CN107636207A

CN107636207A - Surface treated steel plate

Info

Publication number: CN107636207A
Application number: CN201680031662.2A
Authority: CN
Inventors: 柴尾史生; 庄司浩雅
Original assignee: Nippon Steel Corp
Current assignee: Nippon Steel Corp
Priority date: 2015-06-09
Filing date: 2016-06-09
Publication date: 2018-01-26
Anticipated expiration: 2036-06-09
Also published as: WO2016199852A1; MY186934A; JPWO2016199852A1; KR20180015133A; JP6531825B2; TW201710562A; US20180100244A1; CN107636207B; KR102274990B1; MX2017015441A; CA2986369A1; TWI641728B

Abstract

The surface treated steel plate possesses：Steel plate；Formed and coating containing zinc and vanadium or zirconium with the one or two sides in the steel plate, wherein, the coating has：Skeleton containing metallic zinc；And it will be filled between above-mentioned skeleton and the filling region between the crystal of amorphous diffraction pattern is shown in the case of having carried out electron beam diffraction, in the case where the coating contains the vanadium, filling region contains the barium oxide or vanadium hydroxide of hydration between the crystal, in the case where the coating contains zirconium, filling region contains the Zirconium oxide or zirconium hydroxide of hydration between the crystal.

Description

Surface treated steel plate

Technical field

The present invention relates to the surface treatment of the corrosion resistance of the coating in corrosive environment (barrier) and film excellent adhesion Steel plate.

The application based on June 9th, 2015 Japanese publication Patent 2015-116554 and Patent 2015-116604 Number and CLAIM OF PRIORITY and its content is applied at this.

Background technology

Since in the past, electrical article of being in, building materials, automobile etc. utilize plated steel sheet always in diversified field. For plated steel sheet, it is desirable to further improve the corrosion resistance (hereinafter referred to as barrier) of the coating in corrosive environment.

Method as the barrier for improving plated steel sheet, it is contemplated that increase plating amount (the unit area weight of zinc coating Amount).But make zinc coating weight per unit area it is increased in the case of, there is manufacturing cost increase, processability, welding Property reduce the problem of.

In addition, the method for the barrier, outward appearance as raising plated steel sheet, has been widely used in always since conventional Surface forms the technology of film.But if the coating of plated steel sheet and the adaptation of film (film adaptation, are also referred to as Film adhesiveness) it is insufficient, then film is formed even in surface, also can not fully obtain the effect as caused by foring film Fruit.It is therefore desirable to improve film adaptation while the barrier of plated steel sheet is improved.

In recent years, studying always by making to improve barrier containing v element in the zinc coating of plated steel sheet.Example Such as, the skill for making Zn-V oxides carry out compound electrolysis on the surface of the copper coin as negative electrode has been recorded in non-patent literature 1~4 Art.

The skin section recorded in patent document 1 in the coating of electrogalvanized steel plate forms the technology of V concentration layers.

Recorded in patent document 2 about the technology comprising zinc and vanadium, the coating with multiple dendritic arms.

Record to have in the coating containing zinc and vanadium formed on steel plate in patent document 3 and vanadium oxidation in zinc be present The skeleton of thing；Describe and the vanadium containing ratio phase higher than in dendritic crystal body in the part beyond skeleton be present.

Recorded in patent document 4 in the zinc system composite plating steel plate comprising zinc and vanadium hydroxide, the vanadium hydrogen in zinc Oxide eutectoid.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2013-185199 publications

Patent document 2：No. 5273316 publications of Japanese Patent No.

Patent document 3：Japanese Unexamined Patent Publication 2013-108183 publications

Patent document 4：Japanese Unexamined Patent Publication 2011-111633 publications

Non-patent literature

Non-patent literature 1：CAMP-ISIJ volumes 22 (2009) -933~936

Non-patent literature 2：Iron and steel (2007) o. 11th of volume 93, page 49~page 54

Non-patent literature 3：The lecture conference main idea collection of sufacing association the 115th time, 9A-26, page 139~page 140

Non-patent literature 4：Ferrum (Japaneses：ふぇらむ) volume 13, No.4, page 245,2008.4.1

The content of the invention

Invent problem to be solved

But for the conventional surface treated steel plate for there is the coating containing zinc and vanadium on the surface of steel plate, Ask and further improve barrier.

Further, since V (vanadium) is rare element, it is desirable to have the excellent coating of the barrier for substituting almagrerite coating.

The present invention in view of such situation and complete, its problem be to provide surface of steel plate formed with containing zinc and vanadium or The barrier of the coating of zirconium and the surface treated steel plate of film excellent adhesion.

Means for solving the problems

The inventor of the present invention is furtherd investigate repeatedly as shown in the following in order to solve above-mentioned problem.

That is, inventor of the invention using galvanoplastic, using steel plate as negative electrode under various conditions in the surface shape of steel plate Into the coating containing zinc and vanadium or zirconium, and its barrier and film adaptation are investigated.

As a result, present inventors found that：As long as forming following coating, the coating is containing zinc and vanadium Coating, its have between the skeleton containing metallic zinc and the crystal of the barium oxide containing hydration or vanadium hydroxide Filling region.Such coating due to filling region between the crystal with the barium oxide containing hydration or vanadium hydroxide, because This is for example compared with the coated steel sheet for replacing the coating and being formed there is provided zinc coating, and corrosion potential is higher, and barrier is more It is excellent.

In addition, present inventors found that：Under the conditions of certain, around the skeleton formed by metallic zinc Phase formed with the Zirconium oxide comprising hydration or zirconium hydroxide.Distinguish：Such coating is compared with almagrerite coating, barrier Property more than equal and film excellent adhesion, complete the present invention.Each scheme of the present invention is as described below.

(1) surface treated steel plate of a scheme of the invention possesses：Steel plate；With the one or two sides shape in the steel plate Into and containing zinc and vanadium or zirconium coating, wherein, the coating has：Skeleton containing metallic zinc；With by above-mentioned tree It is filled between dendritic crystal and is filled out between the crystal of amorphous diffraction pattern is shown in the case of having carried out electron beam diffraction Region is filled, in the case where the coating contains the vanadium, filling region contains the barium oxide or vanadium of hydration between the crystal Hydroxide, in the case where the coating contains zirconium, filling region contains the Zirconium oxide or zirconium hydrogen of hydration between the crystal Oxide.

(2) surface treated steel plate according to above-mentioned (1), following composition can be used：Contain in the coating described In the case of vanadium, the mol ratio of the vanadium and the zinc between the crystal in filling region is that V/Zn is 0.10~2.00, In the case that the coating contains the zirconium, the mol ratio of the zirconium and the zinc between the crystal in filling region is Zr/ Zn is 1.00~3.00.

(3) surface treated steel plate according to above-mentioned (1) or (2), following composition can be used：Contain in the coating In the case of the vanadium, zinc oxide or zinc hydroxide are contained in the top layer of the skeleton.

(4) surface treated steel plate according to any one of above-mentioned (1)~(3), following composition can be used：Described The mol ratio i.e. Zn/V that zinc and the vanadium are further provided between steel plate and the coating is more than 8.00 substrate coating.

(5) surface treated steel plate according to any one of above-mentioned (1)~(4), following composition can be used：Described The surface of coating is further equipped with the organic resin envelope with the carbon black of polyurethane resin and 1~20 mass %.

(6) manufacture method of the surface treated steel plate of a scheme of the invention is any one of manufacture above-mentioned (1)~(5) institute The method for the surface treated steel plate stated, this method have：Substrate formation process, it is by using containing 0.10~4.00mol/l Zn²⁺The plating bath of the Zr ions of ion and 0.01~2.00mol/l V ions or 0.10~4.00mol/l and with 0~18A/ dm²Current density electroplated, so as to make on the steel plate hydration barium oxide or vanadium hydroxide separate out and formed It is concavo-convex；With upper strata plating process, it is to foring the concavo-convex steel plate using the plating bath and with 21~200A/dm² Current density electroplated.

The effect of invention

According to above-mentioned each scheme, using the teaching of the invention it is possible to provide have excellent barrier and the surface treated steel plate of film adaptation.

Brief description of the drawings

Fig. 1 is the sectional schematic diagram for illustrating an example of the surface treated steel plate of the 1st embodiment.

Fig. 2 is the sectional schematic diagram for illustrating an example of the surface treated steel plate of the 2nd embodiment.

Fig. 3 is an example for representing the used plater when manufacturing the surface treated steel plate of present embodiment Skeleton diagram.

Fig. 4 A are for illustrating to manufacture showing for the precipitation of the vfanadium compound in the process of the surface treated steel plate shown in Fig. 1 It is intended to.

Fig. 4 B are the growths for illustrating to manufacture the skeleton in the process of the surface treated steel plate shown in Fig. 1 Schematic diagram.

Fig. 4 C are the branch portions for illustrating to manufacture the skeleton in the process of the surface treated steel plate shown in Fig. 1 The caused schematic diagram of hydrogen at tip.

Fig. 5 A are the coating of embodiment V4 surface treated steel plate using obtained from transmission electron microscope (TEM) The cross-section photographs in whole thickness direction.

Fig. 5 B are the enlarged photographs of the interface portion of the steel plate and coating in Fig. 5 A section.

Fig. 5 C are the enlarged photographs of the skeleton and its peripheral part in Fig. 5 A section.

Fig. 6 is scanning electron microscope (SEM) photo of the coating of embodiment V4 surface treated steel plate.

Fig. 7 is scanning electron microscope (SEM) photo of the coating of comparative example x2 surface treated steel plate.

Fig. 8 is the photo of the electron beam diffraction picture of the coating for the surface treated steel plate for representing embodiment V4.

Fig. 9 is transmission electron microscope (TEM) photo of the coating of embodiment Z4 surface treated steel plate.

Embodiment

" the 1st embodiment, surface treated steel plate 10 "

Referring to the drawings, to containing vanadium in coating in the case of the surface treated steel plate 10 of the 1st embodiment carry out Describe in detail.

Fig. 1 is the sectional schematic diagram for illustrating an example of the surface treated steel plate 10 of present embodiment.Institute in Fig. 1 The surface treated steel plate 10 shown has sequentially formed basalis 20, coating 30 and table since the side of steel plate 1 respectively on the two sides of steel plate 1 Surface layer 40.Basalis 20, coating 30 and superficial layer 40 that one side (above) side of steel plate 1 is formed only are documented in Fig. 1, is omitted The record of another side (following) side.

In present embodiment, as the steel plate 1 that coating 30 is formed on surface, it is not particularly limited.For example, as steel plate 1, Extremely low c-type (ferrite body tissue), Al-k types (tissue containing pearlite in ferrite), 2 phase constitution type (examples can be used Such as, the tissue containing martensite, the tissue containing bainite in ferrite in ferrite), processing sensing inversion of phases (in iron Tissue containing retained austenite in ferritic), any type of steel plate such as micro crystal type (ferrite body tissue).

As illustrated in figure 1, basalis 20 can be set between steel plate 1 and coating 30.Basalis 20 is to improve The adaptation of steel plate 1 and coating 30 and be arranged as required to.In present embodiment, be preferably provided with thickness for 1~300nm, By the basalis 20 of nickeliferous Crystallization.

Coating 30 has as illustrated in figure 1：Skeleton 31；Filling region 32 between crystal, its configuration are being set Amorphous diffraction pattern is shown between dendritic crystal 31 and in the case where having carried out electron beam diffraction.

" noncrystalline " means in the present invention：Each layer is entered from section direction using transmission electron microscope (TEM) Row electron beam diffraction, the diffraction pattern due to crystal structure can not be obtained.

Filling region 32 includes the barium oxide or vanadium hydroxide of hydration between crystal.It is excellent in order to improve film adaptation Filling region 32 includes vanadium hydroxide between selecting crystal.

Additionally, it is preferred that filling region 32 includes zinc between crystal.Zinc is included by filling region between crystal 32, so that anti-corrosion Property is improved.

In the case that filling region 32 includes the barium oxide or vanadium hydroxide and zinc of hydration between crystal, preferred crystal Between the mol ratio (V/Zn) of vanadium in filling region 32 and zinc be 0.10~2.00.It is above-mentioned by above-mentioned mol ratio (V/Zn) Scope and filling region shows amorphous diffraction pattern between crystal in the case of having carried out electron beam diffraction, so as to Enough obtain excellent corrosion resistance (barrier) and film adaptation.If the mol ratio of the vanadium and zinc between crystal in filling region 32 (V/Zn) it is less than 0.10, then can not stably obtains amorphous diffraction pattern sometimes, corrosion resistance is poor.On the other hand, if Above-mentioned mol ratio is more than 2.00, then the sacrifice corrosion protection deterioration of coating.

As illustrated in figure 1, multiple skeletons 31 are formd in coating 30.The shape of multiple skeletons 31 Shape can also include identical shape with entirely different.The shape of each skeleton 31 can be needle-like, or rod Shape.In addition, each skeleton 31 can be extended or extended with curve-like with linear in length direction.To each The section configuration of skeleton 31 is not particularly limited, such as can be included：Circle, oval, polygon etc..It is in addition, each The section configuration of skeleton 31 can be homogeneous or inhomogenous in length direction.In addition, each dendritic crystal The peripheral dimension of body 31 can be homogeneous or inhomogenous in length direction.

For the surface treated steel plate 10 of present embodiment, as illustrated in figure 1, each skeleton 31 has： The inside 3a of the skeleton and top layer 3b formed on the surface of skeleton 31.The inside 3a of skeleton 31 from The laterally outside of steel plate 1 grows, and has multiple portions of branch.Top layer 3b is to cover the inside 3a of skeleton 31 surface Mode formed with substantially uniform thickness.

Inside 3a with skeleton 31 and the preferred maximum length of skeleton 31 shown in top layer 3b Fig. 1 Breadth Maximum for less than 4.0 μm and when section is observed is less than 0.5 μm.In the maximum length and maximum of skeleton 31 In the case that width is above range, turn into the fine and close coating 30 with fine skeleton 31.Therefore, coating 30 Iris action improves, and can obtain further excellent barrier.In order that barrier further improves, more preferably set The maximum length of dendritic crystal 31 is less than 3.0 μm.In addition, the maximum when section is observed of more preferably skeleton 31 is wide Spend for less than 0.4 μm.

In the present embodiment, " maximum length of skeleton 31 " is by using scanning electron microscope (SEM) section of coating is observed, the maximum length of the skeleton 31 of measure 50, calculates its average value to obtain.

In addition, " Breadth Maximum when section is observed of skeleton 31 " is by using transmission electron microscope (TEM) section of coating is observed, the Breadth Maximum of 50 skeletons 31 is determined, calculates its average value to obtain.

The inside 3a of skeleton 31 preferably comprises metallic zinc.In the inside 3a of skeleton 31, except containing gold Belong to beyond zinc, also containing other metal ingredients such as the nickel higher than the deposition potential of zinc.

In addition, top layer 3b preferably comprises the crystal containing zinc oxide or zinc hydroxide.Top layer 3b further preferably zinc The crystal of oxide.Top layer 3b thickness is preferably 0.1~500nm.

In addition, as illustrated in figure 1, bulk crystalline 3c can be contained in the inside 3a of skeleton 31.Granular crystal Body 3c contains zinc and nickel.Bulk crystalline 3c particle diameter is preferably 0.1~500nm.It is above range in bulk crystalline 3c particle diameter In the case of interior, more excellent film adaptation can be obtained.

For the surface treated steel plate 10 of present embodiment, the mol ratio of contained zinc and vanadium is preferably in coating 30 Zn/V is 0.50 less than 8.00.By Zn/V for 0.50 less than 8.00, so as to obtain by containing vanadium institute The excellent barriers function brought, therefore preferably.

For surface treated steel plate 10, between steel plate 1 and coating 30 (in the case where foring basalis 20, Between basalis 20 and coating 30) the substrate coating (not shown) containing zinc can be formed.Because plated by forming substrate Layer (not shown), the corrosion resistance so as to obtain excellent as caused by the sacrifice corrosion protection of zinc improve effect.

Mol ratio of the substrate coating (not shown) containing zinc and vanadium and the zinc and the vanadium be Zn/V can be 8.00 with On.In addition, substrate coating (not shown) only can be also made up of zinc.

The upper strata coating (not shown) containing zinc can be also formed on the upper strata of coating 30.By formed with upper strata coating (not shown), the corrosion resistance so as to obtain excellent as caused by the sacrifice corrosion protection of zinc improve effect, therefore preferably.

Upper strata coating (not shown) only can be also made up of zinc.In addition, upper strata coating (not shown) can contain zinc and The mol ratio of vanadium and the zinc and the vanadium is that Zn/V can be more than 8.00.

By controlling the current density of plating, the mol ratio of zinc and vanadium is adjusted, so as between steel plate 1 and coating 30 (in the case where foring basalis 20, between basalis 20 and coating 30) forms substrate coating (not shown).

The method same with substrate coating (not shown) can be used, it is (not shown that upper strata coating is formed on coating 30 Go out).

Filling region 32 and skeleton 31 between contained zinc amount (a) and crystal in the inside 3a of skeleton 31 The mol ratio (a/b) of total (b) of contained zinc amount is preferably 0.10~3.00 scope in the 3b of top layer.

If above-mentioned mol ratio (a/b) is more than 0.10, in the case of generating damage on the surface of coating 30, energy Enough effectively obtain and corrosion protection effect is sacrificed as caused by metallic zinc contained in skeleton 31, can obtain more excellent Barrier.Corrosion protection effect is sacrificed as caused by metallic zinc contained in skeleton 31 in order to more effectively obtain, it is more excellent Above-mentioned mol ratio (a/b) is set as more than 0.20 by choosing.

In addition, in the case where above-mentioned mol ratio (a/b) is less than 3.00, can effectively obtain by skeleton Contained zinc oxide or zinc hydroxide are difficult to make sky gas and water carry by the barrier of caused steel plate 1 in 31 top layer Height effect, can obtain more excellent barrier.In order to more effectively obtain as caused by the top layer 3b of skeleton 31 Barrier raising acts on, and above-mentioned mol ratio (a/b) is more preferably less than 0.25.

In addition, zinc amount contained in zinc amount contained in skeleton 31 and the top layer 3b of skeleton 31 is total (A) mol ratio (A/B) of vanadium amount (B) contained in filling region 32 between crystal is preferably 0.05~6.00.Rubbed in above-mentioned In the case that you are more than 0.05 than (A/B), it can effectively obtain and be brought by metallic zinc contained in skeleton 31 Sacrifice corrosion protection effect and the resistance as caused by zinc oxide or zinc hydroxide contained in the top layer 3b of skeleton 31 Acted on every property raising, more excellent barrier can be obtained.

Corrosion protection effect is sacrificed caused by skeleton 31 and by skeleton in order to more effectively obtain Barrier raising caused by 31 top layer 3b acts on, and above-mentioned mol ratio (A/B) is more preferably more than 0.10.In addition, upper In the case that the mol ratio (A/B) stated is less than 6.00, it is high potential to make the corrosion potential as caused by containing vanadium, can more be had Effect ground plays the effect for improving barrier.Acted on to further improve the barrier raising as caused by containing vanadium, it is above-mentioned Mol ratio (A/B) be more preferably less than 5.00, more preferably less than 4.50.

In present embodiment, contained content of vanadium is preferably the mass % of 1 mass %~20 in coating 30.If in coating 30 Vanadium amount be more than 1 mass %, then can obtain more excellent barrier.It is closely sealed in order to further improve barrier and film Property, the content of vanadium in coating 30 are more preferably more than 4 mass %.The situation that content of vanadium in coating 30 is below 20 mass % Under, the top layer 3b of skeleton 31 and skeleton 31 content relatively increases, and can effectively obtain by dendroid Corrosion protection effect is sacrificed caused by crystal 31 and the barrier raising as caused by the top layer 3b of skeleton 31 acts on.

In order to ensure the content of skeleton 31 and the top layer 3b of skeleton 31, the content of vanadium of coating 30 is more preferably For below 15 mass %.

In order to improve barrier, the adhesion amount of coating 30 is preferably 1g/m²More than, more preferably 3g/m²More than.In addition, plating The adhesion amount of layer 30 is preferably 90g/m²Hereinafter, more preferably 50g/m²Hereinafter, more preferably 15g/m²Below.In coating 30 adhesion amount is 15g/m²(it is usually 20g/m with conventional electrogalvanizing in the case of below²Left and right) etc. compare, make to be separated out Amount of metal it is less can solve, from the viewpoint of the metal cost for forming coating 30, power cost, be economically Excellent.

The surface treated steel plate 10 of present embodiment is preferably immersed in the 5% of 25 DEG C using coating 30 as working electrode Natural dipping current potential (corrosion potential) in the case of in the NaCl aqueous solution is more than -0.8V.Above-mentioned corrosion potential preferably compares Coated steel sheet (corrosion potential is -1.0V or so) high more than 0.2V that zinc coating forms is set instead of coating 30.In order to more enter One step improves barrier, and above-mentioned corrosion potential is more preferably more than -0.7V.

As illustrated in figure 1, the superficial layer 40 being made up of more than 1 layer of envelope is formd on the surface of coating 30.Table Surface layer 40 is arranged as required to.By forming superficial layer 40, so that corrosion resistance improves.

More than 1 layer of the envelope formed with superficial layer 40 preferably comprises organic resin (R).

As organic resin (R) contained in envelope, it is not particularly limited, such as can include：Polyurethane resin.

, can be by one kind or two or more organic resin (unmodified organic tree as organic resin (R) contained in envelope Fat) it is used in mixed way, also can be in the presence of at least one kind of organic resin, by one kind or two or more by the way that at least one kind of other are had Organic resin obtained from machine resin is modified is used in mixed way.

As the above-mentioned polyurethane resin used in organic resin (R), such as can include：Make polyol compound with it is more After isocyanate compound reaction, product etc. obtained from cahin extension agent makes chain lengthening.

As the above-mentioned polyol compound of the raw material as polyurethane resin, as long as every 1 molecule contains more than 2 Hydroxyl compound, then be not particularly limited, such as can include：It is ethylene glycol, propane diols, diethylene glycol (DEG), 1,6-HD, new Pentanediol, triethylene glycol, glycerine, trimethylolethane, trimethylolpropane, polycarbonate polyol, PEPA, bis-phenol hydroxyl The PPGs such as base propyl ether, polyester amide polyol, acrylic polyol, polyurethane polyol or their mixing Thing.

As the above-mentioned polyisocyanate compound of the raw material as polyurethane resin, using every 1 molecule contain 2 with The compound of upper NCO, such as can include：It is the aliphatic isocyanates such as hexamethylene diisocyanate (HDI), different The aromatic diisocyanates such as the alicyclic diisocyanates such as isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI) Araliphatic diisocyanate or their mixtures such as ester, methyl diphenylene diisocyanate (MDI).

Used above-mentioned cahin extension agent during as manufacture polyurethane resin, contains more than 1 reactive hydrogen using in intramolecular Compound, such as can include：Ethylenediamine, propane diamine, hexamethylene diamine, diethylenetriamines, dipropylenetriamine, three The fragrance such as the aliphatic polyamines such as ethylene tetra, tetren, toluenediamine, benzene dimethylamine, diaminodiphenyl-methane Ester ring type polyamines, hydrazine, the ambers such as race's polyamines, diaminourea cyclohexyl-methane, piperazine, 2,5- lupetazins, IPD The hydrazines such as acid dihydrazide, adipic dihydrazide, terephthaldehyde's acid dihydrazide, hydroxyethyl diethylenetriamine, 2- [(2- amino second Base) amino] alkanolamine such as ethanol, 3- amino-propanediols etc..These be used as cahin extension agent compounds can be used alone or Two or more is used in mixed way.

In addition, the polyurethane resin used in organic resin (R) can also be the material obtained as follows：Closing will be included The material solution of isocyanate compound and above-mentioned polyol compound is heated to the temperature of sealer dissociation, makes the isocyanide of regeneration The polyol component of perester radical and polyol compound contained in material solution reacts and obtained.

Blocked isocyanate compound is more than the temperature dissociated by being heated to sealer so as to regenerating NCO. As blocked isocyanate compound, such as can use the NCO of above-mentioned polyisocyanate compound public affairs in the past The sealer known carries out the product that masking forms.As sealer, such as dimethyl pyrazole (DMP), methyl ethyl ketoxime can be used Deng.

More than 1 layer of envelope of superficial layer 40 is formed in addition to comprising organic resin (R), further preferably includes and is selected from phosphoric acid 1 kind or 2 kinds in compound (P), organo-silicon compound (W), carbon black (C), fluorine metal complex compound (F) and Tissuemat E (Q) with On raw material.

The phosphate cpd (P) contained in envelope is more preferably the compound that phosphate ion is released in envelope.In phosphoric acid In the case that compound (P) is releases the compound (P) of phosphate ion in envelope, when envelope is formed for forming envelope When coating composition contacts with coating 30, or in envelope the phosphate ion of later autophosphorylation compound is formed from envelope dissolution When, phosphate cpd (P) forms slightly solubility with being reacted in barium oxide existing for the surface of coating 30, on the surface of coating 30 Phosphoric acid-vanadium system envelope.Thereby, it is possible to resistance to white rust is significantly increased.

In the case where phosphate cpd (P) is the compound for the non-solubility for not releasing phosphate ion in the environment, by The phosphate cpd (P) contained in envelope can hinder the movement of the corrosion factors such as water, oxygen, therefore can obtain excellent barrier Property.

As phosphate cpd (P) contained in envelope, such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, three phosphorus can be used Phosphoric acid class, the ammonium dihydrogen phosphates such as acid, four phosphoric acid.These phosphate cpds (P) can be used alone, also can and with two or more come Use.

The content of contained phosphate cpd (P) is preferably 1~20 mass % in terms of phosphate ion in envelope, more preferably 6~18 mass %, most preferably 10~15 mass %.If the concentration of contained phosphate ion is more than 1 mass % in envelope, Excellent barrier can then be obtained.In addition, if the phosphoric acid ion concentration in envelope is below 20 mass %, then can prevent As the film bulging caused by phosphoric acid dissolution.

In the case of containing phosphate cpd (P) in envelope, formed on the surface of steel plate 1 comprising the vanadium in coating 30 and The barrier layer (not shown) for corrosion factor (water, oxygen etc.) with excellent barrier of phosphate cpd in envelope. As a result, compared with not forming the situation of superficial layer 40 on the surface of coating 30, can obtain excellent in resistance to white rust Make the effect for giving birth to red rust delay simultaneously, barrier significantly improves.

As the organo-silicon compound (W) contained in envelope, such as can exemplify：The hydrolytic condensate of silane coupler Deng.

As the silane coupler for organo-silicon compound (W) generation in envelope, such as can include：3- shrinks sweet Oily epoxide propyl trimethoxy silicane, APTES.Above-mentioned silane coupler can be used alone, and can also incite somebody to action Two or more is used in combination.

Organo-silicon compound (W) in envelope preferably by the silane coupler (W1) containing amino and contain epoxy radicals The reaction of silane coupler (W2) and obtain.In this case, the reaction by amino and epoxy radicals and silane coupler (W1) with silane coupler (W2) it is respective between the alkoxysilyl that contains or part thereof hydrolysis product Reaction, so as to form the high fine and close envelope of crosslink density.As a result, the barrier of surface treated steel plate, scratch resistance, resistance to Contaminative further improves.

As the silane coupler (W1) containing amino, such as can exemplify：APTES.As Silane coupler (W2) containing epoxy radicals, such as can exemplify：3- glycidoxypropyltrimewasxysilanes (3- Glycidoxypropyltrimethoxysilane)。

The mol ratio of silane coupler (W1) containing amino and the silane coupler (W2) containing epoxy radicals [(W1)/ (W2) it is preferably] 0.5~2.5, more preferably 0.7~1.6.If mol ratio [(W1)/(W2)] is more than 0.5, can obtain Obtain and sufficiently make film, therefore barrier improves.In addition, if above-mentioned mol ratio is less than 2.5, then can obtain sufficiently Water resistance, therefore excellent barrier can be obtained.

Organo-silicon compound (W) preference such as number-average molecular weight contained in envelope be 1000~10000 it is siliconated Compound, more preferably 2000~10000 organo-silicon compound.If the number-average molecular weight of organo-silicon compound (W) is 1000 More than, then it can turn into the envelope of excellent water resistance, alkali resistance and barrier become better.On the other hand, it is if siliconated The number-average molecular weight of compound (W) is less than 10000, then organo-silicon compound (W) can be made to be used as the water-based of principal component using water Stably dissolve or disperse in medium, have the situation of bin stability reduction.

As the assay method of the number-average molecular weight of organo-silicon compound (W), it can use and use time-of-flight type mass spectrum (TOF-MS：Time of flight mass spectrometry) method carry out direct measure, also can use use chromatography The conversion measure of progress.

The mass ratio (R/W) of organic resin (R) and organo-silicon compound (W) in the envelope is preferably 1.0~3.0. If R/W is more than 1.0, it is difficult to occur to condense to destroy in envelope in processing, processing adaptation becomes good.In addition, If R/W is less than 3.0, the effect as caused by containing organo-silicon compound (W) can be fully obtained, can be obtained hard Spend high envelope.

Organo-silicon compound (W) can for example manufacture with the following method：Above-mentioned silane coupler is set to dissolve or disperse In water, the stipulated time is stirred at an established temperature, obtains hydrolytic condensate.

Envelope containing organo-silicon compound (W) can for example be formed with the following method：Manufacture contains organosilicon compound Raw material of the waterborne liquid or alcohol system liquid of thing (W) as the coating composition of envelope formation, will include the waterborne liquid or The coating composition of alcohol system liquid is coated on coating, is dried.

Waterborne liquid containing organo-silicon compound (W) or alcohol system liquid can for example manufacture with the following method：Make silicon The organo-silicon compound such as the hydrolytic condensate of alkane coupling agent are dissolved or dispersed in water and obtain the method for waterborne liquid；Make silane The organo-silicon compound such as the hydrolytic condensate of coupling agent are dissolved in the alcohol such as methanol, ethanol, isopropanol system organic solvent and obtained Method of alcohol system liquid etc..

In waterborne liquid or alcohol system liquid of the manufacture containing organo-silicon compound (W), except organo-silicon compound (W) and Beyond water or alcohol system organic solvent, in order that silane coupler or its hydrolytic condensate are dissolved or dispersed in waterborne liquid or alcohol system In liquid, acid, alkali, organic solvent, surfactant etc. can be also added.It is particularly steady from the storage of waterborne liquid or alcohol system liquid From the viewpoint of qualitative, organic acid is also preferably added in addition to water or alcohol system organic solvent, by waterborne liquid or alcohol system liquid PH adjust to 3~6.

The solid component concentration of organo-silicon compound (W) in the waterborne liquid or alcohol system liquid of organo-silicon compound (W) Preferably below 25 mass %.If the solid component concentration of organo-silicon compound (W) is below 25 mass %, the aqueous solution The bin stability of body or alcohol system liquid can become good.

In envelope, preferably comprise carbon black (C) and be used as coloring pigment.In the case of containing carbon black in envelope, in coating Fine spot can be concealed existing for surface, turned into beautiful appearance of black, can be obtained excellent design.

As carbon black (C) contained in envelope, such as can include：Furnace black, Ketjen black, acetylene black, channel black The carbon black Deng known to.In addition, as carbon black (C) contained in envelope, it can be used and implement known ozone processing, plasma Processing, the carbon black of liquid phase oxidation processing.

Contained carbon black (C) in envelope as long as dispersiveness of the particle diameter in the coating composition of envelope formation, apply The scope being had no problem in the quality of film, coating, has no special restriction.If making carbon black dispersion in water solvent, It can then be condensed during scattered.Therefore, in general, it is difficult to carbon black is dispersed in water solvent with the state of primary particle size In.Therefore, carbon black contained in the coating composition of envelope formation is with the offspring with the particle diameter bigger than primary particle size Form exist.Thus, the carbon black in the envelope formed using the coating composition also with coating composition in the same manner as with two The form of secondary particle is present.

As the carbon black of the raw material as envelope, such as the carbon black that primary particle size is 10nm~120nm can be used.If Consider the design and barrier of envelope, then the particle diameter of carbon black contained in envelope is preferably 10nm~50nm.

In order to ensure the design and barrier of envelope, the particle diameter of the carbon black for the offspring form disperseed in envelope is Important.The average grain diameter of carbon black in envelope is preferably 20nm~300nm.

The content of contained carbon black (C) is preferably for example set as 1~20 mass %, more preferably 3~15 matter in envelope % is measured, is most preferably defined as 5~13 mass %.If the content of contained carbon black (C) is more than 1 mass % in envelope, can Access uniform appearance of black.In addition, if the content of carbon black (C) contained in envelope is below 20 mass %, then can Ensure the content of the raw material beyond carbon black (C) contained in envelope, therefore excellent barrier can be obtained.

Fluorine metal complex compound (F) can be contained in envelope.Fluorine metal complex compound (F) plays in envelope as crosslinking agent to be made With improving the cohesiveness of envelope.Fluorine metal complex compound (F) is not particularly limited, and from the viewpoint of barrier, is preferably used Fluorine metal complex compound with titanium.As such fluorine metal complex compound (F), such as can include：Titanium etching acid.

Tissuemat E (Q) can be contained in envelope.Tissuemat E (Q) can improve the scratch resistance of envelope.Therefore, if Contain Tissuemat E (Q) in envelope, then the lubricity of above-mentioned surface treated steel plate improves, for example, by steel plate and compacting tool set Contact caused by frictional resistance mitigate, scar when damage at steel plate processing department and disposal steel plate can be prevented.

As Tissuemat E (Q) contained in envelope, it is not particularly limited, known lubricant can be used.It is specific and Speech, as Tissuemat E (Q), preferably using vistanex base lubricant.

As the vistanex base lubricant as Tissuemat E (Q), it is not particularly limited, such as can includes：It is poly- The wax of the hydrocarbon systems such as ethene.

The content of contained Tissuemat E (Q) is the mass % of 0.5 mass %~10 preferably in envelope in envelope, more preferably For the mass % of 1 mass %~5.If the content of Tissuemat E (Q) is more than 0.5 mass %, scratch resistance can be obtained and carried High effect.If the content of Tissuemat E (Q) is below 10 mass %, Tissuemat E contained in envelope is able to ensure that (Q) content of the raw material beyond, therefore excellent barrier can be obtained.

" manufacture method of surface treated steel plate 10 "

Next, the manufacture method of surface treated steel plate 10 is illustrated.

The manufacture method of the surface treated steel plate of present embodiment is characterised by that this method has：Substrate formation process, It is by using the Zn containing 0.10~4.00mol/l²⁺Ion and 0.01~2.00mol/l V ions or 0.10~ The plating bath of 4.00mol/l Zr ions is with 0~18A/dm²Current density electroplated, so as to make the vanadium of hydration on steel plate 1 Oxide or vanadium hydroxide are separated out and formed concavo-convex；With upper strata plating process, it uses the steel plate 1 for foring bumps above-mentioned Plating bath and with 21~200A/dm²Current density electroplated.Above-mentioned substrate formation process be pointed to it is upper in coating The factor that the mol ratio i.e. V/Zn of the vanadium and the zinc between the crystal stated in filling region has an impact.In the substrate The current density of formation process is more than 18A/dm²In the case of, the mol ratio of vanadium and zinc between crystal in filling region is V/Zn As less than 0.10.

In present embodiment, on the two sides for the steel plate 1 for forming coating 30, pre-treatment is carried out as needed.As pre-treatment, It is preferred that carry out thickness on the two sides of steel plate 1 forms basalis 20 for 1~300nm nickel plating.

Then, coating 30 is formed in the one or two sides of steel plate 1.In present embodiment, to use the plating shown in Fig. 3 Device is formed exemplified by the method for coating 30 on the two sides of steel plate 1 using galvanoplastic and illustrated.

Fig. 3 is the skeleton diagram for an example for representing plater.In present embodiment, among roller 4a, 4b, 5a, 5b, Roller 4a, 4b of the top configuration of steel plate 1 play as the connection member (conductor) for electrically connecting power supply (not shown) with steel plate 1 Function.Steel plate 1 with roller 4a, 4b by electrically connecting, so as to turn into negative electrode.In the case of carrying out plating, by the plating shown in Fig. 3 More of coating device arranged in series and use.Substrate formation process shown plater or 4a, 5a in figure 3 in figure 3 Roller with being carried out in 2d, 2f medial fascicle road area encompassed.In addition, upper strata plating process shown plating in figure 3 Carried out in device or 2d, 2f in figure 3 medial fascicle road and roller 4b, 5b area encompassed.

Coating bath 21 has the upper slot 21a on the top for being configured at steel plate 1 and is configured at the lower channel 21b of the bottom of steel plate 1.

As illustrated, the position adjacent with steel plate 1 in upper slot 21a and in lower channel 21b, with steel Compartment of terrain as defined in being had in vain between plate 1 is configured with multiple anodes 3 made of platinum etc..By the face relative with steel plate 1 of each anode 3 By with the surface of steel plate 1 it is almost parallel in a manner of configure.By each anode 3 by connection member (not shown) come with power supply (not Illustrate) electrical connection.

It will be full of in upper slot 21a and with plating bath 2 in lower channel 21b.As illustrated, on the top of coating bath 21 The steel plate 1 for making face direction substantially horizontally move is configured between groove 21a and lower channel 21b.Then, by roller 4a, 4b, 5a, 5b and the steel plate 1 that passes through according to the direction of arrow in the coating bath 21 becomes the plating being impregnated in upper slot 21a and in lower channel 21b State in bath 2.Therefore, in present embodiment, steel plate 1 is made in plating bath by using roller 4a, 4b, 5a, 5b to carry steel plate 1 Moved in 2, become the plating bath 2 of the flow regime of relative flow hence for plating bath 2 for steel plate 1.

As illustrated, to be provided with a manner of penetrating upper slot 21a upper surface upwards in upper slot 21a Pipe arrangement 2a is used in the top supply of portion groove 21a supply plating bath 2.Top supply is branched into outside multiple with pipe arrangement 2a in upper slot 21a All branch path 2c and multiple medial fascicle road 2d (1 is only illustrated in Fig. 3).Medial fascicle road 2d be with overlook in adjacent sun It is configured between pole 3 along the width of steel plate 1 multiple.Medial fascicle road 2d possesses between the anode 3 and steel plate 1 of both sides Supply the opening portion of plating bath 2.Periphery branch path 2c be with overlook between anode 3 and roller 4a, 4b along the width side of steel plate 1 It is multiple to being configured with.Periphery branch path 2c possesses to the opening portion that plating bath 2 is supplied between anode 3 and steel plate 1.

The outlet (not shown) of discharge plating bath 2 is provided with upper slot 21a, (is not schemed via the pipe arrangement for possessing pump Show) it is connected with top supply with pipe arrangement 2a.Therefore, for upper slot 21a, by top supply pipe arrangement 2a supplies, from row The plating bath 2 of outlet discharge becomes the flowing shape for being supplied and being circulated by top supply pipe arrangement 2a again via pipe arrangement using pump The plating bath 2 of state.

In lower channel 21b plating bath 2 is supplied to be provided with a manner of penetrating lower channel 21b lower surface to lower channel 21b Bottom supply use pipe arrangement 2b.Bottom supply branches into lower channel 21b multiple periphery branch path 2e and multiple with pipe arrangement 2b Medial fascicle road 2f (only illustrates 1) in Fig. 3.Medial fascicle road 2f be with overlook between adjacent anode 3 along steel plate 1 Width be configured with it is multiple.Medial fascicle road 2f possesses to the opening that plating bath 2 is supplied between the anode 3 and steel plate 1 of both sides Portion.Periphery branch path 2e be with overlook between anode 3 and roller 5a, 5b be configured with along the width of steel plate 1 it is multiple.Outside All branch path 2e possess to the opening portion that plating bath 2 is supplied between anode 3 and steel plate 1.

The outlet (not shown) of discharge plating bath 2 is provided with lower channel 21b, (is not schemed via the pipe arrangement for possessing pump Show) it is connected with bottom supply with pipe arrangement 2b.Therefore, for lower channel 21b, by bottom supply pipe arrangement 2b supplies, from row The plating bath 2 of outlet discharge becomes the flowing shape for being supplied and being circulated by bottom supply pipe arrangement 2b again via pipe arrangement using pump The plating bath 2 of state.

If the conduction time in substrate formation process is adjusted to 0.05 second~8.00 seconds, filling region 32 between crystal In stably show amorphous diffraction pattern.

In present embodiment, according to presumption：Coating 30 is formed on the surface of steel plate 1 by mechanism as shown below.Fig. 4 A~ Fig. 4 C are the signals for illustrating to manufacture the state on the surface of the steel plate 1 in the process of the surface treated steel plate 10 shown in Fig. 1 Figure.

For the plater shown in Fig. 3, exist from the steel plate 1 that nickel coating (basalis) 20a is formd on surface The part passed through between roller 4a, 5a starts to contact with plating bath 2 successively, with 18A/dm²Following current density starts plating.

That is, roller 4a, 5a is the roller for being powered, also referred to as conductive rollers (Conductor roll).Steel plate and plating Liquid connects afterwards between conductive rollers 4a, 5a have been passed through.

In present embodiment, in surface (solid-liquid circle for having passed through the steel plate 1 for foring nickel coating 20a between roller 4a, 5a Face), before zinc precipitation, as shown in Figure 4 A, start substrate formation process, the process has separated out the vanadium oxygen for including hydration The vfanadium compound 6 of compound or vanadium hydroxide, formed concavo-convex.

According to presumption, because：In 18A/dm²Under following current density, the high vanadium reduction of deposition potential separates out, but analyses Go out the low zinc of current potential not separate out.In addition, in above-mentioned substrate formation process, the barium oxide or vanadium hydrogen for including hydration are separated out The vfanadium compound 6 of oxide.The substrate is different from described basalis 20.The substrate is finally incorporated into coating 30.

For substrate formation process, if starting the precipitation in the vfanadium compound 6 on the surface of steel plate 1, as in Fig. 4 A It is shown such, multiple current convergence portions 61 are formed on the surface of steel plate 1.It can speculate：Current convergence portion 61 is by the table of steel plate 1 The electric current that the few part of the 6 undecomposed part of vfanadium compound in face, amount of precipitation is formed easily flows part.

If set to 21A/dm²Current density above, then Zn deposition potential is reached, the reduction for starting Zn separates out instead Should.As shown in Figure 4 B, current convergence portion 61 turns into starting point, the skeleton 3a growths containing metallic zinc, upper strata plating Process is covered to start.According to presumption：If skeleton 3a grows, in skeleton 3a point, crystallization becomes more to hold Easily growth.

For the plating process of top, with skeleton 3a growth, in multiple branches of skeleton 3a branches The sophisticated electric current in portion becomes to concentrate, according to presumption：As shown in FIG. 4 C, produced at the tip in branch portion and the solid liquid interface of plating bath 2 Raw hydrogen 62.

Hydrogen 62 caused like this rises the pH of skeleton 3a surface and the solid liquid interface of plating bath 2.Estimate it Result is：Crystallization containing zinc oxide or zinc hydroxide is formed by being separated out in a manner of covering the surface of skeleton 31 The skeleton 31 with top layer 3b shown in Fig. 1.In addition, according to presumption：Due to the pH of plating bath 2 rising, adjacent The noncrystalline of the barium oxide containing hydration or vanadium hydroxide is separated out between skeleton 31, forms the crystalline substance shown in Fig. 1 Filling region 32 between body.

In present embodiment, as described above, in substrate formation process, conduction time was controlled at 0.05~8.00 second Scope.Therefore, before the surface of steel plate 1 separates out zinc, start the precipitation of vfanadium compound 6, multiple electricity are formed on the surface of steel plate 1 61 in the middle part of adfluxion.Presumption the result is that：By above-mentioned mechanism, skeleton 31 can be obtained, can obtain carrying out Filling region 32 between the crystal of amorphous diffraction pattern is shown in the case of electron beam diffraction.Pass through the steel plate 1 of interval D Traveling time is more preferably the scope of 1.00~6.00 seconds.

If the conduction time of substrate formation process is less than 0.05 second, separated out before the surface of steel plate 1 separates out zinc Vfanadium compound 6 amount of precipitation deficiency.Therefore, the skeleton 31 formed by metallic zinc becomes to be difficult on the surface of steel plate 1 The current convergence portion 61 of formation grows.In addition, it can not obtain containing the barium oxide being hydrated or be filled out between the crystal of vanadium hydroxide Fill region 32 or even if having obtained filling region 32 between crystal but amorphous diffraction pattern also becomes unstable.

If the conduction time of substrate formation process more than 8.00 seconds, is separated out before the surface of steel plate 1 separates out zinc The amount of precipitation of vfanadium compound 6 become excessive, the quantity in the current convergence portion 61 that the surface of steel plate 1 is formed tails off or disappeared Lose.Therefore, the skeleton 31 formed by metallic zinc becomes to be difficult to grow or can not obtain skeleton 31 and crystal Between filling region 32, or even if having obtained filling region 32 between crystal, amorphous diffraction pattern can also become unstable.

In present embodiment, in substrate formation process, preferably turn into 0~18A/dm in current density²Under conditions of enter Row plating, more preferably as 2~15A/dm²Under conditions of electroplated.By making the current density in substrate formation process As 18A/dm²Below so that the mol ratio (V/Zn) of vanadium and zinc between crystal in filling region 32 turn into 0.10~2.00, and And filling region 32 shows amorphous diffraction pattern between crystal in the case of having carried out electron beam diffraction, as a result, Barrier and film adaptation can be improved.On the other hand, if the current density in substrate formation process is not above range It is interior, then filling region 32 between crystal can not be formed, or even if form filling region 32 between crystal, amorphous diffraction pattern Also can become unstable.

In addition, in the plating process of upper strata, preferably turn into 21~200A/dm in current density²Under conditions of electroplated. By making above-mentioned current density turn into 21A/dm²More than, so as in the tip in the branch portion of skeleton 31 and plating bath 2 Solid liquid interface fully produce hydrogen 62.Therefore, the barium oxide or vanadium hydrogen-oxygen of hydration contained in filling region 32 between crystal The amount of precipitation increase of compound.Thus, it is possible to form the coating 30 that content of vanadium is more, barrier is excellent.In addition, if current density surpasses Cross 200A/dm², then coating structure is thicker, becomes easily to crack, therefore have can for the adaptation between coating 30 and steel plate 1 It can reduce.

The mean flow rate of the plating bath 2 in coating bath 21 when carrying out plating is preferably the scope of 20~300m/ minutes, more preferably For the scope of 40~200m/ minutes.Plating bath 2 mean flow rate be 20~300m/ minutes in the range of in the case of, Neng Goufang Only in coating 30 crackle generation, at the same time can carry out without barrier from ion from plating bath 2 to the surface of steel plate 1 confession Give.

As plating bath 2, the plating bath containing V compounds and Zn compounds is used.In addition, in plating bath 2, except V compounds Beyond Zn compounds, can also add as needed pH adjusting agent, be not V compounds and Zn compounds other metal compounds Thing, additive.

As pH adjusting agent, can include：H₂SO₄, NaOH etc..

As additive, can include：Make the Na of the stable conductivity of plating bath 2₂SO₄Deng.

As other metallic compounds, can include：NiSO₄·6H₂Nickel compounds such as O etc..Contain nickel chemical combination in plating bath 2 In the case of thing, the Ni containing more than 0.01mol/l preferably in plating bath 2²⁺.Thereby, it is possible to form the fully coating containing nickel 30.Coating 30 containing nickel is due to that can obtain excellent plating adaptation, therefore preferably.

As the Zn compounds used in plating bath 2, can include：Metal Zn, ZnSO₄·7H₂O、ZnCO₃Deng.These can be single Solely use, also two or more may be used.

In addition, as the V compounds used in plating bath 2, can include：Ammonium metavanadate (V), potassium metavanadate (V), metavanadic acid Sodium (V), VO (C₅H₇O₂)₂(vanadyl acetylacetonate (IV)), VOSO₄·5H₂O (vanadic sulfate (IV)) etc..These can individually make With also two or more may be used.

As plating bath 2, preferably using containing Zn²⁺And VO²⁺Plating bath.

Contain Zn in plating bath 2²⁺In the case of, preferably comprise 0.10~4.00mol/l Zn²⁺, further preferably 0.35~ 2.00mol/l。

Contain VO in plating bath 2²⁺In the case of, containing 0.01mol/l less than 2.00mol/l preferably in plating bath 2 VO²⁺.By using containing VO within the above range²⁺Plating bath 2, so as to be readily formed, content of vanadium is more, barrier is excellent Different coating 30.The contained VO in plating bath 2²⁺Content be less than above range in the case of, it becomes difficult to ensure in coating 30 Content of vanadium.In addition, if VO contained in plating bath 2²⁺Content exceed above range, then it is a large amount of using expensive in plating bath 2 Vanadium, therefore economically become unfavorable.

In addition, as plating bath 2, it is preferably used in plating bath 2 and contains more than 0.10mol/l Na⁺Plating bath.Such case Under, it is possible to increase the electric conductivity of plating bath 2, it is able to easily form the coating 30 of present embodiment.

The temperature of plating bath 2 is not particularly limited, but in order to easily expeditiously form the coating 30 of present embodiment, preferably For 40~60 DEG C of scope.

In addition, in order to be readily formed the coating 30 of present embodiment, the pH of plating bath 2 is preferably 1~5 scope, more excellent Elect 1.5~4 scope as.

In present embodiment, preferably：After coating 30 is formd, as needed on coating 30 coating improve barrier, The inorganic agent of anti-finger printing, scratch resistance, lubricity, design etc. forms superficial layer 40.

Process more than, can obtain the surface treated steel plate 10 shown in Fig. 1.

" the 2nd embodiment, surface treated steel plate 210 "

Below in coating 230 containing zirconium in the case of the surface treated steel plate 210 of the 2nd embodiment illustrate.

The surface treated steel plate 210 of present embodiment possesses：Steel plate 201；With coating 230, it is in the one side of steel plate or two Face is formed.Contain zinc and zirconium in coating 230.In addition, contain in coating 230：Skeleton 231, it includes metallic zinc；And crystalline substance Filling region 232 between body, it includes one of the Zirconium oxide of hydration or zirconium hydroxide or both.Below to surface treated steel Plate 210 is described in detail.

The steel plate 1 of the embodiment of steel plate 201 and the 1st is same, therefore omits the description.

As described above, coating 230 has：Skeleton 231, it includes metallic zinc；Filling region 232 between crystal, It includes one of the Zirconium oxide of hydration or zirconium hydroxide or both.

Skeleton 231 is the dendritic crystalline phase for including metallic zinc, and filling region 232 includes the zirconium of hydration between crystal One of oxide or zirconium hydroxide or both, it is formed at around skeleton 231, has by electron beam diffraction Amorphous pattern.

Coating 230 has following form：Skeleton 231 first separates out, and then, filling region 232 is in branch between crystal Separated out around shape crystal 231.

As described above, the skeleton 31 of the 1st embodiment has internal 3a and top layer 3b.As described above, dendroid The inside 3a of crystal 31 preferably comprises metallic zinc, can also include other metal ingredients such as nickel.On the other hand, skeleton 31 Top layer 3b preferably comprises zinc oxide or zinc hydroxide, the crystal of the zinc oxide more preferably comprising hydration.On the other hand, originally The skeleton 231 of embodiment is without internal and top layer.

Skeleton 231 can be formed only by metallic zinc, and the precipitation electricity than zinc can be also contained while containing metallic zinc Other metal ingredients such as the high nickel in position.In addition, skeleton 231 has following structure：Along coating 230 thickness direction from The lateral face side of coating 230 of steel plate 201 growth, towards the surface of coating 230 and branch.Metal is included by skeleton 231 Zinc, sacrifice corrosion protection so as to be assigned to coating 230.

Filling region 232 is in addition to one of Zirconium oxide comprising hydration or zirconium hydroxide or both between crystal, Also zinc oxide can be included.Thing is contained comprising these by filling region between crystal 232, hindered so as to be assigned to coating 230 Every property.Further, since filling region 232 therefore is filled out based on the oxide or hydroxide of hydration between crystal between crystal Fill in the case that region 232 forms film, it can be ensured that film adaptation.

Filling region 232 shows amorphous diffraction pattern in the case where having carried out electron beam diffraction between crystal.

In the case that filling region 232 includes the Zirconium oxide or zirconium hydroxide and zinc oxide of hydration between crystal, The mol ratio (Zr/Zn) of zirconium and zinc between preferred crystal in filling region 232 is 1.00~3.00.Pass through above-mentioned mol ratio (Zr/Zn) it is above range, and filling region 232 shows noncrystalline between crystal in the case of having carried out electron beam diffraction Diffraction pattern, so as to obtain excellent corrosion resistance (barrier) and film adaptation.

It may be formed on the upper strata of coating 230 and show amorphous diffraction pattern in the case of having carried out electron beam diffraction Uncrystalline layer 250.

By inference：Uncrystalline layer 250 originally forms when coating 230 is formed.I.e., by inference：On steel plate 201 most Uncrystalline layer 250 is just formed, then, between steel plate 201 and uncrystalline layer 250, comprising being filled out between skeleton 231 and crystal The coating 230 for filling region 232 is grown.

Uncrystalline layer 250 is the layer based on zirconium oxide, can include micro zinc.Uncrystalline layer 250 is by coating 230 upper strata is formed so as to play barrier.

After the formation of coating 230, by the way that the steel plate 201 with coating 230 is impregnated in into acid solution, so as to remove Uncrystalline layer 250.By such process, can be removed from surface treated steel plate 201 by uncrystalline layer 250.

By removing uncrystalline layer 250, so as to expose coating 230.The surface of coating 230 is compared with uncrystalline layer 250, table Face rugosity is high, compared with the situation formed with uncrystalline layer 250, becomes film excellent adhesion.

In order to improve barrier, the adhesion amount of coating 230 is preferably 1g/m²More than, more preferably 3g/m²More than.In addition, The adhesion amount of coating 230 is preferably 60g/m²Hereinafter, more preferably 40g/m²Hereinafter, more preferably 20g/m²Below.Plating The adhesion amount of layer 230 is 20g/m²(it is usually 20g/m with conventional electrogalvanizing in the case of below²Left and right) etc. compare, make institute The amount of metal of precipitation can solve less.In addition, if adhesion amount is excessive, then easily cracked in coating 230.

The thickness of coating 230 is preferably the scope of 0.5~40 μm of scope, more preferably 1.0~20 μm, further preferably For 2.0~15 μm of scope.If the thickness of coating 230 is more than lower limit, barrier can be improved.In addition, if coating 230 thickness is below the upper limit, then is difficult to crack in coating 230.When the thickness of coating 230 can be electroplated by adjusting The electricity of energization is controlled.

The thickness of uncrystalline layer 250 is preferably the scope of 0.20~2.00 μm of scope, more preferably 0.30~1.50 μm, More preferably 0.50~1.00 μm of scope.If the thickness of uncrystalline layer 250 is more than lower limit, can be to coating 230 assign barrier.In addition, if the thickness of uncrystalline layer 250 is below the upper limit, then it can prevent the generation of crackle and ensure Barrier.The thickness of uncrystalline layer 250 can be controlled by the Zr concentration in plating bath during adjustment plating.That is, more improve Zr concentration during plating in plating bath, the thickness of uncrystalline layer 250 can be more set to become big.

For coating 230, Zr is included in terms of mean concentration：3~40 atom %, Zn：3~40 atom %, remainder Include oxygen and impurity.If the Zr in coating 230 is more than 3 atom %, barrier can be improved.In addition, if coating 230 In Zr be below 40 atom %, then can prevent the generation of the crackle in coating 230 and ensure barrier.In addition, if plating Zn in layer 230 is more than 3 atom %, then coating 230 can be assigned and sacrifice corrosion protection result.In addition, if in coating 230 Zn is below 40 atom %, then can relatively ensure Zr amount, it is possible to increase the barrier of coating 230.

As described above, skeleton 231 contains metal Zn, it can also contain Ni etc. in addition.

Skeleton 231 is carrying out electron beam diffraction using transmission electron microscope (TEM) by the section of coating 230 In the case of, the diffraction pattern due to crystal structure can be obtained.

For filling region between crystal 232, Zr is included in terms of mean concentration：10~80 atom %, Zn：3~40 is former Sub- %, remainder include oxygen and impurity.If the Zr between crystal in filling region 232 is more than 10 atom %, can carry High barrier.In addition, if the Zr between crystal in filling region 232 is below 80 atom %, then can prevent in coating 230 The generation of crackle and ensure barrier.In addition, if the Zn between crystal in filling region 232 is more than 3 atom %, then can carry High barrier.In addition, if the Zn between crystal in filling region 232 is below 40 atom %, then it can relatively ensure Zr's Amount, it is possible to increase the barrier of coating 230.

For uncrystalline layer 250, Zr is included in terms of mean concentration：10~60 atom %, Zn：0~15 atom %, residue Part includes oxygen and impurity.If the Zr in uncrystalline layer 250 is more than 10 atom %, barrier can be improved.In addition, such as Zr in fruit uncrystalline layer 250 is below 60 atom %, then can prevent the generation of crackle and ensure barrier.In uncrystalline layer Contain micro Zn in 250, can be free of Zn.

It is same with the 1st embodiment for this point of basalis 220 can be formed between steel plate 201 and coating 230 Sample.

For table can be formed on the upper strata of coating 230 (being uncrystalline layer 250 in the case where foring uncrystalline layer 250) For this point of surface layer 240, in a same manner as in the first embodiment.

The L* values of the expression lightness of the surface treated steel plate 210 of present embodiment show less than 40, have the outer of black See.By the outward appearance with black, so as to be used in various uses.In the case where L* values are more than 40, it is difficult to as tool There is the materials'use of appearance of black.Turn into more than 5 mass % especially by the Zr concentration made in coating 230, so as to true L* values are made to turn into less than 40 on the spot.

In addition, for the surface treated steel plate 210 of present embodiment, the example to foring coating 230 on steel plate 201 Son is illustrated, but present embodiment is not limited to this, can invade plating in plated steel sheet, hot-dipping galvanized steel plate, alloying heat The coating 230 of present embodiment is formed on the zinc coating of zinc steel plate.That is, can further be formed between steel plate 201 and coating 230 The 2nd zinc coating (not shown) containing zinc.By further forming the 2nd zinc coating (not shown), so as to further Improve the corrosion resistance of surface treated steel plate 210.For example, in the case that corrosive deposit has passed through coating 230, can also lead to The 2nd zinc coating (not shown) is crossed to play sacrifice corrosion protection result, it is possible to increase the corrosion resistance of surface treated steel plate 210.

" manufacture method of surface treated steel plate 210 "

Next, the manufacture method of surface treated steel plate 210 is illustrated.The manufacture method of surface treated steel plate 210 From the manufacture method of the surface treated steel plate 1 of the 1st embodiment simply on the composition of plating bath it is different, in terms of other It is same.

There is the manufacture method of surface treated steel plate 210 substrate formation process and upper strata to plate in a same manner as in the first embodiment Cover process.Identical plating bath is used in substrate formation process and upper strata plating process, using including Zr compounds (ZrO²⁺) and Zn compounds (Zn²⁺) plating bath.

As Zr compounds, ZrO is preferably formed in plating bath²⁺The compound of ion, such as can exemplify：Nitric acid oxidation The soluble salt such as zirconium, sulfated zirconia, chlorination nitric acid oxidation zirconium.They can be used alone, and also two or more may be used.

Plating bath preferably comprises 0.10~4.00mol/l Zn²⁺, more preferably comprising 0.50~2.00mol/l.Additionally, it is preferred that ZrO comprising 0.10~4.00mol/l²⁺, more preferably comprising 0.50~2.00mol/l.By using including within the above range ZrO²⁺Plating bath, so as to Zr contents it is more, be able to easily form the excellent coating 230 of barrier.The contained ZrO in plating bath²⁺ Content be less than above range in the case of, it is difficult to ensure the Zr contents in coating 230.In addition, if contained by plating bath ZrO²⁺Content exceed above range, then turn into and largely use Zr in plating bath 2, therefore economically become unfavorable.

In plating bath, in addition to Zr compounds and Zn compounds, pH adjusting agent can be also added as needed, is not Zrization Compound and other metallic compounds of Zn compounds, additive etc..

Current density in substrate formation process and upper strata plating process in a same manner as in the first embodiment, therefore omits the description.

" other examples "

The present invention is not limited to above-mentioned embodiment.

In present embodiment, it is illustrated in case of foring coating on the two sides of steel plate, but coating also may be used Only formed in the one side of steel plate.

Additionally, it is preferred that formed with basalis between steel plate and coating, but can not also form basalis.In addition, in steel plate Two sides form coating in the case of, also only between the steel plate and coating of one side can form basalis.

In present embodiment, coating is described respectively and includes the situation of vanadium and the situation comprising zirconium, but can be also provided simultaneously with These embodiments.

In addition, in the present embodiment, be illustrated in case of foring superficial layer on the surface of coating, but Also superficial layer can not be formed.The surface treated steel plate of present embodiment can be on the surface of coating because barrier is excellent, therefore also The superficial layer for improving barrier is not formed.In addition, in the case of foring coating on the two sides of steel plate, also can be only in one side Coating surface formed superficial layer.

In addition, in present embodiment, using using the plater shown in Fig. 3 come manufacture the situation of surface treated steel plate as Example is illustrated, but the plater for manufacturing surface treated steel plate is not limited to the plater shown in Fig. 3.For example, 4 anodes 3 are configured with plater shown in Fig. 3, but for the number of anode 3, it is several can.In addition, to plating The configuration and shape of groove 21, the size of steel plate 1 and anode 3 and shape, top supply with pipe arrangement 2a and bottom supply pipe arrangement 2b It is not particularly limited, can be suitably determined according to purposes of surface treated steel plate 10 etc..

Embodiment 1

" result of the test of the surface treated steel plate containing vanadium "

It has been made to have on the two sides of steel plate using the plater shown in Fig. 3 and use method as shown below and has contained vanadium Coating surface treated steel plate, evaluated.

Prepare to make the plating bath composition shown in table 1, temperature, pH plating bath to enter by 100m/ minutes of relative mean flow rate The plating bath for the flow regime that row circulation forms.

Table 1

As steel plate, use and be as the thickness of slab of the SPCD of the drawing of cold-rolled steel sheet specified in JIS G 3141 0.5mm steel plate.

Pre-treatment (nickel plating) is carried out to above-mentioned steel plate, as negative electrode.

When being handled before progress, first, plating bath of the following plating bath as nickel plating is prepared for：By ion exchange water, dense sulphur Acid and NiSO₄·6H₂O is mixed, as Ni²⁺Containing 60g/L, the pH at 60 DEG C is 2.0.Then, steel plate is made to be impregnated in plating Bath, using steel plate as negative electrode, using platinum electrode as anode, turns into 200mg/m with Ni adhesion amounts²Mode carried out at electrolysis Reason.

In substrate formation process and upper strata plating process, each conduction time is set as the time shown in table 2 and table 3, Coating is formd using galvanoplastic.

Table 2

Table 3

It should be noted that during the plating bath shown in table 1 forms, ZnSO is used₄·7H₂O uses as Zn compounds VOSO₄·5H₂O further, has used Na as needed as V compounds₂SO₄, NiSO as other metallic compounds₄· 6H₂O.By adjusting their content, so as to adjust as the Zn shown in table 1²⁺、V(V⁴⁺、VO²⁺)、Na⁺、Ni²⁺Concentration.

Using field emission type transmission electron microscope (FE-TEM) (Jeol Ltd.'s system (JED-2100F)) to this The embodiment and the coating of comparative example that sample obtains are observed.

Fig. 5 A~Fig. 5 C are transmission electron microscope (TEM) photos of the coating of embodiment V4 surface treated steel plate. Fig. 5 A are the cross-section photographs in the whole thickness direction of the coating 30 formed on steel plate 1, and Fig. 5 B are the steel plates in Fig. 5 A section With the enlarged photograph of the interface portion of coating, Fig. 5 C are that the amplification of the skeleton and its peripheral part in Fig. 5 A section is shone Piece.

In figure 5b, symbol 51 is basalis, and symbol 52 is filling region between the crystal of steel plate and the near interface of coating. In addition, in figure 5 c, symbol 53 is skeleton, and the filling region between crystal of symbol 54, symbol 55 is in skeleton Surface formed top layer.

As shown in Fig. 5 A~Fig. 5 C, for embodiment V4 surface treated steel plate, tree is formd in coating Filling region, the top layer of skeleton between dendritic crystal, crystal.

For the coating of embodiment V1~V3 and V5~V20 surface treated steel plate, also used in the same manner as embodiment V4 TEM is observed.As a result, filling region between skeleton, crystal, the table of skeleton are formd in coating Layer.

For the coating of embodiment V4 surface treated steel plate, scanning electron microscope (SEM is used from section direction： Hitachi Ltd. A-4300SE) observed.For ease of observing the surface configuration of coating, the observation of coating It is to be carried out after the evaporation golden film of the surface of coating.

Fig. 6 is scanning electron microscope (SEM) photo of the coating of embodiment V4 surface treated steel plate.In figure 6, Symbol 56 is skeleton, and for symbol 57 to be configured at filling region between the crystal between skeleton, symbol 58 is overlay tree The top layer on dendritic crystal surface.In addition, in figure 6 in shown photo, the white portion of coating surface is for observing coating And the golden film being deposited.

Coating of the coating of embodiment V1~V3 and V5~V20 surface treated steel plate also with embodiment V4 is identically formed The top layer of filling region and skeleton between skeleton, crystal.

For the coating of comparative example x1~comparative example x7 surface treated steel plate, entered in the same manner as embodiment V4 using SEM Observation is gone.Fig. 7 is scanning electron microscope (SEM) photo of comparative example x2 surface treated steel plate coating.Such as institute in Fig. 7 Show like that, comparative example x2 coating be formed by skeleton it is single-phase.

It is (Japanese using energy dispersion-type X-ray analytical equipment (EDS) respectively to embodiment V1~embodiment V20 coating Electronics Co., Ltd manufactures (JED-2300T)) carry out filling region between skeleton, crystal, the top layer of skeleton Elementary analysis.Then, element contained in filling region between element (composition) contained in skeleton, crystal has been investigated (composition) and its vanadium amount and zinc amount, skeleton top layer in contained element (composition).

In addition, mol ratio (the V/ of the vanadium amount of filling region and zinc amount between crystal is calculated using the result of elementary analysis Zn)。

For comparative example x1~comparative example x7 coating, also branch has been carried out in the same manner as embodiment V1~embodiment V20 Filling region between shape crystal, crystal, skeleton top layer elementary analysis.

It the results are shown in table 4 and table 5.

Table 4

Table 5

In addition, the coating of the surface treated steel plate for embodiment V1~V20, has used and has been obtained from section direction by TEM The electron beam diffraction picture arrived, it is thus identified that filling region, the top layer of skeleton are individually to have crystalline substance between skeleton, crystal Body structure is noncrystalline.

Fig. 8 is the photo of the electron beam diffraction picture for the coating for representing embodiment V4.The symbol marked in photo shown in Fig. 8 Number correspond respectively between the crystal shown in 5B and Fig. 5 C filling region 54, tree between filling region 52, skeleton 53, crystal The top layer 55 of dendritic crystal.

From the electron beam diffraction picture shown in Fig. 8：Skeleton 53, the top layer 55 of skeleton have crystal Structure.In addition we know：Filling region 52,54 there is no the diffraction pattern due to crystal structure between crystal, be noncrystalline.

The coating of embodiment V1~V3 and V5~V20 surface treated steel plate also confirms branch in the same manner as embodiment V4 Filling region, the top layer of skeleton are individually with crystal structure or are noncrystalline between shape crystal, crystal.Its result can Know：Skeleton, the top layer of skeleton have a crystal structure, and filling region is noncrystalline between crystal.

In addition, having investigated the impurity in dendritic crystal body, as a result C, Si, S, Fe, N are respectively 0.1~5 atom % or so.

X-ray diffraction device (XRD is used to the coating of comparative example x1~comparative example x7 surface treated steel plate：Rigaku Corporation RINT2500) analyzed.As a result, for comparative example x1~comparative example x7 coating, confirm ：Skeleton has Zn crystal structure.Confirm in addition：In addition to comparative example x7, do not formed between crystal and filled out Fill the situation (comparative example x4 and x6) in region, also only obtain unstable amorphous diffraction pattern (comparative example even if foring X1~x3 and x5).

In addition, for embodiment and the coating of comparative example, following project is have rated using method as shown below.

(adhesion amount, vanadium containing ratio in coating)

The adhesion amount of coating is set as examining using fluorescent X-ray device (Rigaku Corporation Simultix14) The Zn elements and total quality of the per unit area of V element measured.In addition, the content of vanadium in coating is penetrated by using fluorescence X V element amount that line apparatus detects divided by above-mentioned adhesion amount are simultaneously calculated with percentage.

" barrier "

By the edge and back side rubber belt sealing of the test film cut out from surface treated steel plate, brine spray examination has been carried out Test (JIS-Z-2371).Then, the white rust of the non-encapsulated parts after observing 72 hours by visual observation produces area occupation ratio, with following Standard is evaluated.Refer to the area of white rust generating unit relative to observation portion it should be noted that white rust produces area occupation ratio The percentage of the area of position.

(standard)

5：White rust produces area occupation ratio and is less than 10%,

4：White rust produces area occupation ratio as 10% less than 25%

3：White rust produces area occupation ratio as 25% less than 50%

2：White rust produces area occupation ratio as 50% less than 75%

1：It is more than 75% that white rust, which produces area occupation ratio,

" sacrifice corrosion protection "

Coating (Kansai Paint Co., Ltd manufactures, Amilac#1000) is coated on rod and cut from surface treated steel plate The test film of taking-up, carry out burning for 20 minutes at 140 DEG C and glue, form the envelope that dry film thickness is 25 μm.Then, by application The edge and back side rubber belt sealing of test film, cut is assigned on surface with NT cut-off knives in a manner of as X-shaped.Then, carry out Salt spraytest (JIS-Z-2371), the time untill red rust produces from cut portion is determined, is carried out with following standard Evaluation.

(standard)

5：Time untill red rust produces is more than 960 hours

4：Time untill red rust produces is for 720 hours less than 960 hours

3：Time untill red rust produces is for 480 hours less than 720 hours

2：Time untill red rust produces is for 120 hours less than 480 hours

1：Time untill red rust produces is less than 120 hours

(pulverability (adaptation between coating and steel plate))

60 ° of v-shaped bending moulds have been used in efflorescence experiment.With the evaluation of the test film cut out from surface treated steel plate Face turns into the mode of the inner side of bending section, and the mould that the radius of curvature using front end is 1mm, bending machining is into 60 °, in bending section Inner side Continuous pressing device for stereo-pattern, adhesive tape is peeled off.Pulverability is have rated by the stripping situation for the coating peeled off together with adhesive tape (to peel off wide Spend (mm)).

(film adaptation)

Coating (Kansai Paint Co., Ltd's manufacture, Amilac#1000) is coated on rod and cut from surface treated steel plate The test film of taking-up, carry out burning for 20 minutes at 140 DEG C and glue, form the envelope that dry film thickness is 25 μm.The application that will be obtained After plate impregnates 30 minutes in boiling water, it placed in the interior of normal temperature 24 hours.Then, cut out for test film using NT cut-off knives The gridiron pattern of 100 1mm square, after it is ejected into 7mm with erichsen tester, carried out in the ejection convex portion using adhesion glue The disbonded test of band, it have rated film adaptation (stripping number).

Table 6

Table 7

As shown in table 6 and table 7, it is known that：Embodiment V1~embodiment V20 surface treated steel plate is satisfied by this hair Bright scope, compared with comparative example x1~comparative example x7 surface treated steel plate, barrier and film excellent adhesion.

In addition, it is 0~18A/dm with regard to the current density in substrate formation process²Embodiment V1~embodiment V20 table It is 25A/dm with the current density in substrate formation process for the coating of face processing steel plate²Comparative example x2 and x3 surface The mol ratio (V/Zn) of the coating of steel plate is different, between crystal in filling region vanadium and zinc is handled as 0.10~2.00, also, Filling region shows amorphous diffraction pattern between crystal in the case of having carried out electron beam diffraction.In addition we know：Resistance It is more excellent every property and film adaptation.

Embodiment 2

" envelope forms the result of the test of the surface treated steel plate containing vanadium "

For being used to form the coating composition of envelope, by organic resin (R), the phosphate cpd shown in table 8 (P), carbon black (C), organo-silicon compound (W), fluorine metal complex compound (F), isocyanate compound (I) and Tissuemat E (Q) are pressed Carried out according to the content (the quality % of solid constituent) shown in table 9 and table 10 in the water as solvent using coating with dispersion machine Stir and make it scattered, be prepared for coating composition.

Table 8

Table 9

Table 10

In the preparation of coating composition, using the waterborne liquid comprising hydrolytic condensate as organo-silicon compound (W), with It is added as the content shown in table 9 and table 10, above-mentioned hydrolytic condensate is to make the second of 3- aminopropyls three shown in table 8 TMOS (W1) and 3- glycidoxypropyltrimewasxysilanes (W2) with shown in table 9 and table 10 ratio [(W1)/ (W2)] it is dissolved in water and generates.

(paint stability)

The coating composition being prepared is stirred at room temperature 30 minutes, observing by visual observation caused by sediment has Nothing.

The situation of no generation sediment is evaluated as paint stability " OK ", the situation for generating sediment is evaluated as Paint stability " NG ".The result of paint stability is shown in table 9 and table 10.

As shown in table 9 and table 10, with regard to the coating composition used in embodiment t1~t14, comparative example w1~w5 For, the result of paint stability is " OK ", excellent in stability.

Next, the embodiment V4 manufactured in embodiment 1 or the surface of the coating of comparative example x3 surface treated steel plate, Aforementioned coating composition is used respectively, and envelope is formd using method as shown below.

First, on the surface of surface treated steel plate, coating composition is coated with using roll coating machine so as to table 11 and table 12 shown in thickness.Then, the surface treated steel plate for being coated with coating composition is heated with so that steel plate reaches Temperature turns into 150 DEG C to be dried, and carries out misting cooling using water, has obtained envelope.Even it should be noted that adding There is also hydrous oxide in coating after hot to 150 DEG C.

Next, each surface treated steel plate for foring envelope on the surface of coating, has carried out appearance uniform respectively Property, corrosion resistance, electric conductivity, process adaptation, scratch resistance evaluation.In addition, as a reference example e2, carry out in embodiment 1 Appearance uniformity, corrosion resistance, electric conductivity, processing adaptation, the scratch resistance of the embodiment V4 of middle manufacture surface treated steel plate Evaluation.

The evaluation result of projects is shown in table 11 and table 12.

Table 11

Table 12

The evaluation method and evaluation criterion of projects described below.

(appearance uniformity)

The L* values of surface treated steel plate are determined using the colour meter (CR-400) of Konica Minolta Opto Inc., under The evaluation criterion stated is evaluated.

(evaluation criterion)

5：L* values are less than 24

4：L* values are 24 less than 27

3：L* values are 27 less than 28

2：L* values are 28 less than 30

1：L* values are more than 30

(corrosion resistance)

By the edge and back side rubber belt sealing of the test film cut out from surface treated steel plate, brine spray examination has been carried out Test (JIS Z 2371).Then, the white rust of the non-encapsulated parts after observing 240 hours by visual observation produces area occupation ratio, and use is following Standard evaluated.White rust produces area occupation ratio and refers to the area of white rust generating unit relative to the hundred of the area of look-out station Divide rate.

(evaluation criterion)

6：White rust generation rate is less than 3%

5：White rust generation rate is 3% less than 10%

4：White rust generation rate is 10% less than 25%

3：White rust generation rate is 25% less than 50%

2：White rust generation rate is 50% less than 75%

1：White rust generation rate is more than 75%

(electric conductivity)

Using the test film cut out from surface treated steel plate, layer is determined using assay method specified in JIS C 2550 Between resistance value (Ω cm²), it have rated electric conductivity with following standard.

(evaluation criterion)

6：Interface resistance value is less than 1.0 Ω cm²

5：Interface resistance value is 1.0 Ω cm²Less than 1.5 Ω cm²

4：Interface resistance value is 1.5 Ω cm²Less than 2.0 Ω cm²

3：Interface resistance value is 2.0 Ω cm²Less than 2.5 Ω cm²

2：Interface resistance value is 2.5 Ω cm²Less than 3.0 Ω cm²

1：Interface resistance value is 3.0 Ω cm²More than

(processing adaptation)

After 180 ° of bending processes are implemented to the test film cut out from surface treated steel plate, the outside of kink is implemented Belt stripping test.The outward appearance for the amplification sem observation adhesive tape stripping portion for being 10 times with magnifying power, is entered with following evaluation criterions Evaluation is gone.Bending process is therebetween to implement 0.5mm dividing plate clamping in 20 DEG C of atmosphere.

(evaluation criterion)

5：Peeled off in film without discovery

4：Find to peel off (peels off area≤2%) in the film of small part

3：Find to peel off (2% ＜ peels off area≤10%) in the film of a part

2：Find to peel off (10% ＜ peels off area≤20%) in film

1：Find to peel off (peels off area ＞ 20%) in film

(scratch resistance)

Make it is closely sealed from the material to be tested that surface treated steel plate is cut out and plated steel sheet (no processing material), in pressurization Material to be tested is set to have rotated 90 ° under state.Pressurization is set as 0.2kg/cm², test temperature is set as 25 DEG C.Then, mesh is passed through Outward appearance depending on have rated material to be tested.

(evaluation criterion)

6：Scuffing is not seen completely.

5：There are tiny scuffing, but exposing without base material

4：Base material exposes a little (exposes area：Less than 3%)

3：Base material, which exposes, (exposes area：3% less than 10%)

2：Base material, which exposes, (exposes area：10% less than 30%)

1：Base material, which exposes, (exposes area：More than 30%)

As shown in tables 11 and 12, has tunicate reality in the coating surface of embodiment V4 surface treated steel plate It is more than the 2 of evaluation criterion to apply t1~t14 evaluation results in all assessment items, shows excellent appearance uniform Property, corrosion resistance, electric conductivity, processing adaptation and scratch resistance.In addition, embodiment t1~t14 on surface with not forming envelope Reference example e2 compare, corrosion resistance and electric conductivity are good.

On the other hand, have the outer of tunicate comparative example w1~w5 in the coating surface of comparative example x3 surface treated steel plate It is 1 to see uniformity, the corrosion resistance after 240 hours, processing adaptation, the evaluation result of scratch resistance, poor performance.

Embodiment 3

" result of the test of the surface treated steel plate containing zirconium "

Using the plater shown in Fig. 2, it has been made to have on the two sides of steel plate using method as shown below and contains zirconium Coating surface treated steel plate, evaluated.

In addition, for item similarly to Example 1, the description thereof will be omitted.

Prepare to make the plating bath composition shown in table 13, temperature, pH plating bath to enter by 100m/ minutes of average relative velocity The plating bath for the flow regime that row circulation forms.

Table 13

Then, steel plate is made as negative electrode using pre-treatment (nickel plating).In substrate formation process and upper strata plating process, lead to The electric time is set as the time shown in table 14 and table 15, and current density is set as the numerical value shown in table 14 and table 15, uses Galvanoplastic form coating.

Table 14

Table 15

In plating bath composition shown in table 13, ZnSO is used₄·7H₂O uses ZrO (NO as Zn compounds₃)₂It is water-soluble Liquid or ZrOSO₄The aqueous solution further, has used Na as needed as Zr compounds₂SO₄, as other metallic compounds NiSO₄·6H₂O.By adjusting their content, so as to adjust as the Zn shown in table 1²⁺、Zr(Zr⁴⁺、ZrO²⁺)、Na⁺、 Ni²⁺Concentration.

As shown in figure 9, distinguish：Skeleton is formd in the coating of present embodiment, around it The uncrystalline layer of filling region and skin section between the crystal of formation.By using energy dispersion-type X-ray analytical equipment (EDS (days This Electronics Co., Ltd system (JED-2300T)) carry out elementary analysis and electron beam diffraction analysis, so as to distinguish：Dendroid Crystal is formed by metal Zn.In addition, distinguish：Filling region includes zirconium oxide and zirconium hydroxide between crystal.And then distinguish： The uncrystalline layer of skin section includes zirconium oxide.

For the coating of other embodiment, also skeleton has been identically formed, around it with embodiment Z4 The uncrystalline layer of filling region and skin section between the crystal of formation.The uncrystalline layer of skin section is removed and obtained in addition, also having Coating.

Energy dispersion-type X-ray analytical equipment (EDS) (day is used respectively for embodiment Z1~embodiment Z20 coating This Electronics Co., Ltd system (JED-2300T)) carry out " skeleton ", " filling region between crystal ", " skeleton The elementary analysis on top layer ".Then, investigated contained in filling region between element (composition) contained in skeleton, crystal Element (composition) and its zirconium amount and zinc amount, skeleton top layer in contained element (composition).

In addition, mol ratio (the Zr/ of the zirconium amount of filling region and zinc amount between crystal is calculated using the result of elementary analysis Zn)。

In comparative example x11~comparative example x16 coating, " tree has also been carried out in the same manner as embodiment Z1~embodiment Z20 The elementary analysis of dendritic crystal ", " filling region between crystal ", " top layer of skeleton ".

It the results are shown in 16~table of table 17.

Table 16

Table 17

For the coating of embodiment Z1~embodiment Z20 surface treated steel plate, it is thus identified that " skeleton ", " crystal Between filling region " and " top layer of skeleton " be individually with crystal structure or be noncrystalline.Knowable to its result, branch Shape crystal, the top layer of skeleton have a crystal structure, and filling region is noncrystalline between crystal.

X-ray diffraction device (XRD is used to the coating of comparative example x11~comparative example x16 surface treated steel plate： Rigaku Corporation RINT2500) analyzed.Its results verification arrives：For comparative example x11~comparative example For x16 coating, skeleton has Zn crystal structure.In addition, confirm：Filling region between crystal is not formed Situation (comparative example x15), even if form also only obtain unstable amorphous diffraction pattern (comparative example x11~x14 and x16)。

(adhesion amount, zirconium containing ratio in coating)

The adhesion amount of coating is set as examining using fluorescent X-ray device (Rigaku Corporation Simultix14) The Zn elements and total quality of the per unit area of Zr elements measured.In addition, the zirconium content in coating is by using fluorescence X Zr amount of element that x-ray apparatus detects divided by above-mentioned adhesion amount are calculated with percentage.

Table 18

Table 19

As shown in table 18 and table 19, it is known that：Embodiment Z1~Z20 is satisfied by the scope of the present invention, with comparative example X11~comparative example x16 surface treated steel plate is compared, barrier and film excellent adhesion.

In addition, it is 0~18A/dm with regard to the current density in substrate formation process²Embodiment Z1~embodiment Z20 table It is 25A/dm with the current density in substrate formation process for the coating of face processing steel plate²Comparative example x12~x13 table The coating of face processing steel plate is different, and the mol ratio (Zr/Zn) of zirconium and zinc between crystal in filling region turns into 1.00~3.00, and And filling region shows amorphous diffraction pattern between crystal in the case of having carried out electron beam diffraction.In addition we know： Barrier and film adaptation are more excellent.

Embodiment 4

" result of the test for forming the surface treated steel plate containing zirconium of envelope "

For being used to form the coating composition of envelope, by organic resin (R), the phosphate cpd shown in table 8 (P), carbon black (C), organo-silicon compound (W), fluorine metal complex compound (F), isocyanate compound (I) and Tissuemat E (Q) are pressed Entered according to the content (the quality % of solid constituent) shown in table 20 and table 21 in the water as solvent using coating with dispersion machine Row stirs and makes it scattered, is prepared for coating composition.

In addition, omitted the description for item similarly to Example 2.

Table 20

Table 21

As shown in table 20 and table 21, with regard to the coating composition used in embodiment u1~u14, comparative example y1~y5 For, the result of paint stability is " OK ", excellent in stability.

Next, the embodiment Z4 or the coating surface of comparative example x13 surface treated steel plate that manufacture in embodiment 3, Aforementioned coating composition is used respectively, and envelope is formd using method as shown below.

First, on the surface of surface treated steel plate, coating composition is coated with using roll coating machine so as to table 22 and table 23 shown in thickness.Then, the surface treated steel plate for being coated with coating composition is heated with so that steel plate reaches Temperature turns into 150 DEG C to be dried, and carries out misting cooling using water, has obtained envelope.Even it should be noted that adding There is also hydrous oxide in coating after hot to 150 DEG C.

Next, each surface treated steel plate for foring envelope on the surface of coating, has carried out appearance uniform respectively Property, corrosion resistance, electric conductivity, process adaptation, scratch resistance evaluation.In addition, as a reference example f1, carry out in embodiment 3 Appearance uniformity, corrosion resistance, electric conductivity, processing adaptation, the scratch resistance of the embodiment Z4 of middle manufacture surface treated steel plate Evaluation.

The evaluation result of projects is shown in table 22 and table 23.

Table 22

Table 23

It is tunicate in the surface tool of the coating of embodiment Z4 surface treated steel plate as shown in table 22 and table 23 For embodiment u1~u14 in all assessment items, evaluation result is more than the 2 of evaluation criterion, is shown excellent outer See uniformity, corrosion resistance, electric conductivity, processing adaptation and scratch resistance.In addition, embodiment u1~u14 on surface with not having shape Reference example f1 into envelope is compared, and corrosion resistance and electric conductivity are good.

On the other hand, has tunicate comparative example y1~y5 on the surface of the coating of comparative example x13 surface treated steel plate Appearance uniformity, the corrosion resistance after 240 hours, processing adaptation, the evaluation result of scratch resistance be 1, poor performance.

It is illustrated above for the preferred embodiment of the present invention, but the present invention is not limited to these realities certainly Example.If those skilled in the art, then various changes obviously can be expected in the scope described in claims Shape example or fixed case, it should be understood that the technical scope of the present invention is also would naturally fall within these contents.

Industrial applicability

According to the respective embodiments described above, using the teaching of the invention it is possible to provide form the barrier of the coating containing zinc and vanadium on the surface of steel plate With the surface treated steel plate of film excellent adhesion.

The explanation of symbol

1st, 201 steel plate

2 plating bath

2a tops supply pipe arrangement

2b bottoms supply pipe arrangement

2c, 2e periphery branch path

2d, 2f medial fascicle road

3 anodes

The inside of 3a skeletons

The top layer of the skeleton of 3b, 55,58

3c bulk crystallines

4a, 5a, 4b, 5b roller

6 vfanadium compound

10th, 210 surface treated steel plate

20th, 51,220 basalis

20a nickel coatings

21 coating baths

21a upper slots

21b lower channels

30th, 230 coating

31st, 53,56,231 skeleton

32nd, filling region between 52,54,57,232 crystal

40th, 240 superficial layer

61 current convergence portions

62 hydrogen

250 uncrystalline layers

Interval between D rollers 4a, 5a and anode 3

Claims (according to the 19th article of modification of treaty)

1. a kind of surface treated steel plate, it is characterised in that it possesses：

Steel plate；With

Formed and coating containing zinc and vanadium or zirconium in the one or two sides of the steel plate,

Wherein, the coating has：

Skeleton containing metallic zinc；With

It will be filled between above-mentioned skeleton and amorphous diffraction pattern shown in the case where having carried out electron beam diffraction Filling region between the crystal of case,

In the case where the coating contains the vanadium, filling region contains the barium oxide or vanadium hydrogen-oxygen of hydration between the crystal Compound,

In the case where the coating contains zirconium, filling region contains the Zirconium oxide or zirconium hydroxide of hydration between the crystal Thing.

2. surface treated steel plate according to claim 1, it is characterised in that enter one between the steel plate and the coating Step is provided with by the basalis of nickeliferous Crystallization.

3. the surface treated steel plate according to claim 1 or claim 2, it is characterised in that in the coating containing In the case of stating vanadium, the mol ratio of the vanadium and the zinc between the crystal in filling region is that V/Zn is 0.10~2.00,

In the case where the coating contains the zirconium, the mol ratio of the zirconium and the zinc between the crystal in filling region That is Zr/Zn is 1.00~3.00.

4. according to surface treated steel plate according to any one of claims 1 to 3, it is characterised in that in the coating containing In the case of stating vanadium, zinc oxide or zinc hydroxide are contained in the top layer of the skeleton.

5. surface treated steel plate according to claim 1, it is characterised in that enter one between the steel plate and the coating The substrate coating that the mol ratio i.e. Zn/V that step is provided with zinc and vanadium is more than 8.00.

6. surface treated steel plate according to claim 2, it is characterised in that enter between the basalis and the coating The substrate coating that the mol ratio i.e. Zn/V that one step is provided with zinc and vanadium is more than 8.00.

7. according to the surface treated steel plate any one of 1~claim 6 of claim, it is characterised in that in the plating The surface of layer is further equipped with the organic resin envelope with the carbon black of polyurethane resin and 1~20 mass %.

8. a kind of manufacture method of surface treated steel plate, it is characterised in that it is any one of manufacturing claims 1~7 Surface treated steel plate method, this method has：

Substrate formation process, it is by using the Zn containing 0.10~4.00mol/l²⁺Ion and 0.01~2.00mol/l V from Son or 0.10~4.00mol/l Zr ions plating bath and with the mean flow rate and 0~18A/dm of 40~200m/ minutes²Electricity Current density is electroplated, and is formed concavo-convex so as to make the barium oxide of hydration or the precipitation of vanadium hydroxide on the steel plate；With

Upper strata plating process, it is to foring the concavo-convex steel plate using the plating bath and with 40~200m/ minutes Mean flow rate and 21~200A/dm²Current density electroplated.

9. the manufacture method of surface treated steel plate according to claim 8, it is characterised in that in the substrate formation process Take a step forward with by using containing Ni²⁺The plating bath of ion is electroplated so that nickeliferous crystal is separated out in the steel plate On process.

Claims

Steel plate；With

Wherein, the coating has：

Skeleton containing metallic zinc；With

2. surface treated steel plate according to claim 1, it is characterised in that contain the situation of the vanadium in the coating Under, the mol ratio of the vanadium and the zinc between the crystal in filling region is that V/Zn is 0.10~2.00,

3. the surface treated steel plate according to claim 1 or claim 2, it is characterised in that in the coating containing In the case of stating vanadium, zinc oxide or zinc hydroxide are contained in the top layer of the skeleton.

4. according to the surface treated steel plate any one of 1~claim 3 of claim, it is characterised in that in the steel The mol ratio i.e. Zn/V that zinc and vanadium are further provided between plate and the coating is more than 8.00 substrate coating.

5. according to the surface treated steel plate any one of 1~claim 4 of claim, it is characterised in that in the plating The surface of layer is further equipped with the organic resin envelope with the carbon black of polyurethane resin and 1~20 mass %.

6. a kind of manufacture method of surface treated steel plate, it is characterised in that it is any one of manufacturing claims 1~5 Surface treated steel plate method, this method has：

Substrate formation process, it is by using the Zn containing 0.10~4.00mol/l²⁺Ion and 0.01~2.00mol/l V from Son or 0.10~4.00mol/l Zr ions plating bath and with 0~18A/dm²Current density electroplated, so as to described The barium oxide or vanadium hydroxide for making hydration on steel plate are separated out and formed concavo-convex；With

Upper strata plating process, it is to foring the concavo-convex steel plate using the plating bath and with 21~200A/dm²Electricity Current density is electroplated.