JP2005146294A - Inorganic-organic composite-treated galvanized steel sheet - Google Patents
Inorganic-organic composite-treated galvanized steel sheet Download PDFInfo
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- JP2005146294A JP2005146294A JP2003380855A JP2003380855A JP2005146294A JP 2005146294 A JP2005146294 A JP 2005146294A JP 2003380855 A JP2003380855 A JP 2003380855A JP 2003380855 A JP2003380855 A JP 2003380855A JP 2005146294 A JP2005146294 A JP 2005146294A
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- steel sheet
- organic
- zinc
- zinc phosphate
- film
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- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 9
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 9
- 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 claims abstract description 45
- 229910000165 zinc phosphate Inorganic materials 0.000 claims abstract description 45
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 27
- 239000010959 steel Substances 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 8
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims description 37
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052725 zinc Inorganic materials 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 20
- 238000007747 plating Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 239000011247 coating layer Substances 0.000 claims description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 22
- 230000007797 corrosion Effects 0.000 abstract description 22
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005246 galvanizing Methods 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 15
- 229910052749 magnesium Inorganic materials 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 nitrate ions Chemical class 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- 239000004593 Epoxy Substances 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- SPDJAIKMJHJYAV-UHFFFAOYSA-H trizinc;diphosphate;tetrahydrate Chemical compound O.O.O.O.[Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SPDJAIKMJHJYAV-UHFFFAOYSA-H 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 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
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、無機有機複合処理亜鉛系めっき鋼板に関する。 The present invention relates to an inorganic / organic composite-treated zinc-based plated steel sheet.
自動車、家電、建材等の用途に用いられる亜鉛系めっき鋼板には、従来、耐食性の向上や塗膜密着性の向上などを目的として、リン酸塩処理やクロメート処理が一般に行われている。特に、リン酸亜鉛処理を施した後に、クロメートによるシーリング処理を行う方法は、耐食性や塗料密着性の向上に効果が大きいために広く実施されてきた。しかし、近年、環境問題の高まりを背景に、毒性の大きいクロメートを用いない表面処理技術の開発が望まれ、下記のような技術が提案されている。 Conventionally, galvanized steel sheets used for applications such as automobiles, home appliances, and building materials have been generally subjected to phosphate treatment and chromate treatment for the purpose of improving corrosion resistance and coating film adhesion. In particular, the method of performing the sealing treatment with chromate after the zinc phosphate treatment has been widely practiced because it has a great effect on improving the corrosion resistance and paint adhesion. However, in recent years, against the background of increasing environmental problems, development of surface treatment technology that does not use highly toxic chromate is desired, and the following technologies have been proposed.
亜鉛系めっき鋼板の表面に、第1層としてニッケル、マンガン及びマグネシウムの中から選ばれる少なくとも1種を含有する付着量0.2〜2.5g/m2のリン酸亜鉛処理皮膜層を有し、その上部に第2層としてエチレン系樹脂、エポキシ系樹脂、ウレタン系樹脂及びアクリル系樹脂の中から選ばれる少なくとも1種の有機樹脂を主成分とする有機系皮膜を有するリン酸亜鉛複合処理鋼板が開示されている(例えば、特許文献1参照。)。 On the surface of the zinc-based plated steel sheet, the first layer has a zinc phosphate-treated film layer having an adhesion amount of 0.2 to 2.5 g / m 2 containing at least one selected from nickel, manganese and magnesium. The zinc phosphate composite-treated steel sheet having an organic film mainly composed of at least one organic resin selected from ethylene resin, epoxy resin, urethane resin and acrylic resin as a second layer on the upper part Is disclosed (for example, see Patent Document 1).
鋼板表面に、亜鉛系めっき皮膜、0.3g/m2以上のリン酸亜鉛処理皮膜、0.3〜2g/m2の有機被膜が順次形成されており、リン酸亜鉛被膜がMgを含有し、リン酸亜鉛処理皮膜中のMg/P(質量比)が0.15以上でかつMg量が20mg/m2以上である有機複合亜鉛系メッキ鋼板が開示されている(例えば、特許文献2参照。)。 The surface of the steel sheet, zinc-based plated coating, 0.3 g / m 2 or more zinc phosphate coating, and organic coating of 0.3 to 2 g / m 2 are sequentially formed, zinc film phosphate containing Mg An organic composite zinc-based plated steel sheet having an Mg / P (mass ratio) of 0.15 or more and an Mg amount of 20 mg / m 2 or more in a zinc phosphate-treated film is disclosed (for example, see Patent Document 2). .)
このような処理を施した亜鉛系めっき鋼板は、通常、プレス成形されアルカリ脱脂洗浄した後、そのまま、あるいは塗装して使用される。このため、無塗装での耐食性および塗装後の耐食性の双方が要求される。 The galvanized steel sheet subjected to such treatment is usually used as it is or after being pressed and alkali degreased and washed. For this reason, both corrosion resistance without painting and corrosion resistance after painting are required.
しかしながら、上述したような方法等によって得られるリン酸亜鉛複合処理鋼板及び有機複合亜鉛系めっき鋼板は、リン酸亜鉛皮膜と有機皮膜間の腐食環境下での結合があまり強くなく、塗装された状態で湿潤率の極めて高い環境におかれると、リン酸亜鉛皮膜と有機皮膜間に剥離を生じ、結果として塗装後耐食性が十分でない場合がある。 However, the zinc phosphate composite-treated steel sheet and organic composite zinc-based plated steel sheet obtained by the method as described above are not very strong in the corrosive environment between the zinc phosphate coating and the organic coating, and are coated. In an environment where the wet rate is extremely high, peeling occurs between the zinc phosphate film and the organic film, resulting in insufficient corrosion resistance after coating.
本発明は、上記現状に鑑み、処理された皮膜中に有害なクロメートを含有せず、優れた耐食性が得られる無機有機複合処理亜鉛系めっき鋼板を提供することを目的とするものである。 The present invention has been made in view of the above situation, and an object of the present invention is to provide an inorganic-organic composite-treated zinc-based plated steel sheet that does not contain harmful chromate in the treated film and that provides excellent corrosion resistance.
亜鉛系めっき上にリン酸亜鉛皮膜と有機皮膜を有する無機有機複合処理亜鉛系めっき鋼板において、リン酸亜鉛皮膜と有機皮膜間の腐食環境下での結合を高める方法を種々検討した結果、リン酸亜鉛皮膜の下地となるZnめっき層の状態が大きく影響することを見出し、本発明に至った。すなわち本発明の要旨とするところは、鋼板上に(002)面の結晶配向が50%以上のZnめっき層を有し、その上層にMgを含有するリン酸亜鉛皮膜を有し、更にその上層に有機皮膜層を有することを特長とする無機有機複合処理亜鉛系めっき鋼板である。リン酸亜鉛皮膜中のMg/P(質量比)が0.1以上であり、Mg量が20mg/m2以上であることが望ましい。また、有機皮膜層がエポキシ樹脂およびまたは変性エポキシ樹脂を含有し、有機皮膜層の付着量が0.3〜5g/m2であることが望ましい。 As a result of various investigations on methods for increasing the bond between a zinc phosphate coating and an organic coating in a corrosive environment in a zinc-plated steel sheet having an inorganic-organic composite treatment having a zinc phosphate coating and an organic coating on the zinc coating. The present inventors have found that the state of the Zn plating layer which is the base of the zinc film is greatly influenced, and have reached the present invention. That is, the gist of the present invention is that a steel plate has a Zn plating layer having a (002) plane crystal orientation of 50% or more, a zinc phosphate film containing Mg as an upper layer, and an upper layer thereof. It is an inorganic-organic composite-treated zinc-based plated steel sheet characterized by having an organic coating layer. It is desirable that Mg / P (mass ratio) in the zinc phosphate coating is 0.1 or more and the amount of Mg is 20 mg / m 2 or more. Moreover, it is desirable that the organic film layer contains an epoxy resin and / or a modified epoxy resin, and the organic film layer has an adhesion amount of 0.3 to 5 g / m 2 .
本発明の無機有機複合処理亜鉛系めっき鋼板は、クロメートを使用せず、良好な耐食性が得られ、製造方法も簡易でコスト的にも優れるので自動車、家電、建材等の各種の用途に好適に使用できる。 The inorganic-organic composite-treated zinc-based plated steel sheet of the present invention does not use chromate, provides good corrosion resistance, is simple in manufacturing and excellent in cost, and is suitable for various applications such as automobiles, home appliances, and building materials. Can be used.
以下、本発明を詳細に説明する。
本発明の無機有機複合処理亜鉛系めっき鋼板のZnめっき層としては、電気めっき、溶融めっき等の手段は問わないが、(002)面の結晶配向が50%以上であることが必要である。ここで、(002)面の結晶配向とは、X線回折装置によりZnメッキ結晶の各ピーク強度を測定し、(002)面に相当する面のピーク強度を各ピーク強度の和で除して百分率としたもの、と定義したものである。Znめっき層の付着量としては、特に限定されないが、より高度の耐食性が要求される場合には20g/m2以上であることが望ましい。
Hereinafter, the present invention will be described in detail.
The Zn plating layer of the inorganic-organic composite-treated zinc-based plated steel sheet of the present invention may be any means such as electroplating or hot dipping, but the (002) plane crystal orientation needs to be 50% or more. Here, the crystal orientation of the (002) plane means that each peak intensity of the Zn plated crystal is measured by an X-ray diffractometer, and the peak intensity of the plane corresponding to the (002) plane is divided by the sum of the peak intensities. It is defined as a percentage. The adhesion amount of the Zn plating layer is not particularly limited, but is desirably 20 g / m 2 or more when higher corrosion resistance is required.
(002)面の結晶配向を50%以上に限定するのは、50%未満では耐食性が悪化するからである。50%以上で良好な耐食性が得られる理由は十分明確でないが、一つにはこの様な状態のめっき層上に形成されるリン酸亜鉛皮膜の性状が変化し、上層の有機皮膜層との密着性が良好になるためと考えられる。またもう一つには、リン酸亜鉛皮膜で被覆されずZnめっき層が露出している部分が存在する場合でも所定のめっき層構造とすることでめっき層と上層の有機皮膜層との密着性が良好になるためと考えられる。 The reason why the crystal orientation of the (002) plane is limited to 50% or more is that if it is less than 50%, the corrosion resistance deteriorates. The reason why good corrosion resistance can be obtained at 50% or more is not clear enough, but in part, the properties of the zinc phosphate film formed on the plating layer in such a state change, This is considered to be because the adhesion is improved. In addition, even when there is a portion where the Zn plating layer is exposed without being covered with the zinc phosphate coating, the adhesion between the plating layer and the upper organic coating layer is achieved by adopting a predetermined plating layer structure. Is considered to be better.
(002)面の結晶配向を高く保つには、Znの析出過電圧が低い条件でめっきすればよい。具体的は、めっき浴濃度、電流密度等で制御でき、めっき浴のZnイオン濃度を高くする、あるいはめっき電流密度を低くする、ことによって(002)面配向を高くすることができる。 In order to keep the crystal orientation of the (002) plane high, plating may be performed under a condition that the Zn precipitation overvoltage is low. Specifically, it can be controlled by the plating bath concentration, current density, etc., and the (002) plane orientation can be increased by increasing the Zn ion concentration of the plating bath or decreasing the plating current density.
リン酸亜鉛処理皮膜は、リン酸イオン及び亜鉛イオンを含有する従来公知のリン酸亜鉛処理剤によって形成することができる。上記亜鉛イオンの供給源としては、亜鉛を含有する化合物であれば特に限定されず、例えば、亜鉛、酸化亜鉛、炭酸亜鉛、硝酸亜鉛等を挙げることができる。上記リン酸イオンの供給源としては、リン酸を含有する化合物であれば特に限定されず、例えば、リン酸、五酸化リン、リン酸二水素ナトリウム等を挙げることができる。また、リン酸亜鉛処理剤に使用される他の成分を適宜含有してもよい。上記リン酸亜鉛処理皮膜は、Mgを含有することが必要である。また更にNi、Mn,Co,Cu,Fe等を単独または複合で含有するものであることが好ましい。これにより、亜鉛系めっき鋼板の耐食性をより向上させ、かつ、後処理皮膜との密着性を高めることができる。 The zinc phosphate-treated film can be formed by a conventionally known zinc phosphate treating agent containing phosphate ions and zinc ions. The zinc ion supply source is not particularly limited as long as it is a compound containing zinc, and examples thereof include zinc, zinc oxide, zinc carbonate, and zinc nitrate. The phosphate ion supply source is not particularly limited as long as it is a compound containing phosphoric acid, and examples thereof include phosphoric acid, phosphorus pentoxide, and sodium dihydrogen phosphate. Moreover, you may contain suitably the other component used for a zinc phosphate processing agent. The zinc phosphate-treated film needs to contain Mg. Furthermore, it is preferable that Ni, Mn, Co, Cu, Fe, etc. are contained alone or in combination. Thereby, the corrosion resistance of a galvanized steel sheet can be improved more, and adhesiveness with a post-process film can be improved.
上記リン酸亜鉛処理皮膜は、皮膜中のマグネシウム/リン(皮膜中のマグネシウムとリンとの質量比)が0.1以上であることが好ましい。0.1未満であると、添加による耐食性の向上がみられないおそれがある。上記リン酸亜鉛処理皮膜は、皮膜中のマグネシウム量が20mg/m2以上であることが好ましい。20mg/m2未満であると、耐食性の向上がみられないおそれがある。
上記リン酸亜鉛処理皮膜は、下限0.3g/m2、上限5g/m2の皮膜量で形成されたものであることが望ましい。0.3g/m2未満であると、耐食性が不十分であるおそれがあり、5g/m2を超えると、厳しい加工を実施した場合に皮膜の剥離が発生するおそれがある。
The zinc phosphate-treated film preferably has a magnesium / phosphorus (mass ratio of magnesium and phosphorus in the film) of 0.1 or more. If it is less than 0.1, there is a risk that the corrosion resistance will not be improved by the addition. In the zinc phosphate-treated film, the amount of magnesium in the film is preferably 20 mg / m 2 or more. If it is less than 20 mg / m 2 , the corrosion resistance may not be improved.
The zinc phosphate-treated film is desirably formed with a film amount having a lower limit of 0.3 g / m 2 and an upper limit of 5 g / m 2 . If it is less than 0.3 g / m 2 , the corrosion resistance may be insufficient. If it exceeds 5 g / m 2 , peeling of the film may occur when severe processing is performed.
上記リン酸亜鉛処理皮膜を形成する処理液としては、リン酸イオン、亜鉛イオンを主成分として、さらに亜鉛以外の金属イオン、硝酸イオン、フッ化物イオン等も必要に応じて添加された市販の処理液が使用できる。リン酸亜鉛処理皮膜中にマグネシウムを含有させる場合には、硝酸マグネシウム等を上記のリン酸亜鉛処理液に添加した浴が好適に用いられる。皮膜中のマグネシウムの量及びマグネシウム/リンの比は、硝酸マグネシウムの添加量によって制御できる。 The treatment liquid for forming the zinc phosphate treatment film is a commercially available treatment mainly containing phosphate ions and zinc ions, and further containing metal ions other than zinc, nitrate ions, fluoride ions and the like as necessary. Liquid can be used. When magnesium is contained in the zinc phosphate-treated film, a bath in which magnesium nitrate or the like is added to the zinc phosphate treatment solution is preferably used. The amount of magnesium in the coating and the magnesium / phosphorus ratio can be controlled by the amount of magnesium nitrate added.
上記リン酸亜鉛処理剤による亜鉛系めっき鋼板のリン酸亜鉛処理方法としては、反応型処理、塗布型処理のいずれの方法によってもリン酸亜鉛処理皮膜を形成させることが可能である。反応型処理としては、たとえば、亜鉛系めっき鋼板に脱脂、水洗、表面調整を行った後に、上記リン酸亜鉛処理液と接触させ、水洗、乾燥を行うことによりリン酸亜鉛処理皮膜を形成することができる。リン酸亜鉛処理皮膜の皮膜量は、たとえば処理時間や処理剤濃度を変化させることにより調整できる。 As a zinc phosphate treatment method for a zinc-based plated steel sheet using the zinc phosphate treatment agent, a zinc phosphate treatment film can be formed by any of a reactive treatment and a coating treatment. As the reactive treatment, for example, after degreasing, rinsing and surface adjustment of a zinc-based plated steel sheet, the zinc phosphate treatment film is formed by contacting with the zinc phosphate treatment solution, washing and drying. Can do. The coating amount of the zinc phosphate-treated film can be adjusted, for example, by changing the treatment time or the treatment agent concentration.
塗布型処理としては、たとえば、亜鉛系めっき鋼板に、必要な皮膜量に応じた量の上記リン酸亜鉛処理液をロールコート法により塗布するほか、浸漬法やスプレー法により塗布した後にロール絞り法により必要な塗布量に調整する方法もある。リン酸亜鉛処理剤を亜鉛系めっき鋼板に塗布した後、乾燥炉等を用いて乾燥させることにより、リン酸亜鉛処理皮膜を形成させる。 As the coating type treatment, for example, the zinc phosphate-treated steel sheet is applied to the zinc-based plated steel sheet by a roll coating method in an amount corresponding to the required coating amount, and after being applied by a dipping method or a spray method, a roll squeezing method There is also a method of adjusting to a necessary coating amount. A zinc phosphate treatment film is formed by applying a zinc phosphate treatment agent to a zinc-based plated steel sheet and then drying it using a drying furnace or the like.
本発明の無機有機複合処理亜鉛系めっき鋼板は、上記リン酸亜鉛処理皮膜上に有機皮膜層を有するものであり、これによって耐食性がいっそう改善される。有機皮膜層は、有機樹脂を含有し、更に耐食性向上の目的で各種の防錆添加剤や架橋剤を配合することが可能である。また目的に応じて、摺動性付与のためのワックス成分や、意匠性付与のための顔料等を配合することも可能である。 The inorganic-organic composite-treated zinc-based plated steel sheet of the present invention has an organic coating layer on the zinc phosphate-treated coating, thereby further improving the corrosion resistance. The organic coating layer contains an organic resin, and various rust preventive additives and crosslinking agents can be blended for the purpose of improving corrosion resistance. Depending on the purpose, a wax component for imparting slidability, a pigment for imparting designability, and the like can also be blended.
有機樹脂としては、密着性の観点から、エポキシ樹脂およびまたは変性エポキシ樹脂を含有することが望ましい。有機皮膜層の付着量としては、0.3〜5g/m2であることが望ましく、下限未満では耐食性が十分でなく、上限を超えると溶接が困難になる場合がある。 The organic resin desirably contains an epoxy resin and / or a modified epoxy resin from the viewpoint of adhesion. The adhesion amount of the organic coating layer is desirably 0.3 to 5 g / m 2 , and if it is less than the lower limit, the corrosion resistance is not sufficient, and if it exceeds the upper limit, welding may be difficult.
有機皮膜層は、コーター、スプレー、ディップ等の方法で塗布した後、焼き付け乾燥を行うことで形成できる。 The organic coating layer can be formed by applying and drying by a method such as coater, spray, dip and the like.
本発明のリン酸亜鉛処理層については、両方の面に処理することが望ましいが、有機皮膜層については、少なくとも一方の面、すなわち無塗装での耐食性がもっとも要求される面に処理すればよい。 The zinc phosphate treatment layer of the present invention is preferably treated on both surfaces, but the organic coating layer may be treated on at least one surface, that is, the surface most required for corrosion resistance without coating. .
以下に実施例によって本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail by way of examples.
(亜鉛めっき鋼板)
電気亜鉛めっき鋼板製造ラインにて、Zn付着量(片面あたり)40g/m2で、めっき浴濃度とめっき電流密度を調整することにより、Zn結晶配向の異なる各種の亜鉛めっき鋼板を製造した。
(Galvanized steel sheet)
In the electrogalvanized steel sheet production line, various zinc plated steel sheets having different Zn crystal orientations were manufactured by adjusting the plating bath concentration and the plating current density at a Zn deposition amount (per one side) of 40 g / m2.
(リン酸亜鉛処理)
前記電気亜鉛めっき鋼板をアルカリ脱脂の後、市販のTiO2コロイド系表面調整処理を行い、リン酸亜鉛処理を行った。リン酸亜鉛処理液はZnイオン2.5g/l、Niイオン2.0g/l、Mnイオン2.5g/l、Mgイオン15g/l、PO4イオン14g/l含有するものを用い、スプレー法により温度45℃で処理時間1〜10秒間処理し、水洗乾燥した。
(Zinc phosphate treatment)
The electrogalvanized steel sheet was subjected to alkaline degreasing, followed by a commercially available TiO2 colloidal surface conditioning treatment and a zinc phosphate treatment. The zinc phosphate treatment solution uses Zn ion 2.5 g / l, Ni ion 2.0 g / l, Mn ion 2.5 g / l, Mg ion 15 g / l, PO 4 ion 14 g / l, spray method Was processed at a temperature of 45 ° C. for 1 to 10 seconds, washed with water and dried.
(有機皮膜処理)
前記リン酸亜鉛処理亜鉛めっき鋼板を用い、有機皮膜処理を行った。有機皮膜処理は、ビニル変性エポキシエステル樹脂にブロックイソシアネート硬化剤、変性ポリエチレンワックス、縮合アゾ系の赤色顔料を配合(それぞれの固形分重量比は、100:10:5:3)した水性樹脂をベースに、コロイダルシリカを固形分重量比で16%になるように添加した塗料を用い、ロールコータにより塗布し、その後到達板温度で150℃になるように焼き付け、水冷した。
(Organic film treatment)
An organic film treatment was performed using the zinc phosphate-treated galvanized steel sheet. The organic film treatment is based on a water-based resin in which a block-modified isocyanate curing agent, a modified polyethylene wax, and a condensed azo-based red pigment are blended into a vinyl-modified epoxy ester resin (each solid content weight ratio is 100: 10: 5: 3). Then, using a coating material in which colloidal silica was added to a solid content weight ratio of 16%, it was applied by a roll coater, and then baked to reach 150 ° C. at the ultimate plate temperature and cooled with water.
(性能評価方法)
(002)面結晶配向;RIGAKU製RINT2000を用い管球Cu、40kV/200mAにて2θ5〜90°のスキャン(4°/min)を行い、Znの各結晶面のピーク強度を測定し、002面強度を各結晶面ピーク強度の和で除して(002)面配向比を求めた。
(Performance evaluation method)
(002) plane crystal orientation; RINT2000 manufactured by RIGAKU was used to scan 2θ5 to 90 ° (4 ° / min) with tube Cu, 40 kV / 200 mA, and the peak intensity of each crystal plane of Zn was measured. The (002) plane orientation ratio was determined by dividing the intensity by the sum of the peak intensity of each crystal plane.
リン酸亜鉛皮膜中Mg,P量;皮膜を全て溶解し、ICP分析により定量した。またリン酸亜鉛皮膜量は、前記P量から、Hopeiteの構造を仮定の上計算で算出した。 The amount of Mg and P in the zinc phosphate coating; all of the coating was dissolved and quantified by ICP analysis. The amount of zinc phosphate coating was calculated from the amount of P, assuming the structure of Hopeite.
有機皮膜量;蛍光X線分析によりSiを定量し、組成比から皮膜量に換算した。
無塗装耐食性;サンプルを市販の洗浄油で洗浄後、Uビード曲げ加工(サンプル幅70mm、BHF=1ton、加工高さ=70mm、ビード部ポンチR=5mm、ビード部ダイスR=3mm、ポンチR=5mm、ダイスR=5mm、加工速度=25spm)を行い、その側面(ダイス側)を切り出して、脱脂した後、端面と裏面をセロテープシールし、CCT試験*を行った。15サイクル後の赤錆発生状況を観察した。「○」;1%未満、「△」;1〜10%、「×」;10%超。
Organic film amount: Si was quantified by fluorescent X-ray analysis, and converted from the composition ratio to the film amount.
Uncoated corrosion resistance; after washing the sample with commercially available cleaning oil, U bead bending (sample width 70 mm, BHF = 1 ton, processing height = 70 mm, bead part punch R = 5 mm, bead part die R = 3 mm, punch R = 5 mm, dice R = 5 mm, processing speed = 25 spm), the side surface (die side) was cut out and degreased, and then the end surface and back surface were sealed with a tape, and a CCT test * was performed. The occurrence of red rust after 15 cycles was observed. “◯”; less than 1%, “Δ”; 1 to 10%, “×”;
塗装密着性;サンプルを市販のアルカリ脱脂液(pH=10.5、40℃、1分浸漬)、自動車用化成処理(日本ペイント製サーフダイン2500MZL)を施した後、自動車用カチオン電着塗装(日本ペイント製V20、20μ、170゜20分焼き付け)を行った。一昼夜放置後50℃温水に浸漬し、10日後取り出して1mm間隔の碁盤目カット疵を入れ、セロテープでの剥離を行った。「○」;剥離なし、「△」;カット疵の周辺の剥離、「×」;剥離。 Coating adhesion; after subjecting the sample to a commercially available alkaline degreasing solution (pH = 10.5, 40 ° C., 1 minute immersion), chemical conversion treatment for automobiles (Surfdyne 2500MZL manufactured by Nippon Paint), cationic electrodeposition coating for automobiles ( (Nippon Paint V20, 20μ, 170 ° 20 minutes baking). After being left for a whole day and night, it was immersed in warm water at 50 ° C., taken out after 10 days, put a grid cut crease with an interval of 1 mm, and peeled off with cello tape. “◯”: no peeling, “Δ”: peeling around the cut ridge, “×”: peeling.
塗装後耐食性;サンプルを市販のアルカリ脱脂液(pH=10.5、40℃、1分浸漬)、自動車用化成処理(日本ペイント製サーフダイン2500MZL)を施した後、自動車用カチオン電着塗装(日本ペイント製V20、20μ、170゜20分焼き付け)を行った。その後地鉄に達するクロスカット疵をつけ、CCT試験*を行った。20サイクル後のフクレ幅を計測した。「○」;1mm未満、「△」;1〜2mm、「×」;2mm超。 Corrosion resistance after painting; after subjecting the sample to a commercially available alkaline degreasing solution (pH = 10.5, 40 ° C., 1 minute immersion) and chemical conversion treatment for automobiles (Surfdyne 2500MZL manufactured by Nippon Paint), cationic electrodeposition coating for automobiles ( (Nippon Paint V20, 20μ, 170 ° 20 minutes baking). After that, a crosscut punch that reaches the ground iron was attached and a CCT test * was conducted. The swelling width after 20 cycles was measured. “◯”: less than 1 mm, “Δ”: 1-2 mm, “×”: more than 2 mm.
*CCT試験条件;塩水噴霧(5%NaCl,35)6時間→乾燥(50℃45%RH)3時間→湿潤(50℃95%RH)14時間→乾燥(50℃45%RH)1時間、を1サイクルとした繰り返し。 * CCT test conditions: salt spray (5% NaCl, 35) 6 hours → dry (50 ° C. 45% RH) 3 hours → wet (50 ° C. 95% RH) 14 hours → dry (50 ° C. 45% RH) 1 hour, Was repeated as one cycle.
以上の評価結果を表1に示した。 The above evaluation results are shown in Table 1.
本発明の実施例では、良好な特性が得られるのに比較し、本発明の範囲から外れる比較例については、特性が悪化した。 In the examples of the present invention, compared with the case where good characteristics were obtained, the characteristics of the comparative examples that were out of the scope of the present invention were deteriorated.
本発明の無機有機複合処理亜鉛系めっき鋼板は、クロメートを使用せず、良好な耐食性が得られ、製造方法も簡易でコスト的にも優れるので自動車、家電、建材等の各種の用途に好適に使用できる。 The inorganic-organic composite-treated zinc-based plated steel sheet of the present invention does not use chromate, provides good corrosion resistance, is simple in manufacturing and excellent in cost, and is suitable for various applications such as automobiles, home appliances, and building materials. Can be used.
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