WO2019188460A1 - Tôle d'acier galvanisée revêtue - Google Patents

Tôle d'acier galvanisée revêtue Download PDF

Info

Publication number
WO2019188460A1
WO2019188460A1 PCT/JP2019/011032 JP2019011032W WO2019188460A1 WO 2019188460 A1 WO2019188460 A1 WO 2019188460A1 JP 2019011032 W JP2019011032 W JP 2019011032W WO 2019188460 A1 WO2019188460 A1 WO 2019188460A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
resin
film
steel sheet
galvanized steel
Prior art date
Application number
PCT/JP2019/011032
Other languages
English (en)
Japanese (ja)
Inventor
山本　哲也
大輝 酒井
礼士 白岩
Original Assignee
株式会社神戸製鋼所
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
Priority claimed from JP2019030545A external-priority patent/JP7112350B2/ja
Application filed by 株式会社神戸製鋼所 filed Critical 株式会社神戸製鋼所
Priority to CN201980021239.8A priority Critical patent/CN111971170B/zh
Priority to KR1020207028776A priority patent/KR102473795B1/ko
Publication of WO2019188460A1 publication Critical patent/WO2019188460A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D

Definitions

  • the present invention relates to a coated galvanized steel sheet having a coating containing an inorganic compound in a resin (hereinafter sometimes referred to as “inorganic coating”) on the surface of the galvanized steel sheet.
  • the surface of the material is severely slid by the roll. For this reason, when a roll forming process is performed on a coated galvanized steel sheet having a resin film on the surface layer, a part of the resin film is peeled off to generate a film residue.
  • the film residue mixes with the coolant liquid for roll forming, adheres to the molded product, and deteriorates the appearance of the molded product. Further, the film residue mixed in the coolant liquid is deposited on the surface of the draining pad for wiping the coolant liquid before cutting the molded product.
  • the film residue deposited on the surface of the draining pad may cause abnormal noise due to friction with the molded product when the coolant liquid adhering to the molded product is wiped by the draining pad, or may cause a defective dimension of the molded product.
  • the roll forming apparatus is provided with a filter for removing film residue mixed in the coolant liquid.
  • the filter is clogged immediately during roll forming, and therefore the frequency of replacement of the filter increases, resulting in a decrease in productivity.
  • magnesium-based compounds exhibit an antirust effect.
  • techniques for highly corrosion resistant coatings containing nano-sized magnesium particles have been developed.
  • Patent Document 1 discloses a coating made of a composition containing nano magnesium hydroxide particles having an average particle diameter of less than 200 nm.
  • Patent Document 2 discloses a rust preventive for metal containing a composite colloid composed of magnesium hydroxide and fine silica. Disclosed is a film formed using an agent.
  • Patent Document 3 includes oxide particles, phosphoric acid and / or a phosphoric acid compound, and a magnesium compound on the surface of a zinc-based plated steel sheet.
  • An organic coated steel sheet having a composite oxide film and having an organic film containing a reaction product of an organic resin and an active hydrogen-containing compound and an antirust additive component on the composite oxide film is disclosed.
  • the coating disclosed in Patent Document 1 has a thickness of 2.5 to 75 ⁇ m and is not assumed to be roll-formed. Further, the coating disclosed in Patent Document 1 does not exhibit a sufficient antirust effect when the thickness is 1 ⁇ m or less.
  • Patent Document 2 requires the use of a metal anticorrosive containing a composite colloid composed of magnesium hydroxide and fine silica during film formation. It is stable and prone to problems in the coating process for gelation. Moreover, since the film disclosed in Patent Document 2 contains a water-soluble component, its water resistance is insufficient, and discoloration due to condensation or water wetting during transportation is conspicuous.
  • the organic coated steel sheet disclosed in Patent Document 3 since the magnesium compound is added in the form of water-soluble ions or molecules when forming the composite oxide film, the treatment liquid stability decreases when the addition amount of the magnesium compound is increased. . For this reason, there exists a limit in improving a corrosion inhibitory effect by complex oxide film. In addition, the organic coated steel sheet disclosed in Patent Document 3 has a problem in that productivity is low and manufacturing cost is high because it is necessary to form an organic film after forming a composite oxide film.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a coated galvanized steel sheet that has less film residue during roll forming and has excellent corrosion resistance.
  • One aspect of the present invention is a coated galvanized steel sheet having a resin film containing silica and magnesium hydroxide on the surface of the galvanized steel sheet, wherein the total content of silica and magnesium hydroxide in the resin film is 75 to 75%. 90% by mass, the content of the resin component of the resin film is 10 to 25% by mass, the mass ratio of the magnesium hydroxide to the silica is 0.15 to 3, and the thickness of the resin film is 0.00. It is a coated galvanized steel sheet having a thickness of 20 to 1.1 ⁇ m.
  • the present inventors examined from various angles in order to achieve the above object. As a result, it has been found that the above object can be achieved brilliantly by appropriately adjusting the total content of silica and magnesium hydroxide in the resin film, the mass ratio of magnesium hydroxide to silica, and the thickness of the resin film.
  • the present invention has been completed.
  • the coated galvanized steel sheet according to an embodiment of the present invention has a resin film containing silica and magnesium hydroxide on the surface of the galvanized steel sheet.
  • the total content of silica and magnesium hydroxide in the resin film is 75 to 90% by mass.
  • the resin component content of the resin film is 10 to 25% by mass.
  • the mass ratio of the magnesium hydroxide to the silica is 0.15 to 3.
  • the resin film has a thickness of 0.20 to 1.1 ⁇ m.
  • the total content of silica and magnesium hydroxide in the resin film is 75 to 90% by mass.
  • the inorganic coating mainly contains an inorganic compound having a specific gravity larger than that of the organic compound, a dense coating with a high barrier effect against corrosion factors can be obtained. Thereby, there exists an advantage which can make the film thickness for obtaining the same corrosion resistance smaller than an organic type film, and it becomes advantageous to generation
  • the inorganic compound contained in the resin film of this embodiment is silica and magnesium hydroxide, and the inorganic film means a resin film containing silica and magnesium hydroxide.
  • the corrosion resistance deteriorates due to insufficient inorganic components.
  • the hardness of the film is not sufficient, film peeling is likely to occur during roll forming.
  • the specific gravity of the film residue is small, it is easy to accumulate on the surface of the draining pad.
  • it is 77 mass% or more, More preferably, it is 80 mass% or more.
  • the corrosion resistance deteriorates.
  • it is 88 mass% or less, More preferably, it is 85 mass% or less.
  • the silica used in the present embodiment is preferably colloidal silica excellent in compatibility with an aqueous resin described later. If the average particle size of the silica is too large, or reduced denseness of the film, there is a possibility that or generating a film defects, it is preferred that the average particle size D 50 is 500nm or less, 450 nm or less It is more preferable that Note that the average particle diameter D 50 of the silica, the integrated value of the silica (integrated value) means the average particle diameter when the 50 mass%.
  • the magnesium hydroxide used in the present embodiment is not particularly limited as long as it is stable as an aqueous dispersion, and the magnesium hydroxide powder and dispersion method are not particularly limited.
  • the average particle diameter D 50 of the magnesium hydroxide in a state of being dispersed in water i.e., the average particle diameter D 50 of magnesium hydroxide in magnesium hydroxide aqueous dispersion is preferably less than that of the resin film thickness, for example, 0. It is preferably 7 ⁇ m or less. Thereby, deterioration of roll moldability and generation
  • the lower limit of the average particle diameter D 50 in a state where magnesium hydroxide is dispersed in water is not particularly limited, but if the average particle diameter D 50 becomes too small, the stability of the dispersion (for example, dispersion) is reduced. Since there exists a possibility that it may fall, it is preferable that it is 0.1 micrometer or more. More preferably, it is 0.14 ⁇ m or more.
  • the average particle diameter D 50 of the magnesium hydroxide means the average particle diameter when the cumulative value of magnesium hydroxide (integrated value) of 50 wt%.
  • a polymer dispersant for example, a water-soluble acrylic resin, a water-soluble styrene acrylic resin, a nonionic surfactant
  • a polymer dispersant for example, a water-soluble acrylic resin, a water-soluble styrene acrylic resin, a nonionic surfactant
  • the content of the resin component in the resin film is 10 to 25% by mass.
  • the content of the resin component in the resin film is 10% by mass or more. Preferably it is 15 mass% or more.
  • the content of the resin component in the resin film is 25% by mass or less. Preferably it is 20 mass% or less.
  • Mass ratio of magnesium hydroxide to silica 0.15 to 3
  • the mass ratio of magnesium hydroxide to silica is 0.15 to 3.
  • Magnesium hydroxide and silica are both known as rust preventives for zinc plating.
  • the present inventors have found that excellent corrosion resistance can be obtained even when the thickness of the coating is 1 ⁇ m or less by blending magnesium hydroxide and silica in the resin coating at a specific mass ratio.
  • the mass ratio [Mg (OH) 2 / SiO 2 ] of magnesium hydroxide to silica is in the range of 0.15 to 3, excellent corrosion resistance is exhibited.
  • the mass ratio is preferably 0.3 or more, and more preferably 2.0 or less.
  • the mechanism by which the corrosion resistance is improved by adjusting the mass ratio to an appropriate range is unknown, but is probably as follows. That is, it is considered that magnesium ions eluted from magnesium hydroxide stabilized a corrosion product having a high protective action against galvanization produced by silica, and improved the barrier effect by the stabilized corrosion product.
  • the protective action against galvanization means a barrier property that blocks corrosion factors such as water and oxygen. And by using particulate magnesium hydroxide, it became possible to increase the addition ratio of the magnesium component in the resin film without impairing the stability of the treatment liquid. It is presumed to show high corrosion resistance.
  • the resin film thickness is 0.20 to 1.1 ⁇ m.
  • the resin film thickness is less than 0.20 ⁇ m, the corrosion resistance deteriorates.
  • the resin film thickness exceeds 1.1 ⁇ m, not only the generation of film residue during roll forming increases, but also it becomes very difficult to ensure conductivity.
  • the resin film thickness is preferably 0.3 ⁇ m or more, and preferably 0.8 ⁇ m or less. More preferably, it is 0.3 to 0.6 ⁇ m.
  • the resin film thickness is in the range of 0.3 to 0.8 ⁇ m, the balance of corrosion resistance, roll mold resistance, and conductivity is excellent, and it is advantageous for application to electrical appliances that require grounding properties. .
  • the type of resin used in the present embodiment is not particularly limited, and any of a water-based resin and a non-aqueous resin can be used.
  • an aqueous dispersion of magnesium hydroxide or colloidal silica it is preferable to use an aqueous resin.
  • Such an aqueous resin is not particularly limited, but is preferably mixed with an aqueous dispersion of magnesium hydroxide and colloidal silica.
  • the aqueous resin in the present embodiment refers to a resin that is an aqueous dispersion or a water-soluble resin.
  • Such water-based resins are preferably polyolefin-based resins, polyurethane-based resins, and polyester-based resins, and among these, polyolefin-based resins and polyurethane-based resins are more preferable.
  • the polyolefin resin and the polyurethane resin will be specifically described.
  • polyolefin resin As the polyolefin resin, an ethylene-unsaturated carboxylic acid copolymer is preferable.
  • the ethylene-unsaturated carboxylic acid copolymer for example, those described in JP-A-2005-246953 and JP-A-2006-43913 can be used.
  • Examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, and the like.
  • An ethylene-unsaturated carboxylic acid copolymer can be obtained by polymerization using a combination method.
  • the copolymerization ratio of unsaturated carboxylic acid to ethylene is preferably 10% by mass or more, more preferably 15% by mass or more when unsaturated monomer is 100% by mass. 40% by mass or less, and more preferably 25% by mass or less.
  • the coating strength emulsion composition
  • the unsaturated carboxylic acid exceeds 40% by mass, the corrosion resistance and water resistance of the resin film may be inferior.
  • the coating liquid can be emulsified (water dispersion) by neutralization with an organic base or metal ion.
  • an amine having a boiling point of 100 ° C. or less under atmospheric pressure is preferable from the viewpoint of not significantly reducing the corrosion resistance of the resin film.
  • Specific examples include tertiary amines such as triethylamine; secondary amines such as diethylamine; primary amines such as propylamine, and the like, and one or more of these can be used in combination. Of these, tertiary amines are preferred, and triethylamine is most preferred.
  • the amine is preferably 0.2 mol or more with respect to 1 mol of the carboxyl group in the ethylene-unsaturated carboxylic acid copolymer, and is preferably 0.8 mol or less. preferable. Further, it is more preferably 0.3 mol or more, and more preferably 0.6 mol or less.
  • the amount of monovalent metal ions is preferably 0.02 mol or more with respect to 1 mol of carboxyl groups in the ethylene-unsaturated carboxylic acid copolymer from the viewpoint of ensuring the emulsion stability of the coating liquid. More preferably, it is 0.03 mol or more. On the other hand, from the viewpoint of ensuring corrosion resistance, the amount is preferably 0.4 mol or less, more preferably 0.3 mol or less, based on 1 mol of the carboxyl group in the ethylene-unsaturated carboxylic acid copolymer.
  • the metal compound for imparting monovalent metal ions is preferably NaOH, KOH, LiOH or the like, and NaOH is most preferable because of its best performance.
  • the ethylene-unsaturated carboxylic acid copolymer is stirred at high speed in a container capable of reacting at a high temperature (about 150 ° C.) and a high pressure (about 5 atm), for example, in the presence of a carboxylic acid polymer described later, if necessary.
  • a high temperature about 150 ° C.
  • a high pressure about 5 atm
  • an appropriate amount of a compound having a surfactant function such as tall oil fatty acid may be added.
  • a hydrophilic organic solvent such as a lower alcohol having about 1 to 5 carbon atoms may be partially added to water.
  • the mass average molecular weight (Mw) of the ethylene-unsaturated carboxylic acid copolymer is preferably 1,000 or more and 100,000 or less in terms of polystyrene.
  • a more preferable lower limit is 3,000 or more, and further preferably 5,000 or more.
  • a more preferable upper limit value is 70,000 or less, and further preferably 30,000 or less. This Mw can be measured by gel permeation chromatography (GPC) using polystyrene as a standard.
  • a carboxylic acid polymer can also be used as the resin component.
  • the carboxylic acid polymer any polymer having an unsaturated carboxylic acid as a constituent unit exemplified as one that can be used for the synthesis of the ethylene-unsaturated carboxylic acid copolymer can be used. Among these, acrylic acid and maleic acid are preferable, and maleic acid is more preferable.
  • the carboxylic acid polymer may contain a constituent unit derived from a monomer other than the unsaturated carboxylic acid, but the constituent unit amount derived from the other monomer is 10% by mass or less in the polymer. More preferably, it is 5 mass% or less, and the carboxylic acid polymer comprised only from unsaturated carboxylic acid is further more preferable.
  • Preferred carboxylic acid polymers include polyacrylic acid, polymethacrylic acid, acrylic acid-maleic acid copolymer, polymaleic acid and the like. Of these, polymaleic acid is more preferable from the viewpoints of resin film adhesion and corrosion resistance. Although the exact mechanism by which the corrosion resistance is improved by using polymaleic acid is unknown, the adhesion between the resin film and the galvanized steel sheet is improved due to the large amount of carboxyl groups. It is done. However, the present invention is not limited to this estimation.
  • the mass average molecular weight (Mw) of the carboxylic acid polymer used in the present embodiment is preferably 500 or more and 30,000 or less in terms of polystyrene.
  • a more preferable lower limit value is 800 or more, more preferably 900 or more, and most preferably 1,000 or more.
  • a more preferable upper limit value is 10,000 or less, more preferably 3,000 or less, and most preferably 2,000 or less. This Mw can be measured by GPC using polystyrene as a standard.
  • the content ratio of the ethylene-unsaturated carboxylic acid copolymer and the carboxylic acid polymer is 1,000: 1 to 10: 1, preferably 200: 1 to 20: 1 in terms of mass ratio. This is because if the content ratio of the carboxylic acid polymer is too low, the effect of combining the olefin-acid copolymer and the carboxylic acid polymer cannot be sufficiently exhibited. On the contrary, if the content ratio of the carboxylic acid polymer is excessive, the olefin-acid copolymer and the carboxylic acid polymer are phase-separated in the first layer forming coating solution, and a uniform resin film is formed. It is because there is a risk of disappearing.
  • polyurethane resin As the polyurethane resin, a carboxyl group-containing polyurethane resin is preferable.
  • the carboxyl group-containing polyurethane resin for example, those described in JP-A-2006-43913 can be used.
  • the carboxyl group-containing polyurethane resin is preferably obtained by chain extension reaction of a urethane prepolymer with a chain extender.
  • the urethane prepolymer is obtained, for example, by reacting a polyisocyanate component and a polyol component.
  • At least one polyisocyanate selected from the group consisting of tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and dicyclohexylmethane diisocyanate (hydrogenated MDI) as the polyisocyanate component.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • hydrophilated MDI dicyclohexylmethane diisocyanate
  • the content of the polyisocyanate is preferably 70% by mass or more of the total polyisocyanate component from the viewpoint of ensuring the corrosion resistance of the resin film and the stability of reaction control.
  • polyisocyanate other than the above polyisocyanate component examples include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecane methylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, and phenylene diisocyanate. One or more of these are used. May be.
  • polyol component it is preferable to use three types of polyols, 1,4-cyclohexanedimethanol, polyether polyol, and polyol having a carboxyl group, as the polyol component.
  • the polyol component it is more preferable to use three kinds of diols of 1,4-cyclohexanedimethanol, polyether diol, and diol having a carboxyl group.
  • the rust prevention effect of the obtained polyurethane resin can be enhanced by using 1,4-cyclohexanedimethanol as the polyol component.
  • the polyether polyol is not particularly limited as long as it has at least two hydroxyl groups in the molecular chain and the main skeleton is composed of alkylene oxide units. Specific examples include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and the like, and it is preferable to use polyoxypropylene glycol or polytetramethylene ether glycol.
  • the number of functional groups of the polyether polyol is not particularly limited as long as it is at least 2 or more, and for example, it may be trifunctional or tetrafunctional or polyfunctional.
  • the average molecular weight of the polyether polyol is preferably about 400 to 4000 from the viewpoint of obtaining a resin film having an appropriate hardness. The average molecular weight can be determined by measuring the OH value (hydroxyl value).
  • the polyol having a carboxyl group is not particularly limited as long as it has at least one carboxyl group and at least two hydroxyl groups. Specific examples include dimethylolpropionic acid, dimethylolbutanoic acid, dihydroxypropionic acid, dihydroxysuccinic acid and the like.
  • the content of the three kinds of polyols is preferably 70% by mass or more of the total polyol components from the viewpoint of ensuring the corrosion resistance of the resin film.
  • the polyol other than the above three types of polyol is not particularly limited as long as it has a plurality of hydroxyl groups.
  • a low molecular weight polyol, a high molecular weight polyol, etc. are mentioned.
  • the low molecular weight polyol is a polyol having an average molecular weight of about 500 or less.
  • diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol; glycerin, trimethylolpropane, hexanetriol, etc.
  • the high molecular weight polyol is a polyol having an average molecular weight exceeding about 500.
  • polyester polyols such as polyethylene adipate (PEA), polybutylene adipate (PBA), and polyhexamethylene adipate (PHMA); lactone polyester polyols such as poly- ⁇ -caprolactone (PCL); polyhexamethylene Polycarbonate polyols such as carbonate; and acrylic polyols.
  • PEA polyethylene adipate
  • PBA polybutylene adipate
  • PHMA polyhexamethylene adipate
  • lactone polyester polyols such as poly- ⁇ -caprolactone (PCL)
  • PCL polyhexamethylene Polycarbonate polyols such as carbonate
  • acrylic polyols such as polyethylene adipate (PEA), polybutylene adipate (PBA), and polyhexamethylene adipate (PHMA)
  • lactone polyester polyols such as poly- ⁇ -caprolactone (PCL)
  • PCL polyhexamethylene Polycarbonate polyols
  • the chain extender is not particularly limited, and examples thereof include polyamines, low molecular weight polyols, and alkanolamines.
  • polyamines aliphatic polyamines such as ethylenediamine, propylenediamine and hexamethylenediamine; aromatic polyamines such as tolylenediamine, xylylenediamine and diaminodiphenylmethane; alicyclic polyamines such as diaminocyclohexylmethane, piperazine and isophoronediamine; hydrazine, And hydrazines such as succinic acid dihydrazide, adipic acid dihydrazide, and phthalic acid dihydrazide.
  • alkanolamine include diethanolamine and monoethanolamine.
  • the carboxyl group-containing polyurethane resin can be emulsified (emulsified) by a known method, for example, the following method. That is, a method in which a carboxyl group of a carboxyl group-containing urethane prepolymer is neutralized with a base and emulsified and dispersed in an aqueous medium to cause chain extension reaction; a carboxyl group-containing polyurethane resin is emulsified with high shear force in the presence of an emulsifier This is a method of dispersing and chain extending reaction.
  • the acid value of the carboxyl group-containing polyurethane resin is preferably 10 mgKOH / g or more from the viewpoint of ensuring the stability of the coating liquid, and on the other hand, 60 mgKOH / g or less from the viewpoint of ensuring the corrosion resistance of the resin film. Is preferred.
  • the acid value is measured according to JIS-K0070 (1992).
  • the resin film is applied to the surface of the galvanized steel sheet using a known coating method, that is, a roll coater method, a bar coater method, a spray method, or a curtain flow coater method, and dried by heating.
  • a known coating method that is, a roll coater method, a bar coater method, a spray method, or a curtain flow coater method, and dried by heating.
  • the coating liquid contains a predetermined amount of silica, magnesium hydroxide and the above resin.
  • the resin solid content in the coating liquid is preferably about 15 to 25% by mass.
  • a coating liquid may contain various additives in the range which does not inhibit the effect of this invention for the purpose of improving membrane
  • additives examples include silane coupling agents, elution inhibitors, rust inhibitors, waxes, crosslinking agents, diluents, antiskinning agents, surfactants, emulsifiers, dispersants, leveling agents, antifoaming agents, and penetrants. , Film forming aids, dyes, pigments, thickeners, lubricants and the like.
  • the resin film becomes dense and the corrosion resistance is improved.
  • the adhesiveness of a galvanized steel plate and a resin film is also improved, and corrosion resistance is improved.
  • glycidoxy-based silane coupling agents are highly reactive and have a large effect of improving corrosion resistance.
  • Glycidyl group-containing silane coupling agents include ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxymethyldimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyl Examples include trimethoxysilane.
  • the amount of the silane coupling agent is preferably 0.1 parts by mass or more, more preferably 3 parts by mass or more, with respect to 100 parts by mass in total of the inorganic compound and the resin component in the inorganic film. More preferably, it is 5 parts by mass or more. If the amount is less than 0.1 parts by mass, the adhesion between the galvanized steel sheet and the resin film and the bonding force between the resin component and colloidal silica may be insufficient, and the toughness and corrosion resistance of the film may be insufficient. is there.
  • the amount of the silane coupling agent is preferably 10 parts by mass or less, more preferably 9 parts by mass or less, with respect to 100 parts by mass in total of the inorganic compound and the resin component in the inorganic film. More preferably, it is 7 parts by mass or less. Even if it exceeds 10 parts by mass, not only the effect of improving the adhesion between the metal plate and the resin film is saturated, but also the functional group in the resin may decrease and the paintability may deteriorate. Moreover, it is because silane coupling agents raise
  • metavanadate which is an elution inhibitor
  • dissolution and elution of a galvanized steel sheet are suppressed by elution of metavanadate, and corrosion resistance is improved.
  • Metavanadate is particularly effective in improving the bare corrosion resistance of the galvannealed steel sheet.
  • the metavanadate include sodium metavanadate (NaVO 3 ), ammonium metavanadate (NH 4 VO 3 ), and potassium metavanadate (KVO 3 ). These 1 type (s) or 2 or more types can be used.
  • the amount of metavanadate is preferably 0.5 parts by mass or more and more preferably 0.7 parts by mass or more with respect to 100 parts by mass in total of the inorganic compound and the resin component in the inorganic coating. Preferably, it is 1.0 part by mass or more. This is because if the amount is less than 0.5 parts by mass, the effect of improving the bare corrosion resistance becomes insufficient.
  • the amount of metavanadate is preferably 5.5 parts by mass or less, and 5.0 parts by mass or less with respect to 100 parts by mass in total of the inorganic compound and the resin component in the inorganic coating. Is more preferable, and it is further more preferable that it is 3.0 mass parts or less.
  • the suitable amount of this metavanadate is a V element conversion amount.
  • the type of galvanized steel sheet used in the present embodiment is not particularly limited, and any of electrogalvanized steel sheet, hot dip galvanized steel sheet, and alloyed hot dip galvanized steel sheet (hereinafter, these may be referred to as “original plates”). Can also be adopted. Moreover, there is no limitation in particular also about the kind of zinc plating layer, An alloying element may be included in a plating layer.
  • the galvanized layer is coated on one side or both sides of the base steel plate, and the resin film is accordingly coated on one side or both sides of the galvanized steel plate.
  • the coated galvanized steel sheet according to one aspect of the present invention is a coated galvanized steel sheet having a resin film containing silica and magnesium hydroxide on the surface of the galvanized steel sheet, and the silica in the resin film and
  • the total content of magnesium hydroxide is 75 to 90% by mass
  • the resin component content of the resin film is 10 to 25% by mass
  • the mass ratio of the magnesium hydroxide to the silica is 0.15 to 3
  • the thickness of the resin film is 0.20 to 1.1 ⁇ m.
  • a coated galvanized steel sheet exhibiting excellent corrosion resistance can be realized with less film residue generated during roll forming while the thickness of the resin film is 1.1 ⁇ m or less.
  • Magnesium hydroxide particles (manufactured by Kyowa Chemical Industry Co., Ltd., trade name: Kisuma 5Q-S) are used as a dispersant and dispersed using a polymer dispersant to obtain an aqueous dispersion (resin solid content: about 30 wt%, average particle size D 50: 0.69 .mu.m) was formulated.
  • the average particle diameter D 50 of the magnesium hydroxide in the dispersion was diluted with 0.2 wt% aqueous solution of sodium hexametaphosphate, a laser diffraction scattering particle size distribution measuring device (Microtrac Bell Co., Ltd., trade name: Micro Measurement was performed using a track MT3300EXII).
  • the above polyethylene resin manufactured by Toho Chemical Co., Ltd. and its aqueous dispersion were prepared by the following method.
  • an ethylene-acrylic acid copolymer manufactured by Dow Chemical Co., Ltd., trade name: Primacol 5990I, structural unit derived from acrylic acid: 20% by mass, mass
  • polymaleic acid aqueous solution manufactured by NOF Corporation, trade name: Nonpole PMA-50W, Mw: about 1100 (polystyrene conversion)
  • the above urethane resin manufactured by Toho Chemical Co., Ltd. and its aqueous dispersion were prepared by the following method.
  • the magnesium hydroxide aqueous dispersion, the polyethylene resin aqueous dispersion or the urethane resin aqueous dispersion, and colloidal silica are mixed to obtain a resin solid content. About 10% by mass of coating liquid was prepared.
  • Hot-dip galvanized steel sheet GI: plate thickness 0.8 mm, zinc basis weight: 60 g / m 2
  • Alloyed galvanized steel sheet GA
  • plate thickness 0.8 mm, zinc basis weight 45 g / m 2
  • Electrogalvanized steel sheet EG: plate thickness 0.8 mm, zinc basis weight: 20 g / m 2
  • Example As shown in Tables 1 and 2 within the above range, using (1) hot dip galvanized steel sheet, (2) galvannealed steel sheet and (3) electrogalvanized steel sheet as the original plate.
  • Various coated galvanized steel sheets (Test Nos. 1 to 17 in Table 1 and Test Nos. 18 to 35 in Table 2) were prepared under various conditions, and roll forming resistance and corrosion resistance of the obtained coated galvanized steel sheets. was evaluated by the following method.
  • X represents the mass per unit area of the silicon element in the coating (mg / m 2 ), and Y represents the composition ratio (mass%) of silica (SiO 2 ) in the coating.
  • the reduction amount (W 0 -W 1 ) of the film adhesion amount was calculated as the generated film residue, and ⁇ and ⁇ were evaluated as acceptable and ⁇ as unacceptable based on the following criteria.
  • the method of the repeated sliding test is as follows. First, a test piece cut out from a coated galvanized steel sheet into a rectangular shape having a width of 40 mm and a length of 300 mm is vertically mounted on a tensile tester, and a flat plate die (material: SKD11) is brought into contact. Next, a jig (semi-cylindrical die, material: SKD11) having a convex portion with a tip radius of 9.1 mm is brought into contact with the other surface (sliding surface) of the test piece, and 2940 N (300 kgf) of the jig is brought into contact with the jig.
  • the sliding operation is performed by moving the jig downward at a speed of 300 mm / min within a range where the flat plate die is in contact with the sliding surface of the test piece while applying a load in the horizontal direction.
  • the jig (semi-cylindrical die) is separated from the sliding surface of the test piece and returned to the position before the sliding operation. Repeat the sliding operation similar to the above 9 times. That is, the process ends after a total of 10 sliding operations.
  • Test No. 14, 15, 31, and 32 are examples in which the mass ratio [Mg (OH) 2 / SiO 2 ] is outside the range of 0.15 to 3, and the corrosion resistance deteriorates when the original plate is either GI or GA. It was. Further, in the examples where the resin film thickness is less than 0.20 ⁇ m (Test Nos. 16, 18, 25, and 33), the corrosion resistance was deteriorated regardless of whether the original plate was GI or GA.
  • the coated galvanized steel sheet of the present invention (test Nos. 1 to 6, 8 to 13, 17, 19 to 23, 26 to 30, 34, and 35) satisfying all of the prescribed requirements is the original plate.
  • any of GI, GA, and EG and in any of the polyethylene resin and the urethane resin, excellent roll resistance was exhibited while exhibiting excellent corrosion resistance.
  • the present invention has wide industrial applicability in the technical fields related to steel plates, galvanized steel plates and methods for producing them.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

Un aspect de la présente invention concerne une tôle d'acier galvanisée revêtue qui a un film de revêtement de résine qui contient de la silice et de l'hydroxyde de magnésium sur la surface d'une tôle d'acier galvanisée, et qui est conçue de sorte que : la teneur totale en silice et en hydroxyde de magnésium dans le film de revêtement de résine est de 75 à 90 % en masse ; la teneur d'un constituant de résine dans le film de revêtement de résine est de 10 à 25 % en masse ; le rapport en masse de l'hydroxyde de magnésium à la silice est de 0,15 à 3 ; et l'épaisseur du film de revêtement de résine est de 0,20 à 1,1 µm.
PCT/JP2019/011032 2018-03-29 2019-03-18 Tôle d'acier galvanisée revêtue WO2019188460A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201980021239.8A CN111971170B (zh) 2018-03-29 2019-03-18 涂装镀锌钢板
KR1020207028776A KR102473795B1 (ko) 2018-03-29 2019-03-18 도장 아연도금 강판

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018-064766 2018-03-29
JP2018064766 2018-03-29
JP2019-030545 2019-02-22
JP2019030545A JP7112350B2 (ja) 2018-03-29 2019-02-22 塗装亜鉛めっき鋼板

Publications (1)

Publication Number Publication Date
WO2019188460A1 true WO2019188460A1 (fr) 2019-10-03

Family

ID=68058799

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/011032 WO2019188460A1 (fr) 2018-03-29 2019-03-18 Tôle d'acier galvanisée revêtue

Country Status (1)

Country Link
WO (1) WO2019188460A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5476441A (en) * 1977-12-01 1979-06-19 Kawasaki Steel Co Production of steel plate with oneeside plating
JP2002322569A (ja) * 2001-04-23 2002-11-08 Nippon Steel Corp 金属用防錆剤および防錆処理鋼材
JP2005200757A (ja) * 2003-02-05 2005-07-28 Kobe Steel Ltd 表面処理金属板
JP2013108126A (ja) * 2011-11-18 2013-06-06 Kobe Steel Ltd 耐食性及び導電性に優れた表面処理金属板
JP2014523457A (ja) * 2011-06-09 2014-09-11 ピーアールシー−デソト インターナショナル，インコーポレイティド 水酸化マグネシウム粒子を含むコーティング組成物および関連のコーティングされた基材
JP2018172779A (ja) * 2017-03-31 2018-11-08 株式会社神戸製鋼所 塗装亜鉛めっき鋼板
JP2018172780A (ja) * 2017-03-31 2018-11-08 株式会社神戸製鋼所 塗装亜鉛めっき鋼板

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5476441A (en) * 1977-12-01 1979-06-19 Kawasaki Steel Co Production of steel plate with oneeside plating
JP2002322569A (ja) * 2001-04-23 2002-11-08 Nippon Steel Corp 金属用防錆剤および防錆処理鋼材
JP2005200757A (ja) * 2003-02-05 2005-07-28 Kobe Steel Ltd 表面処理金属板
JP2014523457A (ja) * 2011-06-09 2014-09-11 ピーアールシー−デソト インターナショナル，インコーポレイティド 水酸化マグネシウム粒子を含むコーティング組成物および関連のコーティングされた基材
JP2013108126A (ja) * 2011-11-18 2013-06-06 Kobe Steel Ltd 耐食性及び導電性に優れた表面処理金属板
JP2018172779A (ja) * 2017-03-31 2018-11-08 株式会社神戸製鋼所 塗装亜鉛めっき鋼板
JP2018172780A (ja) * 2017-03-31 2018-11-08 株式会社神戸製鋼所 塗装亜鉛めっき鋼板

Similar Documents

Publication Publication Date Title
KR100711870B1 (ko) 표면처리금속판
KR101452051B1 (ko) 내식성 및 도전성이 우수한 표면처리 금속판
JP4159998B2 (ja) 表面処理金属板
JP7112350B2 (ja) 塗装亜鉛めっき鋼板
JP4551847B2 (ja) 樹脂塗装金属板
JP6946377B2 (ja) 樹脂塗装金属板
WO2019188460A1 (fr) Tôle d'acier galvanisée revêtue
JP7112349B2 (ja) 塗装亜鉛めっき鋼板
KR102550836B1 (ko) 도장 아연도금 강판
JP7235556B2 (ja) 塗装亜鉛めっき鋼板
WO2019188461A1 (fr) Tôle d'acier galvanisée revêtue
JP5503165B2 (ja) ロール成形時の耐皮膜剥離性に優れた樹脂塗装金属板
WO2019188237A1 (fr) Tôle d'acier galvanisée revêtue
JP2019173125A (ja) 塗装亜鉛めっき鋼板
JP2006272765A (ja) 樹脂塗装金属板
JP2016175257A (ja) 樹脂塗装金属板

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19778149

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20207028776

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 19778149

Country of ref document: EP

Kind code of ref document: A1