KR100256326B1 - Steel coating epoxy resin composition and the preparation of its coated steel plate having anticorrosiveness and good weldding property - Google Patents
Steel coating epoxy resin composition and the preparation of its coated steel plate having anticorrosiveness and good weldding property Download PDFInfo
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- KR100256326B1 KR100256326B1 KR1019950068489A KR19950068489A KR100256326B1 KR 100256326 B1 KR100256326 B1 KR 100256326B1 KR 1019950068489 A KR1019950068489 A KR 1019950068489A KR 19950068489 A KR19950068489 A KR 19950068489A KR 100256326 B1 KR100256326 B1 KR 100256326B1
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- 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
- 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
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
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- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4028—Isocyanates; Thioisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/508—Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
- C08G59/5086—Triazines; Melamines; Guanamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
Abstract
Description
제1도는 윤활제 첨가량에 따른 마찰계수의 변화를 나타내는 그래프이며,1 is a graph showing a change in the friction coefficient according to the amount of lubricant added,
제2도는 윤활제 첨가량에 따른 블랭크홀딩 포스의 변화를 나타내는 그래프이다.2 is a graph showing the change of the blank holding force according to the amount of lubricant added.
본 발명은 용융아연 수지피복 강판에 도포되는 윤활성 및 가공성이 우수한 수지 용액 및 이를 이용하여 용융아연 강판을 처리하는 방법에 관한 것이다.The present invention relates to a resin solution having excellent lubricity and processability applied to a molten zinc resin coated steel sheet and a method of treating the molten zinc steel sheet using the same.
용융아연도금강판은 전기아연도금강판에 비해 생산공정이 간단하고 손쉽게 후도금을 얻을 수 있을 뿐 아니라 제조시 가격이 저렴하고 생산성이 높기 때문에 산업 전반에 걸쳐 수요가 증대되고 있는 실정이다. 그러나 박도금이 곤란하여 가공시 도금피막이 박리되어 금형기기내에 퇴적물로 쌓이므로서 가공제품의 표면이 손상되는 문제점이 있다.Hot-dip galvanized steel sheet is not only easy to obtain a post-plating process compared to electro-galvanized steel sheet, but also cheaper and more productive at the time of manufacture, the demand is increasing throughout the industry. However, there is a problem in that the surface of the processed product is damaged due to the difficulty in thin plating, and the plating film is peeled off during the processing and accumulated as a deposit in the mold machine.
또한 심가공시 도막의 일부가 손상되면서 발생되는 결함부위와 스프레이 도장시 도장이 잘 되지 않는 접합 부위에서 부식이 급격히 진행되어 고내식성을 기대하기가 어렵게 되므로 결함부위의 내식성을 보강하기 위하여 용융도금강판 위에 크로메이트 처리 및 박막으로 수지처리를 실시하여 결함부위의 부식을 방지시켜 기존 용융도금강판보다도 휠씬 더 우수한 고내식성을 기대할 수가 있다. 수지처리된 강판의 물성은 주로 크로메이트의 수지층에 의해 큰 영향을 받으며, 강판상층부에 있는 수지는 부식인자에 의한 1차적인 차폐효과와 하층 크로메이트의 급격한 크롬용출을 방지하여 우수한 내식성을 발휘하게 된다. 그러나 상기 목적으로 처리된 경우 특히 수지피막은 피막자체의 저항성이 크므로 용접시 수지자체의 저항에 의한 발열로 수지가 전극면에 열융착되므로 전극이 손상되고 전기밀도가 저하되어 용접성이 크게 떨어지는 결점이 있으며 무도유에 의한 가공시 마찰에 의해 프레스의 온도가 올라가는 경우 피막의 손상으로 표면외관 및 내식성이 저하된다.In addition, hot-dip galvanized steel sheets are used to reinforce the corrosion resistance of the defects because it is difficult to expect high corrosion resistance due to the rapid progress of corrosion at the joints where the parts of the coating film are damaged during deep processing and the poorly painted joints during spray coating. It is possible to expect much higher corrosion resistance than the existing hot-dip galvanized steel sheet by preventing the corrosion of defects by performing chromate treatment and resin treatment with thin film. Physical properties of the resin-treated steel sheet are largely influenced by the resin layer of the chromate, and the resin in the upper layer of the steel sheet exhibits excellent corrosion resistance by preventing the primary shielding effect by the corrosion factor and rapid chromium elution of the lower chromate. . However, when the resin film is treated for the above purpose, in particular, since the resin film has a high resistance to the film itself, the resin is thermally fused to the electrode surface due to the heat generated by the resistance of the resin itself during welding. If the press temperature rises due to friction during processing by non-oiling, the surface appearance and corrosion resistance decrease due to damage to the coating.
한편 용융 아연 도금강판에 크로메이트 처리를 한후 아크릴변성 에폭시수지에 경화제인 이소시아네이트 수지 혹은 멜라민 수지를 혼합하여 도포한 경우는 수지피막으로 인하여 내식성은 증가하나 수지 자체의 절연성으로 인하여 용접성이 열화된다. 이러한 문제를 해결하기 위해 수지내에 금속분말을 첨가함으로써 용접성은 개선되나, 금속분말 첨가시 분말입자의 크기를 제어하기 어려울 뿐만 아니라 수지용액내의 미세입자가 서로 응집하여 2차 응집입자를 형성함으로 단기간내에 슬러지(Sludge)가 생성되어 용액안정성(용액 저장성)이 저하될 뿐만 아니라 이 수지를 강판상에 도포하게 되면 박막 수지상에 금속성분이 돌출하여 도장후의 표면외관 및 물성이 저하된다.On the other hand, when chromate treatment is applied to a hot dip galvanized steel sheet and mixed with an isocyanate resin or melamine resin, which is a curing agent, to acrylic modified epoxy resin, the corrosion resistance is increased due to the resin coating, but the weldability is degraded due to the insulation of the resin itself. To solve this problem, weldability is improved by adding metal powder in the resin, but it is difficult to control the size of the powder particles when the metal powder is added, and fine particles in the resin solution agglomerate with each other to form secondary aggregated particles within a short period of time. Sludge is formed to reduce solution stability (solution storage property), and when the resin is applied onto a steel sheet, metal components protrude on the thin film resin to reduce surface appearance and physical properties after coating.
따라서, 본 발명은 이와같은 문제를 해결하기 위해 제안된 것으로 금속분말을 첨가함으로서 일어날수 있는 분말들의 균일성 및 2차 응집입자의 형성으로 인하여 발생되는 용액의 안정성 및 저장성을 개선하고, 종래에 비하여 간편하게 수지용액내에 금속염을 이온상으로 존재시켜 수지도막내에 균일하게 존재토록 하여 수지피막에 의한 내식성과 금속이온들에 의한 전기 전도도를 향상시키고 자기 윤활성을 보유할 수 있도록 윤활제가 첨가된 수지용액 및 이를 사용하여 강판을 처리하는 방법을 제공하고자 하는데 그 목적이 있다.Therefore, the present invention has been proposed to solve such a problem, and improves the stability and shelf life of the solution caused by the formation of secondary aggregated particles and the uniformity of powders that may occur by the addition of metal powder, compared to the prior art. Resin solution with lubricating agent added so that metal salt is easily present in the resin solution in the resin solution to be uniformly present in the resin coating film, thereby improving corrosion resistance by the resin film and electric conductivity by metal ions and retaining self-lubricating property. It is an object of the present invention to provide a method for treating a steel sheet using the same.
본 발명의 일견지에 의하면, 아크릴변성 에폭시 수지 용액; 경화제로서 수지 용액의 고형분을 기준으로 멜라민수지 10-40중량% 혹은 이소시아네이트 수지 10-50중량%; 윤활제로서 수지용액의 고형분을 기준으로 올레핀계 왁스 혹은 폴리에틸렌계 왁스를 단독으로 혹은 혼합하여 3-25중량%; 수지용액의 고형분을 기준으로 코발트 오레이트[Co(C18H33O2)2], 망간 오레이트[Mn(C18H33O2)2] 및 망간 옥토에이트[Mn(C8H17O2)2]로 구성된 그룹에서 선택된 1종 혹은 2종이상의 금속염 0.1-0.5중량%; 및 내식성 향상제로서 수지 용액의 고형분을 기준으로 실리카 10-30중량% 혹은 바륨크로메이트(Ba CrO4), 스트로튬크러메이트(SrCrO4), 무수크롬산(CrO3) 및 징크크로메이트(ZnCrO4)로 부터 선택된 1종 혹은 2종을 혼합한 크롬화합물 0.5-10중량%;로 조성된 용접성, 내식성 및 가공성이 우수한 표면처리강판용 수지용액 조성물이 제공된다.According to one aspect of the invention, acrylic modified epoxy resin solution; 10-40% by weight of melamine resin or 10-50% by weight of isocyanate resin based on the solids content of the resin solution as a curing agent; 3-25% by weight of olefinic wax or polyethylene wax alone or mixed based on the solids content of the resin solution as a lubricant; Based on the solids of the resin solution, cobalt ore [Co (C 18 H 33 O 2 ) 2 ], manganese ore [Mn (C 18 H 33 O 2 ) 2 ] and manganese octoate [Mn (C 8 H 17 O 2 ) 0.1-0.5% by weight of one or more metal salts selected from the group consisting of 2 ]; And from 10-30% by weight of silica or from barium chromate (Ba CrO 4 ), strontium chromate (SrCrO 4 ), chromic anhydride (CrO 3 ) and zinc chromate (ZnCrO 4 ) as corrosion resistance enhancers. Provided is a resin solution composition for a surface-treated steel sheet excellent in weldability, corrosion resistance, and workability composed of 0.5-10% by weight of a chromium compound mixed with one or two selected compounds.
본 발명의 다른 견지에 의하면, 상기 수지 조성물을 크로메이트 처리된 용융아연 및 용융아연 합금도금 강판에 건조도막두께가 0.5-3.0㎛가 되도록 도포한 후, 강판온도 130-200℃로 소부처리함을 포함하는 용접성, 내식성 및 가공성이 우수한 강판표면처리 방법이 제공된다.According to another aspect of the present invention, the resin composition is coated on a chromate-treated hot dip galvanized and hot dip galvanized alloy steel sheet so as to have a dry coating thickness of 0.5-3.0 μm, followed by baking at a steel plate temperature of 130-200 ° C. Provided is a steel sheet surface treatment method having excellent weldability, corrosion resistance and workability.
이하, 본 발명에 대하여 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명은 아크릴 변성 에폭시 수지에 적정량의 금속염, 윤활제 그리고 크롬화합물 및 실리카를 첨가함으로써 용융아연도금강판에 사용되는 피막처리 수지의 용접성, 내식성 및 가공성을 개선하는 것이다.The present invention is to improve the weldability, corrosion resistance and processability of the coating resin used in the hot-dip galvanized steel sheet by adding an appropriate amount of metal salt, lubricant, chromium compound and silica to the acrylic modified epoxy resin.
본 발명에 사용되는 수지는 아크릴 변성 에폭시 수지로 바람직하게는 에폭시 그라프트 아크릴레이트이다. 상기 수지는 수평균 분자량이 2,000-6,000인 에폭시수지와 메틸메타크릴레이트(MMA), 아크릴산(AA), 부틸아크릴레이트(BA), 2-하이드록시에틸메타크릴레이트(2-HEMA) 혹은 에틸아크릴레이트(EA)등의구조를 갖는 아크릴레이트 단량체를 상기 아크릴 변성에폭시 수지의 히드록시가(-OH value)가 20-60이 되도록 합성된 것이다.The resin used in the present invention is an acrylic modified epoxy resin, preferably epoxy graft acrylate. The resin is an epoxy resin having a number average molecular weight of 2,000-6,000 and methyl methacrylate (MMA), acrylic acid (AA), butyl acrylate (BA), 2-hydroxyethyl methacrylate (2-HEMA) or ethyl acryl. Such as rate (EA) The acrylate monomer having a structure is synthesized such that the hydroxyl value (-OH value) of the acrylic modified epoxy resin is 20-60.
또한 상기 수지 제조시 100℃에서 중합개시제로 벤조일 퍼오사이드(BPO)가 사용되며, 메틸이소부틸케톤(MIBK)혹은 메틸에틸케톤(MEK)과 같이 극성기를 갖는 용매를 사용하여 수지 고형분의 함량이 20%가 되도록 조절한다.In addition, benzoyl peroxide (BPO) is used as a polymerization initiator at 100 ° C. in preparing the resin, and the resin solid content is 20 using a solvent having a polar group such as methyl isobutyl ketone (MIBK) or methyl ethyl ketone (MEK). Adjust to%.
상기 아크릴 변성 에폭시 수지 제조시, 수평균 분자량이 2000이하인 에폭시 수지는 저온 열건조에 의한 가교반응이 어려우며, 6000이상인 에폭시 수지는 수지의 점도 상승으로 작업성이 떨어지므로 수평균 분자량이 2000-6000인 에폭시 수지를 사용하는 것이 바람직하다.When the acrylic modified epoxy resin is prepared, an epoxy resin having a number average molecular weight of 2000 or less is difficult to crosslink by low temperature heat drying, and an epoxy resin having 6000 or more has a number average molecular weight of 2000-6000 because workability is decreased due to an increase in the viscosity of the resin. Preference is given to using epoxy resins.
또한 에폭시 수지와 아크릴레이트 단량체는 히드록시가(-oH Value)가 20-60이 되도록 합성하는 것이 바람직하다. 히드록시가 60이상인 경우에는 에폭시 수지의 분자량이 너무 적어 원하는 물성을 확보하기 어렵고 20이하인 경우에는 경화제와 충분한 가교 반응을 형성하지 못한다.In addition, the epoxy resin and the acrylate monomer are preferably synthesized such that the hydroxyl value (-oH Value) is 20-60. When hydroxy is 60 or more, the molecular weight of the epoxy resin is too small to secure the desired physical properties, and when it is 20 or less, it does not form a sufficient crosslinking reaction with the curing agent.
상기한 바와같은 아크릴 변성 에폭시수지에 수지의 수지의 물성을 개선하기 위해 윤활제, 경화제, 금속염등이 첨가된다.In order to improve the physical properties of the resin of the resin to the acrylic modified epoxy resin as described above, a lubricant, a curing agent, a metal salt is added.
윤활성을 부여하기 위해 수지용액에 윤활제가 첨가된다. 이때 윤활제로는 올레핀계왁스 및 폴리에틸렌계 왁스를 사용하며, 첨가량은 수지고형분 대비 3-25중량%를 사용하는 것이 바람직하다. 윤활제 첨가량이 3중량% 미만인 경우에는 충분한 윤활성을 나타내지 않으며, 25중량%이상인 경우에는 더이상 첨가효과가 나타나지 않으며 오히려 용액 안정성이 저하된다.Lubricant is added to the resin solution to impart lubricity. In this case, as the lubricant, olefin wax and polyethylene wax are used, and the amount of the additive is preferably 3-25% by weight based on the solid resin content. If the amount of lubricant added is less than 3% by weight does not exhibit sufficient lubricity, when more than 25% by weight does not appear any more additive effect and rather the solution stability is lowered.
경화제로는 멜라민(Melamine)수지 혹은 이소시아네이트 수지가 사용되며 이들 각 수지의 첨가량은 상이하지만 아크릴 변성 에폭시수지의 히드록시가에 비례하여 첨가된다. 수지 고형분의 중량을 기준으로 하여, 멜라민 수지는 10-40중량%, 이소시아네이트 수지는 10-50중량%로 사용된다. 경화제의 첨가량이 하한치보다 적은 경우에는 충분히 경화되지 않으며, 상한치 이상인 경우에는 부반응으로 경화제간에 상호결합이 발생되는등 과다한 경화반응이 이루어져 피막이 부서지기 쉽고 강판에 대한 접착력이 충분하지 않아 물성 저하의 원인이 된다.As the curing agent, melamine resin or isocyanate resin is used, and the amount of each of these resins is different but is added in proportion to the hydroxyl value of the acrylic modified epoxy resin. Based on the weight of the resin solids, melamine resin is used at 10-40% by weight, and isocyanate resin is used at 10-50% by weight. If the amount of the curing agent is less than the lower limit, the curing agent is not sufficiently cured. If the amount of the curing agent is higher than the upper limit, excessive curing reaction occurs, such as cross-linking between the curing agents due to side reactions, and thus the film is brittle and the adhesion to the steel sheet is insufficient. do.
또한 금속염을 첨가함으로써 전도성 및 용접성이 개선된다.The addition of metal salts also improves conductivity and weldability.
금속염으로는 코발트 오레이트[Co(C18H33O2)2], 망간 오레이트[Mn(C18H33O2)2] ,및 망간 옥토에이트[Mn(C8H7O2)2]로 부터 선택된 금속염을 1종 혹은 2종 이상 첨가한다. 첨가량은 수지 고형분 대비 0.1-0.5중량%로 첨가하는 것이 바람직하다. 첨가량이 0.1중량%이하인 경우에는 도막의 전도성이 좋지않아 용접성 향상효과를 기대하기 어려우며 금속염 함량 증가에 따라 전도성도 향상되나 5.0중량%이상인 경우에는 수지도막 표면상에 금속이온이 과다하게 분포되어 내식성이 저하된다.Metal salts include cobalt orate [Co (C 18 H 33 O 2 ) 2 ], manganese orate [Mn (C 18 H 33 O 2 ) 2 ], and manganese octoate [Mn (C 8 H 7 O 2 ) 2 Add one or more metal salts selected from]. It is preferable to add the addition amount in 0.1-0.5 weight% with respect to resin solid content. If the added amount is less than 0.1% by weight, the conductivity of the coating film is not good, so it is difficult to expect the effect of improving the weldability.In addition, when the content of the metal salt is increased, the conductivity is also improved. Degrades.
나아가, 상기 수지 용액에 실리카 혹은 크롬화합물을 첨가하여 내식성을 향상시킬수 있다.Further, by adding a silica or chromium compound to the resin solution can be improved corrosion resistance.
내식성 향상제로 실리카를 첨가하는 경우 오르가노졸 실리카(organosol Silica)혹은 실리카 분말을 수지 고형분 대비 10-30중량%가 되도록 첨가한다. 실리카 함량이 10%이하인 경우에는 충분한 내식성 효과를 나타내기 어려우며, 30%이상이에서는 용액의 점도가 상승되고 안정성이 저하되므로 용액 저장성이 급격히 떨어진다.When silica is added as a corrosion resistance improving agent, organosol silica or silica powder is added so as to be 10-30% by weight relative to the resin solids. When the silica content is less than 10%, it is difficult to exhibit a sufficient corrosion resistance effect, and above 30%, the solution storage ability is drastically deteriorated since the viscosity of the solution is increased and the stability is lowered.
크롬 화합물로는 주로 바륨크로메이트(BaCrO4), 스트론튬 크로메이트(SrCrO4), 무수크롬산(CrO3), 혹은 아연 크로메이트(ZnCrO4)를 1종 혹은 2종 혼합하여 사용하며, 그 첨가량은 수지 고형분 대비 0.5-10중량%로 사용하는 것이 바람직하다. 크롬화합물의 함량이 0.5중량% 미만인 경우에는 충분한 내식성 효과를 나타내지 못하며, 10중량%이상인 경우에는 가공성 및 용접성이 저하된다.As the chromium compound, barium chromate (BaCrO 4 ), strontium chromate (SrCrO 4 ), chromic anhydride (CrO 3 ), or zinc chromate (ZnCrO 4 ) is used in one kind or a mixture of two kinds. Preference is given to using 0.5-10% by weight. If the content of the chromium compound is less than 0.5% by weight does not exhibit a sufficient corrosion resistance effect, when more than 10% by weight is reduced workability and weldability.
이하, 본 발명에 의한 아크릴 변성 에폭시수지를 이용하여 크로메이트로 처리된 용융아연도금강판을 처리하는 방법에 대하여 상세히 설명한다.Hereinafter, a method of treating a hot dip galvanized steel sheet treated with chromate using an acrylic modified epoxy resin according to the present invention will be described in detail.
먼저 용융도금 강판상에 도포형 크로메이트 처리를 한 후 상기 본 발명에 의한 수지용액 조성물로 피막처리한다. 상기 크로메이트 처리시 사용되는 크로메이트 용액은 물에 용해된 무수크롬산, 인산 및 기타 첨가제로 구성된 통상의 용액을 사용할수도 있으나, 크로메이트 용액의 물성을 좌우하는 중요한 인자인 크롬환원율(크롬 6가/총크롬)이 0.3-0.7인 용액을 사용하는 것이 바람직하다. 크롬환원비가 0.3이하일 경우에는 도막밀착성 및 도막이 형성되었을 경우 크롬 피막이 강고하지 못하고 크롬이 쉽게 용출되며, 0.7이상인 경우에는 용액 안정성이 저하된다.First, the coated chromate treatment is performed on the hot dip galvanized steel sheet and then coated with the resin solution composition according to the present invention. The chromate solution used in the chromate treatment may be a conventional solution composed of chromic anhydride, phosphoric acid and other additives dissolved in water, but chromium reduction rate (chromium hexavalent / total chromium), which is an important factor influencing the physical properties of the chromate solution It is preferable to use this 0.3-0.7 solution. When the chromium reduction ratio is 0.3 or less, when the film adhesion and the coating film is formed, the chromium film is not firm and the chromium is easily eluted. When the chromium reduction ratio is 0.7 or more, the solution stability is lowered.
상기한 바와같은 크로메이트 용액으로 처리된 용융아연도금강판에 본 발명의 수지 용액 조성물을 건조 도막 두께가 0.5-3.0㎛가 되도록 도포한 후, 강판온도 130-200℃로 소부처리 하는 것이 바람직하다. 건조 도막 두께가 0.5㎛이하인 경우에는 도막두께가 얇아 충분한 물성을 확보하기 어렵고, 3.0㎛ 이상인 경우에는 가공시 수지 도막의 일부가 박리되어 충분한 내식성을 기대하기 어려우므로 건조 도막두께가 0.5-3.0㎛가 되도록 도포하는 것이 바람직하다. 한편 소부온도가 130℃이하인 경우에는 수지가 충분히 경화되지 않으며, 200℃이상인 경우에는 과소부되어 도막의 특성이 저하될 뿐만 아니라 소부형강판(Bae hardening)의 경우 재질이 변화된다.It is preferable to apply the resin solution composition of this invention to the hot-dip galvanized steel plate treated with the chromate solution as mentioned above so that a dry coating film thickness may be set to 0.5-3.0 micrometers, and to carry out baking at the steel plate temperature 130-200 degreeC. If the dry film thickness is 0.5 μm or less, it is difficult to ensure sufficient physical properties due to the thin film thickness. If the dry film thickness is 3.0 μm or more, a part of the resin coating film is peeled off during processing, so that it is difficult to expect sufficient corrosion resistance. It is preferable to apply as much as possible. On the other hand, when the baking temperature is 130 ° C. or less, the resin is not sufficiently cured. When the baking temperature is 200 ° C. or more, the resin is under-baked to reduce the characteristics of the coating film, and the material is changed in the case of Bae hardening.
이하, 본 발명의 실시예에 대하여 상세히 설명한다.Hereinafter, embodiments of the present invention will be described in detail.
[실시예 1]Example 1
수평균 분자량이 4000인 에폭시수지에 메틸이소부틸케톤을 첨가하여 고형분이 20%가 되도록 희석한 후 메틸메타크릴레이트, 알크릴산, 부틸아크릴레이트, 2-히드록시에틸 메타크릴레이트 등 4종의 아크릴 단량체를 적절한 비율로 혼합하여 첨가하였다. 상기 수지용액에 반응개시제 벤조일 퍼옥사이드를 첨가하여 100℃온도에서 2시간 반응시켜 아크릴 변성 에폭시수지를 제조하였다. 이 수지의 히드록시가 (-OH Value)는 40이었다. 여기에 경화제로 멜라민 수지를 주제함량대비 30중량%로 첨가하여 부틸셀로솔브를 첨가하여 수지 고형분이 20%가 되도록 희석하였다.After adding methyl isobutyl ketone to the epoxy resin having a number average molecular weight of 4000 and diluting it to a solid content of 20%, four kinds of methyl methacrylate, acrylic acid, butyl acrylate and 2-hydroxyethyl methacrylate were added. Acrylic monomers were mixed and added in appropriate proportions. Reaction initiator benzoyl peroxide was added to the resin solution and reacted at 100 ° C. for 2 hours to prepare an acrylic modified epoxy resin. The hydroxyl value (-OH Value) of this resin was 40. Melamine resin was added at 30% by weight relative to the main content as a curing agent, and butyl cellosolve was added to dilute the resin solids to 20%.
그후 상기 경화제가 첨가된 아크릴 변성 에폭시 수지에 망간오레이트 금속염, 실리카 및 무수크롬산(CrO3)을 하기표 1에 기재된 함량으로 각각 첨가하여 발명예 1-9및 비교예 1-5를 제조하였다.Then, to the acrylic modified epoxy resin to which the curing agent was added, manganese acrylate metal salt, silica and chromic anhydride (CrO 3 ) were added in the amounts shown in Table 1, respectively, to prepare Inventive Example 1-9 and Comparative Example 1-5.
상기한 바와같이 제조된 각 수지용액을 아연부착량 및 크롬부착량이 각각 60g/㎡, 60㎎/㎡인 크로메이트 처리된 아연 합금용융도금강판(심가공용 소재, DDQ-Deep drawing quality, 0.7t재 사용)에 도포한 후 강판 온도 150℃로 소부한 다음 공냉시켜 건조수지도막 두께가 1㎛인 수지피복강판을 제조하고 다음과 같이 피막 특성을 평하였으며, 그 결과를 하기표 1에 나타냈다.Each resin solution prepared as described above was zinc-plated zinc alloy hot-dip galvanized steel sheet having a zinc deposition amount and chromium deposition amount of 60 g / m 2 and 60 mg / m 2, respectively (for deep processing materials, DDQ-Deep drawing quality, and 0.7t material). After applying to the steel plate temperature baked 150 ℃ and air-cooled to prepare a resin coated steel sheet having a dry resin coating film thickness of 1㎛ and evaluated the film properties as follows, the results are shown in Table 1 below.
[내식성][Corrosion resistance]
내식성 평가는 복합부식시험기를 이용하여 염수분무(16)시간 → 건조(60℃, 4시간) → 습윤상(95% RH, 50℃, 4시간)을 1사이클(총 24시간, 온도 이행시간 포함)로 하여 일정시간 경과에 따른 각 시편의 5%이내의 적청 발생시간을 조사하였다.Corrosion resistance evaluation was performed by using a composite corrosion tester for 1 cycle (24 hours in total, 24 hours in total temperature, saline spray (16) hours → drying (60 ℃, 4 hours) → wet phase (95% RH, 50 ℃, 4 hours) ), The occurrence time of red blue within 5% of each specimen was examined over time.
[연속타점수][Continuous RBI Score]
스폿용접에 의한 연속타점수 평가는 DAIHEN RPA-33A의 공기압축식 용접기로서 가압력 250Kgf용접시간을 15사이클로 20타점마다 40초가 휴지하였으며 100타점 간격으로 용접부의 인장시험을 행하여 JIS Z 3140의 B급 기준이상으로 되는 용접수로 평하였다.Continuous welding score evaluation by spot welding is air compression welding machine of DAIHEN RPA-33A. The pressure of 250Kgf welding time is 40 cycles every 20 cycles for 15 cycles of pressing force. It was flat with welding water which became the above.
상기 표 1로 부터 금속염, 실리카 및 크롬화합물이 본 발명의 조성범위내로 첨가된 경우에는 우수한 내식성 및 용접성을 나타냄을 알 수 있다. 그러나 금속염이 0.1중량% 미만으로 첨가되는 경우에는 충분한 용접성을 나타내지 않으며, 금속염이 40중량%로 다량 첨가시에는 급격한 내식성의 저하를 가져오며, 더이상의 용접성도 향상되지 않는다. 실리카 및 크롬화합물이 첨가되지 않은 경우와 본 발명의 조성범위 미만으로 첨가된 경우에는 내식성 및 용접성이 열화되었고, 실리카가 30중량%이상 첨가된 경우에는 용액중 첨가제간의 상용성이 저하됨으로 용액 안정성이 저하되어 용액이 겔화되었다.It can be seen from Table 1 that the metal salts, silica and chromium compounds exhibited excellent corrosion resistance and weldability when added within the composition range of the present invention. However, when the metal salt is added in less than 0.1% by weight does not exhibit sufficient weldability, when a large amount of the metal salt is added in 40% by weight, a sharp corrosion resistance is lowered, and further weldability is not improved. When silica and chromium compounds are not added and when added below the composition range of the present invention, corrosion resistance and weldability are deteriorated, and when silica is added by 30% by weight or more, compatibility between additives in solution is reduced, resulting in solution stability. Lowered to gel the solution.
[실시예 2]Example 2
실시예 1의 경화제가 첨가된 아크릴 변성 에폭시 수지에 수지 고형분 대비 망간 오레이트 금속염 20중량% 내식성 향상제로 실리카 20%중량 및 무수크롬산 2중량%를 첨가하여 충분히 교반한 후 올레핀계 왁스및 폴리에틸렌계 왁스의 첨가량은 제 1도에 나타낸 바와같이 변화시켜 수지용액을 제조하였다. 이 수지용액을 실시예 1과 같은 조건으로 용융아연 도금강판에 처리하여 윤활제 함량 변화에 따른 윤활성 및 가공성을 평가하여 다음과 같이 평가하고 그 결과를 제 1도 및 제 2도에 각각 나타내었다.20% by weight of a manganese ore metal salt to a resin-modified epoxy resin added to the curing agent of Example 1, 20% by weight of silica and 2% by weight of chromic anhydride as an anticorrosive enhancer, followed by sufficient stirring, followed by olefin wax and polyethylene wax The addition amount of was changed as shown in FIG. 1 to prepare a resin solution. The resin solution was treated on the hot-dip galvanized steel sheet under the same conditions as in Example 1 to evaluate the lubricity and workability according to the change in lubricant content, and evaluated as follows. The results are shown in FIGS. 1 and 2, respectively.
[마찰계수][Friction coefficient]
마찰계수는 드로오비드 테스터(Draw bead Tester)을 사용하여 상온하에서의 동마찰 계수를 측정하였으며 마찰계수가 작을 수록 윤활성이 좋음을 나타낸다.Friction coefficient was measured by the draw bead tester (Draw bead Tester) at room temperature, the coefficient of dynamic friction, the smaller the coefficient of friction shows the better lubricity.
[가공성-블랭크 홀딩포스][Processability-Blank Holding Force]
가공성 평가는 박판 종합시험기기를 사용하여 가공비(Drawing Ratio)1.96으로 컵 성형시 각 시편의 최대 블랭크 홀딩포스(BHF-Blank Holding Force)를 측정하여 평가하였다.Workability evaluation was evaluated by measuring the maximum blank holding force (BHF-Blank Holding Force) of each specimen during cup forming with a drawing ratio of 1.96 using a thin plate comprehensive tester.
제 1도 및 제 2도에 나타낸 바와 같이 윤활제가 첨가되지 않는 경우에는 윤활성 및 가공성이 매우 저조함을 나타냈다. 그러나 윤활제가 25중량%이상 첨가되는 경우 윤활성 및 가공성은 우수한 반면 용액중 첨가제간의 상용성이 떨어져 오히려 용액 안정성이 저하됨을 나타낸다.As shown in FIG. 1 and FIG. 2, when no lubricant was added, the lubricity and the workability were very poor. However, when more than 25% by weight of the lubricant is added, the lubricity and processability is excellent while the compatibility between the additives in the solution indicates that the solution stability is rather deteriorated.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950068489A KR100256326B1 (en) | 1995-12-30 | 1995-12-30 | Steel coating epoxy resin composition and the preparation of its coated steel plate having anticorrosiveness and good weldding property |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950068489A KR100256326B1 (en) | 1995-12-30 | 1995-12-30 | Steel coating epoxy resin composition and the preparation of its coated steel plate having anticorrosiveness and good weldding property |
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| Publication Number | Publication Date |
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| KR970043291A KR970043291A (en) | 1997-07-26 |
| KR100256326B1 true KR100256326B1 (en) | 2000-05-15 |
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| KR1019950068489A KR100256326B1 (en) | 1995-12-30 | 1995-12-30 | Steel coating epoxy resin composition and the preparation of its coated steel plate having anticorrosiveness and good weldding property |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100550788B1 (en) * | 2001-12-22 | 2006-02-08 | 주식회사 포스코 | Preparation and coating method of resin coating solusion with excellent weldability and formability |
| WO2007013761A1 (en) * | 2005-07-25 | 2007-02-01 | Posco | Pre-sealed steel sheet with improved anti- corrosion and weldability and preparing method thereof |
| KR100782763B1 (en) * | 2001-12-24 | 2007-12-05 | 주식회사 포스코 | Resin coating composition for steel sheet with improved high corroision resistance and the coating method using it |
| KR100833055B1 (en) * | 2001-12-24 | 2008-05-27 | 주식회사 포스코 | Preparation and coating method of resin coating solution with excellent corrosion resistance, formability and heat stability |
| KR101461756B1 (en) | 2012-12-26 | 2014-11-13 | 주식회사 포스코 | High-strength galvanized steel sheet having graphene layer and method for mafacturing the same |
-
1995
- 1995-12-30 KR KR1019950068489A patent/KR100256326B1/en not_active IP Right Cessation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100550788B1 (en) * | 2001-12-22 | 2006-02-08 | 주식회사 포스코 | Preparation and coating method of resin coating solusion with excellent weldability and formability |
| KR100782763B1 (en) * | 2001-12-24 | 2007-12-05 | 주식회사 포스코 | Resin coating composition for steel sheet with improved high corroision resistance and the coating method using it |
| KR100833055B1 (en) * | 2001-12-24 | 2008-05-27 | 주식회사 포스코 | Preparation and coating method of resin coating solution with excellent corrosion resistance, formability and heat stability |
| WO2007013761A1 (en) * | 2005-07-25 | 2007-02-01 | Posco | Pre-sealed steel sheet with improved anti- corrosion and weldability and preparing method thereof |
| KR100957941B1 (en) | 2005-07-25 | 2010-05-13 | 주식회사 포스코 | Pre-sealed steel sheet with improved anti-corrosion and weldability and preparing method thereof |
| KR101461756B1 (en) | 2012-12-26 | 2014-11-13 | 주식회사 포스코 | High-strength galvanized steel sheet having graphene layer and method for mafacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR970043291A (en) | 1997-07-26 |
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