CN107429405A - Zn Mg alloy plating steel plates - Google Patents
Zn Mg alloy plating steel plates Download PDFInfo
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- CN107429405A CN107429405A CN201680019274.2A CN201680019274A CN107429405A CN 107429405 A CN107429405 A CN 107429405A CN 201680019274 A CN201680019274 A CN 201680019274A CN 107429405 A CN107429405 A CN 107429405A
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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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- 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
- 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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- 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
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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
The Zn Mg alloy plating steel plates of the present invention possess steel plate,Zn Mg alloy layers,Corrosion scales and chemical conversion treatment layer,Above-mentioned Zn Mg alloy layers are formed on the surface of above-mentioned steel plate,And contain 1.0~70.0 mass % Mg,Remainder includes Zn and impurity,Above-mentioned corrosion scales are formed on the surface of above-mentioned Zn Mg alloy layers,And any one of Mg salt of alkanesulfonic acid that the Mg salt for the carboxylic acid for being 4~20 containing carbon number is 4~20 with carbon number,Above-mentioned chemical conversion treatment layer is formed on 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 the alkali metal salt of above-mentioned alkanesulfonic acid in the case where above-mentioned corrosion scales contain the Mg salt of above-mentioned alkanesulfonic acid,Wherein,The alkali metal of the alkali metal salt of above-mentioned carboxylic acid contained by above-mentioned chemical conversion treatment layer or the alkali metal salt of above-mentioned alkanesulfonic acid is selected from Li,Na,K,At least one of Rb and Cs.
Description
Technical field
The present invention relates to Zn-Mg alloy plating steel plates.
The application based on April 7th, 2015 Japanese publication Patent 2015-78585 CLAIM OF PRIORITYs, and by it
Appearance is incorporated herein.
Background technology
For the steel for automobile, household electrical appliances, building materials etc., in order that corrosion resistance improves and implements plating sometimes.It is logical
The coating crossed plating and formed in steel surface be roughly divided into barrier anticorrosion plating stratotype and sacrifice anticorrosion plating stratotype both,
Wherein, barrier anticorrosion plating stratotype is from external environment condition masking base metal (steel), and it is to pass through ratio to sacrifice anticorrosion plating stratotype
Base metal more preferentially corrodes carries 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-term use of surface forms coated steel plate (hereinafter referred to as coated steel sheet), to the surface of coated steel sheet
(that is, the surface of coating) implement the surface treatment such as application processing, chemical conversion treatment or lamination process, thus carries rust-preventing characteristic
It is high.The main purpose of chemical conversion treatment is：Improve and processing and assembling phase of the coated steel sheet untill as end article
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 document 1~4, in order to improve corrosion resistance, propose in recent years the surface of steel plate formed with containing
The Zn-Mg alloy platings steel plate of the coating of Zn-Mg alloys replaces Zn coated steel sheets.Zn-Mg alloy plating steel plates are made by Mg
The corrosion product being created under corrosive environment stabilizes, and thus has the corrosion resistance more excellent than Zn coated steel sheet.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2005-146340 publications
Patent document 2：Japanese Unexamined Patent Publication 2007-23309 publications
Patent document 3：Japanese Unexamined Patent Publication 2010-248541 publications
Patent document 4：Japanese Unexamined Patent Publication 2011-219823 publications
The content of the invention
Invent problem to be solved
As described above, Zn-Mg alloy platings steel plate has the corrosion resistance more excellent than Zn coated steel sheet.However, to Zn-
In the case that Mg alloy plating steel plates implement the chemical conversion treatment for Zn coated steel sheets, Zn-Mg alloy plating steel be present
The situation that the situation (hereinafter referred to as blacking phenomenon) of plate color blackening, 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 can consider be due to by coating dissolution Lai Mg ions form non-stoichiometric oxide and
Caused by, formed swelling can consider be due to by coating dissolution Lai Mg ions be continuously formed unstable corrosion product
Caused by and.
The present invention is to complete in view of the foregoing, its object is to：Tool with excellent temporary rust prevention is provided
Have the Zn-Mg alloy plating steel plates of chemical conversion treatment layer.
The means used to solve the problem
Inventor hereins to by by the dissolution of Zn-Mg alloys come Mg ions form stable corrosion product to improve
The method of temporary rust prevention is studied.As a result, inventor hereins are found that：By making chemical conversion treatment
The layer solubility containing Mg salt is small, alkali metal salt solubility is big material, the Mg come under corrosive environment by coating dissolution and
By chemical conversion treatment layer dissolution Lai material combine, form stable corrosion product, coating coated with the stable corrosion product
Erodable section, can suppress blacking phenomenon, formed swelling.
In addition, inventor hereins make further research, and it is found that the interim of Zn-Mg alloy plating steel plates
Rust-preventing characteristic by make alkali metal salt that chemical conversion treatment layer contains the carboxylic acid that carbon number is 4~20 or carbon number be 4~
The alkali metal salt of 20 alkanesulfonic acid and significantly improve, so as to complete the present invention.
The present invention is in order to solve the above problems to realize above-mentioned purpose, using following scheme.
(1) scheme of the invention is related to Zn-Mg alloy plating steel plates, and it possesses steel plate, Zn-Mg alloy layers, corruption
Product layer and chemical conversion treatment layer are lost, above-mentioned Zn-Mg alloy layers are formed on the surface of above-mentioned steel plate, and containing 1.0~
70.0 mass % Mg, remainder include Zn and impurity, and above-mentioned corrosion scales form the table in above-mentioned Zn-Mg alloy layers
Face, and the Mg salt for the carboxylic acid for being 4~20 containing carbon number and carbon number be 4~20 alkanesulfonic acid Mg salt in appoint
One, above-mentioned chemical conversion treatment layer is formed to be contained on the surface of above-mentioned corrosion scales, and in above-mentioned corrosion scales
Contain the alkali metal salt of above-mentioned carboxylic acid in the case of stating the Mg salt of carboxylic acid, contain above-mentioned alkanesulfonic acid in above-mentioned corrosion scales
Contain the alkali metal salt of above-mentioned alkanesulfonic acid in the case of Mg salt, wherein, the above-mentioned carboxylic acid contained by above-mentioned chemical conversion treatment layer
Alkali metal salt or above-mentioned alkanesulfonic acid alkali metal salt alkali metal be selected from least one of Li, Na, K, Rb and Cs.
(2) the Zn-Mg alloy plating steel plates according to above-mentioned (1), wherein it is possible to using above-mentioned Zn-Mg alloy layers
The composition of Mg containing 5.0~70.0 mass %.
(3) the Zn-Mg alloy plating steel plates according to above-mentioned (2), wherein it is possible to using above-mentioned Zn-Mg alloy layers
The composition of Mg containing 10.0~70.0 mass %.
(4) the Zn-Mg alloy plating steel plates according to above-mentioned (3), wherein it is possible to using above-mentioned Zn-Mg alloy layers
The composition of Mg containing 15.0~70.0 mass %.
(5) the Zn-Mg alloy plating steel plates according to either a program in above-mentioned (1)~(4), wherein it is possible to using upper
Zn-Mg alloy layers are stated also to include selected from 0.3~25.0 mass % Al, 0.01~5.00 mass % Si, 1.0~5.0 matter
Measure at least one of % Ca and below 0.1~1.5 mass % Ni composition.
(6) the Zn-Mg alloy plating steel plates according to either a program in above-mentioned (1)~(5), wherein it is possible to using upper
State the composition that alkali metal is Na.
(7) the Zn-Mg alloy plating steel plates according to above-mentioned (6), wherein it is possible to using above-mentioned chemical conversion treatment layer
The content of the alkali metal salt of contained above-mentioned carboxylic acid or the alkali metal salt of above-mentioned alkanesulfonic acid is scaled 10~1500mg/m with Na2
Composition.
(8) the Zn-Mg alloy plating steel plates according to either a program in above-mentioned (1)~(7), wherein it is possible to using upper
The carbon number for stating carboxylic acid or above-mentioned alkanesulfonic acid is 5~20 composition.
(9) the Zn-Mg alloy plating steel plates according to above-mentioned (8), wherein it is possible to using above-mentioned carboxylic acid or above-mentioned alkane
The carbon number of sulfonic acid is 8~12 composition.
(10) the Zn-Mg alloy plating steel plates according to either a program in above-mentioned (1)~(9), wherein it is possible to using upper
State the composition that carboxylic acid is saturated fatty acid.
(11) the Zn-Mg alloy plating steel plates according to either a program in above-mentioned (1)~(10), wherein it is possible to using
Above-mentioned chemical conversion treatment layer does not contain the composition of fluoride, trivalent chromium and vanadium.
Invention effect
According to above-mentioned each scheme, using the teaching of the invention it is possible to provide have possessing for excellent temporary rust prevention to have chemical conversion treatment layer
Zn-Mg alloy plating steel plates.
Brief description of the drawings
Fig. 1 is the synoptic chart of the Rotating fields for the Zn-Mg alloy plating steel plates for representing present embodiment.
Embodiment
Below, the Zn-Mg alloy platings steel plate and manufacture method of embodiment are illustrated referring to the drawings.
(Zn-Mg alloy platings steel plate 1)
Fig. 1 is the synoptic chart for the Rotating fields for representing Zn-Mg alloy platings steel plate 1.Zn-Mg alloy platings steel plate 1 possesses steel
Plate 2, Zn-Mg alloy layers 3, corrosion scales 4 and chemical conversion treatment layer 5, the Zn-Mg alloy layers 3 are formed in steel plate 2
Surface, and containing 10~70 mass % Mg, remainder includes Zn and impurity, and the corrosion scales 4 are formed to be closed in Zn-Mg
The surface of gold plate 3, and the alkanesulfonic acid that the Mg salt for the carboxylic acid for being 4~20 containing carbon number is 4~20 with carbon number
Any one of Mg salt, the chemical conversion treatment layer 5 is formed on the surface of corrosion scales 4, and is contained in corrosion scales 4
There is the alkali metal salt containing carboxylic acid in the case of the Mg salt of carboxylic acid, in the situation of Mg salt of the corrosion scales 4 containing alkanesulfonic acid
Under the alkali metal salt containing alkanesulfonic acid.
For existing Zn-Mg alloy platings steel plate 1, when on Zn-Mg alloy layers 3 formed with chemical conversion treatment
During layer 5, blacking phenomenon, formation swelling are apparent.However, the Zn-Mg alloy platings steel plate 1 for present embodiment
For, just at last in the case of formed with chemical conversion treatment layer 5, by the non-stoichiometric oxide, the shakiness that suppress Mg
Determine the formation of corrosion product, also temporary rust prevention can be significantly improved.
Details can illustrate later, by making chemical conversion treatment layer 5 containing the carboxylic that carbon number is 4~20
The alkali metal salt of acid or alkanesulfonic acid, the effect of above-mentioned raising temporary rust prevention can be obtained.In chemical conversion treatment operation
With under corrosive environment by the dissolution of Zn-Mg alloy layers 3 Lai Mg ions with by the dissolution of chemical conversion treatment layer 5 Lai carboxylate radical from
Son 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.Give birth to
Into the Mg salt of carboxylic acid or the Mg salt of alkanesulfonic acid be deposited in stratiform on Zn-Mg alloy layers 3, formed corrosion scales 4.Carbon
The carboxylic acid or alkanesulfonic acid that atomicity is 4~20 form Mg salt, cladding particularly erodable section by being combined with Mg.Its result
It is that Mg ions are inhibited by the dissolution of Zn-Mg alloy layers 3.
The ＞ of ＜ Zn-Mg alloy layers 3
Zn-Mg alloy layers 3 contain Zn-Mg alloys, can contain as needed in Al, Si, Ca and Ni at least
More than one.And then can also Y, La containing 0~5 mass % or so, Ce, Ti, Cr, Fe, Co, V, Nb, Cu, Sn, Mn, Sr,
The elements such as Sb, Pb.
Below, Mg, Al, Si, Ca, Ni content are illustrated.In addition, the remainder in addition to these alloying elements
Include Zn and impurity.Here, impurity refer to due to raw material, manufacturing process a variety of causes and mixed composition, it is so-called
Inevitable impurity.Remainder in addition to above-mentioned alloying element preferably comprises Zn and inevitable impurity.
＜ Mg：1.0~70.0 mass % ＞
Mg (magnesium) is the essential element that Zn-Mg alloy layers 3 are formed together with Zn.In order to improve sacrifice corrosion protection, Zn-Mg
Mg contents in alloy layer 3 are set as more than 1.0 mass %.It is preferred that the content for making Mg is more than 5 mass %, more preferably 10
More than quality %, more preferably more than 15 mass %.On the other hand, when Mg contents are more than 70.0 mass %, Mg phases exist
Being crystallized in Zn-Mg alloy layers 3, corrosion resistance substantially reduces, so it is not preferred.
As described later, the Mg in Zn-Mg alloy layers 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 the further corrosion proof effect for improving Zn-Mg alloy-layers 3.By above-mentioned
It is preferred that it is the reason that Mg concentration, which makes corrosion resistance further improve, the effect more than corrosion resistance obtained by performance only increase Mg concentration
(Tanaka's additional information).
When Zn-Mg alloy layers 3 do not contain Mg, the Mg salt of carboxylic acid or alkanesulfonic acid described later will not be formed, therefore not
Corrosion scales 4 can be formed.Thus, it cannot get suitable corrosion resistance, so it is not preferred.
＜ Al：0.30~25.0 mass % ＞
Al is the element that the corrosion resistance for the planar portions for making Zn-Mg alloy layers 3 improves.In order to obtain this effect, preferably make
Al of the Zn-Mg alloy layers 3 containing more than 0.30 mass %.On the other hand, in the case where Al content is more than 25.0 mass %,
It is sometimes prone to produce red rust, corrosion resistance reduces, therefore preferably makes the upper limit be below 25.0 mass %.Chemically conversion processing layer 5
Consider that Al content is more preferably below 20.0 mass % with the adaptation of Zn-Mg alloy layers 3.
＜ Si：0.010~5.0 mass % ＞
Si is to suppress to be formed at the growth of the alloy phase of the interface of steel plate 2 and Zn-Mg alloy layers 3 and prevent from processing
The element of the reduction of property, preferably makes Zn-Mg alloy layers 3 contain more than 0.010 mass %.In Si contents more than 5.0 mass %
In the case of, bottom ash is easily formed in plating bath, operability reduces, therefore preferably below 5.0 mass %.
＜ Ca：1.0~5.0 mass % ＞
Ca is to be added to Zn-Mg alloy layers 3 as needed to improve the operational of hot-dip.In manufacture originally
During the Zn-Mg alloy plating steel plates 1 of embodiment, plating bath is used as using the alloy for containing Mg.Contain Mg for molten condition
Alloy suitable oxidation overlay film is formed on surface, the oxidation to preventing Mg preferably added more than 1.0 mass % is effectively first
Plain Ca.Ca deteriorates corrosion resistance sometimes in the case of more than content, therefore preferably makes the Ca contents in Zn-Mg alloy layers 3
The upper limit is 5.0 mass %.
＜ Ni：0.10~1.50 mass % ＞
Ni is the element of wellability when improving plating.When be plated with advance Ni steel plate 2 formed Zn-Mg alloy layers
When 3, compared with when on steel plate 2 formed with Zn-Mg alloy layers 3, at the near interface of steel plate 2 and Zn-Mg alloy layers 3
The formation of Al-Fe series intermetallic compounds is inhibited, and processability improves.On the other hand, in the case of more than Ni contents, sometimes
Corrosion resistance can deteriorate, thus preferably make Zn-Mg alloy layers 3 Ni contents the upper limit be 1.50%.Zn-Mg alloy layers 3
Ni contents are preferably more than 0.10 mass %.
In addition, Ni can both be set as being contained in plating alloy in the form of nickel preplating as described above, can also
It is set as including in the form of a composition in plating alloy in advance.
Sometimes the element for forming the steel plate 2 as mother metal is mixed into Zn-Mg alloy layers 3.Particularly, by hot dipping method
When foring Zn-Mg alloy layers 3 or when implementing heat treatment after forming Zn-Mg alloy layers 3, element is in steel plate 2 and Zn-
The interface phase counterdiffusion of Mg alloy layers 3.In this case, Fe, Al, Zn etc. form alloy phase, thus steel plate 2 and Zn-
The adaptation of Mg alloy layers 3 improves.In addition, be formed at the interface of steel plate 2 and Zn-Mg alloy layers 3 comprising Fe, Al,
Zn alloy is met brings the possibility of influence small to the corrosion resistance of Zn-Mg alloy layers 3.
For the foregoing reasons, just at last plating bath do not include Fe in the case of, the Fe in Zn-Mg alloy layers 3 contains sometimes
Amount can also reach 2.0 mass % or so, but hardly the corrosion resistance to Zn-Mg alloy layers 3 brings influence.Therefore, Zn-
Mg alloy layers 3 can contain the Fe below 2.0 mass %.
The ＞ of ＜ corrosion scales 4
Zn-Mg alloy platings steel plate 1 has corrosion scales 4 on the surface of Zn-Mg alloy layers 3, the corrosion scales 4
The Mg salt for the alkanesulfonic acid that the Mg salt or carbon number for the carboxylic acid for being 4~20 containing carbon number are 4~20.
Carbon number is 4~20 carboxylic acid or the Mg salt of alkanesulfonic acid is to stablize corrosion product, makes Zn-Mg alloy plating steel
The corrosion resistance of 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 ionizes into the aqueous solution under process and corrosive environment.So the obtained ion of generation with it is molten by Zn-Mg alloy layers 3
Mg ionic reactions out, thus generate the Mg salt of carboxylic acid or the Mg salt of alkanesulfonic acid contained by corrosion scales 4.In order to generate
The Mg salt of carboxylic acid or the Mg salt of alkanesulfonic acid, the alkali metal salt of the carboxylic acid contained by chemical conversion treatment layer 5 or the alkali of alkanesulfonic acid
Metal salt needs to be present in the position to connect with Zn-Mg alloy layers 3.
In order that the alkali metal salt dissolution of the alkali metal salt or alkanesulfonic acid of carboxylic acid into the aqueous solution and carboxylic acid Mg salt
Or the Mg salt not dissolutions of alkanesulfonic acid into the aqueous solution, it is necessary to the solubility of the alkali metal salt of carboxylic acid or alkanesulfonic acid and Mg salt it
It is poor big.
In order that the Mg salt of carboxylic acid or alkanesulfonic acid is deposited between chemical conversion treatment layer 5 and Zn-Mg alloy layers 3,
The solubility for needing to make the Mg salt of carboxylic acid or alkanesulfonic acid in water is small.Therefore, it is 4 to make the carbon number of carboxylic acid or alkanesulfonic acid
More than.
In order to make under corrosive environment carboxylic acid or alkanesulfonic acid in the form of ion dissolution into the aqueous solution, it is necessary to make carboxylic acid
Or solubility of the alkali metal salt of alkanesulfonic acid in water is big.Therefore, it is less than 20 to make the carbon number of carboxylic acid or alkanesulfonic acid.
In addition, the preferred carbon number of carboxylic acid or alkanesulfonic acid is 5~20, more preferably 8~12.
As long as carboxylic acid carbon number is just not particularly limited for 4~20, saturated fatty acid, hydroxycarboxylic acid, benzene can be used
Carboxylic acid, dicarboxylic acids, unrighted acid etc..From the viewpoint of economy, preferably carboxylic acid is used as using saturated fatty acid.
As the example of saturated fatty acid, can include：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 particularly preferred compound among saturated fatty acid, can include：Carbon number is 8~12
Octanoic acid, n-nonanoic acid, capric acid and dodecylic acid.
As the example of hydroxycarboxylic acid, can include：Malic acid, citric acid, tartaric acid etc..Benzene carboxylic acid can be enumerated
Go out：Benzoic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), salicylic acid, cinnamic acid etc..
As the example of dicarboxylic acids, can include：Fumaric acid, maleic acid, butanedioic acid, glutaric acid, adipic acid, heptan two
Acid, suberic acid, azelaic acid, decanedioic acid etc..
As the example of unrighted acid, can include：Crotonic acid, sorbic acid, myristoleic acid, palmitoleic acid,
Cis- 6- gaidic acids (sapienic acid), oleic acid, elaidic acid, vaccenic acid, linoleic acid, leukotrienes, arachidonic acid, two
Eicosadienoic acid, eicosapentaenoic acid etc..
For alkanesulfonic acid, as long as carbon number is just not particularly limited for 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 particularly preferred compound among alkanesulfonic acid, can include：Carbon number be 8~12 it is pungent
Alkyl sulfonic acid, decane sulfonic acid and dodecane sulfonic acid.
The ＞ of ＜ chemical conversion treatment layers 5
Zn-Mg alloy platings steel plate 1 has chemical conversion treatment layer 5 on the surface of corrosion scales 4, at the chemical conversion
The alkali metal salt and make film component that reason layer 5 includes carboxylic acid or alkanesulfonic acid.It can also contain as needed in chemical conversion treatment layer 5
There are inhibitor composition and Tissuemat E.Chemical conversion treatment layer 5 is preferably so-called to be free of chromate.
＜ alkali metal ＞
The alkali metal of the alkali metal salt of carboxylic acid or alkanesulfonic acid contained by chemical conversion treatment layer 5 is selected from Li, Na, K, Rb
At least one of with Cs.From the viewpoint of economy, preferred as alkali is only that (alkali metal salt of carboxylic acid or alkanesulfonic acid is only by Na
For carboxylic acid or the Na salt of alkanesulfonic acid, not comprising the alkali metal salt in addition to Na salt).
The content of the alkali metal salt of carboxylic acid or alkanesulfonic acid contained by chemical conversion treatment layer 5 with Na gauge be preferably 10~
1500mg/m2.10mg/m is less than with Na gauge in the content of carboxylic acid or the alkali metal salt of alkanesulfonic acid2In the case of, corrosion product
The amount of the Mg salt of carboxylic acid or alkanesulfonic acid contained by layer 4 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 with Na gauge more than 1500mg/m2In the case of, chemical conversion treatment layer 5 sometimes
Uniformity deterioration.
Solution obtained from chemical conversion treatment layer 5 is impregnated in into pure water is dried, using resulting residue, and
Qualitative analysis and quantitative analysis are carried out by infrared spectrographic method or pyrolysis gas chromatography, now can be to carboxylic acid or alkane
The carboxylic acid composition of the alkali metal salt of sulfonic acid or the material of alkanesulfonic acid are identified.Using the residue obtained as described above,
And qualitative analysis and quantitative analysis are carried out by atomic absorption, alkali metal component can now be identified and right
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 be containing carboxylic acid or alkanesulfonic acid Mg salt, but the carboxylic contained by chemical conversion treatment layer 5
The Mg salt of acid or alkanesulfonic acid is not almost contributed improving corrosion resistance.
In addition, the carboxylic acid or alkanesulfonic acid in chemical conversion treatment layer 5 exist only 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 make film component is free of chromate to be so-called, species is not particularly limited, and can use comprising resin
Composition with one or both of metallic compound,
As the example of resin, can include：Polyurethane resin, epoxy resin, acrylic resin, polyamide.
Metallic compound can include alkaline zirconium compounds, silicon compound etc..As the example of silicon compound, can include：It is organic
Silicon compound, inorganic silicon compound.
Below, 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 with one of silanol group, alkoxysilane group (alkoxysilyl group)
Or both ethene-unsaturated carboxylic acid copolymer resins, the film component of making of silicon oxide particle and organic titanic compound (make film component
C) illustrate.
＜ makes film component A ＞
Make film component A and include at least one of alkaline zirconium compounds, phosphate cpd and cobalt compound and organic acid.
As the example of alkaline zirconium compounds, can include：With [Zr (CO3)2(OH)2]2-、[Zr(CO3)2(OH)2
]2-As the carbonic acid zirconium compounds of cation, the ammonium salt containing these cations, sylvite, sodium salt etc..
As the example of phosphate cpd, can include：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..
As the example of cobalt compound, can include：Cobalt carbonate, cobalt nitrate, cobalt acetate etc..
As the example of organic acid, can include：Glycolic, malic acid, tartaric acid, oxalic acid, citric acid, Vitamin C
The ammonium of acid, lactic acid, dehydrogenation benzoic acid, hydroascorbic acid, gallic acid, tannic acid, phytic acid etc. or these organic acids
Salt.
＜ makes film component B ＞
Make film component B and include organo-silicon compound and aqueous polyurethane resin.
As the example of organo-silicon compound, can include：By the silane coupler containing an amino in molecule with
Compound obtained from silane coupler containing a glycidyl in molecule coordinates.
As the silane coupler containing an amino in molecule, it is not particularly limited, can exemplifies：3- aminopropyls
Triethoxysilane, 3- TSL 8330s etc..As the silane coupler containing a glycidyl in molecule,
It can exemplify：3- glycidoxypropyltrime,hoxysilanes, 3- glycidoxypropyl group triethoxysilanes 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, adaptation, organo-silicon compound with Zn-Mg alloy layers 3 self-crosslinking 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 polyethers system.Polyester polyurethane resin is hydrolyzed due to acid or alkali sometimes,
Polycarbonate polyurethane easily forms hard and crisp epithelium, adaptation, the situation of the corrosion resistance of processing department difference when having processing.
The structure of aqueous polyurethane resin can pass through the 3330cm in infrared measure-1(N-H stretches), 1730cm-1(C
=O stretches), 1530cm-1(C-N)、1250cm-1(C-O) characteristic absorption is analyzed.
＜ makes film component C ＞
Make film component C and include ethene-unsaturation with any one of silanol group and alkoxysilane group or both
Carboxyl acid copolymer resin, silicon oxide particle and organic titanic compound.
Ethene with any one of silanol group and alkoxysilane group or both-unsaturated carboxylic acid copolymer resins example
Such as reacted by the aqueous solution for the copolymer resins for making to be dispersed with ethene and unsaturated carboxylic acid with silane based compound to obtain.As
The example of unsaturated carboxylic acid, such as can include：Acrylic acid, methacrylic acid, maleic anhydride etc..
As silicon oxide particle, preferably using cataloid, aerosil etc..
Organic titanic compound can for example include：Double (conjunction of the triethanolamine root) titaniums of dipropoxy, the double (diethyls of dipropoxy
Hydramine root closes) titanium, double (conjunctions of the triethanolamine root) titanium of dibutoxy, double (conjunction of the diethanol amine root) titaniums of dibutoxy, dipropoxy pair
Double (acetylacetonate) titaniums of (acetylacetonate) titanium, dibutoxy, dihydroxy double (lactate conjunction) titanium mono-ammonium, dihydroxy
Double (lactate conjunction) titanium di-ammonium salts, the epoxide titanium double (ethyl acetoacetates) of propane two, oxo titanium double (single ammonium oxalates) etc..
Making film component C can also include with any in silanol group and alkoxysilane group in addition to mentioned component
The polyurethane resin of person or both.Polyurethane resin with any one of silanol group and alkoxysilane group or both can
With by making polyurethane prepolymer and the alkoxyl silicone alkanes and polyamines of active hydrogen-based react to obtain.
In addition, just at last in the case where making film component C and including unsaturated carboxylic acid, when as described above to by chemical conversion
, can be to carboxylic acid or chain when solution obtained from reason layer 5 is impregnated in pure water is dried and resulting residue is analyzed
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.Thus, chemical conversion treatment layer 5 is preferred
Fluoride, trivalent chromium and vanadium are not contained.
Further, since chemical conversion treatment layer 5 does not contain fluoride, trivalent chromium and vanadium, therefore preferably make film component also not
Contain fluoride, trivalent chromium and vanadium.
Interface and corrosion scales 4 and chemical conversion treatment layer 5 with regard to Zn-Mg alloy layers 3 and corrosion scales 4
For interface, the section of Zn-Mg alloy platings steel plate 1 can be shot by SEM- backscattered electron images, pass through the back of the body
The light and shade of scattered electron image identifies.
(manufacture method of Zn-Mg alloy platings steel plate 1)
Zn-Mg alloy platings steel plate 1 is manufactured by following manner：By plating process steel plate 2 surface shape
Into Zn-Mg alloy layers 3, corrosion scales 4 are formed simultaneously on the surface of Zn-Mg alloy layers 3 by chemical conversion treatment operation
And form chemical conversion treatment layer 5 on the surface of corrosion scales 4.
＜ plating process ＞
By plating process, Zn-Mg alloy layers 3 are formed on the surface of steel plate 2.
The method of plating process is not particularly limited, and can use known hot dipping method.Just Mg is added into Zn plating bath
Deng for, known method can be used.
＜ chemical conversion treatment operations ＞
By chemical conversion treatment operation, corrosion scales 4 are formed on the surface of Zn-Mg alloy layers 3, and corroding
The surface of product layer 4 forms chemical conversion treatment layer 5.
For chemical conversion treatment operation, no matter the species for making film component of chemical conversion treatment layer 5, will make
(hereinafter referred to as chemistry turns solution obtained from water, organic solvent dissolve the alkali metal salt of carboxylic acid or alkanesulfonic acid and make film component
Change treatment fluid) surface of Zn-Mg alloy layers 3 is coated on, 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 dissolution into the aqueous solution and the Mg salt of the Mg salt of carboxylic acid or alkanesulfonic acid not
From the viewpoint of dissolution is into the aqueous solution, preferably 0.1~10 mass %.
The coating method of chemical conversion treatment solution is not particularly limited, such as can use spraying process, infusion process, roller coat
Method, curtain coating (shower ringer method), air knife method etc..
Chemical conversion treatment solution can include surfactant, defoamer, lubricant or filler.
After chemical conversion treatment solution is coated with, in order to make drying, chemical conversion treatment solution can be coated with
Zn-Mg alloy platings steel plate 1 is heated to 50 DEG C~200 DEG C.
Embodiment
Below, examples and comparative examples of the present invention are enumerated, and the present invention is specifically described, but the invention is not restricted to
They.
Using known hot dipping method, the adhesion amount formed on the steel plate that thickness of slab is 0.8mm per two sides is 180g/m2
(adhesion amount per one side is respectively 90g/m2) Zn-Mg alloy layers.And then form what is amounted on Zn-Mg alloy layers
Thickness is 1.2 μm of corrosion scales and chemical conversion treatment layer.
The forming method of corrosion scales and chemical conversion treatment layer is by carboxylic acid or alkanesulfonic acid containing 1 mass %
Alkali metal salt, the 20 mass % chemical conversion treatment solution for making film component and water are coated on Zn-Mg alloy layers with rod.
By the carboxylic acid contained by the composition of Zn-Mg alloy layers, chemical conversion treatment layer or the alkali metal salt of alkanesulfonic acid, make
Film component is shown in table 1~5.Using these Zn-Mg alloy plating steel plates as test film, and as the index pair of temporary rust prevention
Anti-blackening (the also known as black property of resistance) and corrosion resistance are evaluated.Evaluation result is shown in table 6~10.
In addition, for the example described in Tables 1 and 2, the alkali metal salt of carboxylic acid is included in chemical conversion treatment layer；
For the example described in table 3 and table 4, the alkali metal salt of alkanesulfonic acid is included in chemical conversion treatment layer.Table 5 is remembered
For the comparative example of load, the alkali metal salt of carboxylic acid is included in chemical conversion treatment layer sometimes, sometimes the alkali gold comprising alkanesulfonic acid
Belong to salt, do not include any one of both sometimes also.
[anti-blackening]
Using constant temperature and moisture test machine, and test film is stood in the case where 80 DEG C and relative humidity (RH) is 85% atmosphere
144 hours.The tone of the test film before and after standing 144 hours is determined by spectral photometric colour measuring meter, anti-blackening is entered
Evaluation is gone.Specifically, by spectral photometric colour measuring meter to representing CIE colour systems (L*a*b*Colour system) lightness L*Value
It is determined, obtains as the L before standing 144 hours*The L of value and standing after 144 hours*The difference of value (that is, (stands 144
L before hour*Value)-(L after standing for 144 hours*Value)) Δ L*。
According to Δ L*Value, is evaluated anti-blackening as follows.Using " excellent ", " good ", "available" to be qualified.
It is excellent：ΔL*For less than 5
It is good：ΔL*More than 5 and it is less than 10
Can：ΔL*More than 10 and it is less than 15
Difference：ΔL*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
The L of test film before and after putting 144 hours*The difference delta L of value*, anti-blackening is evaluated, Δ L*It is worth smaller expression to stand
Also maintain afterwards more with lightness close before standing.In addition, Δ L*Value is bigger to represent that lightness more (becomes than declining before standing after standing
Secretly).
[corrosion resistance]
By implementing the salt spraytest 240 hours based on JIS Z 2371 to test film, corrosion resistance is commented
Valency.Specifically, corrosion resistance is to the corroded area rate (corroded area of test film after salt spraytest according to following benchmark
With the ratio of surface area) judged.Using " excellent ", " good ", "available" to be qualified.
It is excellent：Corroded area rate is 0%
It is good：Corroded area rate is more than 0% and is less than 5%
Can：Corroded area rate is more than 5% and is less than 30%
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 qualified.
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 | Can | It is good |
| Example 28 | It is good | Can | It is good |
| Example 29 | It is good | Can | It is good |
| Example 30 | It is good | Can | It is good |
| Example 31 | Can | Can | It is good |
| Example 32 | Can | It is good | It is good |
| Example 33 | It is good | Can | It is good |
| Example 34 | It is good | Can | It is good |
| Example 35 | It is good | Can | It is good |
| Example 36 | It is good | Can | It is good |
| Example 37 | It is good | Can | It is good |
| Example 38 | Can | Can | Can |
| Example 39 | Can | Can | Can |
| Example 40 | Can | Can | Can |
| Example 41 | Can | Can | Can |
| Example 42 | Can | Can | Can |
| Example 43 | Can | Can | Can |
| Example 44 | Can | Can | Can |
| Example 45 | Can | Can | Can |
| Example 46 | Can | Can | Can |
| Example 47 | Can | Can | Can |
| Example 48 | Can | Can | Can |
| Example 49 | Can | Can | Can |
| Example 50 | Can | Can | Can |
| Example 51 | Can | Can | Can |
| Example 52 | Can | Can | 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 | Can | It is good |
| Example 80 | It is good | Can | It is good |
| Example 81 | It is good | Can | It is good |
| Example 82 | It is good | Can | It is good |
| Example 83 | Can | Can | It is good |
| Example 84 | Can | It is good | It is good |
| Example 85 | It is good | Can | It is good |
| Example 86 | It is good | Can | It is good |
| Example 87 | It is good | Can | It is good |
| Example 88 | It is good | Can | It is good |
| Example 89 | It is good | Can | It is good |
| Example 90 | Can | Can | Can |
| Example 91 | Can | Can | Can |
| Example 92 | Can | Can | Can |
| Example 93 | Can | Can | Can |
| Example 94 | Can | Can | Can |
| Example 95 | Can | Can | Can |
| Example 96 | Can | Can | Can |
| Example 97 | Can | Can | Can |
| Example 98 | Can | Can | Can |
| Example 99 | Can | Can | Can |
| Example 100 | Can | Can | Can |
| Example 101 | Can | Can | Can |
| Example 102 | Can | Can | Can |
| Example 103 | Can | Can | Can |
| Example 104 | Can | Can | 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 qualified.
And the comparative example 1,2,5 and 6 shown in table 10 be the Mg contents of alloy layer outside the scope of the present invention, resistance to blacking
Property, corrosion resistance and overall merit are imperfect.In addition, comparative example 1 and 5 is the comparative example more than the Mg contents of alloy layer.Just
For comparative example 1 and 5, although formed with corrosion scales, anti-blackening, corrosion resistance and overall merit are imperfect.Its
Reason may be considered：Although in comparative example 1 and 5 there occurs the formation of corrosion scales in itself, it is present in the Mg phases of plating
Corrosion it is fast, can not suppress to corrode.
For comparative example 3,4,7 and 8, the carbon number of carboxylic acid or alkanesulfonic acid is outside the scope of the present invention, resistance to blacking
Property, corrosion resistance and overall merit are imperfect.
For comparative example 9~12, due to the alkali metal salt not comprising carboxylic acid or alkanesulfonic acid, therefore it is anti-blackening, resistance to
Corrosion and overall merit are imperfect.
For comparative example 13, due to not implementing plating on steel plate, therefore anti-blackening, corrosion resistance and overall merit are
It is imperfect.Due to not implementing plating on steel plate in comparative example 13, therefore in the absence of the supply source of Mg ions.Thus, it is possible to
Think：Due to not forming the Mg salt of 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 comprising carboxylic acid or alkanesulfonic acid
Alkali metal salt, therefore anti-blackening, corrosion resistance and overall merit are imperfect.
Comparative example 16 is to make the comparative example that film component contains trivalent chromium, and anti-blackening, corrosion resistance and overall merit are inadequate
Alright.
Comparative example 17 is to make the comparative example that film component contains vanadium, and anti-blackening, corrosion resistance and overall merit are imperfect.
Comparative example 18 is to make the comparative example that film component contains fluorine, and anti-blackening, corrosion resistance and overall merit are imperfect.
As the undesirable reason when making film component and containing trivalent chromium, vanadium or fluorine, it is believed that be because, make film into
Divide in the case of containing 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 applicability
According to said one embodiment, using the teaching of the invention it is possible to provide have possessing for excellent temporary rust prevention to have chemical conversion treatment
The Zn-Mg alloy plating steel plates of layer.
Symbol description
1 Zn-Mg alloy plating steel plates
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 platings steel plate, it possesses steel plate, Zn-Mg alloy layers, corrosion scales and chemical conversion treatment
Layer,
The Zn-Mg alloy layers are formed on the surface of the steel plate, and contain 1.0~70.0 mass % Mg, remainder
Subpackage contains Zn and impurity,
The corrosion scales are formed on the surface of the Zn-Mg alloy layers, and contain the carboxylic acid that carbon number is 4~20
Mg salt and carbon number be any one of 4~20 Mg salt of alkanesulfonic acid,
The chemical conversion treatment layer is formed on the surface of the corrosion scales, and is contained in the corrosion scales described
Contain the alkali metal salt of the carboxylic acid in the case of the Mg salt of carboxylic acid, contain the Mg of the alkanesulfonic acid in the corrosion scales
Contain the alkali metal salt of the alkanesulfonic acid in the case of salt,
Wherein, the alkali metal salt of the alkali metal salt of the carboxylic acid contained by the chemical conversion treatment layer or the alkanesulfonic acid
Alkali metal is selected from least one of Li, Na, K, Rb and Cs.
2. Zn-Mg alloy platings steel plate according to claim 1, it is characterised in that the Zn-Mg alloy layers contain
5.0~70.0 mass % Mg.
3. Zn-Mg alloy platings steel plate according to claim 2, it is characterised in that the Zn-Mg alloy layers contain
10.0~70.0 mass % Mg.
4. Zn-Mg alloy platings steel plate according to claim 3, it is characterised in that the Zn-Mg alloy layers contain
15.0~70.0 mass % Mg.
5. according to Zn-Mg alloy platings steel plate according to any one of claims 1 to 4, it is characterised in that the Zn-Mg is closed
Gold plate also include selected from 0.3~25.0 mass % Al, 0.01~5.00 mass % Si, 1.0~5.0 mass % Ca and
At least one of below 0.1~1.5 mass % Ni.
6. according to Zn-Mg alloy platings steel plate according to any one of claims 1 to 5, it is characterised in that the alkali metal is
Na。
7. Zn-Mg alloy platings steel plate according to claim 6, it is characterised 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. according to Zn-Mg alloy platings steel plate according to any one of claims 1 to 7, it is characterised in that the carboxylic acid or institute
The carbon number for stating alkanesulfonic acid is 5~20.
9. Zn-Mg alloy platings steel plate according to claim 8, it is characterised in that the carboxylic acid or the alkanesulfonic acid
Carbon number be 8~12.
10. according to Zn-Mg alloy platings steel plate according to any one of claims 1 to 9, it is characterised in that the carboxylic acid is
Saturated fatty acid.
11. according to Zn-Mg alloy platings steel plate according to any one of claims 1 to 10, it is characterised in that the chemistry turns
Change process layer and do not contain fluoride, trivalent chromium and vanadium.
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| PCT/JP2016/061404 WO2016163461A1 (en) | 2015-04-07 | 2016-04-07 | Zn-mg alloy coated steel sheet |
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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 |
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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 |
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| JP5505053B2 (en) | 2010-04-09 | 2014-05-28 | 新日鐵住金株式会社 | Organic composite Mg-based plated steel sheet |
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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 |
| JP2005146340A (en) * | 2003-11-14 | 2005-06-09 | Nisshin Steel Co Ltd | HOT DIP Mg-CONTAINING GALVANNEALED STEEL SHEET HAVING 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 |
| 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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| 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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| Publication number | Publication date |
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| JPWO2016163461A1 (en) | 2017-04-27 |
| KR20170120165A (en) | 2017-10-30 |
| MY186250A (en) | 2021-06-30 |
| CN107429405B (en) | 2019-09-10 |
| WO2016163461A1 (en) | 2016-10-13 |
| KR101986930B1 (en) | 2019-06-07 |
| JP6070914B1 (en) | 2017-02-01 |
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