KR100573586B1 - High-anticorosive Coating Solution For Zinc Coated Steel Sheet And Zinc Coated Steel Sheet Having A Coating Made By The Same - Google Patents
High-anticorosive Coating Solution For Zinc Coated Steel Sheet And Zinc Coated Steel Sheet Having A Coating Made By The Same Download PDFInfo
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- KR100573586B1 KR100573586B1 KR1020030091532A KR20030091532A KR100573586B1 KR 100573586 B1 KR100573586 B1 KR 100573586B1 KR 1020030091532 A KR1020030091532 A KR 1020030091532A KR 20030091532 A KR20030091532 A KR 20030091532A KR 100573586 B1 KR100573586 B1 KR 100573586B1
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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
- C23C22/48—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
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
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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
본 발명은 크롬을 사용하지 않는 아연도금 강판용 고내식 방청 코팅용액 및 이 용액이 코팅된 용융아연도금 강판에 관한 것이다. The present invention relates to a highly corrosion-resistant anti-corrosion coating solution for galvanized steel sheet without using chromium and a hot dip galvanized steel sheet coated with this solution.
본 발명에 의하면, 방청코팅용액에 총 중량을 기준으로,리튬 폴리실리케이트(Li2Si5O11)를 함유하는 콜로이드 수용액 5-15중량%;화학식 [TiIV(L1)2(L2)2](여기서 L1= 트리에탄올아미네이트, L2= 이소프로폭시드 )의 유기 티타늄 착화합물 3-5 중량%;화학식 [(CH3O)3Si-C3H6OCH2CH(η-1,2-0)CH2]의 γ-글리시드옥시프로필트리메톡시실란으로 이루어진 실란 가교제 3-5중량%; 화학식 (NH4)2ZrCO3 의 지르코늄 화합물 1-5중량%; 및나머지는 물로 구성되며,여기에 인산(H3PO4)이 첨가되어 pH가 4-6으로 조정된 것을 특징으로 하는 아연도금 강판용 고내식 방청코팅 용액 및 상기 방청코팅 용액이 코팅된 용융아연도금 강판이 제공된다.According to the present invention, 5-15% by weight of a colloidal aqueous solution containing lithium polysilicate (Li 2 Si 5 O 11) based on the total weight in the rust-preventive coating solution; [Formula IV IV (L 1 ) 2 (L 2 ) 2 ] 3-5 wt% of an organic titanium complex of L 1 = triethanol aluminate, L 2 = isopropoxide; Formula [(CH 3 O) 3 Si-C 3 H 6 OCH 2 CH (η-1 , 2-0) CH 2 ] by 3-5 weight percent of a silane crosslinker consisting of γ-glycidoxypropyltrimethoxysilane; 1-5% by weight of zirconium compound of formula (NH 4 ) 2 ZrCO 3 ; And the rest with water A high corrosion-resistant anti-corrosion coating solution for galvanized steel sheet and a hot-dip galvanized steel sheet coated with the rust-coating solution are provided, wherein the pH is adjusted to 4-6 by adding phosphoric acid (H 3 PO 4 ). .
본 발명의 방청코팅 용액은 크롬을 함유하지 않으면서도 우수한 내식성 및 수지 밀착성을 가져 친환경적인 고내식성 아연도금 강판용 방청 코팅 용액으로 유용하다. The anti-corrosive coating solution of the present invention has an excellent corrosion resistance and resin adhesion without containing chromium and is useful as an environmentally friendly anti-corrosion coating solution for galvanized steel sheet.
리튬 폴리실리케이트,유기 티타늄 착화합물,지르코늄 화합물,방청제,아연도금 강판Lithium Polysilicate, Organic Titanium Complex, Zirconium Compound, Antirust Agent, Galvanized Steel Sheet
Description
본 발명은 아연도금 강판용 방청 코팅용액에 관한 것으로, 보다 상세하게는 크롬을 사용하지 않는 아연도금 강판용 고내식 방청 코팅용액 및 이 용액이 코팅된 용융아연도금 강판에 관한 것이다. The present invention relates to an antirust coating solution for galvanized steel sheet, and more particularly, to a high corrosion resistant coating solution for galvanized steel sheet without using chromium and a hot dip galvanized steel sheet coated with this solution.
아연도금 강판의 표면 부식을 방지하기 위해 백 여년 전부터 크로메이트(chromate) 코팅처리를 하여왔다. Cr(VI)를 포함하고 있는 크로메이트는 값싼 반면에 내식성이 우수하여 오랫동안 사용되어져 왔으나, 오늘날 후두암 등을 일으키는 일급 발암물질로 분류됨에 따라 국제적으로 환경유해 물질로 규제되고 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),카드뮴(Cd) 등의 물질이 포함되어 있는 제품 의 폐기를 전면 금지하는 조치를 할 예정이다. 따라서 현재 전 세계적으로 건축,가전 및 자동차용으로 크롬을 사용하지 않는 방청제의 개발에 부심하고 있다. To prevent surface corrosion of galvanized steel sheet, chromate coating has been applied for more than 100 years. Although chromate containing Cr (VI) has been used for a long time due to its low cost and excellent corrosion resistance, it is currently 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 EU has been using waste electrical (electronic) devices. Therefore, the government will take measures to 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 chromium-free rust inhibitors for construction, home appliances and automobiles worldwide.
크롬을 포함하지 않는 방청제의 개발은 다양한 각도에서 행해져 왔는데, 대표적으로 크롬과 동족인 몰리브덴 음이온(Molibdate, MoO4 2- )부동태 피막, 중인산염(MH2PO4)피막을 이용하는 방법, 탄닌산(Tannic acid)등의 유기물 피막에 의한 방법이 있다. The development of chromium-free rust preventives has been conducted from various angles. Representatively, molybdenum anion (Molibdate, MoO 4 2- ) kinetic coating, chromium salt (MH 2 PO 4 ) coating, tannic acid (Tannic) acid) and organic coatings.
그러나 이들 방법은 모두 크로메이트 피막과 비교하여 보호막 특성(barrier)과 자기수복(self-healing)성이 저조하며, 내식성도 불충분하기 때문에 아연도금 강판의 크로메이트 대체용으로는 실용화되지 못하고 있다. 따라서, 크롬을 포함하지 않는 새로운 환경친화형 방청제가 요구되고 있는 실정이다. However, these methods are not practical for the replacement of chromate in galvanized steel sheets because of their low barrier property and self-healing resistance and insufficient corrosion resistance compared to chromate coatings. Therefore, there is a need for a new environmentally friendly antirust agent that does not contain chromium.
본 발명의 목적은 실란 가교제를 포함하는 리튬 폴리실리케이트 수용액에 유기 티타늄 착화합물과 지르코늄 화합물을 첨가함으로써 아연 도금 강판의 내식성, 도포성 및 수지밀착성을 증가시킨, 무기계 고내식 방청코팅 용액을 제공하는 것이다.
SUMMARY OF THE INVENTION An object of the present invention is to provide an inorganic high corrosion-resistant anti-corrosive coating solution which has increased corrosion resistance, coating property and resin adhesion of a galvanized steel sheet by adding an organic titanium complex compound and a zirconium compound to an aqueous lithium polysilicate solution containing a silane crosslinking agent.
본 발명의 다른 목적은 상기 방청코팅 용액이 코팅된 용융아연도금 강판을 제공하는 것이다.
Another object of the present invention is to provide a hot-dip galvanized steel sheet coated with the rust preventing coating solution.
본 발명에 의하면, 아연도금 강판용 방청코팅용액에 총 중량을 기준으로, According to the present invention, on the basis of the total weight in the antirust coating solution for galvanized steel sheet,
[화학식 1] Li2Si5O11의 리튬 폴리실리케이트를 함유하는 콜로이드 수용액 5-15중량%;[화학식 2] [TiIV(L1)2(L2)2](여기서 L1= 트리에탄올아미네이트, L2= 이소프로폭시드 )의 유기 티타늄 착화합물 3-5 중량%;[화학식 3] [(CH3O)3Si-C3H 6OCH2CH(η -1,2-0)CH2]의 γ-글리시드옥시프로필트리메톡시실란으로 이루어진 실란 가교제 3-5중량%; [화학식 4] (NH4)2ZrCO3 의 지르코늄 화합물 1-5중량% , 및 나머지는 물로 구성된 것을 특징으로 하는 아연도금 강판용 방청코팅 용액이 제공된다.5-15% by weight of a colloidal aqueous solution containing lithium polysilicate of Li 2 Si 5 O 11 ; [Formula 2] [Ti IV (L 1 ) 2 (L 2 ) 2 ], wherein L 1 = triethanolami 3-5 weight percent organic titanium complex of Nate, L 2 = isopropoxide) [(CH 3 O) 3 Si-C 3 H 6 OCH 2 CH (η -1,2-0) CH 3-5 wt% of a silane crosslinker consisting of γ-glycidoxypropyltrimethoxysilane of 2 ]; 1-5% by weight of a zirconium compound of (NH 4 ) 2 ZrCO 3 , and the remainder with water An antirust coating solution for galvanized steel sheet is provided.
또한, 본 발명에 의하면 상기 방청코팅 용액이 코팅된 용융아연도금 강판이 제공된다. In addition, the present invention provides a hot-dip galvanized steel sheet coated with the rust preventing coating solution.
이하에 실시예를 통해 본 발명을 상세히 설명한다. 그러나 본 발명의 범위가 이 실시예에 한정되는 것은 아니다. Hereinafter, the present invention will be described in detail through examples. However, the scope of the present invention is not limited to this embodiment.
방청코팅용액의 제조Preparation of antirust coating solution
순수한 물에 상기 [화학식 3]의 실란 가교제(γ-글리시드옥시프로필트리메톡시실란; SinEtsu Chemical 회사 제품)를 표 1에 나타낸 바와 같이 3-5 중량%로 양을 달리하여 첨가한 다음 여기에 인산(H3PO4)을 가하여 pH를 조정한 후, 10시간 이상 교반하였다. 인산(H3PO4)은 실란 가교제의 가수분해를 촉진하기 위해 첨가되는 것으로 코팅용액은 pH가 4-6이 되도록 조정되는 것이 바람직하다. 만일 코팅용액의 pH가 4이하인 경우 가수분해속도가 빠른 장점이 있으나 실리케이트와 혼합할 때 용액 안정성이 떨어지는 단점이 있고,pH가 6 이상인 경우에는 가수분해속도가 너무 느려서 코팅시 고분자 반응이 불안하여 내식성을 저해할 수 있다. 코팅용액의 pH를 약5 정도로 조정하는 것이 가장 바람직한 것으로 나타났으므로 실시예에서는 pH를 5로 조정하였다. To the pure water was added the silane crosslinking agent of [Formula 3] (γ- glycidoxy propyltrimethoxysilane; manufactured by SinEtsu Chemical Co., Ltd.) in varying amounts to 3-5 wt% as shown in Table 1, and then Phosphoric acid (H 3 PO 4 ) was added to adjust the pH, followed by stirring for at least 10 hours. Phosphoric acid (H 3 PO 4 ) is added to promote hydrolysis of the silane crosslinking agent, and the coating solution is preferably adjusted to have a pH of 4-6. If the pH of the coating solution is 4 or less, the hydrolysis rate is faster, but the solution stability is poor when mixed with silicate. If the pH is 6 or more, the hydrolysis rate is too slow. May inhibit. Since the pH of the coating solution was found to be most preferable to about 5, the pH was adjusted to 5 in the examples.
이 교반 용액에 [화학식 1]의 리튬 폴리실리케이트(SiO2 함량 20wt%Lithium polysilicate of [Formula 1] (SiO 2 content 20wt%)
수용액, pH=11; Dupont Chemical 회사제품)용액을 5-15 중량%, [화학식 2]의 유기티타늄 착화합물(2-프로판올내에 80중량%로 용해된 형태 ; Lancaster Synthesis 회사 제품)을 3-5중량%, 및 [화학식 4]의 지르코늄 화합물을 1-5중량%로 첨가한 다음에 교반하여 제조하였다.Aqueous solution, pH = 11; 5-15% by weight of the solution of Dupont Chemical Company), 3-5% by weight of the organotitanium complex (80% by weight in 2-propanol; product manufactured by Lancaster Synthesis) of [Formula 2], and [Formula 4] ] Was added by adding 1-5% by weight of zirconium compound, followed by stirring.
코팅강판의 제조Manufacture of Coated Steel Sheet
상기 조성물의 코팅용액을 바-코터 #-3을 사용하여 합금화 용융아연도금 강판(GA강판), 용융아연도금 강판(GI강판), 전기아연도금 강판(EG강판) 및 Zn-Ni전기아연도금 강판(Zn-Ni강판)에 코팅 두께 0.5-1 ㎛ 로 피복하였다. GA강판의 경우 편면당 도금량은 20-60g/m2 (도금층 내 Fe 함량은 10-14%), GI강판의 경우 편면당 도금량은 40-90g/m2 ), EG강판의 경우 편면당 도금량은 20-60g/m2 ,그리고 Zn-Ni강판의 경우 편면당 도금량은 10-40g/m2 (도금층내 Ni 함량은 10-14%)이었다. 상기 피복된강을 열풍 건조로에서 강판도달온도(PMT) 120-160 ℃ 로 건조하고 공냉하여 방청용액이 피복된 시편을 만들었다.The coating solution of the composition using the bar-coater # -3 alloyed hot-dip galvanized steel sheet (GA steel sheet), hot-dip galvanized steel sheet (GI steel sheet), electro-galvanized steel sheet (EG steel sheet) and Zn-Ni electro-galvanized steel sheet (Zn-Ni steel sheet) was coated with a coating thickness of 0.5-1 mu m. For GA steel, the plating amount per side is 20-60g / m 2 (Fe content in the plating layer is 10-14%), for GI steel, the plating amount per side is 40-90g / m 2 ) and for EG steel, In the case of 20-60 g / m 2 and Zn-Ni steel sheet, the plating amount per side was 10-40 g / m 2 (Ni content in the plating layer was 10-14%). The coated steel was dried at a steel plate reaching temperature (PMT) 120-160 ° C. in a hot air drying furnace and air cooled to prepare specimens coated with rust preventive solution.
한편, 본 발명의 실시예와 비교하기 위하여, 대한민국 특허출원 1999-51479에 기술된 바와 같이, 크롬 환원비(Cr3+/Cr6+)가 0.52이며 콜로이드 실리카, 불산, 인산이 포함된 경화제를 가하여 제조된 도포형 크로메이트 방청용액을 각각의 아연도금 강판에 상기와 동일한 방법으로 피복하여 비교시편을 만들었다.On the other hand, in order to compare with the embodiment of the present invention, as described in the Republic of Korea Patent Application 1999-51479, the chromium reduction ratio (Cr 3 + / Cr 6 + ) is 0.52 and the curing agent containing colloidal silica, hydrofluoric acid, phosphoric acid The coated chromate rust preventive solution prepared by addition was coated on the respective galvanized steel sheets in the same manner as above to make a comparative specimen.
성능평가 방법Performance Evaluation Method
내식성은 만들어진 시편을 염수분무장치(일본공업표준 시험법 JIS E2371)를 이용하여 5% NaCl, 분산압 1Kg/m2 의 분사압력으로 분사한 후 5% 백청 발생까지의 소요시간으로 평가하였다. 가공부 내식성은 시편을 cup drawing 성형( 조건; blank 직경=108mmφ , punch 직경=100mmφ,die직경=50mmφ, blank holder하중=10kN,drawing 높이=25mm) 후 JIS E2731의 염수분무 시험으로 평가하였다.Corrosion resistance was evaluated using the salt spray device (Japanese Industrial Standard Test Method JIS E2371) at a spray pressure of 5% NaCl and a dispersion pressure of 1 Kg / m 2 , and the time required to generate 5% white rust. The corrosion resistance of the machined part was evaluated by the salt spray test of JIS E2731 after cup drawing molding (conditions: blank diameter = 108mmφ, punch diameter = 100mmφ, die diameter = 50mmφ, blank holder load = 10kN, drawing height = 25mm).
도막밀착성 평가는 아연도금 강판에 멜라민 에폭시 수지를 약 1㎛ 두께로 코팅한 다음 강판도달온도(PMT) 160℃ 에서 12초간 소부(baking)하고 수냉하여 시편을 제작하였다. 제작된 시편을 50℃ 의 증류수에 넣고 240시간 동안 침지한 다음 건조시킨다. 이 시편의 도막표면에 2mm 간격으로 바둑판 형태의 눈금을 100개 만든 후 스카치 테잎으로 도막을 박리시켰을 때 테잎에 박리되어 나오는 도막의 갯수로 도막의 밀착성을 평가하였다.Coating adhesion evaluation was prepared by coating a melamine epoxy resin on a galvanized steel sheet to a thickness of about 1㎛, then baked for 12 seconds at 160 ° C steel plate reaching temperature (PMT) and water cooled. The prepared specimen was put in distilled water at 50 ° C. and dipped for 240 hours and then dried. After making 100 checkerboard scales at 2mm intervals on the coating surface of this specimen, the adhesion of the coating film was evaluated by the number of coating films peeled off the tape when the coating film was peeled off with the scotch tape.
표면외관 및 용액안정성은 색상,도포성(wetability),용액의 경시,침전물의 유무 등에 관한 관능검사를 행하였다.Surface appearance and solution stability were tested for color, wettability, solution aging, and presence of precipitates.
본 발명에 의한 실시예와 비교예의 평가결과를 표1에 나타내었다.Table 1 shows the evaluation results of Examples and Comparative Examples according to the present invention.
표1 Table 1
1-4) 유기 티타늄 착화합물과 리튬 포리실리케이트 및 지르코늄 화합물은 Dupont사에서 시판하는 시약을 사용하였고, Silane 가교제는 SinEtsu사로부터 구입하여 사용하였다.1-4) The organotitanium complex, lithium porosilicate and zirconium compound used a reagent sold by Dupont, and Silane crosslinker was purchased from SinEtsu.
5)표면외관은 색상,도포성(Wetability)등에 의한 관능검사로 판단하였다.5) The surface appearance was judged by sensory evaluation by color and wettability.
6)수지밀착성은 상기 실험방법에 의해 테잎에 박리되어 나오는 도막의 개수로 평가하였다.(우수:3개이하,보통:4-10개)6) Resin adhesion was evaluated by the number of coating films peeled off the tape by the above experimental method. (Excellence: 3 or less, usually: 4-10)
7)용액 안정성은 용액의 경시,침전물의 유무 등에 관한 관능검사로 판단하였다.(매우우수:5주 이상 안정 , 우수:1-2주 동안 안정)7) The solution stability was judged by the sensory test of the solution with time and the presence of sediment. (Excellent: stable for more than 5 weeks, excellent: stable for 1-2 weeks)
8),9)평판 및 가공부 내식성 : 5% 백청 발생시까지의 소요시간(매우 우수:200 시간 이상 , 우수:100-200 시간 , 보통: 72-100 시간)8), 9) Corrosion resistance of flat and processed parts: Time required to generate 5% white rust (Very good: 200 hours or more, Excellent: 100-200 hours, Normal: 72-100 hours)
상기 표1에 나타낸 바와 같이, 본 발명에 따른 코팅용액으로 코팅된 아연도금 강판에 대한 내식성은 최소 48시간(백청 5% 발생시간)이상으로 나타나 모두 우수하였으며, 또한 강판과 수지와의 밀착력이 우수한 것으로 나타났다. 우수한 밀착력은 각종 도장 하지(undercoat)용으로 사용될 수 있음을 보여준다고 할 것이다. 또한,본 발명에 따라 제조된 방청코팅용액은 장시간 보관시에도 안정하고 용액의 점도가 낮아 작업성이 우수한 특성을 나타내었다.As shown in Table 1, the corrosion resistance of the galvanized steel sheet coated with the coating solution according to the present invention was at least 48 hours (5% occurrence time of white blue), all excellent, and also excellent adhesion between the steel sheet and the resin Appeared. It will be shown that good adhesion can be used for various undercoats. In addition, the anti-corrosive coating solution prepared according to the present invention was stable even for a long time storage and exhibited excellent workability due to the low viscosity of the solution.
본 발명의 용액이 이와같이 우수한 내식성을 나타내는 것은 각 성분이 3차원의 망상구조의 코팅층을 형성하기 때문인 것으로 판단된다. [화학식 1]의 리튬 폴리실리케이트는 강판에 코팅시 3차원의 코팅층을 형성하므로 그 자체만으로도 내식성이 큰 화합물이다. [화학식 2]의 유기 티타늄 착화합물은 L1리간드가 안정한 킬레이트를 형성하고, 말단 리간드인 이소프로폭시드가 수용액에서 서서히 가수분해되 어 용액을 안정화 시키며 코팅시 서서히 수분과 치환반응하여 [Ti(L1)(OH)2]불용성 피막을 형성하는 것으로 보여진다. 한편, [화학식 3]의 실란 가교제는 수용액에서 메톡시 리간드가 가수분해되어 -Si(OH)3 로 되어 각종 무기물을 바인딩하는 역할을 한다. 따라서 리튬 폴리실리케이트 수용액에 유기 티타늄 착화합물 및 실란 가교제를 첨가한 용액은 장시간 보관 시에도 안정하고, 용액의 점도가 낮아 작업성이 우수하다. [화학식 4]의 지르코늄 화합물을 1-5중량%로 첨가하면 특히 GI강판에 대한 도포성 및 내식성이 보다 향상되는 것으로 나타났다. 지르코늄 화합물이 5중량% 를 초과하는 경우, 용액의 안정성이 떨어져서 엉김현상이 생겼다. The reason why the solution of the present invention exhibits such excellent corrosion resistance is because each component forms a three-dimensional network coating layer. Lithium polysilicate of [Formula 1] is a compound having a high corrosion resistance by itself because it forms a three-dimensional coating layer when coated on a steel sheet. In the organic titanium complex of [Formula 2], L 1 ligand forms stable chelate, and isopropoxide, which is a terminal ligand, is slowly hydrolyzed in aqueous solution to stabilize the solution, and gradually reacts with moisture during coating to [Ti (L 1). ) (OH) 2 ] is shown to form an insoluble coating. On the other hand, the silane crosslinking agent of [Formula 3] is hydrolyzed by the methoxy ligand in the aqueous solution to -Si (OH) 3 serves to bind various inorganic substances. Therefore, a solution in which an organotitanium complex compound and a silane crosslinking agent are added to an aqueous lithium polysilicate solution is stable even when stored for a long time, and the viscosity of the solution is low, thereby providing excellent workability. When the zirconium compound of [Formula 4] is added at 1-5% by weight, the coating property and corrosion resistance of the GI steel sheet are particularly improved. When the zirconium compound is more than 5% by weight, the stability of the solution is inferior and entanglement occurs.
이러한 본 발명의 코팅용액은 크로메이트를 사용한 종래예에 비교하여 동등하거나 그 이상의 내식성을 가질 뿐만 아니라 표면외관 및 용액안정성도 우수한 것으로 나타났다.The coating solution of the present invention was shown to have not only the same or more corrosion resistance than the conventional example using chromate, but also excellent surface appearance and solution stability.
본 발명은 크롬을 함유하지 않는, 환경친화적인 아연 도금강판용 방청 코팅용액을 제공하며,이 코팅용액은 내식성,표면외관 및 용액안정성이 우수하며 작업성이 우수할 뿐만 아니라 제조가 용이하고 기존의 다른 크롬을 함유하지 않는 방청코팅용액에 비하여 저렴한 잇점이 있다. 또한 본 발명의 코팅용액은 수지와 강판에 우수한 밀착성을 제공하므로 각종 강판에 도장 하지용으로 사용될 수 있을 것이다. The present invention provides an rust-free coating solution for an environmentally friendly galvanized steel sheet that does not contain chromium, and this coating solution is excellent in corrosion resistance, surface appearance and solution stability, and excellent in workability, and is easy to manufacture. Compared to the rust-free coating solution containing no chromium, it is inexpensive. In addition, the coating solution of the present invention may be used for coating the various steel sheets because it provides excellent adhesion to the resin and the steel sheet.
Claims (3)
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| WO2016107791A1 (en) * | 2014-12-30 | 2016-07-07 | Ewald Dörken Ag | Passivation composition comprising a silane-modified silicate compound |
| CN107109658A (en) * | 2014-12-30 | 2017-08-29 | 埃瓦尔德德肯有限公司 | Passivation composition comprising silane-modified silicate compound |
| US11759820B2 (en) | 2014-12-30 | 2023-09-19 | Ewald Dorken Ag | Passivation composition comprising a silane-modified silicate compound |
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