JPH11350159A - Zinc phosphate-treated steel sheet excellent in peeling resistance and color tone - Google Patents
Zinc phosphate-treated steel sheet excellent in peeling resistance and color toneInfo
- Publication number
- JPH11350159A JPH11350159A JP10158111A JP15811198A JPH11350159A JP H11350159 A JPH11350159 A JP H11350159A JP 10158111 A JP10158111 A JP 10158111A JP 15811198 A JP15811198 A JP 15811198A JP H11350159 A JPH11350159 A JP H11350159A
- Authority
- JP
- Japan
- Prior art keywords
- zinc phosphate
- steel sheet
- film
- zinc
- treated steel
- 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
- 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 title claims abstract description 121
- 229910000165 zinc phosphate Inorganic materials 0.000 title claims abstract description 121
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 49
- 239000010959 steel Substances 0.000 title claims abstract description 49
- 239000011248 coating agent Substances 0.000 claims abstract description 44
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 239000013078 crystal Substances 0.000 claims abstract description 40
- 239000011701 zinc Substances 0.000 claims abstract description 34
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 15
- 239000008397 galvanized steel Substances 0.000 claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 8
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 15
- 238000007747 plating Methods 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 229910000029 sodium carbonate 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
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LKCUKVWRIAZXDU-UHFFFAOYSA-L zinc;hydron;phosphate Chemical compound [Zn+2].OP([O-])([O-])=O LKCUKVWRIAZXDU-UHFFFAOYSA-L 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 102000004237 Decorin Human genes 0.000 description 1
- 108090000738 Decorin Proteins 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 229910007573 Zn-Mg Inorganic materials 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000007740 vapor deposition 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
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐剥離性および色
調に優れたりん酸亜鉛処理鋼板に関し、詳細には家庭用
電気製品，配電盤，電話交換機パネル，自動車車体，自
動車部品，建材等の素材として好適な耐剥離性および色
調に優れたりん酸亜鉛処理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 a zinc phosphate treated steel sheet having excellent peel resistance and color tone, and more particularly to materials for household electrical appliances, switchboards, telephone exchange panels, automobile bodies, automobile parts, building materials, and the like. The present invention relates to a zinc phosphate treated steel sheet having excellent peel resistance and excellent color tone.
【０００２】[0002]
【従来の技術】上記した各種用途においては、亜鉛めっ
き鋼板や亜鉛合金めっき鋼板（以下、亜鉛めっき鋼板で
代表することがある）を素地鋼板とし、この表面に塗装
が施された表面処理鋼板が汎用されている。そしてこう
した表面処理鋼板を製造するにあたっては、塗装皮膜の
密着性および耐食性を向上させるという観点から、塗装
前にりん酸亜鉛処理がめっき表面に施されている。以下
では、亜鉛めっき鋼板のめっき表面にりん酸亜鉛処理が
施された状態の鋼板を、りん酸亜鉛処理鋼板と呼ぶ。2. Description of the Related Art In the above-mentioned various applications, a galvanized steel sheet or a zinc alloy-coated steel sheet (hereinafter sometimes referred to as a galvanized steel sheet) is used as a base steel sheet, and a surface-treated steel sheet having a surface coated thereon is used. It is widely used. When manufacturing such a surface-treated steel sheet, a zinc phosphate treatment is applied to the plating surface before painting from the viewpoint of improving the adhesion and corrosion resistance of the coating film. Hereinafter, a steel sheet in which a zinc phosphate treatment is applied to a galvanized steel sheet is referred to as a zinc phosphate treated steel sheet.
【０００３】りん酸亜鉛処理鋼板を製造するにあたって
は、まず素地鋼板としての亜鉛めっき鋼板の表面を、水
酸化ナトリウム，ケイ酸ナトリウム，炭酸ナトリウム等
のアルカリ性溶液によって脱脂した後（或いは脱脂と同
時に）、めっき表面にチタンコロイドを析出させる表面
調整を行い、その後めっき表面にりん酸亜鉛皮膜を形成
することが一般的である。りん酸亜鉛皮膜を形成するた
めのりん酸亜鉛処理液は、基本的にりん酸溶液に酸化亜
鉛を溶解させたものであり、反応促進剤として酸化剤
（硝酸塩，亜硝酸塩，塩素酸塩など）を加えることがあ
る。このように亜鉛イオンを共存するりん酸溶液中では
亜鉛は第一りん酸亜鉛［Ｚｎ（Ｈ2 ＳＯ4）2 ］の状態
で溶解しており、次式で示される平衡状態にある。 ３Ｚｎ2+＋２Ｈ2 ＰＯ4 - ⇔ Ｚｎ3(ＰＯ4)2 ＋４Ｈ+ [0003] In manufacturing a zinc phosphate treated steel sheet, first, the surface of a galvanized steel sheet as a base steel sheet is degreased with an alkaline solution such as sodium hydroxide, sodium silicate, sodium carbonate or the like (or simultaneously with degreasing). In general, it is common practice to adjust the surface to precipitate titanium colloid on the plating surface, and then form a zinc phosphate film on the plating surface. A zinc phosphate treatment solution for forming a zinc phosphate film is basically a solution in which zinc oxide is dissolved in a phosphoric acid solution, and an oxidizing agent (nitrate, nitrite, chlorate, etc.) is used as a reaction accelerator. May be added. As described above, in a phosphoric acid solution in which zinc ions coexist, zinc is dissolved in the form of zinc monophosphate [Zn (H 2 SO 4 ) 2 ], and is in an equilibrium state represented by the following equation. 3Zn 2+ + 2H 2 PO 4 − ⇔ Zn 3 (PO 4 ) 2 + 4H +
【０００４】上式の平衡反応は、常温では著しく左辺に
偏っているが、本溶液中に亜鉛めっき鋼板を浸漬する
と、遊離のりん酸により亜鉛が溶解し、Ｈ+ が消費され
てｐＨの上昇が生じる。すると上式の平衡が右辺に移行
し、Ｚｎ3(ＰＯ4)2 が生成されると、溶解度の低い白色
透明なホパイト結晶［Ｚｎ3(ＰＯ4)2 ・４Ｈ2 Ｏ］が析
出して、亜鉛めっき鋼板上にりん酸亜鉛皮膜が形成され
る。[0004] The equilibrium reaction of the above formula is remarkably deviated to the left side at normal temperature, but when a galvanized steel sheet is immersed in this solution, zinc is dissolved by free phosphoric acid, H + is consumed, and the pH rises. Occurs. Then, the equilibrium of the above equation shifts to the right side, and when Zn 3 (PO 4 ) 2 is generated, a white and transparent low-solubility Hopite crystal [Zn 3 (PO 4 ) 2 .4H 2 O] precipitates, A zinc phosphate film is formed on the galvanized steel sheet.
【０００５】この様にして製造されたりん酸亜鉛処理鋼
板には、塗装が施される前に所望の形状に切断されたり
加工されたりすることが一般的である。しかしながら、
加工様式等によってはりん酸亜鉛皮膜の一部が剥離して
押疵の原因となったり、更には塗装密着性が不十分にな
って塗装がはがれるという問題が生じていた。特にりん
酸亜鉛皮膜の付着量が多めの場合に、剥離の問題が顕著
であり、しかもりん酸亜鉛皮膜の色調も黒ずんだ様にな
ることが指摘されていた。[0005] The zinc phosphate-treated steel sheet thus manufactured is generally cut or processed into a desired shape before coating. However,
Depending on the processing method, a part of the zinc phosphate film is peeled off, causing a flaw, and furthermore, the coating adhesion becomes insufficient and the coating is peeled off. In particular, it has been pointed out that when the amount of the zinc phosphate coating is large, the problem of peeling is remarkable, and the color tone of the zinc phosphate coating becomes dark.
【０００６】またりん酸亜鉛皮膜には、塗装密着性およ
び塗装後の耐食性を向上させるという観点から、りん酸
亜鉛処理液中に亜鉛以外の重金属（例えばＦｅ，Ｎｉ，
Ｍｎ，Ｃｏ，Ｃｒ等）を添加して、上記ホパイト結晶中
に上記重金属を共析させるのが一般的であり、特にＮｉ
を共析させる場合が多い。[0006] In addition, from the viewpoint of improving coating adhesion and corrosion resistance after coating, the zinc phosphate coating contains heavy metals other than zinc (for example, Fe, Ni, and the like) in the zinc phosphate treatment solution.
Mn, Co, Cr, etc.) to add the heavy metal to the Hopite crystal.
Are often eutectoid.
【０００７】但し、りん酸亜鉛皮膜にＮｉを共析させる
ことは、塗膜の密着性や塗装後の耐食性の向上に有用で
あるが、その一方でりん酸亜鉛皮膜の表面が黒くなるこ
とがあった。りん酸亜鉛皮膜には塗装が施され、例えば
白色系の塗装の場合には、りん酸亜鉛皮膜鋼板が黒ずん
でいると、塗膜の付着量を多くしなければならない。そ
こで、Ｎｉの含有量を極力低下させることも考えられる
が、りん酸亜鉛皮膜鋼板の外観が黒ずまない程度にＮｉ
の含有量を低下させることは、Ｎｉを共析させることに
よる基本的な作用である塗膜密着性や塗装後の耐食性の
向上が発揮されなくなる。However, co-depositing Ni into the zinc phosphate coating is useful for improving the adhesion of the coating and the corrosion resistance after coating, but on the other hand, the surface of the zinc phosphate coating may be blackened. there were. A coating is applied to the zinc phosphate coating. For example, in the case of a white coating, if the zinc phosphate coating steel sheet is dark, the coating amount of the coating must be increased. Therefore, it is conceivable to reduce the Ni content as much as possible.
In the case where the content of Ni is reduced, the improvement of the adhesion to the coating film and the corrosion resistance after coating, which are the basic functions of eutectoid Ni, cannot be exhibited.
【０００８】[0008]
【発明が解決しようとする課題】本発明は上記事情に着
目してなされたものであって、耐剥離性に優れ、しかも
りん酸亜鉛皮膜鋼板の外観が黒ずむこともなく色調が良
好なりん酸亜鉛処理鋼板を提供しようとするものであ
る。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and has excellent peeling resistance and a good color tone without darkening of the appearance of a zinc phosphate coated steel sheet. It is intended to provide a zinc-treated steel sheet.
【０００９】[0009]
【課題を解決するための手段】上記課題を解決した本発
明とは、亜鉛めっき鋼板または亜鉛合金めっき鋼板の表
面にりん酸亜鉛処理が施されたりん酸亜鉛処理鋼板であ
って、形成されたりん酸亜鉛皮膜表面の任意の場所にお
いて、長さ２０μｍの直交する２本の線分を横切るりん
酸亜鉛結晶の数（以下、りん酸亜鉛結晶密度というか、
或いは単に結晶密度ということがある）が、１５以上４
０以下であり、且つりん酸亜鉛皮膜の付着量が０．８ｇ
／ｍ2 以上３．０ｇ／ｍ2 以下であることを要旨とする
ものである。またりん酸亜鉛処理液中にＮｉを含有させ
てＮｉを皮膜中に共析させる場合には、前記りん酸亜鉛
皮膜中におけるＮｉとＺｎの重量比Ｎｉ／Ｚｎを０．０
５以上０．８以下とすることが望ましい。Means for Solving the Problems The present invention, which has solved the above-mentioned problems, is a zinc phosphate treated steel sheet in which the surface of a galvanized steel sheet or a zinc alloy plated steel sheet is subjected to a zinc phosphate treatment. At any point on the surface of the zinc phosphate film, the number of zinc phosphate crystals crossing two orthogonal line segments having a length of 20 μm (hereinafter referred to as zinc phosphate crystal density,
Or simply the crystal density), but 15 or more 4
0 or less and 0.8 g of zinc phosphate coating
/ M 2 or more and 3.0 g / m 2 or less. When Ni is contained in the zinc phosphate treatment solution and Ni is codeposited in the film, the weight ratio Ni / Zn of Ni and Zn in the zinc phosphate film is set to 0.0.
It is desirable to be 5 or more and 0.8 or less.
【００１０】また亜鉛めっき鋼板または亜鉛合金めっき
鋼板の表面にりん酸亜鉛処理が施されたりん酸亜鉛処理
鋼板において、りん酸亜鉛処理により生成されるりん酸
亜鉛結晶の成長方向を、鋼板表面に対しておおむね垂直
方向とすれば耐剥離性および色調に優れたりん酸亜鉛処
理鋼板を得ることができる。In addition, in a zinc phosphate treated steel sheet in which the surface of a galvanized steel sheet or a zinc alloy plated steel sheet is subjected to a zinc phosphate treatment, the growth direction of zinc phosphate crystals generated by the zinc phosphate treatment is determined by the following equation. On the other hand, when the direction is substantially vertical, a zinc phosphate treated steel sheet having excellent peel resistance and color tone can be obtained.
【００１１】[0011]
【発明の実施の形態】本発明者らは、りん酸亜鉛処理鋼
板の耐剥離性と色調に影響を与える因子について精査し
た結果、りん酸亜鉛皮膜の付着量と共に、りん酸亜鉛の
結晶形態が上記特性に大きな影響を与えていることを見
出し、上記りん酸亜鉛結晶密度が１５以上で、りん酸亜
鉛付着量が３．０ｇ／ｍ2 以下であれば、りん酸亜鉛処
理鋼板の耐剥離性と色調がいずれも非常に良好となるこ
とを突き止め、本発明に想到した。BEST MODE FOR CARRYING OUT THE INVENTION The present inventors examined the factors affecting the peel resistance and the color tone of a zinc phosphate treated steel sheet, and found that the zinc phosphate crystal morphology was determined along with the adhesion amount of the zinc phosphate film. It has been found that the above-mentioned properties are greatly affected, and when the zinc phosphate crystal density is 15 or more and the zinc phosphate adhesion amount is 3.0 g / m 2 or less, the peeling resistance of the zinc phosphate-treated steel sheet is reduced. It was found that the color tone was very good and the present invention was reached.
【００１２】尚、りん酸亜鉛の結晶密度を測定して、耐
剥離性や色調との関連を把握するにあたって、本発明者
らは次の方法を採用した。即ち、図１に模式的に示す様
に、りん酸亜鉛皮膜表面の任意の位置において、長さ２
０μｍの直交する２本の線分ａｂ，ｃｄを仮想的に引
き、夫々の線分を横切るりん酸亜鉛結晶の総数を計測す
る方法によりりん酸亜鉛結晶密度の定量化を行った。
尚、結晶密度を算出するにあたっては、りん酸亜鉛皮膜
表面の任意の１０か所の位置において、夫々の結晶密度
を測定し、平均値を求めた。The present inventors have adopted the following method for measuring the crystal density of zinc phosphate to determine the relationship between peel resistance and color tone. That is, as schematically shown in FIG. 1, at an arbitrary position on the surface of the zinc phosphate film, the length 2
The two orthogonal line segments ab and cd of 0 μm were virtually drawn, and the zinc phosphate crystal density was quantified by a method of measuring the total number of zinc phosphate crystals crossing each line segment.
In calculating the crystal density, each crystal density was measured at arbitrary 10 positions on the surface of the zinc phosphate film, and the average value was obtained.
【００１３】上記結晶密度が大きいということは、りん
酸亜鉛結晶が微細で密に存在していることを示し、換言
すれば、りん酸亜鉛の鱗片状結晶が図２（ａ）に示す様
に、基板に対して垂直に近い角度で成長していることを
示す。また上記結晶密度が小さいということは、りん酸
亜鉛結晶が粗大で疎に存在していることを示し、換言す
れば、りん酸亜鉛の鱗片状結晶が基板に対して水平に近
い角度で成長していることを示す［図２の（ｂ）参
照］。The high crystal density indicates that the zinc phosphate crystals are fine and densely present. In other words, the zinc phosphate scale-like crystals are formed as shown in FIG. , Indicates that the substrate grows at an angle nearly perpendicular to the substrate. The low crystal density indicates that the zinc phosphate crystals are coarse and sparse, in other words, the flake crystals of zinc phosphate grow at an angle nearly horizontal to the substrate. [See FIG. 2 (b)].
【００１４】尚、上記りん酸亜鉛の結晶密度が、１５以
上であれば耐剥離性及び色調は良好であるが、結晶密度
が高くなり過ぎるとりん酸亜鉛処理鋼板本来の目的であ
る塗装密着性が低下する傾向が認められ、しかも工業的
生産ラインにおいて上記密度が４０を超えるりん酸亜鉛
処理鋼板を安定して製造することが困難であることから
上限値を４０とした。上記結晶密度の好ましい範囲は１
７以上３５以下である。またりん酸亜鉛付着量に関して
も、３．０ｇ／ｍ2 以下であれば耐剥離性及び色調は良
好であるが、２．５ｇ／ｍ2 以下であるとより好まし
い。一方、付着量が少な過ぎると、塗膜密着性が低下す
る傾向があることから、０．８ｇ／ｍ2 以上の付着量が
必要であり、１．０ｇ／ｍ2 以上であるとより好まし
い。If the crystal density of the zinc phosphate is 15 or more, the peeling resistance and the color tone are good, but if the crystal density is too high, the paint adhesion which is the original purpose of the zinc phosphate treated steel sheet is obtained. Was observed, and it was difficult to stably produce the zinc phosphate-treated steel sheet having the density exceeding 40 in an industrial production line, so the upper limit was set to 40. The preferred range of the crystal density is 1
7 or more and 35 or less. Regarding the amount of zinc phosphate attached, if it is 3.0 g / m 2 or less, the peel resistance and the color tone are good, but it is more preferably 2.5 g / m 2 or less. On the other hand, if the adhesion amount is too small, the adhesion of the coating film tends to decrease. Therefore, an adhesion amount of 0.8 g / m 2 or more is required, and more preferably 1.0 g / m 2 or more.
【００１５】本発明のりん酸亜鉛の結晶密度が高くなる
ほど、耐剥離性及び色調が良好になる理由としては、以
下の様に推察できる。そもそもりん酸亜鉛皮膜が加工に
より剥離する理由は、りん酸亜鉛結晶が元来硬く脆い性
質を有しているからであり、その為に、加工時の衝撃や
歪みにより皮膜自身が一部欠落したり、亜鉛めっき層と
の界面から剥離するものと考えられる。これに対して、
本発明のりん酸亜鉛皮膜は、りん酸亜鉛結晶を微細で密
に成長させることで、隣接する結晶同士が互いに保持し
あい界面からの剥離を抑制して皮膜の欠落量を少なくで
きるものと考えられる。The reason why the higher the crystal density of the zinc phosphate of the present invention becomes, the better the peel resistance and color tone become can be guessed as follows. In the first place, the zinc phosphate film is peeled off by processing because the zinc phosphate crystal has a hard and brittle nature by nature. Or peeling off from the interface with the galvanized layer. On the contrary,
The zinc phosphate film of the present invention is considered to be able to reduce the amount of film loss by growing zinc phosphate crystals finely and densely, holding adjacent crystals together and suppressing peeling from the interface. .
【００１６】本発明のりん酸亜鉛の結晶密度や付着量を
制御するにあたっては、りん酸亜鉛処理の前処理である
チタンコロイド析出処理（表面調整処理）液の濃度を調
整するか、或いはりん酸亜鉛処理液中のＮｉイオン濃度
やＺｎイオン濃度を変化させればよい。特に、Ｎｉイオ
ン濃度を増加させる方法は、微細で密な成長形態を有す
るりん酸亜鉛結晶を得ることができる上に、塗膜密着性
及び塗装後の耐食性を向上させる効果もあるので推奨さ
れる。但し、りん酸亜鉛処理液中のＮｉイオン濃度を増
加すると、外観が黒くなる［換言すれば、色度計による
明度（Ｌ値）が小さくなる］傾向がある。その原因につ
いては、全てを解明したわけではないが、りん酸塩結晶
中に取り込まれたＮｉは、結晶のＺｎの位置に析出する
と言われており、Ｚｎの位置にＮｉが析出してりん酸亜
鉛結晶の結晶格子が歪むことが、Ｌ値の低下の一因にな
るものと推定される。従って、耐剥離性を満足しつつ、
外観についても優れたものとするには、りん酸亜鉛皮膜
中のＮｉ含有量を適正な範囲に制御することが望まし
く、りん酸亜鉛皮膜中におけるＮｉとＺｎの重量比Ｎｉ
／Ｚｎを０．８以下に制御することが望ましい。上記重
量比は０．８以下であれば、一段と優れた色調を有する
りん酸亜鉛処理鋼板を得ることができるが、上記重量比
が小さ過ぎると、塗膜密着性や塗装後の耐食性が低下す
るので０．０５以上とすることが望ましい。尚、りん酸
亜鉛皮膜中のＮｉ及びＺｎを定量分析するにあたって
は、公知の分析方法を採用すれば良く、本発明者らは、
重クロム酸アンモニウム溶液にてりん酸亜鉛皮膜のみを
溶解し、公知の誘導結合プラズマ発光分光分析法にて上
記溶液中に含まれるＮｉ及びＺｎの定量分析を行った。In controlling the crystal density and the amount of the zinc phosphate of the present invention, the concentration of the titanium colloid deposition treatment (surface conditioning treatment) which is a pretreatment of the zinc phosphate treatment is adjusted, or the concentration of phosphoric acid is adjusted. What is necessary is just to change the Ni ion concentration or Zn ion concentration in the zinc treatment liquid. In particular, the method of increasing the Ni ion concentration is recommended because it can obtain zinc phosphate crystals having a fine and dense growth form and also has the effect of improving the coating film adhesion and the corrosion resistance after coating. . However, when the concentration of Ni ions in the zinc phosphate treatment liquid increases, the appearance tends to be black (in other words, the lightness (L value) measured by a chromaticity meter tends to decrease). Although the cause has not been fully elucidated, it is said that Ni taken into the phosphate crystal precipitates at the Zn position of the crystal. It is presumed that the distortion of the crystal lattice of the zinc crystal causes a decrease in the L value. Therefore, while satisfying the peeling resistance,
In order to make the appearance excellent, it is desirable to control the Ni content in the zinc phosphate film to an appropriate range, and the weight ratio of Ni to Zn in the zinc phosphate film Ni
It is desirable to control / Zn to 0.8 or less. If the weight ratio is 0.8 or less, a zinc phosphate treated steel sheet having a much better color tone can be obtained, but if the weight ratio is too small, the coating film adhesion and the corrosion resistance after coating are reduced. Therefore, it is desirable to set it to 0.05 or more. For quantitative analysis of Ni and Zn in the zinc phosphate film, a known analysis method may be adopted.
Only the zinc phosphate film was dissolved in an ammonium bichromate solution, and quantitative analysis of Ni and Zn contained in the solution was performed by a known inductively coupled plasma emission spectroscopy.
【００１７】りん酸亜鉛処理を施すためのりん酸亜鉛化
成処理液としては、Ｚｎイオン，Ｎｉイオン，りん酸イ
オン，硝酸イオン等を含む市販の処理液（例えば、日本
パーカライジング株式会社製の市販品）を用いればよ
い。りん酸亜鉛皮膜中のＮｉ／Ｚｎ（重量比）は、上記
化成処理液中の（Ｎｉイオン／Ｚｎイオン）濃度比を変
えることによって変化させることができ、またりん酸亜
鉛皮膜の付着量は、Ｚｎイオン濃度を変化させることに
よって調整することができる。As the zinc phosphate chemical conversion treatment solution for performing the zinc phosphate treatment, a commercially available treatment solution containing Zn ion, Ni ion, phosphate ion, nitrate ion and the like (for example, a commercial product manufactured by Nippon Parkerizing Co., Ltd.) ) May be used. Ni / Zn (weight ratio) in the zinc phosphate coating can be changed by changing the (Ni ion / Zn ion) concentration ratio in the chemical conversion treatment solution. It can be adjusted by changing the Zn ion concentration.
【００１８】りん酸亜鉛皮膜中には、ＺｎやＮｉ以外に
もＦｅ，Ｃｏ，Ｍｎ，Ｍｇ，Ｃｒ，Ｓｂ等の元素やアル
カリ土類金属等を不純物程度に微量含んでいても良く、
或は添加剤としてグルコン酸ソーダやポリエーテル等の
有機物を含んでいてもよい。また前記りん酸亜鉛化成処
理液の塗布方法は、浸漬法及びスプレー法のいずれでも
行うことができる。但し、りん酸亜鉛処理の前処理とし
て、コロイダルチタンを含有する表面処理剤で表面の調
整を行うことは、りん酸亜鉛結晶を微細で密に成長させ
る上で好ましい方法である。The zinc phosphate film may contain elements such as Fe, Co, Mn, Mg, Cr, and Sb, as well as alkaline earth metals, in addition to Zn and Ni.
Alternatively, an organic substance such as sodium gluconate or polyether may be contained as an additive. The zinc phosphate chemical conversion treatment solution can be applied by either a dipping method or a spray method. However, adjusting the surface with a surface treatment agent containing colloidal titanium as a pretreatment of the zinc phosphate treatment is a preferable method for growing zinc phosphate crystals finely and densely.
【００１９】また、耐食性の向上を目的として、りん酸
亜鉛処理を行った後に、シーリングクロメート処理を行
ってもよい。For the purpose of improving corrosion resistance, a sealing chromate treatment may be performed after the zinc phosphate treatment.
【００２０】本発明のりん酸亜鉛処理が施される亜鉛め
っき鋼板は、電気めっき法、溶融めっき法、または蒸着
めっき法等の公知のめっき法によって製造されるめっき
鋼板であって、Ｚｎを主成分とするめっき（例えば、Ｚ
ｎめっき，Ｚｎ−Ｎｉ合金めっき，Ｚｎ−Ｆｅ合金めっ
き，Ｚｎ−Ｍｇ合金めっき等）が形成されたものであれ
ば、その種類や付着量により限定されるものではない。The galvanized steel sheet subjected to the zinc phosphate treatment of the present invention is a galvanized steel sheet manufactured by a known plating method such as an electroplating method, a hot-dip plating method, or a vapor deposition plating method. Plating as a component (for example, Z
As long as n-plating, Zn-Ni alloy plating, Zn-Fe alloy plating, Zn-Mg alloy plating, etc. are formed, there is no particular limitation on the type and amount of the plating.
【００２１】以下、本発明を実施例によって更に詳細に
説明するが、下記実施例は本発明を限定する性質のもの
ではなく、前・後記の趣旨に徴して設計変更することは
いずれも本発明の技術的範囲に含まれるものである。Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are not intended to limit the present invention. It is included in the technical range of.
【００２２】[0022]
【実施例】電気亜鉛めっき鋼板（めっき付着量：３ｇ／
ｍ2 ）または溶融亜鉛めっき鋼板（めっき付着量：６０
ｇ／ｍ2 ）を素地鋼板として使用し、通常のチタンコロ
イド系の表面調整剤（日本パーカライジング株式会社製
「プレパランＺ」）に、素地鋼板を室温で１０秒間浸す
ことにより表面調整を行い、次いでりん酸亜鉛処理液
（日本パーカライジング株式会社製「パルボンド３３１
２」）に、ＮｉまたはＺｎを添加することでりん酸亜鉛
皮膜中のＮｉ／Ｚｎを調整して、６５℃で１０〜３０秒
間浸漬させてりん酸亜鉛皮膜を形成した。[Example] Electrogalvanized steel sheet (coating weight: 3 g /
m 2 ) or hot-dip galvanized steel sheet (coating weight: 60
g / m 2 ) as a base steel sheet, and the surface is adjusted by immersing the base steel sheet in a normal titanium colloid-based surface conditioner (“Preparan Z” manufactured by Nippon Parkerizing Co., Ltd.) at room temperature for 10 seconds. Zinc phosphate treatment liquid ("Palbond 331" manufactured by Nippon Parkerizing Co., Ltd.)
2)), Ni / Zn in the zinc phosphate film was adjusted by adding Ni or Zn, and immersed at 65 ° C. for 10 to 30 seconds to form a zinc phosphate film.
【００２３】得られたりん酸亜鉛処理鋼板について、下
記の方法によって耐剥離性および色調と塗膜密着性を評
価した。The obtained zinc phosphate treated steel sheet was evaluated for peel resistance, color tone and coating film adhesion by the following methods.
【００２４】(1) 耐剥離性 りん酸亜鉛皮膜の剥離量は、実加工を模擬した次の試験
により求めた。ＪＩＳ記載の５号片に加工したりん酸亜
鉛処理鋼板を用いて、単軸引張試験機にて３０％の歪み
を付与した後、加工部をセロテープ剥離し（同一箇所に
おいて３回のテープ剥離を実施）、テープに付着したり
ん酸亜鉛皮膜中のＰ量を、誘導結合プラズマ発光分光分
析装置（ＩＣＰ）にて定量分析した。測定した剥離量は
以下の基準で評価した。 ◎：剥離量が８０ｍｇ／ｍ2 未満 ○：剥離量が８０ｍｇ／ｍ2 以上１００ｍｇ／ｍ2 未満 △：剥離量が１００ｍｇ／ｍ2 以上１３０ｍｇ／ｍ2 未
満 ×：剥離量が１３０ｍｇ／ｍ2 以上(1) Peeling Resistance The peeling amount of the zinc phosphate film was determined by the following test simulating actual processing. Using a zinc phosphate treated steel sheet processed into a No. 5 piece described in JIS, applying a 30% strain with a uniaxial tensile tester, and then peeling off the processed part with cellophane tape (three times of tape peeling at the same location). Implementation), the amount of P in the zinc phosphate film adhered to the tape was quantitatively analyzed by an inductively coupled plasma emission spectrometer (ICP). The measured peel amount was evaluated based on the following criteria. ◎: less peeling amount 80mg / m 2 ○: less peeling amount 80 mg / m 2 or more 100mg / m 2 △: Peeling weight 100 mg / m 2 or more 130 mg / m 2 less ×: Peeling weight 130 mg / m 2 or more
【００２５】(2) 色調 色調については、Ｌ値（明度）を色差計（日本電色工業
株式会社製「ＳＺＳ−Σ９０」）で測定して以下の様に
評価した。尚、Ｌ値は大きくなる程、色調は白くなり良
好な外観となる。 ◎：Ｌ値が７０以上 ○：Ｌ値が６５以上７０未満 △：Ｌ値が６０以上６５未満 ×：Ｌ値が６０未満(2) Color Tone For the color tone, the L value (brightness) was measured with a color difference meter (“SZS- # 90” manufactured by Nippon Denshoku Industries Co., Ltd.) and evaluated as follows. It should be noted that as the L value increases, the color tone becomes white and the appearance becomes better. ◎: L value is 70 or more ○: L value is 65 or more and less than 70 Δ: L value is 60 or more and less than 65 ×: L value is less than 60
【００２６】(3) 塗膜密着性 りん酸亜鉛皮膜鋼板に市販の塗料（大日本塗料株式会社
製「デコリン７００」）をバーコード塗装し、２０分間
セッティングした後、１４０℃で２０分間焼付して２５
μｍの塗装膜を形成した。塗装板にカッターナイフで素
地鋼板に到達するように１ｍｍ間隔の碁盤目（１００
個）を切り、エリクセン加工（押出高さ：６ｍｍ）を施
した後、セロテープ剥離を行い、残存の塗膜率により以
下の様に評価した。 ○：塗膜残存率が９０％以上 △：塗膜残存率が７０％以上９０％未満 ×：塗膜残存率が７０％未満(3) Coating Film Adhesion A commercially available coating material ("Decorin 700" manufactured by Dainippon Paint Co., Ltd.) is bar-coded on a zinc phosphate coated steel sheet, set for 20 minutes, and baked at 140 ° C. for 20 minutes. 25
A μm coating film was formed. Use a cutter knife on the painted board so as to reach the base steel plate at intervals of 1 mm (100
Were cut and subjected to Erichsen processing (extrusion height: 6 mm), and then cellophane tape peeling was performed. The remaining coating film ratio was evaluated as follows. ：: Residual rate of coating film is 90% or more △: Residual rate of coating film is 70% or more and less than 90% ×: Residual rate of coating film is less than 70%
【００２７】これらの結果を、素地鋼板の種類，亜鉛め
っき層中のＮｉ含有量，りん酸亜鉛皮膜付着量，および
りん酸亜鉛皮膜中のＮｉ／Ｚｎ（重量％）等と共に、下
記表１に示す。The results are shown in Table 1 below, together with the type of the base steel sheet, the Ni content in the galvanized layer, the amount of zinc phosphate coating, and the Ni / Zn (% by weight) in the zinc phosphate coating. Show.
【００２８】尚、りん酸亜鉛付着量については、りん酸
亜鉛皮膜の溶解除去に重クロム酸アンモニウム溶液を用
いる重量法によって求めた。更に、りん酸亜鉛皮膜溶解
後の溶液中に含まれるＮｉ量及びＺｎ量を、誘導結合プ
ラズマ発光分光分析法にて定量分析し、重量比Ｎｉ／Ｚ
ｎを求めた。また、りん酸亜鉛結晶密度については、皮
膜表面を走査型電子顕微鏡にて１５００倍に拡大した上
で、長さ２０μｍに相当する２本の直交する線分を引
き、いずれかの線分を横切るりん酸亜鉛結晶の数を測定
する作業を任意の１０か所で行い、その平均値を算出し
た。The amount of zinc phosphate attached was determined by a gravimetric method using an ammonium bichromate solution for dissolving and removing the zinc phosphate film. Further, the amounts of Ni and Zn contained in the solution after dissolving the zinc phosphate film were quantitatively analyzed by inductively coupled plasma emission spectroscopy, and the weight ratio Ni / Z was determined.
n was determined. Regarding the zinc phosphate crystal density, the surface of the film was magnified 1500 times with a scanning electron microscope, and then two perpendicular lines corresponding to a length of 20 μm were drawn and crossed either line. The work of measuring the number of zinc phosphate crystals was performed at any 10 locations, and the average value was calculated.
【００２９】[0029]
【表１】 [Table 1]
【００３０】これらの結果から明らかなように、本発明
で規定する要件の全てを満足する実施例（Ｎｏ．１〜３
５）では、耐剥離性及び色調がいずれも優れており、し
かも塗膜密着性が良好である。これに対し、上記要件の
いずれかを欠く比較例（Ｎｏ．３６〜５６）では、いず
れかの特性が劣化していることが分かる。As is clear from these results, Examples (Nos. 1 to 3) satisfying all the requirements specified in the present invention.
In 5), peel resistance and color tone are both excellent, and coating film adhesion is good. On the other hand, in the comparative examples (Nos. 36 to 56) lacking any of the above requirements, it can be seen that any of the characteristics is deteriorated.
【００３１】[0031]
【発明の効果】本発明は以上の様に構成されているの
で、耐剥離性に優れ、色調が良好なりん酸亜鉛処理鋼板
であって、しかも優れた塗膜密着性を発揮するりん酸亜
鉛処理鋼板が提供できることとなった。Since the present invention is constituted as described above, it is a zinc phosphate treated steel sheet having excellent peel resistance and good color tone, and exhibiting excellent coating film adhesion. It is now possible to provide treated steel sheets.
【図１】りん酸亜鉛結晶密度を測定する方法を説明する
模式図である。FIG. 1 is a schematic diagram illustrating a method for measuring a zinc phosphate crystal density.
【図２】りん酸亜鉛結晶の成長形態を模式的に示す断面
説明図である。FIG. 2 is an explanatory sectional view schematically showing a growth form of a zinc phosphate crystal.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１１年４月１２日[Submission date] April 12, 1999
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００３[Correction target item name] 0003
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００３】りん酸亜鉛処理鋼板を製造するにあたって
は、まず素地鋼板としての亜鉛めっき鋼板の表面を、水
酸化ナトリウム，ケイ酸ナトリウム，炭酸ナトリウム等
のアルカリ性溶液によって脱脂した後（或いは脱脂と同
時に）、めっき表面にチタンコロイドを析出させる表面
調整を行い、その後めっき表面にりん酸亜鉛皮膜を形成
することが一般的である。りん酸亜鉛皮膜を形成するた
めのりん酸亜鉛処理液は、基本的にりん酸溶液に酸化亜
鉛を溶解させたものであり、反応促進剤として酸化剤
（硝酸塩，亜硝酸塩，塩素酸塩など）を加えることがあ
る。このように亜鉛イオンを共存するりん酸溶液中では
亜鉛は第一りん酸亜鉛［Ｚｎ（Ｈ2ＰＯ4）2］の状態で
溶解しており、次式で示される平衡状態にある。 ３Ｚｎ2+＋２Ｈ2ＰＯ4 -⇔ Ｚｎ3(ＰＯ4)2＋４Ｈ+ [0003] In manufacturing a zinc phosphate treated steel sheet, first, the surface of a galvanized steel sheet as a base steel sheet is degreased with an alkaline solution such as sodium hydroxide, sodium silicate, sodium carbonate or the like (or simultaneously with degreasing). In general, it is common practice to adjust the surface to precipitate titanium colloid on the plating surface, and then form a zinc phosphate film on the plating surface. A zinc phosphate treatment solution for forming a zinc phosphate film is basically a solution in which zinc oxide is dissolved in a phosphoric acid solution, and an oxidizing agent (nitrate, nitrite, chlorate, etc.) is used as a reaction accelerator. May be added. As described above, in a phosphoric acid solution in which zinc ions coexist, zinc is dissolved in a state of zinc monophosphate [Zn (H 2 PO 4 ) 2 ], and is in an equilibrium state represented by the following equation. 3Zn 2+ + 2H 2 PO 4 − ⇔ Zn 3 (PO 4 ) 2 + 4H +
Claims (3)
板の表面にりん酸亜鉛処理が施されたりん酸亜鉛処理鋼
板であって、 形成されたりん酸亜鉛皮膜表面の任意の場所において、
長さ２０μｍの直交する２本の線分を横切るりん酸亜鉛
結晶の数が、１５以上４０以下であり、且つりん酸亜鉛
皮膜の付着量が０．８ｇ／ｍ2 以上３．０ｇ／ｍ2 以下
であることを特徴とする耐剥離性および色調に優れたり
ん酸亜鉛処理鋼板。Claims: 1. A zinc phosphate-treated steel sheet obtained by subjecting a surface of a galvanized steel sheet or a zinc alloy-plated steel sheet to a zinc phosphate treatment, wherein at an arbitrary position on the surface of the formed zinc phosphate film,
The number of zinc phosphate crystals crossing two orthogonal line segments having a length of 20 μm is 15 or more and 40 or less, and the adhesion amount of the zinc phosphate film is 0.8 g / m 2 or more and 3.0 g / m 2. A zinc phosphate treated steel sheet having excellent peel resistance and color tone, characterized by the following.
ｎの重量比Ｎｉ／Ｚｎが０．０５以上０．８以下である
請求項１に記載のりん酸亜鉛処理鋼板。2. Ni and Z in the zinc phosphate coating.
The zinc phosphate treated steel sheet according to claim 1, wherein the weight ratio of n / Ni / Zn is 0.05 or more and 0.8 or less.
板の表面にりん酸亜鉛処理が施されたりん酸亜鉛処理鋼
板であって、 りん酸亜鉛処理により生成されるりん酸亜鉛結晶の成長
方向が、鋼板表面に対しておおむね垂直方向であること
を特徴とする耐剥離性および色調に優れたりん酸亜鉛処
理鋼板。3. A zinc phosphate treated steel sheet in which zinc phosphate treatment is applied to the surface of a galvanized steel sheet or a zinc alloy plated steel sheet, wherein the growth direction of zinc phosphate crystals generated by the zinc phosphate treatment is: A zinc phosphate treated steel sheet having excellent peel resistance and color tone, which is substantially perpendicular to the steel sheet surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10158111A JP2945654B1 (en) | 1998-06-05 | 1998-06-05 | Zinc phosphate treated steel sheet with excellent peel resistance and color tone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10158111A JP2945654B1 (en) | 1998-06-05 | 1998-06-05 | Zinc phosphate treated steel sheet with excellent peel resistance and color tone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2945654B1 JP2945654B1 (en) | 1999-09-06 |
| JPH11350159A true JPH11350159A (en) | 1999-12-21 |
Family
ID=15664552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10158111A Expired - Lifetime JP2945654B1 (en) | 1998-06-05 | 1998-06-05 | Zinc phosphate treated steel sheet with excellent peel resistance and color tone |
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| Country | Link |
|---|---|
| JP (1) | JP2945654B1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030071206A (en) * | 2002-02-28 | 2003-09-03 | 고우열 | Coloring and membrane same time achievement possibility multifunction phosphate membrane processing method |
| JP2005290551A (en) * | 2004-03-08 | 2005-10-20 | Nisshin Steel Co Ltd | Chemical conversion-treated steel sheet having excellent film adhesion after forming |
| JP2005290552A (en) * | 2004-03-08 | 2005-10-20 | Nisshin Steel Co Ltd | Chemical-conversion-coated steel sheet superior in corrosion resistance, and adhesiveness and adhesivity to paint film |
| WO2021065026A1 (en) * | 2019-09-30 | 2021-04-08 | 日本製鉄株式会社 | Surface-treated zinc-based plated steel sheet and method for manufacturing same |
| WO2021065025A1 (en) * | 2019-09-30 | 2021-04-08 | 日本製鉄株式会社 | Surface-treated galvanized steel plate and method for production thereof |
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1998
- 1998-06-05 JP JP10158111A patent/JP2945654B1/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030071206A (en) * | 2002-02-28 | 2003-09-03 | 고우열 | Coloring and membrane same time achievement possibility multifunction phosphate membrane processing method |
| JP2005290551A (en) * | 2004-03-08 | 2005-10-20 | Nisshin Steel Co Ltd | Chemical conversion-treated steel sheet having excellent film adhesion after forming |
| JP2005290552A (en) * | 2004-03-08 | 2005-10-20 | Nisshin Steel Co Ltd | Chemical-conversion-coated steel sheet superior in corrosion resistance, and adhesiveness and adhesivity to paint film |
| JP4579714B2 (en) * | 2004-03-08 | 2010-11-10 | 日新製鋼株式会社 | Chemically treated steel sheet with excellent film adhesion after forming |
| JP4579715B2 (en) * | 2004-03-08 | 2010-11-10 | 日新製鋼株式会社 | Chemically treated steel sheet with excellent corrosion resistance, coating adhesion, and adhesion |
| WO2021065026A1 (en) * | 2019-09-30 | 2021-04-08 | 日本製鉄株式会社 | Surface-treated zinc-based plated steel sheet and method for manufacturing same |
| WO2021065025A1 (en) * | 2019-09-30 | 2021-04-08 | 日本製鉄株式会社 | Surface-treated galvanized steel plate and method for production thereof |
| JP2021055143A (en) * | 2019-09-30 | 2021-04-08 | 日鉄日新製鋼株式会社 | Galvanized steel plate with surface treatment and manufacturing method of the same |
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