CN107429405B - Zn-Mg alloy plating steel plate - Google Patents
Zn-Mg alloy plating steel plate Download PDFInfo
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- CN107429405B CN107429405B CN201680019274.2A CN201680019274A CN107429405B CN 107429405 B CN107429405 B CN 107429405B CN 201680019274 A CN201680019274 A CN 201680019274A CN 107429405 B CN107429405 B CN 107429405B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C28/02—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 only coatings only including layers of metallic material
- C23C28/021—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 only coatings only including layers of metallic material including at least one metal alloy layer
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- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C28/02—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 only coatings only including layers of metallic material
- C23C28/023—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 only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—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 only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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Abstract
Zn-Mg alloy plating steel plate of the invention has steel plate, Zn-Mg alloy layer, corrosion scales and chemical conversion treatment layer, above-mentioned Zn-Mg alloy layer is formed in the surface of above-mentioned steel plate, and the Mg containing 1.0~70.0 mass %, remainder includes Zn and impurity, above-mentioned corrosion scales are formed in the surface of above-mentioned Zn-Mg alloy layer, and containing carbon atom number be 4~20 carboxylic acid Mg salt and carbon atom number be 4~20 any one of the Mg salt of alkanesulfonic acid, above-mentioned chemical conversion treatment layer is formed in the surface of above-mentioned corrosion scales, and contain the alkali metal salt of above-mentioned carboxylic acid in the case where above-mentioned corrosion scales contain the Mg salt of above-mentioned carboxylic acid, contain above-mentioned alkane in the case where above-mentioned corrosion scales contain the Mg salt of above-mentioned alkanesulfonic acid The alkali metal salt of sulfonic acid, wherein the alkali metal of the alkali metal salt of the alkali metal salt of above-mentioned carboxylic acid or above-mentioned alkanesulfonic acid contained by above-mentioned chemical conversion treatment layer is selected from least one of Li, Na, K, Rb and Cs.
Description
Technical field
The present invention relates to Zn-Mg alloy plating steel plates.
The application based on April 7th, 2015 in the Patent 2015-78585 CLAIM OF PRIORITY of Japanese publication, and will be in it
Appearance is incorporated herein.
Background technique
For the steel for automobile, household electrical appliances, building materials etc., implement plating sometimes to improve corrosion resistance.It is logical
Cross plating and be formed in steel surface coating be roughly divided into barrier anticorrosion plating stratotype and sacrifice anticorrosion plating stratotype both,
Wherein, barrier anticorrosion plating stratotype is to cover base metal (steel) from external environment, and sacrificing anticorrosion plating stratotype is to pass through ratio
Base metal, which more preferentially corrodes, to carry out anticorrosion to base metal.Zn is used for plated steel material all the time, by Zn plating
The coating of formation is classified as sacrifice anticorrosion plating stratotype.
When long-time service surface forms coated steel plate (hereinafter referred to as coated steel sheet), to the surface of coated steel sheet
(that is, surface of coating) implement the surface treatment such as painting treatment, chemical conversion treatment or lamination process, thus mentions rust-preventing characteristic
It is high.The main purpose of chemical conversion treatment is: improving and is processing and assembling phase of the coated steel sheet until becoming final product
Between the temporary rust prevention (also known as rust prevention during manufacture) of antirust is carried out to the surface of coated steel sheet.By chemical conversion treatment,
The layer (hereinafter referred to as chemical conversion treatment layer) that there is suitable adaptation with the surface of coating is formed on the surface of coating.
As shown in Patent Documents 1 to 4, in order to improve corrosion resistance, propose in recent years the surface of steel plate be formed with containing
The Zn-Mg alloy plating steel plate of the coating of Zn-Mg alloy replaces Zn coated steel sheet.Zn-Mg alloy plating steel plate is made by Mg
The corrosion product being created under corrosive environment stabilizes, and thus has corrosion resistance more superior than Zn coated steel sheet.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2005-146340 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2007-23309 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2010-248541 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2011-219823 bulletin
Summary of the invention
Problem to be solved by the invention
As described above, Zn-Mg alloy plating steel plate has corrosion resistance more superior than Zn coated steel sheet.However, to Zn-
In the case that Mg alloy plating steel plate implements the chemical conversion treatment for Zn coated steel sheet, there are Zn-Mg alloy plating steel
The case where the case where plate color blackening (hereinafter referred to as blacking phenomenon), chemical conversion treatment layer form expansion (is hereinafter referred to as formed
Swelling), it cannot get suitable temporary rust prevention sometimes.
In addition, blacking phenomenon may be considered due to by coating dissolve out Lai Mg ion form non-stoichiometric oxide and
Caused by, formed swelling may be considered due to by coating dissolve out Lai Mg ion be continuously formed unstable corrosion product
Caused by and.
The present invention has been made in view of the above-described circumstances, its object is to: the tool with excellent temporary rust prevention is provided
Have the Zn-Mg alloy plating steel plate of chemical conversion treatment layer.
The means used to solve the problem
Inventor hereins to by by Zn-Mg alloy dissolve out come Mg ion form stable corrosion product and improve
The method of temporary rust prevention is studied.As a result, inventor hereins are it is found that by making chemical conversion treatment
The layer solubility containing Mg salt is small, alkali metal salt solubility is big substance, the Mg come in a corrosive environment by coating dissolution and
By chemical conversion treatment layer dissolution Lai substance combine, formed and stablize corrosion product, coating is coated with the stable corrosion product
Erodable section, be able to suppress blacking phenomenon, formed swelling.
In addition, inventor hereins make further research, and have found the interim of Zn-Mg alloy plating steel plate
The alkali metal salt or carbon atom number that rust-preventing characteristic passes through the carboxylic acid for making chemical conversion treatment layer contain carbon atom number 4~20 be 4~
The alkali metal salt of 20 alkanesulfonic acid and significantly improve, so as to complete the present invention.
The present invention realizes above-mentioned purpose to solve the above-mentioned problems, using following scheme.
(1) scheme of the invention is related to Zn-Mg alloy plating steel plate, has steel plate, Zn-Mg alloy layer, corruption
Losing product layer and chemical conversion treatment layer, above-mentioned Zn-Mg alloy layer is formed in the surface of above-mentioned steel plate, and containing 1.0~
The Mg of 70.0 mass %, remainder include Zn and impurity, and above-mentioned corrosion scales are formed in the table of above-mentioned Zn-Mg alloy layer
Face, and containing carbon atom number be 4~20 carboxylic acid Mg salt and carbon atom number be 4~20 alkanesulfonic acid Mg salt in
Any one, above-mentioned chemical conversion treatment layer is formed in the surface of above-mentioned corrosion scales, and contains in above-mentioned corrosion scales
The alkali metal salt for containing above-mentioned carboxylic acid in the case where the Mg salt of above-mentioned carboxylic acid, contains above-mentioned alkanesulfonic acid in above-mentioned corrosion scales
Mg salt in the case where contain above-mentioned alkanesulfonic acid alkali metal salt, wherein above-mentioned carboxylic contained by above-mentioned chemical conversion treatment layer
The alkali metal of the alkali metal salt of the alkali metal salt or above-mentioned alkanesulfonic acid of acid is selected from least one of Li, Na, K, Rb and Cs.
(2) the Zn-Mg alloy plating steel plate according to above-mentioned (1), wherein above-mentioned Zn-Mg alloy layer can be used
The composition of Mg containing 5.0~70.0 mass %.
(3) the Zn-Mg alloy plating steel plate according to above-mentioned (2), wherein above-mentioned Zn-Mg alloy layer can be used
The composition of Mg containing 10.0~70.0 mass %.
(4) the Zn-Mg alloy plating steel plate according to above-mentioned (3), wherein above-mentioned Zn-Mg alloy layer can be used
The composition of Mg containing 15.0~70.0 mass %.
(5) the Zn-Mg alloy plating steel plate according to either a program in above-mentioned (1)~(4), wherein can use upper
Stating Zn-Mg alloy layer also includes Al, the Si of 0.01~5.00 mass %, 1.0~5.0 matter selected from 0.3~25.0 mass %
Measure the composition of the Ca and at least one of 0.1~1.5 mass % Ni below of %.
(6) the Zn-Mg alloy plating steel plate according to either a program in above-mentioned (1)~(5), wherein can use upper
State the composition that alkali metal is Na.
(7) the Zn-Mg alloy plating steel plate according to above-mentioned (6), wherein above-mentioned chemical conversion treatment layer can be used
The content of the alkali metal salt of the alkali metal salt or above-mentioned alkanesulfonic acid of contained above-mentioned carboxylic acid is scaled 10~1500mg/m with Na2
Composition.
(8) the Zn-Mg alloy plating steel plate according to either a program in above-mentioned (1)~(7), wherein can use upper
The carbon atom number of carboxylic acid or above-mentioned alkanesulfonic acid is stated as 5~20 composition.
(9) the Zn-Mg alloy plating steel plate according to above-mentioned (8), wherein above-mentioned carboxylic acid or above-mentioned alkane can be used
The composition that the carbon atom number of sulfonic acid is 8~12.
(10) the Zn-Mg alloy plating steel plate according to either a program in above-mentioned (1)~(9), wherein can use upper
State the composition that carboxylic acid is saturated fatty acid.
(11) the Zn-Mg alloy plating steel plate according to either a program in above-mentioned (1)~(10), wherein can use
Composition of the above-mentioned chemical conversion treatment layer without containing fluoride, trivalent chromium and vanadium.
Invention effect
According to above-mentioned each scheme, it is capable of providing the chemical conversion treatment layer that has with excellent temporary rust prevention
Zn-Mg alloy plating steel plate.
Detailed description of the invention
Fig. 1 is the synoptic chart for indicating the layer structure of Zn-Mg alloy plating steel plate of present embodiment.
Specific embodiment
In the following, being illustrated referring to Zn-Mg alloy plating steel plate and manufacturing method of the attached drawing to embodiment.
(Zn-Mg alloy plating steel plate 1)
Fig. 1 is the synoptic chart for indicating the layer structure of Zn-Mg alloy plating steel plate 1.Zn-Mg alloy plating steel plate 1 has steel
Plate 2, Zn-Mg alloy layer 3, corrosion scales 4 and chemical conversion treatment layer 5, the Zn-Mg alloy layer 3 are formed in steel plate 2
Surface, and the Mg containing 10~70 mass %, remainder includes Zn and impurity, which is formed in Zn-
The surface of Mg alloy layer 3, and containing carbon atom number be 4~20 carboxylic acid Mg salt and carbon atom number be 4~20 chain
Any one of Mg salt of alkyl sulfonic acid, which is formed in the surface of corrosion scales 4, and produces in corrosion
Alkali metal salt containing carboxylic acid in the case where Mg salt of the nitride layer 4 containing carboxylic acid, in Mg salt of the corrosion scales 4 containing alkanesulfonic acid
In the case where the alkali metal salt containing alkanesulfonic acid.
For existing Zn-Mg alloy plating steel plate 1, when being formed with chemical conversion treatment on Zn-Mg alloy layer 3
When layer 5, blacking phenomenon, formation swelling are apparent.However, for the Zn-Mg alloy plating steel plate 1 of present embodiment
For, just at last in the case where being formed with chemical conversion treatment layer 5, by the non-stoichiometric oxide, the shakiness that inhibit Mg
Determine the formation of corrosion product, also can temporary rust prevention be significantly improved.
Details can be illustrated later, by making chemical conversion treatment layer 5 containing the carboxylic of carbon atom number 4~20
The alkali metal salt of acid or alkanesulfonic acid can obtain the effect of above-mentioned raising temporary rust prevention.In chemical conversion treatment operation
With under corrosive environment by Zn-Mg alloy layer 3 dissolution come Mg ion with by chemical conversion treatment layer 5 dissolution Lai carboxylate radical
Ion or alkanesulfonic acid radical ion combine, and generate as the Mg salt for the carboxylic acid for stablizing corrosion product or the Mg salt of alkanesulfonic acid.Institute
The Mg salt of the carboxylic acid of generation or the Mg salt of alkanesulfonic acid are deposited on Zn-Mg alloy layer 3 with stratiform, form corrosion scales 4.
The carboxylic acid or alkanesulfonic acid that carbon atom number is 4~20 form Mg salt and in conjunction with Mg, cladding especially erodable section.It is tied
Fruit is that Mg ion is inhibited by the dissolution of Zn-Mg alloy layer 3.
3 > of < Zn-Mg alloy layer
Zn-Mg alloy layer 3 contains Zn-Mg alloy, can contain in Al, Si, Ca and Ni as needed at least
More than one.In turn, can also Y, La containing 0~5 mass % or so, Ce, Ti, Cr, Fe, Co, V, Nb, Cu, Sn, Mn,
The elements such as Sr, Sb, Pb.
In the following, being illustrated to Mg, Al, Si, Ca, Ni content.In addition, the remainder other than these alloying elements
Include Zn and impurity.Here, impurity refer to due to raw material, manufacturing process a variety of causes and mixed ingredient, be so-called
Inevitable impurity.Remainder other than above-mentioned alloying element preferably comprises Zn and inevitable impurity.
The mass % of < Mg:1.0~70.0 >
Mg (magnesium) is the essential element that Zn-Mg alloy layer 3 is constituted together with Zn.In order to improve sacrifice corrosion protection, Zn-Mg
Mg content in alloy layer 3 is set as 1.0 mass % or more.It is preferred that make the 5 mass % of content or more of Mg, more preferably 10
Quality % or more, further preferably 15 mass % or more.On the other hand, when Mg content is more than 70.0 mass %, Mg phase exists
It being crystallized in Zn-Mg alloy layer 3, corrosion resistance is substantially reduced, so not preferably.
As described later, the Mg in Zn-Mg alloy layer 3 reacts with the carboxylic acid or alkanesulfonic acid for being coated on surface and generates Mg
Salt.The Mg salt when no Mg salt compared with there is the corrosion proof effect of Zn-Mg alloy-layer 3 of further increasing.By above-mentioned
It is preferred that it is the reason that Mg concentration, which further increases corrosion resistance, the effect for only increasing the obtained corrosion resistance of Mg concentration or more is played
Fruit.
When Zn-Mg alloy layer 3 does not contain Mg, the Mg salt of aftermentioned carboxylic acid or alkanesulfonic acid not will form, therefore not
It will form corrosion scales 4.It cannot get suitable corrosion resistance as a result, so not preferably.
The mass % of < Al:0.30~25.0 >
Al is the element that the corrosion resistance for the planar portions for making Zn-Mg alloy layer 3 improves.This effect in order to obtain, preferably makes
Al of the Zn-Mg alloy layer 3 containing 0.30 mass % or more.On the other hand, the case where Al content is more than 25.0 mass %
Under, it is sometimes prone to generate red rust, corrosion resistance reduces, therefore preferably makes 25.0 mass % of the upper limit or less.Chemically conversion processing
Layer 5 and the adaptation of Zn-Mg alloy layer 3 consider that Al content is more preferably 20.0 mass % or less.
The mass % of < Si:0.010~5.0 >
Si is the growth for the alloy phase for inhibiting the interface for being formed in steel plate 2 and Zn-Mg alloy layer 3 and prevents from processing
Property reduced element, preferably make Zn-Mg alloy layer 3 containing 0.010 mass % or more.It is more than 5.0 mass % in Si content
In the case where, it is easy to form bottom ash in plating bath, operability reduces, therefore preferably 5.0 mass % or less.
The mass % of < Ca:1.0~5.0 >
Ca is to be added to Zn-Mg alloy layer 3 as needed to improve the operability of hot-dip.It is manufacturing
When the Zn-Mg alloy plating steel plate 1 of present embodiment, use the alloy that contains Mg as plating bath.For containing for molten condition
The alloy of Mg forms suitable oxidation overlay film on surface, preferably adds the effective to the oxidation for preventing Mg of 1.0 mass % or more
Elements C a.Corrosion resistance is deteriorated sometimes in the case that Ca is more than the content, therefore preferably makes the Ca content in Zn-Mg alloy layer 3
The upper limit be 5.0 mass %.
The mass % of < Ni:0.10~1.50 >
Ni is the element of wellability when improving plating.When in the formation Zn-Mg Alloy Plating of steel plate 2 for being plated with Ni in advance
When layer 3, compared with when being formed with Zn-Mg alloy layer 3 on steel plate 2, the interface vicinity of steel plate 2 and Zn-Mg alloy layer 3
The formation of Al-Fe series intermetallic compound be inhibited, processability improves.On the other hand, in the case where more than the Ni content, have
When corrosion resistance can deteriorate, therefore preferably make Zn-Mg alloy layer 3 Ni content the upper limit 1.50%.Zn-Mg alloy layer 3
Ni content be preferably 0.10 mass % or more.
It, can also be in addition, Ni can both be set as being contained in plating alloy in the form of nickel preplating as described above
Be set as include in the form of an ingredient in plating alloy in advance.
Sometimes the element for constituting the steel plate 2 as base material is mixed into Zn-Mg alloy layer 3.In particular, by hot dipping method
When foring Zn-Mg alloy layer 3 or when implementing heat treatment after forming Zn-Mg alloy layer 3, element is in steel plate 2 and Zn-
The interface phase counterdiffusion of Mg alloy layer 3.In this case, Fe, Al, Zn etc. form alloy phase, thus steel plate 2 and Zn-
The adaptation of Mg alloy layer 3 improves.In addition, be formed in the interface of steel plate 2 and Zn-Mg alloy layer 3 comprising Fe,
The alloy of Al, Zn the meet corrosion resistance to Zn-Mg alloy layer 3 a possibility that affecting, is small.
Based on the above reasons, just at last plating bath do not include Fe in the case where, the Fe in Zn-Mg alloy layer 3 contains sometimes
Amount can also reach 2.0 mass % or so, but hardly affect to the corrosion resistance of Zn-Mg alloy layer 3.Therefore, Zn-
Mg alloy layer 3 can contain 2.0 mass % Fe below.
4 > of < corrosion scales
Zn-Mg alloy plating steel plate 1 has corrosion scales 4, the corrosion scales 4 on the surface of Zn-Mg alloy layer 3
Containing carbon atom number be 4~20 carboxylic acid Mg salt or carbon atom number be 4~20 alkanesulfonic acid Mg salt.
The Mg salt of carboxylic acid or alkanesulfonic acid that carbon atom number is 4~20 is to stablize corrosion product, makes Zn-Mg alloy plating
The corrosion resistance of steel plate 1 improves.
The alkali metal salt of carboxylic acid contained by chemical conversion treatment layer 5 or the alkali metal salt of alkanesulfonic acid are in chemical conversion treatment
Dissolution is ionized into aqueous solution under process and corrosive environment.Generate so obtained ion with it is molten by Zn-Mg alloy layer 3
Mg ionic reaction out thus generates the Mg salt of carboxylic acid contained by corrosion scales 4 or the Mg salt of alkanesulfonic acid.For life
At the Mg salt of carboxylic acid or the Mg salt of alkanesulfonic acid, the alkali metal salt of carboxylic acid contained by chemical conversion treatment layer 5 or alkanesulfonic acid
Alkali metal salt needs are present in the position to connect with Zn-Mg alloy layer 3.
In order to dissolve out alkali metal salt or the alkali metal salt of alkanesulfonic acid of carboxylic acid into aqueous solution and the Mg salt of carboxylic acid
Or the Mg salt of alkanesulfonic acid does not dissolve out in aqueous solution, need the alkali metal salt of carboxylic acid or alkanesulfonic acid and Mg salt solubility it
It is poor big.
In order to be deposited in the Mg salt of carboxylic acid or alkanesulfonic acid between chemical conversion treatment layer 5 and Zn-Mg alloy layer 3,
It needs to keep the solubility of the Mg salt of carboxylic acid or alkanesulfonic acid in water small.Therefore, make the carbon atom number 4 of carboxylic acid or alkanesulfonic acid
More than.
In order to dissolve out carboxylic acid or alkanesulfonic acid into aqueous solution in the form of ion, need to make carboxylic acid
Or the solubility of the alkali metal salt of alkanesulfonic acid in water is big.Therefore, make 20 or less the carbon atom number of carboxylic acid or alkanesulfonic acid.
In addition, the preferred carbon atom number of carboxylic acid or alkanesulfonic acid is 5~20, more preferably 8~12.
Carboxylic acid is not particularly limited as long as carbon atom number is 4~20, and saturated fatty acid, hydroxycarboxylic acid, benzene can be used
Carboxylic acid, dicarboxylic acids, unsaturated fatty acid etc.., it is preferable to use saturated fatty acid is as carboxylic acid from the viewpoint of economy.
It as the example of saturated fatty acid, can enumerate: butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, ten
Two alkanoic acids, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, Heptadecanoic acide, octadecanoid acid, arachic acid etc..
As the example of compound particularly preferred among saturated fatty acid, can enumerate: carbon atom number is 8~12
Octanoic acid, n-nonanoic acid, capric acid and dodecanoic acid.
It as the example of hydroxycarboxylic acid, can enumerate: malic acid, citric acid, tartaric acid etc..Benzene carboxylic acid can be enumerated
Out: benzoic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), salicylic acid, cinnamic acid etc..
It as the example of dicarboxylic acids, can enumerate: fumaric acid, maleic acid, succinic acid, glutaric acid, adipic acid, heptan two
Acid, suberic acid, azelaic acid, decanedioic acid etc..
As the example of unsaturated fatty acid, can enumerate: crotonic acid, sorbic acid, myristoleic acid, palmitoleic acid,
Cis- 6- gaidic acid (sapienic acid), oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, arachidonic acid, two
Eicosadienoic acid, eicosapentaenoic acid etc..
For alkanesulfonic acid, it is not particularly limited as long as carbon atom number is 4~20, butane sulfonic acid, 2- can be used
Butane sulfonic acid, pentanesulfonic acid, hexane sulfonic acid, perfluoroetane sulfonic acid, decane sulfonic acid, dodecane sulfonic acid, tetradecane sulfonic acid, hexadecane sulphur
Acid, octadecane sulfonic acid, eicosane sulfonic acid etc..
As the example of compound particularly preferred among alkanesulfonic acid, can enumerate: carbon atom number be 8~12 it is pungent
Alkyl sulfonic acid, decane sulfonic acid and dodecane sulfonic acid.
5 > of < chemical conversion treatment layer
Zn-Mg alloy plating steel plate 1 has chemical conversion treatment layer 5 on the surface of corrosion scales 4, at the chemical conversion
Reason layer 5 includes the alkali metal salt of carboxylic acid or alkanesulfonic acid and makes film component.It can also contain as needed in chemical conversion treatment layer 5
There are inhibitor ingredient and polyethylene wax.Chemical conversion treatment layer 5 is preferably so-called without chromate.
< alkali metal >
The alkali metal of the alkali metal salt of carboxylic acid contained by chemical conversion treatment layer 5 or alkanesulfonic acid is selected from Li, Na, K, Rb
At least one of with Cs.From the viewpoint of economy, preferred as alkali is only the Na (alkali metal salt of carboxylic acid or alkanesulfonic acid
The only Na salt of carboxylic acid or alkanesulfonic acid, not comprising the alkali metal salt other than Na salt).
The content of the alkali metal salt of carboxylic acid contained by chemical conversion treatment layer 5 or alkanesulfonic acid with Na meter be preferably 10~
1500mg/m2.10mg/m is lower than with Na meter in the content of carboxylic acid or the alkali metal salt of alkanesulfonic acid2In the case where, corrosion product
The amount of the Mg salt of carboxylic acid contained by layer 4 or alkanesulfonic acid is few, therefore cannot get suitable corrosion resistance sometimes.On the other hand, in carboxylic
The content of the alkali metal salt of acid or alkanesulfonic acid is more than 1500mg/m with Na meter2In the case where, chemical conversion treatment layer 5 sometimes
Uniformity deterioration.
It is dried to chemical conversion treatment layer 5 is impregnated in solution obtained from pure water, using obtained residue, and
Qualitative analysis and quantitative analysis are carried out by infrared spectrographic method or pyrolysis gas chromatography, it at this time can be to carboxylic acid or alkane
The carboxylic acid composition of the alkali metal salt of sulfonic acid or the substance of alkanesulfonic acid are identified.Using the residue obtained as described above,
And qualitative analysis and quantitative analysis are carried out by atomic absorption, identification and right can be carried out to alkali metal component at this time
Content is measured.Among alkali metal component, Na can also carry out qualitative analysis and quantitative analysis by acetic acid uranium salt method.
Chemical conversion treatment layer 5 can the Mg salt containing carboxylic acid or alkanesulfonic acid, but carboxylic contained by chemical conversion treatment layer 5
The Mg salt of acid or alkanesulfonic acid does not almost contribute raising corrosion resistance.
In addition, the carboxylic acid or alkanesulfonic acid in chemical conversion treatment layer 5 only exist in the form of alkali metal salt or Mg salt, carboxylic
Acid or alkanesulfonic acid do not exist in chemical conversion treatment layer 5 with simple substance.Similarly, alkali metal is in chemical conversion treatment layer 5
Do not exist with simple substance.
< makes film component >
As long as making film component is so-called without chromate, type is not particularly limited, can be used comprising resin
With the ingredient of one or both of metallic compound,
It as the example of resin, can enumerate: polyurethane resin, epoxy resin, acrylic resin, polyamide.
Metallic compound may include alkaline zirconium compounds, silicon compound etc..As the example of silicon compound, can enumerate: organic
Silicon compound, inorganic silicon compound.
In the following, as the example for preferably making film component, to containing alkaline zirconium compounds, phosphate cpd and cobalt compound
At least one of make film component (making film component A), containing organo-silicon compound and aqueous polyurethane resin with organic acid
Make film component (making film component B), comprising having one of silanol group, alkoxysilane group (alkoxysilyl group)
Or both ethylene-unsaturated carboxylic acid copolymer resins, silicon oxide particle and organic titanic compound film component of making (make film component
C it) is illustrated.
< makes film component A >
Making film component A includes at least one of alkaline zirconium compounds, phosphate cpd and cobalt compound and organic acid.
It as the example of alkaline zirconium compounds, can enumerate: there is [Zr (CO3)2(OH)2]2-、 [Zr(CO3)2(OH)2]2-
As cationic carbonic acid zirconium compounds, ammonium salt, sylvite, sodium salts for containing these cations etc..
As the example of phosphate cpd, can enumerate: phosphoric acid, its ammonium salt for example orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid,
Polyphosphoric acid, phytic acid, phosphonic acids, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate, potassium phosphate etc..
It as the example of cobalt compound, can enumerate: cobalt carbonate, cobalt nitrate, cobalt acetate etc..
It as the example of organic acid, can enumerate: glycolic, malic acid, tartaric acid, oxalic acid, citric acid, Vitamin C
Acid, lactic acid, dehydrogenation benzoic acid, hydroascorbic acid, gallic acid, tannic acid, phytic acid etc., are also possible to the ammonium of these organic acids
Salt.
< makes film component B >
Making film component B includes organo-silicon compound and aqueous polyurethane resin.
As the example of organo-silicon compound, can enumerate: by containing an amino in molecule silane coupling agent with
Compound obtained from silane coupling agent cooperation containing a glycidyl in molecule.
It as the silane coupling agent containing an amino in molecule, is not particularly limited, may be exemplified out: 3- aminopropan
Ethyl triethoxy silicane alkane, 3- TSL 8330 etc..As silane coupled containing glycidyl in molecule
Agent, may be exemplified out: 3- glycidoxypropyltrime,hoxysilane, 3- epoxy propoxy propyl triethoxysilane etc..
The number of functional group in organo-silicon compound is preferably two or more.The situation for being one in the number of functional group
Under, with the adaptation of Zn-Mg alloy layer 3, the self-crosslinking of organo-silicon compound and and polyether-polyurethane resin combination
Property reduce, chemical conversion treatment layer 5 can not be suitably formed sometimes.
The number of the functional group of organo-silicon compound can be analyzed by gas chromatography.
Aqueous polyurethane resin is preferably polyether system.Polyester polyurethane resin is hydrolyzed due to acid or alkali sometimes,
The easy to form hard and crisp epithelium of polycarbonate polyurethane has adaptation, the situation of the corrosion resistance of processing department difference when processing.
The structure of aqueous polyurethane resin can pass through the 3330cm in infrared measure-1(N-H is flexible), 1730cm-1
(C=O is flexible), 1530cm-1(C-N)、1250cm-1(C-O) characteristic absorption is analyzed.
< makes film component C >
Making film component C includes ethylene-unsaturation with any one of silanol group and alkoxysilane group or both
Carboxyl acid copolymer resin, silicon oxide particle and organic titanic compound.
Ethylene with any one of silanol group and alkoxysilane group or both-unsaturated carboxylic acid copolymer resins example
Such as obtained by reacting the aqueous solution for the copolymer resins for being dispersed with ethylene and unsaturated carboxylic acid with silane based compound.As
The example of unsaturated carboxylic acid, such as can enumerate: acrylic acid, methacrylic acid, maleic anhydride etc..
As silicon oxide particle, it is preferable to use colloidal silicon dioxide, fumed silica etc..
Organic titanic compound can for example enumerate: dipropoxy bis- (conjunction of triethanolamine root) titaniums, the bis- (diethyls of dipropoxy
Hydramine root closes) titanium, bis- (conjunction of the triethanolamine root) titaniums of dibutoxy, bis- (conjunction of the diethanol amine root) titaniums of dibutoxy, dipropoxy pair
Bis- (acetylacetonate) titaniums of (acetylacetonate) titanium, dibutoxy, dihydroxy bis- (lactate conjunction) titanium mono-ammoniums, dihydroxy
Bis- (lactate conjunction) the titanium di-ammonium salts of base, two oxygroup titanium of propane bis- (ethyl acetoacetates), oxo titanium bis- (single ammonium oxalates) etc..
Making film component C in addition to the above ingredients can also be comprising with any in silanol group and alkoxysilane group
The polyurethane resin of person or both.Polyurethane resin with any one of silanol group and alkoxysilane group or both can
To be obtained by reacting polyurethane prepolymer with the alkoxyl silicone alkanes and polyamines of active hydrogen-based.
In addition, just at last in the case where making film component C and including unsaturated carboxylic acid, when as described above to will be at chemical conversion
It, can be to carboxylic acid or chain when reason layer 5 is impregnated in solution obtained from pure water and is dried and analyzes obtained residue
The alkali metal salt of alkyl sulfonic acid is differentiated.
When chemical conversion treatment layer 5 contains selected from least one of fluoride, trivalent chromium and vanadium, carboxylic acid or alkane sulphur
The Mg salt of acid will not be precipitated suitably, therefore can not be suitably formed corrosion scales 4.Chemical conversion treatment layer 5 is excellent as a result,
Choosing does not contain fluoride, trivalent chromium and vanadium.
In addition, preferably making film component also not since chemical conversion treatment layer 5 does not contain fluoride, trivalent chromium and vanadium
Contain fluoride, trivalent chromium and vanadium.
Interface and corrosion scales 4 and chemical conversion treatment layer 5 with regard to Zn-Mg alloy layer 3 and corrosion scales 4
For interface, it can be shot by section of the SEM- backscattered electron image to Zn-Mg alloy plating steel plate 1, pass through back
The light and shade of scattered electron image identifies.
(manufacturing method of Zn-Mg alloy plating steel plate 1)
Zn-Mg alloy plating steel plate 1 is manufactured by following manner: by plating process steel plate 2 surface shape
At Zn-Mg alloy layer 3, corrosion scales 4 are formed simultaneously on the surface of Zn-Mg alloy layer 3 by chemical conversion treatment operation
And chemical conversion treatment layer 5 is formed on the surface of corrosion scales 4.
< plating process >
By plating process, Zn-Mg alloy layer 3 is formed on the surface of steel plate 2.
The method of plating process is not particularly limited, and well known hot dipping method can be used.Just Mg is added into Zn plating bath
Deng for, well known method can be used.
< chemical conversion treatment operation >
By chemical conversion treatment operation, corrosion scales 4 are formed on the surface of Zn-Mg alloy layer 3, and in corruption
The surface for losing product layer 4 forms chemical conversion treatment layer 5.
For chemical conversion treatment operation, no matter the type for making film component of chemical conversion treatment layer 5, will make
Water, organic solvent dissolve the alkali metal salt of carboxylic acid or alkanesulfonic acid and make (the hereinafter referred to as chemistry turn of solution obtained from film component
Change treatment fluid) it is coated on the surface of Zn-Mg alloy layer 3, it is allowed to drying.
The concentration of the alkali metal salt of carboxylic acid or alkanesulfonic acid in chemical conversion treatment solution is not particularly limited, from making carboxylic acid
Alkali metal salt or alkanesulfonic acid alkali metal salt dissolve out into aqueous solution and the Mg salt of the Mg salt of carboxylic acid or alkanesulfonic acid not
From the viewpoint of dissolving out in aqueous solution, preferably 0.1~10 mass %.
The coating method of chemical conversion treatment solution is not particularly limited, such as can use spray coating method, infusion process, roller coating
Method, curtain coating (shower ringer method), air knife method etc..
Chemical conversion treatment solution may include surfactant, defoaming agent, lubricant or filler.
After being coated with chemical conversion treatment solution, in order to make it is dry, chemical conversion treatment solution can be coated with
Zn-Mg alloy plating steel plate 1 is heated to 50 DEG C~200 DEG C.
Embodiment
In the following, enumerating examples and comparative examples of the present invention, and the present invention is specifically described, but the present invention is not limited to
They.
Using well known hot dipping method, the adhesion amount that every two sides is formed on the steel plate that plate thickness is 0.8mm is 180g/m2
(adhesion amount of every single side is respectively 90g/m2) Zn-Mg alloy layer.In turn, total is formed on Zn-Mg alloy layer
The corrosion scales and chemical conversion treatment layer that film thickness is 1.2 μm.
The forming method of corrosion scales and chemical conversion treatment layer is will be containing the carboxylic acid or alkanesulfonic acid of 1 mass %
Alkali metal salt, 20 mass % the chemical conversion treatment solution for making film component and water be coated on Zn-Mg alloy layer with stick.
By the alkali metal salt of carboxylic acid contained by the composition of Zn-Mg alloy layer, chemical conversion treatment layer or alkanesulfonic acid, make
Film component is shown in table 1~and 5.Use these Zn-Mg alloy plating steel plates as test film, and the index pair as temporary rust prevention
Anti-blackening (the also known as black property of resistance) and corrosion resistance are evaluated.Show the results of the evaluation table 6~10.
In addition, wrapping alkali metal salt carboxylic-containing acid in chemical conversion treatment layer for the example documented by the Tables 1 and 2；
It include the alkali metal salt of alkanesulfonic acid for the example documented by the table 3 and table 4, in chemical conversion treatment layer.Table 5 is remembered
For the comparative example of load, alkali metal salt carboxylic-containing acid is wrapped in chemical conversion treatment layer sometimes, sometimes the alkali gold comprising alkanesulfonic acid
Any one of both belong to salt, do not include sometimes also.
[anti-blackening]
Test film is stood using constant temperature and moisture test machine, and under the atmosphere that 80 DEG C and relative humidity (RH) are 85%
144 hours.The tone of test film for standing 144 hours front and backs is determined by spectral photometric colour measuring meter, to anti-blackening into
Evaluation is gone.Specifically, by spectral photometric colour measuring meter to expression CIE colour system (L*a*b*Colour system) lightness L*Value
It is determined, finds out as the L before standing 144 hours*The L of value and standing after 144 hours*The difference of value is (that is, (stand 144
L before hour*Value)-(L after standing for 144 hours*Value)) Δ L*。
According to Δ L*Value, as follows evaluates anti-blackening.It is qualification with " excellent ", " good ", "available".
It is excellent: Δ L*It is 5 or less
It is good: Δ L*It more than 5 and is 10 or less
Can: Δ L*It more than 10 and is 15 or less
Difference: Δ L*More than 15
With regard to above-mentioned L*For, it is worth the brighter color of bigger expression, is worth the darker color (black) of smaller expression.Based on quiet
Set the L of the test film of 144 hours front and backs*The difference delta L of value*, anti-blackening is evaluated, Δ L*It is worth smaller expression to stand
Also maintain afterwards more with stand before close lightness.In addition, Δ L*It is worth lightness after bigger expression is stood more (to become than decline before standing
Secretly).
[corrosion resistance]
By salt spraytest 240 hours to test film implementation based on JIS Z 2371, corrosion resistance is commented
Valence.Specifically, corrosion resistance is according to following benchmark to the corroded area rate (corroded area of test film after salt spraytest
With the ratio of surface area) determined.It is qualification with " excellent ", " good ", "available".
Excellent: corroded area rate is 0%
Good: corroded area rate is more than 0% and is 5% or less
Can: corroded area rate is more than 5% and is 30% or less
Difference: corroded area rate is more than 30%
In addition, the overall merit for combining above-mentioned two evaluation is also charged in table 6~10 together.Overall merit be with
" excellent ", " good ", "available" are qualification.
Table 6
| Anti-blackening | Corrosion resistance | Overall merit | |
| Example 1 | It is excellent | It is excellent | It is excellent |
| Example 2 | It is excellent | It is excellent | It is excellent |
| Example 3 | It is excellent | It is excellent | It is excellent |
| Example 4 | It is excellent | It is excellent | It is excellent |
| Example 5 | It is excellent | It is excellent | It is excellent |
| Example 6 | It is excellent | It is excellent | It is excellent |
| Example 7 | It is excellent | It is excellent | It is excellent |
| Example 8 | It is good | It is good | It is good |
| Example 9 | It is good | It is good | It is good |
| Example 10 | It is excellent | It is good | It is excellent |
| Example 11 | It is excellent | It is good | It is excellent |
| Example 12 | It is excellent | It is excellent | It is excellent |
| Example 13 | It is excellent | It is excellent | It is excellent |
| Example 14 | It is excellent | It is excellent | It is excellent |
| Example 15 | It is good | It is good | It is good |
| Example 16 | It is good | It is excellent | It is excellent |
| Example 17 | It is excellent | It is excellent | It is excellent |
| Example 18 | It is excellent | It is excellent | It is excellent |
| Example 19 | It is excellent | It is excellent | It is excellent |
| Example 20 | It is good | It is good | It is good |
| Example 21 | It is good | It is good | It is good |
| Example 22 | It is excellent | It is excellent | It is excellent |
| Example 23 | It is excellent | It is excellent | It is excellent |
| Example 24 | It is excellent | It is excellent | It is excellent |
| Example 25 | It is excellent | It is good | It is good |
| Example 26 | It is excellent | It is good | It is good |
Table 7
| Anti-blackening | Corrosion resistance | Overall merit | |
| Example 27 | It is good | It can | It is good |
| Example 28 | It is good | It can | It is good |
| Example 29 | It is good | It can | It is good |
| Example 30 | It is good | It can | It is good |
| Example 31 | It can | It can | It is good |
| Example 32 | It can | It is good | It is good |
| Example 33 | It is good | It can | It is good |
| Example 34 | It is good | It can | It is good |
| Example 35 | It is good | It can | It is good |
| Example 36 | It is good | It can | It is good |
| Example 37 | It is good | It can | It is good |
| Example 38 | It can | It can | It can |
| Example 39 | It can | It can | It can |
| Example 40 | It can | It can | It can |
| Example 41 | It can | It can | It can |
| Example 42 | It can | It can | It can |
| Example 43 | It can | It can | It can |
| Example 44 | It can | It can | It can |
| Example 45 | It can | It can | It can |
| Example 46 | It can | It can | It can |
| Example 47 | It can | It can | It can |
| Example 48 | It can | It can | It can |
| Example 49 | It can | It can | It can |
| Example 50 | It can | It can | It can |
| Example 51 | It can | It can | It can |
| Example 52 | It can | It can | It can |
Table 8
| Anti-blackening | Corrosion resistance | Overall merit | |
| Example 53 | It is excellent | It is excellent | It is excellent |
| Example 54 | It is excellent | It is excellent | It is excellent |
| Example 55 | It is excellent | It is excellent | It is excellent |
| Example 56 | It is excellent | It is excellent | It is excellent |
| Example 57 | It is excellent | It is excellent | It is excellent |
| Example 58 | It is excellent | It is excellent | It is excellent |
| Example 59 | It is excellent | It is excellent | It is excellent |
| Example 60 | It is good | It is good | It is good |
| Example 61 | It is good | It is good | It is good |
| Example 62 | It is excellent | It is good | It is excellent |
| Example 63 | It is excellent | It is good | It is excellent |
| Example 64 | It is excellent | It is excellent | It is excellent |
| Example 65 | It is excellent | It is excellent | It is excellent |
| Example 66 | It is excellent | It is excellent | It is excellent |
| Example 67 | It is good | It is good | It is good |
| Example 68 | It is good | It is excellent | It is excellent |
| Example 69 | It is excellent | It is excellent | It is excellent |
| Example 70 | It is excellent | It is excellent | It is excellent |
| Example 71 | It is excellent | It is excellent | It is excellent |
| Example 72 | It is good | It is good | It is good |
| Example 73 | It is good | It is good | It is good |
| Example 74 | It is excellent | It is excellent | It is excellent |
| Example 75 | It is excellent | It is excellent | It is excellent |
| Example 76 | It is excellent | It is excellent | It is excellent |
| Example 77 | It is excellent | It is good | It is good |
| Example 78 | It is excellent | It is good | It is good |
Table 9
| Anti-blackening | Corrosion resistance | Overall merit | |
| Example 79 | It is good | It can | It is good |
| Example 80 | It is good | It can | It is good |
| Example 81 | It is good | It can | It is good |
| Example 82 | It is good | It can | It is good |
| Example 83 | It can | It can | It is good |
| Example 84 | It can | It is good | It is good |
| Example 85 | It is good | It can | It is good |
| Example 86 | It is good | It can | It is good |
| Example 87 | It is good | It can | It is good |
| Example 88 | It is good | It can | It is good |
| Example 89 | It is good | It can | It is good |
| Example 90 | It can | It can | It can |
| Example 91 | It can | It can | It can |
| Example 92 | It can | It can | It can |
| Example 93 | It can | It can | It can |
| Example 94 | It can | It can | It can |
| Example 95 | It can | It can | It can |
| Example 96 | It can | It can | It can |
| Example 97 | It can | It can | It can |
| Example 98 | It can | It can | It can |
| Example 99 | It can | It can | It can |
| Example 100 | It can | It can | It can |
| Example 101 | It can | It can | It can |
| Example 102 | It can | It can | It can |
| Example 103 | It can | It can | It can |
| Example 104 | It can | It can | It can |
Table 10
| Anti-blackening | Corrosion resistance | Overall merit | |
| Comparative example 1 | Difference | Difference | Difference |
| Comparative example 2 | Difference | Difference | Difference |
| Comparative example 3 | Difference | Difference | Difference |
| Comparative example 4 | Difference | Difference | Difference |
| Comparative example 5 | Difference | Difference | Difference |
| Comparative example 6 | Difference | Difference | Difference |
| Comparative example 7 | Difference | Difference | Difference |
| Comparative example 8 | Difference | Difference | Difference |
| Comparative example 9 | Difference | Difference | Difference |
| Comparative example 10 | Difference | Difference | Difference |
| Comparative example 11 | Difference | Difference | Difference |
| Comparative example 12 | Difference | Difference | Difference |
| Comparative example 13 | Difference | Difference | Difference |
| Comparative example 14 | Difference | Difference | Difference |
| Comparative example 15 | Difference | Difference | Difference |
| Comparative example 16 | Difference | Difference | Difference |
| Comparative example 17 | Difference | Difference | Difference |
| Comparative example 18 | Difference | Difference | Difference |
As shown in table 6~9, example of the present invention is anti-blackening and corrosion resistance excellent, and overall merit is qualification.
And Comparative Examples 1 and 2 shown in table 10,5 and 6 be the Mg content of alloy layer out of the range of the present invention, resistance to blacking
Property, corrosion resistance and overall merit are imperfect.In addition, comparative example 1 and 5 be alloy layer Mg content more than comparative example.Just
For comparative example 1 and 5, although being formed with corrosion scales, anti-blackening, corrosion resistance and overall merit are imperfect.Its
Reason may be considered: although formation of corrosion scales itself has occurred in comparative example 1 and 5, be present in the Mg phase of plating
Corrosion it is fast, can not inhibit to corrode.
For comparative example 3,4,7 and 8, the carbon atom number of carboxylic acid or alkanesulfonic acid out of the range of the present invention, resistance to blacking
Property, corrosion resistance and overall merit are imperfect.
It is anti-blackening, resistance to due to not including the alkali metal salt of carboxylic acid or alkanesulfonic acid for comparative example 9~12
Corrosion and overall merit are imperfect.
For comparative example 13, due to not implementing plating on the steel plate, anti-blackening, corrosion resistance and overall merit are
It is imperfect.Due to not implementing plating on the steel plate in comparative example 13, the supply source of Mg ion is not present.Thus, it is possible to
Think: due to the Mg salt of not formed carboxylic acid, corrosion scales could not be formed, therefore anti-blackening, corrosion resistance and overall merit are
It is imperfect.
For comparative example 14 and 15, although comprising carboxylic acid or alkanesulfonic acid, due to not including carboxylic acid or alkanesulfonic acid
Alkali metal salt, therefore anti-blackening, corrosion resistance and overall merit are imperfect.
Comparative example 16 is the comparative example made film component and contain trivalent chromium, and anti-blackening, corrosion resistance and overall merit are inadequate
Alright.
Comparative example 17 is the comparative example made film component and contain vanadium, and anti-blackening, corrosion resistance and overall merit are imperfect.
Comparative example 18 is the comparative example made film component and contain fluorine, and anti-blackening, corrosion resistance and overall merit are imperfect.
As reason undesirable when making film component and containing trivalent chromium, vanadium or fluorine, it is believed that be because, make film at
Divide containing in the case where trivalent chromium, vanadium or fluorine, the Mg salt of carboxylic acid or alkanesulfonic acid will not be precipitated suitably, can not be suitably formed
Corrosion scales.
Industrial availability
According to said one embodiment, it is capable of providing and has chemical conversion treatment with excellent temporary rust prevention
The Zn-Mg alloy plating steel plate of layer.
Symbol description
1 Zn-Mg alloy plating steel plate
2 steel plates
3 Zn-Mg alloy layers
4 corrosion scales
5 chemical conversion treatment layers
Claims (11)
1. a kind of Zn-Mg alloy plating steel plate has steel plate, Zn-Mg alloy layer, corrosion scales and chemical conversion treatment
Layer,
The Zn-Mg alloy layer is formed in the surface of the steel plate, and the Mg containing 1.0~70.0 mass %, remainder
Subpackage contains Zn and impurity,
The corrosion scales are formed in the surface of the Zn-Mg alloy layer, and the carboxylic acid for being 4~20 containing carbon atom number
Mg salt and carbon atom number be 4~20 any one of the Mg salt of alkanesulfonic acid,
The chemical conversion treatment layer is formed in the surface of the corrosion scales, and contains in the corrosion scales described
The alkali metal salt for containing the carboxylic acid in the case where the Mg salt of carboxylic acid, contains the Mg of the alkanesulfonic acid in the corrosion scales
Contain the alkali metal salt of the alkanesulfonic acid in the case where salt,
Wherein, the alkali metal salt of the alkali metal salt or alkanesulfonic acid of the carboxylic acid contained by the chemical conversion treatment layer
Alkali metal is selected from least one of Li, Na, K, Rb and Cs.
2. Zn-Mg alloy plating steel plate according to claim 1, which is characterized in that the Zn-Mg alloy layer contains
The Mg of 5.0~70.0 mass %.
3. Zn-Mg alloy plating steel plate according to claim 2, which is characterized in that the Zn-Mg alloy layer contains
The Mg of 10.0~70.0 mass %.
4. Zn-Mg alloy plating steel plate according to claim 3, which is characterized in that the Zn-Mg alloy layer contains
The Mg of 15.0~70.0 mass %.
5. Zn-Mg alloy plating steel plate according to claim 1 or 2, which is characterized in that the Zn-Mg alloy layer is also
Include the Ca and 0.1~1.5 selected from the Al of 0.3~25.0 mass %, the Si of 0.01~5.00 mass %, 1.0~5.0 mass %
At least one of quality % Ni below.
6. Zn-Mg alloy plating steel plate according to claim 1 or 2, which is characterized in that the alkali metal is Na.
7. Zn-Mg alloy plating steel plate according to claim 6, which is characterized in that contained by the chemical conversion treatment layer
The alkali metal salt of the carboxylic acid or the content of alkali metal salt of the alkanesulfonic acid 10~1500mg/m is scaled with Na2。
8. Zn-Mg alloy plating steel plate according to claim 1 or 2, which is characterized in that the carboxylic acid or the alkane sulphur
The carbon atom number of acid is 5~20.
9. Zn-Mg alloy plating steel plate according to claim 8, which is characterized in that the carboxylic acid or the alkanesulfonic acid
Carbon atom number be 8~12.
10. Zn-Mg alloy plating steel plate according to claim 1 or 2, which is characterized in that the carboxylic acid is saturated fat
Acid.
11. Zn-Mg alloy plating steel plate according to claim 1 or 2, which is characterized in that the chemical conversion treatment layer
Without containing fluoride, trivalent chromium and vanadium.
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| JP2015-078585 | 2015-04-07 | ||
| JP2015078585 | 2015-04-07 | ||
| PCT/JP2016/061404 WO2016163461A1 (en) | 2015-04-07 | 2016-04-07 | Zn-mg alloy coated steel sheet |
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| CN107429405B true CN107429405B (en) | 2019-09-10 |
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| JP (1) | JP6070914B1 (en) |
| KR (1) | KR101986930B1 (en) |
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| KR102175582B1 (en) * | 2018-12-19 | 2020-11-06 | 주식회사 포스코 | Heterogeneous plated steel sheet having excellent workbility and corrosion resistance, and method for manufacturing the same |
| TWI820931B (en) * | 2022-03-03 | 2023-11-01 | 日商日本製鐵股份有限公司 | Surface treated steel plate |
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| CN1252456A (en) * | 1998-10-28 | 2000-05-10 | 日本巴卡莱近估股份有限公司 | Composition for metal surface treatment and surface treating liquid and surface treating method |
| CN1479806A (en) * | 2000-12-04 | 2004-03-03 | ������������ʽ���� | Zinc-based metal plated steel and method for production thereof |
| CN101435078A (en) * | 2007-11-13 | 2009-05-20 | Posco公司 | Non-chrome resin composition, method for processing steel plate surface and steel plate |
| CN103069047A (en) * | 2010-06-18 | 2013-04-24 | 日新制钢株式会社 | Chemical conversion coated plated steel sheet and method for producing same |
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| JPH0825553A (en) * | 1994-07-16 | 1996-01-30 | Sumitomo Metal Ind Ltd | Film-treated al-zn alloy plated steel sheet |
| JPH11193452A (en) * | 1998-01-05 | 1999-07-21 | Nippon Steel Corp | Production of hot dip zinc-magnesium-aluminum steel sheet, and hot dipping bath and hot dip zinc-magnesium -aluminum coated steel sheet |
| JP3927167B2 (en) * | 2003-11-14 | 2007-06-06 | 日新製鋼株式会社 | Molten Mg-containing zinc alloy plated steel sheet with excellent corrosion resistance and blackening resistance |
| JP2007023309A (en) * | 2005-07-12 | 2007-02-01 | Nisshin Steel Co Ltd | Hot-dip zinc alloy plated steel sheet having excellent corrosion resistance |
| CN102089458B (en) * | 2008-07-16 | 2012-12-26 | 日本帕卡濑精株式会社 | Aqueous metal-surface-treating agent and surface-treated metal material |
| JP5332848B2 (en) | 2009-04-10 | 2013-11-06 | 新日鐵住金株式会社 | Organic composite Mg-based plated steel sheet |
| JP5505053B2 (en) | 2010-04-09 | 2014-05-28 | 新日鐵住金株式会社 | Organic composite Mg-based plated steel sheet |
| JP2012219365A (en) * | 2011-04-13 | 2012-11-12 | Kobe Steel Ltd | Manufacturing method of metallic material for plastic woking and worked metal product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1252456A (en) * | 1998-10-28 | 2000-05-10 | 日本巴卡莱近估股份有限公司 | Composition for metal surface treatment and surface treating liquid and surface treating method |
| CN1479806A (en) * | 2000-12-04 | 2004-03-03 | ������������ʽ���� | Zinc-based metal plated steel and method for production thereof |
| CN101435078A (en) * | 2007-11-13 | 2009-05-20 | Posco公司 | Non-chrome resin composition, method for processing steel plate surface and steel plate |
| CN103069047A (en) * | 2010-06-18 | 2013-04-24 | 日新制钢株式会社 | Chemical conversion coated plated steel sheet and method for producing same |
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| JP6070914B1 (en) | 2017-02-01 |
| JPWO2016163461A1 (en) | 2017-04-27 |
| WO2016163461A1 (en) | 2016-10-13 |
| MY186250A (en) | 2021-06-30 |
| KR20170120165A (en) | 2017-10-30 |
| CN107429405A (en) | 2017-12-01 |
| KR101986930B1 (en) | 2019-06-07 |
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