及加工时的抗变黑性优良的非铬酸盐表面处理金属材

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5902847A (en) * 1995-07-31 1999-05-11 Kansai Paint Co., Ltd. Coating composition
JP3898302B2 (ja) * 1997-10-03 2007-03-28 日本パーカライジング株式会社 金属材料用表面処理剤組成物および処理方法
US6451382B2 (en) * 2000-02-08 2002-09-17 John B. Schutt Method for improving heat efficiency using silane coatings and coated articles produced thereby
YU64902A (sh) * 2000-02-28 2006-01-16 Adsil Lc. Preparati za prevlačenje bazirani na silanima, proizvodi obloženi na taj način i postupci za njihovo korišćenje
AU2001295609B8 (en) * 2000-10-11 2007-05-10 Chemetall Gmbh Method for pretreating and/or coating metallic surfaces with a paint-like coating prior to forming and use of substrates coated in this way
JP3883831B2 (ja) * 2001-09-27 2007-02-21 Ｊｆｅスチール株式会社 耐白錆性に優れた表面処理鋼板及びその製造方法
JP4128969B2 (ja) * 2004-03-16 2008-07-30 株式会社放電精密加工研究所 亜鉛めっき製品用非クロム表面処理剤
EP1693424B2 (en) * 2003-08-15 2013-08-21 Hoden Seimitsu Kako Kenkyusho Co., Ltd. Steel product coated with a chromium-free metal surface treatment agent
US20060099332A1 (en) * 2004-11-10 2006-05-11 Mats Eriksson Process for producing a repair coating on a coated metallic surface
FR2914631B1 (fr) * 2007-04-06 2009-07-03 Eads Europ Aeronautic Defence Materiau nanostructure particulier, comme revetement protecteur de surfaces metalliques.

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5292549A (en) * 1992-10-23 1994-03-08 Armco Inc. Metallic coated steel having a siloxane film providing temporary corrosion protection and method therefor
CN1299401A (zh) * 1998-03-12 2001-06-13 日本帕卡濑精株式会社 用于金属材料的表面处理组合物和表面处理方法
EP1153089B1 (en) 1999-02-05 2007-03-28 Chemetall Plc Method of treating metals using vinyl silanes and multi-silyl-functional silanes in admixture
US20030049486A1 (en) 1999-07-19 2003-03-13 Wim J. Van Ooij Silane coatings for metal
US20050058843A1 (en) 1999-07-19 2005-03-17 Van Ooij Wim J. Silane coatings for metal
US6955728B1 (en) 1999-07-19 2005-10-18 University Of Cincinnati Acyloxy silane treatments for metals
CN1814860A (zh) * 2005-02-02 2006-08-09 日本帕卡濑精株式会社 金属材料表面处理用组合物和处理方法
CN1887451A (zh) 2005-06-27 2007-01-03 宝山钢铁股份有限公司 具有优异耐碱性和耐溶剂性的镀锌钢板
CN1887449A (zh) 2005-06-27 2007-01-03 宝山钢铁股份有限公司 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
CN101228294A (zh) * 2005-07-22 2008-07-23 新日本制铁株式会社 耐蚀性、耐热性、耐指纹性、导电性、涂装性及加工时的抗变黑性优良的非铬酸盐表面处理金属材

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101249782B1 (ko) * 2011-03-04 2013-04-03 대주나노솔라주식회사 열경화형 침지코팅 조성물
CN111205403A (zh) * 2020-01-13 2020-05-29 东南大学 一种用于核酸快速提取的聚丙烯酰胺微球及其制备方法和应用

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