CN106103799B - Chemical conversion treatment steel plate and its manufacture method and chemical conversion treatment solution - Google Patents

Chemical conversion treatment steel plate and its manufacture method and chemical conversion treatment solution Download PDF

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Publication number
CN106103799B
CN106103799B CN201580014929.2A CN201580014929A CN106103799B CN 106103799 B CN106103799 B CN 106103799B CN 201580014929 A CN201580014929 A CN 201580014929A CN 106103799 B CN106103799 B CN 106103799B
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chemical conversion
conversion treatment
content
steel plate
mass
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CN106103799A (en
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松野雅典
山本雅也
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Nippon Steel Nisshin Co Ltd
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Nisshin Steel Co Ltd
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Priority claimed from PCT/JP2015/001777 external-priority patent/WO2015146188A1/en
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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
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/42—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 molybdates, tungstates or vanadates containing also phosphates
    • 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

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)

Abstract

The chemical conversion treatment steel plate (10) of the present invention has chemical conversion treatment epithelium (12) on the coating (17) of steel plate (11).The substrate resin of chemical conversion treatment epithelium (12) containing the resin beyond fluororesin, fluororesin, sheet metal (13) and chemical conversion treatment composition.It is scaled more than 3.0 mass % with fluorine atom relative to the content of the above-mentioned fluororesin of the total amount of above-mentioned resin, relative to the content of the substrate resin of the mass parts of fluororesin 100 for more than 10 mass parts, the content of the sheet metal (13) in chemical conversion treatment epithelium (12) is more than 20 mass % and is below 60 mass %.

Description

Chemical conversion treatment steel plate and its manufacture method and chemical conversion treatment solution
Technical field
The present invention relates to chemical conversion treatment steel plate and its manufacture method and chemical conversion treatment solution.
Background technology
Clad steel sheet is applied to exterior building materials.Against weather is required to the clad steel sheet for exterior building materials.For The clad steel sheet, it is known that a kind of chemical conversion treatment steel plate, it includes：Clad steel sheet with the zinc system coating containing aluminium and Chemical conversion treatment epithelium (the example containing fluororesin, non-fluororesin and 4A races metallic compound configured on the clad steel sheet Such as, with reference to patent document 1).The chemical conversion treatment steel plate has sufficient against weather in the purposes of exterior building materials.
Prior art literature
Patent document
Patent document 1：International Publication No. 2011/158513
The content of the invention
Problems to be solved by the invention
The chemical conversion treatment steel plate has sufficient against weather in the purposes of exterior building materials.But the chemistry The gloss of conversion processing steel plate is stronger.Therefore, for the consideration of the surrounding enviroment to building, it is desirable to further suppress gloss. Change colour in addition, the chemical conversion treatment steel plate elapses over time sometimes when exposed because coating surface aoxidizes.
The present invention provides with against weather and inhibits gloss and elapse the chemical conversion treatment of discoloration over time Steel plate.
Solution to problem
Present inventors found that in the material for passing through the chemical conversion treatment epithelium on clad steel sheet and use against weather Excellent fluororesin and non-fluororesin and sheet metal, can obtain with appropriateness gloss and do not produce it is above-mentioned over time The chemical conversion treatment steel plate of discoloration is elapsed, and further carries out research and completes the present invention.
That is, the present invention provides following chemical conversion treatment steel plates.
[1] a kind of chemical conversion treatment steel plate, it is included：The coating of surface configuration with steel plate and in the steel plate The chemical conversion treatment epithelium of clad steel sheet and surface configuration in the coating, wherein, the coating is by including 0.05~60 The kirsite of quality % aluminium and 0.5~4.0 mass % magnesium is formed, and the chemical conversion treatment epithelium contains fluororesin, base Material resin, sheet metal and chemical conversion treatment composition, the substrate resin are from polyurethane, polyester, acrylic resin, asphalt mixtures modified by epoxy resin Selected in fat and polyolefin more than one, relative to the fluororesin of the total amount of the fluororesin and the substrate resin Content is scaled more than 3.0 mass % with fluorine atom, in the chemical conversion treatment epithelium relative to the matter of fluororesin 100 The content of the substrate resin of part is measured to be more than 10 mass parts, the sheet metal in the chemical conversion treatment epithelium contains Measure as more than 20 mass % and be below 60 mass %.
[2] the chemical conversion treatment steel plate as described in [1], wherein, the sheet metal is from aluminium flake, aluminum alloy sheet and stainless Selected in steel disc more than one.
[3] the chemical conversion treatment steel plate as described in [1] or [2], wherein, the thickness of the chemical conversion treatment epithelium is 0.5~10 μm.
[4] the chemical conversion treatment steel plate as described in any one in [1]~[3], wherein, the chemical conversion treatment skin The content of the substrate resin relative to the mass parts of fluororesin 100 in film is below 900 mass parts.
[5] the chemical conversion treatment steel plate as described in any one in [1]~[4], wherein, the chemical conversion treatment into Subpackage race containing 4A metallic compound, the 4A races metallic compound include selected from Ti, Zr and Hf more than one, the chemistry The content of 4A races metallic compound in conversion processing epithelium, relative to the chemical conversion treatment epithelium with 4A races metal It is scaled 0.005~5.0 mass %.
[6] the chemical conversion treatment steel plate as described in any one in [1]~[5], wherein, the chemical conversion treatment into Subpackage contains one or both of molybdate and valve metal compound, and the valve metal compound is to include one of V and Nb Or both compound.
[7] the chemical conversion treatment steel plate as described in any one in [1]~[6], wherein, the chemical conversion treatment skin Film further contains one or both of silane coupler and phosphate.
[8] the chemical conversion treatment steel plate as described in any one in [1]~[7], wherein, utilize phosphate cpd or valve Metal ingredient to the clad steel sheet carry out matrix processing, the valve metal composition be include from Ti, Zr, Hf, V, Nb, Ta, Mo, And the composition of more than one selected in W.
[9] the chemical conversion treatment steel plate as described in any one in [1]~[8], wherein, the chemical conversion treatment skin Film further contains pigment.
[10] the chemical conversion treatment steel plate as described in any one in [1]~[9], wherein, the chemical conversion treatment Epithelium further contains wax.
In addition, the present invention provides the manufacture method of following chemical conversion treatment steel plates.
[11] a kind of manufacture method of chemical conversion treatment steel plate, chemical conversion treatment is coated on the coating of clad steel sheet Liquid, and coated chemical conversion treatment solution is dried, so as to manufacture chemical conversion treatment steel plate, wherein, the coating is by wrapping The kirsite of the magnesium of aluminium and 0.5~4.0 mass % containing 0.05~60 mass % is formed, and the chemical conversion treatment solution contains Composition before fluororesin, substrate resin, sheet metal and chemical conversion treatment, the substrate resin are from polyurethane, polyester, acrylic acid Selected in resin, epoxy resin and polyolefin more than one, the content of the fluororesin in the chemical conversion treatment solution It is scaled more than 3.0 mass % with fluorine atom relative to the total amount of the fluororesin and the substrate resin, the chemical conversion The content of the substrate resin relative to the mass parts of fluororesin 100 in treatment fluid is more than 10 mass parts describedization The content for learning the sheet metal in conversion treating solution is more than 20 mass % relative to solid constituent and is below 60 mass %.
[12] manufacture method of the chemical conversion treatment steel plate as described in [11], wherein, the chemical conversion treatment solution contains There are the emulsion of the fluororesin and the emulsion of the substrate resin, the particle diameter of the emulsion of the fluororesin is 10~300nm, described The particle diameter of the emulsion of substrate resin is 10~100nm.
[13] manufacture method of the chemical conversion treatment steel plate as described in [11] or [12], wherein, coating the chemistry Before conversion treating solution, further comprise carrying out matrix processing to the clad steel sheet using phosphate cpd or valve metal composition Process, the valve metal composition is comprising more than one the composition that is selected from Ti, Zr, Hf, V, Nb, Ta, Mo and W.
Also, the present invention provides following chemical conversion treatment solutions.
[14] a kind of chemical conversion treatment solution, containing before fluororesin, substrate resin, sheet metal and chemical conversion treatment into Point, wherein, the substrate resin be selected from polyurethane, polyester, acrylic resin, epoxy resin and polyolefin it is a kind of with On, the content of the fluororesin in the chemical conversion treatment solution relative to the fluororesin and the substrate resin total amount Be scaled more than 3.0 mass % with fluorine atom, in the chemical conversion treatment solution relative to the mass parts of fluororesin 100 The content of the substrate resin is more than 10 mass parts, the content of the sheet metal in the chemical conversion treatment solution relative to Solid constituent is more than 20 mass % and is below 60 mass %.
[15] chemical conversion treatment solution as described in [14], wherein, the chemical conversion treatment solution contains the fluororesin Emulsion and the substrate resin emulsion, the particle diameter of the emulsion of the fluororesin is 10~300nm, the breast of the substrate resin The particle diameter of liquid is 10~100nm.
Invention effect
In accordance with the invention it is possible to provide with against weather and inhibit gloss and elapse the chemistry of discoloration over time Conversion processing steel plate.Not only against weather is excellent for the chemical conversion treatment steel plate of the present invention, and its outward appearance is also good, so being applied to Exterior building materials.
Brief description of the drawings
Fig. 1 is the figure of the layer construction for the chemical conversion treatment steel plate for schematically showing one embodiment of the present invention.
Description of reference numerals
10 chemical conversion treatment steel plates
11 steel plates
12 chemical conversion treatment epitheliums
13 sheet metals
14 waxes
15 4A races metallic compounds
16 silane couplers
17 coating
Embodiment
Hereinafter, one embodiment of the present invention is illustrated.
1. chemical conversion treatment steel plate
The chemical conversion treatment steel plate of present embodiment has the chemical conversion treatment skin in the surface configuration of clad steel sheet Film.Hereinafter, each inscape of the chemical conversion treatment steel plate of present embodiment is illustrated.
[clad steel sheet]
The species of above-mentioned clad steel sheet is not specially limited.The clad steel sheet has steel plate and coating.From corrosion resistance and From the viewpoint of design, the coating is by the aluminium comprising 0.05~60 mass % and the kirsite of 0.5~4.0 mass % magnesium Form.The thickness of above-mentioned clad steel sheet can suitably determine according to the purposes of chemical conversion treatment steel plate, for example, 0.2~ 6mm.Above-mentioned clad steel sheet for example can be flat board or corrugated plating, and the flat shape of clad steel sheet can be rectangle, can To be the shape beyond rectangle.
As the example of above-mentioned clad steel sheet, including：Hot-dip aluminizing-magnesium-zinc steel based on the kirsite containing aluminium and magnesium Plate (hot-dip Al-Mg-Zn steel plates) and hot-dip Al-Si-Mg-zinc steel plate based on the kirsite containing aluminium, magnesium and silicon (hot-dip Al-Mg-Si-Zn steel plates).
For the example of the above-mentioned steel plate (matrix steel plate) of the matrix as above-mentioned clad steel sheet, including mild steel, middle carbon Steel, high-carbon steel and steel alloy.From the viewpoint of the processability for improving chemical conversion treatment steel plate, preferably the matrix steel plate is low Charcoal adds Ti steel or low charcoal to add the deep-draw steel plate such as Nb steel.
[matrix processing epithelium]
Above-mentioned chemical conversion treatment epithelium is substantially made up of above-mentioned clad steel sheet and chemical conversion treatment epithelium described later. Therefore, above-mentioned clad steel sheet can also not have the epithelium beyond the chemical conversion treatment epithelium, can also utilize phosphoric acid chemical combination Thing or valve metal carry out matrix processing to above-mentioned clad steel sheet.That is, the surface in chemical conversion treatment composition described later to coating In the range of working, above-mentioned clad steel sheet can also further have bag between clad steel sheet and chemical conversion treatment epithelium The matrix processing epithelium of phosphorous acid compound or valve metal composition.Matrix processing epithelium is above-mentioned clad steel sheet, by right The layer for the composition that the surface of chemical conversion treatment epithelium is handled and adhered to should be formed.From raising chemical conversion treatment steel plate Corrosion resistance viewpoint and reduce chemical conversion treatment steel plate gloss from the viewpoint of, the matrix processing epithelium be preferred 's.
As the example of the valve metal of above-mentioned valve metal composition, including Ti, Zr, Hf, V, Nb, Ta, Mo and W.Valve metal Composition both can be same modality or different shape in matrix handles epithelium and in matrix treatment fluid described later. Valve metal is coated on clad steel sheet for example in the form of salt, is present in matrix in the form of oxide, hydroxide or fluoride Handle in epithelium.
Orthophosphates and polyphosphate as the example of above-mentioned phosphate cpd, including various metals.Above-mentioned phosphorylation Compound is for example present in the form of soluble or slightly solubility, metal phosphate or composite phosphate in matrix processing epithelium. As the example of the metal of soluble metal phosphate or composite phosphate, including alkali metal, alkaline-earth metal and Mn.As The example of the metal phosphate of slightly solubility or the metal of composite phosphate, including Al, Ti, Zr, Hf and Zn.
Passing through x-ray fluorescence analysis or x-ray photoelectron spectroscopy analysis (ESCA), glow discharge emission spectrum surface When the elementary analyses such as analysis (GDS) are measured to the boundary portion between chemical conversion treatment epithelium and clad steel sheet, detect The above-mentioned distinctive element of phosphate cpd or valve metal, thereby, it is possible to above-mentioned matrix processing epithelium is confirmed.
[chemical conversion treatment epithelium]
Above-mentioned chemical conversion treatment epithelium is the layer of the composition adhered to by the surface treatment of above-mentioned clad steel sheet, is to include The surface of above-mentioned coating and the reaction product of the reaction of composition before the chemical conversion treatment in chemical conversion treatment solution described later The layer of (chemical conversion treatment composition).Above-mentioned chemical conversion treatment epithelium contains fluororesin, substrate resin, sheet metal and chemistry and turned Change processes composition.
Above-mentioned fluororesin is, for example, thermoplastic resin, and it is by roasting of the chemical conversion treatment solution described later to clad steel sheet The fluororesin of a part for the resin component for mutually to be melted with substrate resin described later, turning into the epithelium for forming resin-made is burnt, Improve the against weather (ultra-violet resistance) of chemical conversion treatment epithelium.Fluororesin can be one kind can also be it is a kind of with On.3.0 mass % are scaled with fluorine atom relative to the content of above-mentioned fluororesin and the fluororesin of the total amount of above-mentioned substrate resin More than.If the above-mentioned content of the fluororesin of fluorine atom conversion is less than 3.0 mass %, the against weather of chemical conversion treatment steel plate Sometimes it is insufficient.For example, the fluorine atom in chemical conversion treatment epithelium can be determined by using fluorescent x-ray analyzer Content.
As the example of above-mentioned fluororesin, including Fluorine containing olefine resin.Fluorine containing olefine resin is by the alkyl of composition alkene Part or all of hydrogen atom be replaced into the high-molecular compound of fluorine atom.From prepare chemical conversion treatment epithelium when make fluorine The processing of resin is easy to from the viewpoint of progress, and preferably Fluorine containing olefine resin is the aqueous fluorine-containing tree for also having hydrophilic functional group Fat.
As the example of the above-mentioned hydrophilic functional group in above-mentioned water fluoric resin, including：Carboxyl, sulfo group and they Salt.As the example of the salt, including：Ammonium salt, amine salt and alkali metal salt.From making it possible to form fluororesin without using emulsifying agent Emulsion from the viewpoint of, the content of the hydrophilic functional group preferably in water fluoric resin is 0.05~5 mass %.Above-mentioned In the case that hydrophilic functional group includes both carboxyl and sulfo group, the mol ratio preferably with respect to the carboxyl of sulfo group is 5~60. Can be equal by the content of the above-mentioned hydrophilic functional group of gel permeation chromatography (GPC) measure and the number of above-mentioned water fluoric resin Molecular weight.
From the viewpoint of the water resistance for improving chemical conversion treatment epithelium, the number of preferably above-mentioned water fluoric resin is divided equally Son amount is more than 1000, more preferably more than 10,000, particularly preferably more than 200,000.From the system for preventing chemical conversion treatment epithelium From the viewpoint of gelation when making, preferably the number-average molecular weight is less than 2,000,000.
As the example of water fluoric resin, include the copolymer of fluoroolefins and the monomer containing hydrophilic functional group.As The example of monomer containing hydrophilic functional group, including carboxylic monomer and the monomer containing sulfo group.
As the example of above-mentioned fluoroolefins, including：Tetrafluoroethene, trifluoro-ethylene, CTFE, hexafluoropropene, fluorine second Alkene, vinylidene, pentafluoropropene, 2,2,3,3- tetrafluoropropenes, 3, chloro- 1, the 2- bis- of 3,3- trifluoro propenes, bromo trifluoro-ethylene, 1- PVF and chloro- 2, the 2- difluoroethylenes of 1,1- bis-.Especially, come from the viewpoint for the against weather for improving chemical conversion treatment steel plate See, preferably the perfluoroolefine such as tetrafluoroethene, hexafluoropropene or vinylidene etc..
As the example of above-mentioned carboxylic monomer, including：Unsaturated carboxylic acid, carboxylic vinyl ether monomers, they Ester and their acid anhydrides.
As the example of above-mentioned unsaturated carboxylic acid, including：Acrylic acid, methacrylic acid, vinyl acetate, butenoic acid, Chinese cassia tree Acid, itaconic acid, itaconic acid monoester, maleic acid, maleic mono-ester, fumaric acid, fumaric monoalkylester, 5- hexenoic acids, 5- heptenoic acids, 6- Heptenoic acid, 7- octenoic acids, 8- nonenoic acids, 9- decylenic acids, Shiyixisuan Undecylenic Acid, 11- dodecenoic acids, 17- octadecenoic acids and Oleic acid.
As the example of above-mentioned carboxylic vinyl ether monomers, including：3- (2- alkoxyethoxies carbonyl) propionic acid, 3- (2- alkoxies butoxy carbonyl) propionic acid, 3- (2- vinyloxyethoxies carbonyl) propionic acid and 3- (2- ethyleneoxy butoxy carbonyls Base) propionic acid.
As the example of the above-mentioned monomer containing sulfo group, including：Vinyl sulfonic acid, allyl sulphonic acid, methallyl sulfonic acid, Styrene sulfonic acid, 2- acrylamide -2- methyl propane sulfonic acids, 2- methacryloxies ethane sulfonic acid, 3- methacryloxypropyls Base propane sulfonic acid, 4- methacryloxy butane sulfonic acid, 3- methacryloxy -2- hydroxypropanesulfonic acids, 3- acryloyls Epoxide propane sulfonic acid, allyloxy benzene sulfonic acid, methallyl epoxide benzene sulfonic acid, isoprene sulfonic acid and 3- alkoxy -2- hydroxyls Propane sulfonic acid.
As the monomer of above-mentioned copolymer, the other monomers that can be copolymerized can also be further comprised.As its above-mentioned The example of his monomer, including：Generating vinyl carboxylate esters, alkyl vinyl ethers and non-fluorine system olefines.
Above-mentioned generating vinyl carboxylate esters are used for, for example, improve chemical conversion treatment epithelium in composition intermiscibility or make The glass transition temperature rise of fluororesin.As the example of generating vinyl carboxylate esters, including：Vinyl acetate, vinyl propionate, butyric acid Ethene, vinyl isobutyrate, vinyl pivalate, caproic acid ethene, versatic acid ethene, lauric acid/dodecanoic acid ethene, vinyl stearate, cyclohexyl carboxylic Sour ethene, vinyl benzoate and p-tert-butyl benzoic acid ethene.
Abovementioned alkyl ethene ethers is used for, such as improves the flexibility of chemical conversion treatment epithelium.As alkyl vinyl ethers Example, including methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether.
Above-mentioned non-fluorine system olefines is used for, such as improves the flexibility of chemical conversion treatment epithelium.As non-fluorine system olefines Example, including ethene, propylene, n- butylene and isobutene.
For above-mentioned fluororesin, the copolymer of above-mentioned monomer can be used, market sale product can also be utilized.As the city The example of field sales item, including：(" SIFCLEAR " is the registrar of the said firm to the SIFCLEAR F series of JSR Corp. Mark) and AGC COAT-TECK Co. Ltd. systems OBBLIGATO (" OBBLIGATO " is the registration mark of the said firm).
Above-mentioned substrate resin also in the same manner as above-mentioned fluororesin is for example thermoplastic resin, and it is turned by chemistry described later Change roasting of the treatment fluid to clad steel sheet mutually to be melted with above-mentioned fluororesin, turn into the resin component for the epithelium for forming resin-made A part resin.What above-mentioned substrate resin selected from polyurethane, polyester, acrylic resin, epoxy resin and polyolefin More than one.Substrate resin does not include fluorine atom.
The content of substrate resin in chemical conversion treatment epithelium is 10 mass parts relative to the above-mentioned mass parts of fluororesin 100 More than.If the content is less than 10 mass parts, adhesion and chemical conversion treatment steel plate of the chemical conversion treatment epithelium to coating Corrosion resistance it is sometimes insufficient.Outside when suppression is caused by the against weather reduction of chemical conversion treatment epithelium, exposure Seeing the retentivity of change or sheet metal reduces from the viewpoint of efflorescence, and preferably above-mentioned content is below 900 mass parts, more preferably Below 400 mass parts.
Above-mentioned substrate resin contributes to the retentivity with the adhesion of coating and sheet metal.From this point of view, energy It is enough relative to the above-mentioned mass parts of fluororesin 100, in the range of 10~900 mass parts, it is appropriate to determine chemical conversion treatment skin The content of substrate resin in film.
Chemically from the viewpoint of the easness of the manufacture of conversion processing epithelium and security, preferably above-mentioned polyurethane is water The urethane resin of dissolubility or water dispersible, more preferably self-emulsifying type urethane resin.They have organic polyisocyanates chemical combination The structure of the reaction product of thing and polyol compound.
As the example of above-mentioned organic polyisocyanates compound, including：Aliphatic diisocyanate and alicyclic two different Cyanate.As the example of aliphatic diisocyanate, including：Phenylene diisocyanate, toluene di-isocyanate(TDI), diphenyl-methane two Isocyanates and naphthalene diisocyanate.As the example of alicyclic diisocyanate, including：Cyclohexane diisocyanate, different Buddhist That ketone diisocyanate, norbornene alkyl diisocyanate, XDI and tetramethylxylene two are different Cyanate.
As the example of above-mentioned polyol compound, including polyolefin polyhydric alcohol.As the example of polyolefin polyhydric alcohol, bag Include：PEPA, PPG, polycarbonate polyol, Polyacetal polyols, polyacrylate polyol and polybutadiene Alkene polyalcohol.
For above-mentioned polyurethane, the composite of above-claimed cpd can be used, market sale product can also be utilized.It is used as this The example of market sale product, including：" SUPERFLEX " (registration mark of the said firm) of Di-ichi Kogyo Seiyaku Co., Ltd., And " HYDRAN " (registration mark of the said firm) of Dainippon Ink Chemicals.
For above-mentioned polyester, composite can be used, market sale product can also be utilized.Example as the market sale product Son, including：" VYLONAL " (registration mark of Co., Ltd. is spun by Japan) of STC Co. Ltd. systems is spun by Japan.
For aforesaid propylene acid resin, composite can be used, market sale product can also be utilized.As the market sale The example of product, including：" PATELACOL " (registration mark of the said firm), Ai Ke industrial groups system of Dainippon Ink Chemicals " ULTRASOL " (registration mark of the said firm) and " BONRON " (registrar of the said firm of Mitsui Chemicals, Inc Mark).
For above-mentioned epoxy resin, composite can be used, market sale product can also be utilized.As the market sale product Example, including：" MODEPICS " (registration mark of the said firm) of Arakawa Chemical Industries, Ltd. and Co., Ltd. ADEKA " ADEKA RESIN " (registration mark of the said firm).
For said polyolefins, composite can be used, market sale product can also be utilized.As the market sale product Example, include " ARROW-BASE " (registration mark of the said firm) of Unitika Corp.
Above-mentioned sheet metal suppresses the gloss of chemical conversion treatment steel plate and contributes to the embodiment of anti-blackening.From such From the point of view of viewpoint, the content of the above-mentioned sheet metal preferably in chemical conversion treatment epithelium is 10~60 mass %, if sheet metal is upper State content and be less than 10 mass %, then the gloss of chemical conversion treatment steel plate is too strong, and anti-blackening is sometimes insufficient.If sheet metal Above-mentioned content is more than 60 mass %, then the adhesion of chemical conversion treatment epithelium to coating is sometimes insufficient.
The size of above-mentioned sheet metal can be suitably determined in the range of above-mentioned function is presented.For example, the thickness of sheet metal For 0.01~2 μm, the particle diameter (maximum diameter) of sheet metal is 1~40 μm.SEM (SEM) measure metal can be utilized The size of piece.The numerical value of the size can be the average value or typical value or Directory Value of measured value.
As the example of above-mentioned sheet metal, including：Sheet metal and the sheet glass on surface with the coat of metal.As The example of the metal material of sheet metal, including：Aluminium and its alloy, iron and its alloy, copper and its conjunction gold, silver, nickel and titanium.As aluminium The example of alloy, including Al-Zn, Al-Mg and Al-Si.As the example of ferroalloy, including stainless steel.Example as copper alloy Son, including bronze.From the point of view of the viewpoint such as corrosion resistance or high design, preferably above-mentioned sheet metal be by aluminium flake, aluminum alloy sheet and Selected in stainless steel substrates more than one.In the range of the blacking for not producing sheet metal substantially, the metal of sheet metal is determined The Mg of material content.
Above-mentioned sheet metal can also be surface-treated using surface conditioning agent.By using surface treated metal Piece, it can further improve the water resistance of the sheet metal in the chemical conversion treatment solution illustrated in aftermentioned manufacture method and disperse Property.As the example of the epithelium formed using above-mentioned surface conditioning agent on the surface of sheet metal, including：Molybdic acid epithelium, phosphate Epithelium, silica epithelium and, the epithelium that is formed by silane coupler and organic resin.
As the example of above-mentioned silane coupler, including：MTES, MTMS, diformazan Base dimethoxysilane, trimethylmethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, 3- aminopropans Base trimethoxy silane, N- methyl -3- TSL 8330s, APTES, 3- aminopropans Base three (2- methoxy ethoxies) silane, N- amino-ethyl -3- TSL 8330s, N- amino-ethyl -3- amino Hydroxypropyl methyl dimethoxysilane, 3- methacryloxypropyl trimethoxy silanes, 3- methacryloxymethyls two Methoxy silane, 3- acryloxypropyls trimethoxy silane, 3- glycydoxies trimethoxy silane, 3- contractings Water glycerin ether epoxide hydroxypropyl methyl dimethoxysilane, 3-mercaptopropyi trimethoxy silane, 3- mercaptopropyi triethoxysilicanes Alkane, 3- mercaptopropyis methyl dimethoxysilane, vinyl trichlorosilane, vinyltrimethoxy silane, the ethoxy of vinyl three Base silane, vinyl three (2- methoxy ethoxies) silane, vinyltriacetoxy silane, 3- (3,4- expoxycyclohexyls Ethyl trimethoxy) silane, γ aminopropyltriethoxy silane, N- β-(amino-ethyl)-gamma-amino propyl trimethoxy Silane, 3- ureas propyl-triethoxysilicane, 3- r-chloropropyl trimethoxyl silanes, 3- aniline propyl trimethoxy silicane, 3- (4,5- Glyoxalidine propyl triethoxy) silane, N- phenyl -3- TSL 8330s, 17 fluorine decyl trimethoxy silicon Alkane, ten trifluoro octyl group trimethoxy silanes, trifluoro propyl trimethoxy silane, 3- isocyanatopropyls triethoxysilane and right Styryl trimethoxy silane.
For above-mentioned sheet metal, the conquassation product of metallic particles can be used, market sale product can also be utilized.It is used as this WXM-U75C, EMR-D6390, WL-1100, GD-20X of the example , Bao Kuo East oceans Aluminum Co. Ltd. system of market sale product and PFA4000。
For the thickness of above-mentioned chemical conversion processing epithelium, if excessively thin, with the against weather of chemical conversion treatment steel plate For representative, the desired function brought by chemical conversion treatment epithelium may become insufficient, if blocked up, produce sometimes Rate reduces.From this point of view, preferably above-mentioned thickness is 0.5~10 μm, more preferably 1~4 μm.Above-mentioned thickness being capable of profit Be measured with known film thickness gauge, can utilize the chemical conversion treatment solution illustrated in aftermentioned manufacture method coated weight or Coating number is adjusted to thickness.
Above-mentioned chemical conversion treatment composition is the reaction product on the surface of coating, can be that one kind can also be a kind of More than.As the example of the chemical conversion treatment composition, including：4A races metallic compound, molybdate and valve metal compound.On The form for the compound stated is the form of above-mentioned reaction product, e.g. salt, oxide, fluoride or phosphate.
Above-mentioned 4A races metallic compound is comprising more than one the compound selected from Ti, Zr and Hf.4A races metal Compound contributes to the raising of the corrosion resistance of chemical conversion treatment steel plate and sheet metal in chemical conversion treatment epithelium It is fixed.As the example of 4A races metallic compound, including：Hydrohalogenic acid salt, ammonium salt, the alkali metal of metal comprising these 4A races metals Salt and alkali earth metal salt.Can be luminous by using fluorescent x-ray analyzer or high-frequency inductive coupling plasma body (ICP) Analytical equipment, to determine the content of the 4A races metal in chemical conversion treatment epithelium.
From the viewpoint of the raising of above-mentioned against weather and the fixation of sheet metal, preferably in chemical conversion treatment epithelium The content of 4A races metallic compound 0.005~5.0 mass % is scaled with 4A races metallic atom.If the content is less than 0.005 Quality %, then the raising effect of the corrosion resistance of chemical conversion treatment steel plate can not be fully obtained sometimes, if more than 5.0 matter % is measured, then chemical conversion treatment epithelium is cellular, the processing for the chemical conversion treatment steel plate that chemical conversion treatment epithelium is brought Property and against weather are sometimes insufficient.
Above-mentioned molybdate contributes to the raising of the corrosion resistance of chemical conversion treatment steel plate.As the example of the molybdate, Including ammonium molybdate and alkali metal molybdates.
From the viewpoint of the raising of above-mentioned corrosion resistance, the content of the molybdate preferably in chemical conversion treatment epithelium with Molybdenum atom is scaled 0.005~2.0 mass %.If the content is less than 0.005 mass %, can not fully be improved sometimes The effect of above-mentioned corrosion resistance, if more than 2.0 mass %, sometimes in addition to corrosion resistance raising acts on saturation, treatment fluid Stability can also reduce.Can be by using fluorescent x-ray analyzer or ICP apparatus for analyzing luminosity, to determine chemical conversion Handle the content of the molybdate in epithelium.
Above-mentioned valve metal compound is comprising more than one the compound selected from V, Nb, Ta and W.Especially, preferably For V and Nb.The valve metal compound contributes to raising or the chemical conversion treatment of the corrosion resistance of chemical conversion treatment steel plate The suppression of excessive gloss in steel plate.As the example of the valve metal compound, including the oxide of above-mentioned valve metal, hydroxide Thing and fluoride.
From the viewpoint of raising and gloss adjustment from above-mentioned corrosion resistance, the valve gold preferably in chemical conversion treatment epithelium The content of category compound is scaled 0.005~2.0 mass % with valve metal atoms.If the content is less than 0.005 mass %, have Shi Buneng fully obtains the effect above, if more than 2.0 mass %, the effect above reaches capacity sometimes.Can be by using Fluorescent x-ray analyzer or ICP apparatus for analyzing luminosity, to determine containing for the valve metal compound in chemical conversion treatment epithelium Amount.
In the range of it can obtain the effect of the present invention, above-mentioned chemical conversion treatment epithelium can also further contain fluorine Other compositions beyond resin, substrate resin, sheet metal and chemical conversion treatment composition.As the example of the other compositions, bag Include：Silane coupler, phosphate, etch compounds, pigment and wax.The other compositions can be one kind can also be it is a kind of with On.
Above-mentioned silane coupler contributes to the raising of the adhesion of chemical conversion treatment epithelium.Example as silane coupler Son, including silane compound and its condensation product with bonding functional group.As the example of the bonding functional group, including：Amino, Epoxy radicals, sulfydryl, acryloxy, methacryloxy, alkoxy, vinyl, styryl, NCO and chlorine third Base.Bonding functional group can be that one kind can also be more than one.
From the viewpoint of the raising of above-mentioned adhesion, the content of the silane coupler preferably in chemical conversion treatment epithelium For 0.1~5.0 mass %.If the content is less than 0.1 mass %, the effect of above-mentioned adhesion can not be fully improved sometimes Fruit, if more than 5.0 mass %, the effect of the raising adhesion reaches capacity sometimes.Can be by using x-ray fluorescence analysis Device or ICP apparatus for analyzing luminosity, to determine the content of the silane coupler in chemical conversion treatment epithelium.
Above-mentioned phosphate contributes to the raising of the corrosion resistance of chemical conversion treatment epithelium." phosphate " is cloudy with phosphoric acid The water miscible compound of ion.As the phosphatic example, including：Sodium phosphate, ammonium phosphate, magnesium phosphate, potassium phosphate, phosphoric acid Manganese, trbasic zinc phosphate, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid (diphosphonic acid), triphosphoric acid and four phosphoric acid.
From the viewpoint of the raising of above-mentioned corrosion resistance, phosphatic content preferably in chemical conversion treatment epithelium with Phosphorus atoms are scaled 0.05~3.0 mass %.If the content is less than 0.05 mass %, can not fully be improved sometimes The effect of corrosion resistance is stated, if more than 3.0 mass %, sometimes in addition to corrosion resistance raising acts on saturation, treatment fluid is steady It is qualitative also to reduce.Can be by using fluorescent x-ray analyzer or ICP apparatus for analyzing luminosity, to determine at chemical conversion Manage the phosphatic content in epithelium.
Above-mentioned etch compounds are, for example, comprising more than one the chemical combination selected from Mg, Ca, Sr, Mn, B, Si and Sn Thing.The etch compounds contribute to the water resistance for the chemical conversion treatment epithelium that fine and closely wovenization by chemical conversion treatment epithelium bring Raising.As the example of the etch compounds, include the salt of above-mentioned element.
From the viewpoint of the raising of above-mentioned water resistance, the content of the etch compounds preferably in chemical conversion treatment epithelium 0.005~2.0 mass % is scaled with the atom of above-mentioned element.If the content is less than 0.005 mass %, sometimes can not be abundant Ground obtains the effect above, if more than 2.0 mass %, the effect above reaches capacity sometimes.Can be by using fluorescent X-ray point Analysis apparatus or ICP apparatus for analyzing luminosity, to determine the content of the etch compounds in chemical conversion treatment epithelium.
Above-mentioned pigment contributes to the suppression of the gloss to chemical conversion treatment steel plate.Pigment can be that one kind can also be More than one.Pigment is that inorganic pigment and organic pigment can.As the example of inorganic pigment, including：Carbon black, titanium dioxide Silicon, titanium dioxide and aluminum oxide.As the example of organic pigment, the resin particle such as including allyl resin.In addition, " titanium dioxide " Although including the titanium of 4A races metal, because gloss inhibition is excellent, therefore it is classified as pigment in this manual.
Above-mentioned wax contributes to the processability of chemical conversion treatment steel plate.From the viewpoint of desired processability is embodied, The fusing point of preferred wax is 80~150 DEG C.As the example of the wax, including：Fluorine system wax, polyethylene-based wax and polystyrene wax.
From the viewpoint of the raising of above-mentioned processability, the content of the wax preferably in chemical conversion treatment epithelium is 0.5~5 Quality %.If the content is less than 0.5 mass %, the raising effect of above-mentioned processability can not be fully obtained sometimes, if more than 5 Quality %, then situation about collapsing as load chemical conversion treatment steel plate, collapsing when rolling up or driving piles of product is produced sometimes.Energy Quantitative analysis method known to gas chromatography or high performance liquid chromatography, mass spectrometry etc. is enough utilized, to determine chemical conversion Handle the content of the wax in epithelium.
2. the manufacture method of chemical conversion treatment steel plate
Can be by coating chemical conversion treatment solution on above-mentioned clad steel sheet, and make coated chemical conversion treatment solution Dry, to manufacture above-mentioned chemical conversion treatment steel plate.
Above-mentioned chemical conversion treatment solution contains at above-mentioned fluororesin, above-mentioned substrate resin, above-mentioned sheet metal and chemical conversion Composition before reason, it can also further contain above-mentioned other compositions.Composition is above-mentioned chemical conversion treatment before chemical conversion treatment The presoma of composition.Composition can be identical with above-mentioned chemical conversion treatment composition before the chemical conversion treatment, can also therewith not Together.
The content of fluororesin in above-mentioned chemical conversion treatment solution is former with fluorine relative to the total amount of fluororesin and substrate resin Son is scaled more than 3.0 mass %, and the content of the substrate resin in chemical conversion treatment solution is relative to the mass parts of fluororesin 100 More than 10 mass parts, the content of the sheet metal in chemical conversion treatment solution is 10~60 mass % relative to solid constituent.For The content as the above-mentioned 4A races metallic compound of composition before chemical conversion treatment in chemical conversion treatment solution, relative to solid Composition is scaled 0.005~5.0 mass % with 4A races metallic atom.In addition, for above-mentioned its in chemical conversion treatment solution The content of composition before his chemical conversion treatment, it is scaled relative to solid constituent using the atom of the inorganic elements as its feature 0.005~2.0 mass %.In addition, " solid constituent " in chemical conversion treatment solution refers to, the composition in chemical conversion treatment solution And it is the composition included in above-mentioned chemical conversion treatment epithelium.
Above-mentioned chemical conversion treatment solution can also further contain liquid medium.From resin emulsion can be utilized in the feed It is such, using water-medium as the dispersion of decentralized medium viewpoint and chemically the manufacture of conversion processing steel plate when it is anti- From the viewpoint of quick-fried property, preferably the liquid medium is water.Chemical conversion treatment solution can be suitable in the concentration of above-mentioned solid constituent Coating in the range of, suitably determine the content of the liquid medium.
Chemically from the viewpoint of the productivity ratio of conversion processing steel plate and security during manufacture, for above-mentioned base material tree Fat, preferably using the emulsion of substrate resin.From the resistance to water penetration for improving chemical conversion treatment epithelium and make it possible to more low temperature From the viewpoint of making chemical conversion treatment solution drying, the particle diameter of the emulsion of preferred substrates resin is 10~100nm.If the particle diameter is small In 10nm, then the stability of chemical conversion treatment solution reduces sometimes, if more than 100nm, can not fully obtain chemistry sometimes The effect of the low temperature drying of conversion treating solution.From the viewpoint of identical, for above-mentioned fluororesin, preferably using the breast of fluororesin The particle diameter of the emulsion of liquid, preferably fluororesin is 10~300nm.
Above-mentioned chemical conversion treatment solution can containing the material in chemical conversion treatment epithelium itself, can also contain should The presoma of material." presoma of material " refers to, in chemical conversion treatment solution or can pass through chemical conversion treatment solution Dry and become the composition for turning to the material.As composition before the example of the presoma, including above-mentioned chemical conversion treatment.
As the example of composition before above-mentioned chemical conversion treatment, including：Acylate, carbonic acid comprising above-mentioned 4A races metal Salt and peroxide salt.These are the presomas of above-mentioned 4A races metallic compound, pass through the drying of chemical conversion treatment solution, Neng Gousheng Into hydrohalogenic acid salt, ammonium salt, alkali metal salt or the alkali earth metal salt of the metal comprising 4A races metal.
In addition, the example as composition before above-mentioned chemical conversion treatment, including：ManTiF6(Ma：Alkali metal or alkaline earth eka-gold Category, n：1 or 2), K2[TiO(COO)2]、(NH4)2TiF6、TiCl4、TiOSO4、Ti(SO4)2And Ti (OH)4Deng titanium salt； (NH4)2ZrF6、Zr(SO4)2And (NH4)2ZrO(CO3)2Deng zirconates；And (NH4)6Mo7O24And K2(MoO2F4) etc. molybdenum salt.They It is the presoma of above-mentioned valve metal compound.
In addition, for above-mentioned chemical conversion treatment solution, it can also further contain what is be adapted in chemical conversion treatment solution Additive.As the example of the additive, including：Rheology control agent, etchant and lubricant.
Above-mentioned rheology control agent for example prevents the sedimentation of the sheet metal in chemical conversion treatment solution, contributes at chemical conversion Manage the dispersed raising of the sheet metal in liquid.It is preferred that rheology control agent be from polyurethane series compound, acrylic compounds, Polyolefin, amide compound, anion system activating agent, nonionic system activating agent, polycarboxylic acids, cellulose, METOLOSE and urine The one or more kinds of compounds selected in element.
For above-mentioned rheology control agent, market sale product can be utilized.As the example of the market sale product, including： THIXOL K-130B, THIXOL W300 (Kyoeisha Chemical Co., Ltd.'s system), UH750, SDX-1014 (Asahi Denka Co., Ltd. System), DISPARLON AQ-610 (nanmu this chemical conversion Co. Ltd. system, " DISPARLON " they are the registration marks of the said firm), BYK- 425th, BYK-420 (Bi Ke chemical companies system, " BYK " are the registration marks of the said firm).
Oxide or phosphate as the example of above-mentioned etchant, including Mg, Ca, Sr, V, W, Mn, B, Si or Sn. The etchant is the presoma of above-mentioned etch compounds.Above-mentioned lubricant improves the lubricity of chemical conversion treatment epithelium, helps In the raising of the processability of chemical conversion treatment steel plate.As the example of lubricant, including the inorganic profit such as molybdenum disulfide and talcum Lubrication prescription.
Alternatively, it is also possible to which before the coating of above-mentioned chemical conversion treatment solution, matrix processing is carried out to above-mentioned clad steel sheet. That is, in above-mentioned manufacture method, before chemical conversion treatment solution is coated on into clad steel sheet, can also further comprise utilizing phosphorus The process that acid compound or valve metal carry out matrix processing to clad steel sheet.Can be by the way that above-mentioned valve metal salt or phosphorus will be contained The matrix treatment fluid of acid compound is coated on the surface of above-mentioned clad steel sheet, and makes its drying, to carry out the matrix processing.
Above-mentioned matrix treatment fluid can also further contain the other compositions beyond above-mentioned valve metal salt.For example, at matrix The organic acid with chelation can also further be contained by managing liquid.The organic acid contributes to the stabilization of valve metal salt.It is used as this The example of organic acid, including：Tartaric acid, tannic acid, citric acid, oxalic acid, malonic acid, lactic acid, acetic acid and ascorbic acid.At matrix The content of the organic acid in liquid is managed, such as organic acid is more than 0.02 relative to the mol ratio of valve metal ion.
For example, method known to rolling method, spin-coating method, spraying process, dip-coating method etc. can be utilized, at above-mentioned matrix Reason liquid is coated on clad steel sheet.The coated weight of matrix treatment fluid is for example preferably that the adhesion amount of valve metal is 1mg/m2More than Amount.The coated weight of preferred substrate treatment fluid is to make the amount that the thickness of the matrix to be formed processing epithelium is 3~2000nm.If the thickness Degree is less than 3nm, then can not fully demonstrate the corrosion resistance that above-mentioned matrix processing epithelium is brought sometimes, if more than 2000nm, have When due to clad steel sheet processing and forming when stress and matrix handle epithelium in crack.
For example, for the coat film of the above-mentioned matrix treatment fluid formed on the surface of clad steel sheet, it is not washed It is dried on ground, forms above-mentioned matrix processing epithelium, thus carries out above-mentioned matrix processing.Although also can be with normal temperature to this Coat film is dried, but from the viewpoint of productivity ratio (continuous operation), preferably more than 50 DEG C at a temperature of be dried. From the viewpoint of the thermal decomposition for preventing the composition in above-mentioned matrix treatment fluid, preferably the drying temperature is less than 200 DEG C.
Can will be above-mentioned by painting method known to rolling method, curtain stream method, spin-coating method, spraying process, dip-coating method etc. Chemical conversion treatment solution is coated on the surface of above-mentioned clad steel sheet.Although it can carry out at normal temperatures in above-mentioned clad steel sheet The drying of the chemical conversion treatment solution of surface coating, but from the viewpoint of productivity ratio (continuous operation), preferably more than 50 DEG C At a temperature of carry out.From the viewpoint of the thermal decomposition for preventing the composition in above-mentioned chemical conversion treatment solution, the preferred drying temperature Spend for less than 300 DEG C.
The step of passing through the above, above-mentioned chemical conversion treatment steel plate can be manufactured.
The layer construction of chemical conversion treatment steel plate is schematically shown in Fig. 1.
Chemical conversion treatment steel plate 10 has steel plate 11 and chemical conversion treatment epithelium 12.Have in the surface configuration of steel plate 11 Coating 17, there is chemical conversion treatment epithelium 12 in the surface configuration of coating 17.Kirsite of the coating 17 for example by including aluminium and magnesium Form.Chemical conversion treatment epithelium 12 is configured to stratiform, chemical conversion by above-mentioned fluororesin (not shown) and above-mentioned substrate resin The thickness for handling epithelium 12 is, for example, 1~4 μm.Chemical conversion treatment epithelium 12 includes sheet metal 13, wax 14, the metallization of 4A races Compound 15 and silane coupler 16.
Chemical conversion treatment epithelium 12 is, for example, form, base by the melting of above-mentioned fluororesin and above-mentioned substrate resin In the substantially smooth layer of resin component.Above-mentioned fluororesin and the parent that above-mentioned substrate resin is chemical conversion treatment epithelium 12. The content of the above-mentioned fluororesin relative to the total amount of above-mentioned fluororesin and above-mentioned substrate resin in chemical conversion treatment epithelium 12 It is scaled more than 3.0 mass % with fluorine atom, the mass ratio of above-mentioned fluororesin and above-mentioned substrate resin in this way 1：3.Chemistry turns Change processing epithelium 12 and contain an adequate amount of fluororesin, therefore good against weather is presented in chemical conversion treatment steel plate 10.
In addition, chemical conversion treatment epithelium 12 contains an adequate amount of substrate resin.Thus, present relative to the good of coating 17 Good adhesion.In addition, the content of the sheet metal 13 in chemical conversion treatment epithelium 12 is, for example, 20 mass %.In chemical conversion On the thickness direction for handling epithelium 12, multiple sheet metals 13 overlap each other, in the in-plane of chemically conversion processing epithelium 12 During observation, the distribution of the sheet metal 13 in chemical conversion treatment epithelium 12 is generally uniform, although coating 17 there is also a part not The part covered by sheet metal 13, but major part is covered with.Thus, chemical conversion treatment steel plate 10 can moderately be suppressed Gloss.In addition, substrate resin and sheet metal 13 are fifty-fifty distributed on the in-plane of chemical conversion treatment epithelium 12, therefore i.e. Cosmetic variation can also be suppressed by making coating that blacking occur.
The reasons why blacking of above-mentioned coating can be suppressed, is as follows.It is believed that the above-mentioned parent of chemical conversion treatment epithelium 12 In fluororesin and substrate resin be substantially the same, but due to the strong liquid repellency of fluororesin, so fluororesin and base material Border between resin can turn into the path of liquid.The blacking of above-mentioned coating can consider be due to the operators such as sweat secretion Thing invades above-mentioned path, reaches coating, caused by the Mg oxidations in coating.
Above-mentioned chemical conversion treatment epithelium contains sheet metal.Sheet metal is as described above to cover the most side of coating Formula is configured in chemical conversion treatment epithelium.So as to which, above-mentioned path on the thickness direction of chemical conversion treatment epithelium to avoid The mode of sheet metal extends, and above-mentioned path is elongated.Thus, above-mentioned secretion is not easy to reach coating.In addition, even if above-mentioned secretion Reach coating and coating and blacking occurs, also due to sheet metal covers the major part of coating, blacking portion is hidden by sheet metal from outside Cover, do not observe.Being believed that according to the reasons why above can suppress to be led by the blacking of coating in above-mentioned chemical conversion treatment steel plate The cosmetic variation of cause.
It can be seen from explanation more than, the chemical conversion treatment steel plate of present embodiment has in above-mentioned hot dip galvanizing-Al- Mg alloy-steel plates coating surface configuration above-mentioned chemical conversion treatment epithelium, the chemical conversion treatment epithelium contain fluororesin, Substrate resin, sheet metal and chemical conversion treatment composition, the substrate resin are from polyurethane, polyester, acrylic resin, asphalt mixtures modified by epoxy resin Selected in fat and polyolefin more than one, relative to the content of above-mentioned fluororesin and the fluororesin of the total amount of above-mentioned substrate resin Be scaled more than 3.0 mass % with fluorine atom, in the chemical conversion treatment epithelium relative to the mass parts of fluororesin 100 The content of the substrate resin is more than 10 mass parts, and the content of the sheet metal in the chemical conversion treatment epithelium is more than 20 matter Measure % and be below 60 mass %.Thus, the chemical conversion treatment steel plate has against weather, and the chemical conversion treatment steel Plate can suppress gloss and the discoloration elapsed over time.
In addition, above-mentioned sheet metal is more than one that selected from aluminium flake, aluminum alloy sheet and stainless steel substrates, this is from corrosion-resistant It is more effective from the viewpoint of property, high design.
In addition, the thickness of above-mentioned chemical conversion treatment epithelium is 0.5~10 μm, this is from embodying chemical conversion treatment epithelium It is more effective from the viewpoint of the raising of the viewpoint and productivity ratio of desired function.
In addition, the content of the substrate resin relative to the mass parts of fluororesin 100 in above-mentioned chemical conversion treatment epithelium is Below 900 mass parts, this is chemically more effective from the viewpoint of the against weather of conversion processing epithelium.
In addition, above-mentioned chemical conversion treatment composition includes 4A races metallic compound, the 4A races metallic compound include from Ti, Selected in Zr and Hf more than one, the content of the 4A races metallic compound in above-mentioned chemical conversion treatment epithelium, relative to Above-mentioned chemical conversion treatment epithelium is scaled 0.005~5.0 mass % with 4A races metal, this chemically conversion processing steel plate it is resistance to It is corrosive improve, the sight of the processability of the fixation of sheet metal in chemical conversion treatment epithelium and chemical conversion treatment epithelium It is more effective from the point of view of point.
In addition, above-mentioned chemical conversion treatment composition includes one or both of molybdate and valve metal compound, it is above-mentioned Valve metal compound is the compound comprising one or both of V and Nb, the corrosion resistance of this chemically conversion processing steel plate Raising, gloss adjustment or water resistance raising from the viewpoint of, be more effective.
In addition, above-mentioned chemical conversion treatment epithelium further contains one or both of silane coupler and phosphate, This is chemically more effective from the viewpoint of the raising of the corrosion resistance of conversion processing steel plate.
In addition, carry out matrix processing to above-mentioned clad steel sheet using phosphate cpd or valve metal composition, this is from suppressionization It is more effective from the viewpoint of learning the gloss of conversion processing steel plate and improving corrosion resistance.
In addition, above-mentioned chemical conversion treatment epithelium further contains pigment, this is from the light for suppressing chemical conversion treatment steel plate It is more effective from the viewpoint of pool.
In addition, above-mentioned chemical conversion treatment epithelium further contains wax, this is from the processing for improving chemical conversion treatment steel plate It is more effective from the viewpoint of property.
In addition, the manufacture method of above-mentioned chemical conversion treatment steel plate, is to coat chemical conversion treatment solution on above-mentioned coating, And coated chemical conversion treatment solution is dried, to manufacture the method for chemical conversion treatment steel plate, wherein, at the chemical conversion Reason liquid contains composition before fluororesin, substrate resin, sheet metal and chemical conversion treatment, and substrate resin is from polyurethane, polyester, third Selected in olefin(e) acid resin, epoxy resin and polyolefin more than one, above-mentioned fluororesin in the chemical conversion treatment solution contains Amount is scaled more than 3.0 mass % relative to the total amount of the fluororesin and above-mentioned substrate resin with fluorine atom, above-mentioned chemical conversion The content of the substrate resin relative to the mass parts of fluororesin 100 in treatment fluid is more than 10 mass parts above-mentionedization The content for learning the sheet metal in conversion treating solution is more than 20 mass % relative to solid constituent and is below 60 mass %, Therefore, it is possible to provide with against weather and gloss can be suppressed and elapsed over time the above-mentioned chemical conversion treatment of discoloration Steel plate.
Above-mentioned chemical conversion treatment solution contains the emulsion of above-mentioned fluororesin and the emulsion of above-mentioned substrate resin, above-mentioned fluororesin The particle diameter of emulsion be 10~300nm, the particle diameter of the emulsion of above-mentioned substrate resin is 10~100nm, and this is from improving chemical conversion Handle the resistance to water penetration of epithelium and make it possible to from the viewpoint of making chemical conversion treatment solution drying with more low temperature, be more effective 's.
In addition, in above-mentioned manufacture method, before above-mentioned chemical conversion treatment solution is coated, further comprise utilizing phosphorylation The process that compound or above-mentioned valve metal composition carry out matrix processing to above-mentioned clad steel sheet, this is from suppressing chemical conversion treatment steel plate Gloss and to improve from the viewpoint of corrosion resistance be more effective.
In addition, above-mentioned chemical conversion treatment solution contain before fluororesin, substrate resin, sheet metal and chemical conversion treatment into Point, above-mentioned substrate resin is more than one that selected from polyurethane, polyester, acrylic resin, epoxy resin and polyolefin, on The content of the above-mentioned fluororesin in chemical conversion treatment solution is stated relative to the total amount of above-mentioned fluororesin and above-mentioned substrate resin with fluorine Atom is scaled more than 3.0 mass %, in above-mentioned chemical conversion treatment solution relative to the above-mentioned of the above-mentioned mass parts of fluororesin 100 The content of substrate resin is that more than 10 mass parts the content of the above-mentioned sheet metal in above-mentioned chemical conversion treatment solution is relative to solid Composition is more than 20 mass % and is below 60 mass %, therefore, by the way that the chemical conversion treatment solution is coated on into clad steel sheet And make its drying, using the teaching of the invention it is possible to provide the above-mentioned chemistry for having against weather and suppressing gloss and the discoloration elapsed over time turns Change processing steel plate.
The against weather of above-mentioned chemical conversion treatment steel plate is excellent, and due to excessive gloss can be suppressed so as to design It is excellent.Thus, above-mentioned chemical conversion treatment steel plate is applied to exterior building materials.In addition, for above-mentioned chemical conversion treatment steel plate, Except the discoloration that elapses over time prevent excellent effect in addition to, additionally it is possible to blacking caused by preventing other element, for example make With exterior with the sclerozone of the sweat of the operator of building materials etc. come blacking, therefore except present it is attractive in appearance, for being used using the exterior The raising of the workability of the exterior of building materials is also effective.
Hereinafter, with reference to embodiment, the present invention is described in detail, but the invention is not restricted to these embodiments.
[embodiment]
[making of the Zn systems alloy layer steel plate containing Al]
Using thickness of slab 0.8mm SPCC as base material, made the quality %Al-3 mass %Mg of hot dip galvanizing -6 alloy-steel plates (with Under, also referred to as " clad steel sheet A ").Coating adhesion amount in clad steel sheet A is 45g/m2。
[preparation of chemical conversion treatment solution]
(preparation of material)
Following material is prepared.
(1) resin emulsion
" fluoro-resin emulsion " is fluorine resin (Tg：- 35~25 DEG C, MFT (MFT)：10 DEG C, FR) water system Emulsion, the solid component concentration of the fluoro-resin emulsion are 40 mass %, and the content of the fluorine atom in fluororesin is 25 mass %, breast The average grain diameter of liquid is 150nm.
For urethane resin (PU) emulsion, prepare " HYDRAN " of Dainippon Ink Chemicals.The solid constituent of " HYDRAN " Concentration is 35 mass %.The average grain diameter for thinking emulsion is 10~100nm or so.
For acrylic resin (AR) emulsion, " PATELACOL " (registration of the said firm of Dainippon Ink Chemicals is prepared Trade mark).The solid component concentration of " PATELACOL " is 40 mass %.The average grain diameter for thinking emulsion is 10~100nm or so.
For polyester (PE) emulsion, prepare " VYLONAL " that STC Co. Ltd. systems are spun by Japan.The solid of " VYLONAL " Constituent concentration is 30 mass %.The average grain diameter for thinking emulsion is 10~100nm or so.
For epoxy resin (ER) emulsion, " ADEKA the RESIN " (notes of the said firm of Asahi Denka Co., Ltd. are prepared Volume trade mark)." ADEKA RESIN " solid component concentration is 30 mass %.Think that the average grain diameter of emulsion is left for 10~100nm It is right.
For polyolefin (PO) emulsion, " ARROW-BASE " (note of the said firm of Unitika Corp is prepared Volume trade mark).The solid component concentration of " ARROW-BASE " is 25 mass %.Think that the average grain diameter of emulsion is left for 10~100nm It is right.
(2) sheet metal
For aluminium flake, prepare " WXM-U75C " of East oceans Aluminum Co. Ltd. system.The average grain diameter of aluminium flake is 18 μm, is put down Equal thickness is 0.2 μm.
For stainless steel substrates, prepare " PFA4000 " of East oceans Aluminum Co. Ltd. system.The average grain diameter of stainless steel substrates is 40 μm, average thickness is 0.5 μm.
(3) composition before chemical conversion treatment
For titanium compound (Ti), " H is prepared2TiF6(40% aqueous solution) ".H2TiF6(40%) Ti atoms in contain Measure as 11.68 mass %.
For zirconium compounds (Zr), " the ZIRCOSOL AC-7 " of N. E. Chemcat Corp. are prepared. The content of Zr atoms in ZIRCOSOL AC-7 is 9.62 mass %." ZIRCOSOL " is the registration mark of the said firm.
For vfanadium compound (V), ammonium metavanadate (NH is prepared4VO3).The content of V atoms in ammonium metavanadate is 43.55 Quality %.
For molybdic acid compound (Mo), ammonium molybdate ((NH is prepared4)6Mo7O24·4H2O).Mo atoms in ammonium molybdate Content is 54.35 mass %.
(4) additive
For wax, prepare " HITECH " of Toho Chemical Industry Co., Ltd. (JP) Tokyo-To, Japan.The fusing point of the wax is 120 DEG C.
For rheology control agent (RCA), " BYK-420 " of preparation Liao Bike chemical companies." BYK " is the note of the said firm Volume trade mark.
For pigment A (silica), " the LIGHT STAR " of Nissan Chemical Ind Ltd are prepared.“LIGHT STAR " average grain diameter is 200nm.
For pigment B (carbon black), prepare " KETJENBLACK " of Lion Corporation." KETJENBLACK's " is flat Equal particle diameter is 40nm.
For pigment C (organic pigment), prepare " styrene acrylic resin " of Nippon Paint Co., Ltd.. The average grain diameter of " styrene acrylic resin " is 500nm.
For phosphate cpd, diammonium hydrogen phosphate ((NH is prepared4)2HPO4).The content of P atoms in diammonium hydrogen phosphate For 23.44 mass %.
For silane coupler (SCA), Momentive Performance Materials Japan company systems are prepared " SILQUEST A-186 ".
(embodiment 1：The preparation of chemical conversion treatment solution 1)
Fluoro-resin emulsion, urethane resin emulsion, aluminium flake, titanium compound and appropriate amount of water are mixed, obtained at chemical conversion Manage liquid 1.In chemical conversion treatment solution 1, the content relative to the urethane resin of the mass parts of fluororesin 100 is 10 mass parts.Chemistry (also referred to as " base material contains the content of the resin beyond the fluororesin relative to the mass parts of fluororesin 100 in conversion treating solution 1 Amount ") it is 10 mass parts.In addition, in whole organic resins (total amount of fluororesin and substrate resin) in chemical conversion treatment solution 1 The content (also referred to as " F amounts ") of fluorine atom be 22.7 mass %.Also, in the solid constituent in chemical conversion treatment solution 1 The content of sheet metal is (also referred to as " piece content ") 25 mass %.In addition, the content of the titanium compound in chemical conversion treatment solution 1 0.05 mass % being scaled with Ti atoms in the solid constituent in chemical conversion treatment solution.
(embodiment 2：The preparation of chemical conversion treatment solution 2)
Fluoro-resin emulsion, polyester emulsion, aluminium flake, titanium compound, phosphate cpd and appropriate amount of water are mixed, obtained chemistry Conversion treating solution 2.In chemical conversion treatment solution 2, relative to the mass parts of fluororesin 100, the content of polyester is 100 mass parts, titanium The content of compound is scaled 0.20 mass % in the solid constituent in chemical conversion treatment solution, phosphate cpd with metal Ti Content 0.6 mass % in the solid constituent in chemical conversion treatment solution is scaled with P.Base in chemical conversion treatment solution 2 Material content is 100 mass parts.The content of fluorine atom in chemical conversion treatment solution 2 is 12.5 mass %.Chemical conversion treatment solution 2 In piece content be 40 mass %.
(embodiment 3：The preparation of chemical conversion treatment solution 3)
Phosphate cpd is not added, zirconium compounds is with the addition of and replaces titanium compound, is changed the addition of aluminium flake, be with the addition of Rheology control agent, in addition, in the same manner as chemical conversion treatment solution 2, chemical conversion treatment solution 3 is obtained.At chemical conversion The base material content managed in liquid 3 is 100 mass parts.The content of fluorine atom in chemical conversion treatment solution 3 is 12.5 mass %.Chemistry Piece content in conversion treating solution 3 is 60 mass %, and the content of rheology control agent is 0.5 mass %.
(embodiment 4：The preparation of chemical conversion treatment solution 4)
Change the addition of aluminium flake, with the addition of vfanadium compound instead of zirconium compounds, with the addition of pigment C, in addition, change Learn conversion treating solution 3 similarly, obtain chemical conversion treatment solution 4.Base material content in chemical conversion treatment solution 4 is 100 matter Measure part.The content of fluorine atom in chemical conversion treatment solution 4 is 12.5 mass %.Piece content in chemical conversion treatment solution 4 is 30 mass %.Pigment C content is 0.5 mass % in the solid constituent in chemical conversion treatment solution.
(embodiment 5：The preparation of chemical conversion treatment solution 5)
By fluoro-resin emulsion, urethane resin emulsion, emulsion acrylic resin, polyester emulsion, polyolefin emulsion, aluminium flake, titanium Compound, wax and appropriate amount of water mixing, have obtained chemical conversion treatment solution 5.In chemical conversion treatment solution 5, relative to fluororesin 100 Mass parts, the content of urethane resin are 100 mass parts, and the content of acrylic resin, polyester and polyolefin is all 25 mass parts, wax Content be chemical conversion treatment solution in solid constituent in 2.0 mass %.Base material content in chemical conversion treatment solution 5 is 175 mass parts.The content of fluorine atom in chemical conversion treatment solution 5 is 9.1 mass %.Piece in chemical conversion treatment solution 5 contains Measure as 30 mass %.In addition, the content of the titanium compound in chemical conversion treatment solution 5 is scaled chemical conversion treatment with Ti atoms 0.05 mass % in solid constituent in liquid.
(embodiment 6：The preparation of chemical conversion treatment solution 6)
By fluoro-resin emulsion, urethane resin emulsion, emulsion acrylic resin, polyester emulsion, epoxy resin latex, polyolefin Emulsion, aluminium flake, wax, zirconium compounds and appropriate amount of water mixing, have obtained chemical conversion treatment solution 6.In chemical conversion treatment solution 6, phase For the mass parts of fluororesin 100, the content of urethane resin is 300 mass parts, the content of acrylic resin, polyester and epoxy resin All it is 100 mass parts, the content of polyolefin is 50 mass parts.The content of wax is in the solid constituent in chemical conversion treatment solution 2.0 mass %, the content of zirconium compounds are scaled 0.20 matter in the solid constituent in chemical conversion treatment solution with Zr atoms Measure %.Base material content in chemical conversion treatment solution 6 is 650 mass parts.The content of fluorine atom in chemical conversion treatment solution 6 is 3.3 mass %.Piece content in chemical conversion treatment solution 6 is 25 mass %.
(embodiment 7：The preparation of chemical conversion treatment solution 7)
By fluoro-resin emulsion, urethane resin emulsion, emulsion acrylic resin, aluminium flake, wax, zirconium compounds, phosphate cpd, Silane coupler, rheology control agent and appropriate amount of water mixing, have obtained chemical conversion treatment solution 7.In chemical conversion treatment solution 7, phase For the mass parts of fluororesin 100, the content of urethane resin and acrylic resin is all 150 mass parts, and the content of wax turns for chemistry Change 2.5 mass % in the solid constituent in treatment fluid, the content of zirconium compounds is scaled chemical conversion treatment solution with Zr atoms In solid constituent in 1.00 mass %, the content of phosphate cpd is with the P in the solid constituent in chemical conversion treatment solution 0.6 mass % is scaled, the content of silane coupler is 1.5 mass % in the solid constituent in chemical conversion treatment solution, stream Become the content of conditioning agent as 0.5 mass %.Base material content in chemical conversion treatment solution 7 is 300 mass parts.Chemical conversion treatment The content of fluorine atom in liquid 7 is 6.3 mass %.Piece content in chemical conversion treatment solution 7 is 30 mass %.
(embodiment 8：The preparation of chemical conversion treatment solution 8)
By fluoro-resin emulsion, urethane resin emulsion, polyester emulsion, epoxy resin latex, polyolefin emulsion, aluminium flake, titanizing Compound, phosphate cpd, silane coupler and appropriate amount of water mixing, have obtained chemical conversion treatment solution 8.Chemical conversion treatment solution 8 In, relative to the mass parts of fluororesin 100, urethane resin, polyester, the content of epoxy resin and polyolefin are all 25 mass parts, titanium The content of compound is scaled 0.20 mass % in the solid constituent in chemical conversion treatment solution, phosphate cpd with Ti atoms Content 0.6 mass % in the solid constituent in chemical conversion treatment solution is scaled with P, the content of silane coupler is chemistry 1.5 mass % in solid constituent in conversion treating solution.Base material content in chemical conversion treatment solution 8 is 100 mass parts.Change The content for learning the fluorine atom in conversion treating solution 8 is 12.5 mass %.Piece content in chemical conversion treatment solution 8 is 30 matter Measure %.
(embodiment 9：The preparation of chemical conversion treatment solution 9)
By fluoro-resin emulsion, urethane resin emulsion, emulsion acrylic resin, polyester emulsion, polyolefin emulsion, stainless steel Piece, zirconium compounds and appropriate amount of water mixing, have obtained chemical conversion treatment solution 9.In chemical conversion treatment solution 9, relative to fluororesin 100 mass parts, the content of urethane resin is 50 mass parts, and the content of acrylic resin, polyester and polyolefin is all 25 mass parts, The content of zirconium compounds is scaled 0.50 mass % in the solid constituent in chemical conversion treatment solution with Zr atoms.Chemical conversion Base material content in treatment fluid 9 is 125 mass parts.The content of fluorine atom in chemical conversion treatment solution 9 is 11.1 mass %.Change The piece content learned in conversion treating solution 9 is 30 mass %.
(embodiment 10：The preparation of chemical conversion treatment solution 10)
It is appropriate to have used aluminium flake to replace stainless steel substrates, change the addition of zirconium compounds, used pigment A (two in right amount Silica), in addition, in the same manner as chemical conversion treatment solution 9, obtain chemical conversion treatment solution 10.Chemical conversion treatment In liquid 10, pigment A content is 0.5 mass % in the solid constituent in chemical conversion treatment solution.Chemical conversion treatment solution 10 In base material content be 125 mass parts.The content of fluorine atom in chemical conversion treatment solution 10 is 11.1 mass %.Chemical conversion Piece content in treatment fluid 10 is 21 mass %.In addition, the content of the zirconium compounds in chemical conversion treatment solution 10 is with Zr atoms 0.20 mass % being scaled in the solid constituent in chemical conversion treatment solution.
(embodiment 11：The preparation of chemical conversion treatment solution 11)
Change the addition of urethane resin emulsion and aluminium flake, use titanium compound to replace zirconium compounds, use in right amount Pigment B (carbon black) replaces pigment A, in addition, in the same manner as chemical conversion treatment solution 10, has obtained chemical conversion treatment solution 11.In chemical conversion treatment solution 11, relative to the mass parts of fluororesin 100, the content of urethane resin is 20 mass parts, pigment B's Content is 0.2 mass % in the solid constituent in chemical conversion treatment solution.Base material content in chemical conversion treatment solution 11 is 95 mass parts.The content of fluorine atom in chemical conversion treatment solution 11 is 12.8 mass %.Piece in chemical conversion treatment solution 11 Content is 25 mass %.
(embodiment 12：The preparation of chemical conversion treatment solution 12)
By fluoro-resin emulsion, urethane resin emulsion, emulsion acrylic resin, polyester emulsion, epoxy resin latex, aluminium flake, Stainless steel substrates, molybdic acid compound, pigment C (organic pigment) and appropriate amount of water mixing, have obtained chemical conversion treatment solution 12.Chemistry turns Change in treatment fluid 12, relative to the mass parts of fluororesin 100, the content of urethane resin is 50 mass parts, acrylic resin, polyester and The content of epoxy resin is all 25 mass parts, and the content of molybdic acid compound is scaled consolidating in chemical conversion treatment solution with Mo atoms 0.01 mass % in body composition, pigment C content are 0.5 mass % in the solid constituent in chemical conversion treatment solution.Chemistry Base material content in conversion treating solution 12 is 125 mass parts.The content of fluorine atom in chemical conversion treatment solution 12 is 11.1 matter Measure %.Piece content in chemical conversion treatment solution 12 is 50 mass %.The content of aluminium flake is 30 mass %, the content of stainless steel substrates For 20 mass %.
(embodiment 13：The preparation of chemical conversion treatment solution 13)
Polyolefin emulsion has been used to replace emulsion acrylic resin, change the addition of stainless steel substrates, change molybdic acid The addition of compound, wax has been used in addition, in the same manner as chemical conversion treatment solution 12, to be obtained as additive in right amount Chemical conversion treatment solution 13.In chemical conversion treatment solution 13, relative to the mass parts of fluororesin 100, the content of urethane resin is 50 mass parts, the content of polyester, epoxy resin and polyolefin is all 25 mass parts, and the content of wax is in chemical conversion treatment solution 2.0 mass % in solid constituent.Base material content in chemical conversion treatment solution 13 is 125 mass parts.Chemical conversion treatment solution The content of fluorine atom in 13 is 11.1 mass %.Piece content in chemical conversion treatment solution 13 is 35 mass %.Aluminium flake contains Measure as 30 mass %, the content of stainless steel substrates is 5 mass %.In addition, molybdic acid compound in chemical conversion treatment solution 13 contains Amount is scaled 2.00 mass % in the solid constituent in chemical conversion treatment solution with Mo atoms.
(embodiment 14：The preparation of chemical conversion treatment solution 14)
Aluminium flake has been used to replace stainless steel substrates, used vfanadium compound to replace zirconium compounds in right amount and used in right amount Silane coupler, in addition, in the same manner as chemical conversion treatment solution 9, chemical conversion treatment solution 14 is obtained.At chemical conversion Manage in liquid 14, the content of silane coupler is 1.5 mass % in the solid constituent in chemical conversion treatment solution.At chemical conversion The base material content managed in liquid 14 is 125 mass parts.The content of fluorine atom in chemical conversion treatment solution 14 is 11.1 mass %.Change The piece content learned in conversion treating solution 14 is 30 mass %.In addition, the content of the vfanadium compound in chemical conversion treatment solution 14 is with V Atom is scaled 3.00 mass % in the solid constituent in chemical conversion treatment solution.
(embodiment 15：The preparation of chemical conversion treatment solution 15)
By fluoro-resin emulsion, urethane resin emulsion, emulsion acrylic resin, polyester emulsion, epoxy resin latex, polyolefin Emulsion, aluminium flake, titanium compound, pigment A, pigment C and appropriate amount of water mixing, have obtained chemical conversion treatment solution 15.At chemical conversion Manage in liquid 15, relative to the mass parts of fluororesin 100, the content of urethane resin is 50 mass parts, and acrylic resin and polyester contain Amount is all 25 mass parts, and the content of epoxy resin is 10 mass parts, and the content of polyolefin is 15 mass parts, pigment A and pigment C's Content is all 0.5 mass % in the solid constituent in chemical conversion treatment solution respectively.Base material in chemical conversion treatment solution 15 Content is 125 mass parts.The content of fluorine atom in chemical conversion treatment solution 15 is 11.1 mass %.Chemical conversion treatment solution 15 In piece content be 25 mass %.In addition, the content of the titanium compound in chemical conversion treatment solution 15 is with Ti being scaled of atom Learn 0.20 mass % in the solid constituent in conversion treating solution.
(embodiment 16：The preparation of chemical conversion treatment solution 16)
The addition that changes aluminium flake, the addition for changing zirconium compounds, pigment A is not added with, in addition, with chemistry Conversion treating solution 10 similarly, has obtained chemical conversion treatment solution 16.Base material content in chemical conversion treatment solution 16 is 125 matter Measure part.The content of fluorine atom in chemical conversion treatment solution 16 is 11.1 mass %.Piece content in chemical conversion treatment solution 16 For 25 mass %.In addition, the content of the zirconium compounds in chemical conversion treatment solution 16 is scaled chemical conversion treatment with Zr atoms 0.50 mass % in solid constituent in liquid.
(comparative example 1：The preparation of chemical conversion treatment solution 17)
Titanium compound has been used to replace vfanadium compound, be not added with polyester emulsion and pigment C, in addition, with chemical conversion Treatment fluid 4 similarly, has obtained chemical conversion treatment solution 17.Base material content in chemical conversion treatment solution 17 is 0 mass parts.Change The content for learning the fluorine atom in conversion treating solution 17 is 25.0 mass %.Piece content in chemical conversion treatment solution 17 is 30 matter Measure %.
(comparative example 2：The preparation of chemical conversion treatment solution 18)
Urethane resin emulsion, polyester emulsion, polyolefin emulsion, aluminium flake, zirconium compounds and appropriate amount of water are mixed, changed Learn conversion treating solution 18.In chemical conversion treatment solution 18, relative to the mass parts of urethane resin 50, the content of polyester and polyolefin is all It is 25 mass parts.Base material content in chemical conversion treatment solution 18 is 100 mass parts.Fluorine atom in chemical conversion treatment solution 18 Content be 0 mass %.Piece content in chemical conversion treatment solution 18 is 30 mass %.In addition, in chemical conversion treatment solution 18 The content of zirconium compounds 0.20 mass % in the solid constituent in chemical conversion treatment solution is scaled with Zr atoms.
(comparative example 3：The preparation of chemical conversion treatment solution 19)
Emulsion acrylic resin, polyester emulsion, epoxy resin latex, polyolefin emulsion, aluminium flake, vfanadium compound and water are fitted Amount mixing, has obtained chemical conversion treatment solution 19.In chemical conversion treatment solution 19, relative to the mass parts of acrylic resin 25, gather The content of ester, epoxy resin and polyolefin is all 25 mass parts.Base material content in chemical conversion treatment solution 19 is 100 mass Part.The content of fluorine atom in chemical conversion treatment solution 19 is 0 mass %.Piece content in chemical conversion treatment solution 19 is 30 matter Measure %.In addition, the content of the vfanadium compound in chemical conversion treatment solution 19 is scaled consolidating in chemical conversion treatment solution with V atoms 0.20 mass % in body composition.
(comparative example 4：The preparation of chemical conversion treatment solution 20)
It is appropriate to have used titanium compound to replace zirconium compounds, change the addition of aluminium flake, in addition, with chemical conversion Treatment fluid 16 similarly, has obtained chemical conversion treatment solution 20.Base material content in chemical conversion treatment solution 20 is 125 mass Part.The content of fluorine atom in chemical conversion treatment solution 20 is 11.1 mass %.Piece content in chemical conversion treatment solution 20 is 5 Quality %.In addition, the content of the titanium compound in chemical conversion treatment solution 20 is scaled in chemical conversion treatment solution with Ti atoms Solid constituent in 0.20 mass %.
(comparative example 5：The preparation of chemical conversion treatment solution 21)
The addition of zirconium compounds and the addition of aluminium flake are changed, it is in addition, same with chemical conversion treatment solution 16 Ground, chemical conversion treatment solution 21 is obtained.Base material content in chemical conversion treatment solution 21 is 125 mass parts.At chemical conversion The content for managing the fluorine atom in liquid 21 is 11.1 mass %.Piece content in chemical conversion treatment solution 21 is 65 mass %.In addition, The content of zirconium compounds in chemical conversion treatment solution 21 is scaled in the solid constituent in chemical conversion treatment solution with Zr atoms 0.20 mass %.
The composition of chemical conversion treatment solution 1~16 is as shown in table 1.In addition, the composition of chemical conversion treatment solution 17~21 is such as Shown in table 2.
[table 1]
[table 2]
[embodiment 17]
Chemical conversion treatment solution 1 is coated on clad steel sheet A, to reach 140 DEG C of heat dryings of plate temperature, forms thickness 2.0 μm of chemical conversion treatment epithelium.In this way, having obtained chemical conversion treatment steel plate 1, chemical conversion treatment steel plate 1 is according to upper The content of the content of base material content, fluorine atom in the chemical conversion treatment solution 1 stated, piece content and titanium compound contains above-mentioned each Composition.
[embodiment 18~36]
Species, drying temperature and the thickness of chemical conversion treatment solution are changed as shown in aftermentioned table 3, in addition, In the same manner as chemical conversion treatment steel plate 1, chemical conversion treatment steel plate 2~20 has been obtained.2~20 points of chemical conversion treatment steel plate Do not contain according to base material content in corresponding chemical conversion treatment solution in above-mentioned chemical conversion treatment solution 2~16, fluorine atom The content of amount, piece content and chemical conversion treatment composition etc. contains above-mentioned each composition.
[embodiment 37]
Use and implemented the clad steel sheet A based on the processing of phosphatic matrix, and changed as shown in aftermentioned table 3 The species and thickness of chemical conversion treatment solution, in addition, in the same manner as chemical conversion treatment steel plate 1, chemical conversion is obtained Handle steel plate 21.Chemical conversion treatment steel plate 21 is according to base material content in above-mentioned chemical conversion treatment solution 16, fluorine atom The content of content, piece content and chemical conversion treatment composition contains above-mentioned each composition.
In addition, by by clad steel sheet 0.1 mole/L of phosphoric acid ion concentration 0.1 mole/L and Mn ion concentrations, adjust Impregnated 3 seconds in the whole treatment fluid for 60 DEG C of liquid temperature, handled based on phosphatic matrix.
[embodiment 38]
The clad steel sheet A for implementing the matrix processing based on valve metal has been used, and has been changed as shown in aftermentioned table 3 The species and thickness of chemical conversion treatment solution, in addition, in the same manner as chemical conversion treatment steel plate 1, chemical conversion is obtained Handle steel plate 22.Chemical conversion treatment steel plate 22 is according to base material content in above-mentioned chemical conversion treatment solution 16, fluorine atom The content of content, piece content and chemical conversion treatment composition contains above-mentioned each composition.
In addition, by by H2TiF6(40%), the aqueous solution that is scaled with metal Ti 5g/L, utilize mangle processing of spraying Coated on clad steel sheet, the matrix processing based on valve metal is carried out.
[embodiment 39,40]
As be described hereinafter shown in table 3, chemical conversion treatment solution 16 is changed into chemical conversion treatment solution 3, and thickness is changed from 1 μm It is changed into 0.5 μm, in addition, in the same manner as chemical conversion treatment steel plate 21,22, has respectively obtained chemical conversion treatment steel plate 23、24.Chemical conversion treatment steel plate 23,24 is respectively according to base material content in above-mentioned chemical conversion treatment solution 3, fluorine atom The content of content, piece content and chemical conversion treatment composition contains above-mentioned each composition.
[embodiment 41,42]
As be described hereinafter shown in table 3, chemical conversion treatment solution 16 is changed into chemical conversion treatment solution 10, in addition, with change Learn conversion processing steel plate 21,22 similarly, respectively obtain chemical conversion treatment steel plate 25,26.Chemical conversion treatment steel plate 25, 26 respectively according to the base material content in above-mentioned chemical conversion treatment solution 10, the content of fluorine atom, piece content and chemical conversion at The content of reason composition contains above-mentioned each composition.
[comparative example 6~10]
The species and thickness of chemical conversion treatment solution are changed as shown in aftermentioned table 3, in addition, with chemical conversion Handle steel plate 1 similarly, obtain chemical conversion treatment steel plate C1~C5.Chemical conversion treatment steel plate C1~C5 is respectively according to upper The content of base material content, fluorine atom in the chemical conversion treatment solution 17~21 stated, piece content and chemical conversion treatment composition Content contains above-mentioned each composition.
[evaluation]
(1) gloss
Made gloss meter GMX-203 is studied using Murakami K. K. dye technology, to chemical conversion treatment steel plate 1~ 60 ° of mirror surface luster (G on the surface of the chemical conversion treatment epithelium side of each of 26 and C1~C560), according to by Japanese work " mirror surface luster-assay method " is determined as defined in industry standard JIS Z8741, and is commented according to following benchmark Valency." A " and " B " is set to qualified, " C " and " D " is set to unqualified.
A：60 ° of mirror surface lusters are less than 60
B：60 ° of mirror surface lusters are more than 60 and are less than 150
C：60 ° of mirror surface lusters are more than 150 and are less than 250
D：60 ° of mirror surface lusters are more than 250
(2) adhesion
The test film determined to chemically each of conversion processing steel plate 1~26 and C1~C5, by chemical conversion treatment 4t is bent epithelium laterally, is carried out adhesive tape disbonded test to the part of the bending in chemical conversion treatment epithelium, is tried to achieve this Ratio (the epithelium peels off area of the area of per unit area, chemical conversion treatment epithelium the released part of the part of bending Rate, PA), and evaluated according to following benchmark." A " and " B " is set to qualified, " C " and " D " is set to unqualified.
A：Epithelium peels off area rate is less than 5%
B：Epithelium peels off area rate is more than 5% and is less than 10%
C：Epithelium peels off area rate is more than 10% and is less than 50%
D：Epithelium peels off area rate is more than 50%
(3) corrosion resistance
The end face seal for the test film that chemically each of conversion processing steel plate 1~26 and C1~C5 is determined, foundation As defined in Japanese Industrial Standards JIS Z2371 " salt spraytest method ", using 35 DEG C of the 5%NaCl aqueous solution to the examination The surface for testing the chemical conversion treatment epithelium side of piece has carried out the spraying of 240 hours, tries to achieve in the face of white rust caused by the surface Product rate (white rust produces area occupation ratio, WR), and evaluated according to following benchmark." A " and " B " is set to qualified, by " C " and " D " is set to unqualified.
A：It is less than 5% that white rust, which produces area occupation ratio,
B：White rust produces area occupation ratio more than 5% and is less than 10%
C：White rust produces area occupation ratio more than 10% and is less than 40%
D：White rust produces area occupation ratio more than 40%
(4) absorption of perspiration
Chemical conversion treatment in the test film determined to chemically each of conversion processing steel plate 1~26 and C1~C5 The surface of epithelium side is dripped 100 μ L synthetic perspiration's (alkalescence), and after being impressed with rubber stopper, by the test film, environment is in groove 70 DEG C, stand 240 hours in 95%RH constant temperature and humidity cabinet, to impress portion and the luminosity equation (Δ L*) beyond it of the test film It is determined, and is evaluated using following benchmark." A " and " B " is set to qualified, " C " and " D " is set to not conform to Lattice.
A：Luminosity equation is less than 1
B：Luminosity equation is more than 1 and is less than 2
C：Luminosity equation is more than 2 and is less than 5
D：Luminosity equation is more than 5
(5) against weather
At chemical conversion in the test film determined for chemically each of conversion processing steel plate 1~26 and C1~C5 The surface of epithelium side is managed, will be according to by Japanese Industrial Standards JIS K5600-7-7：Xenon lamp method as defined in 2008 is shone the surface The process that 18 minutes water is sprayed the surface in a period of penetrating the light of 120 minutes xenon arc lamps is set to a circulation (2 hours), by this Process repeats 400 circulations, and made gloss meter GMX-203 is studied to the test film using Murakami K. K.'s dye technology 60 ° of glossiness on above-mentioned surface are measured, and try to achieve gloss retention (400 circulations of 400 front and rear test films of circulation The glossiness of test film afterwards relative to 50 circulation before test film glossiness ratio RG60), and according to following benchmark Evaluated." A " and " B " is set to qualified, " C " and " D " is set to unqualified.
A：Gloss retention is more than 90%
B：Gloss retention is less than 90% and is more than 80%
C：Gloss retention is less than 80% and is more than 60%
D：Gloss retention is less than 60%
For each of chemical conversion treatment steel plate 1~26 and C1~C5, species, the kind for the treatment of fluid of clad steel sheet Class, the thickness of chemical conversion treatment epithelium and matrix processing are as shown in table 3, and above-mentioned evaluation result is as shown in table 4.
[table 3]
[table 4]
It can be seen from 1~table of table 4, with the chemical conversion treatment epithelium made using chemical conversion treatment solution 1~16 Gloss of the chemical conversion treatment steel plate 1~26 all on chemical conversion treatment steel plate, chemical conversion treatment epithelium side surface, change Learn in adhesion, corrosion resistance, absorption of perspiration and the against weather of conversion processing epithelium, show good result.
On the other hand, chemical conversion treatment steel plate C1 is insufficient in above-mentioned adhesion.This is believed that to be due to chemistry Conversion processing epithelium does not contain the organic resin beyond fluororesin, so chemical conversion treatment epithelium is not close contact in firmly fully Coating, in addition, being due to that chemical conversion treatment epithelium is insufficient for the barrier function of synthetic perspiration.
In addition, chemical conversion treatment steel plate C2 and C3 is insufficient in above-mentioned against weather.This, which can consider, is due to Chemical conversion treatment epithelium does not contain fluororesin.In addition, it can be seen from chemical conversion treatment steel plate C1~C3, chemical conversion treatment The parent of resin component in epithelium is substantially made up of fluororesin and substrate resin.
In addition, chemical conversion treatment steel plate C4 above-mentioned gloss is too high, and it is insufficient on above-mentioned absorption of perspiration.This can recognize To be due to, the content of sheet metal is insufficient, therefore the effect for suppressing gloss is insufficient, in addition, chemical conversion treatment steel plate Sheet metal on in-plane is not uniformly distributed fully, therefore generates the discoloration of coating.
In addition, chemical conversion treatment steel plate C5 is insufficient in above-mentioned adhesion.This, which can consider, is due to, sheet metal Content is excessive, and chemical conversion treatment epithelium is insufficient to the adhesion of coating.
[making of the Zn alloy plated steel plate containing Al]
Using thickness of slab 0.8mm SPCC as base material, Zn, Al and Mg in coating alloy are changed as shown in table 5 Content, and coating adhesion amount is changed as shown in table 5, in addition, in the same manner as clad steel sheet A, heat has been made respectively It is clad steel sheet B~E to soak plating Zn-Al-Mg alloy-steel plate.
In addition, changing the content of the Zn and Al in coating alloy as shown in table 5, and change as shown in table 5 Coating adhesion amount, in addition, in the same manner as clad steel sheet A, has made hot dip galvanizing-Al alloy-steel plates i.e. coated steel respectively Plate F, G.
The composition of coating alloy in clad steel sheet B~G and the adhesion amount of coating are as shown in table 5.In table 5, " Al content " It is the quality % of the aluminium in coating, " Mg contents " is the quality % of the magnesium in coating.
[table 5]
[embodiment 43~47]
As be described hereinafter shown in table 6, chemical conversion treatment solution 2,4,7 and 14 is coated on clad steel sheet B respectively, to reach plate temperature 140 DEG C of heat dryings, form the chemical conversion treatment epithelium of 2.0 μm of thickness.In this way, chemical conversion treatment steel is respectively obtained Plate 27~30.In addition, coating chemical conversion treatment solution 15 on clad steel sheet B, to reach 140 DEG C of heat dryings of plate temperature, formed The chemical conversion treatment epithelium of 3.0 μm of thickness.In this way, chemical conversion treatment steel plate 31 is obtained.Chemical conversion treatment steel plate 27~31 contain according to the base material content in above-mentioned chemical conversion treatment solution 2,4,7,14 and 15, the content of fluorine atom, piece respectively Amount and the content of chemical conversion treatment composition etc. contain above-mentioned each composition.
[embodiment 48~52]
As be described hereinafter shown in table 6, clad steel sheet C has been used to replace clad steel sheet B, in addition, with chemical conversion treatment steel Plate 27~31 similarly, has respectively obtained chemical conversion treatment steel plate 32~36.Chemical conversion treatment steel plate 32~36 is pressed respectively According to content, piece content and the chemical conversion of base material content, fluorine atom in above-mentioned chemical conversion treatment solution 2,4,7,14 and 15 It is processed into the content graded and contains above-mentioned each composition.
[embodiment 53~57]
As be described hereinafter shown in table 6, clad steel sheet D has been used to replace clad steel sheet B, in addition, with chemical conversion treatment steel Plate 27~31 similarly, has respectively obtained chemical conversion treatment steel plate 37~41.Chemical conversion treatment steel plate 37~41 is pressed respectively According to content, piece content and the chemical conversion of base material content, fluorine atom in above-mentioned chemical conversion treatment solution 2,4,7,14 and 15 It is processed into the content graded and contains above-mentioned each composition.
[embodiment 58~62]
As be described hereinafter shown in table 6, clad steel sheet E has been used to replace clad steel sheet B, in addition, with chemical conversion treatment steel Plate 27~31 similarly, has respectively obtained chemical conversion treatment steel plate 42~46.Chemical conversion treatment steel plate 42~46 is pressed respectively According to content, piece content and the chemical conversion of base material content, fluorine atom in above-mentioned chemical conversion treatment solution 2,4,7,14 and 15 It is processed into the content graded and contains above-mentioned each composition.
[comparative example 11,12]
As be described hereinafter shown in table 6, chemical conversion treatment solution 18,20 has been used to replace chemical conversion treatment solution 15 respectively, except this In addition, in the same manner as chemical conversion treatment steel plate 31, chemical conversion treatment steel plate C6, C7 have been respectively obtained.Chemical conversion treatment Steel plate C6, C7 respectively according to the base material content in above-mentioned chemical conversion treatment solution 18,20, the content of fluorine atom, piece content and The content of chemical conversion treatment composition etc. contains above-mentioned each composition.
[comparative example 13~18]
As be described hereinafter shown in table 6, clad steel sheet C~E has been used to replace clad steel sheet B respectively, in addition, with chemical conversion Handle steel plate C6, C7 similarly, respectively obtain chemical conversion treatment steel plate C8~C13.Chemical conversion treatment steel plate C8 and C9, C10 and C11 and C12 and C13 is respectively according to base material content in above-mentioned chemical conversion treatment solution 18 and 20, fluorine atom The content of content, piece content and chemical conversion treatment composition etc. contains above-mentioned each composition.
[comparative example 19~24]
As be described hereinafter shown in table 6, clad steel sheet F, G has been used to replace clad steel sheet B respectively, in addition, with chemical conversion Handle steel plate C6, C7 similarly, respectively obtain chemical conversion treatment steel plate C14~C17.In addition, as be described hereinafter shown in table 6, point Do not use clad steel sheet F, G to replace clad steel sheet B, in addition, in the same manner as chemical conversion treatment steel plate 27, respectively obtained Chemical conversion treatment steel plate C18, C19.Chemical conversion treatment steel plate C14 and C15 and C16 and C17 is respectively according to above-mentioned Content, piece content and the chemical conversion treatment composition of base material content, fluorine atom in chemical conversion treatment solution 18 and 20 etc. contain Amount contains above-mentioned each composition.In addition, chemical conversion treatment steel plate C18 and C19 are respectively according in above-mentioned chemical conversion treatment solution 2 Base material content, the content of content, piece content and chemical conversion treatment composition etc. of fluorine atom contain above-mentioned each composition.
It is same with chemical conversion treatment steel plate 1 for each of chemical conversion treatment steel plate 27~46 and C6~C19 Ground, gloss, adhesion, corrosion resistance, absorption of perspiration and against weather are evaluated.For chemical conversion treatment steel plate 27~ Each of 46 and C6~C19, shown in table 6 species of clad steel sheet, the species of chemical conversion treatment solution, drying temperature and The thickness of chemical conversion treatment epithelium, above-mentioned evaluation result is shown in table 7.
[table 6]
[table 7]
It can be seen from table 6, table 7, there is the chemical conversion treatment made using chemical conversion treatment solution 2,4,7,14 and 15 The chemical conversion treatment steel plate 27~46 of epithelium is all on chemical conversion treatment steel plate, chemical conversion treatment epithelium side surface In gloss, the adhesion of chemical conversion treatment epithelium, corrosion resistance, absorption of perspiration and against weather, good result is shown.
Chemical conversion treatment steel plate C6, C8, C10, C12 are insufficient in above-mentioned against weather.This may be considered by Fluororesin is not contained in chemical conversion treatment epithelium.
In addition, chemical conversion treatment steel plate C7, C9, C11 and C13 is insufficient on above-mentioned absorption of perspiration.This can consider It is due to that the content of sheet metal is insufficient, therefore sheet metal is not fully equal on the in-plane of chemical conversion treatment steel plate Even distribution, as a result, generating the discoloration of coating.The particularly content of chemical conversion treatment steel plate C7, C9, C11 sheet metal It is insufficient therefore also insufficient on the point of effect for suppressing gloss.In addition, chemical conversion treatment steel plate C13 gloss is enough Low, this is due to that clad steel sheet E is the sufficiently low clad steel sheet of lustrous surface.
Chemical conversion treatment steel plate C14~C17 corrosion resistance is all insufficient.At this moment because clad steel sheet F, G are resistance to The relatively low clad steel sheet of corrosivity, therefore even if implementing chemical conversion treatment, the raising of corrosion resistance is also insufficient.Also, change Learn conversion processing steel plate C14, C16 and all do not contain fluororesin in its chemical conversion treatment epithelium, so against weather is not also filled Point.In addition, chemical conversion treatment steel plate C15, C17 absorption of perspiration are all insufficient.It is due to that sheet metal is in chemistry that this, which can consider, It is not uniformly distributed fully on the in-plane of conversion processing steel plate, therefore also generates the discoloration of coating.Particularly chemistry turns The content of change processing steel plate C15 sheet metal is insufficient, therefore also insufficient on the point of effect for suppressing gloss.
Chemical conversion treatment steel plate C18 and C19 corrosion resistance are all insufficient.This is because, clad steel sheet F, G are resistance to The relatively low clad steel sheet of corrosivity, therefore even if implementing chemical conversion treatment, the raising of corrosion resistance is also insufficient.
In summary, following chemical conversion treatment steel plates have the change in the surface configuration of the coating of above-mentioned clad steel sheet Learn conversion processing epithelium, the chemical conversion treatment epithelium contain fluororesin, substrate resin, sheet metal and chemical conversion treatment into Point, above-mentioned substrate resin be selected from polyurethane, polyester, acrylic resin, epoxy resin and polyolefin more than one, phase For the above-mentioned fluororesin of the total amount of above-mentioned fluororesin and above-mentioned substrate resin content with fluorine atom be scaled 3.0 mass % with On, the content relative to the substrate resin of the above-mentioned mass parts of fluororesin 100 is more than 10 mass parts above-mentioned chemical conversion treatment skins The content of sheet metal in film is more than 20 mass % and is below 60 mass %, and the chemical conversion treatment steel plate has against weather And gloss and discoloration over time can be suppressed.
The application is willing to No. 2014-066481, in 2014 based on the Japanese patent application laid proposed on March 27th, 2014 The Japanese patent application laid that October 30 proposed is willing to No. 2014-221602, in the Japan Patent Shen that on December 26th, 2014 proposes Please Patent 2014-265602 and on March 27th, 2015 propose Japanese patent application laid be willing to 2015-065617 master Open priority.Content described in the specification and accompanying drawing of this application is all referred in present specification.
Industrial applicibility
The against weather of above-mentioned chemical conversion treatment steel plate is excellent and can suppress excessive gloss and over time Discoloration, so being useful in the various uses such as exterior building materials.For example, above-mentioned chemical conversion treatment steel plate can be applied to Following purposes：1) roof Material of building, 2) outside art work, the steel pipe in vinyl house or agriculture house, shaped steel, branch Part, 3) soundproof wall, baffle-wall, sound-absorbing wall, anti-rampart, guardrail, railing, guard boom, 4) pillar, track are used in post, crossbeam, conveying Vehicle part, stringing part, electrical equipment part, security context part, structure part, solar bracket, sky Adjust outdoor unit etc..

Claims (13)

1. a kind of chemical conversion treatment steel plate, it is included：With steel plate and the steel plate surface configuration coating coating The chemical conversion treatment epithelium of steel plate and surface configuration in the coating, wherein,
The coating is made up of the kirsite of the aluminium comprising 0.05~60 mass % and 0.5~4.0 mass % magnesium,
The chemical conversion treatment epithelium contains fluororesin, substrate resin, sheet metal and chemical conversion treatment composition,
The substrate resin is more than one that selected from polyurethane, polyester, acrylic resin, epoxy resin and polyolefin,
3.0 matter are scaled with fluorine atom relative to the content of the fluororesin of the total amount of the fluororesin and the substrate resin More than % is measured,
The content of the substrate resin relative to the mass parts of fluororesin 100 in the chemical conversion treatment epithelium is 10 It is more than mass parts,
The content of the sheet metal in the chemical conversion treatment epithelium is more than 20 mass % and is below 60 mass %,
The metal material of the sheet metal is selected from aluminium and its alloy, iron and its alloy, copper and its conjunction gold, silver, nickel and titanium More than one the metal material selected,
The chemical conversion treatment composition is the one kind selected from 4A races metallic compound, molybdate and valve metal compound More than,
4A races metallic compound is to include more than one the compound selected from Ti, Zr and Hf,
The valve metal compound is to include one or both of V and Nb compound.
2. chemical conversion treatment steel plate as claimed in claim 1, wherein,
The thickness of the chemical conversion treatment epithelium is 0.5~10 μm.
3. chemical conversion treatment steel plate as claimed in claim 1, wherein,
The content of the substrate resin relative to the mass parts of fluororesin 100 in the chemical conversion treatment epithelium is Below 900 mass parts.
4. chemical conversion treatment steel plate as claimed in claim 1, wherein,
The content of 4A races metallic compound in the chemical conversion treatment epithelium is relative to the chemical conversion treatment skin Film is scaled 0.005~5.0 mass % with 4A races metal.
5. chemical conversion treatment steel plate as claimed in claim 1, wherein,
The chemical conversion treatment epithelium further contains one or both of silane coupler and phosphate.
6. chemical conversion treatment steel plate as claimed in claim 1, wherein,
Further have between the clad steel sheet and the chemical conversion treatment epithelium and include phosphate cpd or valve metal The matrix processing epithelium of composition,
The phosphate cpd is metal phosphate or composite phosphate,
The valve metal composition be comprising selected from Ti, Zr, Hf, V, Nb, Ta, Mo and W more than one oxide, Hydroxide or fluoride.
7. chemical conversion treatment steel plate as claimed in claim 1, wherein,
The chemical conversion treatment epithelium further contains pigment.
8. chemical conversion treatment steel plate as claimed in claim 1, wherein,
The chemical conversion treatment epithelium further contains wax.
9. a kind of manufacture method of chemical conversion treatment steel plate, coats chemical conversion treatment solution on the coating of clad steel sheet, and The chemical conversion treatment solution of coating is dried, so as to manufacture chemical conversion treatment steel plate, wherein,
The coating is made up of the kirsite of the aluminium comprising 0.05~60 mass % and 0.5~4.0 mass % magnesium,
The chemical conversion treatment solution contains composition before fluororesin, substrate resin, sheet metal and chemical conversion treatment,
The substrate resin is more than one that selected from polyurethane, polyester, acrylic resin, epoxy resin and polyolefin,
The content of the fluororesin in the chemical conversion treatment solution is total relative to the fluororesin and the substrate resin Amount is scaled more than 3.0 mass % with fluorine atom,
The content of the substrate resin relative to the mass parts of fluororesin 100 in the chemical conversion treatment solution is 10 matter Measure more than part,
The content of the sheet metal in the chemical conversion treatment solution is more than 20 mass % relative to solid constituent and is 60 Below quality %,
The metal material of the sheet metal is selected from aluminium and its alloy, iron and its alloy, copper and its conjunction gold, silver, nickel and titanium More than one the metal material selected,
Composition is chemical conversion treatment composition and in the chemical conversion treatment solution or passed through before the chemical conversion treatment The change of drying of chemical conversion treatment solution turns to one or both of composition of the chemical conversion treatment composition,
The chemical conversion treatment composition is the one kind selected from 4A races metallic compound, molybdate and valve metal compound More than,
4A races metallic compound is to include more than one the compound selected from Ti, Zr and Hf,
The valve metal compound is to include one or both of V and Nb compound.
10. the manufacture method of chemical conversion treatment steel plate as claimed in claim 9, wherein,
The chemical conversion treatment solution contains the emulsion of the fluororesin and the emulsion of the substrate resin,
The particle diameter of the emulsion of the fluororesin is 10~300nm,
The particle diameter of the emulsion of the substrate resin is 10~100nm.
11. the manufacture method of the chemical conversion treatment steel plate as described in claim 9 or 10, wherein,
Before the chemical conversion treatment solution is coated, further comprise using phosphate cpd or valve metal composition to the plating The process that layer steel plate carries out matrix processing, the phosphate cpd is metal phosphate or composite phosphate, the valve metal into Divide is more than one oxide, hydroxide or fluorination comprising being selected from Ti, Zr, Hf, V, Nb, Ta, Mo and W Thing.
12. a kind of chemical conversion treatment solution, containing composition before fluororesin, substrate resin, sheet metal and chemical conversion treatment, its In,
The substrate resin is more than one that selected from polyurethane, polyester, acrylic resin, epoxy resin and polyolefin,
The content of the fluororesin in the chemical conversion treatment solution is total relative to the fluororesin and the substrate resin Amount is scaled more than 3.0 mass % with fluorine atom,
The content of the substrate resin relative to the mass parts of fluororesin 100 in the chemical conversion treatment solution is 10 matter Measure more than part,
The content of the sheet metal in the chemical conversion treatment solution is more than 20 mass % relative to solid constituent and is 60 Below quality %,
The metal material of the sheet metal is selected from aluminium and its alloy, iron and its alloy, copper and its conjunction gold, silver, nickel and titanium More than one the metal material selected,
Composition is chemical conversion treatment composition and in the chemical conversion treatment solution or passed through before the chemical conversion treatment The drying of chemical conversion treatment solution is converted into one or both of composition of the chemical conversion treatment composition,
The chemical conversion treatment composition is the one kind selected from 4A races metallic compound, molybdate and valve metal compound More than,
4A races metallic compound is to include more than one the compound selected from Ti, Zr and Hf,
The valve metal compound is to include one or both of V and Nb compound.
13. chemical conversion treatment solution as claimed in claim 12, wherein,
The chemical conversion treatment solution contains the emulsion of the fluororesin and the emulsion of the substrate resin,
The particle diameter of the emulsion of the fluororesin is 10~300nm,
The particle diameter of the emulsion of the substrate resin is 10~100nm.
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