JP2784325B2 - Colored and lubricated galvanized steel sheet with high end face corrosion resistance and its manufacturing method - Google Patents
Colored and lubricated galvanized steel sheet with high end face corrosion resistance and its manufacturing methodInfo
- Publication number
- JP2784325B2 JP2784325B2 JP6146468A JP14646894A JP2784325B2 JP 2784325 B2 JP2784325 B2 JP 2784325B2 JP 6146468 A JP6146468 A JP 6146468A JP 14646894 A JP14646894 A JP 14646894A JP 2784325 B2 JP2784325 B2 JP 2784325B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- resin
- film
- weight
- corrosion resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000005260 corrosion Methods 0.000 title claims description 43
- 230000007797 corrosion Effects 0.000 title claims description 43
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims description 22
- 239000008397 galvanized steel Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920005989 resin Polymers 0.000 claims description 80
- 239000011347 resin Substances 0.000 claims description 80
- 229910000831 Steel Inorganic materials 0.000 claims description 74
- 239000010959 steel Substances 0.000 claims description 74
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 36
- 238000007747 plating Methods 0.000 claims description 27
- -1 alkali metal salt Chemical class 0.000 claims description 26
- 239000002585 base Substances 0.000 claims description 26
- 230000001050 lubricating effect Effects 0.000 claims description 26
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 238000005275 alloying Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008199 coating composition Substances 0.000 claims description 7
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- MZZSDCJQCLYLLL-UHFFFAOYSA-N Secalonsaeure A Natural products COC(=O)C12OC3C(CC1=C(O)CC(C)C2O)C(=CC=C3c4ccc(O)c5C(=O)C6=C(O)CC(C)C(O)C6(Oc45)C(=O)OC)O MZZSDCJQCLYLLL-UHFFFAOYSA-N 0.000 claims 2
- 239000010408 film Substances 0.000 description 86
- 238000000576 coating method Methods 0.000 description 19
- 238000012545 processing Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 17
- 239000000049 pigment Substances 0.000 description 17
- 230000003746 surface roughness Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000001993 wax Substances 0.000 description 9
- 238000013461 design Methods 0.000 description 8
- 238000004040 coloring Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 4
- 229910052912 lithium silicate Inorganic materials 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- CHDVXKLFZBWKEN-UHFFFAOYSA-N C=C.F.F.F.Cl Chemical compound C=C.F.F.F.Cl CHDVXKLFZBWKEN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
Landscapes
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Lubricants (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、自動車、家電、建材製
品等の外装用に使用するのに好適な表面外観を有し、か
つ潤滑性と耐食性、特に端面耐食性に優れた、着色化潤
滑処理亜鉛系めっき鋼板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored lubricating material having a surface appearance suitable for use in exteriors of automobiles, home appliances, building materials and the like, and having excellent lubricity and corrosion resistance, particularly excellent end face corrosion resistance. It relates to a treated galvanized steel sheet.
【0002】[0002]
【従来の技術】近年、地球環境破壊の防止対策が世界的
な問題としてとりあげられており、中でも強烈な紫外線
から我々を守っているオゾン層の破壊防止は重要な課題
である。1987年9月モントリオールでフロン規制の議定
書が採択されたのをはじめ、わが国でも1988年に国内法
が成立するなど、フロンや水質汚染の原因となるトリク
レンなどの有機溶剤の使用が規制されるようになってい
る。2. Description of the Related Art In recent years, measures to prevent the destruction of the global environment have been taken up as a global problem. Above all, prevention of destruction of the ozone layer, which protects us from intense ultraviolet rays, is an important issue. The use of organic solvents such as chlorofluorocarbons and trichlene, which causes water pollution, will be regulated, including the adoption of the Protocol on the Regulation of CFCs in Montreal in September 1987 and the enactment of a domestic law in 1988 in Japan. It has become.
【0003】一般に鋼板を加工する際には、摩擦抵抗の
低減のためにプレス油を塗布する。塗布されたプレス油
は、加工後の脱脂工程で脱脂される。この脱脂工程でよ
く用いられるトリクロロエタンはオゾン層破壊物質であ
り、1995年には全廃される予定である。[0003] Generally, when processing a steel sheet, press oil is applied to reduce frictional resistance. The applied press oil is degreased in a degreasing step after processing. Trichloroethane, which is often used in this degreasing process, is an ozone-depleting substance and will be completely abolished in 1995.
【0004】さらに、プレス作業職場の環境改善や脱脂
工程省略によるコストダウンの観点から、プレス油塗布
−脱脂工程が省略できる、予め潤滑処理が施された潤滑
処理鋼板に対するニーズが高まっている。このような情
況から、次に例示する各公報に記載されているように、
種々の潤滑処理鋼板がこれまでに提案されている。[0004] Further, from the viewpoint of improving the environment of the press workplace and reducing costs by omitting the degreasing step, there is an increasing need for a lubricated steel sheet which has been subjected to a lubrication treatment and which can omit the press oil application-degreasing step. Under such circumstances, as described in the following gazettes,
Various lubricated steel sheets have been proposed so far.
【0005】特開平3−96337 号:クロメート処理した
電気亜鉛めっき鋼板の表面に、アクリル化エポキシ樹脂
中にフッ素系樹脂粒子およびシリカ粒子を含有する樹脂
皮膜を形成したプレス加工性に優れる樹脂塗装鋼板。 特開平3−17190 号:クロメート処理した亜鉛めっき鋼
板の表面に、フッ素系樹脂粒子およびシリカ粒子を含有
するモンタンワックス酸化物の被膜を形成した潤滑性、
耐食性に優れる表面処理鋼板。 特開平3−17189 号:クロメート処理した亜鉛めっき鋼
板の表面に、ウレタン変性ポリオレフィン系樹脂中にフ
ッ素系樹脂粒子およびシリカ粒子を含有する樹脂皮膜を
形成した潤滑性、耐食性に優れる樹脂塗装鋼板。JP-A-3-96337: A resin-coated steel sheet having excellent press workability in which a resin film containing fluorine-based resin particles and silica particles in an acrylated epoxy resin is formed on the surface of an electrogalvanized steel sheet subjected to a chromate treatment. . JP-A-3-17190: lubricity in which a coating of montan wax oxide containing fluororesin particles and silica particles is formed on the surface of a chromate-treated galvanized steel sheet;
Surface treated steel sheet with excellent corrosion resistance. JP-A-3-17189: A resin coated steel sheet having excellent lubricity and corrosion resistance in which a resin film containing fluorine resin particles and silica particles in a urethane-modified polyolefin resin is formed on the surface of a chromate-treated galvanized steel sheet.
【0006】特開平3−28380 号:亜鉛系(=亜鉛また
は亜鉛合金)電気めっき鋼板の表面にクロメート皮膜を
形成し、その上にフッ素系樹脂を含有するカルボキシル
化したポリエチレン系ディスパージョンの塗布層を有す
る潤滑性および耐食性に優れる表面処理鋼板。 特開平3−16726 号:亜鉛系電気または溶融めっき鋼板
の表面にクロメート皮膜を形成し、その上に水酸基およ
び/またはカルボキシル基を有する樹脂中にシリカとポ
リオレフィンワックスとを含有する樹脂皮膜を有する成
形性に優れた潤滑樹脂処理鋼板。 これらは、いずれも、電気亜鉛系めっきおよびおよび/
または溶融亜鉛めっき鋼板を母材として使用し、色調と
しては、下地の亜鉛系めっきに特有の金属光沢があるた
め、意匠性に劣る。JP-A-3-28380: A coating layer of a carboxylated polyethylene-based dispersion containing a fluorine-based resin on which a chromate film is formed on the surface of a zinc-based (= zinc or zinc alloy) electroplated steel sheet Surface treated steel sheet with excellent lubricity and corrosion resistance. JP-A-3-16726: Forming a chromate film on the surface of a zinc-based electric or hot-dip coated steel sheet, and forming thereon a resin film containing silica and a polyolefin wax in a resin having a hydroxyl group and / or a carboxyl group. Lubricated resin-treated steel sheet with excellent resistance. These are all electrogalvanized and / or
Alternatively, a hot-dip galvanized steel sheet is used as a base material, and the color tone is poor in design because it has a metallic luster unique to the underlying zinc-based plating.
【0007】近年、コストダウンの観点から、これら潤
滑処理鋼板を、従来はプレコート鋼板が用いられていた
外装用鋼板にも適用しようとする試みがあるが、これま
での潤滑処理鋼板では、外装用としての適用は困難であ
った。[0007] In recent years, from the viewpoint of cost reduction, there has been an attempt to apply these lubricated steel sheets to exterior steel sheets in which a pre-coated steel sheet has been used in the past. Was difficult to apply.
【0008】着色外観を有する潤滑処理鋼板として、特
開平2−263633号公報には、亜鉛系めっき鋼板の表面に
クロメート皮膜を形成し、その上にシリカとポリエチレ
ンワックスと着色顔料とを含有する有機溶剤型塗料組成
物を塗布した高耐食性着色薄膜塗装鋼板が提案されてい
る。この塗装鋼板は、樹脂皮膜を顔料で着色しているだ
け製造コストが高い。さらに、顔料を塗料中に均一に分
散するのが難しいため、均一に着色した樹脂皮膜を安定
して形成することが困難であり、やはり外装用としての
使用は困難な、意匠性が低下したものとなる。As a lubricated steel sheet having a colored appearance, Japanese Patent Application Laid-Open No. Hei 2-263633 discloses an organic material containing a chromate film formed on the surface of a galvanized steel sheet and containing silica, polyethylene wax and a coloring pigment thereon. A highly corrosion-resistant colored thin-film coated steel sheet coated with a solvent-type coating composition has been proposed. The production cost of this coated steel sheet is high because the resin film is colored with a pigment. In addition, it is difficult to uniformly disperse the pigment in the paint, so that it is difficult to stably form a uniformly colored resin film, which is also difficult to use as an exterior, and has a poor design. Becomes
【0009】[0009]
【発明が解決しようとする課題】本発明の目的は、プレ
ス油塗布−脱脂工程を省略して加工することができ、し
かも顔料を使用せずに好ましい外観に着色された、外装
用としての適用が可能な、潤滑性、耐食性、意匠性に優
れた表面処理鋼板を提供することである。SUMMARY OF THE INVENTION It is an object of the present invention to provide an outer casing which can be processed without the press oil application-degreasing step and which is colored to a preferable appearance without using a pigment. It is an object of the present invention to provide a surface-treated steel sheet which is excellent in lubricity, corrosion resistance and design.
【0010】本発明のより具体的な目的は、上述した従
来の潤滑処理鋼板が示すのと同等の潤滑性能を示す(即
ち、潤滑性に優れ、強加工における極圧や金型の温度上
昇に対しても、十分に耐えることができる)と同時に、
顔料を使用せずに着色化してプレコート鋼板なみの意匠
性も兼ね備え、しかも鋼板の端面や鋼板の加工後にも高
耐食性を保持し、溶接も可能な、着色潤滑処理溶融亜鉛
系めっき鋼板を提供することである。A more specific object of the present invention is to exhibit the same lubricating performance as that of the above-mentioned conventional lubricated steel sheet (that is, excellent lubricity, extreme pressure in heavy working and temperature rise of the mold). Can be well tolerated)
To provide a colored lubricated hot-dip galvanized steel sheet that is colored without using a pigment and has the same design properties as a pre-coated steel sheet, yet retains high corrosion resistance even after processing the end face of the steel sheet and the steel sheet and can be welded. That is.
【0011】[0011]
【課題を解決するための手段】前述した従来技術に見ら
れるように、電気亜鉛めっきまたは溶融亜鉛めっき鋼板
の表面にクロメート処理後、潤滑成分を含有する潤滑性
樹脂皮膜を形成すると、母材めっき鋼板の潤滑性、耐食
性を向上させることができる。As described in the above-mentioned prior art, when a lubricating resin film containing a lubricating component is formed on a surface of an electrogalvanized or hot-dip galvanized steel sheet after a chromate treatment, the base material plating Lubricity and corrosion resistance of the steel sheet can be improved.
【0012】本発明者は、これらの従来技術の長所を生
かしつつ、顔料を添加せずにプレコート鋼板なみの意匠
性を有し、外装用にも適用可能な、潤滑処理鋼板を開発
すべく鋭意検討した結果、母材に特定の合金化溶融亜鉛
めっき鋼板を用いて、クロメート処理を施した後、シリ
カ粒子および潤滑成分を含有する潤滑性樹脂皮膜の形成
を行うと、潤滑性および耐食性に優れ、色調としては落
ち着いたグレー色を呈する表面処理鋼板が得られること
を見出した (特願平5−174302号参照) 。その後、さら
に研究を重ねた結果、樹脂皮膜中に特定の塩基性添加剤
を添加することで、特に端面および加工後の耐食性が著
しく向上することを見出した。The inventor of the present invention has been keen to develop a lubricated steel sheet which has the same design properties as a pre-coated steel sheet without adding a pigment and can be applied to exteriors, while taking advantage of these advantages of the prior art. As a result of the examination, using a specific alloyed hot-dip galvanized steel sheet as the base material, after performing chromate treatment, and forming a lubricating resin film containing silica particles and lubricating components, excellent lubrication and corrosion resistance It has been found that a surface-treated steel sheet having a calm gray color can be obtained (see Japanese Patent Application No. 5-174302). Thereafter, as a result of further studies, it was found that the addition of a specific basic additive to the resin film significantly improved the corrosion resistance particularly at the end face and after processing.
【0013】本発明は、合金化溶融亜鉛めっき鋼板の表
面に、Cr換算付着量10〜150 mg/m2のクロメート皮膜
と、その上層の樹脂皮膜とを有し、前記樹脂皮膜が、ベ
ース樹脂(A) 中に、シリカ粒子(B) をSiO2として5〜30
重量%、潤滑機能付与剤(C) を0.5〜30重量%、および
塩基性アルカリ金属塩(D) を1〜10重量%含有し、着色
顔料を含まない、乾燥皮膜重量 0.1〜5g/m2の潤滑性樹
脂皮膜であることを特徴とする、端面耐食性に優れた着
色潤滑処理亜鉛系めっき鋼板を要旨とする。[0013] The present invention provides a galvannealed steel sheet having, on the surface thereof, a chromate film having an adhesion amount of 10 to 150 mg / m 2 in terms of Cr and a resin film thereon, wherein the resin film is a base resin. In (A), silica particles (B) are converted into SiO 2 by 5 to 30.
0.1 to 5 g / m 2 , containing 0.5 to 30% by weight of a lubricating function-imparting agent (C) and 1 to 10% by weight of a basic alkali metal salt (D) and containing no coloring pigment. The present invention provides a colored lubricated zinc-coated steel sheet having excellent end face corrosion resistance, characterized in that it is a lubricating resin film.
【0014】好ましくは、この着色潤滑処理亜鉛系めっ
き鋼板は、表面の色調がJIS Z8729の L* a* b* 表色
系で、50≦ L* ≦62、−1≦ a* ≦0 、−2≦ b* ≦0
である。L * a* b* 表色系において、 L* 値は明度指
数であって、大きいほど明るく、小さいほど暗い。 a*
値は赤緑間の知覚色度 (クロマティクネス) 指数であっ
て、この値が大きいほど赤みが強く、小さい (−の絶対
値が大きい) ほど緑みが強い。 b* 値は黄青間の知覚色
度指数であって、大きいほど黄みが強く、小さい (−の
絶対値が大きい) ほど青みが強い。 L* a* b* の各値
が上記範囲内の色調は実質的にグレーである。[0014] Preferably, the colored lubricated galvanized steel sheet, the color tone of the surface in the L * a * b * color system of JIS Z8729, 50 ≦ L * ≦ 62, -1 ≦ a * ≦ 0, - 2 ≦ b * ≦ 0
It is. In the L * a * b * color system, the L * value is a lightness index. a *
The value is the perceived chromaticity (chromaticity) index between red and green. The larger the value, the more reddish, and the smaller (the absolute value of − is larger), the more greenish. The b * value is a perceived chromaticity index between yellow and blue. The larger the value, the more yellowish, and the smaller (the absolute value of − is larger), the more bluish. The color tone in which each value of L * a * b * is within the above range is substantially gray.
【0015】好適態様にあっては、前記潤滑機能付与剤
(C) は、軟化点90℃以上のポリオレフィン系ワックスお
よび/またはフッ素系樹脂の平均粒径5μm以下の微粉
末からなる。In a preferred embodiment, the lubricating function-imparting agent
(C) is a fine powder of a polyolefin wax having a softening point of 90 ° C. or higher and / or a fluororesin having an average particle diameter of 5 μm or less.
【0016】この着色潤滑処理亜鉛系めっき鋼板は、合
金化度7〜13%の合金化溶融亜鉛めっき鋼板を母材と
し、まずクロメート処理して、めっき表面にCr換算付着
量10〜150 mg/m2のクロメート皮膜を形成した後、不揮
発分合計量に対してシリカ粒子をSiO2として5〜30重量
%、潤滑機能付与剤を 0.5〜30重量%、および塩基性ア
ルカリ金属塩を1〜10重量%含有し、着色顔料を含まな
い樹脂塗料組成物を用いて、クロメート皮膜上に乾燥皮
膜重量で 0.1〜5g/m2の樹脂皮膜を形成することにより
製造できる。This colored lubricated galvanized steel sheet is prepared by using a galvannealed steel sheet having a degree of alloying of 7 to 13% as a base material, and then chromate-treating the coating surface to 10 to 150 mg / Cr equivalent deposition amount on the plating surface. After forming a chromate film of m 2 , 5-30% by weight of silica particles as SiO 2 , 0.5-30% by weight of a lubricating function-imparting agent, and 1-10% It can be produced by forming a resin film having a dry film weight of 0.1 to 5 g / m 2 on a chromate film using a resin coating composition containing no color pigment and containing 0.1% by weight.
【0017】[0017]
【作用】以下に、本発明の着色潤滑処理亜鉛系めっき鋼
板とその製造方法について詳細に説明する。The colored lubricated galvanized steel sheet of the present invention and the method for producing the same will be described in detail below.
【0018】母材めっき鋼板 本発明の着色潤滑処理鋼板の母材は合金化溶融亜鉛めっ
き鋼板 (以下、GA鋼板と略記する) 、即ち、溶融亜鉛
めっき鋼板をめっき後に加熱処理して、めっき皮膜中の
Znの一部を素地のFeと合金化させた亜鉛系めっき鋼板で
ある。母材として用いるGA鋼板は、めっき皮膜の合金
化度(めっき皮膜中の平均Fe%)が7〜13%の範囲内の
ものが望ましい。この合金化度は、より望ましくは9〜
11%である。GA鋼板は、合金化が進み、めっき皮膜の
合金化度が高くなるほど、めっき表面の凹凸が大きくな
り、表面粗さが大きくなる傾向がある。など、GA鋼板
は、Feと合金化させた後、スキンパスで圧下させた (圧
下率0〜3%) ものでもよい。Base Metal Plated Steel Sheet The base material of the colored lubricated steel sheet of the present invention is an alloyed hot-dip galvanized steel sheet (hereinafter abbreviated as GA steel sheet), that is, a hot-dip galvanized steel sheet is subjected to a heat treatment after plating to form a coating film. In
This is a galvanized steel sheet in which a part of Zn is alloyed with the base Fe. The GA steel sheet used as the base material preferably has a degree of alloying of the plating film (average Fe% in the plating film) in the range of 7 to 13%. This alloying degree is more preferably from 9 to
11%. GA steel sheets tend to be alloyed, and the higher the degree of alloying of the plating film, the greater the roughness of the plating surface and the greater the surface roughness. For example, the GA steel sheet may be alloyed with Fe and then reduced by a skin pass (a reduction rate of 0 to 3%).
【0019】本発明の着色潤滑処理鋼板は、このGA鋼
板のめっき皮膜の上にクロメート皮膜を形成し、その上
にシリカ、潤滑成分、および塩基性アルカリ金属塩を含
有し、顔料を含まない樹脂皮膜を形成したものである。
上層の樹脂皮膜は、顔料を含有しないクリアータイプの
ものであるにもかかわらず、樹脂皮膜の被覆により外観
の色調が暗色化し、GA鋼板が有していた金属光沢が消
えて、好ましいグレーの色調に変化し、プレコート鋼板
なみの意匠性をもたらす。The colored lubricated steel sheet of the present invention is a resin which contains a chromate film on the plating film of the GA steel sheet, contains silica, a lubricating component, and a basic alkali metal salt, and contains no pigment. It is a film formed.
Although the upper resin film is of a clear type that does not contain a pigment, the appearance of the color tone is darkened by the coating of the resin film, the metallic luster of the GA steel sheet disappears, and a preferable gray color tone To give a design similar to that of pre-coated steel sheets.
【0020】このように色調が変化する理由は、母材に
表面凹凸の大きい合金化溶融亜鉛めっき鋼板を用いるこ
とで、下地のめっき表面の凹凸が光が乱反射させ、樹脂
中での光路長が長くなることによって、光が樹脂中で吸
収される割合が多くなるため、母材GA鋼板よりも暗く
見えるものと考えられる。The reason why the color tone changes in this way is that the use of an alloyed hot-dip galvanized steel sheet having large surface irregularities as a base material causes irregularities on the plating surface of the base to cause irregular reflection of light, thereby reducing the optical path length in the resin. It is considered that the longer the length, the more light is absorbed in the resin, so that it looks darker than the base GA steel sheet.
【0021】電気亜鉛系めっきや溶融亜鉛めっきなどの
他のめっきでは、表面が比較的平滑であるので、クロメ
ート皮膜と透明樹脂皮膜で被覆した時に、上記のような
暗色化への色調の変化は認められない。即ち、この色調
の変化は、加熱処理により表面粗さが増大したGA鋼板
のめっき皮膜に特有なものである。In other platings such as electro-zinc plating and hot-dip galvanizing, the surface is relatively smooth, so when coated with a chromate film and a transparent resin film, the above-mentioned change in color tone to darkening does not occur. unacceptable. That is, this change in color tone is peculiar to the plating film of the GA steel sheet whose surface roughness has been increased by the heat treatment.
【0022】この暗色化で得られる色調は、GA鋼板の
めっき皮膜の表面粗さによって変化し、表面粗さが大き
くなると、暗色化が進み、色調がより黒っぽくなる。め
っき皮膜の合金化度が7%以下では、その表面粗さが小
さく、めっき皮膜表面の凹凸が不十分なために、十分な
暗さが得られない。しかし、めっき皮膜の合金化度が13
%を超えると、色調としてはさらに暗くなるものの、表
面の凹凸が大きすぎてめっき皮膜が脆くなる結果、加工
時にパウダリング現象を起こしやすくなる。母材として
用いるGA鋼板の合金化度が7〜13%であると、加工性
を低下させずに、好ましくは前述した50≦ L* ≦62、−
1≦ a* ≦0 、−2≦ b* ≦0 で規定される、グレーの
色調の外観を得ることができる。The color tone obtained by this darkening changes depending on the surface roughness of the plating film of the GA steel sheet. As the surface roughness increases, darkening progresses and the color tone becomes darker. When the degree of alloying of the plating film is 7% or less, sufficient darkness cannot be obtained because the surface roughness is small and the unevenness of the plating film surface is insufficient. However, the degree of alloying of the plating film was 13
%, The color tone becomes darker, but the surface irregularities are too large and the plating film becomes brittle, so that the powdering phenomenon is likely to occur during processing. When the degree of alloying of the GA steel sheet used as the base material is 7 to 13%, preferably, the above-mentioned 50 ≦ L * ≦ 62, −
An appearance having a gray color tone defined by 1 ≦ a * ≦ 0 and −2 ≦ b * ≦ 0 can be obtained.
【0023】なお、母材のGA鋼板は、そのめっき表面
に本発明に従ってクロメート皮膜と樹脂皮膜とを形成し
た時に、表面がグレーの色調、好ましくは上記範囲内の
L*値、 a* 値、 b* 値のグレーの色調になればよいわ
けであり、その意味では特に制限されるものではない。
しかし、上に説明したように、合金化度が7〜13%のG
A鋼板を母材とすると上記の色調が一般に得られるの
で、本発明の着色潤滑処理鋼板の製造時にはこのような
合金化度のGA鋼板を母材として使用すればよい。合金
化度が高いほど色調が暗くなるので、所望の色調 (暗
さ) に応じて母材GA鋼板の合金化度を選択することが
できる。The GA steel as the base material, when a chromate film and a resin film are formed on the plated surface according to the present invention, the surface has a gray tone, preferably within the above range.
It suffices if the color tone is a gray tone of L * value, a * value, and b * value, and in that sense, there is no particular limitation.
However, as explained above, G with a degree of alloying of 7-13%
When the steel sheet A is used as a base material, the above color tone is generally obtained. Therefore, when manufacturing the colored lubricated steel sheet of the present invention, a GA steel sheet having such an alloying degree may be used as a base material. Since the higher the degree of alloying, the darker the color tone, the degree of alloying of the base material GA steel sheet can be selected according to the desired color tone (darkness).
【0024】GA鋼板のめっき皮膜の合金化度は前述の
ように表面粗さと相関するので、合金化度の代わりに、
GA鋼板のめっき表面粗さを尺度にして母材のGA鋼板
を選択することもできる。めっき皮膜の表面粗さは一般
にRa= 0.5〜2.0 μmの範囲内が好ましい。この範囲内
で表面粗さが大きいほど色調が暗くなるので、所望の色
調となるように母材GA鋼板をめっき表面粗さで選択す
ることもできる。より好ましい表面粗さの範囲は 0.8〜
1.5 μmである。Since the degree of alloying of the plating film of the GA steel sheet is correlated with the surface roughness as described above, instead of the degree of alloying,
The GA steel sheet of the base material can be selected based on the plating surface roughness of the GA steel sheet. Generally, the surface roughness of the plating film is preferably in the range of Ra = 0.5 to 2.0 μm. Since the color tone becomes darker as the surface roughness increases within this range, the base material GA steel sheet can also be selected based on the plating surface roughness so that the desired color tone is obtained. A more preferable surface roughness range is 0.8 to
1.5 μm.
【0025】GA鋼板のめっき付着量は特に制限されな
いが、耐食性と加工性の兼ね合いから、片面当たり30〜
60 g/m2 の範囲内が好ましい。このように、本発明の着
色潤滑処理鋼板の着色は、最上層の樹脂皮膜中に着色顔
料を添加して得たものではないので、顔料の分散性や安
定性を心配する必要はなく、均一で安定した色調を得る
ことができる。また、高価な着色顔料を使用しないの
で、コスト面でも有利である。The coating weight of the GA steel sheet is not particularly limited. However, from the viewpoint of the balance between corrosion resistance and workability, 30 to 30% per side is required.
It is preferably in the range of 60 g / m 2 . As described above, since the coloring of the colored lubricated steel sheet of the present invention is not obtained by adding a coloring pigment to the uppermost resin film, there is no need to worry about the dispersibility and stability of the pigment, and And a stable color tone can be obtained. In addition, since an expensive coloring pigment is not used, it is advantageous in terms of cost.
【0026】クロメート皮膜 合金化溶融亜鉛めっきのめっき表面 (通常は両面である
が、片面であっても構わない) に形成するクロメート皮
膜は、公知の通常のクロメート皮膜でよく、6価クロム
化合物がCr3+に還元されて難溶化することにより造膜し
たものである。クロメート処理液としては、例えば、無
水クロム酸、クロム酸塩、重クロム酸等の6価クロム化
合物を主剤とする水溶液型のクロメート処理液や、上記
水溶液にコロイダルシリカ等を混合したものなど、公知
のいずれの種類のものも使用でき、処理方法も、浸漬、
塗布、電解、噴霧など特に制限されない。 Chromate film The chromate film formed on the plating surface of the alloyed hot-dip galvanized coating (usually both surfaces, but may be one surface) may be a known ordinary chromate film, and a hexavalent chromium compound may be used. This is a film formed by being reduced to Cr 3+ and becoming hardly soluble. As the chromate treatment liquid, for example, an aqueous solution type chromate treatment liquid mainly containing a hexavalent chromium compound such as chromic anhydride, chromate, and dichromic acid, or a mixture of the above aqueous solution with colloidal silica or the like is known. Any type can be used, and the treatment method is immersion,
There is no particular limitation on application, electrolysis, spraying and the like.
【0027】クロメート皮膜として特に好ましいのは、
耐食性に優れた塗布型クロメート処理液、中でも迅速な
造膜が可能な部分還元タイプのもの (Cr6+の一部がCr3+
に還元されたもの) を使用して形成されたものである。
必要により、処理後に加熱して、クロメート皮膜を形成
する。Particularly preferred as a chromate film is
A coating-type chromate treatment solution with excellent corrosion resistance, especially a partially reduced type that enables rapid film formation (a part of Cr 6+ is Cr 3+
(Reduced to).
If necessary, heat is applied after the treatment to form a chromate film.
【0028】本発明では、クロメート皮膜の付着量は金
属Cr換算で10〜150 mg/m2 、好ましくは30〜90 mg/m2の
範囲内とする。付着量が10 mg/m2未満では、外装用とし
ての十分な耐食性を発揮することができない。一方、15
0 mg/m2 を超えると、付着量の増加の割合に対しての耐
食性向上効果が少なくなり、表面外観も劣化する上、ク
ロメート皮膜が厚くなることでプレス加工時にクロメー
ト皮膜の凝集破壊が起こり、プレス成形性が低下する。In the present invention, the coating amount of the chromate film is in the range of 10 to 150 mg / m 2 , preferably 30 to 90 mg / m 2 in terms of metal Cr. If the adhesion amount is less than 10 mg / m 2 , sufficient corrosion resistance for exterior use cannot be exhibited. Meanwhile, 15
Exceeds 0 mg / m 2, the corrosion resistance improving effect against rate of increase in the deposition amount is small, on the deterioration surface appearance, occur cohesive failure of the chromate film upon press working by chromate film becomes thick In addition, press formability decreases.
【0029】潤滑性樹脂皮膜 このクロメート皮膜の上に、顔料を含有しない実質的に
透明な潤滑性樹脂皮膜を形成する。この樹脂皮膜は、ベ
ース樹脂(A) 中に、シリカ粒子(B) をSiO2として5〜30
重量%、潤滑機能付与剤(C) を0.5 〜30重量%、および
塩基性アルカリ金属塩(D) を1〜10重量%含有し、付着
量は乾燥皮膜重量で 0.1〜5g/m2である。各成分(A) 〜
(D) はいずれも1種または2種以上を使用することがで
きる。 Lubricant Resin Coating On this chromate coating, a substantially transparent lubricating resin coating containing no pigment is formed. This resin film is formed by converting silica particles (B) into SiO 2 in the base resin (A) by 5 to 30%.
% By weight, 0.5 to 30% by weight of a lubricating function-imparting agent (C), and 1 to 10% by weight of a basic alkali metal salt (D), and the coating amount is 0.1 to 5 g / m 2 in terms of dry film weight. . Each component (A) ~
As (D), one or more kinds can be used.
【0030】(A) ベース樹脂:樹脂皮膜のベース樹脂と
しては、加工に耐える十分な強度を有する、透明皮膜を
形成できるものであればよく、特に制限されない。適当
な樹脂としては、ポリウレタン系樹脂、エポキシ樹脂、
アクリル系樹脂、フェノール系樹脂、ポリオレフィン系
樹脂、アルキド系樹脂、メラミン系樹脂、ポリビニルブ
チラール樹脂等が挙げられる。(A) Base resin: The base resin of the resin film is not particularly limited as long as it has sufficient strength to withstand processing and can form a transparent film. Suitable resins include polyurethane resins, epoxy resins,
An acrylic resin, a phenol resin, a polyolefin resin, an alkyd resin, a melamine resin, a polyvinyl butyral resin, and the like can be given.
【0031】(B) シリカ粒子:シリカ粒子は、潤滑処理
鋼板の耐食性を向上させるために樹脂皮膜中に配合す
る。このシリカ粒子は、コロイダルシリカ (水性シリ
カ) 、例えばスノーテックスC〜N (いずれも日産化学
社製) 等、ならびに気相シリカ粉末、例えば疎水性シリ
カ AEROSIL R-811、親水性シリカ AEROSIL 200V(いずれ
も日本アエロジル社製) 等が使用できる。また、加水分
解によりシリカを生ずる有機シリケート (例、エチルシ
リケート) もシリカ粒子の前駆物ではあるが、シリカ粒
子として本発明において使用できる。シリカ粒子の平均
一次粒子径粒径は、5〜100 nm、好ましくは10〜50 nm
の範囲内が好適である。(B) Silica particles: Silica particles are blended in a resin film in order to improve the corrosion resistance of the lubricated steel sheet. The silica particles include colloidal silica (aqueous silica) such as Snowtex C to N (all manufactured by Nissan Chemical Industries, Ltd.), and gas phase silica powder such as hydrophobic silica AEROSIL R-811 and hydrophilic silica AEROSIL 200V (any Also manufactured by Nippon Aerosil Co., Ltd.). Organic silicates (e.g., ethyl silicate) that produce silica by hydrolysis are also precursors of silica particles, but can be used as silica particles in the present invention. The average primary particle size of the silica particles is 5 to 100 nm, preferably 10 to 50 nm.
Is preferably within the range.
【0032】樹脂皮膜中におけるシリカ粒子の量は、Si
O2として5〜30重量%、好ましくは15〜25重量%の範囲
内である。シリカがSiO2として5重量%よりも少ない
と、耐食性が十分ではなく、外装用としての適用は困難
である。一方、30重量%を超えると、樹脂皮膜の硬度が
高まり、成形時に型カジリを生じ、プレス成形性が低下
する。なお、樹脂とシリカ粒子との密着性を向上させる
ために、シリカ粒子に少量のシランカップリング剤を併
用してもよい。The amount of silica particles in the resin film is
O 2 as 5 to 30 wt%, preferably in the range of 15 to 25 wt%. If the silica content is less than 5% by weight as SiO 2 , the corrosion resistance is not sufficient, and it is difficult to apply it for exterior use. On the other hand, when the content exceeds 30% by weight, the hardness of the resin film is increased, the mold is formed at the time of molding, and the press moldability is reduced. In order to improve the adhesion between the resin and the silica particles, a small amount of a silane coupling agent may be used in combination with the silica particles.
【0033】(C) 潤滑機能付与剤:潤滑機能付与剤とし
ては、潤滑 (摩擦係数軽減) 機能を発揮し (即ち、一般
に固体潤滑剤として知られ) 、かつ樹脂皮膜の透明性を
阻害しない固体粉末を使用する。例えば、黒鉛は皮膜を
黒色化させるので、本発明では使用しない。(C) Lubricating function-imparting agent: The lubricating function-imparting agent is a solid that exhibits a lubricating (reducing friction coefficient) function (that is, is generally known as a solid lubricant) and does not impair the transparency of the resin film. Use powder. For example, graphite is not used in the present invention because it blackens the coating.
【0034】本発明で用いるのに適した潤滑機能付与剤
は、ポリオレフィン系ワックスおよびフッ素系樹脂の粉
末であり、これらは平均粒子径5μm以下の微粉末状で
あることが好ましい。連続加工時には金型温度が90℃近
くに達することがあるので、ポリオレフィン系ワックス
は、連続加工時にも軟化しないように、軟化点が90℃以
上、特に 100℃以上のものを使用することが好ましい。The lubricating function-imparting agent suitable for use in the present invention is a powder of a polyolefin wax or a fluororesin, which is preferably in the form of a fine powder having an average particle diameter of 5 μm or less. Since the mold temperature may reach nearly 90 ° C during continuous processing, it is preferable to use a polyolefin wax having a softening point of 90 ° C or higher, particularly 100 ° C or higher, so as not to soften even during continuous processing. .
【0035】特に好ましいポリオレフィン系ワックス粉
末は、平均粒径 0.6〜1.1 μmで、粒径分布幅が小さ
く、比重 (25℃) が0.95〜0.98、軟化点が 100〜150 ℃
のポリエチレン、ポリプロピレンなどのポリオレフィン
系重合体または共重合体の微粉末である。Particularly preferred polyolefin wax powder has an average particle size of 0.6 to 1.1 μm, a small particle size distribution width, a specific gravity (25 ° C.) of 0.95 to 0.98, and a softening point of 100 to 150 ° C.
Of polyolefin-based polymers or copolymers such as polyethylene and polypropylene.
【0036】フッ素系樹脂としては、四フッ化エチレン
樹脂 (PTFE) 、三フッ化塩化エチレン樹脂、フッ化ビニ
リデン樹脂、フッ化ビニル樹脂エチレン/四フッ化エチ
レン共重合体樹脂、四フッ化エチレン/六フッ化プロピ
レン共重合体樹脂などが挙げられる。フッ素系樹脂粉末
の平均粒径は 0.1〜5μm、特に 0.5〜2μmの範囲内
が好ましい。Examples of the fluororesin include ethylene tetrafluoride resin (PTFE), ethylene trifluoride chloride resin, vinylidene fluoride resin, vinyl fluoride resin ethylene / tetrafluoroethylene copolymer resin, and tetrafluoroethylene resin. Hexafluoropropylene copolymer resin and the like. The average particle size of the fluororesin powder is preferably in the range of 0.1 to 5 μm, particularly preferably 0.5 to 2 μm.
【0037】潤滑機能付与剤は、樹脂皮膜中に3〜30重
量%の割合で存在させる。この量が3重量%よりも少な
いと、潤滑性の向上が少なく、30重量%を超えると、素
地との密着性が低下し、かつ樹脂皮膜強度が低下し、外
観も劣化するからである。潤滑機能付与剤の好ましい配
合量は8〜20重量%の範囲内である。The lubricating function-imparting agent is present in the resin film at a ratio of 3 to 30% by weight. If the amount is less than 3% by weight, the improvement in lubricity is small, and if it exceeds 30% by weight, the adhesion to the substrate is reduced, the strength of the resin film is reduced, and the appearance is also deteriorated. The preferred compounding amount of the lubricating function-imparting agent is in the range of 8 to 20% by weight.
【0038】(D) 塩基性アルカリ金属塩 塩基性アルカリ金属塩を樹脂皮膜中に存在させると、潤
滑処理鋼板の耐食性、特に端面と加工後の耐食性がさら
に向上する。即ち、厳しい加工や連続加工を行う場合に
は、シリカ粒子(B) 成分のみでは十分な耐食性を得るこ
とができず、また樹脂皮膜が形成されない端面において
耐食性を確保することができないが、塩基性アルカリ金
属塩の配合によって、このような問題点が解消される。(D) Basic Alkali Metal Salt When a basic alkali metal salt is present in the resin film, the corrosion resistance of the lubricated steel sheet, particularly the corrosion resistance after the end face and after processing, is further improved. In other words, when severe processing or continuous processing is performed, sufficient corrosion resistance cannot be obtained only with the silica particle (B) component, and corrosion resistance cannot be ensured on the end face where the resin film is not formed. Such a problem is solved by blending the alkali metal salt.
【0039】塩基性アルカリ金属塩としては、アルカリ
金属の水酸化物、炭酸塩、珪酸塩、燐酸塩、硼酸塩、有
機酸塩など、各種の塩基性のアルカリ金属塩を使用でき
る。例えば、水酸化物としてはNaOH、KOH 、LiOH、CsO
H、RbOH が、炭酸塩としてはNaHCO3、Na2CO3、KHCO
3 、K2CO3 、LiHCO3等が、珪酸塩としては珪酸ナトリウ
ム(Na2O・xSiO2)、珪酸カリウム(K2O・xSiO2)、珪酸リ
チウム (Li2O・xSiO2)等が、燐酸塩としてはNa2HPO4 、
K2HPO4等が、硼酸塩としてはNaBO2 、KBO2等などが挙げ
られる。アルカリ金属珪酸塩としては、例えば、Na塩
(珪酸ソーダ)ではx値が2(1号)、2.5 (2号) 、3 (3
号) のものがあり、Li塩ではx値が3.5(珪酸リチウム3
5) 、4.5(珪酸リチウム45) 、7.5(珪酸リチウム5) の
ものがある。As the basic alkali metal salt, various basic alkali metal salts such as hydroxides, carbonates, silicates, phosphates, borates and organic acid salts of alkali metals can be used. For example, hydroxides include NaOH, KOH, LiOH, CsO
H and RbOH are carbonates such as NaHCO 3 , Na 2 CO 3 and KHCO
3, K 2 CO 3, LiHCO 3 and the like, sodium silicate as the silicate (Na 2 O · xSiO 2) , potassium silicate (K 2 O · xSiO 2) , lithium silicate (Li 2 O · xSiO 2) etc. , As phosphates, Na 2 HPO 4 ,
K 2 HPO 4 and the like, and borate salts include NaBO 2 , KBO 2 and the like. As the alkali metal silicate, for example, in the case of a sodium salt (sodium silicate), the x value is 2 (1), 2.5 (2), 3 (3
No.), and the x value of Li salt is 3.5 (lithium silicate 3
5), 4.5 (lithium silicate 45) and 7.5 (lithium silicate 5).
【0040】塩基性アルカリ金属塩を添加すると、特に
端面耐食性や加工後耐食性が向上する理由については、
明らかではないが、このアルカリ金属塩が、特に端面や
加工で生じた微細疵部等の腐食因子が侵入し易い部位で
インヒビターとしての機能を発揮し、Cl- 等の腐食因子
を遮断するからではないかと推測される。なお、この塩
基アルカリ金属塩を添加することにより、樹脂皮膜の形
成に用いる塗料組成物のpHは一般に 7.5〜12のアルカ
リ性を示すようになる。The reason why the addition of the basic alkali metal salt particularly improves the corrosion resistance at the end face and the corrosion resistance after processing is as follows.
Although not clear, the alkali metal salts, in particular for them to serve as an inhibitor in an easy site corrosion factor invades fine flaw portion, etc. produced at the end face and machining, Cl - because blocking the corrosive factors such as It is guessed. The pH of the coating composition used for forming the resin film generally becomes 7.5 to 12 by adding the basic alkali metal salt.
【0041】塩基性アルカリ金属塩は樹脂皮膜中に1〜
10重量%の割合で含有させる。この量が1重量%よりも
少ないと、上述したようなインヒビターとしての効果が
少なく、特に端面等での十分な耐食性が得られない。一
方、10重量%を超えると、樹脂皮膜がゲル化し易くな
り、塗装時にムラとなって、外観上の品質が劣化するだ
けでなく、塗膜も不均一になるので、潤滑性、および平
板での耐食性が劣化する。塩基性アルカリ金属塩の好ま
しい配合量は3〜7重量%である。The basic alkali metal salt is contained in the resin film in an amount of 1 to
It is contained at a ratio of 10% by weight. If this amount is less than 1% by weight, the above-mentioned effect as an inhibitor is small, and sufficient corrosion resistance, particularly at the end face, cannot be obtained. On the other hand, if the content exceeds 10% by weight, the resin film is apt to gel and becomes uneven at the time of coating, not only the appearance quality is deteriorated, but also the coating film becomes non-uniform. The corrosion resistance of the steel deteriorates. The preferred compounding amount of the basic alkali metal salt is 3 to 7% by weight.
【0042】ベース樹脂(A) 中に(B) 〜(D) の各成分を
含有する潤滑性樹脂皮膜は、片面当たりの乾燥皮膜重量
として 0.1〜5g/m2の付着量で形成する。この付着量が
0.1g/m2未満では、潤滑性および耐食性向上効果が少な
く、5g/m2を超えると、耐食性は向上するが、プレス成
形性が低下し、コストも増大する。特に加工後にも良好
な外観を得るには、付着量を1.0 g/m2以上とすることが
好ましい。より好ましい付着量の範囲は 2.0〜4.0 g/m2
である。The lubricating resin film containing the components (B) to (D) in the base resin (A) is formed in an amount of 0.1 to 5 g / m 2 as a dry film weight per one surface. This amount
If it is less than 0.1 g / m 2 , the effect of improving lubricity and corrosion resistance is small, and if it exceeds 5 g / m 2 , the corrosion resistance is improved, but the press formability is reduced and the cost is increased. In particular, in order to obtain a good appearance even after processing, the amount of adhesion is preferably 1.0 g / m 2 or more. A more preferable range of the adhesion amount is 2.0 to 4.0 g / m 2
It is.
【0043】樹脂皮膜の形成に用いる樹脂塗料組成物
は、ベース樹脂(A) のほかに、不揮発分合計量に基づい
て上記所定範囲内の量で成分(B) 〜成分(D) を含有す
る。この塗料組成物には、必要に応じて、架橋剤、消泡
剤などの添加剤を添加してもよい。溶媒の種類は、水、
アルコール、有機溶媒のいずれでもよく、使用する樹脂
種に応じて選択する。塗装方法は、ロールコート、カー
テンフローコートを始めとする各種の塗装方法から状況
に応じて選択すればよい。塗装後の塗膜の乾燥温度は、
樹脂や溶媒の種類に応じて選択する。The resin coating composition used for forming the resin film contains, in addition to the base resin (A), components (B) to (D) in an amount within the above-mentioned predetermined range based on the total amount of nonvolatile components. . If necessary, additives such as a crosslinking agent and an antifoaming agent may be added to the coating composition. The type of solvent is water,
Either alcohol or organic solvent may be used, and it is selected according to the type of resin used. The coating method may be selected from various coating methods such as a roll coat and a curtain flow coat depending on the situation. The drying temperature of the paint film after painting is
Select according to the type of resin and solvent.
【0044】このようにして、合金化溶融亜鉛めっき鋼
板上に上記のクロメート皮膜と潤滑性樹脂皮膜とを形成
した着色潤滑処理亜鉛系めっき鋼板はグレーの色調を有
し、好ましくは L* a* b* 表色系で、50≦ L* ≦62、
−1≦ a* ≦0 、−2≦ b*≦0 という表面色調を有す
る。より好ましくは、52≦ L* ≦56、−0.5 ≦ a* ≦−
0.1 、−0.5 ≦ b* ≦−0.1 である。この表面色調は、
具体的には落ちついたグレー色であり、一見してグレー
の塗料で塗装した塗装鋼板のように見え (即ち、プレコ
ート鋼板なみの意匠性を有し) 、金属光沢は実質的に消
失している。The colored lubricated zinc-coated steel sheet having the above-described chromate film and lubricating resin film formed on the alloyed hot-dip galvanized steel sheet has a gray color, preferably L * a *. b * color system, 50 ≦ L * ≦ 62,
It has a surface tone of -1 ≦ a * ≦ 0 and −2 ≦ b * ≦ 0. More preferably, 52 ≦ L * ≦ 56, −0.5 ≦ a * ≦ −
0.1, −0.5 ≦ b * ≦ −0.1. This surface tone is
Specifically, it is a calm gray color, and at first glance it looks like a painted steel sheet painted with gray paint (that is, it has the design property of a pre-coated steel sheet), and the metallic luster has virtually disappeared .
【0045】また、本発明の着色潤滑処理亜鉛系めっき
鋼板は、最上層の樹脂皮膜が十分な摩擦低減作用を示
し、潤滑油を塗布せずに、連続プレス成形や厳しい加工
を施すことができ、しかも加工後や端面の耐食性も十分
に高い。Further, the colored lubricated zinc-coated steel sheet of the present invention can be subjected to continuous press forming or severe processing without applying a lubricating oil, because the uppermost resin film exhibits a sufficient friction reducing effect. In addition, the corrosion resistance after processing and at the end face is sufficiently high.
【0046】[0046]
【実施例】以下に実施例を挙げて本発明をさらに説明す
るが、本発明は実施例により何ら限定されるものではな
い。EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to the examples.
【0047】既存の溶融亜鉛めっきラインで生産された
溶融亜鉛めっき鋼板 (板厚0.6 mm、両面めっき、片面当
たりめっき付着量45 g/m2)を、温度および/または処理
時間を変えて塩浴に浸漬して熱処理し、合金化度の異な
るGA鋼板を作製した。各GA鋼板(300×200 mm) の片
面のめっき表面に、市販の部分還元塗布型クロメート処
理液をスピンコーターにより塗布し、80℃で30秒間乾燥
して、クロメート皮膜を形成した。次いで、このクロメ
ート皮膜の上に、シリカ粒子 (平均粒径20 nm のコロイ
ダルシリカ) 、ポリエチレンワックス (平均粒径1μ
m) 、および塩基性アルカリ金属塩を含有する、無顔料
のクリアー樹脂塗料組成物を、バーコーターにて乾燥後
に所定の付着量となるように塗布し、120 ℃で30秒間乾
燥させ、樹脂皮膜を形成して、着色潤滑処理GA鋼板を
得た。A hot-dip galvanized steel sheet (0.6 mm thick, double-sided plating, coating weight per side of 45 g / m 2 ) produced in the existing hot-dip galvanizing line was subjected to salt bath by changing the temperature and / or the processing time. And heat-treated to produce GA steel sheets having different degrees of alloying. A commercially available partially reduced coating type chromate treatment solution was applied to one plating surface of each GA steel plate (300 × 200 mm) using a spin coater, and dried at 80 ° C. for 30 seconds to form a chromate film. Next, silica particles (colloidal silica having an average particle diameter of 20 nm) and polyethylene wax (an average particle diameter of 1 μm) were placed on the chromate film.
m) and a non-pigmented clear resin coating composition containing a basic alkali metal salt, dried with a bar coater, applied so as to have a predetermined adhesion amount, and dried at 120 ° C. for 30 seconds to obtain a resin film. Was formed to obtain a colored lubricated GA steel sheet.
【0048】表1に、使用した母材GA鋼板のめっき皮
膜の合金化度 (Fe%) および表面粗さ (Ra値) 、クロメ
ート皮膜の付着量、樹脂皮膜のベース樹脂、樹脂皮膜中
のシリカ粒子とポリエチレンワックスの含有量および塩
基性アルカリ金属塩の種類と量、ならびに樹脂皮膜の付
着量をまとめて示す。Table 1 shows the degree of alloying (Fe%) and surface roughness (Ra value) of the plating film of the base material GA steel sheet used, the amount of the chromate film attached, the base resin of the resin film, and the silica in the resin film. The contents of the particles and the polyethylene wax, the type and amount of the basic alkali metal salt, and the adhesion amount of the resin film are collectively shown.
【0049】得られた着色潤滑処理GA鋼板について、
色調、耐食性、加工後耐食性、潤滑性の各性能を下記の
要領で調べた。 [試験方法]色調 :色彩色差計 (ミノルタ社製、CR-300) を用いて、
L* 値、 a* 値、 b* 値を測定した。耐食性 :塩水噴霧(SST) 試験 (JIS Z-2371に準ずる) に
よる白錆発生時間で耐食性を評価した。Regarding the obtained colored lubricated GA steel sheet,
The color tone, corrosion resistance, corrosion resistance after processing, and lubricity were examined in the following manner. [Test method] Color : Using a colorimeter (CR-300, manufactured by Minolta),
L * value, a * value, b * value were measured. Corrosion resistance : The corrosion resistance was evaluated based on the white rust generation time by a salt spray (SST) test (according to JIS Z-2371).
【0050】端面耐食性は、上記のSST 試験において、
白錆発生時の試験片の端面からの白錆発生幅の測定値に
基づき次の基準で評価した。 ◎:1mm以下 ○:1〜3mm △:1〜10mm ×:10mm以上加工後耐食性 :試験片に曲げ直径10 mm の 180°曲げ加
工を行い、その後、耐食性と同様に塩水噴霧試験を行っ
て、白錆発生時間を調べた。The end surface corrosion resistance was determined by the above SST test.
Based on the measured value of the white rust generation width from the end face of the test piece when white rust was generated, evaluation was made according to the following criteria. ◎: 1 mm or less ○: 1 to 3 mm △: 1 to 10 mm ×: 10 mm or more Corrosion resistance : A test piece was subjected to 180 ° bending with a bending diameter of 10 mm, and then a salt spray test was performed in the same manner as the corrosion resistance. The white rust generation time was examined.
【0051】潤滑性:バウデン摩擦試験による摩擦係
数と、ビード付きハット成形試験によるプレス成形性
とで評価した。 バウデン摩擦試験:図1(a) に示す測定装置を用い、
荷重1kg、摺動速度4mm/sec、摺動距離20 mm の条件で
摩擦係数を測定した。 ビード付きハット成形試験:図1(b) に示すビード付
きクランクプレスを使用して、 250×50 mm の試験片を
ハット型に深絞り成形した。ビード高さは7mm、成形高
さは43 mm 、成形速度は70 mm/sec であった。成形品の
しごき部の外観を観察して、◎(良好、観変化なし) →
○ → △ → ×(不可、カジリ発生大、パウダリ
ング大) の4段階で評価した。これらの試験結果は表2
にまとめて示す。 Lubricity : The lubricity was evaluated based on a friction coefficient according to a Bowden friction test and a press moldability according to a hat forming test with beads. Bowden friction test: Using the measuring device shown in FIG.
The friction coefficient was measured under the conditions of a load of 1 kg, a sliding speed of 4 mm / sec, and a sliding distance of 20 mm. Hat forming test with bead: Using a crank press with a bead as shown in FIG. 1 (b), a 250 × 50 mm test piece was deep drawn into a hat shape. The bead height was 7 mm, the forming height was 43 mm, and the forming speed was 70 mm / sec. Observe the appearance of the ironed part of the molded product, ◎ (good, no change) →
→→ で → × (not possible, large occurrence of galling, large powdering). Table 2 shows the test results.
Are shown together.
【0052】[0052]
【表1】 [Table 1]
【0053】[0053]
【表2】 [Table 2]
【0054】[0054]
【発明の効果】表1からわかるように、本発明例の潤滑
処理鋼板はいずれも色調が好ましいの範囲内の良好なグ
レー色を呈し、耐食性 (端面と加工後耐食性を含む) と
潤滑性(摩擦係数とプレス成形性) も良好であった。な
お、ポリエチレンワックス粉末に代えて、フッ素樹脂粉
末 (例、PTFE) を使用した場合にも、表1と同様の結果
が得られることを確認した。一方、本発明の範囲外の条
件 (*印)を含む比較例では、少なくとも一つの性能が
劣化した。As can be seen from Table 1, each of the lubricated steel sheets of the present invention exhibits a good gray color within a preferable range of color tone, and has corrosion resistance (including corrosion resistance after the end face and after processing) and lubricity ( The coefficient of friction and press formability) were also good. In addition, it was confirmed that the same results as in Table 1 were obtained when a fluororesin powder (eg, PTFE) was used instead of the polyethylene wax powder. On the other hand, in a comparative example including a condition (marked with *) out of the range of the present invention, at least one performance was deteriorated.
【0055】本発明による着色潤滑処理亜鉛系めっき鋼
板は、最上層の樹脂皮膜が着色顔料を含有しない透明皮
膜であるにもかかわらず、GA鋼板の金属光沢が消え、
外観は落ち着いたグレー色を呈し、プレコート鋼板並み
の意匠性を有している。従って、そのままで自動車、家
電製品、建材などに外装用としての適用が可能であるた
め、これらの製品の著しいコスト低減が図れる。The colored lubricated galvanized steel sheet according to the present invention has a GA steel sheet whose metallic luster disappears despite the fact that the uppermost resin film is a transparent film containing no coloring pigment.
The appearance is a calm gray color, and it has a design property comparable to that of a precoated steel sheet. Therefore, since it can be applied to automobiles, home electric appliances, building materials, and the like for exterior use, the cost of these products can be significantly reduced.
【0056】また、潤滑性に優れ、強加工における極圧
や金型の温度上昇に対しても、十分に耐えることができ
るため、プレス加工時に、プレス油等の潤滑油を使用せ
ずに、そのままプレス加工が可能である。従って、従
来、需要家で行われていたプレス油塗布作業やそのプレ
ス油を除去する脱脂工程が省略でき、それによるコスト
節減が図れる上に、トリクロロエタンなどの有害な溶剤
の使用が回避されることから、環境破壊の防止にもつな
がる。Further, since it has excellent lubricity and can sufficiently withstand extreme pressure and temperature rise of a metal mold in strong working, the lubricating oil such as press oil is not used at the time of press working. Press working is possible as it is. Therefore, it is possible to omit the press oil application work and the degreasing step of removing the press oil which have been conventionally performed by the consumer, thereby reducing costs and avoiding the use of harmful solvents such as trichloroethane. Therefore, it leads to prevention of environmental destruction.
【0057】さらに、本発明の鋼板は、顔料を使用せず
に着色化されているため、着色が均一で安定しており、
樹脂皮膜の形成時の塗料の塗布も容易である上、顔料を
使用しない分だけ安価である。また、樹脂皮膜が薄いた
め、GA鋼板が持つ溶接性やプレス加工性といった望ま
しい特性が保持され、端面や加工後も高い耐食性を発揮
することができる。このように、本発明の鋼板、そのま
まで外装用に使用するのに適しているが、もちろん塗装
を施して使用してもよい。Furthermore, since the steel sheet of the present invention is colored without using a pigment, the coloring is uniform and stable.
It is easy to apply the paint at the time of forming the resin film, and is inexpensive because no pigment is used. Further, since the resin film is thin, desirable properties such as weldability and press workability of the GA steel sheet are maintained, and high corrosion resistance can be exhibited even at the end face and after processing. As described above, the steel sheet of the present invention is suitable for use as it is for exterior use, but may be of course used after coating.
【図1】実施例で潤滑性の評価に使用した装置を示し、
図1(a) は摩擦係数の測定に用いたバウデン摩擦試験機
の説明図、図1(b) はビード付きハット成形試験のクラ
ンクプレスの形状を示す説明図である。FIG. 1 shows an apparatus used for evaluating lubricity in an example,
FIG. 1A is an explanatory view of a Bowden friction tester used for measuring a friction coefficient, and FIG. 1B is an explanatory view showing a shape of a crank press in a hat forming test with beads.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI // C10M 125/26 C10M 125/26 159/06 159/06 (56)参考文献 特開 平3−219950(JP,A) 特開 平5−171457(JP,A) 特開 昭61−60886(JP,A) 特開 平7−34259(JP,A) (58)調査した分野(Int.Cl.6,DB名) C23C 22/00 - 22/86 B05D 3/10 B05D 7/14 B32B 15/08 C23C 28/00──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification symbol FI // C10M 125/26 C10M 125/26 159/06 159/06 (56) References JP-A-3-219950 (JP, A) JP-A-5-171457 (JP, A) JP-A-61-60886 (JP, A) JP-A-7-34259 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C23C 22/00-22/86 B05D 3/10 B05D 7/14 B32B 15/08 C23C 28/00
Claims (4)
換算付着量10〜150mg/m2のクロメート皮膜と、その上
層の樹脂皮膜とを有し、 前記樹脂皮膜が、ベース樹脂(A) 中に、シリカ粒子(B)
をSiO2として5〜30重量%、潤滑機能付与剤(C) を0.5
〜30重量%、および塩基性アルカリ金属塩(D)を1〜10
重量%含有し、着色顔料を含まない、乾燥皮膜重量 0.1
〜5g/m2の潤滑性樹脂皮膜であることを特徴とする、端
面耐食性に優れた着色潤滑処理亜鉛系めっき鋼板。1. The method according to claim 1, wherein the surface of the galvannealed steel sheet is made of Cr.
It has a chromate film with a converted adhesion amount of 10 to 150 mg / m 2 and a resin film as an upper layer, wherein the resin film is a silica resin (B) in a base resin (A).
Is 5 to 30% by weight as SiO 2 , and the lubricating function-imparting agent (C) is 0.5
To 30% by weight, and 1 to 10% of the basic alkali metal salt (D).
0.1% dry film weight without color pigment
A colored lubricated zinc-coated steel sheet having excellent end face corrosion resistance, characterized by being a lubricating resin film of up to 5 g / m 2 .
表色系で、50≦ L*≦62、−1≦ a* ≦0 、−2≦ b*
≦0 である、請求項1記載の着色潤滑処理亜鉛系めっき
鋼板。2. The color tone of the surface is L * a * b * of JIS Z8729 .
In color system, 50 ≦ L * ≦ 62, −1 ≦ a * ≦ 0, -2 ≦ b *
The colored lubricated galvanized steel sheet according to claim 1, wherein ≤0.
のポリオレフィン系ワックスおよび/またはフッ素系樹
脂の平均粒径5μm以下の微粉末からなる、請求項1ま
たは2記載の着色潤滑処理亜鉛系めっき鋼板。3. The colored lubricating lubricant according to claim 1, wherein the lubricating function-imparting agent (C) comprises a fine powder of a polyolefin wax having a softening point of 90 ° C. or more and / or a fluororesin having an average particle size of 5 μm or less. Treated galvanized steel sheet.
き鋼板をクロメート処理して、めっき表面にCr換算付着
量10〜150 mg/m2のクロメート皮膜を形成した後、不揮
発分合計量に対してシリカ粒子をSiO2として5〜30重量
%、潤滑機能付与剤を 0.5〜30重量%、および塩基性ア
ルカリ金属塩を1〜10重量%含有し、着色顔料を含まな
い樹脂塗料組成物を用いて、クロメート皮膜上に乾燥皮
膜重量で 0.1〜5g/m2の樹脂皮膜を形成することからな
る、端面耐食性に優れた着色潤滑処理亜鉛系めっき鋼板
の製造方法。4. An alloyed hot-dip galvanized steel sheet having a degree of alloying of 7 to 13% is subjected to chromate treatment to form a chromate film with a Cr equivalent adhesion amount of 10 to 150 mg / m 2 on the plating surface. Resin coating composition containing 5 to 30% by weight of silica particles as SiO 2 , 0.5 to 30% by weight of a lubricating function-imparting agent, and 1 to 10% by weight of a basic alkali metal salt based on the amount, and containing no color pigment A method for producing a colored lubricated zinc-coated steel sheet having excellent end face corrosion resistance, comprising forming a resin film having a dry film weight of 0.1 to 5 g / m 2 on a chromate film by using a material.
Priority Applications (1)
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JP6146468A JP2784325B2 (en) | 1994-06-28 | 1994-06-28 | Colored and lubricated galvanized steel sheet with high end face corrosion resistance and its manufacturing method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6146468A JP2784325B2 (en) | 1994-06-28 | 1994-06-28 | Colored and lubricated galvanized steel sheet with high end face corrosion resistance and its manufacturing method |
Publications (2)
Publication Number | Publication Date |
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JPH0813156A JPH0813156A (en) | 1996-01-16 |
JP2784325B2 true JP2784325B2 (en) | 1998-08-06 |
Family
ID=15408326
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JP6146468A Expired - Fee Related JP2784325B2 (en) | 1994-06-28 | 1994-06-28 | Colored and lubricated galvanized steel sheet with high end face corrosion resistance and its manufacturing method |
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JP5187221B2 (en) * | 2009-01-22 | 2013-04-24 | 新日鐵住金株式会社 | Chrome-free coated steel sheet and casing made using the same |
JP5647587B2 (en) * | 2011-09-21 | 2015-01-07 | 株式会社神戸製鋼所 | Pre-coated metal plate |
JP5919020B2 (en) * | 2012-02-14 | 2016-05-18 | 日油株式会社 | Aqueous colored chromium-free treatment solution, colored film forming method and metal product manufacturing method |
EP4092061A4 (en) * | 2020-01-16 | 2024-02-21 | Japan Fine Coatings Co., Ltd. | Radiation polymerizable composition, cured layer of same, optical fiber containing cured layer and method for producing same |
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1994
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