KR20000038944A - Liquid for treating molyphosphate film for galvanized steel sheet and method of manufacturing galvanized steel sheet improved in corrosion resistance after coating resin with the same - Google Patents
Liquid for treating molyphosphate film for galvanized steel sheet and method of manufacturing galvanized steel sheet improved in corrosion resistance after coating resin with the same Download PDFInfo
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- KR20000038944A KR20000038944A KR1019980054119A KR19980054119A KR20000038944A KR 20000038944 A KR20000038944 A KR 20000038944A KR 1019980054119 A KR1019980054119 A KR 1019980054119A KR 19980054119 A KR19980054119 A KR 19980054119A KR 20000038944 A KR20000038944 A KR 20000038944A
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- 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
- C23C22/07—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 containing phosphates
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- 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
- C23C2222/20—Use of solutions containing silanes
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Abstract
Description
본 발명은 아연도금강판용 몰리포스페이트 피막 처리 용액에 관한 것으로, 보다 상세하게는 고분자화합물과의 밀착성이 우수한 것으로 알려진 글리시딜옥시 성분을 커플링제로 첨가함으로써 아연도금강판에 우수한 내식성을 부여하는 몰리포스페이트 피막 처리 용액 및 이를 이용하여 수지도포후까지 내식성이 개선된 아연도금강판 제조 방법에 관한 것이다.The present invention relates to a molten phosphate coating solution for galvanized steel sheet, and more particularly, to a molten phosphate that provides excellent corrosion resistance to a galvanized steel sheet by adding a glycidyloxy component known to have excellent adhesion with a high molecular compound as a coupling agent. The present invention relates to a coating solution and a method for producing a galvanized steel sheet having improved corrosion resistance until after coating.
내식성을 향상시키기 위한 크로메이트 처리 방식은 아연 도금 강판에 있어 널리 알려진 공지 기술이나, 크로메이트 약품 자체가 발암성 물질로서 환경 규제의 대상이 되어 대체 물질을 개발하려는 시도가 계속되어 왔다. 이러한 시도중에 몰리포스페이트 물질계가 기존의 크로메이트 처리계를 대체할 수 있을 것으로 보고되고 있으나, 기존의 크로메이트 처리재에 비하여 내식성이 다소 열위하다는 기술적인 한계를 갖고 있다.The chromate treatment method for improving the corrosion resistance is well known in the galvanized steel sheet, but the chromate drug itself is a carcinogenic substance subject to environmental regulations have been attempted to develop alternative materials. It is reported that the molybdate material system can replace the existing chromate treatment system in this attempt, but has a technical limitation that the corrosion resistance is somewhat inferior to the conventional chromate treatment material.
이에 일본 고베사에서는 영국 특허 2070073에서 칼륨 몰리브데이트(K2MoO4: 10∼200g/ℓ) 용액에 인산, 황산 및 초산을 각각 첨가하여 시험한 결과, 인산 첨가시 내식성이 가장 우수하다는 결과를 얻었다(GB 2B 2070073).In Japan, Kobe company tested the addition of phosphoric acid, sulfuric acid and acetic acid to a solution of potassium molybdate (K 2 MoO 4 : 10-200 g / l) in British Patent 2070073. (GB 2B 2070073).
나아가 Bech-Nielsen은 몰리브덴 농도가 2.9∼9.8g/ℓ이고, 몰리브덴/인의 몰농도비가 0.2∼0.8인 조건하에서 피도체를 -2.5+5.0V(vs SHE)로 산화전류를 인가시키면서 몰리포스페이트 피막을 형성하는 제조 기술을 국제 공개 WO93/10278에서 주장하고 있으나, 반응 시간이 2분 이상 소요되는 것이 기술적 한계로 인식되고 있다.Furthermore, Bech-Nielsen formed molybdate film by applying oxidation current to -2.5 + 5.0V (vs SHE) under the condition that molybdenum concentration is 2.9 ~ 9.8g / l and molybdenum / phosphorus molar concentration ratio is 0.2 ~ 0.8. Although the manufacturing technique to be formed is claimed in WO93 / 10278, it is recognized as a technical limitation that the reaction time takes more than 2 minutes.
이에 본 발명자들은 몰리포스페이트 용액에 산화 촉진제로서 질산을 첨가함으로써 우수한 백색도와 내식성을 나타내는 몰리포스페이트 용액을 발견하고 이를특허출원한 바 있다(대한민국 특허 제1995-68412).Accordingly, the present inventors have found and patented a molybdate solution exhibiting excellent whiteness and corrosion resistance by adding nitric acid to the molybdate solution as an oxidation promoter (Korean Patent No. 195-68412).
그러나 이와 같은 몰리포스페이트 피막상에 소지 강판을 보호하고, 내지문성을 부여할 목적으로 아크릴계 수지 피막을 공업적으로 도포할 경우 몰리포스페이트 피막의 흡습성으로 인하여 오히려 내식성이 열위하여지는 문제가 있다.However, when the acrylic resin film is industrially applied for the purpose of protecting the base steel sheet on the molybdate film and imparting anti-fingerprint, there is a problem that the corrosion resistance is inferior due to the hygroscopicity of the molybphosphate film.
즉, 수지층을 통하여 몰리포스페이트 피막에 물이 침투하는 단면을 나타내는 도 1을 보면, 몰리포스페이트 피막은 Mo-P-OH 성분이 피막 주체이므로 수지와 결합력이 약하고 수지층을 통해 침투되는 수분을 흡수하여 수지도포후에 내식성이 저하되는 문제가 있는 것이다.That is, as shown in Fig. 1 showing a cross-section of water infiltrate the molybdate film through the resin layer, since the Mo-P-OH component is the main coating film, the bonding strength is weak and absorbs moisture that penetrates through the resin layer. Therefore, there is a problem that the corrosion resistance is reduced after the coating.
이에 본 발명의 목적은 몰리포스페이트 피막후 적용되는 수지층과의 결합력을 향상시켜 수지도포후에도 내식성이 우수한 몰리포스페이트 피막 처리 용액을 제공하고자 하는 것이다.Accordingly, an object of the present invention is to provide a molybdate film treatment solution having excellent corrosion resistance even after resin coating by improving the bonding strength with the resin layer applied after the film is coated.
본 발명의 다른 목적은 상기 몰리포스페이트 피막 처리 용액을 이용하여 수지도포후까지 내식성이 우수한 아연도금강판 제조 방법을 제공하고자 하는 것이다.Another object of the present invention is to provide a method for producing a galvanized steel sheet excellent in corrosion resistance until the resin after coating using the molybdate film coating solution.
도 1은 도포된 수지층을 통하여 몰리포스페이트 피막내에 수분이 침투하는 경로를 나타낸 단면 모식도이며,1 is a schematic cross-sectional view showing a path through which moisture penetrates into the molybdate film through the coated resin layer.
도 2는 본 발명에 의한 몰리포스페이트 피막 처리 용액이 도포된 경우 도포된 수지층을 통하여 침투된 수분이 처리되는 반응을 나타낸 단면 모식도이다.Figure 2 is a schematic cross-sectional view showing a reaction in which the water penetrated through the applied resin layer when the molybdate film treatment solution according to the present invention is applied.
본 발명의 일견지에 의하면,According to one aspect of the invention,
몰리브덴 4.0∼30g/ℓ 및 인산 7.0∼14g/ℓ를 기본 성분으로 하고,Molybdenum 4.0 to 30 g / l and phosphoric acid 7.0 to 14 g / l
여기에 질산 8.0∼50g/ℓ 및 γ-글리시딜옥시 프로필 트리메톡시실란 2g/ℓ이상을 첨가하여 제조된 내식성이 개선된 아연도금강판용 몰리포스페이트 피막 처리 용액이 제공된다.Provided therein is a solution for treating a molten phosphate coating for galvanized steel sheet having improved corrosion resistance prepared by adding at least 8.0-50 g / l of nitric acid and 2 g / l of γ-glycidyloxy propyl trimethoxysilane.
본 발명의 제2견지에 의하면,According to the second aspect of the present invention,
아연도금강판을 55∼60℃에서 조성된 상기 몰리포스페이트 피막 처리 용액에 침지시켜 몰리포스페이트 피막을 형성하는 단계; 및Immersing a galvanized steel sheet in the molten phosphate coating solution formed at 55 to 60 ° C. to form a molten phosphate coating; And
제조된 몰리포스페이트 피막상에 아크릴계 수지를 그 부착량이 1000∼1200mg/m2이 되도록 균일하게 도포하는 단계;를 포함하는 수지도포후까지 개선된 내식성을 갖는 아연도금강판 제조 방법이 제공된다.Provided is a method for producing a galvanized steel sheet having improved corrosion resistance until after the resin coating, including the step of uniformly applying an acrylic resin on the prepared molybdate film coating so that the adhesion amount is 1000 ~ 1200mg / m 2 .
이하, 본 발명에 대하여 도면을 참조하여 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to the drawings.
본 발명자들은 글리시딜옥시 성분이 고분자 화합물과의 밀착력이 우수한 물질이며, Si 성분은 무기물과의 결합력이 우수하며, 화성 처리 용액 등에 내식성 향상제로서 주로 이용되는 소수성이 강한 물질이고 질산은 산화 촉진제이기 때문에 이들이 첨가되는 경우에 수지층과의 밀착력이 증대되고 소수성이 강한 Si-Mo 결합이 형성되게 된다는 점에 착안하여 본 발명을 완성하기에 이르렀다.The inventors believe that the glycidyloxy component has excellent adhesion to the high molecular compound, the Si component has excellent bonding strength with the inorganic substance, is a hydrophobic material which is mainly used as a corrosion resistance improving agent in chemical conversion treatment solution, and nitric acid is an oxidation promoter. When these were added, the present invention was completed by paying attention to the fact that the adhesion to the resin layer was increased and a strong hydrophobic Si-Mo bond was formed.
본 발명에서는 몰리브덴 4.0∼30g/ℓ와 인산 7.0∼14g/ℓ을 포함하여 이루어진 용액에 질산 8.0∼50g/ℓ 및 γ-글리시딜옥시 프로필 트리메톡시실란 2g/ℓ이상을 첨가하여 몰리포스페이트 피막 처리 용액을 제조한다.In the present invention, the molybdate film is added by adding 8.0-50 g / l nitric acid and 2 g / l or more of γ-glycidyloxy propyl trimethoxysilane to a solution containing 4.0-30 g / l molybdenum and 7.0-14 g / l phosphoric acid. Prepare a treatment solution.
몰리브덴과 인산의 농도가 상기 범위를 벗어나게 되면 부착량 및 내식성이 모두 감소되므로 바람직하지 않다. 또한 질산의 농도가 8g/ℓ미만인 경우에는 원하는 내식성을 나타내지 않으며, 50g/ℓ이상인 경우에는 과산세로 인하여 아연도금층이 용액내에 용해되어 원하는 피막을 형성하지 못한다. γ-글리시딜옥시 프로필 트리메톡시 실란을 2g/ℓ미만으로 첨가할 경우에는 수지 도포후까지 내식성을 개선시키는 효과를 얻지 못하므로 바람직하지 않다.When the concentration of molybdenum and phosphoric acid is out of the above range, both the adhesion amount and the corrosion resistance are reduced, which is not preferable. In addition, when the concentration of nitric acid is less than 8g / ℓ does not exhibit the desired corrosion resistance, when 50g / ℓ or more the zinc plated layer is dissolved in the solution due to the over-acid tax to form a desired coating. When γ-glycidyloxy propyl trimethoxy silane is added at less than 2 g / L, the effect of improving corrosion resistance until after the resin is not obtained is not preferable.
도 2에서 보듯이, γ-글리시딜옥시 프로필 트리메톡시실란을 첨가한 몰리포스페이트 용액을 아연도금 강판상에 도포하여 피막을 형성할 경우에는 글리시딜옥시 부분이 피막층 상부를 향하게 되고 상대적으로 분자량이 큰 금속 성분인 Si-Mo는 소지 아연도금층을 향하게 되어, 결과적으로 수지층으로 침투하는 수분과의 반발력이 증대되어 내식성이 개선됨을 확인할 수 있다.As shown in FIG. 2, when a molybphosphate solution containing γ-glycidyloxy propyl trimethoxysilane is coated on a galvanized steel sheet to form a coating, the glycidyloxy portion is directed toward the top of the coating layer. Si-Mo, which is a metal component having a large molecular weight, is directed toward the base galvanized layer, and as a result, the repulsive force with water penetrating into the resin layer is increased, thereby improving corrosion resistance.
이와 같이 제조된 몰리포스페이트 용액에 아연 도금 강판을 55∼60℃의 온도에서 수초간 침지시킨 다음 수세후 건조시키면 피막이 형성된다. 용액의 온도가 55℃미만일 경우에는 각 이온성분들의 활성화에너지가 낮아 부착량이 저하되며, 60℃이상일 경우에는 이와 반대로 각 이온 성분들의 활성화 에너지가 증대되어 아연도금강판 상부층에의 부착량은 늘어나나 원하는 내식성을 얻지 못하게 된다.The galvanized steel sheet was immersed for several seconds at a temperature of 55 to 60 ° C. in the molybdate solution thus prepared, and then dried after washing with water to form a film. If the temperature of the solution is less than 55 ℃, the amount of adhesion decreases because the activation energy of each ionic component is low. On the contrary, if the temperature of the solution is higher than 60 ℃, the activation energy of each ionic component increases. You won't get it.
이상과 같이 제조된 몰리포스페이트 피막상에 아크릴계 수지를 그 부착량이 1000∼1200mg/m2이 되도록 조절하면서 균일하게 도포한 다음 건조시켜 수지도포후까지 그 내식성이 개선된 아연도금강판을 제조한다. 상기 범위를 벗어나게 되면, 강판의 내식성 및 내지문성에 있어 원하는 물성을 얻지 못하므로 바람직하지 않다.The acrylic resin on the molybdate film prepared as described above is uniformly applied while controlling the adhesion amount to 1000 ~ 1200mg / m 2 and then dried to prepare a galvanized steel sheet with improved corrosion resistance until after coating. If it is out of the above range, it is not preferable because it does not obtain the desired physical properties in corrosion resistance and fingerprint resistance of the steel sheet.
이하, 실시예에 기초하여 본 발명에 대하여 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on an Example.
＜실시예＞<Example>
본 발명에서는 소디움 몰리브데이트 10g/ℓ, 인산 9g/ℓ, 질산 12g/ℓ로된 용액에 γ-글리시딜옥시 프로필 트리메톡시실란을 하기표 1에 기재한 양을 첨가하여 몰리포스페이트 피막 처리 용액을 제조하였다.In the present invention, γ-glycidyloxy propyl trimethoxysilane is added to a solution composed of sodium molybdate 10 g / l, phosphoric acid 9 g / l, and nitric acid 12 g / l to treat the molybdate film. The solution was prepared.
이와 같이 제조된 피막 처리 용액에 아연도금강판을 60℃에서 3초간 침지시킨 다음 수세후 건조시킨 다음, 제조된 몰리포스페이트 피막상에 표 1에 기재한 바에 따라 수지도포량을 조절하면서 아크릴계 수지를 균일하게 도포한 다음 열풍건조로에서 350℃에서 10초간 건조시켰다.The galvanized steel sheet was immersed at 60 ° C. for 3 seconds in a coating solution prepared in this way, dried after washing with water, and then the acrylic resin was uniformly controlled while adjusting the amount of the resin coating as described in Table 1 on the prepared phosphate coating film. After application, the resultant was dried for 10 seconds at 350 ° C. in a hot air dryer.
몰리포스페이트 피막상에 아크릴 수지가 도포된 아연도금강판으로 부터 γ-글리시딜옥시 프로필 트리메톡시실란의 첨가량에 따른 아연도금강판 상부층에의 Mo부착량과 Si 부착량 및 내식성을 측정하고 그 결과를 하기표 1에 나타내었다.Mo adhesion amount, Si adhesion amount and corrosion resistance were measured from the galvanized steel sheet coated with acrylic resin on the molybdate film to the upper layer of galvanized steel sheet according to the addition amount of γ-glycidyloxypropyl trimethoxysilane. Table 1 shows.
여기서 내식성은 도포가 완료된 다음 내식성을 ASTM-B117에 의거 5% 백청 발생시까지의 소요 시간으로 평가하였으며 피막에의 부착량은 무게감량법에 의해 측정하였다.Corrosion resistance was evaluated by the time required until the completion of the application of 5% white rust according to ASTM-B117 after the coating is completed, the amount of adhesion to the coating was measured by the weight loss method.
*GPS: γ-글리시딜옥시 프로필 트리메톡시실란* GPS: γ-glycidyloxy propyl trimethoxysilane
상기 표에 의하면, γ-글리시딜옥시 프로필 트리메톡시실란을 첨가하지 않고 아크릴수지를 도포한 경우(비교예 2)는 그 내식성이 24시간정도 유지되는데 반하여, γ-글리시딜옥시 프로필 트리메톡시실란을 첨가한 경우(본 발명예)에는 내식성이 최소 80시간이상 유지되는 것으로 부터 그 개선 정도가 탁월한 것을 알 수 있다. 이는 γ-글리시딜옥시 프로필 트리메톡시실란을 첨가함으로써 수지 밀착력이 향상되고 Si-Mo 결합에 의하여 내식성에 향상되는데 기인한 것으로 여겨진다.According to the table, when the acrylic resin is applied without adding γ-glycidyloxy propyl trimethoxysilane (Comparative Example 2), the corrosion resistance is maintained for about 24 hours, whereas γ-glycidyloxy propyl tree is maintained. When methoxysilane is added (example of the present invention), it can be seen that the degree of improvement is excellent since the corrosion resistance is maintained for at least 80 hours. This is believed to be attributable to the improvement of resin adhesion by the addition of γ-glycidyloxy propyl trimethoxysilane and to the improvement of corrosion resistance by Si-Mo bonding.
또한 아크릴계 수지를 도포하지 않은 경우에도 γ-글리시딜옥시 프로필 트리메톡시실란을 첨가한 응용예에서는 그 내식성이 γ-글리시딜옥시 프로필 트리메톡시실란을 첨가하지 않은 비교예 1에 비하여 2배 이상 향상되었음을 알 수 있다. 이또한 Si-Mo 결합에 의한 내식성 향상 효과에 기인한 것으로 여겨진다.In addition, even in the case where no acrylic resin was applied, in the application example in which γ-glycidyloxy propyl trimethoxysilane was added, its corrosion resistance was higher than that in Comparative Example 1 in which γ-glycidyloxy propyl trimethoxysilane was not added. It can be seen that more than doubled. This is also believed to be due to the effect of improving the corrosion resistance by the Si-Mo bond.
상기한 바에 따르면, 몰리포스페이트 용액에 질산과 γ-글리시딜옥시 프로필 트리메톡시실란을 함께 첨가함으로써 수지와의 친화력이 강한 글리시딜옥시 부분에 의해 아크릴 수지층과의 밀착력이 증가되고 소수성이 강한 Si-Mo 결합이 형성되므로써 수지층으로 침투하는 수분(H2O)과의 반발력이 증대되어 몰리포스페이트 피막 적용후, 수지 도포후에도 아연 도금 강판의 내식성이 증대된다.According to the above, by adding nitric acid and γ-glycidyloxy propyl trimethoxysilane together to the molybphosphate solution, the adhesion to the acrylic resin layer is increased by the glycidyloxy moiety having strong affinity with the resin and the hydrophobicity is increased. As a strong Si-Mo bond is formed, the repulsive force with moisture (H 2 O) that penetrates into the resin layer is increased, so that the corrosion resistance of the galvanized steel sheet is increased even after the resin is applied after the molybphosphate coating is applied.
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| KR100544500B1 (en) * | 2001-11-26 | 2006-01-24 | 주식회사 포스코 | Solution for Forming Moly-Phosphate Coating on The Galvanized Steel Sheet and Methods for Manufacturing Moly-Phosphate Treated Steel Sheet and Resin Coated Steel Sheet Using the Solution |
| KR100544499B1 (en) * | 2001-11-26 | 2006-01-24 | 주식회사 포스코 | Solution for Forming Moly-Phosphate Coating on The Galvanized Steel Sheet with High Corrosion Resistance and Methods for Manufacturing Moly-Phosphate Treated Steel Sheet and Resin Coated Steel Sheet with High Corrosion Resistance Using the Solution |
| KR100793561B1 (en) * | 2002-01-07 | 2008-01-14 | 주식회사 포스코 | Resin coating solution and prepartion, coating method of zinc electroplating steel sheets |
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| KR100256361B1 (en) * | 1995-12-30 | 2000-05-15 | 이구택 | The solution of the molybdate-based alternatives as a passivation treatment with white color degree and excellent corrosion resistance and method used therefor |
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