KR100262494B1 - The preparation of lubricating resin solution having high surface lubricating , non-corrosiveness, and good coating properties and the preparation method of surface treatment of steel plate by using thereof - Google Patents

The preparation of lubricating resin solution having high surface lubricating , non-corrosiveness, and good coating properties and the preparation method of surface treatment of steel plate by using thereof Download PDF

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KR100262494B1
KR100262494B1 KR1019950066223A KR19950066223A KR100262494B1 KR 100262494 B1 KR100262494 B1 KR 100262494B1 KR 1019950066223 A KR1019950066223 A KR 1019950066223A KR 19950066223 A KR19950066223 A KR 19950066223A KR 100262494 B1 KR100262494 B1 KR 100262494B1
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resin
weight
parts
lubricating
epoxy
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KR1019950066223A
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Korean (ko)
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KR970043285A (en
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정용균
박찬섭
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이구택
포항종합제철주식회사
신현준
재단법인포항산업과학연구원
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • 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
    • 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
    • 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
    • C09D7/20—Diluents or solvents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

PURPOSE: A process for preparing thermosetting aqueous lubricating resin is provided for accomplishing excellent surface lubricating ability, corrosion-resistance and painting ability by preparing the aqueous epoxy-graft acrylate resin by means of radical polymerization of epoxy portion and acrylic portion in a weight ratio of 1:1-5. CONSTITUTION: The process comprises the first step of preparing the aqueous epoxy-graft acrylate resin by means of radical polymerization of epoxy portion and acrylic portion in a weight ratio of 1:1-5; the second step of neutralizing the resin with the specific neutralizing agent; the third step of diluting the solution with water to have 10-35 wt.% of solid content; the fourth step of adding 5-25 weight parts of the lubricating agent, 10-80 weight parts of silica, 0.05-2 weight parts of silane coupling agent and 4-35 weight parts of hardening agent to the resultant solution based on total 100 weight parts of resin solid content.

Description

표면윤활성, 내식성및 도장성이 우수한 열경화성 수성 윤활수지용액 제조방법 및 이를 이용한 강판 표면 처리방법Method for preparing thermosetting aqueous lubricating resin solution excellent in surface lubricity, corrosion resistance and paintability and method for surface treatment of steel sheet using the same

제1도는 실리카 첨가량과 내식성과의 관계를 나타내는 그래프.1 is a graph showing the relationship between silica addition amount and corrosion resistance.

제2도는 실리카첨가량과 도장성과의 관계를 나타내는 그래프.2 is a graph showing the relationship between silica addition amount and paintability.

본발명은 강판에 대한 표면윤활성, 내식성 및 도장성이 우수한 열경화성 수성 윤활수시지용액 제조 방법 및 이를 이용한 강판 표면처리방법에 관한 것이다.The present invention relates to a method for preparing a thermosetting aqueous lubricating resin solution having excellent surface lubricity, corrosion resistance and paintability to a steel sheet and a method for treating the surface of a steel sheet using the same.

일반적으로 가전, 건재, 자동차등 내식성이 요구되는 용도에 많이 사용되고 있는 아연 또는 아연 합금계 전기도금강판은 통상 방청유를 도포하여 코일 또는 강판상태로 출하된 후 수요자에 의해 가공된다. 이와같은 강판은 가공공정중, 프레스가 공시 크랙발생을 방지하고 가공성을 높이기 위해 고점도의 가공유(윤활유)가 사용된다. 그러나 도유작업시 가공유 비산에 의한 작업환경 문제, 차공정인 탈지시 탈지불량에 의한 화성처리성 저하 및 도장불량등이 발생할 소지가 있으며, 특히, 탈지에 사용되는 유기용제는 작업장의 환경오염뿐 아니라 대기 오존층파괴라는 환경문제를 야기시키는 원인이 되고 있어 이미 선진국에서는 생산공정중에 유기용제를 사용한 제품에 대한 규제가 시작되었고 일본에서도 '95년 이후 전면 생산을 금지하도록 되어 있는 실정에 있다.In general, zinc or zinc alloy-based electroplating steel sheet, which is widely used for applications requiring corrosion resistance such as home appliances, building materials, and automobiles, is usually processed by a consumer after being shipped in a coil or steel sheet by applying antirust oil. Such steel sheet is used in the processing process, high-viscosity processing oil (lubricating oil) in order to prevent the occurrence of cracks in the press and increase the workability. However, there is a possibility of working environment problem caused by scattering of processing oil during oiling work, deterioration of chemical conversion treatment due to poor degreasing, and poor coating.In particular, organic solvents used for degreasing are not only environmental pollution in the workplace. As it causes environmental problems such as the destruction of the atmospheric ozone layer, advanced countries have already begun to regulate products using organic solvents in the production process, and Japan has banned all production since '95.

일본 특허공개공보 평 5-138120에는 용제계수지를 사용함에 따라 수성수지에 비하여 윤활제 및 방청제등 첨가제와의 상용성 및 용액 안정성이 우수한 열경화성 용제계수지를 골격으로 하는 윤활용액으로 처리된 아연도금강판이 개시되어 있다. 이외에도 일본 특허공개공보 평4-130189, 평 4-44840, 평 3-71836, 평 3-16726등에는 강판에 윤활특성을 부여하기 위한 윤활용액이 제시되어 있다.Japanese Patent Application Laid-Open No. 5-138120 discloses a zinc-plated steel sheet treated with a lubricating solution having a thermosetting solvent-based resin having excellent compatibility and solution stability with additives such as lubricants and rust-preventing agents compared to aqueous resins. It is. In addition, Japanese Patent Application Laid-Open Nos. 4-130189, 4-44840, 3-71836, and 3-16726 disclose lubricating solutions for imparting lubricating properties to steel sheets.

그러나, 상기 방법들중 일본 특허공개공보 평 5-138120과 같이 용제계수지를 사용하는 경우, 용제를 사용함으로써 화재위험성, 작업환경의 열화 및 용제 휘발에 따른 공해문제를 여전히 제거할수 없는 것이다. 또한 기타 여러 공지기술에서는 사용된 수지를 명기함에 있어서 용제계인지 수성계인지를 분명히 명기하지 않고 범용수지들의 명칭만을 나열하고 있음으로, 같은 명칭의 수지로서 용제계로 하는것과 수성으로 하는 것에는 첨가제와의 상용성 뿐아니라 수지자체의 물성차이가 현저함은 잘 알려진 사실임으로, 윤활강판에 대한 전체적인 특성을 예측하기 또한 곤란한것입나다.However, in the case of using a solvent-based resin as in Japanese Patent Application Laid-open No. Hei 5-138120, it is still impossible to eliminate the fire hazard, deterioration of the working environment and pollution due to volatilization of the solvent by using the solvent. In addition, various other well-known technologies list only the names of general-purpose resins without clearly specifying whether they are solvent-based or aqueous-based. In addition, additives and aqueous-based resins have the same name. It is well known that not only the compatibility of the resin but also the difference in physical properties of the resin itself is difficult to predict the overall characteristics of the lubricated steel sheet.

한편, 윤활제를 사용함으로써 종래의 수지피복강판에 비해 도장성이 현전히 감소됩니다. 따라서, 가능한 한 미도장부위에 주로 적용됨으로 윤활강판의 적용용도를 확대할수 없는 것입니다.On the other hand, the use of lubricants significantly reduces paintability compared to conventional resin coated steel sheets. Therefore, it is mainly applied to unpainted parts as much as possible, so it is not possible to expand the application of lubricated steel.

이에 본발명의 목적은 종래의 가공유를 도포하는 경우에 비하여 가공성이 우수하며, 상기 탈지공정을 필요로 하지 않고 화재위험성, 및 용제 휘발에 따른 환경공해가 감소되며, 작업환경이 개선되는 표면윤활성및 가공성, 내식정이 우수하고 기존의 박막 수지피복강판에 상응하는 도장성이 우수한 열경화성 수성 윤활수지용액을 제조방법, 및 이를 이용한 표면외관이 미려한 강판 표면처리방법을 제공하는 것이다.Therefore, the object of the present invention is that the processability is superior to that of applying the conventional processing oil, does not require the degreasing process, the risk of fire and environmental pollution due to volatilization of the solvent is reduced, surface lubrication and working environment is improved It is to provide a process for producing a thermosetting aqueous lubricant resin solution excellent in workability, corrosion resistance and excellent paintability corresponding to a conventional thin film resin coated steel sheet, and a steel sheet surface treatment method having a beautiful surface appearance using the same.

본발명의 일견지에 있어서, 에폭시로는 분자량이 1000-5000인 비스페놀형을 그리고 아크릴부로는 아크릴산 및 메타크릴산중 최소 일성분과 메틸메타크릴레이트In one aspect of the present invention, epoxy is a bisphenol type having a molecular weight of 1000-5000 and at least one component of acrylic acid and methacrylic acid and methyl methacrylate is used as the acrylic part.

, 2-히드록시 에틸메타크릴레이트, 에틸 아크릴레이트, 에틸메타크릴레이트, 비닐아세테이트, 및 스티렌로 구성되는 그룹으로부터 선택된 성분을 둘 또는 그 이상으로 혼합하여 에폭시부와 아크릴부가 중량비로 1:1-5가 되도록 라디칼중합하여 열경화성 에폭시 그라프트 아크릴레이트 수지를 제조하는 단계; 상기 제조된 수지에 디메틸에탄올아민, 트리에틸아민 및 암모니아수로 구성되는 그룹으로 부터 선택된 중화제를 첨가하고, 중화반응시켜 상기 수지를 수용화시키는 단계;중화반응 완료후 상기 수지를 순수로 희석하여 수지고형분이 10-35%중량%가 되도록 수정 수지용액을 희석하는 단계;상기 제조된 수지용액에 윤활제로 올레핀계 왁스와 폴리에틸렌계 왁스로 구성되는 그룹으로 부터 선택된 최소 1종및 이들의 혼합물과 파라핀계 왁스를 혼합하여 수지고형분 100중량부당 5-25중량부;유화분산된 실리케이트 혹은 콜로이달형태의 실리카를 수지고형분 100중량부당 10-80중량부;γ-글리실옥시 프로필 트리메톡시실란, γ-글리실옥시 프로필 메틸디메톡시실란, γ-메타크릴옥시 프로핀 트리메톡시실란등으로 구성되는 그룹으로 부터 선택된 1종의 실란커플링제를 전체용액 고형분에 대해 0.05-2중량%;및 아지리딘계, 아미노수지계, 이소시안계 및 요소수지계로 구성되는 그룹으로 부터 선택된 경화제를 수지고형분 100중량부당 4-35중량부 첨가 혼합하는 단계로 구성됨을 특징으로 하는 수성 윤활수지 용액 제조방법이 제공된다., 2-hydroxy ethyl methacrylate, ethyl acrylate, ethyl methacrylate, vinyl acetate, and styrene, by mixing two or more of the components selected from the group consisting of 1: 1 to 1: Preparing a thermosetting epoxy graft acrylate resin by radical polymerization to 5; Adding a neutralizing agent selected from the group consisting of dimethylethanolamine, triethylamine, and ammonia water to the prepared resin, and neutralizing the reaction to accept the resin; after completion of the neutralization reaction, the resin is diluted with pure water to obtain a resin solid. Diluting the modified resin solution to 10-35% by weight; at least one selected from the group consisting of olefin waxes and polyethylene waxes as a lubricant, and mixtures thereof and paraffin wax in the resin solution prepared above. 5 to 25 parts by weight per 100 parts by weight of resin solid content; emulsion-dispersed silicate or silica in colloidal form 10 to 80 parts by weight per 100 parts by weight resin; γ-glyciyloxy propyl trimethoxysilane, γ-glysil One silane coupling agent selected from the group consisting of oxypropyl methyldimethoxysilane, γ-methacryloxy propine trimethoxysilane, and the like. 0.05-2% by weight relative to the total solution solids; and mixing the curing agent selected from the group consisting of aziridine-based, amino-based resin, isocyanate-based and urea-based resin added 4-35 parts by weight per 100 parts by weight of the resin solid An aqueous lubricant resin solution manufacturing method is provided.

또한, 본발명의 다른 견지에 있어서, 강판에 상기 제조된 수성 윤활수지용액을 건조도막 두께가 0.5-5㎛가 되도록 도포한 후, 강판온도 140-200℃로 소부처리함을 특징으로 하는 표면마찰성, 가공성, 내식성, 및 도장성이 우수한 강판표면처리방법이 제공된다.In addition, in another aspect of the present invention, the surface-lubrication property is characterized in that the aqueous lubricating resin solution prepared on the steel sheet is applied so that the dry coating thickness is 0.5-5 탆, followed by baking at a steel sheet temperature of 140-200 ° C. Provided is a steel sheet surface treatment method having excellent workability, corrosion resistance, and paintability.

이하, 본발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본발명의 윤활수지용액을 제조함에 있어서, 먼저 에폭시부와 아크릴부가 중량비로 1:1 - 5가 되도록 라디칼중합하여 열경화형 수성 에폭시그라프트 아크릴레이트 수지를 제조한다. 이때 윤활수지의 피막특성을 고려하여 이차전이온도(Tg)는 20-70℃이내가 되도록 한다. 상기 수지에서 주쇄를 이루는 에폭시로는 분자량이 10In preparing the lubricating resin solution of the present invention, first, the epoxy part and the acrylic part are radically polymerized so that the weight ratio is 1: 1-5, thereby preparing a thermosetting aqueous epoxy graft acrylate resin. At this time, the secondary transition temperature (Tg) is to be within 20-70 ℃ in consideration of the film properties of the lubricant resin. Epoxy constituting the main chain in the resin has a molecular weight of 10

00-5000인 비스페놀형을 그리고 아크릴부로는 아크릴산 및 메타크릴산중 최소 1성분과 메틸메타크릴레이트, 2-히드록시 에틸메타크릴레이트, 에틸아크릴레이트, 에틸메타크릴레이트, 비닐아세테이트 및 스티렌으로 구성되는 그룹으로부터 선택된 성분을 둘 또는 그 이상으로 혼합하여 사용하며, 중합개시제로는 벤조일퍼옥사이드 또는 a, a'-아조비스이소부틸니트릴을 적량 사용한다.The bisphenol type is 00-5000, and the acryl part is composed of at least one component of acrylic acid and methacrylic acid and methyl methacrylate, 2-hydroxy ethyl methacrylate, ethyl acrylate, ethyl methacrylate, vinyl acetate and styrene. Two or more components selected from the group are mixed and used, and a suitable amount of benzoyl peroxide or a, a'-azobisisobutylnitrile is used as a polymerization initiator.

또한, 상기 수지합성시 유기용매로 메틸에틸케톤, 에틸셀로솔브, 프로필셀로솔브, 부틸셀로솔브, n-부탄올 및 메틸이소부틸케론을 1종 또는 혼합하여 사용할 수 있다. 이때 유기용매의 함량은 가능한 적을수록 바람직함으로 합성후 고형분이 최소 55중량%이상이 되도록 한다.In the resin synthesis, one or a mixture of methyl ethyl ketone, ethyl cellosolve, propyl cellosolve, butyl cellosolve, n-butanol, and methyl isobutyl keron may be used. At this time, the content of the organic solvent is preferably as small as possible so that the solid content after synthesis is at least 55% by weight or more.

상기 수지를 제조함에 있어서, 열경화형 수성 에폭시그라프트 아크릴레이트 수지합성에 사용되는 에폭시 올리고머의 분자량이 1000이하일 경우와 아크릴부가 에폭시1부에 대해 5이상일 경우는 수지피막의 경도가 너무 높아 피막이 쉽게 부서지고, 에폭시의 물성이 효과적으로 발휘되지 못하는 단점이 있고, 에폭시 분자량이 5000이상일 경우와 아크릴부가 1이하인 경우에는 수용화 하기 어려움으로 에폭시 올리고머는 분자량이 1000-5000인 것을 사용하며, 에폭시와 아크릴부의 중량비가 1In preparing the resin, when the molecular weight of the epoxy oligomer used for thermosetting aqueous epoxy graft acrylate resin is 1000 or less and when the acrylic part is 5 or more with respect to 1 part of epoxy, the hardness of the resin film is so high that the film easily breaks. When the epoxy molecular weight is 5000 or more and the acrylic part is less than 1, the epoxy oligomer has a molecular weight of 1000-5000 and the weight ratio of epoxy and acryl part is difficult. 1

:1 - 5가 되도록 하는 것이 바람직하다.It is preferable to make it: 1-5.

상기 합성된 수지는 그 자체로는 수용화가 불가능함으로 중화시켜 수용화시킨다. 이 단계에서 사용가능한 중화제로는 디메틸에탄올아민, 트리에틸아민 및 암모니아수가 사용되며, 그 첨가량은 하기 식1에 따라 계산된다.The synthesized resin is neutralized by being solubilized by itself that it is impossible to accept. As the neutralizing agent usable in this step, dimethylethanolamine, triethylamine and ammonia water are used, and the addition amount thereof is calculated according to the following formula (1).

상기 중화반응 완료후, 상기 제조된 수지를 순수로 희석하여 수지고형분이 10-35중량%가 되도록 수지용액을 제조한다. 상기 수지용액제조시 수지고형분이 10중량%미만일 경우에는 첨가제와의 상용성 및 용액안정성이 저하되고 점도가 너무 작아 롤코팅시 작업조건이 매우 까다로워지는 단점이 발생하고, 35중량% 이상일 경우에는 점도가 상승하여 롤코팅시 작업조건을 용이하게 설정할 수 없으므로 수지 고형분이 10-35중량%가 되는 범위로 희석하여 사용하는 것이 바람직하다.After completion of the neutralization reaction, the prepared resin is diluted with pure water to prepare a resin solution so that the resin solid content is 10-35% by weight. When the resin solids content is less than 10% by weight in the production of the resin solution, compatibility with additives and solution stability are lowered, and the viscosity is so small that working conditions become very difficult during roll coating, and when the viscosity is more than 35% by weight It is preferable to dilute the resin solid content in the range of 10-35% by weight since it is not possible to easily set the working conditions during roll coating.

상기 제조된 수지용액에 자기 윤활성을 부여하기 위해 윤활제를 첨가한다.A lubricant is added to impart self-lubricating property to the prepared resin solution.

이하, 각 성분의 양을 나타내는 용어 "중량부"는 각 성분의 고형분 함량을 기준으로 한 것이며, 각 성분은 수지 고형분 100중량부를 기준으로 하여 첨가된다. 윤활제로는 올레핀계 왁스(분자량 1200 - 2500, 입경 0.5-2㎛, 융점 75-110℃)와 폴리에틸렌계 왁스(분자량 1500-3000, 입경 0.5-15㎛, 융점 100-125℃)로 구성되는 그룹에서 선택된 최소 1종 혹은 이들의 혼합물과 파라핀계 왁스(분자량 1000-2000,입경 0.5-2㎛, 융점 55-70℃)를 혼합하여 사용할 수 있으며, 윤활제 성분은 수지 고형분 100중량부 기준으로 5-25중량부로 첨가된다.Hereinafter, the term "parts by weight" indicating the amount of each component is based on the solids content of each component, and each component is added based on 100 parts by weight of the resin solids. Groups composed of olefin waxes (molecular weight 1200-2500, particle size 0.5-2㎛, melting point 75-110 ℃) and polyethylene wax (molecular weight 1500-3000, particle size 0.5-15㎛, melting point 100-125 ℃) At least one selected from or a mixture thereof and paraffin wax (molecular weight: 1000-2000, particle size: 0.5-2 µm, melting point: 55-70 ° C) may be mixed and used, and the lubricant component is based on 100 parts by weight of the resin solid. It is added at 25 parts by weight.

윤활제 첨가량이 수지고형분에 대해 5중량부 미만의 경우에서는 윤활작용이 발휘되지 않고, 25중량부 이상인 경우에는 윤활성능이 더 이상 발휘되지 못할 뿐아니라 도장성이 매우 급격히 감소되고 윤활수지피복강판에서 요구되는 성능이 오히려 저하됨으로 윤활제는 5-25 중량부로 첨가하는 것이 바람직하다.If the amount of lubricant added is less than 5 parts by weight relative to the resin solid content, the lubrication action is not exerted, and when it is 25 parts by weight or more, the lubrication performance is not exhibited any more. It is preferred that the lubricant be added in an amount of 5-25 parts by weight, as the performance is rather degraded.

상기 수지용액에는 내식성 및 도장성향상을 위해 유화분산된 실리케이트나 콜로이달형태의 실리카를 첨가한다. 이때 입자크기는 10-40㎛ 이내의 것으로 수지고형분 100중량부당 10 - 80 중량부를 첨가한다. 함량이 10중량부 미만인 경우에는 내식성이 충분하지 않고 도장성도 거의 개선되지 않으며 80중량부 이상에서는 실라카응집에 의한 스크래치성 흑변이나 파우더링이 발생하는등 표면외관에 결함이 나타나고, 내식성에 있어서도 특별히 향상되지 않고 오히려 다소 감소된다. 또한 도장성 측면에서도 바람직한 수준의 물성 향상이 기대되지 않을 뿐더러, 특히 120중량부이상에서는 오히려 도장성이 저하됨으로 실리케이트나 실리카(이하 실리카로 통칭)는 10-80중량부 이내로 첨가하는 것이 바람직하다.To the resin solution, silicate or colloidal silica, which is emulsified and dispersed, is added to improve corrosion resistance and paintability. At this time, the particle size is within 10-40㎛ add 10 to 80 parts by weight per 100 parts by weight of the resin solid content. If the content is less than 10 parts by weight, the corrosion resistance is not sufficient and the coating property is hardly improved. If the content is more than 80 parts by weight, defects appear on the surface appearance such as scratching black stools or powdering due to the coagulation of silica, particularly in corrosion resistance. It is not improved, but rather reduced. In addition, in terms of paintability, a desirable level of physical property improvement is not expected. In particular, the coating property is deteriorated at 120 parts by weight or more, so that silicate or silica (hereinafter referred to as silica) is preferably added within 10 to 80 parts by weight.

상기 제조된 수지에 도장성향상을 위해 γ-글리실옥시 프로필 트리메톡시실란, γ-글리실옥시 프로필 메틸디메톡시실란, γ-메타크릴옥시 프로필 트리메톡시실란등으로 구성되는 그룹으로 부터 선택된 1종의 실란커플링제를 첨가혼합함으로써 도장성이 향상될뿐아니라 피막자체의 경도가 향상됨으로 다소의 가공성 및 표면외관이 개선되고, 실리카가 균일하게 분산되어 내식성 또한 다소 향상된다. 이때 0To improve the coating property on the prepared resin, γ-glycosyl propyl trimethoxysilane, γ-glyciyloxy propyl methyldimethoxysilane, γ-methacryloxy propyl trimethoxysilane and the like are selected from the group consisting of The addition and mixing of one silane coupling agent not only improves paintability, but also improves the hardness of the film itself, thereby improving some workability and surface appearance, and uniformly dispersing silica, thereby improving corrosion resistance. 0

.05% 이하에서는 물성이 개선되지 않으며 2%이상에서는 더 이상의 물성이 향상되지 않을뿐 아니라 오히려 프레스가공시 피막이 박리(powdering)되어 용액안정성이 저하되는 단점을 나타내게 됨으로 전체용액 고형분에 대해 0.05-2% 이내로 첨가하는 것이 바람직하다.The physical properties do not improve at less than .05%, and the physical properties do not improve at more than 2%. On the contrary, the film is peeled during press processing, resulting in a decrease in solution stability. It is preferable to add within%.

상기 제조된 수지용액에는 수지가 열에 의해 경화되도록 경화제가 또한 첨가 된다. 상기 경화제로는 아지리딘계, 아미노수지계, 블록이소시안계, 및 요소수지계A curing agent is also added to the resin solution thus prepared so that the resin is cured by heat. As the curing agent, aziridine-based, amino resin-based, block isocyanate-based, and urea-based resin

, 이미드계등이 사용될 수 있으며, 경화제의 종류 및 첨가량은 윤활피복강판의 요구물성에 따라 조절가능하지만 수지고형분 100중량부당 4-35중량부로 첨가하는 것이 바람직하다. 즉 아미노수지계 및 아지리딘계를 사용한 경우는 피복강판의 광택도 및 표면경도가 우수하고, 이소시안계, 이미드계 및 요소수지계 경화제를 사용하는 경우에는 피막이 유연하여 심가공에 유리하고 가공후 표면외관이 우수하다.The imide system may be used, and the type and amount of the curing agent may be adjusted according to the required properties of the lubricated coated steel sheet, but it is preferable to add 4-35 parts by weight per 100 parts by weight of the resin solid content. In other words, when amino resin and aziridine are used, the gloss and surface hardness of the coated steel sheet are excellent, and when the isocyanate, imide and urea-based curing agents are used, the film is flexible and is advantageous for deep processing. great.

상기 열경화되도록 첨가되는 경화제의 함량은 수지고형분의 중량기준으로 경화제의 종류에 따라 상이하나 4중량부 미만일 경우에는 충분히 경화되지 않고, 35중량부이상일 경우에는 피막이 부서지기 쉽고 강판에의 접착력이 충분하지 않아 물성이 저하되는 원인이 됨으로 수지의 분자구조와 관련하여 적절한 경화밀도를 유지하기 위해 경화제를 수지고형분 100중량부당 4-35중량부로 첨가하는 것이 바람직하다.The amount of the curing agent added to the thermal curing is different depending on the type of the curing agent on the basis of the weight of the resin solid content, but less than 4 parts by weight is not sufficiently cured, when more than 35 parts by weight of the coating is brittle and sufficient adhesion to the steel sheet It is preferable to add the curing agent at 4-35 parts by weight per 100 parts by weight of the resin mold in order to maintain the proper curing density in relation to the molecular structure of the resin, since the physical properties are deteriorated.

상기한 바와같은 본발명의 방법으로 제조된 용액을 이하, 윤활수지용액이라 한다.The solution prepared by the method of the present invention as described above is hereinafter referred to as a lubricating resin solution.

또한, 상기, 본발명의 윤활수지용액을 강판에 도포하여 표면처리강판을 제조하는 경우, 스프레이법 또는 롤코팅법등 통상의 방법으로 반응형 또는 도포형 크로메이트를 처리하여 크롬부착량이 5 - 100mg/m2인 아연 및 아연계 합금도금강판에 본발명의 윤활용액을 건조피막두께가 0.5-5㎛가 되도록 도포한후 소부처리하여 표면마찰성, 가공성, 내식성 및 도장성이 우수한 표면처리강판을 제조할수 있다.In addition, in the case of manufacturing a surface-treated steel sheet by applying the lubrication resin solution of the present invention to a steel sheet, the chromium deposition amount is 5-100 mg / by treating a reactive or coated chromate by a conventional method such as spraying or roll coating. The lubricating solution of the present invention is coated on m 2 zinc and zinc-based alloy plated steel sheet to have a dry film thickness of 0.5-5 μm, followed by baking to produce a surface treated steel sheet having excellent surface friction, processability, corrosion resistance and paintability. have.

상기 건조피막두께가 0.5㎛ 이하인 경우에는 피막의 윤활성 및 가공성등을 나타내지 못하며 내식성 또한 충분히 발휘되지 않는다. 5㎛ 이상인 경우에는 윤활성및 가공성이 더 이상 개선되지 않으며 오히려 수지박리량이 증가됨으로 건조피막의 두께가 0.5 -5㎛가 되도록 도포하는 것이 바람직하다. 상기 범위내에서 상대적으로 피막이 두꺼울수록, 내식성 및 가공성, 특히 내식성 및 가공후 외관이 우수해짐으로 충분한 내식성 및 미련한 가공후 외관이 요구되는 경우에는 건조피막두께를 본 발명의 범위안에서 향상시키는 것이 바람직하다.When the dry film thickness is 0.5 μm or less, the film may not exhibit lubricity and workability, and corrosion resistance may not be sufficiently exhibited. In the case of 5 µm or more, the lubricity and processability are not improved anymore, and the amount of resin peeling is increased, so that the thickness of the dry coating is preferably 0.5-5 µm. It is preferable to improve the dry film thickness within the scope of the present invention when the thickness is relatively thick within the above range, and the corrosion resistance and workability, in particular, the corrosion resistance and appearance after processing are excellent and sufficient corrosion resistance and appearance after processing are required. .

또한 상기 소부과정시, 본발명의 윤활수지용액은 소부과정중 공급된 열에 의해 경화되는데 수지경화와 관련한 소부온도는 강판온도 140℃ 이하에서는 수지가 완전히 경화되지 못해 물성이 저하되며, 200℃이상인 경우에는 수지는 경화되지만 소재강의 특성이 변화됨으로 바람직한 소부온도는 강판온도 140 - 200℃이다.In addition, during the baking process, the lubricating resin solution of the present invention is cured by the heat supplied during the baking process. The baking temperature associated with resin hardening is not fully cured at the steel sheet temperature of 140 ° C. or below, and thus the physical properties thereof are deteriorated. Although the resin is cured, the preferred baking temperature is 140-200 ° C. because the properties of the material steel change.

이하 본발명의 실시예에 대하여 상세히 설명한다.Hereinafter, embodiments of the present invention will be described in detail.

[실시예]EXAMPLE

크롬부착량 40-45 mg/m2, 아연도금부착량 20/20 g/m2,두께 0.8mm, 재질은 일반강인크로메이트 처리된 전기아연도금강판을 소지강판으로 하고, 상기 강판에 에폭시와 아크릴의 함량비가 1:3.5인 수지용액에 하기 표1에 기재된 바와 같이 융점이 125℃이고 분자량이 1500-3000인 유화분산된 폴리에틸렌계 왁스(대동상사의 PSThe amount of chromium deposited 40-45 mg / m 2 , the amount of zinc coated 20/20 g / m 2, thickness 0.8mm, the material is a steel plate with a general steel chromate-treated electrogalvanized steel sheet, the content of epoxy and acrylic in the steel sheet Emulsified and dispersed polyethylene wax having a melting point of 125 ° C. and a molecular weight of 1500-3000 as shown in Table 1 in a resin solution having a ratio of 1: 3.5

35)와 융점이 75℃이고 유화분산된 파라핀왁스(Cera-Chemi의 Aquacer)가 1:1중량비로 혼합된 윤활제, 실리카(콜로이달실리카 형태의 입자경이 20-40㎛인 일신케미칼의 Snowtex 시리즈)및 실란커플링제(Union Carbide에서 시판되는 1급 시약급 γ-글리실옥시프로필트리메톡시실란)의 함량을 변화시킨 첨가하였으며, 경화제로는 아미노수지계 경화제(Cyctec에서 Cymel시리즈로 판매되는 멜라민수지)를 25중량부로 사용하였다.35) and a melting point of 75 ° C, emulsion-dispersed paraffin wax (Cera-Chemi Aquacer) mixed in a 1: 1 weight ratio, silica (Snowtex series of Ilshin Chemical's particle size in the form of colloidal silica) And a silane coupling agent (a first-grade reagent grade γ-glysiloxypropyltrimethoxysilane commercially available from Union Carbide) was added. The curing agent was an amino resin-based curing agent (melamine resin sold by Cymel series from Cyctec). Was used at 25 parts by weight.

한편, 상기 에폭시와 아크릴의 함량비가 1:3.5인 수지용액은 분자량이 2000인 비스페놀 A형 에폭시수지로 국도화학의 YD 014 50g을 n-부탄올과 브틸셀로솔브가 3:2중량비로 혼합된 용제에 넣고 110℃에서 용해시킨 다음 이에 아크릴단량체로서 Junsei(일본) 및 동양화학의 1급 시약급 메틸메타크릴레이트 110g, 아크릴산 18Meanwhile, the resin solution having a content ratio of 1: 3.5 of epoxy and acryl is a bisphenol A type epoxy resin having a molecular weight of 2000, and a solvent in which 50 g of YD 014 of Kukdo Chemical is mixed with n-butanol and butyl cellosolve in a 3: 2 weight ratio. And dissolve at 110 ° C, and then, as an acrylic monomer, 110 g of first-class reagent grade methyl methacrylate of Junsei (Japan) and Dongyang Chemical, and acrylic acid 18

g, 2-히드록시에틸메타크릴레이트 32g, 스티렌 15g과 반응개시제로서 Aldrich사에서 특급시약으로 판매되는 베조일퍼옥사이드 12g의 혼합용액을 질소분위기하에서 2시간 동안 서서히 적가한 후, 2시간을 더 유지시켜 1차 반응생성물을 완성하였다.g, 32 g of 2-hydroxyethyl methacrylate, 15 g of styrene and 12 g of bezoyl peroxide sold as a special reagent by Aldrich as a reaction initiator were slowly added dropwise under a nitrogen atmosphere for 2 hours, followed by another 2 hours. Maintained to complete the primary reaction product.

1차 반응생성물의 산가를 측정한 다음 환산된 양만큼 수용호를 위해 중화제로서 1급 시약급의 트리에틸아민을 60℃에서 교반하면서 적가하고 약50분간 교반을 유지함으로써 에폭시와 아크릴의 함량비가 1:3.5인 수지용액을 제조하여 사용하였다.The acid value of the primary reaction product was measured, and then triethylamine of first-grade reagent grade was added dropwise while stirring at 60 ° C. as a neutralizing agent for the amount of converted water, and the content ratio of epoxy and acryl was maintained by maintaining the stirring for about 50 minutes. A resin solution of 3.5 was prepared and used.

이와 같이 제조한 윤활용액을 롤코터를 이용하여 수지부착량 1.5g/m2로 도포하여 내지문성, 마찰계수, 가공성(성형성), 내식성, 도장성 및 표면외관을 평가하였으며 그 결과를 하기표 1에 나타내었다.The lubricating solution prepared in this way was coated with a resin coating amount of 1.5 g / m 2 using a roll coater to evaluate fingerprint, friction coefficient, processability (formability), corrosion resistance, paintability, and surface appearance. Shown in

상기 내지문성은 CIF Lab형 색차계(TOKYO DENSHOKU CO.)을 이용하여 윤활강판에 바세린을 도포한후 도포전, 후의 색차(△E)값을 측정하여 다음과 같이 평가하였다.The anti-fingerprint was evaluated using the CIF Lab type color difference meter (TOKYO DENSHOKU CO.) After applying petroleum jelly to the lubricated steel sheet and measuring the color difference (ΔE) values before and after application as follows.

내지문성평가(△E) ◎ : 1.0 미만 O : 10-2.0Fingerprint evaluation (△ E) ◎: less than 1.0 O: 10-2.0

△ : 2.1-2.9 X : 3.0 이상△: 2.1-2.9 X: 3.0 or more

상기 마찰계수는 드로오비드 테스터(Drawbead Tester)로 상온에서의 편면마찰계수를 측정하여 다음과 같이 평가하였다.The friction coefficient was evaluated as follows by measuring the one-sided friction coefficient at room temperature with a Drawbead Tester.

마찰계수평가(μ) ◎ : 0.08미만 O : 0.080 - 0.089Friction Coefficient Evaluation (μ) ◎: Less than 0.08 O: 0.080-0.089

△ : 0.090 - 0.099 X : 0.10 이상△: 0.090-0.099 X: 0.10 or more

상기 가공성평가는 박판종합시험기기를 이용하여 가공비(Drawing Ratio) 1.96으로 컵성형시 각 시편의 최대 BHF(Blank Holding Force)를 측정하여 다음과 같이 평가하였다.The evaluation of the workability was evaluated by measuring the maximum BHF (Blank Holding Force) of each specimen during cup forming with a drawing ratio of 1.96 using a thin plate comprehensive tester.

가공성평가(Ton) ◎ : 25이상 O : 18-24Machinability Evaluation (Ton) ◎: Over 25 O: 18-24

△ : 10-17 X : 10미만△: 10-17 X: less than 10

상기 표면외관은 가공 전후의 강판표면을 육안관찰하여 다음과 같이 평가하였다.The surface appearance was evaluated by visual observation of the steel plate surface before and after processing as follows.

◎ : 흑변없음 O : 미비한 흑변◎: No black edge O: Inadequate black edge

△ : 흑변발생 X : 상당히 흑변함△: blackening occurs X: fairly blacking

상기 내식성평가는 염수분무시험기기로 평판 75 × 150mm로 제작된 시편에 대하여 JIS Z 2731에 의거하여 평가하였으며 백청 초기발생시간을 측정하였다.The corrosion resistance evaluation was evaluated according to JIS Z 2731 for specimens made of flat plate 75 × 150 mm with a salt spray test apparatus and the initial occurrence time of white rust was measured.

상기 도장성은 크로스컷 테스트(Cross cut test)를 이용하여 도장후 도막밀착성 테스트를 실시한 결과로 하기와 같이 평가하였다. 이때 사용된 도료는 아미노 알키드계 도료로서 도막두께는 20-25㎛이고 1mm 간격 100눈금의 크로스컷 테스트를 1,2차 도막밀착성에 대해 실시하였다. 2차 도막밀착성은 내수밀착성과 내충격테스트로 내수밀착성은 끊는물에 30분간 침지후 크로스컷 테스트를 실시하였고 내충격 테스트는 500g의 추를 500mm높이에서 낙하시켜 해당부위에 대해 크로스컷 테스트를 실시한 결과이다.The paintability was evaluated as follows as a result of performing a coating film adhesion test after coating using a cross cut test. At this time, the paint used was an amino alkyd paint, which had a film thickness of 20-25 μm and a crosscut test of 100 divisions of 1 mm interval for the first and second coat adhesion. Secondary film adhesion is water tightness and impact test. Water tightness is immersed in the water for 30 minutes and crosscut test was performed. Impact resistance test is the result of crosscut test on the corresponding part by dropping 500g weight at 500mm height. .

도장성평가 ◎ : 1,2차 테스트 모두 도막박리 없음Paintability evaluation ◎: No peeling off of film

O : 1차 시험시 내수밀착성 양호, 내충격테스트에서 1-3개의 눈금(scale)박리O: Good water resistance at the 1st test, 1-3 scale peeling off at impact test

△ : 내수밀착성과 내충격테스트에서 5개이상의 눈금박리△: 5 or more scale peelings in water tightness and impact test

X : 1차 밀착성에서도 1개이상의 눈금박리X: One or more scale peelings even in the primary adhesion

[표 1]TABLE 1

1. 수지용액제조시 윤활제, 실리카는 수지용액의 고형분 100중량부를 기준으로 하여 윤활제, 실리카의 고형분수준이 각 기재한 양의 중량부가 되도록 첨가됨.1. In preparing the resin solution, the lubricant and silica are added so that the solids level of the lubricant and silica is added by weight based on 100 parts by weight of the solids of the resin solution.

2. 실란커플링제는 전체 용액의 고형분에 대한 중량%로 첨가됨.2. Silane coupling agent is added in weight percent to solids of the total solution.

상기 표1의 결과를 발명예와 비교예를 구분하여 상세히 설명하면 다음과 같다.The results of Table 1 are described in detail by dividing the invention example and the comparative example as follows.

[발명예 1-6]Invention Example 1-6

에폭시그라프트 아크릴레이트(1:3.5)인 수지에 대해 윤활제, 실리카, 실란커플링제, 경화제를 본발명의 조건범위로 혼합한 용액을 제조한 후 이를 강판상에 도포한 제품을 평가한 결과로서 상기 표1과 같이 우수한 물성을 나타낸다.As a result of evaluating a product coated with a lubricant, silica, a silane coupling agent, and a curing agent in the condition range of the present invention for a resin of epoxy graft acrylate (1: 3.5), and then applying it on a steel sheet, Excellent physical properties are shown in Table 1.

[비교예 1-3]Comparative Example 1-3

윤활용액제조시 사용된 실리카의 함량이 수지고형분에 대해 5중량부로 본발명의 조건범위보다 낮은 경우는 충분한 내식성향상및 도장성을 기대하기 어렵고, 실리카함량이 90중량부로 높은 경우에는 마찰계수및 가공성이 뚜렷이 저하되고 실리카 응집에 의한 스크래치성 흑변이 다량 발생하는 등 표면외관이 불량해지는 결함이 발생되었다. 또한 내식성도 더 이상 증가하지 못하고 오히려 다소 감소되었다When the content of silica used in the manufacture of lubricating solution is 5 parts by weight with respect to the solid content, which is lower than the conditions of the present invention, it is difficult to expect sufficient corrosion resistance and paintability, and when the silica content is high by 90 parts by weight, the coefficient of friction and processability These defects were markedly lowered, and a large amount of scratchable black stools caused by silica agglomeration occurred, resulting in defects such as poor surface appearance. Also, the corrosion resistance no longer increased, but rather decreased.

그리고, 실리카 함량이 120중량부 이상이 되면 가공성 및 외관이 저조하며 실리카의 가수분해에 의한 특히 2차 도막밀착성이 급격히 열하됨을 나타냈다.In addition, when the silica content is 120 parts by weight or more, the workability and appearance are poor, and the secondary coating film adhesion due to the hydrolysis of silica is rapidly deteriorated.

[비교예 4-5]Comparative Example 4-5

윤활용액제조시 사용된 윤활제의 함량이 본 발명 조건의 범위보다 낮은 경우는 거의 표면마찰특성 및 가공성이 향상되지 않는 것으로 나타났으며, 윤활제 함량이 높은 경우에서는 도장성이 저조하며, 가공성의 향상이 더 이상 증가되지 않을뿐만아니라 경우에 따라서는, 오히려 저하되는 것으로 평가되었다.When the content of the lubricant used in the manufacture of the lubricating solution is lower than the range of the conditions of the present invention, the surface friction properties and the processability were found to be hardly improved. When the lubricant content is high, the paintability is low and the processability is improved. Not only was it no longer increased, but in some cases, it was evaluated to be rather deteriorated.

[비교예 6-7]Comparative Example 6-7

윤활용액제조시 사용된 실란커플링제의 함량이 본발명조건의 범위보다 낮은 경우는 도장성이 저조하였으며 윤활제 함량이 높은 경우 더 이상 물성이 향상되지 않고 프레스가공시 피막이 쉽게 부서지거나 용액안정성이 크게 감소되는 것으로 나타났다.When the content of the silane coupling agent used in the manufacture of lubricating solution is lower than the range of the present invention, the paintability is poor. When the lubricating agent is high, the coating property is no longer improved, and the coating is easily broken or the solution stability is greatly reduced during press processing. Appeared to be.

[비교예 8]Comparative Example 8

본발명에 의한 윤활수지용액의 특성을 보다 분명하게 고찰하기 위해 윤활용액제조시 실리카와 실란커플링제를 첨가하지 않은 경우로 내식성과 도장성이 본발명의 윤활수지 용액보다 현저하게 낮음을 알 수 있다.In order to examine the characteristics of the lubrication resin solution according to the present invention more clearly, the corrosion resistance and paintability of the lubrication solution solution are not significantly lower than those of the lubrication resin solution of the present invention. .

Claims (2)

에폭시로는 분자량이 1000-5000인 비스페놀형을 그리고 아크릴부는 아크릴산 및 메타크릴산중 최소 일성분 그리고 메틸 메타크릴레이트, 2-하이드록시에틸메타크릴레이트, 에틸아크릴레이트, 에틸메타크릴레이트, 비닐아세테이트 및 스티렌으로부터 선택된 둘 또는 그 이상의 성분을 혼합하여 에폭시부와 아크릴부가 중량비로 1:1 - 5가 되도록 라디칼중합하여 열경화성 수성 에폭시그라프트 아크릴레이트 수지를 제조하는 단계;상기 제조된 수지에 디메틸에탄올아민, 트리에틸아민 및 암모니아수로 구성되는 그룹으로부터 선택된 중화제를 첨가하여 중화반응시켜 상기 수지를 수용화시키는 단계;중화반응 완료후, 상기 수지를 순수로 희석하여 수지 고형분이 10-35중량%가 되도록 수성수지용액을 희석하는 단계;상기 제조된 수지용액에 윤활제로 올레핀계 왁스와 폴리에틸렌계 왁스로 구성되는 그룹으로부터 선택된 최소 1종 혹은 이들의 혼합물과 파라핀계 왁스를 혼합하여 수지고형분 100중량부당 5-25중량부; 수지고형분 100중량부를 기준으로 유화분산된 실리케이트나 콜로이달 형태의 실리카 10 - 80중량부; γ -글리실옥시 프로필트리메톡시실란, γ -글리실옥시 프로필 메틸디메톡시실란, γ -메타크릴옥시 프로필트리메톡시실란등으로 구성되는 그룹으로 부터 선택된 1종의 실란커플링제를 전체용액 고형분에 대해 0.05-2중량%; 아미노수지계, 아지리딘계, 이소시안계 및 요소수지계로 구성되는 그룹으로 부터 선택된 경화제를 수지고형분 100중량부당 4-35중량부 첨가하여 혼합하는 단계;로 구성되는 윤활수지용액 제조방법.Epoxy has a bisphenol type having a molecular weight of 1000-5000, and the acrylic part has at least one component of acrylic acid and methacrylic acid and methyl methacrylate, 2-hydroxyethyl methacrylate, ethyl acrylate, ethyl methacrylate, vinyl acetate and Preparing a thermosetting aqueous epoxy graft acrylate resin by radically polymerizing two or more components selected from styrene so that the epoxy portion and the acryl portion are 1: 1 to 5 in a weight ratio; dimethylethanolamine, Neutralizing the reaction by adding a neutralizing agent selected from the group consisting of triethylamine and ammonia water to solubilize the resin; after completion of the neutralization reaction, the resin is diluted with pure water so that the resin solid content is 10-35% by weight. Diluting the olefin with a lubricant in the resin solution prepared above Wax and polyethylene type for at least one selected from the group consisting of wax species or a mixture of resin solids and mixtures thereof and a paraffin-based wax per 100 parts by weight of 5-25 parts by weight; 10 to 80 parts by weight of silicate or colloidal silicate emulsion-dispersed based on 100 parts by weight of resin; 1 type of silane coupling agents selected from the group consisting of γ-glycosyl propyltrimethoxysilane, γ-glyciyloxy propyl methyldimethoxysilane, and γ-methacryloxy propyl trimethoxysilane 0.05-2% by weight; And adding 4-35 parts by weight of a curing agent selected from the group consisting of an amino resin, aziridine, isocyanate and urea resins to 100 parts by weight of resin. 강판에 청구범위 1항의 윤활수지용액을 건조피막 두께가 0.5-5㎛가 되도록 도포한후, 강판온도 140-200℃로 소부처리함을 특징으로 하는 표면 윤활성, 내식성 및 도장성이 우수한 강판표면처리방법.Apply the lubricating resin solution of claim 1 to the steel sheet so as to have a dry film thickness of 0.5-5 μm, and then bake it at a steel plate temperature of 140-200 ° C., characterized by excellent surface lubricity, corrosion resistance and paintability Way.
KR1019950066223A 1995-12-29 1995-12-29 The preparation of lubricating resin solution having high surface lubricating , non-corrosiveness, and good coating properties and the preparation method of surface treatment of steel plate by using thereof KR100262494B1 (en)

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WO2009072738A1 (en) * 2007-12-05 2009-06-11 Lg Electronics Inc. Anti-fingerprint coating material for stainless steel outer case of home appliance

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KR100312119B1 (en) * 1997-12-17 2001-12-12 이구택 Surface treatment method and composition giving self-lubricating property to cold rolled steel sheet
KR100673789B1 (en) * 2003-12-12 2007-01-23 현대하이스코 주식회사 Method of Cr-free anti-fingerprint steel sheet having high corrosion resistance and Conductivity

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009072738A1 (en) * 2007-12-05 2009-06-11 Lg Electronics Inc. Anti-fingerprint coating material for stainless steel outer case of home appliance
KR101043527B1 (en) * 2007-12-05 2011-06-23 엘지전자 주식회사 Stainless steel out-case of home appliance having anti-fingerprint coating
US8138275B2 (en) 2007-12-05 2012-03-20 Lg Electronics Inc. Anti-fingerprint coating material for stainless steel outer case of home appliance

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