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WO2003074760A1 - Feuille en acier traitee en surface et son procede de production - Google Patents

Feuille en acier traitee en surface et son procede de production Download PDF

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Publication number
WO2003074760A1
WO2003074760A1 PCT/JP2002/002052 JP0202052W WO03074760A1 WO 2003074760 A1 WO2003074760 A1 WO 2003074760A1 JP 0202052 W JP0202052 W JP 0202052W WO 03074760 A1 WO03074760 A1 WO 03074760A1
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WO
WIPO (PCT)
Prior art keywords
steel sheet
component
film
phosphoric acid
oxide film
Prior art date
Application number
PCT/JP2002/002052
Other languages
English (en)
Japanese (ja)
Inventor
Tatsuya Miyoshi
Satoru Ando
Akira Matsuzaki
Naoto Yoshimi
Takahiro Kubata
Masaaki Yamashita
Original Assignee
Jfe Steel Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP2000271454A priority Critical patent/JP3707375B2/ja
Priority claimed from JP2000271454A external-priority patent/JP3707375B2/ja
Application filed by Jfe Steel Corporation filed Critical Jfe Steel Corporation
Priority to PCT/JP2002/002052 priority patent/WO2003074760A1/fr
Priority to EP02705083A priority patent/EP1482074A4/fr
Priority to KR1020037016869A priority patent/KR100608137B1/ko
Priority to CNA028136810A priority patent/CN1524133A/zh
Publication of WO2003074760A1 publication Critical patent/WO2003074760A1/fr

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Classifications

    • 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
    • C23C22/06—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 acidic solutions with pH less than 6
    • C23C22/07—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 acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating

Definitions

  • the present invention relates to a surface-treated steel sheet having excellent heat resistance and scratch resistance, which can be used for various parts of automobiles, home appliances, and building materials, and a method for producing the same. Background leakage
  • dumbbell-plated steel sheets are used in a wide range of fields, such as automobiles, home appliances, and building materials.
  • a zinc-based plated steel sheet is subjected to chromate treatment, and a thin resin coating with a thickness of several meters is further formed on the surface. Is being done.
  • Chromate treatment uses hexavalent chromium, which is a pollution control substance, and this hexavalent chromium is treated in a closed system in the treatment process, and is completely reduced and recovered, and is not released to nature. Sealing with organic composite film Since the elution from the chromate film can be reduced to almost zero by the action, the environment and human body are not substantially polluted by hexavalent chromium.
  • recent global environmental issues have led to a growing trend to voluntarily reduce the use of heavy metals, including hexavalent chromium.
  • a method using a mixture of tannic acid such as a method using a mixed product of an aqueous resin and ⁇ fffiphenol carboxylic acid (for example, JP-A-8-325760).
  • a surface treatment method of applying an aqueous solution of a hydrazine derivative to the surface of a tin or zinc iron plate for example, JP-B-53-27694, JP-B-56-10386)
  • a composition for surface treatment comprising an organic resin containing a monomer containing a 7-acid-monomer as a copolymerization component and a phosphoric acid compound of phosphoric acid or metal (JP-A-9-208859, JP-A-9-241856) )
  • the conventional technology of (4) uses a ladder type silicone resin formed on a zinc-plated steel sheet with a chemical conversion coating, but has a cross-linked structure called a ladder type.
  • the cured film became too thick, resulting in poor scratch resistance during processing and poor adhesion of the film during processing.
  • the conventional technology of (5) had both heat resistance and scratch resistance.
  • chromate in order to improve corrosion resistance, chromate
  • An object of the present invention is to provide a surface-treated steel sheet which is excellent in both heat resistance and flaw resistance at high temperatures, does not use chromium in the treatment step, is safe and has excellent corrosion resistance, and a method for producing the same. Is to do.
  • the present inventors have developed a composite oxide film composed of oxide fine particles and a phosphate compound as a first layer on a zinc-based plated steel sheet surface, and a resin film mainly composed of a specific straight silicone resin as a second layer.
  • a new zinc-coated steel sheet with excellent heat discoloration resistance, smoke emission when heated, corrosion resistance after heating and scratch resistance has been newly discovered.
  • a composite oxide film containing (a) oxide fine particles and (] 3) phosphoric acid and Z or a phosphoric acid compound as constituent elements as the first layer is formed by the above-mentioned component ( shed) and P 2 0 5 the above ingredients () total amount of adhered and formed so that Do and 5 ⁇ 4000mg / m 2 of at the exchange, 0 straight silicone resin film with Si0 2 calculated as the second layer of the upper layer .:! Surface-treated steel sheet, characterized in that the ⁇ 3 g / m 2 formed.
  • the composite oxide film further contains (a) one or more of Mg, Ca, Sr, Ii, Mn, Fe, Co, Ni, Zn, Al, La, and Ce as components, and wherein the One composite oxide fine particles (the P 2 0 5 above components in terms of oxide film in (3), the total deposition amount of the metal conversion calculated mass of the component ( ⁇ ) is 5 ⁇ 4000Mgm 2
  • components contained in the composite oxide film (alpha) is silicon dioxide and in an amount ranging adhesion of. 5 to 95 wt% as a mass ratio to the total deposition amount of the composite oxide film at the Si0 2 in terms of The surface-treated steel sheet according to any one of the above [1] to [3], wherein:
  • C6 One or more components (a) of Mg, Ca, Sr, li, Mn, Fe, Co> Ni, Zn, Al, La, Ce contained in the composite oxide film, and a component ( in terms of metal amount of P 2 0 5 in terms of weight and Ingredient ( ⁇ ) 3) (molar ratio of the metal that the sum of respective terms of a metal amount in the case of two or more) (P 2 0 5 ZME) is lZ2 ⁇
  • the (mouth) phosphoric acid and / or phosphoric acid compound is treated with an aqueous solution containing 0.001 ⁇ 6.0Mol / l in P 2 0 5 in terms of weight, by heating and drying thereafter, as the first layer coating on the plated steel sheet surface ,
  • FIG. 1 is a schematic front view of a testing machine for evaluating the scratch resistance of a test material.
  • a composite oxide film is formed as a first layer on the surface of a zinc-coated steel sheet.
  • the composite oxide film containing silicon dioxide of the present invention as a component is
  • the Arukarishirike Ichito treatment film typified by 2 treatment composition
  • oxide fine particles which is one of the constituent elements of the composite oxide film
  • silicon dioxide is preferable, and colloidal silica, for example, Snowtex 0, OS, OXS, OUP, AK manufactured by Nissan Chemical Industries, Ltd. :, 040, O and OZL (more acidic solution), Snowtex XS, S, XS, NS, N, QAS-25, LSS-35, LSS-45, LSS-75 (more alkaline solution) etc.
  • Cataloid S, SI-350, SI-40, SA aboveve alkaline solution
  • Cataloid SN aboveve acidic solution
  • Asahi Denka Kogyo Co., Ltd. Adelite AT-20-50, AT- 20N, AT-300, AT-300S (more alkaline solution), Adelite AT20Q (more acidic solution), etc.
  • colloidal silica for example, Snowtex 0, OS, OXS, OUP, AK manufactured by Nissan Chemical Industries, Ltd. :
  • those having a particle size of 14 nm or less, and particularly those having a particle size of 8 nm or less are preferable from the viewpoint of corrosion resistance.
  • a material obtained by dispersing dry-type fine particles in a coating composition solution may be used.
  • the fumed silica AEROS1L 200, 300, 300CF, 380, etc., manufactured by Nippon Aerosil Co., Ltd. can be used.
  • those having a particle diameter of 12 nm or less, preferably 7 nm or less are preferable.
  • oxide fine particles a colloid solution or a fine powder of aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, antimony oxide, or the like can be used.
  • Phosphoric acid and Z or phosphate compound For example, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, and the like, and metal salts and compounds thereof can be added to a film composition to be combined as a film component.
  • the first phosphate is preferred from the viewpoint of the stability of the coating composition solution.
  • ammonium primary phosphate, ammonium secondary phosphate, and ammonium phosphate tertiary were added to the coating composition solution as phosphates, a tendency was observed to improve the corrosion resistance. The reason for this is not clear, but when these ammonium salts are used, the gel does not gelate even if the pH of the skin solution is increased. In general, metal salts become insoluble in an alkaline region, so that when formed from a composition solution having a high pH, it is considered that a more sparingly soluble compound is generated in the drying process.
  • the presence state of phosphoric acid and Z or a phosphoric acid compound in the film is not particularly limited, and may be crystalline or non-crystalline.
  • the ionicity and solubility of phosphoric acid and Z or a phosphoric acid compound in the film are not particularly limited.
  • Mg, Ca, Sr, Ii, Mn, Fe, Co, Ni, Zn, Al, La, Ce are not particularly limited in the state of existence in the film. Presumably exist as a metal, or as a compound such as an oxide, 7jC oxide, hydrated oxide, or phosphate compound, or as a complex compound or a metal.
  • a metal or as a compound such as an oxide, 7jC oxide, hydrated oxide, or phosphate compound, or as a complex compound or a metal.
  • the ionicity, solubility, and the like of these compounds, hydroxides, hydrated oxides, and phosphate compounds are not particularly limited.
  • Mn and A1 have better corrosion resistance than the other components (a). The reason for this is not clear, but hydroxides are likely to be formed in the corrosive environment, neutral pH, and form a network for complexation with phosphate compounds, silica, etc., resulting in a dense film. It is thought that it is.
  • the method of introducing the component ( r ) into the film is not particularly limited, but Mg, Ca, Sr, Ii, Mn, Fe, Co, Ni, Zn, Al, La, Ce phosphate, nitrate, It may be added to the coating composition solution as a sulfate, chloride, or the like.
  • Adhesion of the composite Sani ⁇ coating the components in the oxide particles (a) and P 2 0 5 in terms of (beta).
  • the component ( ⁇ ) is present, as the sum of the metal mass in terms is suitably 5 ⁇ 4000mg / m 2.
  • Preferably from 50: L000mg / m 2 more preferably from 100 to 500 mg / m 2, further preferably 200 to 400 mg / m 2. If the adhesion amount is less than 5 mg / m 2 , the corrosion resistance is not sufficient, while if it exceeds 4000 mg / m 2 , the appearance of the coating and the appearance after heating are deteriorated, and the conductivity is further reduced. to degrade.
  • a composite oxide ⁇ components of the medium but silicon dioxide, total adhesion of the composite Sani ⁇ coating adhesion amount is defined above in the Si0 2 in terms of silicon dioxide It is desirable that the mass ratio be in the range of 5 to 95 wt%, preferably 10 to 60 wt%.
  • the proportion of the metal component is a phosphoric acid and / or phosphoric acid compound and a component which is a component of the composite oxide (3) ( ⁇ ), and [rho 2 0 5 in terms of component (beta) in terms of metal amount of Ingredient ( ⁇ ) if (metal in the case of two or more respective sum of terms of a metal amount) is 1 Bruno 2-2 1 molar ratio (P 2 0 5 ZME) and A better corrosion resistance can be obtained.
  • additives such as polyphosphate, phosphate (eg, zinc phosphate, aluminum dihydrogen phosphate, zinc phosphite, etc.), molybdate, and phosphorus are further added as additives for further suppressing corrosion resistance.
  • Molybdate such as aluminum phosphomolybdate
  • organic phosphoric acid and its salts phytic acid, phytate, phosphonic acid, phosphonate and their metal salts, alkali metal ⁇
  • organic inhibitors eg hydrazine derivatives , Thiol compounds, dithiol rubamates, etc.
  • coupling agents for example, silane coupling agents, titanium coupling agents, etc.
  • organic resin Any addition is not preferable because it causes smoke and appearance deterioration after heating at a high temperature.
  • the plated steel sheet of the present invention has a film formed by applying and baking a treatment liquid mainly containing a specific straight silicone resin as a second layer on the surface of the first layer.
  • Silicone is a general term for materials that have a siloxane (one Si—0—Si—) portion. Trees J !, oil, rubber, etc. are used.
  • Siloxane one Si—0 to Si—
  • a hydroxyl group —OH
  • an alkoxyl group —OH
  • R is an organic group or an organic group bonded to the material, which has both organic and inorganic properties, and is characterized by not being modified with other organic resins.
  • the film is flexible because it does not have a bridge structure, and is characterized by excellent scratch resistance.
  • the organic group bonded with silicofluoride atom, a methyl group (- CH 3), Echiru group (one C 2 3 ⁇ 4), phenyl group (an C 6 H 5), a vinyl group (- CH C3 ⁇ 4), butyl Group (-QH 7 ) and the like.
  • the straight silicone resin used may contain these organic groups alone or may contain two or more different organic groups. It is not preferable to use a modified silicone resin other than the straight silicone resin, because the modified organic resin component is thermally decomposed during heating, causing discoloration and smoking.
  • organic groups those having a methyl group having a small number of carbon atoms are more preferable from the viewpoint of preventing smoke caused by ⁇ of the organic component due to heating.
  • S i0 2 component contained in the straight silicone resin is preferably 60% or more of the total film weight.
  • This other Si0 2 component of the straight silicone resin are the water acid group or an organic group, smoke with an organic group is increased in order to Retsui spoon.
  • the reason why the organic lubricant is added to the silicone resin film is that the organic lubricant has an effect of more effectively preventing the resin film and the adhered surface from being scratched and galling due to roll forming and press molding. Because it has.
  • the reason for using an organic lubricant having a softening point of 70 ° C. or higher is not preferable if the temperature is lower than 70 ° C. because organic components are easily decomposed and smoke is inferior.
  • organic lubricants having a softening point of 70 ° C or higher include: Microcrossing phosphorus wax (softening point 70 to 90 ° C), polyethylene (softening point 90 to 140 ° C), and polypropylene (softening point 140 to 170 ° C). C), tetrafluoroethylene (softening point 320 ° C), etc. I can do it.
  • the above-mentioned lubricants may be added alone, or two or more different lubricants may be used in combination.
  • the acid phosphorus value of the micro phosphorus phosphorus wax, polyethylene, and polypropylene may be 0 or more than 0, or a combination thereof. Since the silicone resin is of a solvent type, it is preferably added in the form of powder or in a state of being dispersed in a solvent in advance, and the particle size is preferably 20 m or less from the viewpoint of scratch resistance.
  • crystalline lubricants include inorganic lubricants such as graphite, boron nitride, and molybdenum disulfide. Such a lubricant can be preferably used when fuming is important, but it may be slightly inferior in scratch resistance as compared with organic ones. You can do it.
  • the organic lubricant is preferably added in an amount of 20 parts by mass or less based on 100 parts by mass of the silicone resin. If the amount is more than 20 parts by mass, the amount of organic components increases, and the smoke emission during heating is inferior. A more preferable addition amount is 10 parts by mass or less from the viewpoint of fuming properties. In the case of an inorganic lubricant, if the addition amount exceeds 20 parts by mass, the flaw resistance deteriorates, which is not preferable.
  • a coating mainly composed of a straight silicone resin as described above is applied to the surface of a zinc-based steel plate, heated and dried to form a film.
  • the coated steel sheets that form the above-mentioned coatings include galvanized steel sheets manufactured by electroplating, hot-dip plating, and vapor deposition, zinc, as well as nickel, iron, aluminum, cobalt, and molybdenum.
  • hot-rolled aluminized steel sheet without zinc plating, cold-rolled steel sheet without Steel plates can also be used.
  • the steel sheet used as the base of the zinc-based plated steel sheet is not particularly limited, and various compositions, surface roughness, and rolling methods can be used.
  • the formation of the composite oxide film and the resin film on the surface of the zinc-based plated steel sheet is performed as follows. That is, the treatment solution for the composite oxide film composition described above is applied to the surface of the zinc-based plated steel sheet by a known method such as a roll coater, a force flow coater, or spray coating, and the hot air stove or induction heater is applied. A predetermined amount of the coating film is formed by applying the above-mentioned paint mainly composed of the straight silicone resin similarly to the surface of the composite oxide film formed by drying by a known method such as a heating furnace. To form Next, the zinc-coated steel sheet coated with the paint was heated using a hot air stove or induction heating device.
  • the solvent in the paint is volatilized to form a resin film.
  • the concentration of the processing solution is limited to the above range for the following reason.
  • Was or phosphoric acid and Z Rinsani ⁇ product is fried unfavorable such secured a predetermined coating weight is less than O.OOlmoVl with P 2 0 5 in terms of weight, poor processing solution stability at 6.0 mol / l greater Therefore, it is not preferable.
  • the oxidized fine particles are less than O.OOlmol / 1, it is not preferable because a predetermined amount of the particles cannot be secured, and if it is more than 3.0mol / l, the stability of the treatment liquid is inferior.
  • the metal conversion amount of the metal If the total is less than O.OOlmoW, the effect of adding metal ions is not obtained, which is not preferable. If the total is more than 3.0 mol / l, the stability of the treatment liquid is inferior.
  • the baking temperature of the above-mentioned resin film should be in the range of 80 to 300 ° C. If the baking temperature is lower than 80 ° C, the resin film is not sufficiently cured, and the scratch resistance during processing is poor. On the other hand, if the temperature exceeds 300 ° C., the curing of the resin film proceeds excessively, and the organic groups in the straight silicone resin are decomposed and volatilized, which is not preferable because of poor scratch resistance.
  • the treatment liquids (film compositions) for forming the first layer film shown in Tables 1 and 2 were prepared.
  • the adjusted second layer film forming treatment solution shown in Table 3-5 (the coating composition) £
  • Oxide fine particles ( ⁇ ) Phosphoric acid / phosphate compound () Metal component (r)
  • Component 1 Component 2 Primary particles of the present invention (mol / l) (mol / l) Molar ratio; Tatsuna Total composition Condition suitability Type Trade name Diameter (nm) * 1 type * 2 ( ⁇ ) ⁇ ) Type (mol / l) Type (mol / l) Mole amount * 3
  • the total coating weight (oxide particles mass + () 8) [rho 2 0 5 reduced mass in the (y3) phosphoric acid and / or phosphoric acid compound ten (r) components of the metal equivalent weight
  • GF Hot-dip zinc-5% aluminum alloy coated steel sheet
  • GL Hot-dip zinc-55 '/.
  • the total coating weight ( «) oxide particles mass + (js) p 2 o 5 reduced mass in the (beta) phosphoric acid and / or phosphoric acid compound + (r) components of the metal equivalent weight
  • UZ Electro-galvanized steel sheet
  • EZN Sub-nickel alloy-plated steel sheet
  • GI Hot-dip galvanized steel sheet
  • GA Alloyed hot-dip galvanized steel sheet
  • GF Fused zinc-5% aluminum alloy coated steel sheet
  • GL Fused zinc-55% aluminum alloy coated steel sheet
  • the total coating weight oxide particles mass + (jS) P 2 0 5 in terms of mass (/ 3) phosphoric acid and / or phosphoric acid compound + (r) components of the metal equivalent weight
  • the coating composition mainly composed of the straight silicone resin shown in Tables 3 to 5 was applied by a roll coating method (adhesion amount was adjusted by wet application amount), and this was applied to an induction heating furnace.
  • the test material was prepared by baking at an ultimate plate temperature of 60 to 400 ° C.
  • Electro-galvanized steel sheet sheet thickness 0.8 mm, coating weight 20 gm 2 )
  • Hot-dip galvanized steel sheet (sheet thickness 0.8 mm, coating weight 90 g / m 2 )
  • Hot-dip galvanized steel sheet with 5% aluminum alloy (sheet thickness 0.8 nm, coating weight 90 g / m ")
  • Tables 3 to 5 show the amount of composite oxide attached to the first layer and the amount of resin film attached to the second layer of each sample.
  • the prepared test materials were evaluated for heat discoloration resistance, smoke generation, pre-calo heating, post-heating corrosion resistance, and scratch resistance. The results are shown in Tables 6-8.
  • the performance evaluation method is described below.
  • the i3 ⁇ 4B criteria are as follows.
  • test pieces of 70 mm ⁇ 150 mm were cut out from the test material, and the test pieces were subjected to a salt spray test specified in JIS Z 2371, and the whitening area after 500 hours was visually determined.
  • the evaluation criteria are as follows.
  • test material After reaching the plate temperature of 600 ° C, the test material was heat-treated for 1 hour, and several 70mm x 150mm test pieces were cut out and subjected to salt spray test specified in JIS Z 2371. The test was carried out, and the reddish area after 500 hours was visually determined.
  • the evaluation criteria are as follows.
  • the test machine shown in the schematic front view in FIG. 1 was used.
  • the tester includes a female die 1 having a flat surface fixed to one side 2a of a box-shaped frame 2 as shown in FIG. 1, and a substantially horizontal protrusion having a predetermined height facing the female die 1.
  • Male dice 4 with Article 3 and male dice 4 And a hydraulic cylinder 5 fixed to the other side 2b of the frame 2 for horizontally moving the male die 4 toward the female die 1.
  • the male die 4 is fixed to a rod 5 a of a hydraulic cylinder 5 via a load cell 6.
  • the width of the ridge 3 of the male die 4 is 10 mm, and the length of its tip is lmm.
  • test material 7 is 50 kgf (500 kg ⁇ cm) by the female die 1 and the male die 4. 2 ) Pressed with pressure.
  • test material 7 was pulled upward at a speed of 500 mm / min, as indicated by the arrow, and the coating and the adhesion damage of the portion slid at that time were visually evaluated.
  • the evaluation criteria are as follows.
  • the zinc-coated steel sheets on which the coating according to the present invention is formed are all resistant to heat discoloration, smoke, corrosion resistance before and after caro heat, and scratch resistance. Is also excellent.
  • the comparative examples are inferior in heat discoloration resistance, smoke generation, corrosion resistance before or after heating, and scratch resistance.
  • the surface-treated steel sheet of the present invention has excellent thermochromic properties and smoke generating properties in an environment exposed to high temperatures, and has excellent corrosion resistance before and after heating without using chromium. Have. Furthermore, it has excellent properties such as scratching of the coating and plating surface when processing as a part and adhesion of the coating.

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  • Engineering & Computer Science (AREA)
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  • Mechanical Engineering (AREA)
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Abstract

L'invention concerne une feuille en acier traitée en surface qui comprend une feuille en acier à placage métallique à base de zinc, un film d'oxyde de composite formé sur la feuille en acier, et un film de résine de silicone pure formé sur le film d'oxyde. Le film d'oxyde de composite comprend (α) de fines particules d'oxyde et (β) un acide phosphorique et/ou un dérivé d'acide phosphorique comme constituant.
PCT/JP2002/002052 2000-09-07 2002-03-06 Feuille en acier traitee en surface et son procede de production WO2003074760A1 (fr)

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JP2000271454A JP3707375B2 (ja) 2000-09-07 2000-09-07 亜鉛系めっき鋼板およびその製造方法
PCT/JP2002/002052 WO2003074760A1 (fr) 2000-09-07 2002-03-06 Feuille en acier traitee en surface et son procede de production
EP02705083A EP1482074A4 (fr) 2002-03-06 2002-03-06 Feuille en acier traitee en surface et son procede de production
KR1020037016869A KR100608137B1 (ko) 2002-03-06 2002-03-06 표면처리 강판 및 그 제조방법
CNA028136810A CN1524133A (zh) 2002-03-06 2002-03-06 表面处理钢板及其制造方法

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JP2000271454A JP3707375B2 (ja) 2000-09-07 2000-09-07 亜鉛系めっき鋼板およびその製造方法
PCT/JP2002/002052 WO2003074760A1 (fr) 2000-09-07 2002-03-06 Feuille en acier traitee en surface et son procede de production

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JP5205845B2 (ja) * 2007-07-31 2013-06-05 Ｊｆｅスチール株式会社 耐油ぬれ拡がり性に優れた表面処理鋼板
CN105908226B (zh) * 2011-06-07 2018-07-17 杰富意钢铁株式会社 热压用钢板
KR102029029B1 (ko) * 2015-03-31 2019-10-08 닛폰세이테츠 가부시키가이샤 용융 아연계 도금 강판
CN105177594A (zh) * 2015-08-19 2015-12-23 合肥市田源精铸有限公司 一种水性防锈剂
CN108779561A (zh) * 2016-03-22 2018-11-09 新日铁住金株式会社 化学转化处理钢板及化学转化处理钢板的制造方法
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JP6962216B2 (ja) * 2018-01-24 2021-11-05 日本製鉄株式会社 溶接鋼管用防錆処理液、溶接鋼管の化成処理方法、溶接鋼管および溶接鋼管の成形加工品
JP6733839B2 (ja) * 2018-04-03 2020-08-05 日本製鉄株式会社 亜鉛系電気めっき鋼板
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KR20040016893A (ko) 2004-02-25
EP1482074A4 (fr) 2005-06-15
CN1524133A (zh) 2004-08-25
EP1482074A1 (fr) 2004-12-01
KR100608137B1 (ko) 2006-08-02

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