KR100244650B1 - The method of electric zn coating steel with polymer treatment - Google Patents
The method of electric zn coating steel with polymer treatment Download PDFInfo
- Publication number
- KR100244650B1 KR100244650B1 KR1019960039091A KR19960039091A KR100244650B1 KR 100244650 B1 KR100244650 B1 KR 100244650B1 KR 1019960039091 A KR1019960039091 A KR 1019960039091A KR 19960039091 A KR19960039091 A KR 19960039091A KR 100244650 B1 KR100244650 B1 KR 100244650B1
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- resin
- steel sheet
- solution
- phr
- treated
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 31
- 239000010959 steel Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000011248 coating agent Substances 0.000 title abstract description 27
- 238000000576 coating method Methods 0.000 title abstract description 27
- 229920000642 polymer Polymers 0.000 title 1
- 229920005989 resin Polymers 0.000 claims abstract description 67
- 239000011347 resin Substances 0.000 claims abstract description 67
- -1 imine ester Chemical class 0.000 claims abstract description 23
- 238000012545 processing Methods 0.000 claims abstract description 20
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 11
- 239000004640 Melamine resin Substances 0.000 claims abstract description 10
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000573 polyethylene Polymers 0.000 claims abstract description 9
- 239000004698 Polyethylene Substances 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000010409 thin film Substances 0.000 claims abstract description 8
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 6
- 239000008397 galvanized steel Substances 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims 1
- 238000009501 film coating Methods 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 29
- 239000011737 fluorine Substances 0.000 abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001993 wax Substances 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000003666 anti-fingerprint Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2502/00—Acrylic polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
본 발명은 수지도막에 윤활성을 부여함으로서 스크레치 방지 및 가공시 다이면과 강판과의 저항으로 발생하는 손상을 방지할 수 있는 가공후의 내흑화성이 우수한 수지처리 전기아연도금강판의 제조방법을 제공하고자 하는데 목적이 있다.The present invention is to provide a method for producing a resin-treated electro zinc plated steel sheet having excellent blackening resistance after processing that can prevent scratches and damage caused by resistance between the die surface and the steel sheet during processing by imparting lubricity to the resin coating film. There is a purpose.
상기 목적을 달성하기 위한 본 발명은 크로메이트 처리된 전기아연도금강판에 박막의 수지를 도포하여 수지처리 전기아연도금강판을 제조하는 방법에 있어서, 아크릴 우레탄수지 혹은 에스테르 우레탄수지 용액을 주제용액으로 하고, 상기 주제용액에 주제용액 대비 2-6phr의 이민에스테르 혹은 10-30phr의 멜라민수지가 첨가되고, 주제용액 대비 2-18phr의 불소수지로 치환된 포리에틸렌계 왁스가 첨가되고, 또한, 여기에 주제용액 대비 10-20phr의 실리카가 포함된 용액을 크로메이트 처리된 전기 아연도금강판에 박막으로 도포한 후, 강판온도가 120-180℃인 범위에서 소부 건조시키는 가공후 내흑화성이 우수한 수지처리 전기아연도금강판의 제조방법에 관한 것을 그 요지로 한다.The present invention for achieving the above object is a method of producing a resin-treated electrogalvanized steel sheet by applying a thin film of resin to a chromate-treated electrogalvanized steel sheet, the acrylic urethane resin or ester urethane resin solution as a main solution, To the main solution, 2-6 phr imine ester or 10-30 phr melamine resin is added to the main solution, and a polyethylene wax substituted with 2-18 phr of fluorine resin to the main solution is added. A resin-treated galvanized steel sheet having excellent blackening resistance after processing by coating a solution containing 10-20 phr silica in a thin film on a chromate-treated electrogalvanized steel sheet and then baking the steel sheet at a range of 120-180 ° C. The manufacturing method of this is made into the summary.
Description
본 발명은 전기아연도금강판의 수지처리 방법에 관한 것으로, 보다 상세하게는 가공후 흑화를 방지할 수 있는 수지용액을 이용하여 크로메이트된 전기아연도금강판을 수지처리하는 방법에 관한 것이다.The present invention relates to a resin treatment method of an electrogalvanized steel sheet, and more particularly, to a resin treatment method of a chromate-plated electrogalvanized steel sheet using a resin solution that can prevent blackening after processing.
전기아연도금강판은 균일한 도금부착량 확보, 소지철과의 밀착성 및 우수한 표면외관으로 인하여 가전제품 등에 많이 사용되고 있지만, 수요가의 처리공정에 투입되어 작업이 행해질 때 작업자에 의한 지문이나, 작업장내의 환경으로 인하여 유기물질 등으로 표면이 쉽게 오염될 뿐만 아니라 오염된 부위는 내식성 및 도장성에 까지 악영향을 미치기 때문에 박막의 크로메이트 및 수지처리를 하는 일종의 내지문처리가 행해지고 있다. 그러나 상기 내지문처리에 의한 강판은 일반적으로 수지도막이 유연하여 수요가에 의한 취급시 도막에 스크레치(scratch)가 발생되기도하며, 또한 가공시 수지도막이 가공 다이(Die)의 저항을 이겨내지 못하여 수지도막이 파열되면서 도금면까지 손상을 입힘으로서 가공후에 발생하는 흑화(흑색의 점상)에 의해 품질이 떨어진다는 문제점도 가지고 있다.Electro-galvanized steel sheet is widely used in home appliances because of its uniform coating amount, adhesion to base iron, and excellent surface appearance, but it is applied to the processing process of demand, and work is performed by workers or environment in the workplace. Due to this, not only the surface is easily contaminated with organic materials and the like, but the contaminated portion adversely affects corrosion resistance and paintability, so that a kind of rubbing treatment for chromate and resin treatment of the thin film is performed. However, the steel plate by the anti-fingerprint treatment is generally flexible resin coating may cause scratches in the coating film when the demand is handled, and the resin coating film does not withstand the resistance of the processing die during processing, the resin coating film ruptures In addition, there is a problem that the quality is degraded by blackening (black spots) generated after processing by damaging the plated surface.
본 발명자들은 상기 문제점을 해결하기 위하여 연구와 실험을 거듭하고, 그 결과에 근거하여 본 발명을 제한하게 된 것으로, 본 발명은 수지도막에 윤활성을 부여함으로서 스크레치 방지 및 가공시 다이면과 강판과의 저항으로 발생하는 손상을 방지할 수 있는 가공후의 내흑화성이 우수한 수지처리 전기아연도금강판의 제조방법을 제공하고자 하는데 목적이 있다.The present inventors have repeatedly conducted research and experiments to solve the above problems, and the present invention has been limited based on the results, and the present invention provides lubricity to the resin coating film to prevent scratching and processing of the die surface and the steel sheet. It is an object of the present invention to provide a method for producing a resin-treated electrogalvanized steel sheet having excellent blackening resistance after processing that can prevent damage caused by resistance.
제1도는 본 발명의 수지용액에 의한 수지도막의 수지부착량에 따른 백청발생정도를 나타내는 그래프.1 is a graph showing the degree of white rust generated according to the resin adhesion amount of the resin coating film by the resin solution of the present invention.
상기 목적을 달성하기 위한 본 발명은 크로메이트 처리된 전기아연도금강판에 박막의 수지를 도포하여 수지처리 전기아연도금강판을 제조하는 방법에 있어서, 아크릴 우레탄수지 혹은 에스테르 우레탄수지 용액을 주제용액으로 하고, 상기 주제용액에 주제용액 대비 2-6phr의 이민에스테르 혹은 10-30phr의 멜라민수지가 첨가되고, 주제용액 대비 2-18phr의 불소수지로 치환된 포리에틸렌계 왁스가 첨가되고, 또한, 여기에 주제용액 대비 10-20phr의 실리카가 첨가된 용액을 크로메이트 처리된 전기아연도금강판에 박막으로 도포한 후, 강판온도가 120-180℃인 범위에서 소부 건조시키는 가공후 내흑화성이 우수한 수지처리 전기아연도금강판의 제조방법에 관한 것이다.The present invention for achieving the above object is a method of producing a resin-treated electrogalvanized steel sheet by applying a thin film of resin to a chromate-treated electrogalvanized steel sheet, the acrylic urethane resin or ester urethane resin solution as a main solution, To the main solution, 2-6 phr imine ester or 10-30 phr melamine resin is added to the main solution, and a polyethylene wax substituted with 2-18 phr of fluorine resin to the main solution is added. The resin-treated galvanized steel sheet having excellent blackening resistance after processing was coated with a thin film on the chromate-treated galvanized steel sheet after the addition of 10-20 phr of silica to the chromate-treated galvanized steel sheet. It relates to a manufacturing method of.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 크로메이트 처리된 전기아연도금강판상에 수지를 도포하여 수지피복강판을 제조하는 방법으로, 먼저 수지피막을 형성하기 위한 수지용액에 대하여 설명한다.The present invention is a method of manufacturing a resin coated steel sheet by coating a resin on a chromate-treated electrogalvanized steel sheet. First, a resin solution for forming a resin film will be described.
본 발명에서의 수지처리 용액은 아크릴 우레탄(Acryl 변성 Urethane)수지 혹은 에스테르 우레탄(Ester 변성 Urethane)수지(이하, '주제용액'이라 한다)에 경화제인 이민에스테르(Imine Ester) 혹은 멜라민수지를 주제용액 대비 각각 2-6phr(perhundred, 용매 100중량부당 첨가된 용질의 양), 10-30phr의 함량으로 첨가한다. 상기 경화제는 이민에스테르와 멜라민수지 둘중 어느것을 사용하여도 무방하나 이들의 투입량에 있어서는 서로 다르기 때문에 주의해야 한다. 상기 이민에스테르의 경우는 주제용액 대비 2-6phr의 함량이 적당한데, 그 함량이 2phr이하가 되면 경화반응을 일으킬 수 있는 경화제의 함량이 부족하여 강고한 피막을 얻을 수 없는 단점이 있고, 6phr이상이 되면 용액안정성이 저하하기 때문이다. 그리고 상기 멜라민수지의 경우는 주제용액 대비 10-30phr의 함량이 적당한데, 그 함량이 10phr이하가 되면 도막의 경화반응이 충분치 않으며, 30phr이상이 되면 첨가에 대한 경화 향상효과가 없기 때문이다.The resin treatment solution in the present invention is an acrylic urethane (Eryl modified urethane) resin or ester urethane (Ester modified urethane) resin (hereinafter referred to as 'the main solution') the imine ester (Imine Ester) or melamine resin as a curing agent 2-6 phr (perhundred, the amount of solute added per 100 parts by weight of solvent) and 10-30 phr, respectively. The curing agent may be used either of the imine ester and melamine resin, but care should be taken because their dosage is different. In the case of the imine ester, a content of 2-6 phr is appropriate compared to that of the main solution, and when the content is less than 2 phr, there is a disadvantage in that a hard film cannot be obtained because of insufficient content of a curing agent that can cause a curing reaction. This is because solution stability is lowered. And in the case of the melamine resin, the content of 10-30phr compared to the main solution is appropriate, because the content is less than 10phr hardening reaction of the coating film is not sufficient, if more than 30phr does not improve the curing effect for the addition.
그러나, 상기 아크릴 우레탄수지 혹은 에스테르 우레탄수지 용액에 이민에스테르 혹은 멜라민수지가 첨가된 수지용액을 이용하여 수지처리 강판을 제조할 경우 수지자체의 점성 때문에 가공시 프레스기의 다이(Die)면과 수지와의 마찰로 인하여 수지도막의 일부가 파열되면서 하지층의 아연도금을 손상시킨다. 상기 손상에 의한 미세 아연분말은 수지와 섞여 혼합됨으로서 가공면이 흑색으로 변색되어 표면외관을 해치게 된다. 이러한 현상을 방지하기 위하여 수지용액내에 윤활성이 있는 소량의 왁스를 첨가하게 된다. 이때 첨가되는 왁스로서 일반적인 왁스 즉, 포리에틸렌계 또는 포리프로필렌계 왁스를 사용하면 마찰계수의 감소(가공성 양호)를 가져오지만 가공후 흑화개선에는 영향을 미치지 못하기 때문에 본 발명에서는 슬립성과 윤활성을 함께 겸비한 불소수지 변성 포리에틸렌계 왁스를 사용한다. 즉, 상기 이민에스테르 혹은 멜라민수지를 혼합시킨 주제용액에 불소수지로 변성된 포리에틸렌계 왁스를 주제용액 대비 2-18phr의 함량으로 첨가하는 것이다. 상기 왁스의 함량이 2phr이하로 첨가되면 왁스에 의한 충분한 윤활작용이 되지않아 내흑화성을 기대하기 어렵고, 18phr이상으로 첨가되면 수지피복강판 상부에 도장이 될 경우 도막밀착성이 저하하기 때문에 2-18phr의 함량으로 첨가한다.However, when manufacturing a resin-treated steel sheet using a resin solution in which an imine ester or melamine resin is added to the acrylic urethane resin or ester urethane resin solution, due to the viscosity of the resin itself, Part of the resin film ruptures due to friction, which damages the zinc plating of the underlying layer. The fine zinc powder due to the damage is mixed with the resin and mixed with the resin, thereby discoloring the processed surface to black to damage the surface appearance. In order to prevent this phenomenon, a small amount of lubricious wax is added to the resin solution. In this case, if the wax is added as a general wax, that is, polyethylene or polypropylene wax, the friction coefficient is reduced (good processability), but it does not affect the improvement of blackening after processing. A fluororesin modified polyethylene wax is used. That is, a polyethylene wax modified with fluorine resin is added to the main solution in which the imine ester or melamine resin is mixed in an amount of 2-18 phr compared to the main solution. When the content of the wax is added below 2phr, it is difficult to expect blackening resistance because it is not sufficiently lubricated by the wax, and when it is added at 18phr or more, the coating film adhesion is reduced when it is coated on the resin coated steel sheet. Add in content.
또한, 내식성 확보를 위해 주제용액 대비 10-20phr의 실리카가 첨가되는데, 10phr이하의 함량에서는 내식성의 효과가 불충분하고 20phr이상에서는 투입량의 증가에 따른 내식성의 증가가 나타나지 않기 때문이다.In addition, in order to ensure corrosion resistance, 10-20 phr of silica is added to the main solution, since the effect of corrosion resistance is insufficient at a content of 10 phr or less, and at 20 phr or more, the increase in corrosion resistance does not appear due to an increase in the input amount.
다음으로, 상기와 같은 구성의 수지용액을 이용하여 소지강판상에 수지처리하는 방법에 대해 설명한다.Next, the method of resin-processing on a steel plate using the resin solution of the above structure is demonstrated.
일반적으로 수지피복강판 제조시 도막두께에 의해 물성의 영향이 크게 좌우되기 때문에 본 발명에서는 상기 수지용액을 도포하여 소부 건조후의 두께를 0.5-3.0㎛의 범위로 제한하였다. 도막두께가 0.5㎛이하이면 도막두께가 너무 얇아 충분한 물성을 확보하기가 어렵고, 3.0㎛이상이면 가공시 수지도막의 일부가 박리되어 충분한 내식성을 기대하기가 어렵게 된다.In general, since the influence of physical properties largely depends on the thickness of the coating film during the production of the resin coated steel sheet, in the present invention, the thickness after baking the baking by applying the resin solution is limited to the range of 0.5-3.0 μm. If the film thickness is 0.5 탆 or less, the film thickness is too thin to ensure sufficient physical properties. If the thickness is 3.0 탆 or more, a part of the resin film is peeled off during processing, so that it is difficult to expect sufficient corrosion resistance.
한편, 수지용액을 도포후 소부함에 있어, 소부는 120-200℃ 범위의 강판온도에서 실시하는 것이 바람직한데, 상기 강판온도가 120℃이하에서 소부되면 수지의 경화반응이 충분치 못하여 도막의 물성이 저하하며, 반대로 강판온도가 200℃이상에서 소부되면 소지강판의 재질변화와 함께 BH(베이크하드닝)강판의 성질을 보존할 수 없기 때문이다.On the other hand, in the baking after the resin solution is applied, baking is preferably performed at a steel sheet temperature in the range of 120-200 ° C. If the baking is carried out at 120 ° C. or lower, the curing reaction of the resin is insufficient and the physical properties of the coating film are lowered. On the contrary, when the steel sheet is baked at 200 ° C. or higher, the material of the steel sheet cannot be preserved and the properties of the BH (baking hardening) steel sheet cannot be preserved.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예]EXAMPLE
아연부착량과 크롬부착량이 각각 20g/m2, 50mg/m2인 크로메이트처리된 아연전기도금강판에 수지용액을 도포한 후 강판온도가 150℃에서 소부한 다음 수냉시켜 건조수지 도막도께가 1㎛인 수지피복강판을 제조하였다.The resin solution was applied to the chromate-treated zinc electroplated steel sheets with zinc deposition amount and chromium deposition amount of 20 g / m 2 and 50 mg / m 2 , respectively.Then, the steel plate was baked at 150 ℃ and then cooled with water to make the dry resin coating film 1㎛. Phosphorous resin coated steel sheet was prepared.
물성평가중 용액안정성은 상온에서 15일간 용액이 겔이 되는 정도를 5등급으로 나누어 평가하였으며, 평가기준은 다음과 같다.Solution stability was evaluated by dividing the degree of solution gel into 5 grades at room temperature for 15 days, and the evaluation criteria are as follows.
◎ : 용액의 점도 변화폭이 2cps 이하◎: Viscosity change range of solution is 2 cps or less
○ : 용액의 점도 변화폭이 2-4cps(Circle): The viscosity change range of a solution is 2-4cps
□ : 용액의 점도 변호폭이 4-6cps□: Viscosity width of solution is 4-6cps
△ : 용액의 점도 변화폭이 6-8cps(Triangle | delta): The viscosity change range of a solution is 6-8cps
× : 용액의 점도 변화폭이 10cps 이상×: Viscosity change range of the solution is 10 cps or more
내화학성평가는 MEK(메틸에틸케톤)로 도막을 문질렀을 경우 수지도막의 박리 및 변색되는 정도를 5등급으로 나누어 평가하였으며, 평가기준은 다음과 같다.Chemical resistance was evaluated by dividing the degree of peeling and discoloration of the resin coating film into five grades when rubbing the coating film with MEK (methyl ethyl ketone). The evaluation criteria are as follows.
◎ : 수지도막의 박리가 없고 색차(처리전의 색차대비) ΔE 1이하(Double-circle): Color difference (relative to the color difference before processing) (DELTA) E 1 or less, without peeling of the resin coating film
○ : 수지도막의 박리가 없고 색차(처리전의 색차대비) ΔE 2-4(Circle): Color difference (contrast color difference before processing) (DELTA) E 2-4
□ : 수지도막의 박리가 없고 색차(처리전의 색차대비) ΔE 5이상□: No peeling of resin film and color difference (compared to color difference before treatment) ΔE 5 or more
△ : 수지도막의 부분박리(박리부분이 수지 전도포면의 30%이하)(Triangle | delta): Partial peeling of resin coating film (The peeling part is 30% or less of resin conductive cloth surface.)
× : 수지도막의 완전박리(박리부분이 수지 전도포면의 50%이상)X: complete peeling of the resin coating film (the peeled portion is more than 50% of the resin conductive cloth surface)
그리고, 내식성평가는 염수분무시험기를 이용하였으며 내식성평가시 평판재와 가공재로 나누어 평가하였는데, 가공재는 직경 30mm, 높이 6mm의 돔으로 만들어 300시간이 경과한 후 반출하여 순수로 세척하고 건조한 다음 발생한 백청율을 조사하였다. 이때 염수분무시험의 온도는 35℃, 분무량은 80ml/cm2/day, 분무압은 1kg/cm2으로 하였다.The corrosion resistance was evaluated by using a salt spray tester. The corrosion resistance was divided into flat and processed materials. The processed materials were made of 30mm diameter and 6mm high domes, which were taken out after 300 hours, washed with pure water, dried, and then produced white rust. The rate was investigated. At this time, the salt spray test temperature was 35 ℃, the spray amount was 80ml / cm 2 / day, the spray pressure was 1kg / cm 2 .
가공성평가는 평면 마찰계수로서 측정하였는데, 마찰계수의 경우는 40×300mm의 시편으로 절단하여 하기식의 조건에 의해 측정하였고, 이때 시험에 가하는 압력은 0.27kg/cm3, 인발속도(drawing speed)는 1000mm/min으로 하였다.Workability evaluation was measured as a planar friction coefficient, and the friction coefficient was measured by the following equation after cutting into a specimen of 40 × 300 mm, and the pressure applied to the test was 0.27kg / cm 3 , drawing speed Was 1000 mm / min.
마찰계수(μ)=Fd/Fn Coefficient of friction (μ) = F d / F n
(여기서, Fd는 인발력(drawing force), Fn은 수직항력(normal force)을 나타낸다.) 또한, 가공후의 흑화현상은 마찰계수를 측정한 다음의 도막표면 외관을 상대 비교 평가하였고, 도막밀착성은 멜라민-알키드(melamine-alkyd)를 사용하여 150℃에서 20분간 소부건조하여 건조피막이 20㎛가 되도록 상도도장을 한후 1mm간격으로 바둑판눈금을 만든 다음 일정한 압력을 가하고 테이프박리를 실시하여 박리된 갯수로서 도막밀착성을 평가하였다.(F d is the drawing force and F n is the normal force.) In addition, the blackening phenomenon after processing was evaluated by comparing the appearance of the film surface after measuring the coefficient of friction. Silver-baked using melamine-alkyd at 150 ° C for 20 minutes to coat the coating so that the dry film becomes 20㎛. As a result, coating film adhesion was evaluated.
[실시예 1]Example 1
주제용액(아크릴우레탄수지 혹은 에스테르우레탄수지)에 경화제를 하기표 1과 같은 함량으로 첨가하고, 불소수지로 치환된 포리에틸렌계 왁스와 실리카는 각각 주제용액 대비 10phr, 13phr를 첨가하여 수지용액을 제조하고, 상기와 같은 시편제조조건으로 시편을 제조한 다음 함량별 용액안정성을 평가하고, 내화학성을 평가하여 하기표 1에 나타내었다A curing agent was added to the main solution (acrylic urethane resin or ester urethane resin) in the amount as shown in Table 1 below, and for the polyethylene-based wax and silica substituted with fluorine resin, 10 phr and 13 phr were added to the main solution to prepare a resin solution. In addition, the specimens were prepared under the conditions for preparing the specimens as described above, the solution stability of each content was evaluated, and the chemical resistance was evaluated and shown in Table 1 below.
상기표 1에서 알 수 있는 바와같이, 이민에스테르와 멜라민수지의 함량이 각각 본 발명의 제한범위 이하인 1phr, 5phr의 경우에는 모두 용액안정성은 양호하나 경화가 불충분하였고, 이와 반대로 제한범위 이상인 8phr, 40phr의 경우에는 경화는 충분하나 용액안정성에서 뒤떨어지는 문제가 있을 뿐만아니라 경화제의 다량첨가에 의한 물성향상의 영향이 없었다.As can be seen in Table 1, in the case of 1phr, 5phr of the content of the imine ester and the melamine resin, respectively, below the limit of the present invention, all of the solution stability was good but the curing was insufficient, on the contrary, 8phr, 40phr of the above limit In the case of curing, the curing was sufficient, but there was a problem inferior in solution stability, and there was no effect on the physical properties due to the addition of a large amount of the curing agent.
[실시예 2]Example 2
주제용액(아크릴우레탄수지 혹은 에스테르우레탄수지)에 경화제인 멜라민 수지를 주제용액 대비 20phr 첨가, 실리카를 주제용액 대비 13phr 첨가하고, 각종 왁스를 하기표 2과 같은 함량으로 첨가하여 수지용액을 제조하고, 상기한 바와같은 시편제조조건으로 시편을 제조한 다음 마찰계수, 가공후 흑화 및 도막밀착성을 평가하여 하기표 2에 나타내었다.Into the main solution (acrylic urethane resin or ester urethane resin), melamine resin as a curing agent was added 20 phr to the main solution, silica was added to 13 phr to the main solution, and various waxes were added in the amounts shown in Table 2 to prepare a resin solution. The specimens were prepared under the specimen preparation conditions as described above, and the coefficients of friction, blackening after processing, and coating film adhesion were shown in Table 2 below.
상기표 2에서 알 수 있는 바와같이, 왁스는 불소/에틸렌계 공중합체를 사용하는 것이 바람직하고, 불소수지로 치환된 포리에틸렌계 왁스의 함량이 20phr이상이 되면 마찰계수는 증가하나 도장밀착성이 불량해졌다.As can be seen in Table 2, the wax is preferably a fluorine / ethylene-based copolymer, the friction coefficient increases when the content of the polyethylene-based wax substituted with fluorine resin is more than 20phr, but poor coating adhesion Done
[실시예 3]Example 3
상기 실시예 2에서의 발명예 3의 조건으로 제조된 수용성 수지용액을 상기 조건으로 시편을 제조한 다음 수지두께 변화에 따른 내식성평가를 하고, 그 결과를 도 1에 나타내었다. 도 1에 나타난 바와같이 수지도막의 두께가 0.5㎛이하인 경우 피막부착량이 균일하지 못하여 내식성이 저하하며, 두께가 3.0㎛이상인 경우 가공시 수지피막이 탈락되어 내식성이 저하되는 것을 알 수 있다.The water-soluble resin solution prepared under the condition of Inventive Example 3 in Example 2 was prepared under the above conditions, and the corrosion resistance was evaluated according to the resin thickness change. The results are shown in FIG. 1. As shown in FIG. 1, when the thickness of the resin coating film is 0.5 μm or less, the coating amount is not uniform, and the corrosion resistance is lowered. When the thickness is 3.0 μm or more, the resin film is dropped and the corrosion resistance is reduced.
상기와 같은 본 발명의 방법에 의하면, 아크릴우레탄 수지 혹은 에스테르우레탄 수지에 경화제인 이민에스테르 혹은 멜라민을 첨가한 수지용액에 불소수지로 치환된 포리에틸렌계 왁스를 첨가한 수지처리용액을 사용하여 가공후 내흑화성이 우수한 수지처리된 전기아연 도금강판을 얻을 수 있다.According to the method of the present invention as described above, after processing using a resin treatment solution in which a polyethylen wax substituted with a fluorine resin is added to a resin solution in which an imine ester or melamine, which is a curing agent, is added to an acrylic urethane resin or an ester urethane resin. A resin-treated electrogalvanized steel sheet excellent in blackening resistance can be obtained.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019960039091A KR100244650B1 (en) | 1996-09-10 | 1996-09-10 | The method of electric zn coating steel with polymer treatment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019960039091A KR100244650B1 (en) | 1996-09-10 | 1996-09-10 | The method of electric zn coating steel with polymer treatment |
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| Publication Number | Publication Date |
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| KR19980020581A KR19980020581A (en) | 1998-06-25 |
| KR100244650B1 true KR100244650B1 (en) | 2000-03-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1019960039091A Expired - Lifetime KR100244650B1 (en) | 1996-09-10 | 1996-09-10 | The method of electric zn coating steel with polymer treatment |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100345710B1 (en) * | 1998-07-03 | 2002-09-18 | 주식회사 포스코 | Method for producing resin solution for anti-fingerprint steel sheet excellent in blackening resistance and blackening resistance, and method for producing resin coated steel sheet using this resin solution |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100388895B1 (en) * | 2001-06-08 | 2003-06-25 | 현대하이스코 주식회사 | Process for producing High Corrosion, Anti-Finger Printer Resin having excellent Formability and Anti-corrosion |
| KR100388896B1 (en) * | 2001-06-08 | 2003-06-25 | 현대하이스코 주식회사 | High-lubricant·anti-finger print steel sheet superior in the formability and the blackenning of surface on pressing in low temperature and the process thereof |
| KR100388897B1 (en) * | 2001-06-08 | 2003-06-25 | 현대하이스코 주식회사 | High-lubricant anti finger print steel sheet without chromate that is developed the deep drawing ability, the corrosion resistance in low temperature |
| KR100388894B1 (en) * | 2001-06-08 | 2003-06-25 | 현대하이스코 주식회사 | Process for Manufacturing High Lubricant Anti-Finger Printer Resin having excellent Appearance and Lubricating Property |
| KR20030053762A (en) * | 2001-12-24 | 2003-07-02 | 주식회사 포스코 | A Coating Composition for Fingerprint Resistance Steel Plate Having Superior Chemical Resistance and Adhesive |
| KR100627473B1 (en) * | 2001-12-24 | 2006-09-22 | 주식회사 포스코 | Anti-fingerprint steel plate resin coating solution with excellent stain resistance and steel plate manufacturing method using the same |
| KR100510008B1 (en) * | 2002-11-11 | 2005-08-26 | 주식회사 포스코 | Resin composition for coating Organic coating steel plate with preventing pollution excellently and Organic coating steel plate coated therewith |
| KR102373171B1 (en) | 2019-12-05 | 2022-03-10 | 주식회사 포스코 | Surface treatment composition for galvanized steel sheet, surface treated galvanized steel sheet using same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR900018412A (en) * | 1988-05-31 | 1990-12-21 | 야기 야스히로 | Lubricated resin treated steel sheet with excellent moldability and corrosion resistance |
-
1996
- 1996-09-10 KR KR1019960039091A patent/KR100244650B1/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR900018412A (en) * | 1988-05-31 | 1990-12-21 | 야기 야스히로 | Lubricated resin treated steel sheet with excellent moldability and corrosion resistance |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100345710B1 (en) * | 1998-07-03 | 2002-09-18 | 주식회사 포스코 | Method for producing resin solution for anti-fingerprint steel sheet excellent in blackening resistance and blackening resistance, and method for producing resin coated steel sheet using this resin solution |
Also Published As
| Publication number | Publication date |
|---|---|
| KR19980020581A (en) | 1998-06-25 |
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