JPH08120461A - Organic composite coated steel sheet excellent in corrosion resistance and electrodeposition coating suitability - Google Patents
Organic composite coated steel sheet excellent in corrosion resistance and electrodeposition coating suitabilityInfo
- Publication number
- JPH08120461A JPH08120461A JP6258357A JP25835794A JPH08120461A JP H08120461 A JPH08120461 A JP H08120461A JP 6258357 A JP6258357 A JP 6258357A JP 25835794 A JP25835794 A JP 25835794A JP H08120461 A JPH08120461 A JP H08120461A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- corrosion resistance
- film
- coated steel
- organic composite
- 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.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 68
- 239000010959 steel Substances 0.000 title claims abstract description 68
- 238000005260 corrosion Methods 0.000 title claims abstract description 31
- 230000007797 corrosion Effects 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 23
- 239000011248 coating agent Substances 0.000 title abstract description 31
- 238000000576 coating method Methods 0.000 title abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000011347 resin Substances 0.000 claims abstract description 42
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000003746 surface roughness Effects 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 abstract description 14
- 229920000647 polyepoxide Polymers 0.000 abstract description 14
- 229910001335 Galvanized steel Inorganic materials 0.000 abstract 2
- 239000008397 galvanized steel Substances 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000000049 pigment Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000003431 cross linking reagent Substances 0.000 description 7
- 235000019592 roughness Nutrition 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 238000005237 degreasing agent Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000019587 texture Nutrition 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/38—Chromatising
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、自動車、家電製品、建
材等の材料として好適な、耐食性および電着塗装性に優
れた有機複合被覆鋼板に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic composite coated steel sheet which is suitable as a material for automobiles, home electric appliances, building materials and the like and which is excellent in corrosion resistance and electrodeposition coating property.
【０００２】[0002]
【従来の技術】近年、自動車用をはじめとして、多くの
産業分野で各種の表面処理金属板 (主として鋼板) が使
用されている。使用量の増加に伴い、性能への要求も高
まる一方であり、特に自動車用においては、「耐孔あき
10年保証」というような長期的な高耐食性が求められて
いる。2. Description of the Related Art In recent years, various surface-treated metal plates (mainly steel plates) have been used in many industrial fields including those for automobiles. As the amount of use increases, the demand for performance is also increasing. Especially for automobiles, "perforation resistance
Long-term high corrosion resistance such as "10-year warranty" is required.
【０００３】従来より自動車車体用の防錆鋼板として、
数々の表面処理鋼板が発明され、実用化されてきた。そ
の中でも、亜鉛または亜鉛系合金めっき鋼板の上に、ク
ロメート皮膜層と薄い樹脂皮膜層を有する、いわゆる有
機複合被覆鋼板は、クロメート皮膜の防食作用、有機被
覆の腐食環境遮断効果などの作用により、種々の防錆鋼
板の中でも、圧倒的に優れた耐食性を有している。しか
し、近年自動車メーカの耐食性向上ニーズはより一層高
度化し、より耐食性能の優れた表面処理鋼板が要求され
ている。Conventionally, as a rustproof steel plate for automobile bodies,
Many surface-treated steel sheets have been invented and put to practical use. Among them, on a zinc or zinc-based alloy plated steel sheet, having a chromate film layer and a thin resin film layer, so-called organic composite coated steel sheet, by the action of the anticorrosion effect of the chromate film, the corrosive environment blocking effect of the organic coating, etc., It has overwhelmingly superior corrosion resistance among various rustproof steel sheets. However, in recent years, the needs for improving the corrosion resistance of automobile manufacturers have become more sophisticated, and surface-treated steel sheets having more excellent corrosion resistance are required.
【０００４】これまで、例えば特開平２−145774号公報
には、母材たるめっき鋼板の表面粗度ＲMAX を有機樹脂
皮膜の12倍以上で、かつPPI を30以上と、鋼板の表面粗
度を規定した有機複合被覆鋼板が、また、特開平２−27
0546号公報には、表面粗度Ｒz を有機樹脂皮膜厚の1.0
〜5.0 倍とした有機複合被覆鋼板が報告されている。い
ずれも、表面粗度を有機樹脂皮膜厚より大きくすること
で、有機樹脂皮膜を施す際、局所的に皮膜の薄い部分を
作り、スポット溶接性を確保しようとするものである。
しかしながら、両技術では凸部でクロメート皮膜や有機
樹脂皮膜が薄いかまたは形成されない状態となる。その
結果、凸部で腐食が進行し易く、耐食性を低下させる問
題を生じる。Up to now, for example, in Japanese Unexamined Patent Publication (Kokai) No. 2-145774, the surface roughness R MAX of the plated steel sheet as the base material is 12 times or more that of the organic resin film, and the PPI is 30 or more. The organic composite coated steel sheet that defines the
No. 0546 discloses that the surface roughness Rz is 1.0 of the organic resin film thickness.
It has been reported that the organic composite coated steel sheet is up to 5.0 times. In both cases, when the surface roughness is made larger than the thickness of the organic resin film, when the organic resin film is applied, a thin portion of the film is locally formed to secure spot weldability.
However, in both technologies, the chromate film or the organic resin film is thin or not formed on the convex portion. As a result, corrosion easily progresses at the convex portion, which causes a problem of reducing corrosion resistance.
【０００５】さらにクロメートを塗布する際、鋼板表面
の凹部にクロメート液が溜まり、焼き付け後のクロメー
ト付着量が微視的に不均一になる。クロメート付着量と
電着塗装膜厚の間には相関があり、５mm2 当たり0.1 μ
ｇ以下の付着量では、電着塗装膜厚が厚くなる傾向があ
る。そのため、クロメート付着量が微視的に不均一であ
れば、電着塗装後に塗装むらを発生させる。Further, when the chromate is applied, the chromate solution accumulates in the recesses on the surface of the steel sheet, and the amount of chromate adhered after baking becomes microscopically non-uniform. There is a correlation between the amount of chromate deposited and the film thickness of electrodeposition coating, which is 0.1 μ per 5 mm 2.
If the adhesion amount is less than or equal to g, the electrodeposition coating film thickness tends to increase. Therefore, if the chromate adhesion amount is microscopically non-uniform, coating unevenness occurs after electrodeposition coating.
【０００６】そのため、クロメート付着量を増したり有
機樹脂皮膜を厚くする方法が考えられるが、経済的でな
く、また溶接時の鋼板表面の電気抵抗が高くなりすぎ、
電極表面へのカーボン汚れが増大するなどの理由によ
り、溶接性を著しく低下させるなどの問題を生じる。Therefore, a method of increasing the amount of chromate deposited or thickening the organic resin film can be considered, but it is not economical and the electric resistance of the steel sheet surface during welding becomes too high.
Due to the increase of carbon stains on the electrode surface, there is a problem that weldability is significantly reduced.
【０００７】その他、特開平４−381 号公報では合金化
溶融亜鉛めっき鋼板に限定してＲzを1.2 μｍ以下にす
ることで、良好な耐食性が得られるとの報告がある。し
かし、クロメートに関する規定がなされていない。In addition, Japanese Patent Laid-Open No. 4-381 reports that good corrosion resistance can be obtained by limiting the Rz to 1.2 μm or less only for galvannealed steel sheets. However, there is no provision for chromate.
【０００８】また、クロメートの微視的な付着量分布に
ついて記載したものとして特開平６−57447 号公報 (特
願平４−212505号) および特開平６−116778号公報( 特
願平４−264833号) があり、どちらもEPMAの点分析でCr
の特性Ｘ線強度の平均値Ｘとその標準偏差σとの比が、
σ／Ｘ≦0.3 とした有機複合被覆鋼板について報告して
いる。この場合、クロメートは鋼板上に均一に分散して
おり、その結果、優れた溶接性および耐チッピング性が
得られると報告している。しかし、これらには表面粗度
に関する記載がなされていない。Further, as a description of the microscopic amount distribution of chromate deposition, JP-A-6-57447 (Japanese Patent Application No. 4-212505) and JP-A-6-116778 (Japanese Patent Application No. 4-264833). No.), both of which are Cr in EPMA point analysis.
The ratio of the average value X of the characteristic X-ray intensities and the standard deviation σ is
This paper reports on an organic composite coated steel sheet with σ / X ≦ 0.3. In this case, it is reported that the chromate is uniformly dispersed on the steel sheet, and as a result, excellent weldability and chipping resistance are obtained. However, there is no description regarding surface roughness in these documents.
【０００９】[0009]
【発明が解決しようとする課題】本発明では上記問題点
を解決し、耐食性および電着塗装性に優れた有機複合被
覆鋼板を提供することを目的とする。具体的には本発明
の目的は、自動車内外装用材料に耐えうる耐食性および
電着性 (評点合計≧16点) を備えた有機複合被覆鋼板を
提供することである。SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems and provide an organic composite coated steel sheet having excellent corrosion resistance and electrodeposition coating property. Specifically, an object of the present invention is to provide an organic composite coated steel sheet having corrosion resistance and electrodeposition (total score ≧ 16 points) that can withstand materials for automobile interiors and exteriors.
【００１０】[0010]
【課題を解決するための手段】上記の事情に鑑み、本発
明者らは有機複合被覆鋼板の耐食性および電着塗装性を
向上させる方法を鋭意検討した結果、有機複合被覆鋼板
に使用する亜鉛めっきもしくは亜鉛系合金めっきの表面
粗度Ｒz(十点平均粗さ) とＲa(中心線平均粗さ) がＲa
≦0.13×Ｒz なる関係を満たし、かつPPI が30以上であ
り、さらにそのような鋼板上の任意の部分において、そ
の上層にCr付着量として、５mm2 当たり、0.1 μｇ以上
のクロメート皮膜を有する有機複合被覆鋼板が有効であ
るという知見を得て、本発明に至ったのである。In view of the above circumstances, the inventors of the present invention have earnestly studied a method for improving the corrosion resistance and the electrodeposition coatability of an organic composite coated steel sheet, and as a result, have found that zinc coating used for the organic composite coated steel sheet. Alternatively, the surface roughness Rz (ten-point average roughness) and Ra (center line average roughness) of zinc-based alloy plating are Ra
An organic material that satisfies the relationship of ≦ 0.13 × Rz, has a PPI of 30 or more, and has a chromate film of 0.1 μg or more per 5 mm 2 as Cr deposition amount on the upper portion of any portion of such a steel sheet. The present invention has been achieved by finding that the composite coated steel sheet is effective.
【００１１】ここに、本発明の要旨とするところは、亜
鉛めっきもしくは亜鉛系合金めっき鋼板の少なくとも片
面上に、第１層として鋼板上の任意の５mm2 に、Cr付着
量として0.1 μｇ以上のクロメート皮膜を有し、その上
層に第２層として0.1 μｍ以上の有機樹脂皮膜を有する
有機複合被覆鋼板であって、母材たる前記めっき鋼板の
中心線平均粗さＲa と十点平均粗さＲz がＲa ≦0.13×
Ｒz なる関係を満たし、かつ、該めっき鋼板の下記表面
粗度パラメータＰＰＩが30以上であることを特徴とする
耐食性および電着塗装性に優れた有機複合被覆鋼板であ
る。ＰＰＩ：１インチ当たりの山の数。但し、しきい値
をＲMAX の30％以上とする。Here, the gist of the present invention is that, on at least one side of a galvanized or zinc-based alloy-plated steel sheet, an arbitrary 5 mm 2 on the steel sheet as the first layer, and a Cr deposition amount of 0.1 μg or more. An organic composite-coated steel sheet having a chromate film and an organic resin film of 0.1 μm or more as a second layer on the chromate film, the center line average roughness Ra and the ten-point average roughness R of the plated steel sheet being a base material. z is Ra ≦ 0.13 ×
An organic composite-coated steel sheet excellent in corrosion resistance and electrodeposition coatability, characterized in that the following surface roughness parameter PPI of the plated steel sheet is 30 or more while satisfying the relationship of R z . PPI: Number of peaks per inch. However, the threshold value is set to 30% or more of R MAX .
【００１２】[0012]
【作用】以下、本発明の構成と作用について詳述する。
本発明は、従来の有機複合被覆鋼板の母材のめっき鋼板
として、Ｒz(十点平均粗さ) とＲa(中心線平均粗さ) が
Ｒa ≦0.13×Ｒz なる関係を満たし、かつPPIが30以上
である鋼板を使用し、その上に第１層として鋼板上の任
意の５mm2 を測定し、Cr付着量として0.1 μｇ以上のク
ロメート皮膜を有する点に特徴がある。したがって、母
材のめっき鋼板の種類やめっき付着量、第１層クロメー
ト皮膜、第２層有機樹脂皮膜などについては、従来の有
機複合被覆鋼板と同様でよく、特に制限されないが、こ
れらについても次に簡単に説明する。The structure and operation of the present invention will be described in detail below.
The present invention, as a base steel plated steel sheet of a conventional organic composite coated steel sheet, satisfies the relationship of Rz (ten-point average roughness) and Ra (center line average roughness) Ra ≤ 0.13 × Rz, and has a PPI of 30. The above-mentioned steel sheet is used, and an arbitrary 5 mm 2 on the steel sheet is measured as the first layer on the steel sheet, and a characteristic feature is that it has a chromate film of 0.1 μg or more as a Cr adhesion amount. Therefore, the type of the coated steel sheet of the base material, the amount of the deposited coating, the first-layer chromate coating, the second-layer organic resin coating, and the like may be the same as those of the conventional organic composite-coated steel sheet, and are not particularly limited. Briefly explained.
【００１３】母材めっき鋼板 本発明に用いられるめっき鋼板は亜鉛もしくは亜鉛系合
金めっき鋼板で、その製法は電気めっき、溶融めっき等
の常法により、特に制限されず、片面めっきおよび両面
めっきのいずれでもよい。めっき付着量は特に制限され
ないが、加工性と耐食性のバランスから片面当たり10〜
60g/m2の範囲内が好ましい。本発明において、鋼板はＲ
a ≦0.13×Ｒz を満たし、かつPPI が30以上のものを用
いる。Base material plated steel sheet The plated steel sheet used in the present invention is a zinc or zinc-based alloy plated steel sheet, and its production method is not particularly limited by ordinary methods such as electroplating and hot dip plating. But it's okay. The amount of plating applied is not particularly limited, but from the balance of workability and corrosion resistance 10 to 10 per side
It is preferably within the range of 60 g / m 2 . In the present invention, the steel plate is R
A material satisfying a ≤0.13 × Rz and having a PPI of 30 or more is used.
【００１４】ここで、Ｒa ≦0.13×Ｒz は鋼板表面粗度
の上限を規定しており、一方、PPIが30以上ということ
は、鋼板表面凹凸の数が30％以上であることを意味す
る。ただし、「しきい値をＲMAX の30％以上とする」と
は、Max の30％以上の凸部を１山として数えることを意
味する。Here, Ra ≦ 0.13 × Rz defines the upper limit of the surface roughness of the steel sheet, while the PPI of 30 or more means that the number of surface irregularities of the steel sheet is 30% or more. However, "to set the threshold value to 30% or more of R MAX " means to count the convex portions of 30% or more of Max as one peak.
【００１５】したがって、本発明において母材鋼板の表
面性状を上述のように規定することの作用効果上の意義
は次の通りである。上述の範囲内の表面凹凸を有する鋼
板を使用すれば、クロメート層および有機樹脂皮膜層を
均一に塗布できることを意味する。Therefore, in the present invention, the meaning of the action and effect of defining the surface texture of the base steel sheet as described above is as follows. If a steel sheet having surface irregularities within the above range is used, it means that the chromate layer and the organic resin film layer can be applied uniformly.
【００１６】上述のような表面粗さを得るためには鋼板
をショットダル、レーザーダル等のロールで圧延処理す
る方法がある。Ｒa ＞0.13×Ｒz なる関係にある鋼板で
は鋼板表面の凸部で有機樹脂皮膜が薄いまたは形成され
ない状態となり、耐食性が低下する。さらに、クロメー
トが凹部に偏り電着塗装後の外観を劣化させる。また、
PPI が30未満の鋼板でも同様のことが言える。In order to obtain the above-mentioned surface roughness, there is a method of rolling a steel sheet with rolls such as shot dull and laser dull. In the steel plate having a relation of Ra> 0.13 × Rz, the organic resin film is thin or not formed on the convex portion of the steel plate surface, and the corrosion resistance is deteriorated. Further, the chromate is biased to the concave portion and deteriorates the appearance after electrodeposition coating. Also,
The same can be said for steel plates with a PPI of less than 30.
【００１７】さらに、どちらか一方のみを満たす場合も
同様のことが言え、耐食性および電着塗装性が低下す
る。そこで、鋼板Ｒa ≦0.13×Ｒz を満たし、かつPPI
が30以上のものを用いることとする。Further, the same can be said when only one of them is satisfied, and the corrosion resistance and the electrodeposition coating property are deteriorated. Therefore, the steel plate Ra ≤ 0.13 × Rz is satisfied, and the PPI is
Shall be 30 or more.
【００１８】第１層クロメート皮膜 クロメート皮膜の形成方法は、耐食性に特に優れている
塗装型クロメート皮膜が好ましい。すなわち、ロールコ
ーターをはじめとする慣用手段により塗布した後、80〜
250 ℃の温度で焼き付けるのが好ましい。 The first layer chromate film is preferably formed by a coating type chromate film which is particularly excellent in corrosion resistance. That is, after applying by a conventional means such as a roll coater, 80 ~
Baking at a temperature of 250 ° C. is preferred.
【００１９】クロメート皮膜の付着量は金属Cr量として
鋼板上の任意の５mm2 を測定し、0.1 μｇ以上であるこ
とが必要である。好ましくは0.2 〜0.6 μｇである。Cr
量が0.1 μｇ以下では十分な耐食性が得られず、さら
に、電着塗装後の外観が劣化する。また0.6 μｇを超え
ると、スポット溶接においてチップの損傷が激しくなる
場合がある。It is necessary that the amount of the chromate film adhered is 0.1 μg or more when an arbitrary 5 mm 2 on the steel plate is measured as the amount of metallic Cr. It is preferably 0.2 to 0.6 μg. Cr
If the amount is 0.1 μg or less, sufficient corrosion resistance cannot be obtained, and the appearance after electrodeposition coating deteriorates. On the other hand, if it exceeds 0.6 μg, the tip may be severely damaged in spot welding.
【００２０】クロメート液の組成としては、Cr3+／全Cr
[＝Cr3+/(Cr3+＋Cr6+ )] の比を0.4 〜0.6 程度にする
のが好ましい。0.4 未満であると還元効率が劣り、0.6
を超えるとCr6+が過剰になり、処理液の安定性が損なわ
れる恐れがある。The composition of the chromate solution is Cr 3+ / total Cr
It is preferable to set the ratio of [= Cr 3+ / (Cr 3+ + Cr 6+ )] to about 0.4 to 0.6. If it is less than 0.4, the reduction efficiency is poor and 0.6
If it exceeds, Cr 6+ becomes excessive and the stability of the treatment liquid may be impaired.
【００２１】また、耐食性向上を目的として所望により
乾性シリカをクロメート中に添加すると良い。この時、
Si／Crは0.1 未満ではSiO2添加の効果が見られず、２超
では溶接性の低下が心配されるため、Si／Crで0.1 〜２
のSiO2を含有するのが望ましい。If desired, dry silica may be added to the chromate for the purpose of improving the corrosion resistance. This time,
If Si / Cr is less than 0.1, the effect of adding SiO 2 is not seen, and if it exceeds 2, there is a concern that weldability will deteriorate.
It is desirable to contain SiO 2 of.
【００２２】第２層有機樹脂皮膜 上述のように形成された第１層クロメート皮膜の上に、
有機樹脂皮膜を0.1 μｍ以上の厚みで設ける。好ましく
は0.1 〜2.0 μｍである。0.1 μｍ未満では耐食性が不
十分となり、2.0 μｍを超えると溶接性が低下する。 Second layer organic resin film On the first layer chromate film formed as described above,
Provide an organic resin film with a thickness of 0.1 μm or more. It is preferably 0.1 to 2.0 μm. If it is less than 0.1 μm, the corrosion resistance becomes insufficient, and if it exceeds 2.0 μm, the weldability deteriorates.
【００２３】この有機樹脂皮膜は、従来より塗装鋼板の
製造に使用されてきた各種の樹脂系被覆組成物を使用し
て形成することができる。有機樹脂皮膜は、装置が簡便
で造膜も速い熱硬化型皮膜が工業的には好ましいが、紫
外線または電子線硬化型皮膜や常温乾燥型皮膜とするこ
ともできる。This organic resin film can be formed using various resin-based coating compositions that have been conventionally used for producing coated steel sheets. The organic resin film is industrially preferably a thermosetting film which has a simple apparatus and a quick film formation, but may be an ultraviolet or electron beam curing film or a room temperature drying film.
【００２４】熱硬化型の有機樹脂皮膜は、架橋剤を含有
する樹脂液を塗布した後、適当な温度に加熱して塗膜を
焼き付けることにより形成される。好ましい樹脂種はエ
ポキシ系樹脂である。The thermosetting organic resin film is formed by applying a resin liquid containing a cross-linking agent, heating the film at an appropriate temperature and baking the film. A preferred resin type is an epoxy resin.
【００２５】塗布に用いる樹脂液中には、樹脂および架
橋剤の他に、必要により希釈用の溶媒や、１種もしくは
２種以上の添加剤を含有していてもよい。このような任
意の添加剤としては、無機充填剤、顔料類 (防錆顔料、
体質顔料、特に着色顔料) 、可塑剤、潤滑性付与成分な
どがある。In addition to the resin and the cross-linking agent, the resin liquid used for coating may optionally contain a solvent for dilution and one or more additives. Such optional additives include inorganic fillers, pigments (rust preventive pigments,
Extender pigments, especially coloring pigments), plasticizers, and components for imparting lubricity.
【００２６】好ましい樹脂種であるエポキシ系樹脂とし
ては、ビスフェノールＡ系、ビスフェノールＦ系、ノボ
ラック型、臭素化エポキシ等の任意のグリシジルエーテ
ル系エポキシ樹脂が使用できる。また、エポキシ樹脂中
のエポキシ基およびヒドロキシル基を乾性油脂肪酸中の
カルボキシル基と反応させたエポキシエステル樹脂、イ
ソシアネートと反応させることにより得られるウレタン
変性エポキシ樹脂などの変性エポキシ樹脂も使用でき
る。As the epoxy type resin which is a preferable resin type, any glycidyl ether type epoxy resin such as bisphenol A type, bisphenol F type, novolac type and brominated epoxy can be used. Further, a modified epoxy resin such as an epoxy ester resin obtained by reacting an epoxy group and a hydroxyl group in an epoxy resin with a carboxyl group in a drying oil fatty acid and a urethane modified epoxy resin obtained by reacting with an isocyanate can also be used.
【００２７】また、本発明においてエポキシ樹脂の１種
として好適に使用できるものに、ポリヒドロキシポリエ
ーテル樹脂がある。この樹脂は、単核型もしくは二核型
の２価フェノールもしくは単核型と二核型との混合２価
フェノールを、アルカリ触媒の存在下にほぼ等モル量の
エピハロヒドリンと重縮合させて得られる重合体であ
る。In addition, polyhydroxypolyether resin is preferably used as one kind of epoxy resin in the present invention. This resin is obtained by polycondensing mononuclear type or binuclear type dihydric phenol or a mixed divalent phenol of mononuclear type and binuclear type with an approximately equimolar amount of epihalohydrin in the presence of an alkali catalyst. It is a polymer.
【００２８】エポキシ系樹脂液中には、皮膜の種々の性
能 (例、加工性、可撓性、潤滑性、電着塗装性など) を
改善する目的で、エポキシ系以外の樹脂を添加してもよ
い。例えば、皮膜に可撓性を与えるためのブチラール樹
脂の添加、電着塗装性を向上するための水溶性樹脂の添
加などである。エポキシ系以外の樹脂の添加量は、あま
り多くなると耐食性の低下を招くので、樹脂液中の全樹
脂固形分の50重量％以下とする。For the purpose of improving various properties of the film (eg, processability, flexibility, lubricity, electrodeposition coating property, etc.), the epoxy resin liquid may contain a resin other than the epoxy resin. Good. For example, addition of a butyral resin for imparting flexibility to the coating, addition of a water-soluble resin for improving electrodeposition coating property, and the like. If the amount of the resin other than the epoxy resin added is too large, the corrosion resistance is deteriorated. Therefore, the amount of the resin solid content in the resin liquid is 50% by weight or less.
【００２９】エポキシ系樹脂用の架橋剤としては、フェ
ノール樹脂、アミノ樹脂、ポリアミド、アミノポリアミ
ド、アミン、ブロックイソシアネート、酸無水物などの
公知の各種の架橋剤を１種もしくは２種以上使用するこ
とができる。架橋剤を使用すると、皮膜の耐食性が一層
向上する。架橋剤の添加量は、エポキシ系樹脂中のエポ
キシ基とヒドロキシル基の合計量に対する架橋剤中の官
能基のモル比が0.1 〜２の範囲内が好ましい。As the cross-linking agent for the epoxy resin, one or more known cross-linking agents such as phenol resin, amino resin, polyamide, amino polyamide, amine, blocked isocyanate and acid anhydride may be used. You can The use of the crosslinking agent further improves the corrosion resistance of the film. The addition amount of the cross-linking agent is preferably such that the molar ratio of the functional groups in the cross-linking agent to the total amount of epoxy groups and hydroxyl groups in the epoxy resin is in the range of 0.1 to 2.
【００３０】樹脂皮膜の耐食性向上を目的として所望に
より無機充填材を樹脂液中に添加してもよい。有用な無
機充填材の例としては、乾性シリカ、コロイダルシリ
カ、各種ケイ酸塩鉱物、アルミナ、炭酸カルシウム、リ
ン酸亜鉛、リン酸カルシウム、リンモリブデン酸亜鉛、
リンモリブデン酸アルミニウムなどが挙げられる。無機
充填剤の添加量は、樹脂固形分に対して１〜30重量％の
範囲内が好ましい。If desired, an inorganic filler may be added to the resin liquid for the purpose of improving the corrosion resistance of the resin film. Examples of useful inorganic fillers include dry silica, colloidal silica, various silicate minerals, alumina, calcium carbonate, zinc phosphate, calcium phosphate, zinc phosphomolybdate,
Aluminum phosphomolybdate etc. are mentioned. The addition amount of the inorganic filler is preferably in the range of 1 to 30% by weight based on the resin solid content.
【００３１】顔料としては、高い防食性向上効果を示す
ことが知られているクロム酸ストロンチウム、クロム酸
亜鉛などの金属クロム酸塩系防錆顔料が耐食性向上の目
的に有効である。また、本発明の有機複合被覆が片面の
みに形成される場合には、最上層の樹脂皮膜に着色顔料
を含有させて皮膜を着色しておくと、表裏の識別が容易
となり、ユーザーの作業に好都合である。着色顔料とし
ては、酸化鉄、酸化チタン顔料、カーボンなどの無機系
顔料以外に、有機系顔料も使用可能である。As the pigment, metal chromate-based rust preventive pigments such as strontium chromate and zinc chromate, which are known to show a high anticorrosive effect, are effective for the purpose of improving anticorrosion. Further, when the organic composite coating of the present invention is formed on only one side, if the uppermost resin film contains a coloring pigment and the film is colored, it becomes easy to distinguish the front and back, and it is easy for the user to work. It is convenient. As the coloring pigment, in addition to inorganic pigments such as iron oxide, titanium oxide pigment and carbon, organic pigments can be used.
【００３２】上述した樹脂液をロールコーターなどの適
当な塗布手段でクロメート皮膜上に塗布し、加熱して塗
膜を硬化させ、有機樹脂皮膜を形成する。加熱温度は、
エポキシ系樹脂の場合で80〜250 ℃、好ましくは120 〜
200 ℃である。素地鋼板が焼付け硬化型の場合には、こ
の時の加熱温度も150 ℃以下が好ましい。The above-mentioned resin liquid is applied onto the chromate film by an appropriate applying means such as a roll coater and heated to cure the applied film, thereby forming an organic resin film. The heating temperature is
In the case of epoxy resin, 80 to 250 ℃, preferably 120 to 250 ℃
It is 200 ℃. When the base steel sheet is bake hardenable, the heating temperature at this time is also preferably 150 ° C or lower.
【００３３】[0033]
【実施例】表面粗さＲz 、Ｒa およびＰＰＩを種々変化
させた母材 (各種めっき鋼板) を用いて、表１、表２に
示す皮膜構成および皮膜組成の有機複合被覆鋼板を作製
した。Example Using the base materials (various plated steel sheets) having variously changed surface roughnesses R z , Ra and PPI, organic composite coated steel sheets having the coating configurations and coating compositions shown in Tables 1 and 2 were produced.
【００３４】このとき、クロメート処理には市販の塗布
型クロメート処理液を原液で用いた。また、有機樹脂皮
膜の形成は、ビスフェノールＡ型エポキシ樹脂65重量
部、フェノール樹脂型硬化剤15重量部、乾性シリカ15重
量部、潤滑成分５重量部をシクロヘキサノンに溶解し、
NV (不揮発成分) ＝20％に調製した樹脂液を用いて行っ
た。このようにして得られた有機複合被覆鋼板における
耐食性および電着塗装性を以下に示す方法で評価した。At this time, a commercially available coating type chromate treatment liquid was used as a stock solution for the chromate treatment. Further, the organic resin film is formed by dissolving 65 parts by weight of a bisphenol A type epoxy resin, 15 parts by weight of a phenol resin type curing agent, 15 parts by weight of dry silica, and 5 parts by weight of a lubricating component in cyclohexanone,
NV (nonvolatile component) = 20% was performed using a resin solution prepared. The corrosion resistance and electrodeposition coatability of the thus obtained organic composite coated steel sheet were evaluated by the following methods.
【００３５】[耐食性]70mm×150 mmの試験片を切り出
し、この未加工の平板を脱脂剤 SD270TO (日本ペイント
社製) で45℃にて210 秒間浸漬脱脂し、水洗後、165 ℃
で25分間の空焼きを行った。次いで、下に示すサイクル
設定の複合腐食試験を行った。[Corrosion resistance] A 70 mm × 150 mm test piece was cut out, and this unprocessed flat plate was immersed and degreased with a degreasing agent SD270TO (manufactured by Nippon Paint Co., Ltd.) at 45 ° C for 210 seconds, washed with water, and then washed at 165 ° C.
It was baked for 25 minutes at. Then, a complex corrosion test with a cycle setting shown below was performed.
【００３６】[0036]
【数１】 [Equation 1]
【００３７】評価は、上記の腐食サイクル試験を120 サ
イクル実施後、赤錆発生面積率(%)を次のような段階に
区分して評価した。 ◎：赤錆発生なし ○： ５％以下 △： 20％以下 ×： 30％以下 ××： 30％超。The evaluation was carried out by conducting the above corrosion cycle test for 120 cycles, and then dividing the red rust generation area ratio (%) into the following stages. ⊚: No red rust occurred ○: 5% or less △: 20% or less ×: 30% or less XX: more than 30%
【００３８】[電着塗装製]70mm×150 mmの試験片を切り
出し、この未加工の平板を、脱脂剤リドリン SD270TO
(日本ペイント社製) で脱脂し、フィキソジン5TO(日本
ペイント社製) で表面調整した後、グラノチン SD2500M
Z(日本ペイント社製) を用いて化成処理を行い、次い
で、M635 (日本ペイント社製) で厚さ20±１μｍのカチ
オン電着塗装を施し、165 ℃で25分間焼き付けた。その
後、塗装外観で次のように評価した。 ○： 良好 △： 電着塗装むら弱 ×： 電着塗装むら強[Electrodeposition coating] A 70 mm x 150 mm test piece was cut out, and this unprocessed flat plate was used as a degreasing agent Rydrin SD270TO.
After degreasing with (Nippon Paint Co., Ltd.) and adjusting the surface with Fexogin 5TO (Nippon Paint Co., Ltd.), granotin SD2500M
A chemical conversion treatment was performed using Z (manufactured by Nippon Paint Co., Ltd.), and then a cationic electrodeposition coating with a thickness of 20 ± 1 μm was applied using M635 (manufactured by Nippon Paint Co., Ltd.) and baked at 165 ° C. for 25 minutes. Then, the coating appearance was evaluated as follows. ○: Good △: Electrodeposition uneven coating weak ×: Electrodeposition uneven coating strong
【００３９】[0039]
【表１】 [Table 1]
【００４０】[0040]
【表２】 [Table 2]
【００４１】[0041]
【表３】 [Table 3]
【００４２】[0042]
【発明の効果】本発明の有機複合被覆鋼板は、従来の有
機複合被覆鋼板にない高い耐食性および電着塗装性を兼
ね備えており、自動車、家電製品、建材用に有用であ
る。EFFECT OF THE INVENTION The organic composite-coated steel sheet of the present invention has high corrosion resistance and electrodeposition coatability that conventional organic composite-coated steel sheets do not have, and is useful for automobiles, home electric appliances and building materials.
Claims (1)
板の少なくとも片面上に、第１層として鋼板上の任意の
５mm2 に、Cr付着量として0.1 μｇ以上のクロメート皮
膜を有し、その上層に第２層として0.1 μｍ以上の有機
樹脂皮膜を有する有機複合被覆鋼板であって、母材たる
前記めっき鋼板の中心線平均粗さＲaと十点平均粗さＲ
z がＲa ≦0.13×Ｒz なる関係を満たし、かつ、該めっ
き鋼板の下記表面粗度パラメータＰＰＩが30以上である
ことを特徴とする耐食性および電着塗装性に優れた有機
複合被覆鋼板。 ＰＰＩ：１インチ当たりの山の数。但し、しきい値をＲ
MAX の30％以上とする。1. A zinc-plated or zinc-based alloy-plated steel sheet having a chromate film having a Cr deposit of 0.1 μg or more on any 5 mm 2 of the steel sheet as a first layer on at least one surface of the steel sheet. An organic composite coated steel sheet having an organic resin film of 0.1 μm or more as two layers, wherein the center line average roughness Ra and the ten-point average roughness R of the plated steel sheet as a base material
z satisfies Ra ≦ 0.13 × R z the relationship, and, organic composite coated steel sheet excellent in corrosion resistance and electrodeposition paintability, characterized in that following surface roughness parameters PPI of the plated steel sheet is 30 or more. PPI: Number of peaks per inch. However, the threshold value is R
30% or more of MAX .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6258357A JP2797983B2 (en) | 1994-10-24 | 1994-10-24 | Organic composite coated steel sheet with excellent corrosion resistance and electrodeposition coating properties |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6258357A JP2797983B2 (en) | 1994-10-24 | 1994-10-24 | Organic composite coated steel sheet with excellent corrosion resistance and electrodeposition coating properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08120461A true JPH08120461A (en) | 1996-05-14 |
| JP2797983B2 JP2797983B2 (en) | 1998-09-17 |
Family
ID=17319115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6258357A Expired - Fee Related JP2797983B2 (en) | 1994-10-24 | 1994-10-24 | Organic composite coated steel sheet with excellent corrosion resistance and electrodeposition coating properties |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2797983B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002052065A3 (en) * | 2000-12-22 | 2002-12-05 | Doerken Ewald Ag | Piece finished with a coating of zinc and applied electrophoretic dip varnish and method for the production thereof |
| EP1391539A2 (en) * | 2002-07-29 | 2004-02-25 | JFE Steel Corporation | Coated steel sheet provided with electrodeposition painting having superior appearance |
| WO2010035847A1 (en) * | 2008-09-24 | 2010-04-01 | Ｊｆｅスチール株式会社 | Rust-proof steel sheet and method for producing the same |
| US20150298430A1 (en) * | 2009-02-04 | 2015-10-22 | Bruno Gay | Process for Coating Discrete Articles with a Zinc-Based Alloyed Layer and Articles Obtained Therefrom |
| JP2021529883A (en) * | 2018-07-06 | 2021-11-04 | ポスコＰｏｓｃｏ | Manufacturing method of surface-treated zinc-nickel alloy electroplated steel sheet with excellent corrosion resistance and paintability |
-
1994
- 1994-10-24 JP JP6258357A patent/JP2797983B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002052065A3 (en) * | 2000-12-22 | 2002-12-05 | Doerken Ewald Ag | Piece finished with a coating of zinc and applied electrophoretic dip varnish and method for the production thereof |
| EP1391539A2 (en) * | 2002-07-29 | 2004-02-25 | JFE Steel Corporation | Coated steel sheet provided with electrodeposition painting having superior appearance |
| EP1391539A3 (en) * | 2002-07-29 | 2006-02-01 | JFE Steel Corporation | Coated steel sheet provided with electrodeposition painting having superior appearance |
| WO2010035847A1 (en) * | 2008-09-24 | 2010-04-01 | Ｊｆｅスチール株式会社 | Rust-proof steel sheet and method for producing the same |
| JP2010100936A (en) * | 2008-09-24 | 2010-05-06 | Jfe Steel Corp | Rust-proof steel sheet and method for producing the same |
| KR101375510B1 (en) * | 2008-09-24 | 2014-03-18 | 제이에프이 스틸 가부시키가이샤 | Rust-proof steel sheet and method for producing the same |
| CN104801476A (en) * | 2008-09-24 | 2015-07-29 | 杰富意钢铁株式会社 | Rustproof steel sheet and method for manufacturing the same |
| US20150298430A1 (en) * | 2009-02-04 | 2015-10-22 | Bruno Gay | Process for Coating Discrete Articles with a Zinc-Based Alloyed Layer and Articles Obtained Therefrom |
| US9623632B2 (en) * | 2009-02-04 | 2017-04-18 | Umicore | Process for coating discrete articles with a zinc-based alloyed layer and articles obtained therefrom |
| JP2021529883A (en) * | 2018-07-06 | 2021-11-04 | ポスコＰｏｓｃｏ | Manufacturing method of surface-treated zinc-nickel alloy electroplated steel sheet with excellent corrosion resistance and paintability |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2797983B2 (en) | 1998-09-17 |
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