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WO2017078105A1 - Agent aqueux de traitement de surface pour un matériau en acier zingué ou un matériau en acier plaqué avec un alliage à base de zinc, procédé de revêtement et matériau en acier revêtu - Google Patents

Agent aqueux de traitement de surface pour un matériau en acier zingué ou un matériau en acier plaqué avec un alliage à base de zinc, procédé de revêtement et matériau en acier revêtu Download PDF

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Publication number
WO2017078105A1
WO2017078105A1 PCT/JP2016/082690 JP2016082690W WO2017078105A1 WO 2017078105 A1 WO2017078105 A1 WO 2017078105A1 JP 2016082690 W JP2016082690 W JP 2016082690W WO 2017078105 A1 WO2017078105 A1 WO 2017078105A1
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WIPO (PCT)
Prior art keywords
zinc
mass
plated steel
treatment agent
steel material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/082690
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English (en)
Japanese (ja)
Inventor
邦彦 東新
浩雅 莊司
圭一 上野
山本　茂樹
圭一 中島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nihon Parkerizing Co Ltd
Nippon Steel Corp
Original Assignee
Nihon Parkerizing Co Ltd
Nippon Steel and Sumitomo Metal Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nihon Parkerizing Co Ltd, Nippon Steel and Sumitomo Metal Corp filed Critical Nihon Parkerizing Co Ltd
Priority to JP2017548833A priority Critical patent/JP6510670B2/ja
Priority to KR1020187015268A priority patent/KR102115686B1/ko
Priority to CN201680062542.9A priority patent/CN108350578B/zh
Priority to MYPI2018701704A priority patent/MY198115A/en
Publication of WO2017078105A1 publication Critical patent/WO2017078105A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C09D5/02—Emulsion paints including aerosols
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C23C22/40—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 containing molybdates, tungstates or vanadates
    • C23C22/42—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 containing molybdates, tungstates or vanadates containing also phosphates

Definitions

  • the present invention relates to an aqueous surface treating agent for galvanized steel or zinc-based alloy plated steel, a coating method using this treating agent, and a coated steel obtained using this method.
  • rust preventive coatings are required to have performance such as corrosion resistance, corrosion resistance after degreasing, coating adhesion, coating adhesion after degreasing, blackening resistance, anti-condensation whitening, treatment agent stability, and actual machine operability.
  • Patent Document 1 contains a raw material of a olefinic wax surface-modified with a cationic resin, a siloxane compound, a titanium compound, a vanadium compound, and preferably a silicon compound in a zinc-based plated steel sheet base material in a specific ratio.
  • a technique for forming a poorly water-soluble film in which the total content of strong electrolyte components remaining in the film is less than 0.3 mg ⁇ m ⁇ 2 by application of an aqueous treatment liquid and baking drying.
  • the stability of the treatment agent is not sufficiently considered. It has been found. As a result of studies to improve the stability of the treatment agent, it has been found that when acetic acid is added to the surface treatment agent described in Patent Document 1, the treatment agent stability of the surface treatment agent is improved.
  • Stack whitening resistance means the resistance to whitening of the surface-treated film in a state simulating the storage conditions during coil storage of the surface-treated steel sheet, and its performance evaluation is consistent with the surface-treated steel sheet under high temperature and high humidity conditions. Pressure is applied (stack), and the appearance after a certain period of time is evaluated.
  • the filament tape resistance means using the filament tape to temporarily fix the end of the coil of the surface-treated steel sheet, but means the resistance of the surface-treated film to the filament tape, and its performance evaluation is After applying the filament tape to the surface-treated steel sheet, the appearance after peeling the filament tape after a certain period of time under high temperature and high humidity conditions is evaluated.
  • the cause of the deterioration of stack whitening resistance is that acetic acid remaining in the surface treatment film becomes water-containing due to high humidity, and the zinc galvanized layer of the galvanized steel sheet, which is the base material, is attacked. This is thought to be due to the tendency to occur.
  • the cause of the deterioration of the resistance to filament tape is that acetic acid remaining in the surface-treated film becomes water-containing due to high humidity, and the adhesive layer of the filament tape is damaged, thereby reducing the adhesion of the filament tape. This is thought to be due to film damage to the attachment part of the ment tape.
  • the present invention has been made in view of the above circumstances, and is corrosion resistance, corrosion resistance after degreasing, coating adhesion, coating adhesion after degreasing, blackening resistance, condensation whitening resistance, processing agent stability, actual machine operability.
  • Water-based surface treatment agent for galvanized steel or zinc-base alloy-plated steel material that can form a film with excellent resistance to stack whitening and filament tape, and a coating method using this treatment agent, and An object is to provide a coated steel material obtained by using this method.
  • the present inventor has obtained a cationic polyurethane resin, a cationic phenol resin, a silane coupling agent, an acetylacetone complex of titanium, a vanadium compound, and an olefin wax.
  • An aqueous surface treatment agent for galvanized steel or zinc-based alloy-plated steel that can form a film with excellent stack whitening resistance and filament tape resistance by adding an acetic acid component and a phosphoric acid component to water. Based on this finding, the present invention has been completed.
  • the present invention includes a cationic polyurethane resin (A), a cationic phenol resin (B), a silane coupling agent (C), an acetylacetone complex of titanium (D), a vanadium compound (E), and acetic acid.
  • A cationic polyurethane resin
  • B cationic phenol resin
  • C silane coupling agent
  • D acetylacetone complex of titanium
  • E vanadium compound
  • acetic acid acetic acid
  • a water-based surface treatment agent for galvanized steel or zinc-based alloy-plated steel material comprising a component (G) and a phosphoric acid component (H) mixed in water, wherein the solid content (V) of the water-based surface treatment agent
  • the ratio (ND) / (NV) to the mass (ND) in terms of Ti of the acetylacetone complex (D) is 0.0170 to 0.0240, and the vanadium compound (E) with respect to the mass of the solid content (V).
  • Ratio (NE) / (NV) to mass (NE) in terms of V is 0.0070 to 0.0090
  • ratio of mass of acetic acid component (G) to mass of solid content (V) (NG) / (NV) is 0.040 to 0.140
  • the ratio (NH) / (NV) of the phosphoric acid component (H) to the mass of the solid content (V) is 0.025 to 0.075.
  • the ratio (ND) / (NE) of the acetylacetone complex (D) of titanium to the mass of Ti of the vanadium compound (E) in terms of V is 2.10 to 2.90, the acetic acid component ( The ratio (NH) / (NG) of the phosphoric acid component (H) to the mass of G) is 0.25 to 1.10, and the mass (ND) in terms of Ti of the acetylacetone complex (D) of titanium. To the mass of the phosphoric acid component (H) ( H) / (ND) is 1.11 to 3.19, which is for galvanized steel or zinc base alloy plated steel product for aqueous surface-treating agent.
  • the water-based surface treatment agent for galvanized steel or zinc-based alloy-plated steel further includes a ratio of the olefin wax (F) to the mass of the olefin wax (F) with respect to the mass of the solid content (V). It may contain 0.035 to 0.060 as (NF) / (NV).
  • the olefin wax (F) is surface-modified with a silane coupling agent (I), and the ratio of the mass of the silane coupling agent (I) to the mass of the olefin wax (F) (NI / NF). ) May be 0.025 to 0.035.
  • the olefin wax (F) may have an average particle size of 0.05 to 0.15 ⁇ m.
  • the vanadium compound (E) may be an acetylacetone complex of vanadium.
  • the olefin wax (F) may be surface-modified with an epoxy group-containing silane coupling agent.
  • the cationic polyurethane resin (A) is a polycarbonate-based water-dispersible cationic polyurethane resin containing a structural unit represented by the general formula (1) There may be.
  • R is an aliphatic alkylene group having 4 to 9 carbon atoms
  • n is an integer corresponding to a number average molecular weight in the range of 500 to 5000.
  • the cationic phenol resin (B) may be a polymer molecule having an average polymerization degree of 2 to 50 having a repeating unit represented by the general formula (2).
  • Y1 and Y2 each independently represent hydrogen or a Z group represented by the general formula (3) or (4), and the average number of substitutions of Z groups per benzene ring is 0.2. ⁇ 1.0.
  • R1, R2, R3, R4 and R5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms, - represents a hydroxide ion or an oxo acid ions.
  • the present invention is a coating method in which a coating is formed by applying the above-described aqueous surface treatment agent for galvanized steel or zinc-base alloy-plated steel to galvanized steel or zinc-base alloy-plated steel.
  • the present invention is a coated steel material obtained by the above coating method.
  • an aqueous surface treatment agent for galvanized steel or zinc-based alloy-plated steel material capable of forming a film excellent in stack whitening resistance and filament tape resistance, a coating method using this treatment agent, and this It becomes possible to provide the coated steel material obtained by using the method.
  • the present invention is excellent in the anti-condensation whitening property, which is one of the important required properties regarding the surface appearance quality of the surface-treated steel sheet used without coating, and further contains an olefin wax (F) as an optional component.
  • F olefin wax
  • Aqueous surface treatment agent for galvanized steel or zinc-based alloy-plated steel (component) ⁇ Cationic polyurethane resin (A)> ⁇ Cationic phenol resin (B)> ⁇ Silane coupling agent (C)> ⁇ Titanium acetylacetone complex (D)> ⁇ Vanadium compound (E)> ⁇ Olefin wax (F)> ⁇ Acetic acid component (G)> ⁇ Phosphoric acid component (H)> ⁇ Unsuitable component> (Mixing ratio) ⁇ (NC) / (NV)> ⁇ (ND) / (NV)> ⁇ (NE) / (NV)> ⁇ (NF) / (NV)> ⁇ (NG) / (NV)> ⁇ (Mixing ratio) ⁇ (NC) / (NV)> ⁇ (ND) / (NV)> ⁇ (NE) / (NV)> ⁇ (NF) / (NV)> ⁇ (NG) / (NV)>
  • the aqueous surface treating agent for galvanized steel or zinc-based alloy-plated steel includes at least a cationic polyurethane resin (A), a cationic phenol resin (B), a silane coupling agent (C), This is an aqueous surface treatment agent comprising titanium acetylacetone complex (D), vanadium compound (E), acetic acid component (G), and phosphoric acid component (H) in water. Moreover, the compounding ratio of each component in this aqueous surface treating agent is as follows.
  • the ratio (NC) / (NV) of the silane coupling agent (C) to the mass in terms of SiO 2 with respect to the mass of the solid content (V) of the aqueous surface treating agent of the present invention is 0.16 to 0.00.
  • the ratio (ND) / (NV) of the mass of acetylacetone complex (D) of titanium to the mass (ND) in terms of Ti with respect to the mass of solid content (V) is 0.0170 to 0.0240.
  • the ratio (NE) / (NV) of the vanadium compound (E) to the mass (NE) in terms of V with respect to the mass of the solid content (V) is 0.0070 to 0.0090.
  • the ratio (NG) / (NV) of the mass of the acetic acid component (G) to the mass of the solid content (V) is 0.040 to 0.140.
  • the ratio (NH) / (NV) of the mass of the phosphoric acid component (H) to the mass of the solid content (V) is 0.025 to 0.075.
  • the ratio (ND) / (NE) of the acetylacetone complex of titanium (D) to the mass in terms of Ti with respect to the mass in terms of V of the vanadium compound (E) is 2.10 to 2.90.
  • the ratio (NH) / (NG) of the mass of the phosphoric acid component (H) to the mass of the acetic acid component (G) is 0.25 to 1.10.
  • the ratio (NH) / (ND) of the phosphoric acid component (H) to the mass (ND) in terms of Ti of the acetylacetone complex (D) of titanium is 1.11 to 3.19.
  • composition component, compounding ratio
  • physical properties of the aqueous surface treatment agent for galvanized steel or zinc-based alloy plated steel according to the present invention will be described in detail.
  • the cationic polyurethane resin (A) is blended as an essential component in the aqueous surface treatment agent of the present invention, and is formed using the aqueous surface treatment agent of the present invention (that is, formed by application and drying of the aqueous surface treatment agent). It is a resin that forms the main component of a poorly water-soluble film (hereinafter also simply referred to as “slightly water-soluble film”). Since the treating agent to be used is aqueous, an aqueous resin is used as the cationic polyurethane resin (A) to be contained in the treating agent. Water-based resins are roughly classified into water dispersibility, emulsion, and water solubility.
  • a water dispersible resin in order to obtain a film having condensation whitening resistance and water resistance.
  • the water-soluble resin is an equilibrium dissolution system
  • a strong electrolyte component fluorine, lithium, sodium, potassium, chlorine, bromine, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, acetic acid, formic acid, propionic acid, Ions such as sulfonic acids, etc.
  • condensation whitening is likely to occur when the strong electrolyte component substantially remains in the film
  • the surfactant remains in the film, This is because the water resistance may deteriorate.
  • the water-dispersible resin is preferably a type in which the resin particle surface is amine-modified and cation-dispersed, that is, a cationic water-dispersible resin.
  • cation dispersion coexistence with a silane coupling agent (C) described later becomes possible.
  • the treatment agent becomes alkaline and the silane coupling agent becomes unstable.
  • the silane coupling agent can be added to the alkaline treatment agent by dissolving the silane coupling agent using lithium hydroxide, sodium hydroxide or the like as a counter cation, but the addition of strong electrolyte ions such as lithium and sodium This is not preferable because the condensation whitening resistance deteriorates.
  • the particle size of the water dispersible resin is preferably in the range of 9 nm to 200 nm. The larger the particle size of the water-dispersible resin, the more the adverse effect of hydrophilization due to amine modification can be reduced.
  • a cationic polyurethane resin (A) is blended in the treating agent. Since the film mainly composed of the cationic polyurethane resin (A) has an excellent balance between tensile strength and elongation, processability and adhesion are improved.
  • the cationic polyurethane resin (A) is preferably a polycarbonate-based water-dispersible cationic polyurethane resin containing a structural unit represented by the following general formula (1).
  • a structural unit represented by the following general formula (1) When the cationic polyurethane resin (A) contains a structural unit represented by the following general formula (1), more excellent barrier properties are imparted, and condensation whitening resistance is improved.
  • R is an aliphatic alkylene group having 4 to 9 carbon atoms
  • n is a number average molecular weight of a carbonate-based polyol that is a raw material of the polycarbonate-based cationic polyurethane resin (A) of 500 to An integer corresponding to the range of 5000.
  • ⁇ Cationic phenol resin (B)> In addition to the cationic polyurethane resin (A), a cationic phenol resin (B) is further blended as an essential component in the aqueous surface treating agent of the present invention.
  • the aqueous surface treating agent of the present invention contains the cationic phenol resin (B)
  • the stability of the treating agent is improved.
  • membrane of this invention contains a cationic phenol resin (B)
  • topcoat water-resistant secondary adhesiveness will improve.
  • the cationic phenol resin (B) preferably has a repeating unit represented by the following general formula (2), and more preferably a polymer molecule having an average degree of polymerization of 2 to 50 of the repeating unit. When the average degree of polymerization is within this range, the water resistance of the film is improved.
  • the average degree of polymerization of the repeating unit of formula (2) can be determined from the integration ratio by 1 H-NMR.
  • Y1 and Y2 each independently represent hydrogen or a Z group represented by the general formula (3) or (4), and the average number of substitutions of Z groups per benzene ring is 0.00. 2 to 1.0.
  • the average number of substitutions of the Z group can be determined from the integration ratio by 1 H-NMR.
  • R1, R2, R3, R4 and R5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms
  • a ⁇ represents a hydroxide ion or an oxo acid (eg, nitric acid, sulfuric acid, phosphoric acid, carbonic acid, carboxylic acid, etc.) ion.
  • the counter anion of the cationic resin (cationic polyurethane resin (A) and cationic phenol resin (B)) used in the present invention is an anion that volatilizes under dry film formation, specifically formic acid or Acetate ions are preferred.
  • the counter anion of the cationic resin is a hydroxide ion, the treatment agent is inclined to alkalinity, and as described above, the silane coupling agent is easily gelled and the liquid becomes unstable.
  • the counter anion of the cationic resin is formic acid or acetate ion
  • formic acid or acetic acid volatilizes during dry film formation.
  • the amine loses its charge, and irreversible aggregation as a film-forming reaction occurs due to the hydrophobicity of the resin particles.
  • volatilization of the counter anion increases the pH, and the silane coupling agent silanolized by hydrolysis advances irreversible gelation and condensation as a film-forming reaction.
  • a network of resin, siloxane, metalloxane bond is formed by reaction between the side chain of the cationic polyurethane resin (A) and the cationic phenol resin (B) and the silane coupling agent, and reaction between the silanol and the plating substrate. Therefore, a strong film excellent in adhesion, corrosion resistance, and solvent resistance can be formed.
  • a silane coupling agent (C) is blended as an essential component.
  • the silane coupling agent (C) undergoes hydrolysis and condensation in the film formation (baking) process to form a siloxane-type film that is three-dimensionally crosslinked by a siloxane bond. That is, the poorly water-soluble film of the present invention contains a siloxane compound (C ′).
  • the corrosion resistance, adhesion, and solvent resistance of the formed film are improved. Performance is significantly improved.
  • silane coupling agent (C) used as a raw material for the siloxane compound (C ′) it is preferable to use an alkoxysilane having 2 or more, preferably 3 or more alkoxy groups.
  • the partial hydrolyzate can also be used.
  • silane coupling agent (C) The alkoxy group of the silane coupling agent (C) is hydrolyzed by addition to an aqueous system to form silanol (—Si—OH). Silanol dispersion stability is obtained at pH 6.5 or less. If the pH of the treatment agent exceeds 6.5, pot life cannot be obtained due to gelation.
  • silane coupling agent Commercial products can also be used as the silane coupling agent (C).
  • Examples of commercially available products include N- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and the like.
  • Preferred silane coupling agents (C) are those having a functional group reactive with the cationic polyurethane resin (A) and the cationic phenol resin (B) to be used (for example, 3-aminopropyltriethoxysilane, 3-glycol Sidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like are preferable, and 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are particularly preferable.
  • the kind of reaction with these cationic resins may be polymerization reaction, condensation reaction, addition reaction or the like, and is not particularly limited.
  • ⁇ Titanium acetylacetone complex (D)> In the aqueous surface treatment agent of the present invention, an acetylacetone complex (D) of titanium is also blended as an essential component.
  • the titanium acetylacetone complex (D) is blended with the treating agent of the present invention, and the hardly water-soluble film formed contains a titanium compound (D ′) that is a reaction precipitate of the titanium acetylacetone complex (D). Corrosion resistance is greatly improved.
  • titanium acetylacetone complex When a titanium acetylacetone complex is added to the treatment agent, the corrosion resistance of the poorly water-soluble film formed is further improved, and acetylacetonate and acetylacetone remaining in the dry film-forming film are weakly ionic and dew condensation occurs. Does not adversely affect whitening. Titanium acetylacetone complex reacts with the plating substrate under dry film formation to form a hardly water-soluble film. Of the titanium chelate compounds, the triethanolamine complex having a cationic property is preferable in that it does not adversely affect condensation whitening, but the triethanolamine remaining in the film after dry film formation exhibits water absorption, so that it has corrosion resistance. The improvement effect is greater with the acetylacetone complex. Titanium hydrofluoric acid and ammonium titanium fluoride are not suitable because fluorine is liberated and the resistance to condensation whitening deteriorates.
  • the vanadium compound (E) is also blended as an essential component.
  • the vanadium compound (E) is blended with the treatment agent of the present invention, and the formed hardly water-soluble film contains the vanadium compound (E ′) which is a reaction precipitate of the vanadium compound (E), so that the corrosion resistance is very high. improves.
  • vanadium compound (E) examples include vanadium pentoxide not containing a strong electrolyte, metavanadate and its salt (for example, ammonium metavanadate), vanadium trioxide, vanadium dioxide, vanadium oxyacetylacetonate, vanadium acetylacetonate, and the like. And vanadium acetate which is a salt with a volatile acid. Considering the effect of improving corrosion resistance, vanadium acetylacetone complexes such as vanadium acetylacetonate and vanadium oxyacetylacetonate are preferable. As will be described later, the vanadium compound (E ′) is immobilized in the film as an oxide or an acetylacetone complex.
  • the olefin wax (F) is preferably blended as an optional component.
  • the olefin wax (F) is more preferably surface-modified with a silane coupling agent (I).
  • a silane coupling agent (I) When the poorly water-soluble film of the present invention contains the olefin wax (F) surface-modified with the silane coupling agent (I), it is dispersed in the film without being exposed to the surface, so that it is oil-free lubrication And handleability, that is, coil deformation resistance and cut plate pile load collapse resistance can both be achieved.
  • the reason why the olefinic wax (F) is dispersed in the film is thought to be because the surface tension of the silane coupling agent (I) increases the surface tension of the wax and the wettability to the treatment agent increases.
  • the wax is concentrated on the film surface by liquid convection under dry film formation, and it is not easy to uniformly disperse the wax in the film.
  • the wax particles can be uniformly dispersed in the film by surface modification with a silane coupling agent.
  • silane coupling agent (I) a silane coupling agent having a reactive functional group is preferably used.
  • the surface modification with the silane coupling agent (I) can be carried out by directly mixing the silane coupling agent (I) into the olefin wax emulsion.
  • a surface-modified olefin wax that is stable in an acidic treatment solution having a pH of 6.5 or less containing a cationic polyurethane resin, a cationic phenol resin, and a silane coupling agent is obtained.
  • the olefin wax (F) examples include polyethylene wax, oxidized polyethylene wax, oxidized polypropylene wax, and the like.
  • olefin wax (F) surface-modified with the silane coupling agent (I) of the present invention a silane coupling agent containing an epoxy group in a polyethylene wax emulsion having a carboxyl group that is stable in an acidic treatment solution (for example, The surface-modified olefin wax obtained by directly mixing glycidylpropyltrimethoxysilane) is preferable.
  • the ratio (NI / NF) of the mass of the silane coupling agent (I) to the mass of the olefin wax (F) is preferably 0.025 to 0.035.
  • NI / NF 0.025 or more handleability can be improved.
  • workability can be improved by making NI / NF 0.035 or less.
  • the addition amount of the silane coupling agent (I) is preferably equimolar or more with the acid value of the wax dispersion.
  • the average particle diameter of the olefin wax (F) is preferably 0.05 to 0.15 ⁇ m. If the wax particle size is 0.15 ⁇ m or less, the volume of the wax present on the surface of the film is reduced and the handleability is improved, and if it is 0.05 ⁇ m or more, the processability is improved and the treatment agent is stabilized by wax aggregation. There is little adverse effect on sex.
  • the average particle diameter of the olefin wax (F) is a value measured by a laser diffraction / scattering method.
  • blending an acetic acid component (G) the liquid stability (processing agent stability) of a processing agent improves. This is presumed to be because the pH buffering action of the acetic acid component (G) stabilizes the pH of the treatment agent in the vicinity of 3.5 to 4.0, and the condensation reaction of the silane coupling agent (C) becomes slow. .
  • the pH at which the condensation reaction of the silane coupling agent (C) is slowest is around 3.5 to 4.0.
  • Acetic acid has a boiling point of 118 ° C., but the organic acid having a buffering action has a low boiling point and is relatively difficult to remain in the film. For this reason, it is suitable as an organic acid to be contained in the surface treatment agent.
  • acetic acid component (G) examples include acetic acid, ammonium acetate, potassium acetate, and sodium acetate. Considering the effect of improving the treatment agent stability, acetic acid is particularly preferable.
  • the phosphoric acid component (H) is blended as an essential component.
  • the poorly water-soluble film formed contains the phosphoric acid component (H)
  • it reacts with the galvanized layer of the galvanized steel or zinc-base alloy-plated steel material. Since zinc phosphate film is generated, elution of zinc from the galvanized layer can be suppressed. As a result, the occurrence of white rust of zinc is suppressed, and the stack whitening resistance is improved.
  • the amount of acetic acid remaining in the film can be reduced by adding the phosphoric acid component (H) to the treatment agent. As a result, the adhesive layer of the filament tape is not attacked and the filament tape is closely attached. Deterioration can be suppressed.
  • Examples of the phosphoric acid component (H) include inorganic phosphoric acid such as phosphoric acid and inorganic phosphoric acid compounds such as ammonium phosphate, potassium phosphate, sodium phosphate, and monosodium dihydrogen phosphate.
  • inorganic phosphoric acid compounds and inorganic phosphoric acid are preferable, and phosphoric acid is particularly preferable.
  • the aqueous surface treatment agent of the present invention preferably contains no colloidal silica.
  • the silane coupling agent (C) reacts with the colloidal silica and the treatment agent stability decreases, which is not preferable.
  • the aqueous surface treatment agent of the present invention preferably contains no basic alkali silicate.
  • the aqueous surface treatment agent of the present invention is acidic, and if an alkaline basic silicate that is alkaline is blended, the treatment agent stability is lowered, which is not preferable.
  • the ratio (NC) / (NV) of the silane coupling agent (C) to the mass in terms of SiO 2 with respect to the mass of the solid content (V) of the aqueous surface treating agent of the present invention is 0.16 to 0.19. Yes, preferably from 0.16 to 0.18.
  • (NC) / (NV) exceeds 0.19, the primary adhesion is lowered, and when it is less than 0.16, sufficient planar portion corrosion resistance cannot be obtained.
  • the ratio (ND) / (NV) of the mass of acetylacetone complex (D) of titanium to the mass (ND) of Ti with respect to the mass of the solid content (V) is 0.0170 to 0.0240, preferably 0. 0190-0.0230.
  • (ND) / (NV) is less than 0.0170, the corrosion resistance after degreasing deteriorates, and when it exceeds 0.0240, the effect of improving the corrosion resistance after degreasing is saturated and the adhesion after degreasing is reduced. To do.
  • ⁇ (NE) / (NV)> The ratio (NE) / (NV) of the vanadium compound (E) to the mass (NE) in terms of V with respect to the mass of the solid content (V) is 0.0070 to 0.0090, preferably 0.0075. ⁇ 0.0090.
  • (NE) / (NV) is less than 0.0070, a sufficient effect of improving the corrosion resistance of the cut portion cannot be obtained, and when it is more than 0.0090, the effect of improving the corrosion resistance of the cut portion is saturated and the secondary adhesion is achieved. Decreases.
  • the ratio (NF) / (NV) of the mass of the olefin wax (F) to the mass of the solid content (V) is preferably 0.035 to 0.060, more preferably 0.040 to 0. .055.
  • (NF) / (NV) is 0.035 or more, sufficient oil-free lubricity is obtained, so that workability is improved.
  • (NF) / (NV) is 0.060 or less, the coil deformation resistance and the cut plate pile load collapse resistance are improved, and the handleability is improved.
  • the ratio (NG) / (NV) of the mass of the acetic acid component (G) to the mass of the solid content (V) is 0.040 to 0.140, preferably 0.050 to 0.130. More preferably, it is 0.060 to 0.120.
  • (NG) / (NV) is less than 0.040, a sufficient effect of improving the stability of the processing agent cannot be obtained, and when it exceeds 0.140, the effect of improving the stability of the processing agent is saturated and the condensation resistance is increased. Whitening property decreases.
  • the ratio (NH) / (NV) of the mass of the phosphoric acid component (H) to the mass of the solid content (V) is 0.025 to 0.075, preferably 0.030 to 0.070. More preferably, it is 0.035 to 0.065.
  • (NH) / (NV) is less than 0.025, a sufficient zinc elution suppression effect from the plating layer cannot be obtained, and when it exceeds 0.075, the zinc elution suppression effect is saturated and black resistance Denaturation is reduced.
  • the ratio (ND) / (NE) of the acetylacetone complex (D) of titanium to the mass of Ti in terms of V to the mass of vanadium compound (E) in terms of V is 2.10 to 2.90, preferably 2.20 to 2.80, more preferably 2.30 to 2.70.
  • (ND) / (NE) is less than 2.10, the fixing rate of the vanadium compound (E) to the film is lowered, and the corrosion resistance of the processed part is lowered.
  • (ND) / (NE) is more than 2.90, the fixing ratio of titanium to the acetylacetone complex (D) is lowered, and the processed portion corrosion resistance is lowered.
  • ⁇ (NH) / (NG)> The ratio (NH) / (NG) of the mass of the phosphoric acid component (H) to the mass of the acetic acid component (G) is 0.25 to 1.10.
  • (NH) / (NG) is less than 0.25 and more than 1.10, stack whitening resistance is deteriorated.
  • (NH) / (NG) is preferably 0.30 to 1.00, more preferably 0.35 to 0.90.
  • ⁇ (NH) / (ND)> The ratio (NH) / (ND) of the mass of the phosphoric acid component (H) to the mass (ND) in terms of Ti of the acetylacetone complex (D) of titanium is 1.11 to 3.19.
  • (NH) / (ND) is less than 1.11 and more than 3.19, the resistance to filament tape deteriorates.
  • (NH) / (ND) is preferably 1.40 to 3.00, and more preferably 1.80 to 2.81.
  • a surface treatment agent used for film formation in the present invention can be prepared.
  • Each component is adjusted so as to have a predetermined ratio in the film, and accordingly, adjusted to have a predetermined ratio with respect to the total amount of the non-volatile content (solid content) excluding the solvent and the volatile component.
  • the solvent may be only water, but for the purpose of improving the drying property of the film, the water-soluble organic solvent (for example, alcohols) that does not contain the above-mentioned strong electrolyte. May be contained in a small amount (for example, within 30% by mass of the entire solvent).
  • additives commonly used in coating treatment liquids such as leveling agents and antifoaming agents can be added to the treatment agents.
  • the aqueous surface treatment agent of the present invention contains the cationic polyurethane resin (A) and the cationic phenol resin (B) as essential components, and also for the dispersion stabilization of the silane coupling agent (C).
  • the pH is in an acidic region of 6.5 or less.
  • the preferred pH range of the aqueous surface treatment agent is 2.0 to 6.5. If necessary, volatile acids such as acetic acid and formic acid can be added to adjust the acidity (pH) of the treatment agent.
  • the above-described aqueous surface treatment agent for galvanized steel or zinc-base alloy-plated steel is applied to the galvanized steel or zinc-base alloy-plated steel (more specifically, galvanized steel or This is a surface treatment method for forming a film on the surface of a galvanized steel material or a zinc-based alloy-plated steel material by bringing it into contact with a zinc-based alloy-plated steel material and then drying it.
  • Examples of the galvanized steel material or zinc base alloy plated steel material used in the present invention include zinc-nickel plated steel material, zinc-iron plated steel material, zinc-chromium plated steel material, zinc-aluminum plated steel material, zinc-titanium plated steel material, zinc -Zinc-coated steel materials such as magnesium-plated steel materials, zinc-manganese-plated steel materials, zinc-aluminum-magnesium-plated steel materials, zinc-aluminum-magnesium-silicon-plated steel materials, and small amounts of different metal elements or impurities in these plated layers
  • an inorganic substance such as cobalt, molybdenum, tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, bismuth, antimony, tin, copper, cadmium, arsenic, etc., silica, alumina, titania, etc. Is distributed
  • the present invention can also be applied to multilayer plating in which the above plating layer and other types of plating layers such as iron plating, iron-phosphorus plating, nickel plating, cobalt plating, etc. are combined.
  • the formation of the plating layer is not particularly limited, and can be performed using any known method such as electroplating, hot dipping, vapor deposition, dispersion plating, and vacuum plating.
  • the amount of plating adhesion is not particularly limited, and may be within the conventional general range.
  • the plating may be either single-sided plating or double-sided plating.
  • a film can be formed on one side or both sides of the plated steel plate.
  • the contact method of the treatment agent of the present invention to the galvanized steel material or zinc-base alloy-plated steel material can be carried out by any conventional contact method such as dipping, spraying, roll coating or the like.
  • Bake drying after contact The heating temperature at that time is selected so that volatile components in the treatment agent (for example, acetic acid or formic acid derived from the counter anion of the cationic resin) are volatilized. It is preferable to perform the drying so that the maximum plate temperature (PMT) is in the range of 60 to 150 ° C. Baking and drying can be performed by hot air drying or oven drying.
  • the amount of the poorly water-soluble film attached may be 100 mg / m 2 or more for the purpose of primary rust prevention (measures against rust during delivery to users), but bare use (omitting painting of final product) Is intended to be 300 mg / m 2 or more.
  • the upper limit of the coating amount is 3000 mg / m 2 . If the adhesion amount is larger than that, the top coatability is lowered, and the handleability is also deteriorated even if the film does not contain wax. When spot welding is performed, it is preferable that the coating amount be 1500 mg / m 2 or less.
  • the coated steel material of the present invention comprises at least a cationic polyurethane resin (A), a cationic phenol resin (B), a siloxane compound (C ′), a titanium compound (D ′), a vanadium compound (E ′), and an acetic acid component (G ) And a phosphoric acid component (H), a poorly water-soluble film is formed on the surface of the galvanized steel material or the zinc-base alloy plated steel material. Therefore, not only is it excellent in resistance to condensation whitening and corrosion, but it is also excellent in resistance to stack whitening and resistance to filament tape.
  • the coating when the coating contains an olefinic wax and further contains an olefinic wax (F) surface-modified with a silane coupling agent (I), the coating has no oil-coated lubricity. Moreover, since the wax is dispersed in the film without being exposed to the surface, the coil deformation resistance and the cut plate pile load collapse resistance are excellent.
  • Electro-galvanized steel sheet “NS Zincoat (registered trademark)” (hereinafter referred to as “EG”) and hot-dip galvanized steel sheet “NS Silver Zinc (registered trademark)” (hereinafter referred to as “GI”) manufactured by Nippon Steel & Sumitomo Metal Corporation.
  • EG Electro-galvanized steel sheet “NS Zincoat (registered trademark)”
  • GI hot-dip galvanized steel sheet “NS Silver Zinc (registered trademark)”
  • Galvannealed steel sheet “NS Silver Alloy (registered trademark)” (hereinafter referred to as “GA”), zinc-aluminum-magnesium-silicon alloy plated steel sheet “Superdimer (registered trademark)” ( Hereinafter referred to as “SD”), zinc-nickel alloy plated steel sheet “NS Zinclite (registered trademark)” (hereinafter referred to as “ZL”), and zinc-aluminum alloy plating manufactured by Nippon Steel & Sumikin Steel Sheet Co., Ltd.
  • GA Silver Alloy
  • SD zinc-aluminum-magnesium-silicon alloy plated steel sheet
  • ZL zinc-nickel alloy plated steel sheet
  • ZL zinc-aluminum alloy plating manufactured by Nippon Steel & Sumikin Steel Sheet Co., Ltd.
  • A1 Polycarbonate-based cationic polyurethane resin Superflex 650 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • A2 Polyester-based cationic polyurethane resin Adekabon titer HUX-680 manufactured by ADEKA Corporation
  • A3 Polyether-based cationic polyurethane resin Superflex 600 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • A4 Polyether-based anionic polyurethane resin Adekabon titer HUX-350 manufactured by ADEKA Corporation
  • Olefin wax (F) The olefin wax whose surface was modified with a silane coupling agent (3-glycidoxypropyltrimethoxysilane) shown in Table 1 below was used.
  • G1 Acetic acid
  • G2 Ammonium acetate
  • the processing agents used in the following Examples and Comparative Examples were prepared by mixing the components listed above in the composition shown in Table 2 below. In addition, solid content in a processing agent was adjusted so that it might become 11 mass%.
  • the content of component (C) is the content in terms of SiO 2
  • the content of component (D) is the content in terms of Ti
  • the content of component (E) is in terms of V Content.
  • Test plate preparation process Using the silicate alkaline degreasing agent Fine Cleaner E6406 (manufactured by Nihon Parkerizing Co., Ltd.) dissolved in water to a concentration of 20 g / L, the above-mentioned test was conducted for 10 seconds at a temperature of 60 ° C. What was applied to the material, further washed with pure water for 30 seconds and then dried was used in the following test. Each treatment agent was applied by a bar coater and dried in a hot air drying furnace so as to have a predetermined ultimate plate temperature (PMT). The details such as the amount of adhesion are shown in Table 3 below.
  • PMT ultimate plate temperature
  • Corrosion resistance tests were performed on unprocessed ones (planar part), cross-cut with a NT cutter until the substrate was reached (cross-cut part), and Erichsen 7 mm extruded (worked part). .
  • the evaluation method is as follows. 1-1 (corrosion resistance of flat surface): Based on the salt spray test method JIS-Z-2371, the white rust generation area ratio 72 hours after the salt spray was determined and evaluated. The evaluation criteria are shown below.
  • White rust generation area ratio is less than 10% ⁇ : White rust generation area ratio is 10% or more and less than 30% ⁇ : White rust generation area ratio is 30% or more and less than 60% ⁇ : White rust generation area ratio is 60 % Or more ( ⁇ or more is practical performance) 1-2 (corrosion resistance of the cross cut part): Based on the salt spray test method JIS-Z-2371, the occurrence of white rust 72 hours after the salt spray was evaluated with the naked eye. The evaluation criteria are shown below.
  • Fine cleaner E6406 manufactured by Nihon Parkerizing Co., Ltd. was bathed at 20 g / L, the test plate was immersed in a degreasing aqueous solution adjusted to 65 ° C. for 2 minutes, washed with water, and dried at 80 ° C. About this board, corrosion resistance was evaluated by the conditions and evaluation method of planar part corrosion resistance described in said (1).
  • Coating adhesion The coating was applied to the test plate under the following conditions, and a coating film adhesion test was conducted. Paint condition paint: Amirac # 1000 (registered trademark) (white paint) manufactured by Kansai Paint Co., Ltd. Coating method: Bar coating method Baking and drying conditions: 140 ° C., 20 minutes Coating thickness: 25 ⁇ m
  • the evaluation method is as follows. 3-1 (cross-cut primary adhesion): With respect to the test plate, 100 mm grids of 1 mm square were cut with an NT cutter, a peel test with an adhesive tape was performed, and the number of coating films peeled was evaluated. The evaluation criteria are shown below.
  • the “number of peeled coating films” referred to here means the number of pieces from which more than half of each grid has been peeled (the “number of peeled coating films” described below has the same meaning).
  • ⁇ Number of peeled less than 1 ⁇ : Number of peeled 1 or more and less than 10 ⁇ : Number of peeled 10 or more, less than 50 x: Number of peeled 50 or more 3-2 (secondary cross-cut adhesion): The test plate was immersed in boiling water for 2 hours, left standing for a whole day and night, 1 mm square, 100 grids were cut with an NT cutter, a peel test with an adhesive tape was performed, and the number of peeled films was evaluated. The evaluation criteria are shown below. ⁇ : Number of peeled less than 1 ⁇ : Number of peeled 1 or more and less than 10 ⁇ : Number of peeled 10 or more, less than 50 ⁇ : Number of peeled 50 or more ( ⁇ or more is practical performance)
  • the evaluation method is as follows. (Crosscut primary adhesion after degreasing) With respect to the test plate, 100 mm grids of 1 mm square were cut with an NT cutter, a peel test with an adhesive tape was performed, and the number of coating films peeled was evaluated. The evaluation criteria are shown below. ⁇ : Number of peeled less than 1 ⁇ : Number of peeled 1 or more and less than 10 ⁇ : Number of peeled 10 or more, less than 50 ⁇ : Number of peeled 50 or more ( ⁇ or more is practical performance)
  • ⁇ Dynamic friction coefficient is less than 0.16, and seizure occurrence sliding frequency is 25 times or more.
  • ⁇ Dynamic friction coefficient is less than 0.16, seizure occurrence sliding frequency is 20 times or more and less than 25 times, or dynamic friction coefficient. Is 0.16 or more and less than 0.18, and seizure occurrence sliding frequency is 25 times or more.
  • ⁇ - Dynamic friction coefficient is 0.16 or more and less than 0.18, seizure occurrence sliding frequency is 20 times or more and less than 25 times.
  • Dynamic friction coefficient is 0.18 or more, seizure occurrence sliding number is 20 times or more, or dynamic friction coefficient is 0.16 or more and less than 0.18, seizure occurrence number is less than 20 times
  • Dynamic friction coefficient is 0 .18 or more and seizure occurrence sliding frequency is less than 20 times ( ⁇ or more is practical performance).
  • Sliding friction coefficient ⁇ : ⁇ m3 ⁇ h / (m1 + m2) ⁇ L (Equation 1)
  • m1 weight of steel plate 1 + weight 1 (g)
  • m2 weight of steel plate 2 + cart
  • m3 weight of weight 2 (g)
  • h fall distance of weight 2 (mm)
  • L sliding distance (mm)
  • Sliding friction coefficient is 0.85 or more
  • O Sliding friction coefficient is 0.84 or more and less than 0.85
  • Sliding friction coefficient is 0.83 or more and less than 0.84
  • Sliding friction coefficient is less than 0.83 (The above is the practical performance.)
  • ⁇ Area ratio of whitened area is less than 1% (no whitening)
  • ⁇ Area ratio of whitened portion is 1% or more and less than 5%
  • ⁇ - Area ratio of whitened portion is 5% or more and less than 25%
  • ⁇ Area ratio of whitened portion is 25% or more
  • 50 Less than% ⁇ Area ratio of whitened portion is 50% or more ( ⁇ or more is practical performance)
  • Examples 1 to 78 using the treating agent containing the essential components of the present invention and containing these essential components in a blending ratio within the scope of the present invention are all corrosion resistance, alkali resistance, Excellent or practically satisfied with all evaluations of coating adhesion, coating adhesion after degreasing, blackening resistance, stack whitening resistance, filament tape resistance, condensation whitening resistance, processing agent stability and actual machine operability It became performance.
  • Examples 1-27 and 29-78 blended with the olefin wax (F) were excellent in workability and handleability, or had practically satisfactory performance.
  • Comparative Examples 1 to 14 and 17 to 22 which do not contain the essential component of the present invention or whose blending ratio of the essential component is outside the range of the present invention are corrosion resistance, alkali resistance, Performance that at least one of coating adhesion, coating adhesion after degreasing, blackening resistance, stack whitening resistance, filament tape resistance, condensation whitening resistance, treatment agent stability and actual machine operability is not satisfied in practice. It became.
  • Comparative Examples 15 and 16 using the anionic polyurethane resin A4 since the treatment agent could not be prepared, the evaluations (1) to (12) were not performed.

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Abstract

[Problème] La présente invention vise à fournir : un agent aqueux de traitement de surface pour un matériau en acier zingué ou un matériau en acier plaqué avec un alliage à base de zinc, qui présente des propriétés satisfaisantes telles que la résistance à la corrosion, la résistance à la corrosion après dégraissage, l'adhésion du revêtement, l'adhésion du revêtement après dégraissage, la résistance au noircissement, la résistance au blanchiment par condensation, la stabilité aux agents de traitement, l'aptitude à l'exploitation réelle du dispositif, et similaire, et qui peut former un revêtement ayant une excellente résistance au blanchiment de l'empilement et une excellente résistance du ruban de filament ; un procédé de revêtement utilisant ledit agent de traitement ; et un matériau en acier revêtu obtenu en utilisant ledit procédé. [Solution] Selon l'invention, on obtient un agent aqueux de traitement de surface pour un matériau en acier zingué ou un matériau en acier plaqué avec un alliage à base de zinc en mélangeant une résine polyuréthanne cationique (A), une résine phénolique cationique (B), un agent de couplage au silane (C), un complexe de titane-acétylacétone (D), une cire d'oléfine (F), un composé de vanadium (E), un composant d'acide acétique (G), un composant d'acide phosphorique (H), et de l'eau.
PCT/JP2016/082690 2015-11-06 2016-11-02 Agent aqueux de traitement de surface pour un matériau en acier zingué ou un matériau en acier plaqué avec un alliage à base de zinc, procédé de revêtement et matériau en acier revêtu Ceased WO2017078105A1 (fr)

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KR1020187015268A KR102115686B1 (ko) 2015-11-06 2016-11-02 아연 도금 강재용 또는 아연기 합금 도금 강재용 수계 표면 처리제, 피복 방법 및 피복 강재
CN201680062542.9A CN108350578B (zh) 2015-11-06 2016-11-02 镀锌钢材用或镀锌基合金钢材用水系表面处理剂、包覆方法及包覆钢材
MYPI2018701704A MY198115A (en) 2015-11-06 2016-11-02 Aqueous Surface Treatment Agent for Zinc Plated Steel Material or Zinc Based Alloy Plated Steel Material, Coating Method, and Coated Steel Material

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JP2019143237A (ja) * 2018-02-16 2019-08-29 Ｊｆｅスチール株式会社 高強度めっき鋼板の製造方法
CN115326515A (zh) * 2022-08-30 2022-11-11 西安热工研究院有限公司 用于高湿环境合金钢现场金相覆膜的辅助装置及辅助方法
EP4136174A4 (fr) * 2020-04-15 2023-12-20 Henkel AG & Co. KGaA Composition de revêtement anti-noircissement

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CN110670010B (zh) * 2019-11-20 2021-06-01 安徽汇源镀锌有限公司 一种降低热镀锌板黑斑缺陷的方法
CN113817391A (zh) * 2020-09-07 2021-12-21 帕珂表面处理技术(上海)有限公司 不锈钢材料用表面处理剂

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JP2011183307A (ja) * 2010-03-09 2011-09-22 Sumitomo Metal Ind Ltd 耐結露白化性と耐食性に優れた表面処理鋼板
JP2012067369A (ja) * 2010-09-24 2012-04-05 Jfe Steel Corp 亜鉛系めっき鋼板用の表面処理液ならびに亜鉛系めっき鋼板およびその製造方法

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JP2019143237A (ja) * 2018-02-16 2019-08-29 Ｊｆｅスチール株式会社 高強度めっき鋼板の製造方法
EP4136174A4 (fr) * 2020-04-15 2023-12-20 Henkel AG & Co. KGaA Composition de revêtement anti-noircissement
CN115326515A (zh) * 2022-08-30 2022-11-11 西安热工研究院有限公司 用于高湿环境合金钢现场金相覆膜的辅助装置及辅助方法

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