JP2020117816A - 金属材料の防錆処理方法 - Google Patents
金属材料の防錆処理方法 Download PDFInfo
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- JP2020117816A JP2020117816A JP2020078859A JP2020078859A JP2020117816A JP 2020117816 A JP2020117816 A JP 2020117816A JP 2020078859 A JP2020078859 A JP 2020078859A JP 2020078859 A JP2020078859 A JP 2020078859A JP 2020117816 A JP2020117816 A JP 2020117816A
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- metal material
- chemical conversion
- treatment liquid
- film
- coating
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- 239000007769 metal material Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 28
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- 230000002265 prevention Effects 0.000 title abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 91
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 239000007788 liquid Substances 0.000 claims abstract description 72
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 29
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 27
- 230000003449 preventive effect Effects 0.000 claims description 19
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 16
- 239000008119 colloidal silica Substances 0.000 claims description 11
- 238000007739 conversion coating Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 65
- -1 zirconium ions Chemical class 0.000 description 30
- 239000002904 solvent Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
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- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
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- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 2
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- 239000000956 alloy Substances 0.000 description 2
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- OJLGWNFZMTVNCX-UHFFFAOYSA-N dioxido(dioxo)tungsten;zirconium(4+) Chemical compound [Zr+4].[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O OJLGWNFZMTVNCX-UHFFFAOYSA-N 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 239000011135 tin Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HLERILKGMXJNBU-UHFFFAOYSA-N norvaline betaine Chemical compound CCCC(C([O-])=O)[N+](C)(C)C HLERILKGMXJNBU-UHFFFAOYSA-N 0.000 description 1
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BAQNULZQXCKSQW-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4] BAQNULZQXCKSQW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229940099874 potassium lauroyl glutamate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940045944 sodium lauroyl glutamate Drugs 0.000 description 1
- IWIUXJGIDSGWDN-UQKRIMTDSA-M sodium;(2s)-2-(dodecanoylamino)pentanedioate;hydron Chemical compound [Na+].CCCCCCCCCCCC(=O)N[C@H](C([O-])=O)CCC(O)=O IWIUXJGIDSGWDN-UQKRIMTDSA-M 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical class F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
Classifications
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—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
- C23C22/34—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 fluorides or complex fluorides
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- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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Abstract
Description
(工程1)金属材料をジルコニウム化合物及び両性界面活性剤を含有する化成処理液Aで処理する工程、又は
(工程2)下記工程2a及び2bを含む工程;
(工程2a)金属材料をジルコニウム化合物を含有する化成処理液Bで処理する工程、及び
(工程2b)工程2aで得られた化成処理済金属材料をシリカ質皮膜形成用処理液で処理する工程、
を含む、金属材料の処理方法。
前記防錆皮膜が、下記皮膜1又は2:
(皮膜1)ジルコニウム及び両性界面活性剤を含有する化成処理皮膜1、又は
(皮膜2)下記皮膜2a及び2bからなる皮膜2;
(皮膜2a)ジルコニウムを含有する化成処理皮膜2a、及び
(皮膜2b)前記化成処理皮膜2a上のシリカ質皮膜2b、
からなる、防錆皮膜含有金属材料。
(工程1)金属材料をジルコニウム化合物及び両性界面活性剤を含有する化成処理液Aで処理する工程、又は
(工程2)下記工程2a及び2bを含む工程;
(工程2a)金属材料をジルコニウム化合物を含有する化成処理液Bで処理する工程、及び
(工程2b)工程2aで得られた化成処理済金属材料をシリカ質皮膜形成用処理液で処理する工程、
を含む、防錆皮膜含有金属材料を製造する方法。
1−1.金属材料
化成処理工程の処理対象物は金属材料である。金属材料は、その少なくとも一部の表面が金属で構成されている材料である限り特に制限されない。金属としては、例えば、亜鉛、アルミニウム、マグネシウム、コバルト、ニッケル、鉄、銅、錫、金、これらの合金などの各種の金属が挙げられ、好ましくは亜鉛が挙げられる。金属材料として、より具体的には、金属のみからなる物品、金属以外のその他の物品(例えば、セラミックス材料、プラスチックス材料等)と金属とが組み合わされた複合品、表面に金属めっき皮膜を有するめっき処理品(例えば、表面に亜鉛めっき皮膜又は亜鉛合金めっき皮膜を有する鋼のめっき処理品)等が挙げられる。また、金属材料の表面を構成している金属は、未処理の金属であってもよく、脱脂処理や酸活性処理等の前処理が施された金属であってもよい。
化成処理液は、ジルコニウム化合物を含有する。ジルコニウム化合物は、溶媒に溶解してジルコニウムイオンを供給可能な化合物である限り特に制限されない。ジルコニウム化合物の具体例としては、フッ化ジルコニウムアンモニウム(III)、フッ化ジルコニウムナトリウム(III)、フッ化ジルコニウムカリウム(III)等のジルコニウムフッ化物; 塩化ジルコニウム(III)、塩化ジルコニウム(IV)等のジルコニウム塩化物; 酸化ジルコニウム(IV); タングステン酸ジルコニウム(IV)等が挙げられる。ジルコニウム化合物は、一種単独又は二種以上混合して用いることができる。
化成処理は、金属材料を化成処理液で処理することにより行われる。処理の態様は、金属材料表面の金属上に、ジルコニウムを含有する化成処理皮膜が形成される態様である限りにおいて、特に制限されない。
2−1.化成処理済金属材料
シリカ質皮膜形成処理の処理対象物は、工程2aで得られた化成処理済金属材料である。
シリカ質皮膜形成用処理液は、化成処理済金属材料におけるジルコニウムを含有する化成処理皮膜上にシリカ質皮膜を形成できるものである限り、特に制限されない。シリカ質皮膜形成用処理液は、代表的にはアルコキシシランオリゴマーを含有する処理液である。
シリカ質皮膜形成処理は、化成処理済金属材料をシリカ質皮膜形成用処理液で処理することにより行われる。処理の態様は、化成処理済金属材料の化成処理皮膜上に、シリカ質皮膜が形成される態様である限りにおいて、特に制限されない。
亜鉛めっき鋼板(大きさ100×60×0.3mm)を、アルカリ脱脂処理した後、0.5%硝酸水溶液に10秒間浸漬して酸活性処理して、被処理物である金属材料を得た。
亜鉛めっき鋼板(大きさ100×60×0.3mm)を、アルカリ脱脂処理した後、0.5%硝酸水溶液に10秒間浸漬して酸活性処理して、被処理物である金属材料を得た。
実施例1〜12と同じ被処理物(亜鉛めっき鋼板をアルカリ脱脂処理後に酸活性処理して得られた金属材料)を試験試料として、実施例1〜12と同様の方法で塩水噴霧試験を行い、試料表面積に対する白錆の発生面積比率が10%となるまでの時間を求めた。結果を下記表1に示す。
化成処理をしない以外は、実施例4〜12と同様にして試験試料を得た。試験試料に対して、実施例1〜12と同様の方法で塩水噴霧試験を行い、試料表面積に対する白錆の発生面積比率が10%となるまでの時間を求めた。結果を下記表1に示す。
Claims (10)
- 下記工程1又は2:
(工程1)金属材料をジルコニウム化合物及び両性界面活性剤を含有する化成処理液Aで処理する工程、又は
(工程2)下記工程2a及び2bを含む工程;
(工程2a)金属材料をジルコニウム化合物を含有する化成処理液Bで処理する工程、及び
(工程2b)工程2aで得られた化成処理済金属材料をシリカ質皮膜形成用処理液で処理する工程、
を含む、金属材料の処理方法。 - 前記両性界面活性剤がベタイン型両性界面活性剤である、請求項1に記載の処理方法。
- 前記シリカ質皮膜形成用処理液がアルコキシシランオリゴマーを含有する処理液である、請求項1又は2に記載の処理方法。
- 前記シリカ質皮膜形成用処理液がさらにシリカ超微粒子を含有する、請求項3に記載の処理方法。
- 前記シリカ超微粒子がコロイダルシリカである、請求項4に記載の処理方法。
- 金属材料の防錆処理方法である、請求項1〜5のいずれかに記載の処理方法。
- ジルコニウム化合物及び両性界面活性剤を含有する、金属材料の化成処理液。
- アルコキシシランオリゴマーを含有する、金属材料上のジルコニウム含有化成処理皮膜に対するシリカ質皮膜形成用処理液。
- 金属材料、並びに前記金属材料表面上の防錆皮膜を含み、且つ
前記防錆皮膜が、下記皮膜1又は2:
(皮膜1)ジルコニウム及び両性界面活性剤を含有する化成処理皮膜1、又は
(皮膜2)下記皮膜2a及び2bからなる皮膜2;
(皮膜2a)ジルコニウムを含有する化成処理皮膜2a、及び
(皮膜2b)前記化成処理皮膜2a上のシリカ質皮膜2b、
からなる、防錆皮膜含有金属材料。 - 下記工程1又は2:
(工程1)金属材料をジルコニウム化合物及び両性界面活性剤を含有する化成処理液Aで処理する工程、又は
(工程2)下記工程2a及び2bを含む工程;
(工程2a)金属材料をジルコニウム化合物を含有する化成処理液Bで処理する工程、及び
(工程2b)工程2aで得られた化成処理済金属材料をシリカ質皮膜形成用処理液で処理する工程、
を含む、防錆皮膜含有金属材料を製造する方法。
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