KR20160078773A - Low temperature curable anti-corrosion coating composition excellent in corrosion resistance and zinc plated steel sheet using the same - Google Patents
Low temperature curable anti-corrosion coating composition excellent in corrosion resistance and zinc plated steel sheet using the same Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/02—Polysilicates
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- 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
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
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- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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Abstract
Description
내부식성이 우수한 저온 경화형 방청코팅 조성물 및 이를 이용한 아연도금 강판에 관한 것이다.
Temperature curing type anticorrosive coating composition excellent in corrosion resistance and a galvanized steel sheet using the same.
지난 십 수년 동안 세계적으로 환경문제에 대한 관심이 높아지고 있는 가운데, 환경 오염물질인 중금속 및 유기 할로겐 화합물 등에 대한 사용규제가 강화되어 왔다. 특히, EU에서 도입한 유해물질 사용제한 지침(RoHS; Restriction of Hazardous Substances, '06.7.1 시행), 폐가전 처리지침(WEEE; Waste from Electrical and Electronic Equipment, 2006.7.1 시행), 폐차 처리지침(ELV; End-of-Life Vehicles, 2007.1.1 시행) 등이 대표적인 예로서, 이에 따라 산업분야에서 환경 친화적인 제품의 개발에 많은 노력을 기울여왔다.
Over the past decade, as global environmental concerns have increased, restrictions on the use of environmental pollutants such as heavy metals and organohalogen compounds have been strengthened. In particular, the EU has introduced Restriction of Hazardous Substances (RoHS), Waste Electrical and Electronic Equipment (WEEE) ELV; End-of-Life Vehicles, Jan. 1, 2007). As a result, many efforts have been made to develop eco-friendly products in the industrial field.
종래에는, 자동차, 가전 및 건축분야의 용도로 사용되는 아연도금강판, 아연계 합금도금강판 및 알루미늄계 합금도금강판의 표면에 크롬을 주성분으로 하는 크로메이트 피막을 코팅하여 사용내식성 및 도장 밀착성 등을 부여하였다.
Conventionally, a chromate film containing chromium as a main component is coated on the surface of a galvanized steel sheet, a zinc-based alloy coated steel sheet and an aluminum-based alloy coated steel sheet which are used for automobile, home appliance and building applications, and corrosion resistance and paint adhesion are given Respectively.
그러나, 강판의 도금층 표면에 도포된 Cr(III) 화합물은 인체에 유해한 Cr(VI)으로 전환되므로, 십 여년 전부터 크롬-프리 강판 코팅용 조성물으로 전환되고 있다. 대표적으로, 아크릴, 우레탄 등과 같이 고분자 수지를 주성분으로 하고, 실리카졸과 금속화합물 인히비터(inhibiter)를 포함하는 강판 코팅용 조성물을 사용하여 강판을 처리했다.
However, since the Cr (III) compound coated on the surface of the plating layer of the steel sheet is converted into Cr (VI) harmful to human body, it has been converted into a composition for chrome-free steel sheet coating for a decade. Typically, a steel sheet is treated using a composition for steel sheet coating comprising a polymer resin as a main component such as acryl, urethane, etc., and silica sol and a metal compound inhibitor.
다만, 고분자 수지로 이루어진 크롬-프리 강판 코팅용 조성물은 경화온도가 높아 고온의 건조설비가 필요하나, 일부 철강사의 아연도금 설비는 100℃ 이내의 건조설비로 구성되어 있으므로, 저온에서 경화반응이 가능한 크롬-프리 용액 조성물의 개발이 요구되고 있다.
However, since a composition for coating a chromium-free steel sheet made of a polymer resin has a high curing temperature and needs to be dried at a high temperature, zinc plating facilities of some steelmakers are composed of drying facilities within 100 ° C, Development of a chromium-free solution composition is required.
한편, 최근에는 실란 화합물을 포함한 크롬-프리 강판 코팅용 조성물로 처리하여 저온에서 경화 가능한 표면처리 기술을 개시하고 있으나, 내식성이 충분하지 못하고 용액 안정성이 나쁜 단점이 있다
On the other hand, recently, a surface treatment technique capable of being cured at a low temperature by treating with a chromium-free steel sheet coating composition containing a silane compound has been disclosed, but the corrosion resistance is poor and the solution stability is poor
본 발명은 인체에 유해한 크롬을 함유하지 않으며 저온경화가 가능한 강판 코팅용 조성물을 제공하고, 상기 조성물로 처리된 내부식성이 우수한 아연도금 강판을 제공하고자 한다.
The present invention provides a composition for coating a steel sheet which does not contain chromium harmful to the human body and which can be cured at low temperatures, and provides a galvanized steel sheet excellent in corrosion resistance treated with the composition.
본 발명의 일 실시예에 따르면, 실란 화합물 5 내지 30 중량%, 폴리실리케이트 화합물 1 내지 10 중량%, 티타늄 화합물 0.1 내지 5 중량%, 왁스 0.1 내지 5 중량% 및 저온경화용 알코올 1 내지 15 중량%를 포함하는 수용액인 내부식성이 우수한 저온 경화형 방청코팅 조성물을 제공한다.According to an embodiment of the present invention, there is provided a process for producing a curable composition comprising 5 to 30 wt% of a silane compound, 1 to 10 wt% of a polysilicate compound, 0.1 to 5 wt% of a titanium compound, 0.1 to 5 wt% of a wax, Curable anti-corrosive coating composition excellent in corrosion resistance.
상기 실란 화합물은 에폭시계 실란 화합물, 아미노계 실란 화합물, 이들의 가수분해물 및 상기 가수분해물의 축합물에서 선택된 하나 이상일 수 있다.The silane compound may be at least one selected from an epoxy silane compound, an amino silane compound, a hydrolyzate thereof, and a condensate of the hydrolyzate.
상기 실란 화합물은 아미노계 실란 화합물 및 에폭시계 실란 화합물의 혼합물이며, 상기 아미노계 실란 화합물 및 에폭시계 실란 화합물의 혼합 비율은 1: 0.2 내지 10일 수 있다. The silane compound is a mixture of an amino-based silane compound and an epoxy-based silane compound, and the mixing ratio of the amino-based silane compound and the epoxy-based silane compound may be 1: 0.2 to 10.
상기 실란 화합물은 비닐메톡시실란, 비닐트리메톡시실란, 비닐에폭시실란, 비닐트리에폭시실란, 3-아미노프리필트리에폭시실란, 3-글리시독시프로필트리메톡시실란, 3-메타글리독시프로필트리메톡시실란, 3-메르캅토프로필트리메톡시실란, N-(1,3-디메틸부틸리덴)-3-(트리에폭시실란)-1-프로판아민, N,N-비스[3-(트리메톡시실릴)프로필]에틸렌디아민, N-β(아미노에틸)-γ-아미노프로필트리메톡시실란, N-β(아미노에틸)-γ-아미노프로필트리에톡시실란, N-β(아미노에틸)-γ-아미노프로필메틸트리에톡시실란, N-(β-아미노에틸)-γ-아미노프로필메틸디메톡시실란, N-(β-아미노에틸)-γ-아미노프로필트리메톡시실란, γ-글리시독시프로필트리에톡시실란, γ-글리시독시트리메틸디메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, γ-메타크릴옥시프로필트리메톡시실란, γ-메타크릴옥시프로필트리에톡시실란, γ-메르캅토프로필트리메톡시실란, γ-메르캅토프로필트리에톡시실란, 및 N-[2-(비닐벤질아미노) 에틸]-3-아미노프로필트리메톡시실란으로 구성되는 그룹에서 선택된 하나 이상일 수 있다.Wherein the silane compound is selected from the group consisting of vinyl methoxy silane, vinyl trimethoxy silane, vinyl epoxysilane, vinyl triepoxy silane, 3-aminopentyl triethoxy silane, 3-glycidoxypropyl trimethoxy silane, 3- (Triepoxysilane) -1-propanamine, N, N-bis [3- (tri (methoxysilyl) (Aminoethyl) -? - aminopropyltriethoxysilane, N -? (Aminoethyl) -? - aminopropyltrimethoxysilane, N- -aminopropyltrimethoxysilane, N- (? -aminoethyl) -? - aminopropylmethyldimethoxysilane, N- (? -aminoethyl) -? - aminopropyltrimethoxysilane,? - gly Glycidoxytrimethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyl tri (meth) acrylate, Methacryloxypropyltriethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Mercaptopropyltriethoxysilane, and N- [2- (vinylbenzylamino) ethyl] -3 -Aminopropyltrimethoxysilane. ≪ / RTI >
상기 폴리실리케이트 화합물은 리튬 폴리실리케이트, 소디움 폴리실리케이트, 포타슘 폴리실리케이트 및 콜로이달 실리카에서 선택된 하나 이상일 수 있다. The polysilicate compound may be at least one selected from lithium polysilicate, sodium polysilicate, potassium polysilicate and colloidal silica.
상기 티타늄 화합물로는 티타늄 카보네이트, 이소프로필디트리에탄올아미노 티타네이트, 락틱산 티타늄킬레이트 및 티타늄 아세틸아세토네이트에서 선택된 하나 이상일 수 있다.The titanium compound may be at least one selected from titanium carbonate, isopropyl ditriethanol aminotitanate, titanium lactate lactate, and titanium acetylacetonate.
상기 왁스는 폴리에틸렌, 폴리테트라플루오르에틸렌 또는 이들의 혼합물일 수 있다.The wax may be polyethylene, polytetrafluoroethylene or mixtures thereof.
상기 저온경화용 알코올은 에탄올, 프로판올 및 이스프로판올에서 선택된 하나 이상일 수 있다.
The low-temperature curing alcohol may be at least one selected from ethanol, propanol and isopropanol.
본 발명의 다른 실시예에 따르면, 강판; 상기 강판 상의 일면 또는 양면에 형성된 아연 도금층 및 상기 아연 도금층 상에 형성된 코팅층을 포함하며, 상기 코팅층은 상술한 방청코팅 조성물의 경화물인 내부식성이 우수한 아연도금 강판을 제공한다.According to another embodiment of the present invention, And a coating layer formed on the zinc plating layer, wherein the coating layer is a cured product of the corrosion inhibiting coating composition, wherein the coating layer is excellent in corrosion resistance.
상기 방청코팅 조성물은 경화 온도가 50 내지 150℃일 수 있다.The rust-inhibiting coating composition may have a curing temperature of from 50 to 150 < 0 > C.
상기 코팅층은 건조도막 부착량이 0.05 내지 2.0 g/㎡일 수 있다.The coating layer may have an adhesion amount of from 0.05 to 2.0 g / m < 2 >
상기 아연 도금층은 전기아연 도금층, 용융아연 도금층, 합금화 용융아연 도금층 또는 알루미늄 합금 아연 도금층일 수 있다.
The zinc plated layer may be an electro-galvanized layer, a hot-dip galvanized layer, a galvannealed hot-dip galvanized layer or an aluminum alloy galvanized layer.
본 발명에 의해 제공되는 강판 코팅용 조성물은 크롬을 함유하지 않아 인체에 무해하고 표면 처리 작업시 용액안정성이 우수하며, 저온 경화가 가능하다. 또한, 상기 조성물로 처리된 강판은 내부식성과 심용접성이 우수한 효과가 있다.The steel sheet coating composition provided by the present invention is harmless to the human body because it does not contain chromium and has excellent solution stability during surface treatment and can be cured at a low temperature. In addition, the steel sheet treated with the composition has an excellent corrosion resistance and core weldability.
도 1은 본 발명의 일 실시예인 방청코팅 조성물로 처리된 아연도금 강판의 단면을 보여주는 도면이다.
도 2는 실시예와 비교예의 표면처리 강판에 대한 내연료성 평가 이미지이다.
도 3은 실시예와 비교예의 표면처리 강판에 대한 심용접 전류범위의 값을 나타낸 그래프이다.
도 4는 실시예와 비교예의 표면처리 강판에 대한 내부식성 평가 이미지이다.1 is a cross-sectional view of a galvanized steel sheet treated with a rust-preventive coating composition according to an embodiment of the present invention.
Fig. 2 is an image for evaluating resistance to fuel for the surface-treated steel sheets of Examples and Comparative Examples.
3 is a graph showing values of seam welding current range for the surface treated steel sheets of Examples and Comparative Examples.
4 is an image for evaluating the corrosion resistance of the surface treated steel sheets of Examples and Comparative Examples.
이하, 첨부된 도면을 참조하여 본 발명의 바람직한 실시 형태를 설명한다. 그러나, 본 발명의 실시 형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다.
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.
본 발명의 일 실시예는 내부식성이 우수한 저온 경화형 방청코팅 조성물을 제공하는 것으로, 구체적으로 실란 화합물 5 내지 30 중량%, 폴리실리케이트 화합물 1 내지 10 중량%, 티타늄 화합물 0.1 내지 5 중량%, 왁스 0.1 내지 5 중량% 및 저온경화용 알코올 1 내지 15 중량%를 포함하는 수용액인 내부식성이 우수한 저온 경화형 방청코팅 조성물을 제공한다.
In one embodiment of the present invention, there is provided a low temperature curing type anticorrosive coating composition excellent in corrosion resistance, which comprises 5 to 30 wt% of a silane compound, 1 to 10 wt% of a polysilicate compound, 0.1 to 5 wt% of a titanium compound, 0.1 To 5% by weight of an alcohol for low temperature curing and 1 - 15% by weight of an alcohol for low temperature curing.
상기 실란 화합물은 에폭시계 실란 화합물, 아미노계 실란 화합물, 이들의 가수분해물 및 상기 가수분해물의 축합물에서 선택된 하나 이상일 수 있다. 상기 가수분해물은 실란 화합물이 가수분해되어 얻을 수 있는 실란올 화합물이며, 상기 축합물은 상기 가수분해물이 축합반응하여 생성되는 올리고머(Oligomer)일 수 있다.
The silane compound may be at least one selected from an epoxy silane compound, an amino silane compound, a hydrolyzate thereof, and a condensate of the hydrolyzate. The hydrolyzate is a silanol compound obtained by hydrolyzing a silane compound, and the condensate may be an oligomer produced by the condensation reaction of the hydrolyzate.
본 발명의 조성물에 사용되는 실란 화합물의 함량은, 전체 조성물 100중량%에 대하여, 5 내지 30중량%인 것이 바람직하며, 더욱 바람직하게 5 내지 20중량%일 수 있다. 상기 실란 화합물의 함량이 5중량% 미만이면 내식성 및 가공성의 향상 효과가 부족하며, 30중량% 초과하면 조성물의 제조가 어려우며 용액안정성이 저하되어 바람직하지 않다.
The content of the silane compound used in the composition of the present invention is preferably 5 to 30% by weight, more preferably 5 to 20% by weight, based on 100% by weight of the total composition. If the content of the silane compound is less than 5% by weight, the effect of improving the corrosion resistance and processability is insufficient. If the content is more than 30% by weight, the composition is difficult to prepare and the solution stability is deteriorated.
상기 실란 화합물이 아미노계 실란 화합물 및 에폭시계 실란 화합물의 혼합물인 경우, 상기 아미노계 실란 화합물 및 에폭시계 실란 화합물의 혼합 비율은 1: 0.2 내지 10인 것이 바람직하며, 1: 0.5 내지 4.3인 것이 더욱 바람직하다. 아미노계 실란 화합물에 대하여 에폭시계 실란 화합물의 함량이 0.2 배 미만이면 아미노계 실란 화합물의 함량이 증가함으로 인해 아미노계 실란간의 반응이 증가하여 도막의 물성이 나빠지며, 10배 초과하면 에폭시계 실란 화합물의 함량이 증가함으로 인해 에폭시계 실란 화합물간의 반응이 증가하여 도막의 물성이 나빠질 수 있다..
When the silane compound is a mixture of an amino silane compound and an epoxy silane compound, the mixing ratio of the amino silane compound and the epoxy silane compound is preferably 1: 0.2 to 10, more preferably 1: 0.5 to 4.3 desirable. If the content of the epoxy-based silane compound is less than 0.2 times the content of the amino-based silane compound, the reaction between the amino-based silane increases due to the increase of the content of the amino-based silane compound, The reaction between the epoxy silane compounds increases and the physical properties of the coating film may deteriorate.
본 발명의 내부식성이 우수한 저온 경화형 방청코팅 조성물에 포함되는 실란 화합물은 특별히 제한하는 것은 아니나, 예를 들어, 비닐메톡시실란, 비닐트리메톡시실란, 비닐에폭시실란, 비닐트리에폭시실란, 3-아미노프리필트리에폭시실란, 3-글리시독시프로필트리메톡시실란, 3-메타글리독시프로필트리메톡시실란, 3-메르캅토프로필트리메톡시실란, N-(1,3-디메틸부틸리덴)-3-(트리에폭시실란)-1-프로판아민, N,N-비스[3-(트리메톡시실릴)프로필]에틸렌디아민, N-β(아미노에틸)-γ-아미노프로필트리메톡시실란, N-β(아미노에틸)-γ-아미노프로필트리에톡시실란, N-β(아미노에틸)-γ-아미노프로필메틸트리에톡시실란, N-(β-아미노에틸)-γ-아미노프로필메틸디메톡시실란, N-(β-아미노에틸)-γ-아미노프로필트리메톡시실란, γ-글리시독시프로필트리에톡시실란, γ-글리시독시트리메틸디메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, γ-메타크릴옥시프로필트리메톡시실란, γ-메타크릴옥시프로필트리에톡시실란, γ-메르캅토프로필트리메톡시실란, γ-메르캅토프로필트리에톡시실란, 및 N-[2-(비닐벤질아미노) 에틸]-3-아미노프로필트리메톡시실란으로 구성되는 그룹에서 선택된 하나 이상일 수 있다.
The silane compound contained in the low temperature curing type anticorrosive coating composition excellent in corrosion resistance of the present invention is not particularly limited, and examples thereof include vinyl methoxy silane, vinyl trimethoxy silane, vinyl epoxysilane, vinyl triepoxy silane, 3- 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) Propylamine, N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N -? (Aminoethyl) -? - aminopropyltrimethoxysilane, (Aminoethyl) -? - aminopropyltriethoxysilane, N -? - aminopropylmethyltriethoxysilane, N- (? - aminoethyl) -? - aminopropylmethyldimet (? -Aminoethyl) -? - aminopropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Glycidoxytrimethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Methacryloxypropyltriethoxysilane,? - May be at least one member selected from the group consisting of mercaptopropyltrimethoxysilane,? -Mercaptopropyltriethoxysilane, and N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane .
상기 조성물에 포함되는 상기 폴리실리케이트 화합물은 이로써 한정하는 것은 아니지만, 리튬 폴리실리케이트, 소디움 폴리실리케이트, 포타슘 폴리실리케이트 및 콜로이달 실리카에서 선택된 하나 이상일 수 있다. 상기 폴리실리케이트 화합물의 함량은 1 내지 10 중량%인 것이 바람직하며, 2 내지 8 중량%인 것이 더욱 바람직하다. 상기 폴리실리케이트 화합물의 함량이 1중량% 미만이면 충분한 내부식성을 얻기 어렵고, 10중량% 초과하면 도막이 잘 부서지며 용액의 안정성이 저하되어 물성이 현저히 저하된다.
The polysilicate compounds included in the composition may be, but are not limited to, one or more selected from lithium polysilicate, sodium polysilicate, potassium polysilicate, and colloidal silica. The content of the polysilicate compound is preferably 1 to 10% by weight, more preferably 2 to 8% by weight. When the content of the polysilicate compound is less than 1% by weight, it is difficult to obtain sufficient corrosion resistance. When the content of the polysilicate compound exceeds 10% by weight, the coating film breaks poorly and the stability of the solution deteriorates and the physical properties are significantly deteriorated.
또한, 본 발명의 조성물에 포함되는 티타늄 화합물은 피막의 가교반응 촉진 및 밀착성 향상에 기여할 수 있다. 상기 티타늄 화합물은 이로써 한정하는 것은 아니지만, 티타늄 카보네이트, 이소프로필디트리에탄올아미노 티타네이트, 락틱산 티타늄킬레이트 및 티타늄 아세틸아세토네이트에서 선택된 하나 이상일 수 있다. 상기 티타늄 화합물의 함량은 0.1 내지 5중량%인 것이 바람직하며, 티타늄 화합물의 함량이 0.1중량% 미만이면 가교 반응이 완전하지 않으며 내부식성이 미흡하고, 5중량% 초과하면 용액의 안정성과 도막물성에 바람직하지 않다.
In addition, the titanium compound contained in the composition of the present invention can contribute to accelerating the crosslinking reaction of the coating film and improving the adhesion. The titanium compound may be one or more selected from, but not limited to, titanium carbonate, isopropyl di-triethanol aminotitanate, lactic acid titanium chelate, and titanium acetylacetonate. If the content of the titanium compound is less than 0.1% by weight, the crosslinking reaction is not complete and the corrosion resistance is insufficient. When the content of the titanium compound is more than 5% by weight, the stability of the solution and the physical properties of the coating film It is not preferable.
본 발명의 조성물은 도막의 가공성 향상하기 위해 왁스 화합물을 포함할 수 있으며, 상기 왁스 화합물인 이에 한정하는 것은 아니나, 폴리에틸렌, 폴리테트라플루오르에틸렌 또는 이들의 혼합물일 수 있다. 상기 왁스 화합물의 함량은 0.1 내지 5중량%의 함량인 것이 바람직하며, 상기 왁스 화합물의 함량이 0.1중량% 미만이면 윤활기능을 제대로 발휘하지 못하고, 5중량% 초과하면 코팅강판의 표면품질 저하의 원인이 된다.
The composition of the present invention may contain a wax compound to improve the workability of a coating film, and may be polyethylene, polytetrafluoroethylene or a mixture thereof, though not limited thereto. If the amount of the wax compound is less than 0.1% by weight, the lubricating function is not exhibited properly. If the amount of the wax compound is more than 5% by weight, the surface quality of the coated steel sheet .
또한, 조성물의 저온건조 및 웨이팅성 향상을 위해 저온경화용 알코올을 포함할 수 있다. 상기 저온경화용 알코올은 이제 제한되는 것은 아니나, 에탄올, 프로판올 및 이소프로판올에서 선택된 하나 이상일 수 있다. 상기 저온경화형 알코올의 함량은 1 내지 15중량%인 것이 바람직하며, 상기 저온경화형 알코올의 함량이 1중량% 미만이면 저온에서 건조가 완전하지 않고, 12중량% 초과하면 작업 중에 알코올의 휘발로 고형분 변화가 심한 단점이 있다.
Further, the composition may contain an alcohol for low-temperature curing in order to improve low-temperature drying and weighting of the composition. The low-temperature curing alcohol may be at least one selected from the group consisting of ethanol, propanol and isopropanol. The content of the low-temperature curable alcohol is preferably 1 to 15% by weight. When the content of the low-temperature curable alcohol is less than 1% by weight, drying is not completed at a low temperature. If the content is more than 12% by weight, There is a severe disadvantage.
본 발명의 다른 실시예에 따르면, 강판; 상기 강판 상의 일면 또는 양면에 형성된 아연 도금층 및 상기 아연 도금층 상에 형성된 코팅층을 포함하며, 상기 코팅층은 상술한 방청코팅 조성물의 경화물인 내부식성이 우수한 아연도금 강판을 제공한다.
According to another embodiment of the present invention, And a coating layer formed on the zinc plating layer, wherein the coating layer is a cured product of the corrosion inhibiting coating composition, wherein the coating layer is excellent in corrosion resistance.
상기 코팅층은 건조도막 부착량이 0.05 내지 2.0 g/㎡인 것이 바람직하며, 0.1 내지 1.0 g/㎡인 것이 더욱 바람직하다. 부착량이 0.05 g/m2 미만이면 내식성과 내연료성 확보가 어렵게 되고, 2.0 g/m2 초과하면 절연성이 커져 용접성이 나빠지게 되므로 바람직하지 않다. 또한, 상기 아연 도금층은 전기아연 도금층, 용융아연 도금층, 합금화 용융아연 도금층 또는 알루미늄 합금 아연 도금층일 수 있다.
The coating layer preferably has an adhesion amount of the dry film of 0.05 to 2.0 g /
본 발명에 따른 내부식성이 우수한 아연도금 강판은 아연 도금층 상에 상술한 방청코팅 조성물을 코팅하는 코팅 단계 및 코팅된 강판을 경화처리하여 코팅층을 형성하는 단계로 제조된다.
The zinc-plated steel sheet having excellent corrosion resistance according to the present invention is prepared by coating the above-described rust-preventive coating composition on a zinc-plated layer and curing the coated steel sheet to form a coating layer.
상기 코팅은 그 방법을 한정하지 않으나, 롤코팅, 캐스팅, 스크린 프린팅, 스프레이, 그라비아 코팅 및 침적법에서 선택된 어느 하나의 방법으로 수행될 수 있으며, 그 중에서 롤코팅 방법이 가장 바람직하다. 방청코팅 조성물을 롤코팅 방법으로 아연도금 강판에 도포할 때, 건조도막 부착량이 0.05 내지 2.0g/㎡이 되도록 제어하는 것이 바람직하다.
The coating is not limited thereto, but can be carried out by any one method selected from roll coating, casting, screen printing, spraying, gravure coating and immersion, among which the roll coating method is most preferred. When the rust-preventive coating composition is applied to the galvanized steel sheet by the roll coating method, it is preferable to control the adhesion amount of the dry coat to 0.05 to 2.0 g /
상기 방청코팅 조성물은 경화 온도가 50 내지 150℃인 수 있으며, 상기 경화건조 온도가 50 ℃ 미만이면 유기계 조성물과 무기계 조성물의 경화반응이 미흡하여, 내부식성 및 내연료성의 효과가 나타나기 어려우며, 150℃ 초과하면 아미노계 실란 화합물과 에폭시계 실란 화합물 간의 선택적인 반응인 가교 반응이 감소하여 도막이 딱딱해져 가공성이 나빠지는 단점이 있다.
The rust-inhibiting coating composition may have a curing temperature of 50 to 150 ° C. When the curing drying temperature is less than 50 ° C, the curing reaction of the organic-based composition and the inorganic-based composition is insufficient and the effects of corrosion resistance and fuel- , The crosslinking reaction which is a selective reaction between the amino-based silane compound and the epoxy-based silane compound is reduced, resulting in a stiffer coating film, resulting in poor processability.
이하, 구체적인 실시예를 통해 본 발명을 보다 구체적으로 설명한다. 하기 실시예는 본 발명의 이해를 돕기 위한 예시에 불과하며, 본 발명의 범위가 이에 한정되는 것은 아니다.
Hereinafter, the present invention will be described more specifically by way of specific examples. The following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto.
실시예Example
상업적으로 구입 가능한 전기아연 도금강판(EG, electrogalvanized steel), 합금화 용융 아연도금 강판(GA, galvanealed steel) 및 용융 아연도금 강판(GI, galvanizing steel)을 사용하였다. 상기 전기아연도금(EG) 강판은 10 내지 40g/m2의 도금 부착량을 가지며, 상기 합금화 용융 아연도금(GA) 강판은 20 내지 60g/m2의 도금 부착량을 가지며, 도금층 내 Fe함량은 7 내지 15%이고, 또한, 상기 용융 아연도금(GI) 강판은 40 내지 200g/m2의 도금 부착량을 가지는 강판을 사용하였다.
Commercially available electrogalvanized steel (EG), galvanized steel (GA), galvanized steel (GI) and galvanized steel were used. Wherein the electrogalvanized (EG) steel sheet has a plating adhesion amount of 10 to 40 g / m 2 , the galvannealed steel (GA) steel sheet has a plating adhesion amount of 20 to 60 g / m 2 , 15%, and the hot-dip galvanized (GI) steel sheet has a coating weight of 40 to 200 g / m 2 .
[실시예 1] [Example 1]
전체 조성물 100 중량%에 대하여, 에폭시계 실란 화합물인 3-글리시독시프로필트리메톡시실란 3중량%와 아미노계 실란 화합물인 N-β(아미노에틸)-γ-아미노프로필트리메톡시실란을 7중량%를 혼합하여 가수분해하였다. 그리고, 리튬 폴리실리케이트 3중량%를 용해시킨 후 30분간 교반하였다. 최종적으로, 디이소프로필트리에탄올아민티타네이트 3중량%, PTFE 왁스 1중량%, 저온건조를 위해 이소프로필 알콜 3중량% 및 순수를 첨가하여 수용액을 제조한 후 추가로 30분간 상온에서 100rpm의 속도로 교반하여 방청코팅 조성물을 제조하였다.
3% by weight of 3-glycidoxypropyltrimethoxysilane as an epoxy silane compound and N-beta (aminoethyl) -? - aminopropyltrimethoxysilane as an amino-based silane compound were added to 100% By weight were mixed and hydrolyzed. After dissolving 3% by weight of lithium polysilicate, the mixture was stirred for 30 minutes. Finally, 3% by weight of diisopropyltriethanolamine titanate, 1% by weight of PTFE wax, 3% by weight of isopropyl alcohol for low-temperature drying, and pure water were added to prepare an aqueous solution and further stirred for 30 minutes at a rate of 100 rpm Followed by stirring to prepare a rust-preventive coating composition.
[실시예 2-12][Example 2-12]
전체 조성물 100 중량%에 대하여, 조성물의 각 성분의 함량을 표 1에 기재된 바와 같이 조정하여, 실시예 1에서의 방법과 같이 조성물을 제조하였다.
The composition was prepared as in Example 1, with the contents of each component of the composition being adjusted as described in Table 1, for 100 wt.% Of the total composition.
[비교예 1-3][Comparative Example 1-3]
전체 조성물 100 중량%에 대하여, 조성물의 각 성분의 함량을 표 1에 기재된 바와 같이 조정하여, 실시예 1에서의 방법과 같이 조성물을 제조하였다.
The composition was prepared as in Example 1, with the contents of each component of the composition being adjusted as described in Table 1, for 100 wt.% Of the total composition.
하기 조건으로 실시예 1 내지 12 및 비교예 1 내지 3의 금속 방청코팅 조성물에 대하여 자동차 연료에 대한 내부식성, 용액안정성, 마찰특성 및 심용접성에 대한 성능을 평가하고, 그 결과를 표 1에 나타내었다.
The metal corrosion inhibiting coating compositions of Examples 1 to 12 and Comparative Examples 1 to 3 were evaluated for corrosion resistance, solution stability, friction characteristics and core weldability against automobile fuel under the following conditions, and the results are shown in Table 1 .
< 내연료성 평가>≪ Evaluation of fuel resistance &
내연료성 평가는 열화 가솔린, 열화 디젤, 바이오 에탄올 및 바이오 디젤으로 내연료성으로 평가하였다. 평가시편은 상기와 같이 컵 가공(Blank 크기: 115×15 mm; Cup 크기, Punch 직경 50mm, Drawing 높이 30mm, Punch R = Die R = 6R) 후 컵에 연료를 넣고 오링과 유리판을 이용하여 덮어 고정하여 평가하였다.
The evaluation of fuel resistance was evaluated as fuel resistance with degraded gasoline, deteriorated diesel, bioethanol and biodiesel. The evaluation specimen was filled with cups and filled with o-rings and glass plates after cupping (blank size: 115 × 15 mm; cup size, punch diameter 50 mm, drawing height 30 mm, Punch R = Die R = 6R) Respectively.
상기 열화 가솔린의 연료 조성은 일반 가솔린 연료에 5 중량% 순수와 개미산 20 ppm을 첨가하여, 60℃에서 분당 60 사이클의 속도로 흔들면서 1000시간 방치한 다음 강판의 부식상태를 평가하였다. 상기 바이오 에탄올의 연료 조성은 일반 가솔린 연료에 바이오 에탄올 20 중량% 첨가한 후, 순수 5 중량%와 개미산 20 ppm을 첨가하여, 60℃에서 분당 60 사이클의 속도로 흔들면서 1000시간 방치한 다음 강판의 부식상태를 평가하였다.
The fuel composition of the deteriorated gasoline was as follows: 5 wt% pure water and 20 ppm formic acid were added to ordinary gasoline fuel and allowed to stand for 1000 hours while shaking at a rate of 60 cycles per minute at 60 캜, and then the corrosion state of the steel sheet was evaluated. The fuel composition of the bioethanol was prepared by adding 20 wt% of bioethanol to general gasoline fuel, adding 5 wt% of pure water and 20 ppm of formic acid, shaking at 60 DEG C per minute at a rate of 60 cycles, The corrosion state was evaluated.
또한, 상기 열화 디젤의 연료 조성은 일반 디젤 연료에 순수 5 중량%와 개미산 20ppm을 90℃에서 분당 60 사이클의 속도로 흔들면서 8주 방치 후 강판의 부식상태를 평가하였다. 상기 바이오 디젤의 연료 조성은 일반 디젤 연료에 바이오 디젤 20 중량%를 혼합한 후, 순수 5 중량%와 개미산 20ppm을 90℃에서 분당 60 사이클의 속도로 흔들면서 8주 방치 후 강판의 부식상태를 평가하였다.
In addition, the fuel composition of the deteriorated diesel was evaluated by evaluating the corrosion state of the steel sheet after leaving for 8 weeks while shaking the general diesel fuel at a rate of 5 wt% pure water and 20 ppm formic acid at 90 ° C and 60 cycles per minute. The fuel composition of the biodiesel was prepared by mixing 20 wt% of biodiesel with general diesel fuel and then measuring the corrosion state of the steel sheet after 8 weeks of shaking at 5% by weight of pure water and 20 ppm of formic acid at a rate of 60 cycles / Respectively.
실시예와 비교예에 대한 내부식성 평가이미지를 도 2에 나타내었고, 다음 기준에 따라 평가한다. 도 2는 실시예와 비교예의 표면처리 강판에 대한 내연료성 평가 이미지이다.
The corrosion resistance evaluation image for Examples and Comparative Examples is shown in Fig. 2 and evaluated according to the following criteria. Fig. 2 is an image for evaluating resistance to fuel for the surface-treated steel sheets of Examples and Comparative Examples.
◎ : 부식면적이 0% ○ : 부식면적이 5%이하◎: Corrosion area is 0% ○: Corrosion area is not more than 5%
△ : 부식면적이 5~30% × : 부식면적이 30%이상
?: Corrosion area 5 to 30% X: corrosion area 30% or more
<용액안정성 평가>≪ Evaluation of solution stability &
수용성 유-무기계 금속 방청코팅 조성물을 60℃의 항온 장치 내에 1주간 저장한 후 조성물의 점도상승, 겔화 및 침전의 상태를 관찰하고, 다음 기준에 따라 평가한다.
After the water-soluble organic-inorganic metal anti-corrosive coating composition is stored in a thermostat at 60 ° C. for 1 week, the viscosity rise, gelation and precipitation of the composition are observed and evaluated according to the following criteria.
◎ : 조성물의 점도상승, 겔화 및 침전 등의 변화가 인정되지 않는다.?: No change such as increase in viscosity of the composition, gelation and precipitation was observed.
○ : 조성물의 4% 이상의 점도 상승의 변화가 인정된다.?: Change in the viscosity increase of 4% or more of the composition is recognized.
△ : 조성물의 10% 이상의 점도 상승의 변화가 인정된다.?: A change in viscosity increase of 10% or more of the composition is recognized.
× : 조성물의 점도상승, 겔화 및 침전 등의 변화가 인정된다.
X: Changes in the composition such as viscosity increase, gelation and precipitation are recognized.
<심용접성 평가><Evaluation of seam weldability>
심용접성은 Ironman(Inverter DC Seam 용접기)을 이용하여 가압력 4kN, 용접속도 3mpm, 통전시간 33ms, 휴지시간 10ms 에서 스패이트(Spatter)가 없으며 일정한 강도를 유지하는 것으로 평가하였다. 평가 기준은 용접이 가능한 전류범위로 평가하였다. 실시예와 비교예에 대한 심용접전류범위 값을 도 3에 나타내었다. 도 3은 실시예와 비교예의 표면처리 강판에 대한 심용접 전류범위의 값을 나타낸 그래프이다.
Seam weldability was evaluated by using Ironman (Inverter DC Seam Welder) to maintain constant strength without spatter at 4kN pressing force, 3mpm welding speed, 33ms energization time and 10ms downtime. The evaluation criteria were evaluated by welding current range. The seam welding current range values for Examples and Comparative Examples are shown in Fig. 3 is a graph showing values of seam welding current range for the surface treated steel sheets of Examples and Comparative Examples.
◎ : 1.5kA 이상 ○ : 1.0 이상 1.5kA 이하 △ : 1.0kA 이하
?: 1.5 kA or more?: 1.0 to 1.5 kA or less?: 1.0 kA or less
<내부식성 평가>≪ Evaluation of corrosion resistance &
내식성 평가는 염수농도 5%, 35℃에서 1kg/cm2의 분무압 조건에서 복합코팅한 강판이 480시간이 지난 후 표면에 발생한 적녹(Red Rust)의 발생면적으로 평가하였다. 실시예와 비교예에 대한 내부식성 평가이미지를 도 4에 나타내었다.
The corrosion resistance was evaluated by the surface area of red rust which occurred on the surface after 480 hours of the coated steel sheet at 5% salinity concentration and spray pressure of 1 kg / cm 2 at 35 ° C. The corrosion resistance evaluation image for the example and the comparative example is shown in Fig.
◎ : 부식면적이 0% ○ : 부식면적이 5% 이하◎: Corrosion area is 0% ○: Corrosion area is not more than 5%
△ : 부식면적이 5~30% × : 부식면적이 30% 이상
?: Corrosion area 5 to 30% X: corrosion area 30% or more
상기 표 1에 나타난 바와 같이, 실시예 1 내지 12의 조성물은 경화 온도가 80 내지 120℃인 조건에서도 유-무기 복합조성물의 경화반응이 우수함을 나타내므로, 내연료성, 내부식성 및 심용접성이 우수한 결과를 나타냈다.
As shown in Table 1, the compositions of Examples 1 to 12 show excellent curing reaction of the oil-and-mineral composite composition even at a curing temperature of 80 to 120 ° C, so that the fuel resistance, corrosion resistance and seam weldability Excellent results were obtained.
한편, 비교예 1 내지 3의 조성물에 포함된 아크릴 수지는 경화 온도가 80 내지 120℃인 조건에서 고분자의 경화반응이 완전하지 않기에, 내부식성과 내연료성 및 심용접성에서 취약한 결과를 나타낸 것으로 보인다.
On the other hand, the acrylic resin contained in the compositions of Comparative Examples 1 to 3 exhibited poor results in corrosion resistance, fuel resistance, and seam weldability because the curing reaction of the polymer was not completed under the curing temperature of 80 to 120 ° C see.
따라서, 본 발명에 따른 실시예 1 내지 12의 경우에는 저온 경화형의 용액안정성과 내부식성이 우수한 자동차 연료탱크에 사용되는 아연도금 강판용 방청코팅 조성물이다.
Thus, Examples 1 to 12 according to the present invention are anti-corrosive coating compositions for zinc-coated steel sheets for use in automotive fuel tanks, which have low-temperature curing type solution stability and corrosion resistance.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, It will be obvious to those of ordinary skill in the art.
Claims (12)
Which is an aqueous solution containing 5 to 30 wt% of a silane compound, 1 to 10 wt% of a polysilicate compound, 0.1 to 5 wt% of a titanium compound, 0.1 to 5 wt% of a wax and 1 to 15 wt% of an alcohol for low- Low temperature curing type anticorrosive coating composition.
The composition according to claim 1, wherein the silane compound is at least one selected from an epoxy silane compound, an amino silane compound, a hydrolyzate thereof, and a condensate of the hydrolyzate.
The method of claim 1, wherein the silane compound is a mixture of an amino-based silane compound and an epoxy-based silane compound, and the mixing ratio of the amino-based silane compound and the epoxy-based silane compound is 1: 0.2 to 10, Coating composition.
The method of claim 1, wherein the silane compound is selected from the group consisting of vinylmethoxysilane, vinyltrimethoxysilane, vinylepoxysilane, vinyltriepoxysilane, 3-aminopentyltriepoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 (Meth) acrylate, methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triepoxysilane) (Aminoethyl) -? - aminopropyltriethoxysilane, N -? - aminopropyltrimethoxysilane, N -? - aminoethyl) -? - aminopropylmethyltriethoxysilane, N- (? -aminoethyl) -? - aminopropylmethyldimethoxysilane, N- (? -aminoethyl) Glycidoxypropyltriethoxysilane,? -Glycidoxytrimethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Metacin Methacryloxypropyltriethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Mercaptopropyltriethoxysilane, and N- [2- (vinylbenzylamino) ethyl ] -3-aminopropyltrimethoxysilane. ≪ / RTI >
The composition of claim 1, wherein the polysilicate compound is at least one selected from the group consisting of lithium polysilicate, sodium polysilicate, potassium polysilicate, and colloidal silica.
The composition according to claim 1, wherein the titanium compound is at least one selected from the group consisting of titanium carbonate, isopropylditriethanolaminotitanate, titanium lactate lactate, and titanium acetylacetonate.
The composition according to claim 1, wherein the wax is polyethylene, polytetrafluoroethylene or a mixture thereof, and is excellent in corrosion resistance.
The composition of claim 1, wherein the alcohol for low-temperature curing is at least one selected from the group consisting of ethanol, propanol and isopropanol.
상기 강판 상의 일면 또는 양면에 형성된 아연 도금층 및
상기 아연 도금층 상에 형성된 코팅층을 포함하며,
상기 코팅층은 제 1항 내지 제 8항 중 어느 한 항의 방청코팅 조성물의 경화물인 내부식성이 우수한 아연도금 강판.
Steel plate;
A zinc plated layer formed on one surface or both surfaces of the steel sheet,
And a coating layer formed on the zinc plating layer,
Wherein the coating layer is a cured product of the rust-preventive coating composition according to any one of claims 1 to 8, which is excellent in corrosion resistance.
10. The galvanized steel sheet according to claim 9, wherein the corrosion inhibiting coating composition is excellent in corrosion resistance at a curing temperature of 50 to 150 DEG C.
10. The galvanized steel sheet according to claim 9, wherein the coating layer is excellent in corrosion resistance with an adhesion amount of dry film of 0.05 to 2.0 g / m < 2 >.
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KR20180009957A (en) * | 2016-07-20 | 2018-01-30 | 강원대학교산학협력단 | Organic/inorganic hybridized anticorrosive coating composition and preparation method thereof |
KR101896011B1 (en) * | 2017-06-16 | 2018-09-06 | (주)넥스트에어로스 | Anti-corrision varnish composition and forming method for anti-corrision coating layer using the same |
KR20200103690A (en) * | 2017-11-28 | 2020-09-02 | 엔오에프 메탈 코팅스 유럽 | Solid dehydrated coating composition, method for producing the same, and method for rehydrating the same |
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CN105733328A (en) | 2016-07-06 |
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