KR0122345B1 - Resin solution for surface treatment of steel plate and manufacturing method of steel plate using it - Google Patents

Resin solution for surface treatment of steel plate and manufacturing method of steel plate using it

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Publication number
KR0122345B1
KR0122345B1 KR1019940040100A KR19940040100A KR0122345B1 KR 0122345 B1 KR0122345 B1 KR 0122345B1 KR 1019940040100 A KR1019940040100 A KR 1019940040100A KR 19940040100 A KR19940040100 A KR 19940040100A KR 0122345 B1 KR0122345 B1 KR 0122345B1
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South Korea
Prior art keywords
resin
weight
type
epoxy
resin solution
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KR1019940040100A
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Korean (ko)
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KR960023251A (en
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박찬섭
정용균
노상걸
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김만제
포항종합제철주식회사
신창식
재단법인 산업과학기술연구소
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Priority to KR1019940040100A priority Critical patent/KR0122345B1/en
Publication of KR960023251A publication Critical patent/KR960023251A/en
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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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • 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
    • 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
    • B05D7/24—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 for applying particular liquids or other fluent materials
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/65—Additives macromolecular

Abstract

The surface treated steel plates used for appliance, automobile and the like are made by using the resin solution of excellent lubricant and weldability prepared by adding paraffin type wax, metal salt and amino resin type curer into thermosetting water soluble epoxy type resin. The surface treated steel plates having dry coating thickness of 0.5-4.0 micrometer, are prepared by coating the chromate treated surface treated steel plates with resin solution comprising 3-25 wt% of lubricant such as paraffin type wax, olefin type wax and the like, 0.5-10 wt% of metal salt such as nickel, copper, magnesium and the like masked with citric acid, and 4-35 wt% of amino resin type curer, isocyan type curer and the like with respect to 100 weight part of thermosetting water soluble epoxy type resin such as epoxy graft acrylate and so on which the weight ration of epoxy region and acrylic region of 1:1.5, and annealing at 140-200 deg.C.

Description

윤활성 및 용접성이 우수한 표면처리강판용 수지용액 및 이를 이용한 표면처리강판의 제조방법Resin solution for surface-treated steel sheet with excellent lubricity and weldability, and method for producing surface-treated steel sheet using the same

제1도는 발명용액을 도포한 표면처리강판의 피막두께에 따른 품질특성의 변화를 나타내는 그래프.1 is a graph showing a change in quality characteristics according to the film thickness of the surface-treated steel sheet coated with the invention solution.

본 발명은 가전, 건재 또는 자동차등에 사용되는 표면처리강판에 도포되는 수지용액 및 이 수지용액을 이용한 표면처리강판의 제조방법에 관한 것으로서, 보다 상세하게는 강판을 프레스 가공시 윤활성을 부여하고 또한 용접시 강판의 용접성이 우수하도록 하는 수지용액 및 이 수지용액을 도포하여 표면처리강판을 제조하는 방법에 관한 것이다.The present invention relates to a resin solution applied to a surface-treated steel sheet used in home appliances, building materials, or automobiles, and to a method for producing a surface-treated steel sheet using the resin solution. The present invention relates to a resin solution for excellent weldability of steel sheets and a method for producing a surface-treated steel sheet by applying the resin solution.

최근 가전, 건재, 자동차 등의 내식성이 요구되는 용도에 많이 사용되고 있는 아연 또는 아연합금계 전기도금강판은 일정기간 유통 및 보관중에 녹발생 방지를 억제하기 위해 통상 방청유를 도포하여 코일 또는 강판상태로 출하되고 수요가의 가공공정을 거치게 된다. 이때, 수요가 가공공정중에 프레스가공시 크랙발생을 방지하고 가공성을 높이기 위하여 고점도의 가공유(윤활유)를 사용하게 되는데, 도유작업시 가공유 비산에 의한 작업환경의 문제점, 차공정인 탈지시 탈지불량에 의한 화성처리성 저하 및 도장불량등의 발생소지가 있고, 특히, 탈지에 사용되는 유기용제는 작업장의 환경오염뿐 아니라 대기 오존층 파괴라는 환경문제를 야기시키는 원인이 되고 있다.Recently, zinc or zinc alloy-based electroplating steel sheets, which are widely used for applications requiring corrosion resistance of home appliances, building materials, automobiles, etc., are usually shipped in a coil or steel sheet state by applying anti-rust oil to prevent rust generation during distribution and storage for a period of time. It goes through the processing of the demand price. At this time, high demand processing oil (lubricating oil) is used to prevent cracking during press processing and increase workability during the processing process.In case of oiling work, there is a problem of working environment due to scattering of processing oil and degreasing failure during degreasing. There is a possibility of deterioration of chemical conversion treatment and poor coating, and in particular, the organic solvents used for degreasing cause environmental problems such as environmental pollution of the workplace as well as destruction of the atmospheric ozone layer.

한편, 이러한 문제점을 해결하기 위하여 종래에는 수지용액 자체에 윤활특성을 부여하여 프레스가공성을 높이는 방법들을 개발하였는데, 예를 들면, 일본 특개평 5-138120호에 제시된 바에 의하면 열경화성 용제계 수지를 골격으로 하는 윤활용액으로 처리된 아연도금강판에 제조방법이 제안되어 있다. 이외에도 일본 특개평 4-130189, 평 4-44840, 평 3-71836 및 3-16726호등에 제시된 바에 의하면 강판의 윤활특성을 부여하기 위한 윤활용액이 제안되어 있다.Meanwhile, in order to solve such a problem, conventionally, methods for improving press workability by imparting lubrication characteristics to the resin solution itself have been developed. For example, as disclosed in Japanese Patent Application Laid-Open No. 5-138120, the thermosetting solvent-based resin is used as a skeleton. A manufacturing method has been proposed for a galvanized steel sheet treated with a lubricating solution. In addition, Japanese Patent Laid-Open Nos. 4-130189, 4-44840, 3-71836, and 3-16726 have proposed lubricating solutions for imparting lubricating properties of steel sheets.

그런, 상기 방법들은 용제계 수지 또는 범용의 수지들을 사용함에 따라 첨가제와의 상용성 뿐만 아니라 화재위험성, 작업환경의 열화 및 용제휘발에 따른 공해문제를 여전히 감소시킬 수 없는 단점이 있다.Such methods, however, have disadvantages that the use of solvent-based resins or general-purpose resins can still reduce the pollution problem due to fire hazard, deterioration of working environment and solvent volatilization as well as compatibility with additives.

따라서, 본 발명은 이와같은 문제점을 해결하기 위해 제안된 것으로 강판에 윤활성이 우수한 수용성 수지를 도포하므로서, 수요가 가공시 가공유의 사용이 필요치 않아 탈지공정의 생략을 가능케하고 제품의 용접시 용접성이 우수하도록 하는 수지용액 및 이를 이용한 표면 처리강판의 제조방법을 제공하고자 하는데, 그 목적이 있다.Therefore, the present invention has been proposed to solve such a problem and by applying a water-soluble resin having excellent lubricity to the steel sheet, the demand does not require the use of processing oil during processing, it is possible to omit the degreasing process and excellent weldability when welding the product It is to provide a resin solution and a method for producing a surface-treated steel sheet using the same, the purpose of which is to.

이하, 본 발명을 설명한다.Hereinafter, the present invention will be described.

본 발명은, 열경화성 수용성 에폭시계 수지고형분 100중량부를 기준으로 파라핀계 왁스 올레핀계 왁스 및 폴리에틸렌계 왁스중에서 선택된 1종 또는 2종 이상의 윤활제 : 3-25중량부; 1종 또는 2종 이상의 금속염; 0.5-10중량부; 및 아미노수지계, 이소시안계 및 요소수지계 중에서 선택된 1종의 경화제; 4-35중량부를 포함하여 조성되는 윤활성 및 용접성이 우수한 표면처리강판용 수지용액에 관한 것이다.One or two or more lubricants selected from paraffin wax olefin wax and polyethylene wax based on 100 parts by weight of thermosetting water-soluble epoxy resin solid content: 3-25 parts by weight; One or two or more metal salts; 0.5-10 parts by weight; And one kind of curing agent selected from amino resins, isocyanates and urea resins; It relates to a resin solution for a surface-treated steel sheet excellent in lubricity and weldability, including 4-35 parts by weight.

또한, 본 발명은 상기 수지용액을 강판에 도포한 후, 140-200℃의 온도에서 소부(baking)하여 건조피막 두께가 0.5∼4.0㎛가 되도록 하는 윤활성 및 용접성이 우수한 표면처리강판의 제조방법에 관한 것이다.In addition, the present invention is a method for producing a surface-treated steel sheet excellent in lubricity and weldability after applying the resin solution to a steel sheet, baking at a temperature of 140-200 ℃ to dry film thickness of 0.5 ~ 4.0㎛ It is about.

이하, 본 발명에 따른 수지용액에 대하여 상세히 설명한다.Hereinafter, the resin solution according to the present invention will be described in detail.

본 발명에서 사용되는 수지는 열경화성 수성 에폭시계 수지로 바람직하게는 에폭시 그라프트 아크릴레이트이고, 그 수지구성은 에폭시부와 아클리부가 중량비로 1 : 1-5인 것을 사용한다. 이때, 주쇄를 이루는 에폭시는 분자량이 1000-5000인 비스페놀형을 사용함이 바람직하며, 아크릴부는 아크릴산, 메틸메타크릴레이트, 2-하이드록시에틸메타크릴레이트, 에틸라크릴레이트, 에틸메타크릴레이트, 스티렌을 2종 또는 그 이상의 조합으로 구성된 것을 사용한다. 또한 중합개시제로는 벤조일퍼옥사이드를 적량 사용한다.The resin used in the present invention is a thermosetting water-based epoxy resin, preferably epoxy graft acrylate, and the resin composition is one in which the epoxy portion and the acli portion are 1: 1 by weight. At this time, the epoxy forming the main chain is preferably a bisphenol type having a molecular weight of 1000-5000, the acrylic portion acrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, ethyl acrylate, ethyl methacrylate, styrene Is used consisting of two or more combinations. In addition, a suitable amount of benzoyl peroxide is used as the polymerization initiator.

만일 열경화성 수성 에폭시 그라프트 아크릴레이트 수지합성에 사용되는 에폭시 올리고머의 분자량이 1000 이하일 경우와 아크릴부가 에폭시부 1에 대해 5 이상일 경우는 수지피막의 경도가 너무 높아 피막이 쉽게 부서지는 단점이 있고, 에폭시 분자량이 5000 이상일 경우와 아크릴부가 1 이하의 작은 범위에서는 수용화가 용이치 못한 단점이 발생됨으로 에폭시올리고머는 분자량이 1000-5000 미만의 것을 사용하며, 에폭시부와 아크릴부의 비가 1 : 1-5를 유지하는 것이 바람직하다.If the molecular weight of the epoxy oligomer used for thermosetting aqueous epoxy graft acrylate resin synthesis is 1000 or less and the acrylic part is 5 or more with respect to epoxy part 1, the hardness of the resin film is too high and the film easily breaks. The epoxy oligomer uses a molecular weight of less than 1000-5000, and the ratio of the epoxy part and the acryl part is maintained at 1: 1-5 because the disadvantage of insolubility is not easily generated when the acryl part is less than 1 and in the small range of 1 or less. It is preferable.

상기 수지합성시의 용제는 합성반응물의 고형비가 55-65wt% 정도를 유지하도록 가능한 적은 량을 사용하는데, 사용되는 주용제는 메틸에틸케톤, 에틸셀로솔브, 부틸셀로솔브, 메틸이소부틸케톤 등으로 1종 또는 혼합사용한다. 그러나 이 반응생성물 그 자체로서는 수용화가 불가함으로 다음과정으로 수용화를 위한 중화단계를 거치게 되는데, 디메틸에탄올아민, 트리에틸아민, 암모니아수등의 중화제를 용액내에 첨가한다. 중화반응 완료후 반응생성물을 순수로 희석하여 수지고형분이 10-35wt%인 수지용액을 제조한다. 이때, 수지고형분이 10wt% 미만일 경우는 첨가제와의 상용성 및 용액안정성이 저하되고, 35wt% 이상일 경우는 수시합성시 잔존하는 용제함량의 비중이 상대적으로 증가하게 됨으로 수용화의 의미가 미흡해지기 때문에 가급적 35wt% 이상은 사용을 배제하는 것이 바람직하다.In the resin synthesis, a small amount of the solvent used to maintain the solid ratio of the synthetic reactant is about 55-65 wt%, and the main solvent used is methyl ethyl ketone, ethyl cellosolve, butyl cellosolve, and methyl isobutyl ketone. 1 type or mixed use. However, since the reaction product itself is not solvable, a neutralization step for solubilization is carried out in the following process. Neutralizing agents such as dimethylethanolamine, triethylamine, and ammonia water are added to the solution. After completion of the neutralization reaction, the reaction product is diluted with pure water to prepare a resin solution having a resin solid content of 10-35wt%. At this time, if the resin solid content is less than 10wt%, compatibility with the additives and solution stability are lowered, and if it is 35wt% or more, the specific solvent content remaining at the time of synthesis is relatively increased, so the meaning of solubilization becomes insufficient. For this reason, it is desirable to exclude the use of more than 35wt%.

한편, 수지용액내 경화제 첨가이전에 자기 윤활성을 보유할 수 있도록 상기 수성 수지용액에 윤활제를 1종 또는 2종 이상 혼합첨가하는데, 이때 사용되는 윤활제는 파라핀계 왁스(융점 55-70℃), 올레핀계 왁스(융점 75-110℃), 폴리에틸렌계 왁스(융점 100-125℃)등을 들 수 있으며, 윤활제 첨가량은 상기 수지고형분 대비 3-25중량부를 사용함이 바람직하다. 만일 윤활제 첨가량이 수지고형분에 대해 3중량부 미만의 경우에는 충분한 윤활작용이 발휘되지 않고, 25중량부 이상의 첨가범위에서는 윤활성능이 그 이상 발휘되지 못할 뿐더러 윤활수지피복강판의 요구성능이 오히려 저하되고 용액안정성이 떨어지는 등의 문제점이 나타나게 된다.Meanwhile, one or two or more lubricants are added to the aqueous resin solution to maintain self-lubrication prior to addition of the curing agent in the resin solution. The lubricant used here is paraffin wax (melting point 55-70 ° C.), olefin. And waxes (melting point 75-110 ° C.), polyethylene waxes (melting point 100-125 ° C.), and the like. The amount of lubricant added is preferably 3 to 25 parts by weight relative to the resin solid content. If the amount of lubricant added is less than 3 parts by weight with respect to the resin solid content, sufficient lubrication is not exerted, and in the range of 25 parts by weight or more, the lubrication performance is not exhibited any more, and the required performance of the lubrication resin coated sheet is rather deteriorated. Problems such as poor solution stability will appear.

또한, 수지도포에 따른 용접성 저하를 막기 위해 수지내에 금속염을 1종 내지 2종 이상 혼합 첨가하는데, 이때 사용되는 금속염은 니켈, 구리, 망간, 마그네슘염등을 들 수 있다. 그리고, 상기 금속염은 수지고형분 대비 0.5-10중량부 첨가하는 것이 바람직한데, 그 이유는 금속염 첨가량이 0.5중량부 이하일 경우 용접성 향상 효과가 나타나지 않고, 10중량부 이상일 경우 용액의 안정성이 저하하고 용접성에 대한 더 이상의 효과가 기대되지 않기 때문이다. 또한, 상기 금속염은 수지내에 곧 바로 넣을 경우 침전이 형성되므로 사전에 시트릭산으로 마스킹 해 주는 것이 바람직하다.In addition, in order to prevent a decrease in weldability due to resin coating, a metal salt is added to the resin in one or two or more kinds, and the metal salts used herein include nickel, copper, manganese and magnesium salts. In addition, the metal salt is preferably added 0.5-10 parts by weight relative to the resin solid content, the reason is that when the addition amount of the metal salt is 0.5 parts by weight or less does not appear to improve the weldability, when more than 10 parts by weight of the solution stability and weldability This is because no further effect is expected. In addition, the metal salt is preferably masked with citric acid in advance because precipitation is formed when directly put into the resin.

마지막으로 본 발명 수지용액은 열에 의한 경화반응이 수행되도록 경화제를 첨가하는데, 이때 사용되는 경화제는 아미노수지계, 이소시안계, 요소수지계등으로 이루어진 그룹중에서 선택된 1종을 사용할 수 있고, 경화제 종류 및 첨가량은 윤활피복 강판의 요구물성에 따라 상이할 수 있으나, 사용량의 범위는 상기 수지 고형분에 대해 4-35중량부 정도가 바람직하다.Finally, the resin solution of the present invention adds a curing agent to perform a curing reaction by heat, wherein the curing agent used may be one selected from the group consisting of amino resins, isocyanates, urea resins, etc. The silver may vary depending on the required physical properties of the coated steel sheet, but the amount of the used amount is preferably about 4-35 parts by weight based on the resin solid content.

만일, 경화제함량이 수지고형분에 대비 4중량부 미만일 경우에는 충분한 경화가 수행되지 않고, 35중량부 이상일 경우에서는 부반응으로 경화제가 상호결합이 발생되는 등 과다한 경화반응이 이루어져 피막이 부서지기 쉽고 강판에의 접착력이 충분하지 않아 물성저하의 원인이 된다.If the amount of the curing agent is less than 4 parts by weight relative to the resin solid content, sufficient curing is not performed. If the amount of the curing agent is 35 parts by weight or more, an excessive curing reaction occurs, such as cross-linking of the curing agent due to side reaction. Insufficient adhesive force may cause property deterioration.

이하, 본 발명에 따른 수지용액을 이용한 표면처리강판의 제조방법에 대하여 상세히 설명한다.Hereinafter, the manufacturing method of the surface-treated steel sheet using the resin solution according to the present invention will be described in detail.

상기와 같이 제조된 수지용액은 통상적으로 크로메이트 처리된 표면처리강판위에 도포하여 표면처리 강판을 제조하게 되는데, 이때, 140-200℃ 온도범위에서 소부시키고, 도막두께는 건조후 피막두께 0.5-4.0㎛로 하는 것이 바람직하다.The resin solution prepared as described above is typically coated on a chromate-treated surface treated steel sheet to produce a surface treated steel sheet. At this time, the plate is baked at a temperature range of 140-200 ° C., and the film thickness is 0.5-4.0 μm after drying. It is preferable to set it as.

만일 상기 수지용액을 강판에 도포 후 140℃ 이하에서 소부하는 경우 수지의 경화반응이 충분히 일어나지 않아 도막의 물성저하가 일어나며, 200℃ 이상에서는 과소부되어 피막의 박리원인이 될 가능성이 커지므로 소부온도는 140-200℃로 관리되는 것이 바람직하다.If the resin solution is baked on a steel sheet at 140 ° C. or lower, the hardening reaction of the resin does not occur sufficiently, resulting in deterioration of the physical properties of the coating film. Is preferably managed at 140-200 ° C.

그리고, 소부후 건조피막두께는 0.5㎛ 이하로 관리될 경우, 가공성이 크게 저하되어 아연계 도금강판의 경우 흑연발생원인으로 작용하며, 4㎛ 이상의 경우 용접성의 저하를 가져오므로 도막두께는 0.5-4.0㎛이내로 관리하는 것이 바람직하다.In addition, if the dry film thickness after baking is controlled to 0.5 μm or less, the workability is greatly reduced, which causes graphite generation in the case of zinc-based galvanized steel sheet. It is preferable to manage within 4.0 micrometers.

이하, 본 발명을 실시예를 통하여 구체적으로 설명한다.Hereinafter, the present invention will be described in detail through examples.

(실시예 1)(Example 1)

하기 표 1과 같은 조성을 갖도록 에폭시그라프트 아크릴레이트 수지에 주화제로는 아미노수지계인 싸이멜 385를 윤활제로는 올레핀 왁스와 폴리에틸렌 왁스를 첨가하고, 교반을 충분히 행한 후 시트락산으로 마스킹된 니켈 설페이트 용액을 첨가하여 수지용액을 제조하였다.In order to have a composition as shown in Table 1 below, the epoxy resin acrylate resin was added to Cymel 385, which is an amino resin-based main agent, to an olefin wax and polyethylene wax as a lubricant, and sufficiently stirred. It was added to prepare a resin solution.

이후, 크롬부착량 40mg/m2, 아연도금부착량 20.20g/m2, 두께 0.8mm의 크로메이트 처리된 전기아연도금 강판을 소지강판으로 하여, 상기 강판에 상기 제조된 수지용액을 롤 코터를 이용하여 도포한 다음, 가열건조로에서 하기 표 1과 같은 소부온도로 소부를 행하여 건조피막 두께를 1.2㎛로 제조하였으며 표면처리된 강판에 대하여 품질특성을 평가하고 그 결과를 하기 표 1에 나타내었다.Thereafter, a chromium deposition amount of 40 mg / m 2 , a zinc plating amount of 20.20 g / m 2 , and a chromate-treated electrogalvanized steel sheet having a thickness of 0.8 mm were used as steel plates, and the resin solution prepared above was applied to the steel sheet using a roll coater. Then, the baking was carried out at a baking temperature as shown in Table 1 in a heating drying furnace to prepare a dry film thickness of 1.2 μm.

상기 강판의 품질 특성평가중 마찰계수는 드로오비드 테스틱(Drawbead Tester)에 의한 상온하에서의 동마찰계수를 측정하였는데, 이때 마찰계수는 수치가 작을 수록 윤활성이 우수한 값을 나타내게 된다. 아래의 수치기준으로 특성을 비교하였다.Friction coefficient of the quality characteristics of the steel sheet was measured by the dynamic friction coefficient at room temperature by the Drawbead Tester (Drawbead Tester), wherein the smaller the friction coefficient is the better the lubricity shows. The characteristics were compared based on the following numerical criteria.

또한 가공성 평가는 박판 종합시험기기로서 가공비(Drawing Ratio)1.96으로 컵성형시 각 시편의 최대 블랭크 홀딩코스(BHF-Blank Holding Force)를 측정하여 다음과 같이 평가하였다.In addition, the workability evaluation was evaluated by measuring the maximum blank holding force (BHF-Blank Holding Force) of each specimen when forming cups with a drawing ratio of 1.96 as a comprehensive sheet tester.

그리고, 용접성 평가는 공압식 교류 스폿용접기를 이용하여 연속타점수를 측정하였는데, 이때 용접전극은 Cu-Cr계 합금의 캡형으로 가압력을 250kgf, 초기가압을 20싸이클, 통전시간을 15싸이클의 조건으로 시험을 실시하여 용접부의 인장시험을 행하여 적정기준치 이내의 값을 확보하는 연속타점수를 아래의 기준에 의해 비교하였다.In addition, the weldability was measured by using a pneumatic AC spot welder. The welding electrode was a cap of Cu-Cr alloy, and the test was performed under conditions of 250 kgf pressing force, 20 cycles of initial pressure, and 15 cycles of energization time. Tensile scores were obtained by conducting a tensile test of the welded portion and securing a value within an appropriate standard value according to the following criteria.

[표 1]TABLE 1

＊ 윤활제 및 금속염은 수지고형분 대비 중량부＊ Lubricants and metal salts by weight relative to the resin solids

상기 표 1에 나타난 바와같이, 윤활제의 첨가량이 수지고형분 대비 3% 미만인 경우(비교예 1)윤활제의 첨가효과가 거의 나타나지 않고, 과량으로 첨가시(비교예 2)는 윤활성능의 효과는 있으나 용접성의 저하 및 용액안정성의 저하를 가져오게 됨을 알 수 있다. 또한 금속염의 경우 0.3%의 미량 첨가시(비교예 3) 용접성의 확보가 불가한 것으로 나타났으며, 과량으로 첨가시(비교예 4) 용접성은 우수하나 용액의 안정성이 저하되어 슬러지등이 생기게 되는 단점이 나타나게 되어 실사용시 제약을 받게 된다. 한편, 소부온도의 경우 저온으로 처리시(비교예 5) 수지의 충분한 경화가 일어나지 않아 가공성이 저하되는 현상을 보이며 고온으로 처리(비교예 6)에는 가공시 일부피막이 박리되는 현상이 나타나게 됨을 알 수 있다.As shown in Table 1, when the amount of the lubricant is less than 3% of the solid content (Comparative Example 1), the effect of adding the lubricant is hardly seen, and when added in excess (Comparative Example 2), there is an effect of lubricating performance, but weldability It can be seen that this results in lowering of the solution stability and lowering of solution stability. In addition, when 0.3% of the metal salt was added (Comparative Example 3), it was impossible to secure weldability, and when it was added in excess (Comparative Example 4), the weldability was excellent, but the stability of the solution decreased, resulting in sludge. Disadvantages appear and are constrained in practical use. On the other hand, in the case of baking temperature, when processing at low temperature (Comparative Example 5), there was a phenomenon that the workability was deteriorated due to insufficient curing of the resin. have.

이에 반하여, 본 발명의 조건범위를 만족하는 용액을 사용하여 적정 소부온도로 처리된 경우(발명예 1-9)에는, 윤활성 뿐만아니라 용접성이 우수함을 알 수 있다.On the contrary, when treated at the appropriate baking temperature using a solution that satisfies the condition range of the present invention (Invention Example 1-9), it can be seen that not only lubricity but also weldability are excellent.

(실시예 2)(Example 2)

수지부착량에 따른 가공성 및 용접성을 살펴보기 위하여 실시예 1의 발명예(6)과 같은 조건으로 하되, 피막두께를 0.5-5㎛로 변화시키면서 표면처리강판을 제조하고, 상기 강판에 대하여 가공성 및 용접성을 평가하여 그 결과를 제1도에 나타내었다.In order to examine the processability and weldability according to the resin deposition amount, the same conditions as in Example (6) of Example 1 were made, but the surface-treated steel sheet was manufactured while changing the film thickness to 0.5-5 μm. Was evaluated and the result is shown in FIG.

제1도에 나타난 바와같이, 수지피막부착량이 0.5㎛ 이하인 경우 가공성의 저하와 함께 흑변이 발생하여 표면외관이 불량한 것으로 나타났으며, 부착량이 5㎛의 후막일 경우 수지피막의 영향으로 용접성이 일부 저하되는 경향이 나타나게 된다.As shown in FIG. 1, when the amount of resin coating was 0.5 μm or less, blackness occurred along with deterioration of workability, resulting in poor surface appearance. When the thickness was 5 μm, the weldability was partially affected by the resin coating. A tendency to deteriorate.

반면에, 본 발명의 조건범위인 0.5-4.0㎛의 피막두께를 갖는 경우에는 용접성 및 가공성이 양호하게 나타남을 알 수 있다.On the other hand, in the case of having a film thickness of 0.5-4.0 μm, which is the condition range of the present invention, it can be seen that weldability and workability are excellent.

상술한 바와같이, 본 발명은 강판을 가공시 윤활성이 우수하도록 수용성 수지에 윤활제를 첨가하고 용접 사용시 용접성이 우수하도록 금속염을 첨가하므로서, 이 수지 용액을 크로메이트 강판에 도포하여 제조된 표면처리강판의 프레스가공성 및 용접성을 향상시킬 뿐만아니라 가공유 사용이 필요치 않아 탈지공정이 생략될 수 있고, 또한 환경오염문제를 개선할 수 있는 효과가 있다.As described above, the present invention is a press of the surface-treated steel sheet produced by applying a lubricant to the chromate steel sheet by adding a lubricant to the water-soluble resin so as to have excellent lubricity when processing the steel sheet and a metal salt so as to have excellent weldability when using the welding. In addition to improving workability and weldability, the use of processing oil is not required, so that the degreasing process can be omitted, and the environmental pollution problem can be improved.

Claims (3)

열경화성 수용성 에폭시계 수지고형분 100중량부를 기준으로 파라핀계 왁스, 올레핀계 왁스 및 폴리에틸렌계 왁스 중에서 선택된 1종 또는 2종 이상의 윤활제; 3-25중량부; 니켈, 구리, 망간, 마그네슘염에서 선택된 1가지 이상의 금속염으로써 시트르산으로 마스킹된 금속염 : 0.5-10중량부; 및 아미노수지계, 이소시안계 및 요소수지계중에서 선택된 1종의 경화제 : 4-35중량부를 포함하여 조성됨을 특징으로 하는 윤활성 및 용접성이 우수한 표면처리강판용 수지용액.One or two or more lubricants selected from paraffin waxes, olefin waxes and polyethylene waxes based on 100 parts by weight of the thermosetting water-soluble epoxy resin solid content; 3-25 parts by weight; Metal salt masked with citric acid with at least one metal salt selected from nickel, copper, manganese and magnesium salts: 0.5-10 parts by weight; And one type of curing agent selected from amino resins, isocyanates and urea resins: 4-35 parts by weight of the resin solution having excellent lubricity and weldability. 제1항에 있어서, 상기 열경화성 수용성 에폭시계 수지는 수용성 에폭시 그라프트 아크릴레이트이고, 그 수지의 에폭시부와 아크릴부가 중량비로 1 : 1-5가 되도록 구성되고, 상기 에폭시는 분자량이 1000-5000인 비스페놀형임을 특징으로 하는 수지용액.The method of claim 1, wherein the thermosetting water-soluble epoxy resin is a water-soluble epoxy graft acrylate, the epoxy portion and the acrylic portion of the resin is configured to be 1: 1-5 by weight ratio, the epoxy has a molecular weight of 1000-5000 Resin solution characterized in that the bisphenol type. 특허청구 제1항의 용액을 강판에 도포한 후, 140-200℃의 온도에서 소부하여 건조피막 두께가 0.5-4.0㎛가 되도록 함을 포함하여 구성됨을 특징으로 하는 윤활성 및 용접성이 우수한 표면처리강판의 제조방법.After applying the solution of claim 1 to the steel sheet, it is baked at a temperature of 140-200 ℃ to dry film thickness of 0.5-4.0㎛ comprising a surface treated steel sheet having excellent lubricity and weldability Manufacturing method.
KR1019940040100A 1994-12-30 1994-12-30 Resin solution for surface treatment of steel plate and manufacturing method of steel plate using it KR0122345B1 (en)

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