KR100370472B1 - Cr Solution for Coating Steel Sheets - Google Patents

Cr Solution for Coating Steel Sheets Download PDF

Info

Publication number
KR100370472B1
KR100370472B1 KR10-1998-0052470A KR19980052470A KR100370472B1 KR 100370472 B1 KR100370472 B1 KR 100370472B1 KR 19980052470 A KR19980052470 A KR 19980052470A KR 100370472 B1 KR100370472 B1 KR 100370472B1
Authority
KR
South Korea
Prior art keywords
solution
corrosion resistance
trivalent chromium
coating
chromium
Prior art date
Application number
KR10-1998-0052470A
Other languages
Korean (ko)
Other versions
KR20000037738A (en
Inventor
강춘호
김형준
Original Assignee
주식회사 포스코
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 주식회사 포스코 filed Critical 주식회사 포스코
Priority to KR10-1998-0052470A priority Critical patent/KR100370472B1/en
Publication of KR20000037738A publication Critical patent/KR20000037738A/en
Application granted granted Critical
Publication of KR100370472B1 publication Critical patent/KR100370472B1/en

Links

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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (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)

Abstract

본 발명은 아연도금강판 상에 코팅되어, 아연도금 강판의 내식성 및 표면 외관을 향상시켜주는 3가 크롬용액에 관한 것으로, 3가 크롬과 인산염재 첨가제와, Zr 또는 Ti계의 커플링재(coupling agent)가 혼합되어 조성된다. 이러한 3가 크롬 용액은, 인체에 치명적인 해가 되는 6가크롬을 사용한 크롬 피막과 유사한 피막을 아연도금 강판에 형성시키지만, 오히려 내식성, 표면외관, 피막부착량, 피막처리성, 용액안정성에서 우수한 효과를 나타낸다.The present invention relates to a trivalent chromium solution coated on a galvanized steel sheet to improve the corrosion resistance and surface appearance of a galvanized steel sheet. The present invention relates to a trivalent chromium and phosphate additive and a Zr or Ti-based coupling agent (coupling agent). ) Is mixed to form. This trivalent chromium solution forms a film similar to a chromium film using hexavalent chromium, which is harmful to the human body, on the galvanized steel sheet. However, the trivalent chromium solution has excellent effects on corrosion resistance, surface appearance, coating amount, coating treatment, and solution stability. Indicates.

Description

강판의 내식성 및 표현외관을 향상시키는 3가 크롬 용액{Cr Solution for Coating Steel Sheets}Trivalent chromium solution to improve the corrosion resistance and appearance of steel sheet {Cr Solution for Coating Steel Sheets}

본 발명은 아연도금강판의 내식성 및 표면외관을 향상시키는 3가 크롬 용액에 관한 것으로, 상세하게 설명하면 3가 크롬과 인산염계 첨가제와 Zn 또는 Ti계 커플링제(coupling agent)로 조성된 3가 크롬 용액에 관한 것이다.The present invention relates to a trivalent chromium solution for improving the corrosion resistance and surface appearance of a galvanized steel sheet, and in detail, trivalent chromium composed of a trivalent chromium and a phosphate additive and a Zn or Ti coupling agent (coupling agent). It is about a solution.

일반적으로, 아연계 도금에 의한 내식성은 하지금속을 충분히 보호하기 위해서 형성된 도금층의 두께에 의해서 좌우된다. 그러나, 부식환경에 노출된 아연도금 강판은 백청이 형성되며, 부식이 진행되게 되어 우수한 내식성을 확보하기 위하여는 도금층위에 후처리를 실시하게 된다.In general, the corrosion resistance by zinc-based plating depends on the thickness of the plating layer formed to sufficiently protect the underlying metal. However, the galvanized steel sheet exposed to the corrosive environment is white blue, and the corrosion progresses, so as to secure excellent corrosion resistance, the post-treatment is performed on the plated layer.

후처리로는 인산염 처리, 크로메이트처리, 도장처리등이 주로 사용되나, 인산염 처리는 도장처리하기 위한 전단계로서 도장 밀착성 향상을 위하여 사용되며, 내식성을 향상시키기 위한 목적으로는 크로메이트, 도장처리를 실시하고 있다.Phosphate treatment, chromate treatment, and painting treatment are mainly used for post-treatment, but phosphate treatment is used to improve paint adhesion as a preliminary step for painting treatment, and chromate and coating treatment for the purpose of improving corrosion resistance. have.

그러나, 내식성 향상을 위한 도장처리는, 도장 밀착성 확보를 위한 인산염 처리가 전처리로 실시되어야 하는 번거로움이 있으며, 아연도금 물질에 대한 도장계 선정의 어려움으로 인하여 크로메이트처리가 주로 실시되고 있다.However, in the coating treatment for improving the corrosion resistance, the phosphate treatment for securing the adhesion of the coating has to be carried out as a pretreatment, and chromate treatment is mainly performed due to the difficulty in selecting a coating system for the galvanized material.

크로메이트 처리의 용도를 세분하면, 1차 방청용으로 사용되는것과 인산염 처리후 씰링제(sealing agent) 및 도장하지용으로 분류되며, 1차 방청용은 내식성 증대에 목적이 있어, 염수분무시간 24-72시간을 견뎌내는 것이 요구되며, 씰링의 목적은 도장 후 내식성 및 내스크래치(scratch)성의 확보를 위하여 처리하고 있다.Subdivided into the use of chromate treatment, it is classified as being used for primary rust prevention and sealing agent after coating the phosphate and not for coating. The primary rust prevention purpose is to increase corrosion resistance, so that salt spraying time is 24- It is required to endure 72 hours, and the purpose of sealing is to ensure corrosion resistance and scratch resistance after painting.

그러나, 상술한 바와 같이, 산업기기에 널리 이용되는 크로메이트 처리에 소요되는 크롬산은, 미량으로도 암을 유발시키는 유독성물질일 뿐아니라, 폐수처리시 환경문제를 유발시키는 물질로 각국에서는 이에 대한 규제가 엄격하게 시행되고 있다.However, as described above, chromic acid required for chromate treatment widely used in industrial equipment is not only a toxic substance causing cancer, but also a substance causing environmental problems in wastewater treatment. It is strictly enforced.

상기와 같은 문제를 해결하고 크로메이트 처리와 동등한 효과를 얻을수 있는 도포제를 개발하고 있으나, 산업에 적용하기에는 여러 한계가 있다.To solve the above problems and to develop a coating agent that can achieve the same effect as the chromate treatment, there are a number of limitations to apply to the industry.

대표적인 물질로 몰리브데이트(molybydate)는 크로메이트 대체물질로 유력하나, 반응시간이 길고 내식성에서도 미흡한 면이 있는 실정이다.As a representative material, molybdate is a strong chromate substitute, but the reaction time is long and the corrosion resistance is insufficient.

따라서, 본발명이 이루고자하는 기술적 과제는, 상술한 인체에 치명적인 해가 되는 6가 크롬을 사용하지 않고, 인체 및 환경에 치명적인 해가 되지 않는 3가 크롬 처리용액을 이용하여 크로메이트 처리를 행함으로써, Cr의 장점인 우수한 내식성을 갖는 3가 크롬용액을 제공함에 있다.Accordingly, the technical problem to be achieved by the present invention is to perform chromate treatment using a trivalent chromium treatment solution that does not use hexavalent chromium that is a fatal harm to the human body described above, and which is not a fatal injury to the human body or the environment. It is to provide a trivalent chromium solution having excellent corrosion resistance which is an advantage of Cr.

본 발명에 따른 3가 크롬 용액은, 아연도금 강판의 내식성 및 표면외관 향상을 위한 크로메이트 처리에 사용되는 크롬용액에 있어서, Cr+30.3∼2.0g/Litter, 인산염계 첨가제 0.5∼3g/Litter, Zr 또는 Ti계의 커플링제 0.08∼0.15wt%로 구성된다.Trivalent chromium solution according to the present invention, in the chromium solution used for the chromate treatment for improving the corrosion resistance and surface appearance of galvanized steel sheet, Cr +3 0.3 ~ 2.0g / Litter, phosphate additive 0.5 ~ 3g / Litter, It is comprised from 0.08 to 0.15 wt% of Zr or Ti coupling agent.

이하 상세히 설명하면 다음과 같다.Hereinafter will be described in detail.

Cr+3(3가 크롬)을 0.3∼2.0g/Litter로 제한한 것은, 3가 크롬이 0.3g/Litter 이하인 경우에는 내식성 향상에 기여하는 크롬의 양이 충분치 않아 우수한 내식성을 확보할수 없으며, 2.0g/Litter 이상일 경우에는 내식성은 확보되지만 처리된 강판의 표면외관이 불량해지고, 피막 밀착성이 열화되어 바람직하지 않다.The limit of Cr +3 (trivalent chromium) to 0.3 to 2.0 g / liter is that when the trivalent chromium is less than 0.3 g / liter, the amount of chromium that contributes to the improvement of corrosion resistance is not sufficient, and excellent corrosion resistance cannot be secured. In the case of g / Litter or more, corrosion resistance is secured, but the surface appearance of the treated steel sheet is poor, and the film adhesion is deteriorated, which is not preferable.

인산염계 첨가제의 경우 0.5∼3g/Litter로 한정한 것은, 적정량의 첨가제를 사용하는 경우, 첨가제에 의해 넓은 pH 범위에걸쳐 3가 크롬이 안정되게 유지되어 크롬산화물이 아연도금 표면에 적절하게 석출되며 균일한 속도로 인해 안정된 피막이 이루어지게 되나, 첨가제가 0.5g/Litter 이하인 경우에는 아연도금강판과의 충분한 반응이 발생되지 못하여 균일한 피막이 형성되지 못하고 표면외관은 물론 내식성이 불량해지게 된다.In the case of phosphate-based additives, it is limited to 0.5-3 g / Litter. When an appropriate amount of additive is used, trivalent chromium is stably maintained over a wide pH range by the additive, and chromium oxide is properly deposited on the surface of zinc plating. Due to the uniform speed, a stable film is formed, but when the additive is 0.5g / Litter or less, sufficient reaction with the galvanized steel sheet does not occur, so that a uniform film is not formed and surface appearance as well as corrosion resistance are poor.

또한, 3g/Litter 이상의 경우에는 강판과의 반응이 지나쳐 크롬피막보다 인산염 반응에 의한 인산염 피막이 형성되어 내식성이 떨어져 바람직하지 않다.In addition, in the case of 3g / Litter or more, the reaction with the steel sheet is excessive, and the phosphate film formed by the phosphate reaction is formed rather than the chromium film, which is not preferable because of poor corrosion resistance.

Zr 또는 Ti계 커플링제를 0.08∼0.15Wt%로 제한한 것은, 피막의 밀착성을 향상시키기 위한 것으로, 0.08Wt%이하에서는 충분한 피막 밀착성의 확보가 어려우며, 0.15Wt% 이상에서는 용액의 안정성을 기하기 어렵다.The Zr or Ti-based coupling agent is limited to 0.08 to 0.15 Wt% in order to improve the adhesion of the film, and it is difficult to secure sufficient film adhesion at 0.08 Wt% or less, and to stabilize the solution at 0.15 Wt% or more. it's difficult.

물론, 상술한 한정수치들은 수많은 실험실시에 의해 산출된 것으로, 다음에 도시된 대표적인 실시예로 설명한다.Of course, the above-mentioned limit values are calculated by a number of laboratories, and will be described in the exemplary embodiments shown below.

[실시예]EXAMPLE

본 실시예는 3가 크롬, 인산염계 첨가제, 커플링제의 적정량을 산정하기 위하여 피막의 내식성 및 표면에 영향을 주는 3가지 인자 중 2가지의 첨가량을 고정하고, 다른 1가지의 인자 투입량을 변경하는 방법으로 3인자의 적정량을 산출하였으며 스프레이 방법을 이용하여 용액을 표면처리된 EG 소재에 코팅하여 건조시켜 3가 크롬 피막을 형성시킨 후 내식성, 표면외관, 부착량을 평가하였다.In this embodiment, in order to calculate an appropriate amount of trivalent chromium, a phosphate-based additive, and a coupling agent, two of the three factors affecting the corrosion resistance and the surface of the film are fixed, and the other one factor input amount is changed. The appropriate amount of the three factors was calculated by the method, and the solution was coated on the surface-treated EG material and dried to form a trivalent chromium film, and then corrosion resistance, surface appearance, and adhesion amount were evaluated.

내식성 평가방법으로는 염수분무장치를 이용하여 5% NaCl, 35℃, 분산압 1Kg/㎡로 분사한 후, 5% 백청발생시간을 측정하였다.Corrosion resistance evaluation method using a brine spraying apparatus was sprayed at 5% NaCl, 35 ℃, dispersion pressure 1Kg / ㎡, and 5% white rust development time was measured.

표면외관은 색차계를 이용하여 백색도 측정, 광택계를 이용하여 광택도를 측정하여 평가하였다.Surface appearance was evaluated by measuring whiteness using a color difference meter and glossiness using a glossmeter.

3가 크롬피막 부착량 측정은 시편 50φ의 피막을 HCl을 이용하여 제거시킨 용액의 크롬을 분석하여 부착량을 구하였다.Trivalent chromium film adhesion amount measurement was obtained by analyzing the chromium of the solution in which the 50 φ coating film was removed using HCl.

용액안정성은 3가 크롬용액을 20일 이상 보존하여 용액의 엉김이나 침전상태로 평가하였다.Solution stability was evaluated in the form of entanglement or precipitation of the solution by preserving the trivalent chromium solution for 20 days or more.

상술한 바와 같은 평가 방법으로 실험실시한 결과, 다음과 같은 표를 얻었다.As a result of laboratory evaluation by the above-mentioned evaluation method, the following table | surface was obtained.

물론 실시된 실험은 하기표에 나타난것에 국한되지 않으며, 많은 실험을 행하였으나 대표적인 예만 표기된 것이다.Of course, the experiments carried out are not limited to those shown in the following table, but many experiments have been made but only representative examples are shown.

[표 1]TABLE 1

상기 표에서 알 수 있듯이, 3가 크롬이 0.3g/ℓ이하인 경우에는 내식성, 피막부차량, 피막처리성이 우수하지 못하며, 2g/ℓ이상에서는 두꺼우며 균일하지 못한 피막으로 표면외관과 피막처리성이 저하됨을 알 수 있었다.As can be seen from the above table, when the trivalent chromium is 0.3g / l or less, the corrosion resistance, the amount of coating portion, and the coating treatment performance are not excellent, and the surface appearance and the coating treatment property are thick and uneven coating at 2g / l or more. This was found to be degraded.

첨가제의 경우에는 0.5g∼3g/ℓ범위에서는 내식성, 표면외관, 피막부착량, 피막처리성, 용액안전성이 우수하게 나타나는 반면, 0.5g/ℓ이하에서는 용액안정성을 제외한 모든 항목이 우수하지 못하며, 3.0g/ℓ이상에는 내식성 표면외관, 피막처리성이 양호하지 못한 것을 알 수 있다.In the case of additives, the corrosion resistance, surface appearance, coating weight, coating treatment, and solution safety are excellent in the range of 0.5 g to 3 g / l, while all items except solution stability are less than 0.5 g / l. It can be seen that the corrosion resistance surface appearance and the coating treatment property are not more than g / l.

이는 과다한 투입으로 크롬피막보다는 인산염 반응에 의한 인산염피막을 형성시킴에 기인한다.This is due to excessive input to form a phosphate coating by phosphate reaction rather than chromium coating.

커플링제의 경우에도 0.08∼0.15Wt%에서는 모든 평가항목이 우수하게 나타나고 있으나, 0.08Wt% 이하에서는 피막부착량, 피막처리성이 우수하지 못하며, 0.15Wt% 이상시에도 피막부착량 및 처리성이 저하되며, 특히 용액의 안정성을 해침을 알 수 있었다.In the case of the coupling agent, all evaluation items are excellent at 0.08 to 0.15 Wt%, but the coating amount and the coating treatment property are not excellent at 0.08 Wt% or less, and the coating amount and the treatment property are deteriorated even at 0.15 Wt% or more. In particular, the stability of the solution was found to be impaired.

따라서, 상술한 내용을 종합하면, 3가 크롬 0.3∼2g/ℓ, 첨가제 0.5∼3g/ℓ, 커플링제 0.08∼0.15Wt%로 구성된 크롬용액이 최상의 효과를 얻을 수 있음을 알려준다.Therefore, in summary, the chromium solution composed of trivalent chromium 0.3 to 2 g / l, additive 0.5 to 3 g / l, and coupling agent 0.08 to 0.15 Wt% can obtain the best effect.

본 발명의 효과로는, 인체에 치명적인 해가되는 6가 크롬을 사용하지 않고, 인체 및 환경에 치명적인 해가 되지 않는 3가 크롬 용액을 이용하여 크로메이트 처리를 행함으로써, Cr의 장점인 우수한 내식성과 표면의 수려함을 얻을 수 있는 효과가 있다.Advantageous Effects of the Invention The chromate treatment is performed by using a trivalent chromium solution which does not use hexavalent chromium that is harmful to the human body and is not harmful to the human body or the environment. There is an effect that can be obtained the surface gorgeousness.

Claims (1)

아연도금강판의 내식성 및 표면외관 향상을 위한 크로메이트 처리에 사용되는 크롬용액에 있어서,In the chromium solution used for chromate treatment to improve the corrosion resistance and surface appearance of galvanized steel sheet, Cr+30.3g~2.0g/Litter, 인산염계 첨가제 0.5g∼3g/Litter, Zr 또는 Ti계의 커플링제 0.08∼0.15Wt%가 포함된 것을 특징으로 하는 강판의 내식성 및 표면외관을 향상시키는 3가 크롬 용액.Cr +3 0.3g ~ 2.0g / Litter, phosphate-based additive 0.5g ~ 3g / Litter, Zr or Ti-based coupling agent 0.08 ~ 0.15Wt% containing 3 to improve the corrosion resistance and surface appearance Chromium solution.
KR10-1998-0052470A 1998-12-02 1998-12-02 Cr Solution for Coating Steel Sheets KR100370472B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR10-1998-0052470A KR100370472B1 (en) 1998-12-02 1998-12-02 Cr Solution for Coating Steel Sheets

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR10-1998-0052470A KR100370472B1 (en) 1998-12-02 1998-12-02 Cr Solution for Coating Steel Sheets

Publications (2)

Publication Number Publication Date
KR20000037738A KR20000037738A (en) 2000-07-05
KR100370472B1 true KR100370472B1 (en) 2003-04-10

Family

ID=19560940

Family Applications (1)

Application Number Title Priority Date Filing Date
KR10-1998-0052470A KR100370472B1 (en) 1998-12-02 1998-12-02 Cr Solution for Coating Steel Sheets

Country Status (1)

Country Link
KR (1) KR100370472B1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100790269B1 (en) * 2006-12-21 2008-01-02 한국선재(주) Method of making wire and steel wire
KR20190053514A (en) 2017-11-10 2019-05-20 주식회사 지에스켐텍 coloured trivalent chromate treating agent for galvanizing zincing, Manufacturing method thereof, and chromating method of galvanizing zincing products

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6256580A (en) * 1985-09-05 1987-03-12 Nippon Parkerizing Co Ltd Chromating solution for galvanized steel sheet
JPS6439399A (en) * 1987-08-06 1989-02-09 Nippon Steel Corp Production of zinc-chromium composite electroplated steel sheet
KR940014899A (en) * 1992-12-30 1994-07-19 박득표 Chromate solution excellent in corrosion resistance and appearance and manufacturing method of chromate film using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6256580A (en) * 1985-09-05 1987-03-12 Nippon Parkerizing Co Ltd Chromating solution for galvanized steel sheet
JPS6439399A (en) * 1987-08-06 1989-02-09 Nippon Steel Corp Production of zinc-chromium composite electroplated steel sheet
KR940014899A (en) * 1992-12-30 1994-07-19 박득표 Chromate solution excellent in corrosion resistance and appearance and manufacturing method of chromate film using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100790269B1 (en) * 2006-12-21 2008-01-02 한국선재(주) Method of making wire and steel wire
KR20190053514A (en) 2017-11-10 2019-05-20 주식회사 지에스켐텍 coloured trivalent chromate treating agent for galvanizing zincing, Manufacturing method thereof, and chromating method of galvanizing zincing products

Also Published As

Publication number Publication date
KR20000037738A (en) 2000-07-05

Similar Documents

Publication Publication Date Title
EP0922785B1 (en) Treating solution and treating method for forming protective coating films on metals
CA2355855C (en) Metal-surface-treating composition and surface-treated metal material
DE69403339T2 (en) COMPOSITION AND METHOD FOR TREATING PHOSPHATED METAL SURFACES
KR100553401B1 (en) Anticorrosive coating material and method of rust prevention
JPH1129724A (en) Rust-preventive coating agent and rust-preventive treatment
JPH07216268A (en) Surface treatment agent for zinc-containing metal-coated steel sheet, excellent in corrosion resistance and coating adhesion
KR20040046347A (en) The trivalent chromate which contains no trace of hexavalent chrome nor any oxidizing agent
EP0048718B2 (en) Process for inhibiting corrosion of metal surfaces
KR100370472B1 (en) Cr Solution for Coating Steel Sheets
AU767115B2 (en) Galvanized steel for use in vehicle body
MXPA01012107A (en) Phosphate-treated electrogalvanized steel sheet excellent in corrosion resistance and coating suitability.
JPH11343582A (en) Chromate rust preventive processing agent
KR100428562B1 (en) Coating compositions for gavanized steel sheets and gavanized steel sheets treated with them
KR20010042321A (en) Metallic material with organic composite coating excellent in corrosion resistance and coatability and reduced in finger mark adhesion and process for producing the same
JP3475908B2 (en) Method for improving the weather resistance of zinc-based plating materials
JP3706518B2 (en) Non-chromium surface-treated zinc-coated steel sheet
KR940006039B1 (en) Chromate solution for galvanized sheets with an excellent corrosion resistance and black stain resistance
JP2003293162A (en) Coated plated steel sheet having excellent corrosion resistance
JPH07331160A (en) Composition, fluid, and method for treating surface of steel sheet plated with zinc-and/or aluminum-containing metal
KR100437634B1 (en) Resin for non-Cr passivation steel sheet
KR100345883B1 (en) Free chrome treating solution for improving the corrosing resistance of the galvanized steel iron
JP2002371371A (en) Phosphate treated galvanized steel sheet superior in front and back discrimination properties
JPH0432576A (en) Solution for zinc phosphate chemical conversion treatment
CA1090029A (en) Metal surface treatment
KR960007772B1 (en) Method for manufacturing a covered chromate galvanized steel plate with an excellent surface appearance

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20130117

Year of fee payment: 11

FPAY Annual fee payment

Payment date: 20140116

Year of fee payment: 12

FPAY Annual fee payment

Payment date: 20150113

Year of fee payment: 13

FPAY Annual fee payment

Payment date: 20160118

Year of fee payment: 14

FPAY Annual fee payment

Payment date: 20170118

Year of fee payment: 15

EXPY Expiration of term