KR101079392B1 - Anticorrosive coating solution for zinc coated steel sheet and the zinc coated steel sheet therefrom - Google Patents
Anticorrosive coating solution for zinc coated steel sheet and the zinc coated steel sheet therefrom Download PDFInfo
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- 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
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Abstract
본 발명은 아연 도금강판용 방청코팅용액에 관한 것으로, The present invention relates to an antirust coating solution for galvanized steel sheet,
콜로이드 실리카 용액에 총 중량을 기준으로,Based on the total weight in the colloidal silica solution,
[화학식 1] [Ti(L1)(L2)], [화학식 2] [Ti(L2)2(L3)2] 및 [화학식 3] [Ti(L4)2(L5)2](NH4)2(여기서, L1=트리에탄올아미네이토, L2=이소프로폭시드, L3=아세틸아세토네이트, L4=락테이토이며 그리고 L5=히드록시드임)으로 구성된 그룹으로부터 선택된 최소 하나의 Ti-계 착화합물 또는 이들의 혼합물이 5-30중량%로 첨가된 아연 도금강판용 방청코팅용액 및 이 용액이 코팅된 아연도금 강판이 제공된다.[Ti (L 1 ) (L 2 )], [Formula 2] [Ti (L 2 ) 2 (L 3 ) 2 ] and [Formula 3] [Ti (L 4 ) 2 (L 5 ) 2 ] (NH 4 ) 2 , wherein L 1 = triethanolamineto, L 2 = isopropoxide, L 3 = acetylacetonate, L 4 = lactate and L 5 = hydroxy An antirust coating solution for galvanized steel sheet to which at least one Ti-based compound selected from the group or a mixture thereof is added at 5-30% by weight, and a galvanized steel sheet coated with the solution are provided.
본 발명에 의해 크롬을 사용하지않고, Ti-계 착화합물을 이용하여 환경친화적인 고내식성 아연 도금강판용 방청 코팅용액을 제조할 수 있다.According to the present invention, an anti-corrosive coating solution for an environmentally friendly high corrosion resistant galvanized steel sheet can be prepared using a Ti-based compound without using chromium.
티타늄, 착화합물, 방청제, 아연도금 강판, 실리카Titanium, Complex, Antirust, Galvanized Steel, Silica
Description
본 발명은 아연 도금강판용 방청코팅용액 및 이 용액이 코팅된 아연도금강판에 관한 것으로, 보다 상세하게는 크롬을 사용하지않고 특정 Ti-계 착화합물이 첨가된 아연 도금강판용 방청코팅용액 및 이 용액이 코팅된 아연도금 강판에 관한 것이다.The present invention relates to an anti-corrosive coating solution for galvanized steel sheet and a galvanized steel sheet coated with this solution, and more particularly, to an anti-corrosive coating solution for galvanized steel sheet added with a specific Ti-based compound without using chromium and coated with this solution. To a galvanized steel sheet.
아연도금 강판의 표면 부식을 방지하기 위해 백여년 전부터 크로메이트(Chromate) 코팅처리를 하였다. Cr(VI)를 포함하고 있는 크로메이트는 저렴하면서도 내식성이 우수하여 오랫동안 부식방지용으로 사용되어져 왔으나, 오늘날 후두암 등을 일으키는 일급 발암물질로 분류됨에 따라 국제적으로 환경유해 물질로 규제하고 있다. 자동차 업계에서는 2003년부터 납(Pb), 니켈(Ni), 구리(Cu) 등과 함께 Cr(VI)에 대한 사용을 규제하고 있으며, 유럽연합(EU)에서는 2008년부터 폐 전기(전자)기기에 있어서 크롬(Cr), 납(Pb), 수은(Hg) 및 카드뮴(Cd) 등의 물질이 포함되어 있는 제품의 폐기를 전면 금지하는 규제를 할 예정이다. 따라서 현재 전 세계적으로 건축, 가전 및 자동차용으로 크롬을 사용하지않는 부식 방지제 즉, 방청제의 개발에 부심하고 있다.In order to prevent surface corrosion of galvanized steel sheet, Chromate coating process has been performed for more than 100 years. Chromate, which contains Cr (VI), has been used for corrosion protection for a long time due to its low cost and excellent corrosion resistance, but it is regulated as an environmentally harmful substance internationally as it is classified as a primary carcinogen causing laryngeal cancer. The automotive industry has regulated the use of Cr (VI) with lead (Pb), nickel (Ni) and copper (Cu) since 2003.In 2008, the European Union (EU) regulated the use of waste electrical (electronic) devices. The company is planning to completely prohibit the disposal of products containing substances such as chromium (Cr), lead (Pb), mercury (Hg) and cadmium (Cd). Therefore, we are currently striving to develop corrosion inhibitors that do not use chromium, that is, rust inhibitors, for construction, home appliances, and automobiles worldwide.
크롬을 포함하지 않는 방청제의 개발은 오래 전부터 다양한 각도에서 행해져 왔다. 대표적으로 크롬과 동족인 몰리브덴 음이온(Molybdate, MoO4 2-) 부동태 피막, 중인산염(MH2PO4) 피막을 이용한 방법, 탄닌산(Tannic acid) 등의 유기물의 피막에 대한 연구 등이 행해져 왔다. 그러나 이들 방법은 모두 크로메이트 피막과 비교하여 보호막 특성(barrier)과 자기수복(self-healing)성이 저조하며, 내식성도 불충분하기때문에, 아연도금 강판의 크로메이트 대체용으로는 실용화되지 못하고 있다. 따라서, 크롬을 포함하지않은 새로운 환경친화형 방청제가 계속 요구되고 있다.The development of rust free agents that do not contain chromium has been done for a long time from various angles. Representative examples of the molybdenum anion (Molybdate, MoO 4 2- ) passivation film, a method using a MH 2 PO 4 film, and tannic acid, such as tannic acid, have been studied. However, these methods are not practically used as a substitute for chromate of galvanized steel sheets because of their low barrier property and self-healing and poor corrosion resistance compared to chromate coatings. Therefore, there is a continuing need for new environmentally friendly rust inhibitors that do not contain chromium.
이에 본 발명의 목적은 콜로이드 실리카 수용액에 특정 Ti-계 착화합물이 첨가된, 크롬을 포함하지 않으면서 내식성이 우수한 환경친화적인 아연도금 강판용 방청코팅용액을 제공하는 것이다.Accordingly, an object of the present invention is to provide an anticorrosive coating solution for an environmentally friendly galvanized steel sheet which does not contain chromium, in which a specific Ti-based complex compound is added to an aqueous colloidal silica solution.
본 발명의 다른 목적은 상기 아연도금 강판용 방청코팅용액이 코팅된 아연도금 강판을 제공하는 것이다.Another object of the present invention is to provide a galvanized steel sheet coated with the rustproof coating solution for the galvanized steel sheet.
삭제delete
본 발명의 일견지에 의하면, According to one aspect of the invention,
콜로이드 실리카 용액에 총 중량을 기준으로,Based on the total weight in the colloidal silica solution,
[화학식 1] [Ti(L1)(L2)], [화학식 2] [Ti(L2)2(L3)2] 및 [화학식 3] [Ti(L4)2(L5)2](NH4)2(여기서, L1=트리에탄올아미네이토, L2=이소프로폭시드, L3=아세틸아세토네이트, L4=락테이토이며 그리고 L5=히드록시드임)으로 구성된 그룹으로부터 선택된 최소 하나의 Ti-계 착화합물 또는 이들의 혼합물이 5-30중량%로 첨가된 아연도금 강판용 방청코팅용액이 제공된다.[Ti (L 1 ) (L 2 )], [Formula 2] [Ti (L 2 ) 2 (L 3 ) 2 ] and [Formula 3] [Ti (L 4 ) 2 (L 5 ) 2 ] (NH 4 ) 2 , wherein L 1 = triethanolamineto, L 2 = isopropoxide, L 3 = acetylacetonate, L 4 = lactate and L 5 = hydroxy There is provided an anticorrosive coating solution for galvanized steel sheet in which at least one Ti-based compound selected from the group or a mixture thereof is added at 5-30% by weight.
본 발명의 다른 견지에 의하면, 상기 아연도금 강판용 방청코팅용액이 코팅된 아연도금 강판이 제공된다.According to another aspect of the present invention, there is provided a galvanized steel sheet coated with the rustproof coating solution for galvanized steel sheet.
삭제delete
이하, 본 발명에 대하여 상세히 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명은 크롬을 함유하지 않고, 강판 특히, 아연도금강판에 우수한 내식성을 부여할 수 있는 방청코팅용액을 제조하기위해 콜로이드 실리카 용액에 특정 Ti- 계 착화합물을 첨가하여 제조함을 특징으로 한다.
The present invention is characterized in that it does not contain chromium and is prepared by adding a specific Ti-based compound to the colloidal silica solution in order to produce an anticorrosive coating solution which can impart excellent corrosion resistance to steel sheets, especially galvanized steel sheets.
즉, 종래 일반적으로 사용되는 크롬을 사용하지않고 콜로이드 실리카 용액에 특정 Ti-계 착화합물을 첨가함으로써 환경친화적이면서도 고 내식성을 부여할 수 있는 아연도금강판용 방청코팅용액을 제조하는 것이 가능하다.
That is, by adding a specific Ti-based compound to the colloidal silica solution without using chromium, which is generally used in the related art, it is possible to prepare an anti-corrosive coating solution for galvanized steel sheet that can provide environmentally friendly and high corrosion resistance.
본 발명에 사용되는 Ti-계 착화합물은 하기 화학식 1, 2 및 3으로 구성된 그룹으로부터 최소 하나로 선택되거나 또는 이들의 혼합물이다.The Ti-based complex compounds used in the present invention are selected from at least one of the groups consisting of Formulas 1, 2 and 3 or mixtures thereof.
[화학식 1][Formula 1]
[Ti(L1)(L2)] [Ti (L 1 ) (L 2 )]
[화학식 2][Formula 2]
[Ti(L2)2(L3)2] 및 [Ti (L 2 ) 2 (L 3 ) 2 ] and
[화학식 3](3)
[Ti(L4)2(L5)2](NH4)2 [ Ti (L 4 ) 2 (L 5 ) 2 ] (NH 4 ) 2
(단, 상기 화학식 1-3에서, L1=트리에탄올아미네이토, L2=이소프로폭시드, L3=아세틸아세토네이트, L4=락테이토이며 그리고 L5=히드록시드임)(However, in the above formula 1-3, L 1 = triethanol aminato, L 2 = isopropoxide, L 3 = acetylacetonate, L 4 = lactate and L 5 = hydroxide)
아연도금 강판의 내식성은 화성처리 혹은 수지의 도포에 의해 확보될 수 있으나, 단순한 보호막 특성에 의해서는 단면부와 같은 곳에서는 고내식성을 얻을 수 없다. 이러한 고내식성 아연도금 강판을 얻기 위해 여러가지 산화상태가 가능한 전이금속 착화합물을 이용한 코팅피막 형성이 적용될 수 있다. 본 발명에 따라 Ti(IV)-착화합물을 코팅막으로 이용할 경우 가수분해 반응과 산화-환원반응에 의한 자기수복 효과(self-healing effect)를 기대할 수 있다. 따라서 고내식 아연도금 강판을 얻기 위하여 내식성과 수지 접착성이 우수한 Ti-착화합물과 콜로이드 실리카를 함유하는 새로운 코팅용액을 이용하여 아연도금 강판에 피막을 형성한다.Corrosion resistance of the galvanized steel sheet can be secured by chemical conversion treatment or resin application, but high corrosion resistance cannot be obtained at the same places as the cross-section due to simple protective film properties. In order to obtain such a highly corrosion-resistant galvanized steel sheet, coating film formation using a transition metal complex compound capable of various oxidation states may be applied. According to the present invention, when the Ti (IV) -complex compound is used as a coating film, a self-healing effect due to a hydrolysis reaction and an oxidation-reduction reaction can be expected. Therefore, in order to obtain a high corrosion-resistant galvanized steel sheet, a film is formed on the galvanized steel sheet by using a new coating solution containing Ti-complex compound and colloidal silica having excellent corrosion resistance and resin adhesion.
이때, 상기 화학식 1, 2 또는 3의 Ti-계 착화합물을 서로 혼합하여 사용하는 경우에, 그 혼합은 각각 서로 1:1의 몰비로 혼합되는 것이 바람직하다. 상기 각 Ti-계 착화합물을 몰비로 서로 1:1로 혼합하여 사용하면, 서로 다른 가수분해 및 산화-환원 반응속도에 의해 코팅피막의 증가된 내식성을 나타낼 수 있다.At this time, when using the Ti-based complex compounds of the general formula (1), (2) or (3) are mixed with each other, the mixing is preferably mixed with each other in a molar ratio of 1: 1. When the Ti-based complex compounds are mixed with each other in a molar ratio of 1: 1, the corrosion resistance of the coating film may be increased by different hydrolysis and redox reaction rates.
특히, 상기 Ti-계 착화합물중에서 화학식 1의 착화합물이 사용되는 것이 바람직하다. In particular, it is preferable that the complex compound of formula 1 is used among the Ti-based complex compounds.
이러한 Ti-계 착화합물은 콜로이드 실리카 용액에 총 중량을 기준으로 5-30중량%로 함유될 수 있다. 예를들어, 본 발명의 방청코팅용액은 상기 Ti-계 착화합물이 콜로이드 실리카 용액내에 5-30중량%의 농도가 되도록 첨가된 것일 수 있다. 만일 5중량%미만으로 함유하는 경우 Ti-계 착화합물의 농도가 너무 묽어져서 내식성을 기대할 수 없으며, 30중량%이상으로 함유하는 경우에는 내식성은 더이상 증가하지않아 비경제적이다. 바람직하게, 상기 Ti-계 착화합물은 콜로이드 실리카 용액에 총 중량을 기준으로 15중량%의 양으로 첨가된다. Such Ti-based compounds may be contained in the colloidal silica solution of 5-30% by weight based on the total weight. For example, the anti-corrosive coating solution of the present invention may be added so that the Ti-based complex compound has a concentration of 5-30% by weight in the colloidal silica solution. If the content is less than 5% by weight, the concentration of the Ti-based compound is too thin to be expected from corrosion resistance. If the content is more than 30% by weight, the corrosion resistance does not increase any more, which is uneconomical. Preferably, the Ti-based complex is added to the colloidal silica solution in an amount of 15% by weight based on the total weight.
또한, 상기 Ti-계 착화합물은 적절한 용매내에 용해된 형태인 것을 사용할 수 있다. 예를들어, 상기 Ti-계 착화합물은 2-프로판올내에 80중량%로 용해된 형태로 첨가될 수 있다. In addition, the Ti-based complex compound may be used in the form dissolved in a suitable solvent. For example, the Ti-based complex compound may be added in a form dissolved at 80% by weight in 2-propanol.
한편, 본 발명에 사용되는 콜로이드 실리카 용액은 일반적으로 시중에서 판매되는 어느 것이 사용될 수 있으나, 바람직하게 pH 8-9, 보다 바람직하게 pH 8.9인 것을 사용하는 경우 가장 우수한 내식성 및 용액 안정성을 나타낸다. 예를들어, LUDOX AM-30(Aldrich Chemical Co.) 콜로이드 실리카 용액이 바람직하다.
On the other hand, the colloidal silica solution used in the present invention may be generally used on the market, but preferably shows the best corrosion resistance and solution stability when using a pH of 8-9, more preferably pH 8.9. For example, LUDOX AM-30 (Aldrich Chemical Co.) colloidal silica solution is preferred.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다.
Hereinafter, the present invention will be described in more detail by way of examples.
실시예Example
발명예 1-35 : Ti-계 착화합물을 첨가하여 제조된 아연도금 강판용 방청코팅용액 제조 Inventive Example 1-35: Preparation of antirust coating solution for galvanized steel sheet prepared by adding Ti-based complex compound
[화학식 1] [Ti(L1)(L2)], [화학식 2] [Ti(L2)2(L3)
2] 및 [화학식 3] [Ti(L4)2(L5)2](NH4)2(여기서, L1
=트리에탄올아미네이토, L2=이소프로폭시드, L3=아세틸아세토네이트, L4=락테이토이며 그리고 L5=히드록시드임)을 사용하여 본 발명의 아연도금 강판용 방청코팅용액을 하기와 같이 제조하였다.
[Ti (L 1 ) (L 2 )], [Formula 2] [Ti (L 2 ) 2 (L 3 ) 2 ] and [Formula 3] [Ti (L 4 ) 2 (L 5 ) 2 ] (NH 4 ) 2 , where L 1 = triethanolamineto, L 2 = isopropoxide, L 3 = acetylacetonate, L 4 = lactate and L 5 = hydroxy The anti-corrosive coating solution for galvanized steel sheet of the present invention was prepared as follows.
발명예 1~5 : [Ti(LInventive Examples 1-5: [Ti (L 1One )(L) (L 22 )]가 첨가된 경우)] Is added
순수를 가하여 15중량%로 희석된 LUDOX AM-30(Aldrich Chemical Co.) 콜로이드 실리카 용액 1L에 착화합물, [Ti(L1)(L2)](2-프로판올내에 80중량%로 용해된 형태이며, 여기서, L1=트리에탄올아미네이토이며 L2=이소프로폭시드임)을 5, 15, 30중량%로 각각 첨가하고, 잘 혼합하여 아연도금 강판용 방청코팅용액을 제조하였다(발명예 1, 2, 3). 또한, 콜로이드 실리카 용액으로는 순수를 가하여 15중량%로 희석된 LUDOX HS-30(Aldrich Chemical Co.) 및 TMA(Aldrich Chemical Co.)용액을 사용하고 상기 착화합물을 15중량%로 각각 첨가한 것을 제외하고 상기와 동일한 방법으로 아연도금 강판용 방청코팅용액을 제조하였다(발명예 4, 5).Was added to the pure LUDOX diluted to 15% by weight of AM-30 (Aldrich Chemical Co.) complex in the colloidal silica solution 1L, [Ti (L 1) (L 2)] (2- propanol dissolved form to 80% by weight in a , Where L 1 = triethanolamine and L 2 = isopropoxide) were added at 5, 15 and 30% by weight, respectively, and mixed well to prepare an anticorrosive coating solution for galvanized steel sheet (Invention Example 1, 2, 3). As the colloidal silica solution, LUDOX HS-30 (Aldrich Chemical Co.) and TMA (Aldrich Chemical Co.) solutions diluted to 15% by weight of pure water were used, and 15% by weight of the complex were added. And to prepare a rustproof coating solution for galvanized steel sheet in the same manner as described above (Invention Examples 4, 5).
발명예 6~10 : [Ti(LInventive Examples 6-10: [Ti (L 22 )) 22 (L(L 33 )) 22 ]가 첨가된 경우] Is added
순수를 가하여 15중량%로 희석된 LUDOX AM-30 콜로이드 실리카 용액 1L에 착화합물, [Ti(L2)2(L3)2](2-프로판올내에 75중량%로 용해된 형태이며, 여기서, L2=이소프로폭시드이며 L3=아세틸아세토네이트임)을 5, 15, 30중량%로 각각 첨가하고, 잘 혼합하여 아연도금 강판용 방청코팅용액을 제조하였다(발명예 6, 7, 8). 또한, 콜로이드 실리카 용액으로는 순수를 가하여 15중량%로 희석된 LUDOX HS-30 및 TMA 용액을 사용하고 상기 착화합물을 15중량%로 각각 첨가한 것을 제외하고 상기와 동일한 방법으로 아연도금 강판용 방청코팅용액을 제조하였다(발명예 9, 10).1L of LUDOX AM-30 colloidal silica solution diluted to 15% by weight of pure water was dissolved in 75% by weight in [Ti (L 2 ) 2 (L 3 ) 2 ] (2-propanol), where L 2 = isopropoxide and L 3 = acetylacetonate) were added at 5, 15 and 30% by weight, respectively, and mixed well to prepare an anticorrosive coating solution for galvanized steel sheet (Invention Examples 6, 7, 8). As a colloidal silica solution, an anti-corrosive coating solution for galvanized steel sheet was prepared in the same manner as described above, except that LUDOX HS-30 and TMA solutions diluted to 15% by weight of pure water were added and 15% by weight of the complex compound were added. Was prepared (Inventive Example 9, 10).
발명예 11~15 : [Ti(LInventive Examples 11-15: [Ti (L 44 )) 22 (L(L 55 )) 22 ](NH] (NH 44 )) 2 2 가 첨가된 경우Is added
순수를 가하여 15중량%로 희석된 LUDOX AM-30 콜로이드 실리카 용액 1L에 착화합물, [Ti(L4)2(L5)2](NH4)2(물에 50중량%로 용해된 수용액 형태이며, 여기서, L4=락테이토이며 그리고 L5=히드록시드임)을 5, 15, 30중량%로 각각 첨가하고, 잘 혼합하여 아연도금 강판용 방청코팅용액을 제조하였다(발명예 11, 12, 13). 또한, 콜로이드 실리카 용액으로는 순수를 가하여 15중량%로 희석된 LUDOX HS-30 및 TMA 용액을 사용하고 상기 착화합물을 15중량%로 각각 첨가한 것을 제외하고 상기와 동일한 방법으로 아연도금 강판용 방청코팅용액을 제조하였다(발명예 14, 15).1L of LUDOX AM-30 colloidal silica solution diluted to 15% by weight of pure water was added as a complex, [Ti (L 4 ) 2 (L 5 ) 2 ] (NH 4 ) 2 (in the form of an aqueous solution dissolved at 50% by weight in water). Where L 4 = lactate and L 5 = hydroxide) were added at 5, 15, and 30% by weight, respectively, and mixed well to prepare an anti-corrosive coating solution for galvanized steel sheet (Invention Examples 11, 12). , 13). As a colloidal silica solution, an anti-corrosive coating solution for galvanized steel sheet was prepared in the same manner as described above, except that LUDOX HS-30 and TMA solutions diluted to 15% by weight of pure water were added and 15% by weight of the complex compound were added. Was prepared (Invention Examples 14, 15).
발명예 16~20 : [Ti(LInventive Examples 16-20: [Ti (L 1One )(L) (L 22 )]/[Ti(L)] / [Ti (L 2 2 )) 22 (L(L 33 )) 22 ](몰비로 1:1)가 첨가된 경우] (1: 1 in molar ratio)
순수를 가하여 15중량%로 희석된 LUDOX AM-30 콜로이드 실리카 용액 1L에 착화합물, [Ti(L1)(L2)]/[Ti(L2)2(L3)2](몰비로 각각 1:1로 혼합되어 2-프로판올내에 80중량%로 용해된 형태이며, 여기서, L1=트리에탄올아미네이토, L2=이소프로폭시드이며 L3=아세틸아세토네이트임)을 5, 15, 30중량%로 각각 첨가하고, 잘 혼합하여 아연도금 강판용 방청코팅용액을 제조하였다(발명예 16, 17, 18). 또한, 콜로이드 실리카 용액을 순수를 가하여 15중량%로 희석된 LUDOX HS-30 및 TMA 용액으로 사용하고 상기 착화합물을 15중량%로 각각 첨가한 것을 제외하고 상기와 동일한 방법으로 아연도금 강판용 방청코팅용액을 제조하였다(발명예 19, 20).1L of LUDOX AM-30 colloidal silica solution diluted to 15% by weight of pure water was added to complex, [Ti (L 1 ) (L 2 )] / [Ti (L 2 ) 2 (L 3 ) 2 ] Mixed in the form of 1 : dissolved in 2-propanol at 80% by weight, wherein L 1 = triethanolaminetoce, L 2 = isopropoxide and L 3 = acetylacetonate). Each was added in weight percent and mixed well to prepare a rust preventing coating solution for galvanized steel sheet (Invention Examples 16, 17, 18). In addition, the anticorrosive coating solution for galvanized steel sheet was prepared in the same manner as above except that the colloidal silica solution was used as a LUDOX HS-30 and TMA solution diluted to 15% by weight of pure water and 15% by weight of the complex was added. Prepared (Inventive Example 19, 20).
발명예 21~25 : [Ti(LInventive Examples 21-25: [Ti (L 1One )(L) (L 22 )]/[Ti(L)] / [Ti (L 4 4 )) 22 (L(L 55 )) 22 ](NH ] (NH 44 )) 22 (몰비로 1:1)가 첨가된 경우(1: 1 in molar ratio)
순수를 가하여 15중량%로 희석된 LUDOX AM-30 콜로이드 실리카 용액 1L에 착화합물, [Ti(L1)(L2)]/[Ti(L4)2(L5)2](NH4)2(몰비로 각각 1:1로 혼합되어 2-프로판올내에 80중량%로 용해된 형태이며, 여기서, L1=트리에탄올아미네이토, L2=이소프로폭시드, L4=락테이토이며 그리고 L5=히드록시드임)을 5, 15, 30중량%로 각각 첨가하고, 잘 혼합하여 아연도금 강판용 방청코팅용액을 제조하였다(발명예 21, 22, 23). 또한, 콜로이드 실리카 용액을 순수를 가하여 15중량%로 희석된 LUDOX HS-30 및 TMA 용액으로 사용하고 상기 착화합물을 15중량%로 각각 첨가한 것을 제외하고 상기와 동일한 방법으로 아연도금 강판용 방청코팅용액을 제조하였다(발명예 24, 25).To 1 L of LUDOX AM-30 colloidal silica solution diluted to 15% by weight of pure water, a complex, [Ti (L 1 ) (L 2 )] / [Ti (L 4 ) 2 (L 5 ) 2 ] (NH 4 ) 2 (Mixed at a molar ratio of 1: 1 each, dissolved in 2-propanol at 80% by weight, where L 1 = triethanolamineto, L 2 = isopropoxide, L 4 = lactate and L 5 = 15 hydroxides were added at 5, 15 and 30% by weight, respectively, and mixed well to prepare an anti-corrosive coating solution for galvanized steel sheet (Invention Examples 21, 22, and 23). In addition, the anticorrosive coating solution for galvanized steel sheet was prepared in the same manner as above except that the colloidal silica solution was used as a LUDOX HS-30 and TMA solution diluted to 15% by weight of pure water and 15% by weight of the complex was added. Prepared (Invention Examples 24, 25).
발명예 26~30 : [Ti(LInventive Examples 26-30: [Ti (L 22 )(L) (L 33 )) 22 ]/[Ti(L] / [Ti (L 44 )) 22 (L(L 55 )) 22 ](NH] (NH 44 )) 22 (몰비로 1:1)가 첨가된 경우(1: 1 in molar ratio)
순수를 가하여 15중량%로 희석된 LUDOX AM-30 콜로이드 실리카 용액 1L에 착화합물, [Ti(L2)(L3)2]/[Ti(L4)2(L5)2](NH4)2(몰비로 각각 1:1로 혼합되어 2-프로판올내에 80중량%로 용해된 형태이며, 여기서, L2=이소프로폭시드, L3=아세틸아세토네이트, L4=락테이토이며 그리고 L5=히드록시드임)을 5, 15, 30중량%로 각각 첨가하고, 잘 혼합하여 아연도금 강판용 방청코팅용액을 제조하였다(발명예 26, 27, 28). 또한, 콜로이드 실리카 용액을 순수를 가하여 15중량%로 희석된 LUDOX HS-30 및 TMA 용액으로 사용하고 상기 착화합물을 15중량%로 각각 첨가한 것을 제외하고 상기와 동일한 방법으로 아연도금 강판용 방청코팅용액을 제조하였다(발명예 29, 30).To 1 L of LUDOX AM-30 colloidal silica solution diluted to 15% by weight of pure water complex, [Ti (L 2 ) (L 3 ) 2 ] / [Ti (L 4 ) 2 (L 5 ) 2 ] (NH 4 ) 2 (mixed at a molar ratio of 1: 1 each, dissolved in 2-propanol at 80% by weight, where L 2 = isopropoxide, L 3 = acetylacetonate, L 4 = lactate, and L 5 = hydroxide, 5, 15, 30% by weight were added, and mixed well to prepare an anti-corrosive coating solution for galvanized steel sheet (Invention Examples 26, 27, 28). In addition, the anticorrosive coating solution for galvanized steel sheet was prepared in the same manner as above except that the colloidal silica solution was used as a LUDOX HS-30 and TMA solution diluted to 15% by weight of pure water and 15% by weight of the complex was added. Prepared (Inventive Example 29, 30).
발명예 31~35 : [Ti(LInventive Examples 31-35: [Ti (L 1One )(L) (L 22 )]/[Ti(L)] / [Ti (L 2 2 )(L) (L 33 )) 22 ]/[Ti(L] / [Ti (L 44 )) 22 (L(L 55 )) 22 ](NH] (NH 44 )) 22 (몰비로 1:1:1)가 첨가된 경우(1: 1: 1 in molar ratio)
순수를 가하여 15중량%로 희석된 LUDOX AM-30 콜로이드 실리카 용액 1L에 착화합물, [Ti(L1)(L2)]/[Ti(L2)(L3)2]/[Ti(L4)2(L5)2](NH4)2(몰비로 각각 1:1:1로 혼합되어 2-프로판올내에 80중량%로 용해된 형태이며, 여기서, L1=트리에탄올아미네이토, L2=이소프로폭시드, L3=아세틸아세토네이트, L4=락테이토이며 그리고 L5=히드록시드임)을 5, 15, 30중량%로 각각 첨가하고, 잘 혼합하여 아연도금 강판용 방청코팅용액을 제조하였다(발명예 31, 32, 33). 또한, 콜로이드 실리카 용액을 순수를 가하여 15중량%로 희석된 LUDOX HS-30 및 TMA 용액으로 사용하고 상기 착화합물을 15중량%로 각각 첨가한 것을 제외하고 상기와 동일한 방법으로 아연도금 강판용 방청코팅용액을 제조하였다(발명예 34, 35).To 1 L of LUDOX AM-30 colloidal silica solution diluted to 15% by weight of pure water complex, [Ti (L 1 ) (L 2 )] / [Ti (L 2 ) (L 3 ) 2 ] / [Ti (L 4 ) 2 (L 5 ) 2 ] (NH 4 ) 2 (mixed at a molar ratio of 1: 1: 1 and dissolved at 80% by weight in 2-propanol, where L 1 = triethanolamineto, L 2 Isopropoxide, L 3 = acetylacetonate, L 4 = lactate and L 5 = hydroxide) at 5, 15 and 30% by weight, respectively, and mixed well to prevent corrosion coating for galvanized steel sheet. Solutions were prepared (Inventive Examples 31, 32, 33). In addition, the anticorrosive coating solution for galvanized steel sheet was prepared in the same manner as above except that the colloidal silica solution was used as a LUDOX HS-30 and TMA solution diluted to 15% by weight of pure water and 15% by weight of the complex was added. (34, 35).
비교예 1~7Comparative Examples 1-7
순수를 가하여 15중량%로 희석된 LUDOX AM-30 콜로이드 실리카 용액 1L에 상기 각 착화합물 또는 이들의 혼합 착화합물의 첨가량을 3중량%로 첨가한 것을 제외하고, 상기 발명예 1~35와 동일한 방법으로 아연도금 강판용 방청코팅용액을 제조하였다.
Zinc was added in the same manner as in Examples 1 to 35, except that 3% by weight of each of the complex compounds or mixed complex compounds thereof was added to 1 L of LUDOX AM-30 colloidal silica solution diluted to 15% by weight of pure water. An antirust coating solution for plated steel sheet was prepared.
종래예Conventional example
대한민국 특허 출원 1999-51479에 기술된 바와 같이, 크롬환원비(Cr3+/Cr6+)가 0.52이며, 콜로이드 실리카, 불산, 인산이 첨가된 주제용액에, 에폭시계 실란 가교제와 인산이 포함된 경화제를 가하여 제조된 Zn-Ni 전기도금 강판에 적용하는 도포형 크로메이트 방청용액을 제조하였다.
As described in Korean Patent Application No. 1999-51479, the chromium reduction ratio (Cr3 + / Cr6 +) is 0.52, and is prepared by adding an epoxy silane crosslinking agent and a curing agent containing phosphoric acid to a main solution containing colloidal silica, hydrofluoric acid, and phosphoric acid. The coated chromate rust preventing solution applied to the prepared Zn-Ni electroplating steel sheet was prepared.
성능평가Performance evaluation
상기 발명예 1-21 및 종래예에서 제조된 아연도금강판용 방청코팅용액을 바코트 #-3을 사용하여 합금화 용융 아연도금강판(GA)에 도포하고(막두께: 약 1㎛) 열풍 건조로에서 강판 도달 온도 160℃(PMT)로 10초간 건조하여 코팅시편을 제조하였다. 이 시편을 수냉으로 냉각한 수 염수분무장치(JIS E2731)를 이용하여 5% NaCl, 분산압 1Kg/㎡의 분사압력으로 분사한 후 5% 백청 발생까지의 소요시간을 측정하여 내식성을 조사하였다. 또한, 표면외관과 용액안정성에 대하여 색상, 도포성(wetability), 용액의 경시, 침전물의 유무 등에 관한 관능검사를 행하였다. 그 결과를 하기 표 1에 나타내었다.The anti-corrosive coating solution for galvanized steel sheet prepared in Inventive Examples 1-21 and the prior art was applied to the alloyed hot dip galvanized steel sheet (GA) using bar coat # -3 (film thickness: about 1 μm) and the steel sheet in a hot air drying furnace. A coating specimen was prepared by drying at an reaching temperature of 160 ° C. (PMT) for 10 seconds. The specimen was sprayed with a water-cooled brine spray device (JIS E2731) at 5% NaCl and 1 Kg / m2 of dispersion pressure, and then measured for 5% white blue. In addition, the sensory test was performed on the surface appearance and the solution stability regarding the color, wettability, the aging of the solution, the presence or absence of precipitates, and the like. The results are shown in Table 1 below.
1) 콜로이드 실리카는 Aldrich Chemical Co.에서 시판하는 LUDOX AM-30(pH 8.9), HS-30(pH 9.8) 및 TMA(pH 4.7)를 사용하였다.1) Colloidal silica was used as LUDOX AM-30 (pH 8.9), HS-30 (pH 9.8) and TMA (pH 4.7) commercially available from Aldrich Chemical Co.
2) 표면외관은 색상, 도포성(wetability), 침전물의 유무 등에 관한 관능검사를 행하였다. 2) The surface appearance was subjected to sensory tests on color, wettability, and the presence or absence of sediment.
3) 용액 안정성은 용액의 경시현상을 기준으로 평가하였다(매우 우수-2주이상 유지, 우수-1주일 유지, 양호-3일 정도 유지, 저조-24시간이내 경시현상).3) Solution stability was evaluated based on the aging of the solution (very good-more than 2 weeks, good-1 week, good-3 days, low-24 hours over time).
4) 내식성은 5% 백청 발생까지의 소요시간을 기준으로 평가하였다(매우 우수-96시간이상, 우수-72시간 내지 96시간, 양호-48시간 내지 72시간, 저조-48시간 미만).4) Corrosion resistance was evaluated based on the time required to develop 5% white rust (very good-more than 96 hours, good-72 to 96 hours, good-48 to 72 hours, low-48 hours).
* [화학식 1] [Ti(L1)(L2)], [화학식 2] [Ti(L2)2(L3)
2] 및 [화학식 3] [Ti(L4)2(L5)2](NH4)2 에서, L1
=트리에탄올아미네이토, L2=이소프로폭시드, L3=아세틸아세토네이트, L4=락테이토이며 그리고 L5=히드록시드임.
* [Ti (L 1 ) (L 2 )], [Formula 2] [Ti (L 2 ) 2 (L 3 ) 2 ] and [Formula 3] [Ti (L 4 ) 2 (L 5 ) 2 ] (NH 4 ) 2 , L 1 = triethanolamineto, L 2 = isopropoxide, L 3 = acetylacetonate, L 4 = lactate and L 5 = hydroxy.
상기 표 1에 나타낸 바와 같이, 콜로이드 실리카에 화학식 1-3의 Ti-계 착화합물을 5-30중량%로 첨가한 경우 표면외관, 용액안정성 및 내식성이 우수하게 나타남을 알 수 있다. 특히, 화학식 1의 착화합물 [Ti(L1)(L2)]을 포함하는 경우에 대체로 코팅용액의 내식성이 매우 우수하였으며, 이는 L1 리간드 즉, 트리에탄올아미네이토가 안정한 킬레이트 고리를 형성하고 말단기 리간드인 L2 리간드 즉, 이소프로폭시드의 음이온이 상대적으로 안정하여 용액을 안정화시키고, 코팅후 서서히 가수분해되어 Ti(L1)(OH) 불용성 피막을 형성하고, 최종적으로 Ti-O 계통의 산화물로 전환되기때문인 것으로 사료된다. As shown in Table 1, it can be seen that the surface appearance, solution stability and corrosion resistance were excellent when 5-30% by weight of the Ti-based complex compound of Formula 1-3 was added to the colloidal silica. In particular, in the case of containing the complex compound [Ti (L 1 ) (L 2 )] of the general formula ( 1 ), the corrosion resistance of the coating solution was generally excellent, which means that the L 1 ligand, ie, triethanolamineto form a stable chelate ring. The short-term ligand, L 2 ligand, that is, the anion of isopropoxide is relatively stable to stabilize the solution, and then slowly hydrolyze after coating to form a Ti (L 1 ) (OH) insoluble coating, and finally a Ti-O strain It is believed to be due to the conversion to oxides.
또한, 특히 콜로이드 실리카가 약 염기성인 LUDOX AM-30(pH 8.9)를 사용한 경우 상대적으로 우수한 용액 안정성 및 내식성이 나타나 pH 8.9의 조건하에서 수행되는 것이 바람직함을 알 수 있었다. In addition, especially when LUDOX AM-30 (pH 8.9) in which colloidal silica was about basic, relatively good solution stability and corrosion resistance were observed, and thus, it was found that the colloidal silica was preferably performed under the condition of pH 8.9.
이러한 본 발명의 코팅용액은 크로메이트를 사용한 종래예에 비교하여 동등하거나 그 이상의 내식성을 가질 뿐만아니라 표면외관 및 용액안정성도 우수하므로 합금화 용융아연 도금강판의 내식성 보강을 위한 무-크롬 도포형 코팅 방청제로 적용하는 경우에 매우 유용할 것으로 판단된다.
Since the coating solution of the present invention has not only the same or more corrosion resistance than the conventional example using chromate, but also has excellent surface appearance and solution stability, it is a chromium-free coating type anticorrosive for reinforcing corrosion resistance of alloyed hot-dip galvanized steel sheet. It will be very useful when applied.
본 발명에 따라 크롬을 사용하지않고, Ti-계 착화합물을 이용한 환경친화적인 아연 도금강판용 방청 코팅용액이 제공된다.According to the present invention, there is provided an environmentally friendly antirust coating solution for galvanized steel sheet using Ti-based compounds without using chromium.
또한, 본 발명의 아연 도금강판용 방청 코팅용액은 제조하기가 비교적 간편하며, 내식성이 우수할 뿐만아니라, 표면외관 및 용액안정성이 우수하다.In addition, the anti-corrosive coating solution for galvanized steel sheet of the present invention is relatively easy to prepare, excellent corrosion resistance, and excellent surface appearance and solution stability.
Claims (6)
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| JP2000160054A (en) * | 1998-11-25 | 2000-06-13 | Teikoku Chem Ind Corp Ltd | Coating fluid for forming hydrophilic coating film, hydrophilic coating film prepared therefrom, and its formation |
| JP2001200202A (en) * | 2000-01-21 | 2001-07-24 | Yamaha Livingtec Corp | Method of forming inorganic film |
| KR20020065904A (en) * | 2000-01-12 | 2002-08-14 | 인터내셔널 코팅스 리미티드 | Ambient temperature curing coating composition |
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| US3244639A (en) * | 1961-09-20 | 1966-04-05 | Nalco Chemical Co | Method of producing a stable titaniacoated silica sol |
| US4495156A (en) * | 1983-01-05 | 1985-01-22 | American Can Company | Primary system |
| JPH10204323A (en) * | 1997-01-23 | 1998-08-04 | Nissan Motor Co Ltd | Coating liquid for forming hydrophilic coating film and its production |
| JP2000160054A (en) * | 1998-11-25 | 2000-06-13 | Teikoku Chem Ind Corp Ltd | Coating fluid for forming hydrophilic coating film, hydrophilic coating film prepared therefrom, and its formation |
| KR20020065904A (en) * | 2000-01-12 | 2002-08-14 | 인터내셔널 코팅스 리미티드 | Ambient temperature curing coating composition |
| JP2001200202A (en) * | 2000-01-21 | 2001-07-24 | Yamaha Livingtec Corp | Method of forming inorganic film |
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