CN100585006C - Clear-coated stainless steel sheet excelling in design and process for producing the material - Google Patents
Clear-coated stainless steel sheet excelling in design and process for producing the material Download PDFInfo
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- CN100585006C CN100585006C CN200680001695A CN200680001695A CN100585006C CN 100585006 C CN100585006 C CN 100585006C CN 200680001695 A CN200680001695 A CN 200680001695A CN 200680001695 A CN200680001695 A CN 200680001695A CN 100585006 C CN100585006 C CN 100585006C
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/62—Treatment of iron or alloys based thereon
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
A clear-coated stainless steel sheet excelling in whiteness degree, characterized in that it includes a stainless steel sheet consisting of a ferrite stainless steel sheet containing 0.2 to 0.8 mass% of Si, the stainless steel sheet from its surface to a depth of 50 AA furnished with a surface oxide film of = 0.6 Cr/Si/Al/Fe atomic concentration ratio [(Cr+Si+Al)/Fe], and further includes a coating film of 1 to 10 [mu]m clear coating material thickness from a chemical treatment agent consisting of one or two members of aminosilane and epoxysilane agents, the chemical treatment agent adhering in an amount of 2 to 20 mg/m<2> (amount of SiO2 measured by fluorescent X-ray). Further, there is provided a process for producing the material.
Description
Technical field
During good aspect the peculiar well-designed of metal raw sheet that the present invention relates to have, application at stainless steel not the utilizable clear-coated stainless steel sheet of parts of xanchromatic household electrical appliances, building materials, automobile etc.
Background technology
Stainless steel has good solidity to corrosion and designability, therefore uses with naked state at household electrical appliances, kitchen, automobile, building materials field.Recently, in the good designability of the metalluster etc. of performance stainless steel plate, and the clear-coated stainless steel sheet that has added the function of stain resistance, solidity to corrosion etc. increases being suitable for just constantly of field of household appliances.
These clear-coated stainless steel sheets, from the designability aspect, except colourless clear-coated, also be suitable for gradually by painted clear-coated steel plate such as pigment or the coated steel plate that added the pigment of pearl tone or metal tone.But the interpolation of these pigment reduces the transparent feel of transparent coating, and the distinctive texture with metalluster of stainless steel is reduced.
On the other hand, colourless clear-coated stainless steel sheet owing to the chromate treating of bottom layer treatment has yellow color, not only damages designability, and when the angle that difference is observed is seen, exists and see black blackened problem.For these problems, in patent documentation 1 and patent documentation 2, once studied the influence of treatment solution composition and coating amount to the chromic salt epithelium.In patent documentation 3, once studied the improvement of phosphoric acid and silicon-dioxide to the aesthetic appearance of bottom stainless steel plate, the stain resistance of filming and ovenable roasting property.
Patent documentation 1: the spy opens flat 5-106057 communique
Patent documentation 2: the spy opens flat 11-269660 communique
Patent documentation 3: the spy opens flat 8-281864 communique
Patent documentation 4: the spy opens clear 56-259 communique
Patent documentation 5: the spy opens clear 62-156253 communique
Patent documentation 6: the spy opens flat 11-254585 communique
Summary of the invention
If only improve chromate treating method as described above, then can not obtain the clear-coated stainless steel sheet that whiteness is good and transparency is high.Problem of the present invention is: the characteristic and the application condition on condition, raw sheet surface are handled in the research chemical conversion, and good clear-coated stainless steel sheet of whiteness and manufacture method thereof are provided.
Present inventor's result of study is, jaundice about colourless clear-coated stainless steel sheet painted (flavescence), except resulting from the chromate treating, it is painted to have distinguished that transparent coating on the stainless steel plate surface tempering color takes place when baking, the painted reason that also becomes flavescence of this tempering color.Therefore clear and definite change to that the thickness optimizing of the epithelium that chemical conversion handles is handled, made simultaneously to non-chromate and by using the good stainless steel plate of anti-tempering color, can realize the flavescence that prevents when clear-coated as the stainless steel plate that clear-coated stainless steel sheet is suitable for by chemical conversion being handled from chromate treating.
Known to the stainless steel plate that has increased Si, Al is carried out clean annealing, contain SiO in surface of steel plate formation
2, Al
2O
3Oxide scale film, can suppress the tempering color of stainless steel plate.That is, follow the increase of the content of Si or Al, form the oxide scale film of Si, Al enrichment easily, anti-tempering color raising.As such stainless steel, known high Si steel is arranged (patent documentation 4,5) and high Al steel (patent documentation 5) etc.
In addition, as the heat-resisting clear-coated stainless steel that Al or Si with the ferrite series stainless steel plate surface are limited in 4.5～6 atom %, known have a patent documentation 6.
The present inventor concentrates on studies to the means process that solves above-mentioned problem, the result is as mentioned above, handle the characteristic and the application condition on condition, raw sheet surface by the research chemical conversion, established clear-coated stainless steel sheet and the manufacture method thereof of using the good ferrite series stainless steel plate of whiteness.
Main idea of the present invention is as follows.
(1) the good clear-coated stainless steel sheet of a kind of whiteness is characterized in that: described stainless steel plate is the ferrite series stainless steel plate that contains Si:0.2～0.8% in quality %, and this steel plate has from its surface to 50
Till Cr, Si, Al, the Fe atomic percent at degree of depth place be surface oxidation epithelium more than 0.6 than (Cr+Si+Al)/Fe; The chemical conversion treating agent of filming constitutes by a kind or 2 kinds in aminosilane system and the epoxy silane system, measures SiO by fluorescent X-ray
2Amount, the adhesion amount of this chemical conversion treating agent is 2～20mg/m
2The thickness that has by the formed transparent coating of Clear paint is filming of 1～10 μ m.
(2) according to the good clear-coated stainless steel sheet of above-mentioned (1) described whiteness, it is characterized in that: above-mentioned stainless steel plate also contains Al:0.005～0.15% in quality %.
(3) according to the good clear-coated stainless steel sheet of above-mentioned (1) described whiteness, it is characterized in that: above-mentioned stainless steel plate also contains Nb:0.1～0.7% in quality %.
(4) the good clear-coated stainless steel sheet of a kind of whiteness, it is characterized in that: described stainless steel plate is the ferrite series stainless steel plate that contains Si:0.2～0.8%, Al:0.005～0.15%, Nb:0.1～0.7% in quality %, and this steel plate has from its surface to 50
Till Cr, Si, Al, the Fe atomic percent at degree of depth place be surface oxidation epithelium more than 0.6 than (Cr+Si+Al)/Fe; The chemical conversion treating agent of filming constitutes by a kind or 2 kinds in aminosilane system and the epoxy silane system, measures SiO by fluorescent X-ray
2Amount, the adhesion amount of this chemical conversion treating agent is 2～20mg/m
2The thickness that has by the formed transparent coating of Clear paint is filming of 1～10 μ m.
(5) according to the manufacture method of the good clear-coated stainless steel sheet raw sheet of (1) described whiteness, it is characterized in that: the temperature T 1 of final clean annealing (℃) and the dew point T2 of annealing atmosphere (℃) satisfy under the condition of formula (1) and formula (2) and anneal.
750≤T1≤5 * T2+1200 ... formula 1
-70≤T2≤-30 ... formula 2
The manufacture method of the clear-coated stainless steel sheet raw sheet that (6) a kind of whiteness is good, it is characterized in that: for the good clear-coated stainless steel sheet raw sheet of whiteness, the temperature T 1 of final clean annealing (℃) and the dew point T2 of annealing atmosphere (℃) satisfy under the condition of formula (1) and formula (2) and anneal; Wherein, described stainless steel plate is the ferrite series stainless steel plate that contains Si:0.2～0.8%, Al:0.005～0.15% in quality %, and this steel plate has from its surface to 50
Till Cr, Si, Al, the Fe atomic percent at degree of depth place be surface oxidation epithelium more than 0.6 than (Cr+Si+Al)/Fe; The chemical conversion treating agent of filming constitutes by a kind or 2 kinds in aminosilane system and the epoxy silane system, measures SiO by fluorescent X-ray
2Amount, the adhesion amount of this chemical conversion treating agent is 2～20mg/m
2The thickness that has by the formed transparent coating of Clear paint is filming of 1～10 μ m.
750≤T1≤5 * T2+1200 ... formula 1
-70≤T2≤-30 ... formula 2
The manufacture method of the clear-coated stainless steel sheet raw sheet that (7) a kind of whiteness is good, it is characterized in that: for the good clear-coated stainless steel sheet raw sheet of whiteness, the temperature T 1 of final clean annealing (℃) and the dew point T2 of annealing atmosphere (℃) satisfy under the condition of formula (1) and formula (2) and anneal; Wherein, described stainless steel plate is the ferrite series stainless steel plate that contains Si:0.2～0.8%, Al:0.005～0.15%, Nb:0.1～0.7% in quality %, and this steel plate has from its surface to 50
Till Cr, Si, Al, the Fe atomic percent at degree of depth place be surface oxidation epithelium more than 0.6 than (Cr+Si+Al)/Fe; The chemical conversion treating agent of filming constitutes by a kind or 2 kinds in aminosilane system and the epoxy silane system, measures SiO by fluorescent X-ray
2Amount, the adhesion amount of this chemical conversion treating agent is 2～20mg/m
2The thickness that has by the formed transparent coating of Clear paint is filming of 1～10 μ m;
750≤T1≤5 * T2+1200 ... formula 1
-70≤T2≤-30 ... formula 2
The manufacture method of the clear-coated stainless steel sheet raw sheet that (8) a kind of whiteness is good, it is characterized in that: for the good clear-coated stainless steel sheet raw sheet of whiteness, the temperature T 1 of final clean annealing (℃) and the dew point T2 of annealing atmosphere (℃) satisfy under the condition of formula (1) and formula (2) and anneal; To carrying out imposing final clean annealing after the surface grinding through cold rolling ferrite series stainless steel plate.Wherein, described stainless steel plate is the ferrite series stainless steel plate that contains Si:0.2～0.8% in quality %, and this steel plate has from its surface to 50
Till Cr, Si, Al, the Fe atomic percent at degree of depth place be surface oxidation epithelium more than 0.6 than (Cr+Si+Al)/Fe; The chemical conversion treating agent of filming constitutes by a kind or 2 kinds in aminosilane system and the epoxy silane system, measures SiO by fluorescent X-ray
2Amount, the adhesion amount of this chemical conversion treating agent is 2～20mg/m
2The thickness that has by the formed transparent coating of Clear paint is filming of 1～10 μ m;
750≤T1≤5 * T2+1200 ... formula 1
-70≤T2≤-30 ... formula 2
(9) according to the manufacture method of the good clear-coated stainless steel sheet raw sheet of (6) described whiteness, it is characterized in that: carrying out imposing final clean annealing after the surface grinding through cold rolling ferrite series stainless steel plate.
(10) according to the manufacture method of the good clear-coated stainless steel sheet raw sheet of (7) described whiteness, it is characterized in that: carrying out imposing final clean annealing after the surface grinding through cold rolling ferrite series stainless steel plate.
Description of drawings
Fig. 1 is the figure that the relation between adhesion amount and the clear-coated stainless variable color Δ b* is handled in the expression chemical conversion.
Fig. 2 is that expression is from surface to 50
Till the oxide scale film at degree of depth place in Cr, Si, Al, Fe atom concentration ratio (Cr+Si+Al)/Fe, and the variable color Δ b* of 224 ℃ of bakings and the clear-coated stainless steel sheets that cause between the figure of relation.
Fig. 3 be the expression storing temperature that grinds the steel plate of the clean annealing that imposes the scope of the invention after precision work stainless steel plate and the grinding, and the variable color Δ b* of clear-coated stainless steel sheet between the figure of relation.
Fig. 4 be the expression clean annealing annealing temperature T1 (℃), dew point T2 (℃) with from surface to 50
Till the oxide scale film at degree of depth place in concentration ratio (the Cr+Si+Al)/Fe of Cr, Si, Al, Fe atom between the figure of relation.
Embodiment
The present inventor studies the pre-treatment of designability of clear-coated stainless steel sheet and the characteristic on raw sheet surface, found that, in order to obtain the good clear-coated stainless steel sheet of whiteness, below 2 be important.At first the 1st is, is not chromic salt as the chemical conversion treating agent of pre-treatment, is chemical conversion treating agent and be to use aminosilane system, epoxy silane, simultaneously the adhesion amount of this chemical conversion treating agent is determined at optimum range.The 2nd is, as the stainless steel plate raw sheet, makes the composition of surface enrichment Cr, Si, Al, prevents painted by tempering color and raw sheet variable color that cause when coating baking.And, about colourless Clear paint, can be any resin system such as vibrin system, acrylic resin, acrylated polyurethane resin system, epoxy modified polyester resin system.
Transparent chemical conversion processing of the present invention is described.
Transparent chemical conversion treating agent of the present invention constitutes by a kind or 2 kinds in aminosilane system and the epoxy silane system.The reason of selecting aminosilane system, epoxy silane system be since when using them tack good, compare with the situation of using the chromate treating agent in addition, can prevent yellow coloring.Adhesion amount with chemical conversion treating agent is 2～20mg/m
2(measure SiO by fluorescent X-ray
2Amount) condition is handled, and is that 60～140 ℃ condition is toasted and dry with the surface temperature (MT) of stainless steel plate raw sheet.
Fig. 1 investigated make Japanese Parkerizing company the adhesion amount of E206 (aminosilane system) under 100 ℃ from 2mg/m
2To 50mg/m
2The acrylated polyurethane resin that adhesion amount changes, apply 2 μ m with roller coat is Clear paint, in 200 ℃ of the storing temperatures tonal variation of the clear-coated stainless steel sheets of coating down.By using from surface to 50
Till degree of depth place atomic percent than (Cr+Si+Al)/Fe (hereinafter narration) be SUS430/ clean annealing material 0.6 or more as the stainless steel plate raw sheet that uses in clear-coated, " flavescence " extremely minimizing that the tempering color that results from is painted.The ordinate zou of Fig. 1 (Δ b*) is that the adhesion amount that makes chemical conversion treating agent such shown in the X-coordinate changes, the b* (1) during from baking coating Clear paint deducts the b* (2) of steel plate raw sheet and the value that obtains.That is Δ b*=b* (1)-b* (2).
Consequently, as shown in Figure 1, the adhesion amount of chemical conversion treating agent surpasses 20mg/m
2The time, the stainless gloss of application descends, and has some yellow simultaneously.At adhesion amount is 20mg/m
2When following, Δ b* is below 0.3, and it is less that the tonal variation that causes is handled in chemical conversion.On the other hand, the not enough 2mg/m of chemical conversion treating agent adhesion amount
2The time, epithelium inequality and transparent coating and stainless adhesivity reduce.Therefore, for the present invention, the adhesion amount of chemical conversion treating agent is set at 2～20mg/m
2And, by using fluorescent X-ray to stainless steel plate surface measurements SiO
2Measure, can measure the adhesion amount of chemical conversion treating agent.
Transparent coating thickness is to the scope below the 10 μ m from 1 μ m.This is because when 1 μ m is following, is difficult to obtain stable tone, when 10 μ m are above, the manufacturing difficulty of 1 coating and the high cause of cost of filming.Be preferably scope from 2 μ m to 5 μ m.
Secondly, the raw sheet of clear-coated stainless steel sheet of the present invention is narrated.
The invention is characterized in: " have from its surface to 50 by using
Till Cr, Si, Al, the Fe atomic percent at degree of depth place be the steel plate of the surface oxidation epithelium more than 0.6 than (Cr+Si+Al)/Fe ", the tempering color when preventing coating baking is painted, thereby prevents flavescence.Contain ferrite series stainless steel plate more than the Si:0.2 quality % by use, and this steel plate is carried out clean annealing with the temperature and the atmosphere of regulation, the atomic percent that can make surface of steel plate is than becoming above-mentioned suitable scope.
The stainless steel of clear-coated stainless steel sheet is the ferrite series stainless steel plate that contains Si:0.2～0.8% in quality %.Elements Diffusion speed in the ferrite-group stainless steel makes Cr and Si enrichment in epithelium easily than fast in the austenite stainless steel, and therefore, the present invention is defined as ferrite series stainless steel plate.The special steel grade (Cr-Al steel or Cr-Si steel) that particularly contains Al or Si than being easier to enrichment, is narrated in patent documentation 4 and 5.But, promptly contain the steel of Si:0.2～0.8% for ferrite-group stainless steel of the present invention, below narration is necessary in order to make Cr, Si, the Al technology of enrichment in epithelium.
For the present invention, in order to form the surface oxidation epithelium of enrichment Si at stainless steel surface, the Si that contains more than 0.2% is necessary, and in this occasion, Si is used as the deoxidant element when making steel and contains.The upper limit 0.8% of Si shows that especially the present invention is general ferrite-group stainless steel.If when containing, then surpass for example SUS430 or add the composition range of the SU430J1L of Nb of general ferrite-group stainless steel than its more Si.That is, surpass 0.8% Si,, be not suitable for conventional application because the solution strengthening effect makes the processibility deterioration if add.
For the present invention, wish to contain the trace of Al more than 0.005%, below 0.15%.Because Al is the same with Si, as following,, has the effect of the increase of b* when suppressing the transparent coating baking by being enriched in the clean annealing epithelium.Al can add more than 0.005% as deoxidant element.The Al that adds volume makes the processibility deterioration, and therefore, Al content is preferably 0.005～0.15%.
For the present invention,, can be set at the scope of 16.0～20.0 quality % as the content of the Cr of the basal component of ferrite series stainless steel plate.And in order to make the good transparent stainless steel plate of whiteness, Cr content is more as far as possible is advisable.Because the effect that promotes Cr enrichment in epithelium is arranged when clean annealing.And, preferably contain Nb 0.1～0.7% for the present invention.Because the oxide compound of Nb than the oxide compound Thermodynamically stable of Cr, can think to have same effect with chromium.
Secondly, for the ferrite-group stainless steel that contains Si:0.2～0.8%, the technology that is used for Cr, Si, Al are enriched in oxide scale film is described.
, after cold rolling and annealing, carry out clean annealing to grind accurately machined material through No.4, and clean annealing temperature and atmosphere are changed as the SUS430 of ferrite-group stainless steel, Cr, the Si in the oxide scale film, the ratio of Al, Fe are changed.Atomic percent being adjusted into the material of 0.15～3.5 scope than (Cr+Si+Al)/Fe, handling as chemical conversion, is 10mg/m with the adhesion amount
2Mode to apply aminosilane be chemical conversion treating agent, be Clear paint in 100 ℃ of thick acrylated polyurethane resins of baking dry back roller coating 2 μ m.When Fig. 2 represents that the storing temperature after the Clear paint coating is made as 224 ℃, atomic percent is than the relation between (Cr+Si+Al)/Fe and the Δ b*.Difference Δ b* with the b* of standard material (clear-coated stainless steel sheet raw sheet) estimates by the baking back.Fig. 2 clearlys show, atomic percent is adjusted into material more than 0.6 than (Cr+Si+Al)/Fe, because the tonal variation that application and baking cause is less, and Δ b* less than 1, variable color is less.
Secondly, prepared atomic percent is adjusted into the material 0.6 or more and atomic percent is adjusted into the material of less than 0.6 than (Cr+Si+Al)/Fe than (Cr+Si+Al)/Fe, storing temperature changes to 250 ℃, the variation of observation tone from 150 ℃.Except storing temperature difference and kind difference, identical with the situation of above-mentioned Fig. 2.Among Fig. 3, about zero and the △ material, its atomic percent is about 3 than (Cr+Si+Al)/Fe.About ● and ▲ material, atomic percent is respectively about 0.4 and about 0.2 than (Cr+Si+Al)/Fe.Consequently, as shown in Figure 3, by clean annealing, atomic percent is adjusted into material more than 0.6 than (Cr+Si+Al)/Fe, owing to the tonal variation that application and baking cause is less.On the other hand, after grinding precision work, do not carry out the material of clean annealing or handle with the outer clean annealing condition of the scope of the invention, atomic percent is adjusted into the material of less than 0.6 than (Cr+Si+Al)/Fe, to be the xanchromatic variable color bigger after application and baking, is significant at storing temperature under up to the situation more than 200 ℃ especially.
For the present invention, the composition in the surface oxidation epithelium is analyzed according to AES (auger electron spectroscopic analysis method), as the atomic percent of oxygen concn vertex than (Cr+Si+Al)/Fe.For the present invention, be extremely important than the surface oxidation epithelium that (Cr+Si+Al)/Fe was controlled to be more than 0.6, made Cr and Si enrichment with atomic percent.At this moment, Si is enriched in the skin of surface oxidation epithelium, near the internal layer enrichment of Al matrix.To be the clean annealing condition be reductive condition, be oxidizing condition to Si and Al Cr its reason, simultaneously Al
2O
3Decomposition pressure compare SiO
2Due to low.And can think, though according to the measuring method difference of surface oxidation epithelium, (Cr+Si+Al)/and the optimum range of Fe is also different, and the structure of necessary surface oxidation epithelium is same as described above.
Atomic percent in the surface oxidation epithelium of cold rolled annealed material, grinding precision work material is about 0.2 than (Cr+Si+Al)/Fe.For this reason, the present inventor has studied the clean annealing condition, and stainless steel plate is imposed clean annealing, and it is formed from its surface to 50
Till Cr, Si, Al, concentration ratio (the Cr+Si+Al)/Fe of Fe atom at degree of depth place be the oxide scale film more than 0.6.
Clean annealing is H at hydrogen and nitrogen usually
2: N
2=(1～9): carry out in the reducing atmosphere of the mixed of 1 scope, this moment according to annealing temperature T1 (℃) and the dew point T2 of atmosphere (℃) make up different, the composition in the oxide scale film after the annealing changes.
For cold rolling SUS430J1L and SUS430 steel plate, impose cold rolled annealed or be equivalent to the mechanical mill of No.4 precision work (JIS G 0203 No.5349), with various annealing temperature T1 (℃) and the dew point T2 of atmosphere (℃) carry out the Fig. 4 that the results are shown in of clean annealing.Annealing temperature T1 is that X-coordinate, atmosphere dew point T2 are ordinate zou, from surface to 50
Till the atomic percent at degree of depth place stabilize to T1 more than 0.6 than (Cr+Si+Al)/Fe and the T2 scope is as follows respectively:
750≤T1≤5 * T2+1200 ... formula 1
-70≤T2≤-30 ... formula 2
The scope of formula 1 and formula 2 is conditions of being reduced of Cr, is the oxidized condition of Si and Al on the other hand, therefore because effective constituent (Si, Al) thus enrichment is effectively carried out in selected oxidation in epithelium.The temperature T 1 of clean annealing (℃) under the situation of 750 ℃ of less thaies, be that the diffusion of the effective element (Si, Al) at center is moved slowly with Cr, can not become atomic percent than sufficient oxide scale film.And, T1 (℃) surpass and (under 5 * T2+1200) ℃ the situation,, can not form atomic percent than sufficient oxide scale film because the scope that exceeds formula 1 becomes the condition of reduction side, so has suppressed the selective oxidation of Si and Al.Therefore, clean annealing temperature T 1 (℃) preferably by with dew point T2 (℃) the scope of formula 1 of relation decision.Be preferably more than 800 ℃, below 1000 ℃.Be preferably more than 800 ℃ again, below 900 ℃.
The dew point T2 of clean annealing (℃) when surpassing-30 ℃, the oxidation of Fe aggravation, the enrichment of Fe in the oxide scale film on surface is inevitable, and be because tempering color causes variable color, therefore as the raw sheet of clear-coated stainless steel sheet, not preferred.And not enough-70 ℃ gas dew point is in industrial extremely difficult realization, so the dew point of clean annealing is preferably in the scope of formula 2.Be preferably more than-60 ℃ and not enough-35 ℃.
Though having put down in writing in the patent documentation 5 in Si concentration is that 0.3% o'clock tempering color is painted few, Si concentration is among 0.3% the embodiment, to be 3 minutes (yellow) when the painted scoring of tempering color in the document, and this can not be as the good clear-coated stainless steel sheet of whiteness.For the present invention, stipulated that clearly the atomic percent in the oxide scale film is more than 0.6 than (Cr+Si+Al)/Fe, by clear and definite in addition to realizing creating conditions of this atomic percent ratio, even Si concentration is the low Si concentration below 0.8%, also may make the good clear-coated stainless steel sheet of whiteness.
Giving the grinding precision work material of the surface detail of stainless steel uniqueness by grinding order, is very important as the parts of paying attention to designability.But, because implemented Cr, Si in the stainless surperficial epithelium of surface grinding, the Al enrichment is considerably less, flavescence when therefore applying transparent coating can not obtain the transparent coating stainless steel plate of the good high designability of whiteness.At this, be necessary to implement to be used for making Cr, Si, Al to be enriched in the clean annealing of surperficial epithelium, if but to having implemented the ferrite series stainless steel plate of common softening annealing, when imposing clean annealing after surface grinding, then manufacturing process is complicated and become the essential factor that cost raises.At this,,, preferably impose final clean annealing through after the surface grinding for through cold rolling ferrite series stainless steel plate for the present invention.According to the technology of cold rolling-surface grinding-clean annealing, be used for making the softening annealing of material and Cr, Si, Al enrichment (Cr+Si+Al)/Fe to surperficial epithelium, can implement simultaneously by 1 clean annealing.For ferrite series stainless steel plate of the present invention, consistent with Cr, Si, the Al enrichment temperature in surperficial epithelium especially in order to make the softening temperature, can control and adjust recrystallization temperature by the content of Nb.In addition, under the situation of austenite stainless steel plate, solutionizing annealing is generally more than 1000 ℃, and is inconsistent with Cr, Si, the Al enrichment temperature in surperficial epithelium.Therefore, through cold rolling-after grinding, 2 annealing carrying out solutionizing annealing and be used to form the clean annealing of oxide scale film are necessary.
Embodiment
Table 1 expression embodiments of the invention and comparative example.The surface finishing of ferrite series stainless steel plate is divided into 3 kinds of No.4 (meticulous purpose grinding precision work), HL (the grinding precision work of hair line) and 2B (saddening surface after the pickling).These ferrite steel plates are imposed clean annealing with the condition of table 1.The accurately machined ferrite series stainless steel plate of 2B is to impose the annealed manufacturing process after cold rolling, and in contrast to this, other surface finishing steel plate is not impose annealing after cold rolling, therefore by clean annealing softening is also carried out simultaneously.In addition, for the condition suitability of clean annealing condition, " zero " symbolic representation condition is fit to, and " * " symbolic representation condition is not suitable for.Equally, for whiteness, with " zero " symbolic representation, the expression whiteness is good; With " * " symbolic representation, the expression whiteness is bad.
About each ferrite series stainless steel plate behind the clean annealing, from surface to 50
Till the oxide scale film at degree of depth place in Cr, Si, Al, Fe atomic percent ratio, measure with AES (auger electron spectroscopic analysis method), obtain atomic percent than (Cr+Si+Al)/Fe.
For each ferrite series stainless steel plate behind the clean annealing, handle as chemical conversion, use the aminosilane system of chemical conversion treating agent (E-206) of Japanese Parkerizing company and the chemical conversion treating agent that epoxy silane is, make its adhesion amount from 2mg/m
2To 50mg/m
2Scope in change.For relatively, impose processing as chemical conversion treating agent with chromic salt.Then, to the transparent epithelium of 1～10 μ m of acrylated polyurethane resin system, handle for 220 ℃ with storing temperature.
Tone after clear-coated is measured with b* (JIS Z8729), estimates the degree of variable color.
In the example of the present invention, the atomic percent ratio in the oxide scale film on ferrite series stainless steel plate surface is more than 0.6, handles by the chemical conversion of a kind or 2 kinds formation in aminosilane system and the epoxy silane system, and making adhesion amount is 2～20mg/m
2, can access b* thus and be the good clear-coated steel plate of whiteness below 2, in contrast to this, become b* in the comparative example and surpass 2 yellowy clear-coated steel plate, from a different perspective, can see black blackened tone.
In comparative example 20, (Cr+Si+Al)/Fe that the Si composition of stainless steel plate departs from lower limit, the oxide scale film departs from lower limit, and b* is that whiteness is bad more than 2.In the comparative example 21～25, the temperature T 1 of clean annealing condition and the side among the dew point T2 depart from its bound, and therefore, (the Cr+Si+Al)/Fe in the oxide scale film departs from lower limit, and b* is that whiteness is bad more than 2.Particularly in comparative example 25, the tempering color of stainless steel plate raw sheet can be observed significantly, does not therefore measure (Cr+Si+Al)/Fe.In the comparative example 26～32, although (the Cr+Si+Al)/Fe of raw sheet is more than 0.6, the condition of chemical conversion treating agent departs from scope of the present invention.In the comparative example 26, the adhesion amount of chemical conversion treating agent departs from lower limit, and adhesivity is bad.The adhesion amount of the chemical conversion treating agent of comparative example 27 departs from the upper limit, and the chemical conversion treating agent of comparative example 28 is chromate treating agent, is not that non-chromate of the present invention is a treatment agent, and b* is that whiteness is bad more than 2 thus.The thickness of the transparent coating in the comparative example 29 and 31 departs from lower limit, the tone instability.The thickness of the Clear paint in the comparative example 30 and 32 departs from the upper limit, makes difficulty.
More than, ideal embodiment of the present invention has been described, but the present invention is not limited to these embodiment.As long as in the scope that does not break away from purport of the present invention, can carry out increase, omission, displacement and other change of structure.The present invention is not considered as being limited by the foregoing description, and only is subjected to the restriction of accompanying Claim book.
According to the present invention of the relation of the designability of having studied clear-coated stainless steel sheet and tone, b* (degree of colourity, Huang/indigo plant, JIS Z8729) is from 0 to 2 scope, can make the good clear-coated steel plate of whiteness.It is yellow that the b* of general clear-coated stainless steel sheet is when being 4～6 left and right sides, from different viewing angles, sees dim tone.On the other hand, clear-coated stainless steel sheet of the present invention is a white light tone and at different direction of observations, does not see dim tone.
Claims (10)
1. clear-coated stainless steel sheet that whiteness is good, it is characterized in that: described stainless steel plate is the ferrite series stainless steel plate that contains Si:0.2～0.8% in quality %, this steel plate have from its surface to
Till Cr, Si, Al, the Fe atomic percent at degree of depth place be surface oxidation epithelium more than 0.6 than (Cr+Si+Al)/Fe; The chemical conversion treating agent of filming constitutes by a kind or 2 kinds in aminosilane system and the epoxy silane system, measures SiO by fluorescent X-ray
2Amount, the adhesion amount of this chemical conversion treating agent is 2～20mg/m
2The thickness that has by the formed transparent coating of Clear paint is filming of 1～10 μ m, and it is that coating, acrylic resin coating, acrylated polyurethane resin are that coating, epoxy modified polyester resin are any in the coating that described Clear paint is selected from vibrin.
2. the good clear-coated stainless steel sheet of whiteness according to claim 1, it is characterized in that: above-mentioned stainless steel plate also contains Al:0.005～0.15% in quality %.
3. the good clear-coated stainless steel sheet of whiteness according to claim 1, it is characterized in that: above-mentioned stainless steel plate also contains Nb:0.1～0.7% in quality %.
4. clear-coated stainless steel sheet that whiteness is good, it is characterized in that: described stainless steel plate is the ferrite series stainless steel plate that contains Si:0.2～0.8%, Al:0.005～0.15%, Nb:0.1～0.7% in quality %, this steel plate have from its surface to
Till Cr, Si, Al, the Fe atomic percent at degree of depth place be surface oxidation epithelium more than 0.6 than (Cr+Si+Al)/Fe; The chemical conversion treating agent of filming constitutes by a kind or 2 kinds in aminosilane system and the epoxy silane system, measures SiO by fluorescent X-ray
2Amount, the adhesion amount of this chemical conversion treating agent is 2～20mg/m
2The thickness that has by the formed transparent coating of Clear paint is filming of 1～10 μ m, and it is that coating, acrylic resin coating, acrylated polyurethane resin are that coating, epoxy modified polyester resin are any in the coating that described Clear paint is selected from vibrin.
5. the manufacture method of the clear-coated stainless steel sheet that the described whiteness of claim 1 is good, it is characterized in that: for the ferrite series stainless steel plate raw sheet that contains Si:0.2～0.8% in quality %, the temperature T 1 of final clean annealing (℃) and the dew point T2 of annealing atmosphere (℃) satisfy under the condition of formula 1 and formula 2 and anneal, make have from its surface to
Till Cr, Si, Al, the Fe atomic percent at degree of depth place be the steel plate raw sheet of the surface oxidation epithelium more than 0.6 than (Cr+Si+Al)/Fe;
Described steel plate raw sheet is carried out following chemical conversion handle, a kind or 2 kinds of chemical conversion treating agents that constitute that utilize by in aminosilane system and the epoxy silane system are handled in described chemical conversion, measure SiO by fluorescent X-ray
2Amount, the adhesion amount of this chemical conversion treating agent is 2～20mg/m
2
It is that coating, acrylic resin coating, acrylated polyurethane resin are that coating, epoxy modified polyester resin are any in the coating that coating Clear paint and to form thickness be filming of 1～10 μ m, described Clear paint are selected from vibrin;
750≤T1≤5 * T2+1200 ... formula 1
-70≤T2≤-30 ... formula 2.
6. the manufacture method of the clear-coated stainless steel sheet that a whiteness is good, it is characterized in that: for the ferrite series stainless steel plate raw sheet that contains Si:0.2～0.8%, Al:0.005～0.15% in quality %, the temperature T 1 of final clean annealing (℃) and the dew point T2 of annealing atmosphere (℃) satisfy under the condition of formula (1) and formula (2) and anneal, make have from its surface to
Till Cr, Si, Al, the Fe atomic percent at degree of depth place be the steel plate raw sheet of the surface oxidation epithelium more than 0.6 than (Cr+Si+Al)/Fe;
Described steel plate raw sheet is carried out following chemical conversion handle, a kind or 2 kinds of chemical conversion treating agents that constitute that utilize by in aminosilane system and the epoxy silane system are handled in described chemical conversion, measure SiO by fluorescent X-ray
2Amount, the adhesion amount of this chemical conversion treating agent is 2～20mg/m
2
It is that coating, acrylic resin coating, acrylated polyurethane resin are that coating, epoxy modified polyester resin are any in the coating that coating Clear paint and to form thickness be filming of 1～10 μ m, described Clear paint are selected from vibrin;
750≤T1≤5 * T2+1200 ... formula 1
-70≤T2≤-30 ... formula 2.
7. the manufacture method of the clear-coated stainless steel sheet that a whiteness is good, it is characterized in that: for the ferrite series stainless steel plate raw sheet that contains Si:0.2～0.8%, Al:0.005～0.15%, Nb:0.1～0.7% in quality %, the temperature T 1 of final clean annealing (℃) and the dew point T2 of annealing atmosphere (℃) satisfy under the condition of formula (1) and formula (2) and anneal, make have from its surface to
Till Cr, Si, Al, the Fe atomic percent at degree of depth place be the steel plate raw sheet of the surface oxidation epithelium more than 0.6 than (Cr+Si+Al)/Fe;
Described steel plate raw sheet is carried out following chemical conversion handle, a kind or 2 kinds of chemical conversion treating agents that constitute that utilize by in aminosilane system and the epoxy silane system are handled in described chemical conversion, measure SiO by fluorescent X-ray
2Amount, the adhesion amount of this chemical conversion treating agent is 2～20mg/m
2
It is that coating, acrylic resin coating, acrylated polyurethane resin are that coating, epoxy modified polyester resin are any in the coating that coating Clear paint and to form thickness be filming of 1～10 μ m, described Clear paint are selected from vibrin;
750≤T1≤5 * T2+1200 ... formula 1
-70≤T2≤-30 ... formula 2.
8. the manufacture method of the clear-coated stainless steel sheet that a whiteness is good, it is characterized in that: carry out cold rolling for the ferrite series stainless steel plate raw sheet that contains Si:0.2～0.8% in quality %, after surface grinding, the temperature T 1 of final clean annealing (℃) and the dew point T2 of annealing atmosphere (℃) satisfy under the condition of formula (1) and formula (2) and anneal, make have from its surface to
Till Cr, Si, Al, the Fe atomic percent at degree of depth place be the steel plate raw sheet of the surface oxidation epithelium more than 0.6 than (Cr+Si+Al)/Fe;
Described steel plate raw sheet is carried out following chemical conversion handle, a kind or 2 kinds of chemical conversion treating agents that constitute that utilize by in aminosilane system and the epoxy silane system are handled in described chemical conversion, measure SiO by fluorescent X-ray
2Amount, the adhesion amount of this chemical conversion treating agent is 2～20mg/m
2
It is that coating, acrylic resin coating, acrylated polyurethane resin are that coating, epoxy modified polyester resin are any in the coating that coating Clear paint and to form thickness be filming of 1～10 μ m, described Clear paint are selected from vibrin;
750≤T1≤5 * T2+1200 ... formula 1
-70≤T2≤-30 ... formula 2.
9. the manufacture method of the clear-coated stainless steel sheet that whiteness according to claim 6 is good is characterized in that: to carrying out imposing described final clean annealing after the surface grinding through cold rolling described ferrite series stainless steel plate raw sheet.
10. the manufacture method of the clear-coated stainless steel sheet that whiteness according to claim 7 is good is characterized in that: to carrying out imposing described final clean annealing after the surface grinding through cold rolling described ferrite series stainless steel plate raw sheet.
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| JP4786576B2 (en) * | 2007-03-23 | 2011-10-05 | 日新製鋼株式会社 | Stainless steel material excellent in temper color resistance and its manufacturing method |
| JP5264577B2 (en) * | 2008-03-25 | 2013-08-14 | 日新製鋼株式会社 | Heat-resistant non-adhesive clear painted stainless steel plate without temper color |
| KR101119498B1 (en) * | 2009-02-09 | 2012-03-13 | 김영희 | Method for Manufacturing High Corrosion Resistant Steel Materials and Components |
| JP2010229488A (en) * | 2009-03-27 | 2010-10-14 | Nisshin Steel Co Ltd | Method for manufacturing polish-finished material of ferritic-stainless steel |
| US10907071B2 (en) * | 2009-10-13 | 2021-02-02 | Axalta Coating Systems IP Co. LLC | Organosilane condensate coating composition |
| CN103938195B (en) * | 2014-04-29 | 2016-04-13 | 浙江大学 | The method of alkyltrichlorosilanes class self-assembled monolayer is prepared at stainless steel surface |
| WO2016039429A1 (en) * | 2014-09-10 | 2016-03-17 | 新日鐵住金株式会社 | Austenitic stainless steel sheet which is not susceptible to diffusion bonding |
| JP6301402B2 (en) * | 2016-07-01 | 2018-03-28 | 日新製鋼株式会社 | Ferritic stainless steel sheet and manufacturing method thereof |
| JP7069407B2 (en) * | 2019-03-28 | 2022-05-17 | 日鉄ステンレス株式会社 | Clear painted stainless steel plate |
| WO2023032377A1 (en) * | 2021-09-02 | 2023-03-09 | Ｊｆｅスチール株式会社 | Ferritic stainless steel sheet and method for producing same |
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| JP3112195B2 (en) * | 1992-01-21 | 2000-11-27 | 日本冶金工業株式会社 | Manufacturing method of polished finish ferritic stainless steel sheet with excellent oxidation resistance |
| JP2880906B2 (en) * | 1993-05-19 | 1999-04-12 | 川崎製鉄株式会社 | Ferritic stainless steel with excellent weather resistance and crevice corrosion resistance |
| JPH08281864A (en) * | 1995-04-11 | 1996-10-29 | Nkk Corp | Clear coating stainless steel panel |
| JPH08295999A (en) * | 1995-04-21 | 1996-11-12 | Nippon Steel Corp | Polishing-finished stainless steel sheet excellent in temper color resistance and its production |
| JPH0985880A (en) * | 1995-09-25 | 1997-03-31 | Nkk Corp | Clear coating stainless steel sheet |
| JP4622171B2 (en) * | 2000-07-25 | 2011-02-02 | Ｊｆｅスチール株式会社 | Ferritic stainless steel sheet excellent in room temperature workability and mechanical properties at high temperature and method for producing the same |
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| JP2004122409A (en) * | 2002-09-30 | 2004-04-22 | Sumitomo Metal Ind Ltd | Clear coating stainless steel sheet |
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