CN110462101A - Coating galvanized steel plain sheet - Google Patents

Coating galvanized steel plain sheet Download PDF

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Publication number
CN110462101A
CN110462101A CN201880020432.5A CN201880020432A CN110462101A CN 110462101 A CN110462101 A CN 110462101A CN 201880020432 A CN201880020432 A CN 201880020432A CN 110462101 A CN110462101 A CN 110462101A
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CN
China
Prior art keywords
resin
galvanized steel
magnesium hydroxide
steel plain
plain sheet
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Granted
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CN201880020432.5A
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CN110462101B (en
Inventor
山本哲也
江口彻
酒井大辉
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Jinsyo System Co Ltd
Kobe Steel Ltd
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Jinsyo System Co Ltd
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Priority claimed from JP2017249153A external-priority patent/JP6923432B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • 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
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/20—Deep-drawing
    • 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
    • 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
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide

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

Abstract

The present invention relates to a kind of coating galvanized steel plain sheets, it is the coating galvanized steel plain sheet on the surface of galvanized steel plain sheet with the resin involucra containing silica and magnesium hydroxide, total content of silica and magnesium hydroxide in the resin involucra is 50~75 mass %, and the content of the resin component of the resin involucra is 25~50 mass %, the magnesium hydroxide is 0.3~6 relative to the quality ratio of the silica, the resin involucra with a thickness of 0.3~1.5 μm, the average grain diameter D of magnesium hydroxide when water dispersion50It is 0.6 μm or less.

Description

Coating galvanized steel plain sheet
Technical field
The present invention relates to a kind of on the surface of galvanized steel plain sheet have in resin comprising inorganic compound epithelium (with Under, sometimes referred to as " inorganic system's epithelium ") coating galvanized steel plain sheet.
Background technique
In coating galvanized steel plain sheet on the surface of galvanized steel plain sheet with inorganic system's epithelium, since its inorganic system's epithelium is hard Matter, and it is resistant to the harshly sliding with mold, so being frequently used for the utilization drawing process of such as oil strainer shell The use of manufactured product is on the way.In addition, due to good fine and close of barriering effect that inorganic system's epithelium can obtain corrosion factor Epithelium, so compared with organic system epithelium, can filming, and be on the way also suitable for requiring the use of good electric conductivity Suitable.
In the stringent processing as the deep-draw deep processing, cut by the epithelium at the position that mold slided, therefore The decline of corrosion resistance (being referred to as " corrosion resistance after processing ") after processing is obvious.In order to improve corrosion resistance after processing, Although the epithelium debris generated in processing will increase it is contemplated that increasing the leather film thickness before processing.In addition, if increasing epithelium Thickness, then electric conductivity can reduce, it is therefore desirable to manufacture respectively by each purposes, the productivity for producing route can reduce.For this purpose, i.e. It is the film that can ensure electric conductivity, also requires inorganic system's epithelium of excellent corrosion resistance after processing.
Known magnesium based compound is for zinc-plated performance rust-proof effect.In recent years, the height of the magnesium particle containing nano-scale is resistance to The technology of corrosivity epithelium is studied.
As in such technology, such as patent document 1, proposition has " comprising having receiving for the average grain diameter lower than 200nm The coating composition of rice magnesium hydroxide particles ".However, in the art, it is noted that leather film thickness is 20 μm or more, and is not expected Punch process purposes.In addition, not making any consideration for the compound added together with magnesium hydroxide, only adding magnesium hydroxide Shi Bingwei plays sufficient rust-proof effect in the regional scope that leather film thickness is several μm.
In addition, in patent document 2, propose to have " comprising metals oxidations such as magnesia with 100nm average grain diameter below The corrosion resistance particle coating composition of object and silica as corrosion resistance particle ".The composition is for etching priming coat Purposes, not in view of not having the purposes of finishing coat epithelium (top coating film).In addition, even having presentation high resistance to The case where corrosive finishing coat epithelium, also due to leather film thickness is excessive, so there is no using punch process as purposes.
On the other hand, patent document 3 proposition have " as lower layer formed the acid mineral coating containing magnesium compound and It is formed on alkaline organo-mineral complexing coating, therefrom the surface treated zinc-based metal plated steel sheet of series of strata epithelium in pairs ".At this In technology, by using above structure, the corrosion resistant of flaw portion and end face is able to maintain that reducing the weight per unit area of zinc Corrosion, and seek the balance to other each performances.
In the patent document 3, although disclosing the inorganic layer that magnesium compound is contained in lower layer, there is no energetically have Effect utilizes the corrosion-suppressing effect of magnesium compound, is not in addition by particle but is added in the form of ion or molecule, Therefore increase the additive amount of magnesium and there is limitation to improve corrosion-suppressing effect.In addition, because being the double-deck system, it can be in productivity Reduction or cost in terms of lead to the problem of.
The present invention is made in view of situation as described above, maintains good conduction its purpose is to provide a kind of Property, and after processing, plays the coating galvanized steel plain sheet of excellent corrosion resistance.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open Publication 2014-523457
Patent document 2: Japanese Patent Laid-Open Publication 2009-506175
Patent document 3: Japanese patent gazette the 5457611st
Summary of the invention
The coating galvanized steel plain sheet that one embodiment of the present invention is related to is that have to contain dioxy on the surface of galvanized steel plain sheet The coating galvanized steel plain sheet of the resin involucra of SiClx and magnesium hydroxide, the conjunction of silica and magnesium hydroxide in the resin involucra Meter content is 50~75 mass %, and the content of the resin component of the resin involucra is 25~50 mass %, the hydroxide Magnesium is 0.3~6 relative to the quality ratio of the silica, the resin involucra with a thickness of 0.3~1.5 μm, water dispersion When the magnesium hydroxide average grain diameter D50It is 0.6 μm or less.
Detailed description of the invention
Fig. 1 is the explanatory diagram when forming slide mark on test film.
Specific embodiment
The present inventors in order to achieve the above objectives, is studied from all angles.The result found that by resin Contain silica and magnesium hydroxide in epithelium, and appropriately adjusts their total content and the thickness of quality ratio, resin involucra Degree etc., and appropriately provide water dispersion when the magnesium hydroxide average grain diameter D50, thus reach above-mentioned purpose well, And complete the present invention.
According to the present invention, it by above-mentioned composition, may be implemented to maintain good electric conductivity, and corrosion resistance after processing Excellent coating galvanized steel plain sheet.
Hereinafter, being specifically described with regard to embodiments of the present invention, but the present invention is not limited by above-mentioned these.
[total content of silica and magnesium hydroxide: 50~75 mass %]
In the present embodiment, total content of the silica in resin involucra and magnesium hydroxide is set as 50~75 matter Measure %.Inorganic system's epithelium is hard, is resistant to sliding harshly with mold when punching press.In addition, with organic system epithelium It compares, because largely containing heavy inorganic compound, good fine and close of barriering effect of corrosion factor can be obtained Epithelium.However, being used as adhesive if total content of silica and magnesium hydroxide in resin involucra is more than 75 mass % Resin component it is insufficient, become the epithelium more than defective part and corrosion resistance deteriorates.Preferably 70 mass % are hereinafter, more preferably 65 Quality % or less.
On the other hand, if total content of silica and magnesium hydroxide is lower than 50%, resin component becomes more, in addition to tree Except corrosion resistance caused by compactness decline in rouge epithelium reduces, also generation epithelium occur softening and when punch process The increased worry of epithelium debris.Preferably 55 mass % or more.
Silica used in present embodiment is preferably aftermentioned with aqueous resin colloid two excellent in compatibility Silica.In addition, there is the compactness of epithelium to decline or occur the worry of epithelium defect if average particle diameter became is excessive, because This average grain diameter D50Preferably 500nm or less.More preferably 450nm or less.In addition, if magnesium hydroxide is steady as aqueous dispersion Fixed, then used magnesium hydroxide powder and dispersing method are not particularly limited.
[content of the resin component of resin involucra: 25~50 mass %]
In present embodiment, the content of the resin component of resin involucra is set as 25~50 mass %.As described above, if resin The resin component deficiency of epithelium, then become the epithelium more than defective part and corrosion resistance deteriorates.From the viewpoint, resin skin The resin component of film needs to be set as 25 mass % or more.Preferably 30 mass % or more.However, if the resin component of resin involucra Become excessive, then other than corrosion resistance caused by the decline of the compactness of resin involucra reduces, also generation epithelium occurs soft Change and the increased worry of epithelium debris when punch process.From the viewpoint, the resin component needs of resin involucra are set For 50 mass % or less.Preferably 45 mass % or less.
[quality ratio of the magnesium hydroxide relative to silica: 0.4~6]
In present embodiment, magnesium hydroxide is set as 0.4~6 relative to the quality ratio of silica.Known magnesium hydroxide It is used as with silica for zinc-plated antirust agent.The present inventors discovery: by resin involucra with specific quality Ratio cooperates magnesium hydroxide and silica, even film can also obtain excellent corrosion resistance.Magnesium hydroxide relative to Quality ratio [the Mg (OH) of silica2/SiO2] in the range of 0.4~6 when, show good corrosion resistance.The matter Measuring ratio is preferably 0.7 or more or 5 or less.
It is although indefinite come the mechanism for improving corrosion resistance by the way that above-mentioned quality ratio is adjusted to appropriate range, but this Inventors think approximately as.That is, presumption: by using the magnesium hydroxide of particle shape (for being averaged for magnesium hydroxide particles Partial size D50It can be improved the stability for the treatment of fluid as described later), and can be improved the addition ratio of magnesium component, as a result, Play the synergistic effect of magnesium hydroxide and silica.
[resin involucra thickness: 0.3~1.5 μm]
In present embodiment, resin involucra thickness is set as 0.3~1.5 μm.When resin involucra thickness is lower than 0.3 μm, even if It is that the resin involucra of which class all becomes difficult to sufficiently be coated galvanizing surface, causes corrosion resistance insufficient.Preferably 0.5 μm or more. On the other hand, if leather film thickness is more than 1.5 μm, good electric conductivity cannot be accessed.Preferably 1.3 μm or less.
[the average grain diameter D of magnesium hydroxide when water dispersion50: 0.6 μm or less]
In present embodiment, the average grain diameter D of magnesium hydroxide50It is set as 0.6 μm or less.Particle is added into resin involucra When, if its partial size becomes excessive compared with leather film thickness, becomes easy from epithelium and fall off.Especially by harsh in mold When the deep-draw deep processing of sliding, the average grain diameter that magnesium hydroxide particles need to have appropriate is average in terms of the state of aqueous dispersion Partial size D50It is 0.6 μm or less.Preferably 0.3 μm or less.
The average grain diameter D of the aqueous dispersion of magnesium hydroxide particles50Lower limit be not particularly limited, if but D50It is excessively small, then The stability of dispersion is likely to decrease, and preferably 0.1 μm or more.More preferably 0.14 μm or more.
It is explained, " the average grain diameter D50" refer to that the value (aggregate-value) for being accumulated by magnesium hydroxide is 50 matter Measure average grain diameter when %.
Meet the coating galvanized steel plain sheet of the present embodiment of important document as described above, can become and maintain good electric conductivity simultaneously And the steel plate of corrosion resistance after excellent processing is played, such as the steel plate for being used for deep-draw deep processing purposes be extremely useful 's.
[type of resin]
The type of the resin used in present embodiment, is not particularly limited, and is able to use aqueous resin and non-aqueous It is any in resin.Using the aqueous dispersion (for example, aqueous dispersions) or colloidal silicon dioxide for having used magnesia In the case of, it is preferable to use aqueous resin.The aqueous resin is not particularly limited, mixing magnesium hydroxide water dispersion is preferably able to Body and colloidal silicon dioxide.
As the aqueous resin, preferred polyolefm system resin, polyurethane series resin, polyester based resin, wherein it is preferred that polyene Hydrocarbon system resin.So-called aqueous resin in present embodiment refers to the resin or water-soluble resin as aqueous dispersion.
As polyolefin-based resins, optimal ethylene-copolymers of unsaturated carboxylic acids.As the ethylene-unsaturated carboxylic acid copolymerization Object is able to use Japanese Patent Laid-Open Publication 2005-246953, Japanese Patent Laid-Open Publication 2006-43913 In documented ethylene-copolymers of unsaturated carboxylic acids.
As unsaturated carboxylic acid, (methyl) acrylic acid, crotonic acid, iso-crotonic acid, maleic acid, fumaric acid, clothing health can be enumerated One or more of these are polymerize by acid etc. with ethylene with well known high temperature high-pressure polymerization process etc., and thus, it is possible to be copolymerized Object.
Copolymerization ratio about unsaturated carboxylic acid relative to ethylene, if monomer total amount is 100 mass %, unsaturated carboxylic acid Preferably 10~40 mass %.If unsaturated carboxylic acid is less than 10 mass %, intermolecular form is formed by due to becoming ion cluster The carboxyl of the starting point of conjunction is reduced, so epithelium intensity effect can not be played, and the emulsion stability of emulsion composition is poor, therefore not It is preferred that.The lower limit of the copolymerization ratio of preferred unsaturated carboxylic acid is 15 mass %.On the other hand, if unsaturated carboxylic acid is more than 40 Then there is the deterioration of the corrosion resistance or water resistance of first layer sometimes in quality %.The preferred upper limit is 25 mass %.
Since above-mentioned ethylene-copolymers of unsaturated carboxylic acids has carboxyl, so by being neutralized with organic base or metal ion, And it being capable of emulsification (aqueous dispersion).In present embodiment, as organic base, it is (excellent that primary amine, secondary amine, tertiary amine can be enumerated It is selected as triethylamine).
(boiling point preferably under atmospheric pressure is 100 DEG C of amine below to the amine of low boiling point；Such as triethylamine) be not likely to make The corrosion resistance of resin involucra reduces.Additionally, it is preferred that the metal ion of 1 valence is also used with amine together.It is preferred that amine relative to 1 mole of carboxyl in ethylene-copolymers of unsaturated carboxylic acids is 0.2~0.8 mole (20~80 moles of %).The metal of known 1 valence The amount of ion affects steam permeability, if the metallic compound of 1 valence is more using quantitative change, resin and water it is affine Property increase, steam permeability becomes larger, therefore is preferably with respect to 1 mole of carboxyl in ethylene-copolymers of unsaturated carboxylic acids 0.02~0.2 mole (2~20 moles of %).In addition, superfluous alkali composition becomes the reason of corrosion resistance deteriorates, thus amine and Total usage amount of metal ion is set as 0.3~1.0 and rubs relative to 1 mole of carboxyl in ethylene-copolymers of unsaturated carboxylic acids Your range is advisable.It is explained, for assigning the metallic compound of metal ion of 1 valence preferred NaOH, KOH, LiOH etc., NaOH performance is best and preferred.
When emulsifying (emulsification), the chemical combination with surfactant function of ready denier oil acid etc. can also be added in right amount Object.Above-mentioned ethylene-copolymers of unsaturated carboxylic acids can according to need in the presence of aftermentioned carboxylic acid polyalcohol, if in high temperature It is carried out high-speed stirred 1~6 hour in the container that can be reacted of (150 DEG C or so), high pressure (5 air pressures or so), then emulsion occurs Change.Alternatively, it is also possible to which a small amount of hydrophilic organic solvent, such as the lower alcohol etc. of carbon number 1~5 or so are added in water.
Ethylene-copolymers of unsaturated carboxylic acids matter average molecular weight (Mw) is in terms of polystyrene conversion, and preferably 1,000~10 Ten thousand, more preferably 3,000~70,000, further preferably 5,000~30,000.The Mw can be utilized and be used using polystyrene as standard Gel permeation chromatography (Gel Permeation Chromatography:GPC) be measured.
As resin component, carboxylic acid polyalcohol also can be used.As carboxylic acid polyalcohol, as in above-mentioned ethylene-insatiable hunger With it is being able to use in the synthesis of polymers of carboxylic acid and exemplify can be with by the polymer of Component units of unsaturated carboxylic acid It uses.Wherein preferred acrylic acid and maleic acid, more preferable maleic acid.Carboxylic acid polyalcohol can be containing other than unsaturated carboxylic acid Monomer Component units, but the Component units amount from other monomers in the polymer be preferably 10 mass % hereinafter, more excellent 5 mass % are selected as hereinafter, the carboxylic acid polyalcohol being more preferably only made of unsaturated carboxylic acid.It, can as preferred carboxylic acid polyalcohol Enumerate such as polyacrylic acid, polymethylacrylic acid, acid-co-maleic acid, poly etc., wherein from resin involucra From the viewpoint of adaptation and corrosion resistance, more preferable poly.Corrosion resistance etc. is improved by using poly Correct mechanism is although unclear, but the present inventors believe that: since carboxyl amount is more, so the adaptation of resin involucra and metal plate It improves, is also improved with its corrosion resistance.But, the present invention is not limited by the presumption.
The Mw of carboxylic acid polyalcohol used in present embodiment is in terms of polystyrene conversion, and preferably 500~30,000, it is more excellent It is selected as 800~10,000, further preferably 900~3,000, most preferably 1,000~2,000.The Mw, which can be used, to be used with poly- Styrene is that the GPC of standard is measured.
The containing ratio of ethylene-copolymers of unsaturated carboxylic acids and carboxylic acid polyalcohol is 1,000:1~10:1 by quality ratio, Preferably 200:1~20:1.If the containing ratio of carboxylic acid polyalcohol is too low, by alkene-acid copolymer and carboxylic acid polyalcohol into Effect after row combination can not give full play to；In contrast, if the containing ratio of carboxylic acid polyalcohol is superfluous, in first layer shape It is mutually separated at alkene-acid copolymer in coating fluid with carboxylic acid polyalcohol generation, it is possible to not formed uniform resin involucra.
Coating liquid when forming resin involucra can contain silane coupling agent.If using silane coupling agent, galvanized steel plain sheet It improves with the adaptation of resin involucra, is also improved with its corrosion resistance.In addition, having makes resin component and colloidal silicon dioxide Binding force improve effect, and improve epithelium obdurability.Wherein, the reactivity of the silane coupling agent of glycidoxy system Height, corrosion resistance improvement effect are big.As with glycidyl ether silane coupling agent, γ-glycidoxy third can be enumerated Ylmethyl diethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidyl oxy methyl dimethoxy silicon Alkane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane etc..
Total 100 mass parts of the silane coupled dosage relative to inorganic compound and resin component in inorganic system's epithelium, Preferably 0.1~10 mass parts.If being less than 0.1 mass parts, it is likely that the adaptation of generation metal plate and resin involucra is insufficient, Or the binding force deficiency of resin component and colloidal silicon dioxide occurs, so that the obdurability of epithelium or corrosion resistance become not fill Point.In contrast, if more than 10 mass parts, the adaptation improvement effect of galvanized steel plain sheet and resin involucra is saturated, and It is possible that due to the functional group in resin reduces, coating declines.In addition, hydrolysis-condensation reaction occurs between silane coupling agent, apply The stability for filling liquid reduces, it is possible to cause the precipitating of gelation or colloidal silicon dioxide.Preferred silane coupled dosage is 3 ~9 mass parts, further preferably 5~7 mass parts.
In the coating liquid used when forming resin involucra, resin solid content is preferably set as 15~25 mass % or so. In the coating liquid, in a range that does not hinder the effect of the present invention, it can also be prevented containing wax, crosslinking agent, diluent, skinning Agent, surfactant, emulsifier, dispersing agent, levelling agent, defoaming agent, bleeding agent, membrane producing promoter, dyestuff, pigment, tackifier, profit Lubrication prescription etc..In addition, the coating method of coating liquid is not particularly limited, it can be using method well known to roller coating etc..
For the type of the galvanized steel plain sheet with resin involucra as described above, it is not particularly limited, plated steel sheet, Any in hot-dip galvanized steel sheet, alloy galvanized steel plate (hereinafter, these are known as " raw sheet " sometimes) can adopt With.In addition, the type for zinc coat is also not particularly limited, alloying element can also be contained in coating.It is explained, it is zinc-plated Layer is coated on the single side of matrix steel plate, and perhaps correspondingly resin involucra is also coated on single side or the two sides of galvanized steel plain sheet on two sides.
This specification discloses the technology of various embodiments as described above, and major technique is summarized as follows.
The coating galvanized steel plain sheet that one embodiment of the present invention is related to is that have to contain dioxy on the surface of galvanized steel plain sheet The coating galvanized steel plain sheet of the resin involucra of SiClx and magnesium hydroxide, the conjunction of silica and magnesium hydroxide in the resin involucra Meter content is 50~75 mass %, and the content of the resin component of the resin involucra is 25~50 mass %, the hydroxide Magnesium is 0.3~6 relative to the quality ratio of the silica, the resin involucra with a thickness of 0.3~1.5 μm, water dispersion When the magnesium hydroxide average grain diameter D50It is 0.6 μm or less.
According to this constitution, may be implemented to maintain good electric conductivity, and after processing play it is excellent corrosion-resistant The coating galvanized steel plain sheet of property.
In addition, coating galvanized steel plain sheet of the invention is highly useful as the steel plate for deep-draw deep processing purposes.
Hereinafter, being particularly shown functions and effects of the invention by embodiment, but following embodiments are not intended to limit this hair It is bright, it is all contained in technical protection scope of the invention according to the design alteration above addressing following objectives and carrying out.
Embodiment
(magnesium hydroxide)
The various magnesium hydroxide particles that the average grain diameter of following (a)~(e) is different are used.
(a) " 139-13951 " (number): Wako Pure Chemical Industries, Ltd.'s manufacture
(b) magnesium hydroxide particles that average grain diameter is 83 μm: Kanto Electrization Industrial Co., Ltd's manufacture
(c) " MH-30 " (trade name): Yan Gu chemical industry Co., Ltd. manufacture
(d) " KISUMA5Q-S " (trade name): Kyowa Chemical Industry Co., Ltd's manufacture
(e) " ECOMAGZ-10 " (trade name): Tateho Chemical Industries Co. Ltd.'s manufacture
(silica)
The colloidal silicon dioxide " SNOWTEX XS " (trade name) for having used Nissan Chemical Ind Ltd to manufacture.With Under, sometimes will " SNOWTEX XS " be abbreviated as " ST-XS ".
(resin)
Resin when as formation resin involucra, the polyurethane resin (" HUX541 ": quotient for having used ADEKA company to manufacture The name of an article) or eastern nation's Chemical Co., Ltd. product polyvinyl resin.It is explained, above-mentioned polyvinyl resin is with following sides Method manufacture.
[manufacturing method of polyvinyl resin]
Have with blender, thermometer, temperature controller emulsifying device autoclave in, be added ethylene-propylene Acid copolymer (" PRIMACOR 5990I " (trade name) of Dow Chemical's manufacture；Component units from acrylic acid: 20 matter % is measured, matter average molecular weight (Mw): 20,000, melt index (MI): 1300, acid value: 150) 200.0 mass parts, poly aqueous solution (" NONPOL PMA-50W " (trade name) of You company manufacture；Mw: about 1100 (polystyrene conversions), 50 mass % products) 8.0 mass parts, 35.5 mass parts of triethylamine (carboxyl relative to ethylene-acrylic acid copolymer is 0.63 equivalent), 48% 6.9 mass parts of NaOH aqueous solution (carboxyl relative to ethylene-acrylic acid copolymer is 0.15 equivalent), ready denier oil acid (are breathed out Riamb is melted into " Hartall FA3 " (trade name) of Co., Ltd.'s manufacture) 792.6 mass of 3.5 mass parts and ion exchange water It part is simultaneously sealed, high-speed stirred 3 hours, is then cooled to 30 DEG C under 150 DEG C and 5 air pressures.
Then, silane coupling agent (Momentiff Performance Material Co., Ltd manufacture of the addition containing glycidoxy " TSL8350 " (trade name)), γ-glycidoxypropyltrime,hoxysilane) 10.4 mass parts, contain carbodiimide Compound " CARBODILITE SV-02 " (trade name) of manufacture (Nisshinbo Co., Ltd.), poly- carbodiimide, Mw:2, 700,40 mass % of solid component) after 72.8 mass parts of 31.2 mass parts and ion exchange water, stir 10 minutes, thus second Alkene-acrylic copolymer emulsifies, and having obtained the emulsion mixed with each ingredient, (20.3 mass % of solid component, is based on JIS K6833 is measured).
(allotment of magnesium hydroxide dispersion liquid)
Use water to make its dispersion as dispersing agent above-mentioned magnesium hydroxide particles, the dispersion of following (A)~(E) has been made Liquid.The dispersing agent used at this time does not specify, but, it is preferable to use adverse effect to corrosion resistance when being made resin involucra Small macromolecule dispersing agent (such as water soluble acrylic resin, water-soluble styrene acrylic resin, nonionic system surface-active Agent).
Dispersion liquid (A)
The magnesium hydroxide particles of (a) are used, resin solid content: about 30 mass %, average grain diameter D50: 0.14 μm
Dispersion liquid (B)
The magnesium hydroxide particles of (b) are used, resin solid content: about 30 mass %, average grain diameter D50: 0.17 μm
Dispersion liquid (C)
The magnesium hydroxide particles of (c) are used, resin solid content: about 30 mass %, average grain diameter D50: 0.30 μm
Dispersion liquid (D)
The magnesium hydroxide particles of (d) are used, resin solid content: about 30 mass %, average grain diameter D50: 0.69 μm
Dispersion liquid (E)
The magnesium hydroxide particles of (e) are used, resin solid content: about 30 mass %, average grain diameter D50: 1.1 μm
With regard to the average grain diameter D of the magnesium hydroxide particles in dispersion liquid50For, by by the dispersion liquid with 0.2 mass %'s After sodium hexametaphosphate solution dilution, Microtrac " MT3300EXII device " (commodity for being manufactured using Mai Qike Bayer AG Name) it is determined.
(allotment of coating liquid)
Used raw material: magnesium hydroxide aqueous dispersions [dispersion liquid of above-mentioned (A)~(E)], aqueous resin and colloid Silica (ST-XS)
Resin solid content: about 5%
(type of raw sheet)
(1) plated steel sheet (EG)
Plate thickness: 0.8mm
The weight per unit area of zinc: 18g/m2
(2) galvanized steel plain sheet (GI) is dissolved
Plate thickness: 0.8mm
The weight per unit area of zinc: 90g/m2
(pre-treatment of galvanized steel plain sheet)
Degreasing: alkali degreasing (Nihon Parkerizing Co., Ltd.'s manufacture, " FINE CLEANER " (trade name) series)
It is dry: to make its heated-air drying, so that moisture be made to evaporate.
(coating process)
Method: stick applies
The thickness of resin involucra: the number of stick is selected in the way of the specified thickness for obtaining resin involucra.
(drying means)
Method: air drier
Time: 1 minute
Condition: 80 DEG C of the maximum temperature reached of coated plate (with thermal label (thermo-label) confirmation)
[embodiment 1]
In above-mentioned range, as described in Table 1, change various conditions, makes (the test of various coating galvanized steel plain sheets No.1~6), and the corrosion resistance and electric conductivity of the coating galvanized steel plain sheet for obtaining are evaluated with following methods.
[corrosion resistance]
Flat part: salt spraytest as defined in 72 hours JIS Z2371 (2015) is implemented.After calculating test White rust incidence (area %), and evaluated with following evaluation criteria.
Sliding part: with method shown in FIG. 1, pressure is applied to test film 1 on one side, is extracted on one side, utilizes plate mould 2 Slide mark (in Fig. 1, each symbol expression 1: test film and 2: plate mould) is imparted to the surface of test film 1.Then, 48 are implemented Salt spraytest as defined in the JIS Z2371 (2015) of hour.With following evaluation criteria, has rated and be formed with slide mark Sliding part nearby and its degree of the white rust on periphery, discoloration.It is explained, condition when assigning slide mark is as described below.
Apply pressure: 300kgf/cm2(29.4MPa)
Extraction speed: 300mm/ minutes
The material of plate mould 1: SKD11 (JIS G4404:2006: alloy tool steel steel)
Lubricant: it is not used
(evaluation criteria)
1. flat part
Zero: white rust incidence is 20 area % or less
△: white rust incidence is more than 20 area % and is 30 area % or less
×: white rust incidence is more than 30 area %
2. sliding part
Zero: in sliding part and its nearby without white rust or discoloration
△: slight white rust or discoloration in sliding part and its are nearby confirmed
×: in sliding part and its nearby confirm white rust or discoloration
[electric conductivity]
Using tester (Japanese CUSTOM company manufactures, " analog tester CX-270N "), end is slipped in specimen surface Thus son determines resistance value.
(evaluation criteria)
It is good (being expressed as "○") that electric conductivity is evaluated as when resistance value is lower than 500 Ω, when by resistance value being 500 Ω or more It is bad (being expressed as "×") to be evaluated as electric conductivity.
By the result and when manufacturing each coating galvanized steel plain sheet condition (type of raw sheet, the composition ratio of inorganic system's epithelium, [Mg(OH)2/SiO2], the thickness of resin involucra) be shown in following table 1 together.
In test No.1~6 of table 1, resin involucra thickness is influenced to carry out to the characteristic bring of coating galvanized steel plain sheet Research.
Be clear that by the result: in coating galvanized steel plain sheet of the invention, the thickness of resin involucra is up to 0.2 μm of example Corrosion resistance deteriorates after the processing of (test No.1).In addition, example of the thickness of the resin involucra of coating galvanized steel plain sheet up to 2 μm The electric conductivity decline of (test No.6).
In contrast, it is known that: appropriately have adjusted coating galvanized steel plain sheet (the test No.2 of the invention of the thickness of resin involucra ~5) good electric conductivity, is maintained, and has played corrosion resistance after excellent processing.
[embodiment 2]
In above-mentioned range, as described in Table 2, change various conditions, makes (the test of various coating galvanized steel plain sheets No.7~9), and the corrosion resistance and electric conductivity of the coating galvanized steel plain sheet for obtaining pass through method similarly to Example 1 It is evaluated.
By the result and when manufacturing each coating galvanized steel plain sheet condition (type of raw sheet, the composition ratio of inorganic system's epithelium, [Mg(OH)2/SiO2], the thickness of resin involucra) be shown in following table 2 together.
In test No.7~9 of table 2, for silica and magnesium hydroxide total content to coating galvanized steel plain sheet spy Property bring influence studied.
Be clear that by the result: in coating galvanized steel plain sheet of the invention, if silica in resin involucra and The content of magnesium hydroxide increases (test No.7), then corrosion resistance deteriorates.In addition, if the content of the resin in resin involucra increases More (test No.9), then the compactness of epithelium is also deteriorated, so that corrosion resistance deteriorates.
In contrast, it is known that: appropriately have adjusted the content of silica in resin involucra, magnesium hydroxide and resin Coating galvanized steel plain sheet (test No.8) of the invention, maintains good electric conductivity, and played corrosion resistant after excellent processing Corrosion.
[embodiment 3]
In above-mentioned range, as described in Table 3, change various conditions, makes (the test of various coating galvanized steel plain sheets No.10~21), and the corrosion resistance and electric conductivity of the coating galvanized steel plain sheet for obtaining pass through side similarly to Example 1 Method is evaluated.
By the result and when manufacturing each coating galvanized steel plain sheet condition (type of raw sheet, the composition ratio of inorganic system's epithelium, [Mg(OH)2/SiO2], the thickness of resin involucra) be shown in following Table 3 together.
Quality ratio [Mg (OH) in test No.10~21 of table 3, for magnesium hydroxide relative to silica2/ SiO2] to coating galvanized steel plain sheet characteristic bring influence studied.
It is clear that by the result: in coating galvanized steel plain sheet of the invention, quality ratio [Mg (OH)2/SiO2] be detached from The example (test No.10,11,16,17,21) of 0.3~6 range, corrosion resistance deteriorates after processing.
In contrast, it is known that: appropriately have adjusted quality ratio [Mg (OH)2/SiO2] coating galvanized steel plain sheet of the invention (test No.12~15,18~20), maintain good electric conductivity, and played corrosion resistance after excellent processing.
[embodiment 4]
In above-mentioned range, as described in Table 4, change various conditions, makes (the test of various coating galvanized steel plain sheets No.22~26), and the corrosion resistance and electric conductivity of the coating galvanized steel plain sheet for obtaining pass through side similarly to Example 1 Method is evaluated.
By the result and when manufacturing each coating galvanized steel plain sheet condition (type of raw sheet, the composition ratio of inorganic system's epithelium, [Mg(OH)2/SiO2], the thickness of resin involucra) be shown in following table 4 together.
In test No.22~26 of table 4, for the average grain diameter D of magnesium hydroxide50(dispersion liquid (A)~(E) above-mentioned) gives The characteristic bring influence of coating galvanized steel plain sheet is studied.
It is clear that by the result: in coating galvanized steel plain sheet of the invention, the average grain diameter D of magnesium hydroxide50More than 0.6 μm example (test No.25,26), corrosion resistance deteriorates after processing.
In contrast, it is known that: appropriately have adjusted the average grain diameter D of magnesium hydroxide50Coating galvanized steel plain sheet of the invention (examination Test No.22~24), good electric conductivity is maintained, and played corrosion resistance after excellent processing.
The application is with Japanese Patent Application Patent 2017-71277 filed on March 31st, 2017 and in December, 2017 Based on Japanese Patent Application Patent 2017-249153 filed in 26 days, content includes in this application.
In order to state the present invention, above carries out appropriate to the present invention by above embodiment and has adequately illustrated, It should be realized that those skilled in the art are easy that above embodiment is changed and/or improved.Therefore, art technology The variant embodiment or improvement embodiment that personnel implement, as long as not being detached from the claim recorded in claims Protection scope level, the variant embodiment or improvement embodiment may be interpreted as the protection for being comprised in the claim In range.
Industrial availability
The present invention is in galvanized steel plain sheet technical field, especially in the technical field of coating galvanized steel plain sheet, has extensive Industrial availability.

Claims (2)

1. a kind of coating galvanized steel plain sheet, it is characterized in that having on the surface of galvanized steel plain sheet containing silica and magnesium hydroxide The coating galvanized steel plain sheet of resin involucra,
Total content of silica and magnesium hydroxide in the resin involucra is 50~75 mass %, and the resin involucra Resin component content be 25~50 mass %,
The magnesium hydroxide relative to the silica quality ratio be 0.3~6, the resin involucra with a thickness of 0.3 ~1.5 μm,
The average grain diameter D of magnesium hydroxide when water dispersion50It is 0.6 μm or less.
2. coating galvanized steel plain sheet according to claim 1 is used for deep-draw deep processing purposes.
CN201880020432.5A 2017-03-31 2018-02-26 Coated galvanized steel sheet Active CN110462101B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2017-071277 2017-03-31
JP2017071277 2017-03-31
JP2017249153A JP6923432B2 (en) 2017-03-31 2017-12-26 Painted galvanized steel sheet
JP2017-249153 2017-12-26
PCT/JP2018/006871 WO2018180092A1 (en) 2017-03-31 2018-02-26 Coated galvanized steel sheet

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005200757A (en) * 2003-02-05 2005-07-28 Kobe Steel Ltd Surface-treated metallic sheet
CN103703067A (en) * 2011-06-09 2014-04-02 Prc-迪索托国际公司 Coating compositions including magnesium hydroxide and related coated substrates

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5478588B2 (en) * 2011-11-18 2014-04-23 株式会社神戸製鋼所 Surface-treated metal plate with excellent corrosion resistance and conductivity

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005200757A (en) * 2003-02-05 2005-07-28 Kobe Steel Ltd Surface-treated metallic sheet
CN103703067A (en) * 2011-06-09 2014-04-02 Prc-迪索托国际公司 Coating compositions including magnesium hydroxide and related coated substrates

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