WO2002061175A1 - Agent de traitement de surface pour materiau metallique et procede de traitement de surface - Google Patents
Agent de traitement de surface pour materiau metallique et procede de traitement de surface Download PDFInfo
- Publication number
- WO2002061175A1 WO2002061175A1 PCT/JP2001/001500 JP0101500W WO02061175A1 WO 2002061175 A1 WO2002061175 A1 WO 2002061175A1 JP 0101500 W JP0101500 W JP 0101500W WO 02061175 A1 WO02061175 A1 WO 02061175A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- metal
- benzene ring
- phosphate
- compound
- Prior art date
Links
- 239000007769 metal material Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 26
- 235000021317 phosphate Nutrition 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- -1 phosphorus compound Chemical class 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 6
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 5
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 239000010452 phosphate Substances 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 238000004381 surface treatment Methods 0.000 claims description 10
- 239000012756 surface treatment agent Substances 0.000 claims description 10
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 20
- 238000005260 corrosion Methods 0.000 abstract description 20
- 239000011651 chromium Substances 0.000 abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052804 chromium Inorganic materials 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 24
- 239000011701 zinc Substances 0.000 description 16
- 229910000831 Steel Inorganic materials 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003973 paint Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 2
- 239000001263 FEMA 3042 Substances 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 2
- 229940033123 tannic acid Drugs 0.000 description 2
- 235000015523 tannic acid Nutrition 0.000 description 2
- 229920002258 tannic acid Polymers 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 101000927799 Homo sapiens Rho guanine nucleotide exchange factor 6 Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 102100033202 Rho guanine nucleotide exchange factor 6 Human genes 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- OXAUNDBQHKIUSD-UHFFFAOYSA-N azanium;titanium;fluoride Chemical compound [NH4+].[F-].[Ti] OXAUNDBQHKIUSD-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- BFDQRLXGNLZULX-UHFFFAOYSA-N titanium hydrofluoride Chemical compound F.[Ti] BFDQRLXGNLZULX-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
Definitions
- the present invention relates to a surface-treating agent for metal sheets, and to a surface-treated metal sheet having excellent end face corrosion resistance when it is applied to a metal sheet and used as a coating base, and in particular, does not contain toxic chromium. It is. Background art
- This metal sheet is a metal sheet that has been subjected to a base treatment and a metal sheet coated with an organic film, and has the property of having good workability, good corrosion resistance, and good appearance. I have.
- Japanese Patent Application Laid-Open No. H08-1688723 discloses a technique for obtaining a pre-coated steel sheet having excellent workability, stain resistance, and hardness by defining the structure of a film.
- Japanese Patent Application Laid-Open No. H03-1000180 discloses a precoated steel sheet having improved end face corrosion resistance by using a specific chromate treatment solution.
- pre-coated steel sheets have workability and paint adhesion, as well as corrosion resistance due to the combined effect of chromate treatment and organic coating, and omission of post-work coating to improve productivity and quality. Is widely used.
- a treatment technique using an aqueous solution containing nin or tannic acid is disclosed.However, when a pre-coated metal plate is manufactured using this protection method, if it is applied to home appliances or automobiles with severe processing shapes, processing There is a problem that the adhesion of the coating film in the part is greatly inferior.
- Japanese Patent Application Laid-Open No. 59-116163 / 81 discloses a technique for improving the whiteness resistance and paint adhesion by treating the surface with an aqueous solution containing tannic acid and a silane coupling agent. Although disclosed, this method also cannot ensure the required processing adhesion of the precoated metal plate.
- phosphate treatment is still used as pre-treatment when painting after processing. However, this phosphate treatment requires surface conditioning before the treatment and complicates the process such as washing and drying after the treatment. Therefore, shortening of the process and cost reduction are required. Disclosure of the invention
- an object of the present invention is to provide a surface-treated metal plate that is non-chromium-based and has excellent end face corrosion resistance when used as a coating base.
- the present inventors have conducted intensive studies in order to solve the above problems of the prior art, and as a result, used a phosphate, a water-soluble polymer and / or a metal compound in combination as a metal surface treatment agent. By doing so, it has been found that the corrosion resistance of the metal material and the adhesion between the coating resin and the metal plate are dramatically improved, and that the above-mentioned problems can be solved. That is, the present invention is (1) a surface treating agent for a metal material, comprising water, the following (A), (B) and / or (C).
- An inorganic binder having at least one selected from a silicon compound, a phosphorus compound, a zirconium compound, and a titanium compound.
- X in the formula (1) is a hydrogen atom, a hydroxyl group, a C1-C5 alkyl group, a C1-C5 hydroxyalkyl group, and a C6-C12 aryl group.
- R1 and R2 in the formula (2) represent a hydrogen atom, a hydroxy group, a C1-C5 alkyl group or a C1-C10 hydroxyalkyl group, respectively, and the formulas (1) and (2) ), Y1 and Y2 bonded to the benzene ring are each independently a hydrogen atom or a Z group represented by the following formulas (3) and (4):
- R3, R4, R5, R6 and R7 in the above formulas (3) and (4) are each independently a hydrogen atom, ⁇ 1 to 10 alkyl groups or 1 to 1; X, Y1, and Y2 bonded to each benzene ring in the polymer molecule represent 10 hydroxyalkyl groups, and X, Y1, and Y2 each bonded to another benzene ring.
- the average value of the number of substitution of the Z group in each benzene ring in the polymer molecule is from 0.2 to 1.0. ].
- the surface treatment agent for a metal material described in (1) or (2) is applied to the surface of the metal material, dried and coated with 0.05 to 5 g / m 2 in terms of phosphate (A).
- This is a surface treatment method for metal materials characterized by the following.
- A includes the following examples. Normally, phosphates of divalent or trivalent metals exist as hydrates such as dihydrate and tetrahydrate, but the number of water of hydration is not limited with respect to the effects of the present invention. Illustrated in the form of an anhydrous salt.
- the particle size of the phosphate film crystals formed on the plating surface considering the corrosion resistance and the adhesion of the coating film as an undercoat film, it is preferable to coat the plating surface uniformly and densely. However, it can be inferred that the smaller the particle size of the phosphate film, the better. In order to stably disperse in the processing solution, the arithmetic average particle size of the divalent or trivalent metal phosphate used in the present invention is 5 m or less. Is desirable.
- the inorganic binder (B) used in the present invention has at least one selected from a silicon compound, a phosphorus compound, a zirconium compound, and a titanium compound.
- examples of such inorganic binders include, in the case of silicon compounds, alkali silicates such as sodium silicate, potassium silicate and lithium silicate, and polymer silica such as colloidal silica.
- Examples of the phosphorus compound include phosphoric acid, aluminum phosphate, pyrophosphoric acid, and tripolyphosphoric acid.
- Examples of the zirconium compound include water-dispersible zirconium colloid, zirconium carbonate ammonium, zircon ammonium fluoride, zircon fluorination power, and sodium zirconium fluoride.
- Examples of the titanium compound include water-dispersible titanium colloid, water-soluble inorganic titanium compounds such as titanium sulfate, titanium oxysulfate, titanium hydrofluoric acid, titanium fluoride ammonium, and titanium alkoxide.
- the polymer component (C) used in the present invention is an oligomer or a polymer containing 5 polymerized units represented by the formula (1), and the average polymerization degree of the polymerized unit of the formula (1) is 2 to 2.
- Y 1 and Y 2 bonded to the benzene ring each independently have a hydrogen atom or a Z group represented by the formulas (3) and (4).
- R 3, R 4, R 5, R 6 and R 7 in the formulas (3) and (4) each independently represent a hydrogen atom, an alkyl group of C1 to G10 or a hydroxyalkyl group of G10 to C10.
- the average value of the number of substitution of the Z group in each benzene ring in the polymer molecule is 0.2 to 1.0.
- R3, R4, R5, R6 and R7 in the formulas (3) and (4) each independently represent a hydrogen atom, a C1-G10 alkyl group or a C1-C10 hydroxyalkyl.
- the content of the phosphate (A) in the surface treatment for a metal material of the present invention is based on the total solid content. It is preferably in the range of 5% by weight to 95% by weight. If the content is less than 5% by weight, the corrosion resistance after coating becomes insufficient due to the small amount of phosphate used as a corrosion inhibitor. If the content exceeds 95% by weight, the amount of phosphate in the film is excessive and the effect of the binder is insufficient, so that the adhesion is reduced. A more preferred range is 105 weight. /. 770% by weight.
- the surface treatment agent for a metal material of the present invention is preferably applied to the surface of the metal material, dried, and coated in a range of 0.05 to 5 g Zm 2 in terms of phosphate (A). If it is less than 0.05 g Zm 2 , the corrosion resistance becomes insufficient because the amount of the film is small. On the other hand, if the coating amount exceeds 5 g / m 2 , the adhesion after processing may be insufficient or the cost may be disadvantageous. A more preferred range is 0.1 to 2 g Zm 2 .
- the surface treatment of the present invention includes cold-rolled steel sheet, hot-rolled steel sheet, hot-dip galvanized steel sheet, electro-zinc-plated steel sheet, hot-dip galvanized steel sheet, aluminum-plated steel sheet, aluminum-zinc alloy-plated steel sheet, and stainless steel sheet
- the present invention can be applied to generally known metal materials such as an aluminum plate, a copper plate, a titanium plate, and a magnesium plate and a plating plate.
- the surface treatment of the present invention is characterized in that a chemical solution containing phosphate fine particles, a water-soluble polymer and / or a metal compound, etc. is applied and dried.
- Phosphate has been used for a long time as a pretreatment agent for painting, but it has been confirmed that it has insulating properties and interfacial buffering effects. It is estimated to be 0.
- a phosphate film with high added value has been produced by contacting a metal material with a chemical containing zinc ions, phosphate ions, an accelerator, etc., depositing a zinc phosphate film, washing with water, and removing excess water.
- the surface treatment of the present invention uses inorganic and organic binders.6. It is characterized by being provided on the surface.
- the binder type must be non-corrosive to the steel sheet and one that does not adversely affect the topcoat paintability.
- Surface treatment of the present invention The agent can be applied by conventional coating methods, such as mouth coating, curtain flow coating, air spray, airless spraying, immersion, vacuum coating, brushing, and the like. Examples and comparative examples
- test material was immersed in an aqueous solution with a concentration of 20 g / L and a temperature of 60 ° C for 10 seconds using an alkali degreasing agent CL—N364S (manufactured by Nippon Parkerizing) for 10 seconds. After washing with water, it was dried.
- CL—N364S manufactured by Nippon Parkerizing
- the electrodeposition coating was performed under the following conditions.
- the salt spray test specified in JIS-Z2371 was performed for 120 hours on the test material that also used GI material.
- the whiteness resistance was visually measured and evaluated.
- the evaluation criteria are as follows. '
- ⁇ Whiteness occurrence rate 10% or more, less than 50%
- X Whiteness rate 50% or more.
- Example 2 No 2 GA ⁇ .
- Example 3 No 3 SPC ⁇ ⁇
- Example 4 No 4 SPC ⁇ ⁇ ⁇
- Comparative Example 6 PB-L30Z0 SPC ⁇ ⁇
- Examples 1 to 11 using the surface treatment agent of the present invention were excellent in coating adhesion and corrosion resistance, and the current coatings shown in Comparative Examples 5 and 6 The performance was equal to or better than that of mouth mate treatment or phosphate conversion treatment.
- Comparative Examples 1 to 4 had compositions outside the scope of the claims of the present invention, but had poor paint adhesion and poor corrosion resistance. , Industrial applicability
- the present invention it has become possible to provide a surface-treated steel sheet having excellent coating adhesion and corrosion resistance without using environmentally toxic chromium. Therefore, it can be said that the present invention is an invention having extremely high industrial value.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Paints Or Removers (AREA)
Abstract
L'invention concerne un agent de traitement de surface pour matériau métallique, caractérisé en ce qu'il contient (A) un ou plusieurs phosphates d'un ou plusieurs métaux choisis parmi Zn, Fe, Mn, Ni, Co, Ca, Mg, et Al, ayant une granulométrie de 5 µm ou moins ; (B) un liant inorganique choisi parmi un composé silicium, un composé phosphore, un composé zirconium, et un composé titane ; et, (C) un ou plusieurs composants polymères contenant un ou plusieurs polymères représentés par la formule (1) et ayant un degré de polymérisation moyen de 2 à 50. L'agent de traitement de surface selon l'invention ne contient pas de chrome et peut conférer au métal une excellente résistance à la corrosion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002561106A JPWO2002061175A1 (ja) | 2001-01-31 | 2001-02-28 | 金属材料用表面処理剤および表面処理方法 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001-23192 | 2001-01-31 | ||
| JP2001023192 | 2001-01-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2002061175A1 true WO2002061175A1 (fr) | 2002-08-08 |
Family
ID=18888506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2001/001500 WO2002061175A1 (fr) | 2001-01-31 | 2001-02-28 | Agent de traitement de surface pour materiau metallique et procede de traitement de surface |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPWO2002061175A1 (fr) |
| WO (1) | WO2002061175A1 (fr) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007126699A (ja) * | 2005-11-02 | 2007-05-24 | Kobe Steel Ltd | 耐食性および耐アブレージョン性に優れた表面処理亜鉛系メッキ鋼板およびその製造方法 |
| JP2007277690A (ja) * | 2006-04-11 | 2007-10-25 | Million Kagaku Kk | マグネシウム合金の化成処理液およびこれを用いた化成処理方法ならびに化成処理物 |
| JP2010053404A (ja) * | 2008-08-28 | 2010-03-11 | Nippon Steel Corp | プレコート金属板の切断端面の補修液及びそれを用いた補修方法 |
| JP2011006757A (ja) * | 2009-06-26 | 2011-01-13 | Toyota Central R&D Labs Inc | 耐食導電性皮膜、耐食導電材、固体高分子型燃料電池とそのセパレータおよび耐食導電材の製造方法 |
| US8613807B2 (en) | 2009-02-06 | 2013-12-24 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Conductive film, corrosion-resistant conduction film, corrosion-resistant conduction material and process for producing the same |
| CN104109469A (zh) * | 2014-06-19 | 2014-10-22 | 锐展(铜陵)科技有限公司 | 一种石油醚铝合金表面处理剂 |
| CN104109472A (zh) * | 2014-06-19 | 2014-10-22 | 锐展(铜陵)科技有限公司 | 一种耐腐蚀铝合金表面处理剂 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990012902A1 (fr) * | 1989-04-21 | 1990-11-01 | Henkel Corporation | Procede et composition servant au revetement d'aluminium |
| WO1995028449A1 (fr) * | 1994-04-15 | 1995-10-26 | Henkel Corporation | Composition polymere et procede de traitement de surfaces metalliques |
| WO1995028509A1 (fr) * | 1994-04-15 | 1995-10-26 | Henkel Corporation | Composition et procede pour traiter la surface de metaux alumineux |
| WO1997003226A1 (fr) * | 1995-07-10 | 1997-01-30 | Nippon Paint Co., Ltd. | Traitements de surface de metaux, procede de traitement de surface de metaux et materiau metallique ayant subi un traitement de surface |
| WO1998056963A1 (fr) * | 1997-06-11 | 1998-12-17 | Henkel Corporation | Solution apres rinçage sans chrome et a faible contenu organique pour couche de conversion |
| JPH11264075A (ja) * | 1998-03-17 | 1999-09-28 | Nippon Parkerizing Co Ltd | スズめっきスチール製表面処理缶およびスズめっきスチール製缶の表面処理方法 |
-
2001
- 2001-02-28 WO PCT/JP2001/001500 patent/WO2002061175A1/fr active Application Filing
- 2001-02-28 JP JP2002561106A patent/JPWO2002061175A1/ja active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990012902A1 (fr) * | 1989-04-21 | 1990-11-01 | Henkel Corporation | Procede et composition servant au revetement d'aluminium |
| WO1995028449A1 (fr) * | 1994-04-15 | 1995-10-26 | Henkel Corporation | Composition polymere et procede de traitement de surfaces metalliques |
| WO1995028509A1 (fr) * | 1994-04-15 | 1995-10-26 | Henkel Corporation | Composition et procede pour traiter la surface de metaux alumineux |
| WO1997003226A1 (fr) * | 1995-07-10 | 1997-01-30 | Nippon Paint Co., Ltd. | Traitements de surface de metaux, procede de traitement de surface de metaux et materiau metallique ayant subi un traitement de surface |
| WO1998056963A1 (fr) * | 1997-06-11 | 1998-12-17 | Henkel Corporation | Solution apres rinçage sans chrome et a faible contenu organique pour couche de conversion |
| JPH11264075A (ja) * | 1998-03-17 | 1999-09-28 | Nippon Parkerizing Co Ltd | スズめっきスチール製表面処理缶およびスズめっきスチール製缶の表面処理方法 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007126699A (ja) * | 2005-11-02 | 2007-05-24 | Kobe Steel Ltd | 耐食性および耐アブレージョン性に優れた表面処理亜鉛系メッキ鋼板およびその製造方法 |
| JP2007277690A (ja) * | 2006-04-11 | 2007-10-25 | Million Kagaku Kk | マグネシウム合金の化成処理液およびこれを用いた化成処理方法ならびに化成処理物 |
| JP2010053404A (ja) * | 2008-08-28 | 2010-03-11 | Nippon Steel Corp | プレコート金属板の切断端面の補修液及びそれを用いた補修方法 |
| US8613807B2 (en) | 2009-02-06 | 2013-12-24 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Conductive film, corrosion-resistant conduction film, corrosion-resistant conduction material and process for producing the same |
| JP2011006757A (ja) * | 2009-06-26 | 2011-01-13 | Toyota Central R&D Labs Inc | 耐食導電性皮膜、耐食導電材、固体高分子型燃料電池とそのセパレータおよび耐食導電材の製造方法 |
| CN104109469A (zh) * | 2014-06-19 | 2014-10-22 | 锐展(铜陵)科技有限公司 | 一种石油醚铝合金表面处理剂 |
| CN104109472A (zh) * | 2014-06-19 | 2014-10-22 | 锐展(铜陵)科技有限公司 | 一种耐腐蚀铝合金表面处理剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2002061175A1 (ja) | 2004-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3548979B2 (ja) | 塗膜に非クロム化合物防錆顔料を使用した塗装金属板 | |
| JP3883831B2 (ja) | 耐白錆性に優れた表面処理鋼板及びその製造方法 | |
| KR101829483B1 (ko) | 무기계 크로뮴-프리 금속 표면 처리제 | |
| JP4799862B2 (ja) | プレス成形性に優れるプレコート金属板及びその製造方法 | |
| TWI550099B (zh) | Galvanized steel sheet containing aluminum and its manufacturing method | |
| WO2010004651A1 (fr) | Liquide de traitement chimique pour une couche primaire de revêtement d'un matériau de type acier, et procédé de traitement | |
| WO2007064008A1 (fr) | Tôle d'acier traitée en surface | |
| JP2001240977A (ja) | 金属表面処理方法 | |
| JP2007238976A (ja) | 金属材料表面処理用のノンクロメート水系表面処理剤 | |
| CN1882713B (zh) | 化学转化处理金属板 | |
| US6890648B2 (en) | CR-free paint compositions and painted metal sheets | |
| JP4300607B2 (ja) | 耐食性に優れた表面処理鋼板の製造方法 | |
| JP4509425B2 (ja) | 塗装下地処理剤、表面処理方法、金属材、加工方法、及び金属製品 | |
| WO2002061175A1 (fr) | Agent de traitement de surface pour materiau metallique et procede de traitement de surface | |
| JP2002187234A (ja) | 耐食性に優れた非クロム系塗装鋼板 | |
| JP2002317279A (ja) | 水性塗料を用いた環境負荷の小さな塗装鋼板 | |
| JP3923419B2 (ja) | 非クロム系化成処理鋼板のノンクロム処理 | |
| JPH0751620A (ja) | 耐食性に優れかつ無害性のプレコート鋼板 | |
| JP3962123B2 (ja) | 有機系表面処理金属板および有機系金属表面処理液 | |
| WO2023017668A1 (fr) | Liquide de traitement de surface aqueux sans chrome hexavalent, métal traité en surface, et procédé de traitement en surface | |
| JPH11140665A (ja) | 端面耐食性に優れた塗装鋼板およびその製造方法 | |
| JP2001234350A (ja) | 耐食性、塗装性、耐指紋性及び加工性に優れた金属板材料及びその製造方法 | |
| JP3903900B2 (ja) | 耐食性、塗料密着性及び加工性に優れた非クロム系リン酸亜鉛処理鋼板 | |
| JP5000802B2 (ja) | 無機膜形成用塗布剤、その無機膜形成方法、そのものを用いて得られる無機膜被覆アルミニウム材及び無機膜被覆鋼材 | |
| JP2000319786A (ja) | 耐食性に優れた表面処理鋼板 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AU AZ BA BB BG BR BY CA CN CU CZ EE GD GE GH GM HR HU ID IL IN IS JP KE KG KR KZ LC LK LR LS LT LV MD MG MK MN MW MX NO NZ PL RO RU SD SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR |
|
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| WWE | Wipo information: entry into national phase |
Ref document number: 2002561106 Country of ref document: JP |
|
| 122 | Ep: pct application non-entry in european phase |