KR101372758B1 - Self-healing material, coating composition comprising the same, and a production method therefor - Google Patents
Self-healing material, coating composition comprising the same, and a production method therefor Download PDFInfo
- Publication number
- KR101372758B1 KR101372758B1 KR1020120153987A KR20120153987A KR101372758B1 KR 101372758 B1 KR101372758 B1 KR 101372758B1 KR 1020120153987 A KR1020120153987 A KR 1020120153987A KR 20120153987 A KR20120153987 A KR 20120153987A KR 101372758 B1 KR101372758 B1 KR 101372758B1
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- KR
- South Korea
- Prior art keywords
- self
- healing
- weight
- coating composition
- agent
- Prior art date
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
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Abstract
본 발명은 의장성, 내식성, 도막밀착성, 윤활성 및 밴딩성이 우수한 피막을 형성할 수 있고, 더불어, 자기치유특성이 우수한 자기치유제, 상기 자기치유제를 포함하는 코팅 조성물 및 이 코팅 조성물 피막을 갖는 강판을 제공하고자 한다.The present invention can form a coating having excellent design, corrosion resistance, coating adhesion, lubricity and bending properties, and has a self-healing agent having excellent self-healing properties, a coating composition comprising the self-healing agent, and the coating composition coating. To provide a steel sheet having.
Description
본 발명은 자기치유제, 상기 자기치유제를 포함하는 코팅 조성물 및 이 코팅 조성물 피막을 갖는 강판에 관한 것이다.
The present invention relates to a self-healing agent, a coating composition comprising the self-healing agent, and a steel sheet having the coating composition film.
최근 들어 가전업체 간 PDP, LCD, LED TV 등의 가전용 전자제품의 내ㆍ외장재의 박형화 경쟁에 따라 상기 내ㆍ외장재의 소재가 기존에 사용되어왔던 플라스틱 사출물에서 철강 박판재로 급격히 대체되고 있다. 특히, 외장재의 경우 추가적인 도장공정 없이 프레스 가공 후 바로 제품에 장착할 수 있도록 하기 위해, 미려하면서 색상을 띠는 표면을 가지고 있는 흑색수지 강판과 같은 수지피복 강판 등이 적용되고 있다.
In recent years, the interior and exterior materials of the above-mentioned interior and exterior materials have been rapidly replaced by steel thin plate materials from plastic injection materials that have been used in the past, due to competition for thinning of interior and exterior materials of household electric appliances such as PDP, LCD, and LED TV among home appliance companies. In particular, a resin-coated steel sheet such as a black resin steel plate having a beautiful and colored surface is applied to the exterior material so that the exterior material can be directly attached to the product after the press processing without additional coating process.
수지피복 강판은 도 1에 나타난 바와 같이, 통상의 경우 상도층(1), 하도층(3), 강판(일례로 아연도금강판)(2)의 구조로 조성되어 있으며, 상도층(1)은 폴리에스테르 수지와 멜라민 수지가 주성분으로 10 ~ 50 ㎛의 두께를 가지며, 하도층(3)은 아크릴우레탄에스테르 수지를 주성분으로 0.5 ~ 2.0 ㎛의 두께를 갖는다.
As shown in FIG. 1, the resin coated steel sheet is usually formed of a structure of a top coat layer 1, a bottom coat layer 3, and a steel plate (for example, a galvanized steel sheet) 2. The polyester resin and the melamine resin have a thickness of 10 to 50 µm as a main component, and the undercoat 3 has a thickness of 0.5 to 2.0 µm as a main component of the acrylic urethane ester resin.
이러한 수지피복 강판은 추가 도장 공정 없이 프레스 가공 후 바로 외장재로 적용이 가능하며, 표면외관상 상도층은 흑색을 선호하여 흑색도(흑색도= 100-L*, L*= 백색도) 75~98 수준으로 생산하고 있다.
This resin coated steel sheet can be applied as an exterior material immediately after press processing without additional coating process, and the top coat layer on the surface appearance prefers black to black level (blackness = 100-L *, L * = whiteness) to 75 ~ 98 level. Produces.
수지피복 강판은 흑색도를 표현하는 안료의 특성으로 인하여 열을 흡수/방열하는 능력이 증가하게 된다. 이때, 열이 전달하는 방법으로는 물체를 통한 직접 열전달, 열대류, 복사열로 구분될 수 있으며 흑색도가 증가할수록 복사열에 의한 흡수/방열성이 증가한다. 특히, 영상 가전용 백커버(Back-Cover) 소재 분야에서 "심미안적 요소"와 "영상기기 내부의 열방출" 특성 때문에 흑색을 선호하게 된다.
The resin coated steel sheet has an ability to absorb / heat heat due to the characteristic of the pigment expressing blackness. At this time, the heat transfer method can be divided into direct heat transfer through the object, tropical flow, radiant heat, and as the blackness increases, absorption / heat dissipation by radiant heat increases. In particular, in the field of back-cover material for home appliances, black is preferred because of the "aesthetic factor" and "heat release inside the video device" characteristics.
상기와 같은 영상 가전용 백커버는 금형을 이용하여 프레스 가공을 행한 후, 최종제품으로 제조된다. 상기 프레스 가공에 사용되는 금형은 한번 제작하는데 제작비가 많이 들어가게 되므로, 생산성을 고려하여 한번 제작된 금형은 최대한 장기간 사용되는 것을 프레스 가공사에서는 원하고 있는 실정이다.
The back cover for an image household appliance as described above is manufactured into a final product after press working using a mold. Since the mold used for the press working is a lot of manufacturing costs to produce once, considering the productivity, the mold produced once, the press working company wants to be used as long as possible.
그러나, 금형의 표면은 장기간 사용함에 따라 표면이 거칠어지게 되며, 이러한 거칠어짐은 상기 영상 가전용 백커버의 프레스 공정 중에 부품의 표면에 미세한 스크레치 또는 스크레치로 인한 부식을 발생시킬 우려가 있다.
However, as the surface of the mold is used for a long time, the surface becomes rough, and such roughness may cause corrosion due to minute scratches or scratches on the surface of the part during the pressing process of the back cover for the home appliance.
본 발명은 의장성, 내식성, 도막밀착성, 윤활성 및 밴딩성이 우수한 피막을 형성할 수 있고, 더불어, 자기치유특성이 우수한 자기치유제, 상기 자기치유제를 포함하는 코팅 조성물 및 이 코팅 조성물 피막을 갖는 강판을 제공하고자 한다.
The present invention can form a coating having excellent design, corrosion resistance, coating adhesion, lubricity and bending properties, and has a self-healing agent having excellent self-healing properties, a coating composition comprising the self-healing agent, and the coating composition coating. To provide a steel sheet having.
본 발명의 일측면인 자기치유제는 부식억제제가 침투된 고분자 시드와 상기 고분자 시드를 둘러싸는 쉘을 포함하고, 상기 부식억제제는 전체 자기치유제 중 30~60중량%로 포함되고, 자기치유제의 평균입경은 0.1~30㎛인 것을 특징으로 한다.
Self-healing agent, which is an aspect of the present invention, includes a polymer seed penetrating a corrosion inhibitor and a shell surrounding the polymer seed, wherein the corrosion inhibitor is comprised of 30 to 60% by weight of the total self-healing agent, and self-healing agent The average particle diameter of is characterized in that 0.1 ~ 30㎛.
본 발명의 다른 일측면인 유화중화방법에 의하여 제조되는 자기치유제의 제조방법은 400~500g의 증류수에 고분자 시드를 첨가하여 70~90℃로 온도를 유지하고, 새로운 증류수 5~25g에 소듐퍼설페이트 0.3~0.7g을 녹여 중탕액을 준비하는 단계, 부틸아크릴레이트 3~5g, 메틸메타크릴레이트 40~60g, 메타크릴릭애시드 0.5~2.5g을 혼합하여 제 1 혼합액을 준비하는 단계, 40~60g의 증류수에 계면활성제 소듐도데실설페이트 0.3~0.5g과 소듐퍼설페이트 0.5~0.7g, 스타이렌 100~120g을 넣고 혼합하여 제 2 혼합액을 준비하는 단계, 농도가 각각 0.1~0.3M인 트리에탄올아민과 칼슘클로라이드을 혼합하여 제 3 혼합액을 준비하는 단계, 상기 준비된 제 1 내지 제 3 혼합액을 순서대로 상기 준비된 중탕액에 첨가하여 최종 중탕액을 제조하는 단계 및 상기 최종 중탕액을 건조하는 단계를 포함한다.
In another aspect of the present invention, a method of preparing a self-healing agent prepared by an emulsion neutralization method is performed by adding a polymer seed to 400 to 500 g of distilled water to maintain a temperature at 70 to 90 ° C., and adding sodium per 5 to 25 g of distilled water. Dissolving 0.3-0.7 g of sulfate to prepare a bath solution, preparing a first mixed liquid by mixing butyl acrylate 3-5 g, methyl methacrylate 40-60 g, and methacrylic acid 0.5-2.5 g, 40- To prepare a second mixture by mixing 0.3-0.5 g of sodium dodecyl sulfate, 0.5-0.7 g of sodium persulfate, and 100-120 g of styrene in 60 g of distilled water, triethanolamine having a concentration of 0.1-0.3 M, respectively. Preparing a third mixed solution by mixing calcium chloride and preparing the third mixed solution, adding the prepared first to third mixed solutions in order to prepare the final heated solution, and drying the final heated solution. The.
본 발명의 다른 일측면은 흑색안료 분산체: 1~45중량%, 자기치유 첨가제: 0.1~20중량%, 수성유기수지: 20~80중량%, 무기금속 졸: 1~10중량%, 방청제: 1~10중량%, 부착증진제: 0.1~5중량%, 레벨링제: 0.01~5중량%, 왁스: 0.1~5중량%, 가교제: 5~50중량% 및 촉매: 3중량% 이하를 포함하고, 상기 자기치유 첨가제는 상기 자기치유 첨가제는 부식억제제가 침투된 고분자 시드와 상기 고분자 시드를 둘러싸는 쉘을 포함하는 자기치유 코팅 조성물을 제공한다.
Another aspect of the present invention is a black pigment dispersion: 1 to 45% by weight, self-healing additive: 0.1 to 20% by weight, aqueous organic resin: 20 to 80% by weight, inorganic metal sol: 1 to 10% by weight, rust inhibitor: 1 to 10% by weight, adhesion promoter: 0.1 to 5% by weight, leveling agent: 0.01 to 5% by weight, wax: 0.1 to 5% by weight, crosslinking agent: 5 to 50% by weight and catalyst: 3% by weight or less, The self-healing additive provides a self-healing coating composition comprising a polymer seed penetrated by a corrosion inhibitor and a shell surrounding the polymer seed.
본 발명의 다른 일측면은 흑색안료 분산체: 1~45중량%, 자기치유 첨가제: 0.1~20중량%, 수성유기수지: 20~80중량%, 무기금속 졸: 1~10중량%, 방청제: 1~10중량%, 부착증진제: 0.1~5중량%, 레벨링제: 0.01~5중량%, 왁스: 0.1~5중량%, 가교제: 5~50중량% 및 촉매: 3중량% 이하를 포함하고, 상기 자기치유 첨가제는 상기 자기치유 첨가제는 부식억제제가 침투된 고분자 시드와 상기 고분자 시드를 둘러싸는 쉘을 포함하는 자기치유 코팅 조성물을 강판에 코팅하고 경화하여 형성된 피막층을 포함하며, 상기 피막층의 두께는 2~30㎛인 자기치유 코팅 강판을 제공한다.
Another aspect of the present invention is a black pigment dispersion: 1 to 45% by weight, self-healing additive: 0.1 to 20% by weight, aqueous organic resin: 20 to 80% by weight, inorganic metal sol: 1 to 10% by weight, rust inhibitor: 1 to 10% by weight, adhesion promoter: 0.1 to 5% by weight, leveling agent: 0.01 to 5% by weight, wax: 0.1 to 5% by weight, crosslinking agent: 5 to 50% by weight and catalyst: 3% by weight or less, The self-healing additive includes a coating layer formed by coating and curing a self-healing coating composition comprising a polymer seed penetrating a corrosion inhibitor and a shell surrounding the polymer seed on a steel sheet, wherein the thickness of the coating layer is It provides a self-healing coated steel sheet of 2 ~ 30㎛.
덧붙여 상기한 과제의 해결수단은, 본 발명의 특징을 모두 열거한 것은 아니다. 본 발명의 다양한 특징과 그에 따른 장점과 효과는 아래의 구체적인 실시형태를 참조하여 보다 상세하게 이해될 수 있을 것이다.
In addition, the solution of the above-mentioned problems does not list all the features of the present invention. The various features of the present invention and the advantages and effects thereof will be more fully understood by reference to the following specific embodiments.
본 발명에 의하면, 의장성, 흑색도, 윤활성, 도막밀착성, 밴딩성, 내식성 및 자기회복력이 우수한 자기치유제, 상기 자기치유제를 포함하는 코팅 조성물 및 이 코팅 조성물 피막을 갖는 강판을 제공할 수 있다.
According to the present invention, it is possible to provide a self-healing agent excellent in designability, blackness, lubricity, coating film adhesion, banding property, corrosion resistance and self-recovering ability, a coating composition comprising the self-healing agent, and a steel sheet having the coating composition coating film. have.
도 1은 흑색수지강판의 구조를 나타낸 사시도이다.
도 2는 발명예 1의 자기치유 코팅 조성물의 전자주사 현미경(SEM) 사진이다.1 is a perspective view showing the structure of a black resin steel sheet.
2 is an electron scanning microscope (SEM) photograph of the self-healing coating composition of Inventive Example 1. FIG.
본 발명자들은 상도층의 박막화로 인하여 발생되는 종래의 문제점을 해결하고자 연구를 행한 결과, 자기치유 능력이 있는 코팅 조성물을 강판에 피복시킴으로써, 의장성, 흑색도, 윤활성, 도막밀착성, 밴딩성, 내식성 및 자기회복이 우수한 강판을 제안하게 되었다.
The present inventors conducted a study to solve the conventional problems caused by the thinning of the top coat layer, and as a result, by coating the steel sheet with a coating composition having a self-healing ability, design, blackness, lubricity, coating film adhesion, bending resistance, corrosion resistance And the steel sheet excellent in self-recovery has been proposed.
이하, 본 발명의 일측면인 자기치유제에 대하여 상세히 설명한다.
Hereinafter, the self-healing agent which is an aspect of the present invention will be described in detail.
본 발명의 일측면인 자기치유제는 부식억제제가 침투된 고분자 시드와 상기 고분자 시드를 둘러싸는 쉘을 포함하고, 상기 부식억제제는 전체 자기치유제 중 30~60중량%로 포함되고, 자기치유제의 평균입경은 0.1~30㎛인 것을 특징으로 한다.
Self-healing agent, which is an aspect of the present invention, includes a polymer seed penetrating a corrosion inhibitor and a shell surrounding the polymer seed, wherein the corrosion inhibitor is comprised of 30 to 60% by weight of the total self-healing agent, and self-healing agent The average particle diameter of is characterized in that 0.1 ~ 30㎛.
상기 자기치유 첨가제는 고분자 시드에 부식억제제를 침투시킨 뒤, 상기 고분자 시드의 외곽에 쉘을 형성시키는 과정으로 제조되는 것이 바람직하다.
The self-healing additive is preferably prepared by injecting a corrosion inhibitor into the polymer seed and then forming a shell on the outside of the polymer seed.
상기 자기치유첨가제는 고분자 시드와 이를 둘러싸는 쉘로 이루어진 고분자 캡슐에 부식억제제를 수용하고 있어, 소지강판에 피복된 부분에 스크래치가 발생되었을 경우, 캡슐 내부의 부식억제제가 방출되어 스크래치 부위에 노출된 소지강판을 보호하여 소지강판의 내식성을 향상시키는 역할을 한다.
The self-healing additive contains a corrosion inhibitor in a polymer capsule consisting of a polymer seed and a shell surrounding it, and when a scratch occurs in a portion coated on a steel sheet, the corrosion inhibitor inside the capsule is released and exposed to the scratch site. It protects the steel plate and serves to improve the corrosion resistance of the steel sheet.
또한, 상기 자기치유 첨가제는 고분자 시드와 이를 둘러싸는 쉘로 이루어진 고분자 캡슐: 40~70중량% 및 잔부 부식억제제로 구성되어 있는 것이 바람직하다. 상기 고분자 캡슐이 40중량% 미만인 경우에는 의장성 및 용액안정성이 저하되고 70중량%를 초과하는 경우에는 자기치유성이 저하된다.
In addition, the self-healing additive is preferably composed of a polymer capsule consisting of a polymer seed and a shell surrounding it: 40 to 70% by weight and the residual corrosion inhibitor. When the polymer capsule is less than 40% by weight, the designability and solution stability are lowered, and when it exceeds 70% by weight, the self-healing property is lowered.
또한, 상기 자기치유 첨가제의 평균입경은 0.1~30㎛인 것이 바람직하다. 0.1㎛ 미만인 경우에는 자기치유성이 저하되고, 30㎛를 초과하는 경우에는 의장성과 용액안정성이 저하된다.
In addition, the average particle diameter of the self-healing additive is preferably 0.1 ~ 30㎛. When less than 0.1 micrometer, self-healing property falls, and when it exceeds 30 micrometers, design and solution stability fall.
또한, 고분자 시드의 직경은 자기치유 첨가제의 직경의 90%미만인 것이 바람직하다. 상기 고분자 시드의 직경이 90% 이상인 경우에는 자기치유성이 열위해지는 문제가 있다. 보다 바람직하게는 자기치유 첨가제의 직경의 60% 미만의 고분자 시드의 직경을 가진다.
In addition, the diameter of the polymer seed is preferably less than 90% of the diameter of the self-healing additive. If the diameter of the polymer seed is 90% or more, there is a problem of inferior self-healing. More preferably has a diameter of the polymer seed less than 60% of the diameter of the self-healing additive.
더불어, 쉘을 직경방향으로 자르면 양쪽에 위치하는데 이때, 한쪽편의 쉘 두께는 쉘 전체 직경의 30% 미만인 것이 바람직하다. 쉘의 두께가 30% 이상인 경우에는 자기치유성이 열위해지는 문제가 있다. 보다 바람직하게는 자기치유 첨가제의 직경의 20% 미만의 쉘의 두께를 가진다. 상기와 같이 쉘의 두께가 5% 미만으로 얇은 경우에는 쉘의 두께가 너무 얇은 경우에는 구조 안전성에 문제가 있으므로, 5% 이상의 두께를 가지는 것이 바람직하다.
In addition, when the shell is cut in the radial direction, it is located on both sides, where the shell thickness of one side is preferably less than 30% of the total diameter of the shell. If the thickness of the shell is 30% or more, there is a problem that self-healing is inferior. More preferably has a thickness of the shell less than 20% of the diameter of the self-healing additive. If the thickness of the shell is less than 5% as described above, if the thickness of the shell is too thin, there is a problem in the structural safety, it is preferable to have a thickness of 5% or more.
고분자 시드 또는 고분자 쉘(이들은 동종의 재료로 이루어 질 수도 있으며, 이종의 재료로 이루어 질 수도 있음)의 비제한적인 예로는 폴리메틸메타크릴레이트, 폴리스타이렌 및 폴리아크릴레이트로 중 1종 이상을 포함하는 것이 바람직하다.
Non-limiting examples of polymeric seeds or polymeric shells, which may be of the same or different types of materials, include one or more of polymethylmethacrylate, polystyrene, and polyacrylates. It is preferable.
상기 부식억제제는 염기성 부식억제제 또는 이온계 부식억제제 중 1종 이상을 포함하는 것이 바람직하며, 보다 자세하게는 트리에탄올아민, 디메틸에탄올아민, 암모니아, 소듐하이드록사이드, 포타슘하이드록사이드, 칼슘하이드록사이드, 디에탄올아민으로 이루어지는 염기성 부식억제제 및 칼슘이온, 마그네슘이온, 아연이온, 칼륨이온으로 이루어지는 이온계 부식억제제 중 1종 이상을 포함하는 것이 바람직하다.
The corrosion inhibitor preferably contains at least one of a basic corrosion inhibitor or an ionic corrosion inhibitor, more specifically triethanolamine, dimethylethanolamine, ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, It is preferable to include at least 1 type of the basic corrosion inhibitor which consists of diethanolamine, and the ionic corrosion inhibitor which consists of calcium ion, magnesium ion, zinc ion, and potassium ion.
본 발명의 다른 일측면인 유화중화방법에 의하여 제조되는 자기치유제의 제조방법은 400~500g의 증류수에 고분자 시드를 첨가하여 70~90℃로 온도를 유지하고, 새로운 증류수 5~25g에 소듐퍼설페이트 0.3~0.7g을 녹여 중탕액을 준비하는 단계, 부틸아크릴레이트 3~5g, 메틸메타크릴레이트 40~60g, 메타크릴릭애시드 0.5~2.5g을 혼합하여 제 1 혼합액을 준비하는 단계, 40~60g의 증류수에 계면활성제 소듐도데실설페이트 0.3~0.5g과 소듐퍼설페이트 0.5~0.7g, 스타이렌 100~120g을 넣고 혼합하여 제 2 혼합액을 준비하는 단계, 농도가 각각 0.1~0.3M인 트리에탄올아민과 칼슘클로라이드을 혼합하여 제 3 혼합액을 준비하는 단계, 상기 준비된 제 1 내지 제 3 혼합액을 순서대로 상기 준비된 중탕액에 첨가하여 최종 중탕액을 제조하는 단계 및 상기 최종 중탕액을 건조하는 단계를 포함한다.
In another aspect of the present invention, a method of preparing a self-healing agent prepared by an emulsion neutralization method is performed by adding a polymer seed to 400 to 500 g of distilled water to maintain a temperature at 70 to 90 ° C., and adding sodium per 5 to 25 g of fresh distilled water. Dissolving 0.3-0.7 g of sulfate to prepare a bath solution, preparing a first mixed liquid by mixing butyl acrylate 3-5 g, methyl methacrylate 40-60 g, and methacrylic acid 0.5-2.5 g, 40- To prepare a second mixture by mixing 0.3-0.5 g of sodium dodecyl sulfate, 0.5-0.7 g of sodium persulfate, and 100-120 g of styrene in 60 g of distilled water, triethanolamine having a concentration of 0.1-0.3 M, respectively. Preparing a third mixed solution by mixing calcium chloride and preparing the third mixed solution, adding the prepared first to third mixed solutions in order to prepare the final heated solution, and drying the final heated solution. The.
상기 중탕액에 상기 제 1 내지 제 3 혼합액을 첨가할 때, 50~70분간 1300~1700rpm에서 교반하여 첨가하는 것이 바람직하다.
When adding the said 1st thru | or 3rd liquid mixture to the said bath liquid, it is preferable to add it, stirring at 1300-1700 rpm for 50-70 minutes.
상기 최종 중탕액은 pH가 9.5~11.5인 것이 바람직하다.
The final hot water is preferably a pH of 9.5 ~ 11.5.
이하, 본 발명의 다른 일측면인 자기치유제를 포함하는 코팅 조성물에 대하여 상세히 설명한다.
Hereinafter, the coating composition including the self-healing agent which is another aspect of the present invention will be described in detail.
본 발명의 다른 일측면은 흑색안료 분산체: 1~45중량%, 자기치유 첨가제: 0.1~20중량%, 수성유기수지: 20~80중량%, 무기금속 졸: 1~10중량%, 방청제: 1~10중량%, 부착증진제: 0.1~5중량%, 레벨링제: 0.01~5중량%, 왁스: 0.1~5중량%, 가교제: 5~50중량% 및 촉매: 3중량% 이하를 포함하고, 상기 자기치유 첨가제는 상기 자기치유 첨가제는 부식억제제가 침투된 고분자 시드와 상기 고분자 시드를 둘러싸는 쉘을 포함하는 자기치유 코팅 조성물을 제공한다.
Another aspect of the present invention is a black pigment dispersion: 1 to 45% by weight, self-healing additive: 0.1 to 20% by weight, aqueous organic resin: 20 to 80% by weight, inorganic metal sol: 1 to 10% by weight, rust inhibitor: 1 to 10% by weight, adhesion promoter: 0.1 to 5% by weight, leveling agent: 0.01 to 5% by weight, wax: 0.1 to 5% by weight, crosslinking agent: 5 to 50% by weight and catalyst: 3% by weight or less, The self-healing additive provides a self-healing coating composition comprising a polymer seed penetrated by a corrosion inhibitor and a shell surrounding the polymer seed.
본 발명에서 흑색안료 분산체는 높은 흑색도와 의장성을 확보하기 위하여 매우 작은 크기의 흑색안료 입자를 사용하는데, 이로 인하여 흑색안료 입자의 표면적은 매우 넓어지게 되고, 코팅 조성물 내에 흑색안료 입자를 균일하게 분산시킬 수 있다.
In the present invention, the black pigment dispersion uses black pigment particles having a very small size in order to secure high blackness and designability, and thus, the surface area of the black pigment particles becomes very wide, and uniformly disperses the black pigment particles in the coating composition. Can be dispersed.
보다 바람직한 분산을 위해서는 단순한 용액 교반을 행하는 것 보다 밀링과 같은 기계적인 교반을 행하는 것이 보다 바람직하다.
For more preferable dispersion, it is more preferable to perform mechanical stirring such as milling than to perform simple solution stirring.
상기 흑색안료 분산체가 1중량% 미만으로 포함되면 흑색도와 의장성이 저하되고, 반면에 흑색안료 분산체가 45중량%를 초과하는 경우에는 내식성, 도막밀착성이 저하된다. 따라서, 상기 흑색안료 분산체는 1~45중량%로 포함하는 것이 바람직하다.
If the black pigment dispersion is contained in an amount of less than 1% by weight, the blackness and decorative properties are lowered. On the other hand, when the black pigment dispersion exceeds 45% by weight, corrosion resistance and film adhesion are lowered. Therefore, the black pigment dispersion is preferably contained in an amount of 1 to 45% by weight.
또한, 본 발명에 사용 가능한 흑색안료 분산체는 분산용 수성유기수지 및 흑색안료로 구성되어 있는 것이 바람직하다. 보다 바람직하게는 상기 흑색안료 분산체의 분산 안정성 확보 및 분산 과정에서 점도 조절을 위하여 분산안정제 및 물을 포함시키는 것이 바람직하다. 즉, 상기 흑색안료 분산체는 흑색도와 의장성이 우수한 물질을 포함하고 있어, 소지 강판에 본 발명이 제안한 자기치유 코팅 조성물을 피복할 때, 소지 강판의 흑색도, 용액안정성 및 의장성을 향상시킬 수 있다.
In addition, the black pigment dispersion usable in the present invention is preferably composed of an aqueous organic resin for dispersion and a black pigment. More preferably, it is preferable to include a dispersion stabilizer and water for viscosity control in securing the dispersion stability and dispersion process of the black pigment dispersion. That is, the black pigment dispersion contains a material having excellent blackness and designability, and when the self-healing coating composition proposed by the present invention is coated on the steel sheet, the blackness, solution stability and designability of the steel sheet are improved. Can be.
따라서, 한가지 바람직한 측면에 따르면 상기 흑색안료 분산체는 분산용 수성유기수지: 10~85중량%, 흑색안료: 5~60중량%, 분산안정제: 0.5~10중량% 및 물: 5~40중량%로 포함할 수 있다.
Thus, according to one preferred aspect, the black pigment dispersion is an aqueous organic resin for dispersion: 10 to 85% by weight, black pigment: 5 to 60% by weight, dispersion stabilizer: 0.5 to 10% by weight and water: 5 to 40% by weight It can be included as.
상기 분산용 수성유기수지는 흑색안료를 균일하게 분산시키기 위한 것으로 그 함량이 10중량% 미만인 경우에는 용액 안정성과 의장성이 저하될 수 있다. 반면에, 85중량%를 초과하는 경우에는 흑색도와 의장성이 저하된다.
The dispersion aqueous organic resin is to uniformly disperse the black pigment, when the content is less than 10% by weight may reduce solution stability and designability. On the other hand, when it exceeds 85 weight%, blackness and designability fall.
본 발명에 사용 가능한 상기 분산용 수성유기수지는 흑색안료를 잘 분산시킬 수 있는 수성유기수지라면 특별히 한정하지 않지만, 비제한적인 예로는 수분산 우레탄 수지, 수분산 아크릴 수지, 수용성 에폭시, 수용성 폴리에스테르 수지 및 수용성 아미노 수지로 이루어진 그룹에서 선택된 1종 이상을 포함할 수 있다.
The aqueous organic resin for dispersion that can be used in the present invention is not particularly limited as long as it is an aqueous organic resin capable of dispersing black pigments, but non-limiting examples include water-dispersed urethane resins, water-dispersed acrylic resins, water-soluble epoxy resins and water-soluble polyester resins. And it may include one or more selected from the group consisting of a water-soluble amino resin.
흑색안료는 원하는 색상을 나타내기 위한 것으로 그 함량이 5 중량% 미만인 경우에는 흑색도와 의장성이 저하되고, 60중량%를 초과하는 경우에는 지나치게 많은 포함되어 흑색안료의 뭉침현상으로 인해 용액안정성과 의장성이 저하된다.
The black pigment is intended to show the desired color. When the content is less than 5% by weight, the blackness and the designability are lowered, and when the content exceeds 60% by weight, the black pigment is included in the solution stability and design due to the aggregation of the black pigment. The castle is degraded.
더불어, 본 발명에 사용 가능한 상기 흑색안료 입자의 비제한적인 예로는 탄소 나노튜브(CNT: Carbon nano Tube), 탄소 섬유, 카본 블랙(CB: Carbon Black), 그래파이트 및 그래핀 중 1종 이상을 선택할 수 있다.
In addition, as a non-limiting example of the black pigment particles usable in the present invention, one or more selected from carbon nanotubes (CNT: Carbon nanotube), carbon fiber, carbon black (CB: Carbon Black), graphite and graphene Can be.
또한, 수지 피복 강판의 적절한 흑색도를 구현하기 위해서 상기 흑색안료 입자의 평균 입경은 2~10000㎚인 것이 바람직하다. 상기 흑색안료 분산체의 평균 입경이 2㎚미만인 경우에는 용액의 안전성이 저하되며, 10000㎚를 초과하는 경우에는 흑색도와 의장성이 저하된다.
In addition, in order to realize the appropriate blackness of the resin coated steel sheet, the average particle diameter of the black pigment particles is preferably 2-10000 nm. When the average particle diameter of the black pigment dispersion is less than 2 nm, the safety of the solution is lowered, and when it exceeds 10000 nm, the blackness and the designability are lowered.
또한, 흑색안료 입자는 용액에 직접 교반을 통해서는 적절한 분산안정성을 구현하기가 어려울 뿐만 아니라, 불균일한 분산 상태는 안료의 적절한 흑색도를 구현하는데 어렵다. 따라서, 용이한 분산을 위해서는 통상의 용액 교반 대신 밀링이라는 별도의 분산과정을 통하는 것이 바람직하다. 상기 흑색안료 입자는 수성유기수지에 분산시켜 사용하는 것이 바람직하다. 다만, 그 상태로는 분산이 충분하지 않으므로 0.5~10%의 분산안정제를 더 포함하여 사용하는 것이 바람직하다. 또한, 점도 조절을 위하여 5~40%의 물을 더 포함하여 사용하는 것이 바람직하다.
In addition, the black pigment particles are not only difficult to achieve proper dispersion stability through direct stirring in the solution, but also the uneven dispersion state is difficult to achieve the proper blackness of the pigment. Therefore, for easy dispersion, it is preferable to use a separate dispersion process called milling instead of the usual solution agitation. The black pigment particles are preferably used after being dispersed in an aqueous organic resin. However, since the dispersion is not enough in that state, it is preferable to further include 0.5 to 10% of a dispersion stabilizer. In addition, it is preferable to further include 5 to 40% of water for viscosity control.
또한, 상기 전술한 방법으로 제조된 자기치유제는 0.1~20중량% 포함되는 것이 바람직하다. 상기 자기치유 첨가제가 0.1중량% 미만인 경우에는 자기치유성이 저하되며, 20 중량%를 초과하는 경우에는 의장성 및 용액 안정성이 저하된다.
In addition, the self-healing agent prepared by the above-described method is preferably included 0.1 to 20% by weight. When the self-healing additive is less than 0.1% by weight, the self-healing property is lowered. When the self-healing additive is more than 20% by weight, the designability and solution stability are lowered.
또한, 본 발명에서는 내식성, 도막 밀착성 및 의장성을 향상시키기 위하여 수성 유기수지를 포함한다.
In addition, the present invention includes an aqueous organic resin to improve the corrosion resistance, coating film adhesion and design.
상기 수성 유기수지가 20중량% 미만인 경우에는 본 발명이 의도하는 효과를 발휘할 수 없으며, 80중량%를 초과하는 경우에는 흑색도가 저하된다.
When the aqueous organic resin is less than 20% by weight, the intended effect of the present invention cannot be exhibited, and when the aqueous organic resin exceeds 80% by weight, the blackness is lowered.
본 발명에 사용 가능한 수성 유기수지의 비제한적인 예로는 수분산 우레탄 수지, 수분산 아크릴 수지, 수용성 에폭시, 수용성 폴리에스테르 수지 및 수용성 아미노 수지 중 1종 이상을 선택할 수 있다.
Non-limiting examples of the aqueous organic resin usable in the present invention may be selected from one or more of water-dispersed urethane resins, water-dispersed acrylic resins, water-soluble epoxy, water-soluble polyester resins and water-soluble amino resins.
또한, 본 발명에서는 내식성을 향상시키기 위하여 무기금속 졸 및 방청제를 포함한다.
In addition, the present invention includes an inorganic metal sol and rust inhibitor to improve the corrosion resistance.
이들은 각각 1~10중량%로 포함되는 것이 바람직한데, 상기 무기금속 졸 및 방청제가 1 중량% 미만인 경우에는 본 발명에서 의도하고자 하는 내식성을 확보할 수 없고, 10 중량%를 초과하는 경우에는 용액 안정성이 저하된다.
They are preferably contained in 1 to 10% by weight, respectively, when the inorganic metal sol and the rust preventive agent is less than 1% by weight can not secure the corrosion resistance intended in the present invention, when it exceeds 10% by weight solution stability Is lowered.
본 발명에 사용 가능한 무기금속 졸의 비제한적인 예는 실리카 졸, 알루미나 졸, 티타니아 졸 및 지르코니아 졸 중 1종 이상을 선택할 수 있다.
Non-limiting examples of inorganic metal sols usable in the present invention may select one or more of silica sol, alumina sol, titania sol and zirconia sol.
더불어, 본 발명에 사용 가능한 방청제는 알루미늄 또는 중인산 알루미늄과 같은 금속 화합물, 헥사암모늄 헵타몰리브데이트 테트라하이드레이트의 인산 수용액, 아연, 몰리브덴, 불소 및 붕산 중 1종 이상을 선택할 수 있다.
In addition, the rust inhibitors usable in the present invention may select at least one of a metal compound such as aluminum or aluminum phosphate, an aqueous solution of phosphate of hexaammonium heptamolybdate tetrahydrate, zinc, molybdenum, fluorine and boric acid.
또한, 본 발명에서는 도막밀착성 및 내식성을 향상시키기 위하여 부착증진제를 포함한다.
In addition, the present invention includes an adhesion promoter to improve coating film adhesion and corrosion resistance.
상기 부착증진제가 0.1 중량% 미만인 경우에는 본 발명에서 의도하고자 하는 도막밀착성 및 내식성을 확보할 수 없고, 5 중량%를 초과하는 경우에는 용액 안정성이 저하된다.
If the adhesion promoter is less than 0.1% by weight, it is not possible to secure the coating film adhesion and corrosion resistance intended in the present invention, when it exceeds 5% by weight solution stability is lowered.
본 발명에 사용 가능한 부착증진제의 비제한적인 예는 비닐 트리에톡시 실란, 2-글리실 옥시 프로필 트리메톡시실란, 3-글리실 옥시프로필메틸 디메톡시실란, N-2-(아미노에틸)-3-아미노프로필 트리에톡시 실란, 4-아미노프로필 트리에톡시 실란 등으로 이루어지는 실란계 커플링제, 티타늄 아세틸 아세토네이트, 이소-부톡시 티타늄 에틸 아세토 아세테이트, 테트라 이소프로필 티타네이트, 테트라 노말 부틸 티타네이트로 등으로 이루어지는 티타늄계 커플링제 및 테트라 노말-프로필 지르코네이트, 테트라 노말-부틸 지르코네이트, 트리에탄올 아민 지르코네이트, 헥사플루오로 지르코네이트 등으로 이루어지는 지르코늄계 커플링제 중 1종 이상을 선택할 수 있다.
Non-limiting examples of adhesion promoters that can be used in the present invention include vinyl triethoxy silane, 2-glycyl oxy propyl trimethoxysilane, 3-glycyl oxypropylmethyl dimethoxysilane, N-2- (aminoethyl)- Silane coupling agent consisting of 3-aminopropyl triethoxy silane, 4-aminopropyl triethoxy silane and the like, titanium acetyl acetonate, iso-butoxy titanium ethyl aceto acetate, tetra isopropyl titanate, tetra normal butyl titanate At least one selected from the group consisting of a titanium-based coupling agent and tetra-normal-propyl zirconate, tetra-normal-butyl zirconate, triethanol amine zirconate, hexafluoro zirconate, etc. Can be.
또한, 본 발명에서는 자기치유 코팅 조성물의 용제로 사용되는 물의 표면장력과 수지 및 각종 첨가제로 사용되는 고분자 물질의 표면장력 차이를 감소시켜 크레이터 발생, 얼룩 현상 등을 최소화하여 표면 처리강판의 의장성을 향상키시기 위하여 레벨링제를 포함한다.
In addition, in the present invention, by reducing the difference in the surface tension of the water used as the solvent of the self-healing coating composition and the surface tension of the polymer and the polymer material used as various additives to minimize the crater generation, staining, etc. design of the surface-treated steel sheet Includes leveling agent to improve.
상기 레벨링제가 0.01중량% 미만인 경우에는 본 발명에서 확보하고자 하는 의장성을 확보할 수 없고, 5중량%를 초과하는 경우에는 용액 안정성 및 도막 밀착성이 저하된다.
If the leveling agent is less than 0.01% by weight, the designability to be secured in the present invention cannot be secured. If the leveling agent is more than 5% by weight, the solution stability and the coating film adhesion decrease.
본 발명에 사용 가능한 레벨링제의 비제한적인 예는 폴리실록산, 폴리아크릴레이트, 플루오르카본 폴리실록산, 플루오르카본 폴리아크릴레이트, 디메틸폴리실록산, 폴리메틸 알킬실록산, 실리콘 오일 및 메틸페닐폴리실록산 중 1종 이상을 선택할 수 있다.
Non-limiting examples of leveling agents usable in the present invention may select one or more of polysiloxanes, polyacrylates, fluorocarbon polysiloxanes, fluorocarbon polyacrylates, dimethylpolysiloxanes, polymethyl alkylsiloxanes, silicone oils and methylphenylpolysiloxanes. .
또한, 본 발명에서는 윤활성을 향상시키기 위하여 왁스를 포함한다.
In the present invention, wax is included to improve lubricity.
상기 왁스가 0.1중량% 미만인 경우에는 본 발명에서 확보하고자 하는 윤활성을 확보할 수 없고, 5 중량%를 초과하는 경우에는 도막밀착성이 저하된다.
If the wax is less than 0.1% by weight, the lubricity to be secured in the present invention cannot be secured, and if the wax is more than 5% by weight, the coating film adhesiveness is lowered.
본 발명에 사용 가능한 왁스의 비제한적인 예는 칸델릴라(Candelilla) 왁스, 카나우바(Carnauba) 왁스, 캐스터 왁스, 에스팔토 왁스, 오우리큐리 왁스, 베이베리 왁스, 조조바 왁스, 라이스브랜 왁스, 소이 왁스 등의 식물성 왁스군과 파라핀 왁스, 폴리에틸렌 왁스, 피셔-트롭스 왁스, 아마이드 왁스, 폴리프로필렌 왁스, 폴리올레핀 왁스 및 이들의 변성 왁스를 포함하는 합성수지 왁스 중 1종 이상을 선택할 수 있다.
Non-limiting examples of waxes that can be used in the present invention include Candelilla wax, Carnauba wax, Caster wax, Espalto wax, Ouerkyl wax, Bayberry wax, Jojoba wax, Rice bran wax, Wax, and synthetic waxes including paraffin wax, polyethylene wax, Fischer-Tropsch wax, amide wax, polypropylene wax, polyolefin wax, and modified waxes thereof.
또한, 본 발명에서는 경화성을 향상시키기 위하여 가교제 및 촉매를 포함한다.
In addition, the present invention includes a crosslinking agent and a catalyst in order to improve the curability.
상기 가교제가 5 중량% 미만인 경우에는 경화가 완료되지 않지 않을 수 있으며, 50 중량%를 초과하면 과경화로 인해 밴딩성이 부족하다.
If the crosslinking agent is less than 5% by weight, the curing may not be completed. If the crosslinking agent is more than 50% by weight, bending properties are insufficient due to overcuring.
더불어, 상기 촉매가 3 중량%를 초과하는 경우에는 첨가 대비 경화속도가 향상되지 않을 뿐만 아니라, 용액 안정성이 저하된다.
In addition, when the catalyst exceeds 3% by weight, not only does the curing rate increase compared to the addition, but the solution stability is lowered.
본 발명에 사용 가능한 가교제는 멜라민계 가교제, 이소시아네이트계 가교제 및 아지리딘계 가교제 중 1종 이상을 선택하여 포함할 수 있다.
The crosslinking agent usable in the present invention may include at least one selected from a melamine crosslinking agent, an isocyanate crosslinking agent and an aziridine crosslinking agent.
또한, 본 발명에 사용 가능한 촉매는 파라톨루엔 설포닉애시드, 알키드벤젠 설포닉애시드, 아세틸아세톤 및 벤질 알코올 중 1종 이상을 포함할 수 있다.
In addition, the catalyst usable in the present invention may include at least one of paratoluene sulfonic acid, alkydbenzene sulfonic acid, acetylacetone and benzyl alcohol.
상기 코팅 조성물을 이용하여 강판의 표면에 코팅층을 형성시킬 수 있다. 상기 코팅은 어떠한 코팅방법에 제한되는 것은 아니며, 코팅할 수 있는 방법이라면, 어느 방법으로도 실시될 수 있다. 상기 용액을 강판에 코팅하는 일부 예로서 침지, 분사, 도포 등 본 기술분야에서 통상적으로 사용되는 방법을 적용할 수 있다
The coating composition can be used to form a coating layer on the surface of the steel sheet. The coating is not limited to any coating method, and any method can be used as long as it is a coating method. As some examples of coating the solution on a steel sheet, methods commonly used in the art, such as dipping, spraying, and coating may be applied.
본 발명의 다른 일측면은 흑색안료 분산체: 1~45중량%, 자기치유 첨가제: 0.1~20중량%, 수성유기수지: 20~80중량%, 무기금속 졸: 1~10중량%, 방청제: 1~10중량%, 부착증진제: 0.1~5중량%, 레벨링제: 0.01~5중량%, 왁스: 0.1~5중량%, 가교제: 5~50중량% 및 촉매: 3중량% 이하를 포함하고, 상기 자기치유 첨가제는 상기 자기치유 첨가제는 부식억제제가 침투된 고분자 시드와 상기 고분자 시드를 둘러싸는 쉘을 포함하는 자기치유 코팅 조성물을 강판에 코팅하고 경화하여 형성된 피막층을 포함하며, 상기 피막층의 두께는 2~30㎛인 자기치유 코팅 강판을 제공한다.
Another aspect of the present invention is a black pigment dispersion: 1 to 45% by weight, self-healing additive: 0.1 to 20% by weight, aqueous organic resin: 20 to 80% by weight, inorganic metal sol: 1 to 10% by weight, rust inhibitor: 1 to 10% by weight, adhesion promoter: 0.1 to 5% by weight, leveling agent: 0.01 to 5% by weight, wax: 0.1 to 5% by weight, crosslinking agent: 5 to 50% by weight and catalyst: 3% by weight or less, The self-healing additive includes a coating layer formed by coating and curing a self-healing coating composition comprising a polymer seed penetrating a corrosion inhibitor and a shell surrounding the polymer seed on a steel sheet, wherein the thickness of the coating layer is It provides a self-healing coated steel sheet of 2 ~ 30㎛.
상기와 같이 본 발명의 자기치유 코팅 조성물을 사용하여 강판에 형성된 자기치유 코팅 강판의 두께는 2~30㎛인 것이 바람직하다. 상기 피막층의 두께가 2㎛ 미만인 경우에는 본 발명이 의도하는 표면처리 강판의 의장성, 자기치유성 및 내식성이 구현되지 못하며, 반면에 30㎛를 초과하는 경우에는 표면처리 강판의 도막밀착성 및 밴딩성이 저하되는 문제가 있다.
As described above, the thickness of the self-healing coated steel sheet formed on the steel sheet using the self-healing coating composition of the present invention is preferably 2 to 30 µm. If the thickness of the coating layer is less than 2㎛ the designability, self-healing and corrosion resistance of the surface-treated steel sheet intended by the present invention is not realized, whereas if the thickness of the coating layer exceeds 30㎛ coating film adhesion and banding properties of the surface-treated steel sheet This has a problem of deterioration.
더불어, 본 발명의 강판은 자기치유 코팅 조성물을 피복시키는 경우라면 다른 코팅층을 피복시키는 경우 포함하더라도 상관 없다. 비제한적인 일례로, 도 1에 나타난 바와 같이 소지강판(2) 위에 하도층(3)을 형성시킨 후 자기치유 코팅 조성물과 같은 상도층(1)을 피복시키는 경우 본 발명의 효과를 더욱 향상시킬 수 있다.
In addition, the steel sheet of the present invention may be included in the case of coating the self-healing coating composition in the case of coating another coating layer. As a non-limiting example, when the undercoat 3 is formed on the
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 한다. 다만, 하기의 실시예는 본 발명을 예시하여 보다 상세하게 설명하기 위한 것일 뿐, 본 발명의 권리범위를 한정하기 위한 것이 아니라는 점에 유의할 필요가 있다. 본 발명의 권리범위는 특허청구범위에 기재된 사항과 이로부터 합리적으로 유추되는 사항에 의해 결정되는 것이기 때문이다.
Hereinafter, the present invention will be described more specifically by way of examples. It should be noted, however, that the following examples are intended to illustrate the invention in more detail and not to limit the scope of the invention. The scope of the present invention is determined by the matters set forth in the claims and the matters reasonably inferred therefrom.
(실시예 1)(Example 1)
하기 표 1 및 표 2에 나타난 바와 같은 조성 및 성분범위를 갖는 구성을 지르코니아 볼에 첨가한 후, 볼 밀에서 3500rpm 으로 2시간 작동시켜 흑색안료 분산체를 제조하였다. 이때, 수성유기수지는 폴리우레탄 수성 수지 Sancure 898 (Lubrizol)을 사용하였고, 분산안정제는 Solsperse 27000 (Lubrizol)을 사용하였다.
A composition having a composition and component range as shown in Table 1 and Table 2 was added to the zirconia ball, and then operated at 3500 rpm in a ball mill for 2 hours to prepare a black pigment dispersion. At this time, the aqueous organic resin was used as a polyurethane aqueous resin Sancure 898 (Lubrizol), the dispersion stabilizer was Solsperse 27000 (Lubrizol).
함량(%)Aqueous organic resin
content(%)
함량(%)Dispersion Stabilizer
content(%)
함량(%)Distilled water
content(%)
함량(%)Aqueous organic resin
content(%)
함량(%)Dispersion Stabilizer
content(%)
함량(%)Distilled water
content(%)
상기 제조된 흑색안료 분산체 20중량%, 자기치유 첨가제 9중량%, 폴리우레탄 수성 수지 Sancure 898 (Lubrizol) 48 중량%, 실리카 졸(Snowtex-N, Nissin Chemical사(제)) 4 중량%, 방청제 FAC-600 (FTC Korea) 3 중량%, 부착증진제 Tyzor-LA (DuPont) 0.5 중량%, 레벨링제 EFKA 3030 (EFKA) 0.5 중량%, 왁스 Microspersion 523 (Micro powders, inc.) 3.5 중량%, 가교제 Cymel 303 (CYTEC) 11 중량% 및 촉매 Nacure 2547 (King) 0.5 중량%를 상온에서 교반하여 자기치유 코팅 조성물을 제조하였다.
20% by weight of the prepared black pigment dispersion, 9% by weight of self-healing additive, polyurethane aqueous resin Sancure 898 (Lubrizol) 48% by weight, silica sol (Snowtex-N, Nissin Chemical Co., Ltd.) 4% by weight, rust inhibitor FAC-600 (FTC Korea) 3% by weight, adhesion promoter Tyzor-LA (DuPont) 0.5% by weight, leveling agent EFKA 3030 (EFKA) 0.5% by weight, wax Microspersion 523 (Micro powders, inc.) 3.5% by weight, crosslinking agent Cymel 11 wt% of 303 (CYTEC) and 0.5 wt% of the catalyst Nacure 2547 (King) were stirred at room temperature to prepare a self-healing coating composition.
이때, 자기치유 첨가제는 다음과 같은 과정에 의해 제조하였다. 80℃로 온도를 유지하고 있는 450g의 증류수에 라텍스 코어 60g (KCC, H9180)을 첨가하여 고분자 시드 용액을 제조하였다. 상기 제조된 고분자 시드 용액에 증류수 15g에 소듐퍼설페이트 0.5g가 혼합된 수용성 퍼설페이트계 중합개시제 용액을 혼합하였다. 상기와 같이 혼합된 고분자 시드 용액에 부틸아크릴레이트 4g, 메틸메타크릴레이트 50g, 메타크릴릭애시드 1.5g을 혼합한 후, 증류수 50g에 계면활성제 소듐도데실설페이트 0.4g과 소듐퍼설페이트 0.6g, 스타이렌 110g이 혼합된 계면활성제 용액을 혼합하였다. 마지막으로 각각 0.1M의 농도를 가진 트리에탄올아민과 칼슘클로라이트를 혼합하여 트리에탄올아민과 칼슘클로라이트 혼합용액 혼합하여 pH가 10.5인 중합 용액을 제조하였다. 상기와 같이 제조된 중합 용액을 건조하여 평균입경이 2㎛인 자기치유 첨가제를 제조하였다. 이때, 혼합은 온도의 변화가 최소화 되도록 중탕액에서 제조하였으며, 60분간 1500rpm의 교반속도로 혼합하였다.
At this time, the self-healing additive was prepared by the following process. A polymer seed solution was prepared by adding 60 g of latex core (KCC, H9180) to 450 g of distilled water maintained at 80 ° C. A water-soluble persulfate-based polymerization initiator solution in which 0.5 g of sodium persulfate was mixed with 15 g of distilled water was mixed with the prepared polymer seed solution. After mixing 4 g of butyl acrylate, 50 g of methyl methacrylate, and 1.5 g of methacrylic acid in the mixed polymer seed solution as described above, 0.4 g of surfactant sodium dodecyl sulfate and 0.6 g of sodium persulfate were added to 50 g of distilled water. The surfactant solution mixed with 110 g of lene was mixed. Finally, triethanolamine and calcium chlorite having a concentration of 0.1 M were mixed, and triethanolamine and calcium chlorite mixed solution were mixed to prepare a polymerization solution having a pH of 10.5. The polymerization solution prepared as described above was dried to prepare a self-healing additive having an average particle diameter of 2 μm. At this time, the mixing was prepared in a bath solution so that the change in temperature is minimized, and mixed at a stirring speed of 1500rpm for 60 minutes.
상기와 같이 제조된 자기치유 코팅 조성물을 아연 부착량이 각각 20 g/m2인 전기아연도금 강판(강판 두께: 0.45 mm)에 롤 코터를 이용하여 코팅 후 180℃에서 건조 및 경화하여 건조 후 두께가 12 ㎛가 되도록 강판을 제조하였다. 상기와 같이 제조된 강판을 하기 기재한 평가 기준에 의하여 흑색도, 도막밀착성, 밴딩성 및 의장성을 측정한 후, 그 결과를 하기 표 3 및 4에 나타내었다.
The self-healing coating composition prepared as described above was coated on an electrogalvanized steel sheet (steel sheet thickness: 0.45 mm) having a zinc adhesion amount of 20 g / m 2 , respectively, using a roll coater, dried and cured at 180 ° C., and then dried. Steel sheet was prepared to be 12 μm. After measuring the blackness, coating film adhesion, bending and designability of the steel sheet prepared as described above by the evaluation criteria described below, the results are shown in Tables 3 and 4 below.
1) 흑색도 측정1) blackness measurement
제조된 강판을 Lab 색차계(ColorEye XTH, GretagMacbeth사(제))를 이용하여 강판의 L 좌표 값(백색도 값)을 측정하였고, 하기와 같은 평가 기준에 따라 흑색도를 평가하였다.
The L-coordinate value (whiteness value) of the steel sheet was measured using a Lab colorimeter (ColorEye XTH, GretagMacbeth Co., Ltd.), and the blackness was evaluated according to the following evaluation criteria.
<흑색도의 평가 기준><Evaluation Criteria of Blackness>
○: 표면처리 강판의 L 좌표 값이 26 이하인 경우?: When the L coordinate value of the surface-treated steel sheet is 26 or less
×: 표면처리 강판의 L 좌표 값이 26 초과인 경우
X: When the L coordinate value of the surface-treated steel sheet exceeds 26
2) 도막밀착성 측정2) Coating film adhesion measurement
제조된 강판을 150cm×75cm(가로×세로)의 크기로 재단하여 시편을 제조하고, 상기 시편의 표면을 크로스 컷 가이드(cross cut guide)를 이용하여 1 mm의 간격으로 가로 및 세로 각각 100 개의 칸을 형성하도록 줄을 그은 후, 상기 100 개의 칸이 형성된 부분을 에릭슨(erichsen) 시험기를 이용하여 6 mm의 높이로 밀어 올리며, 밀어 올린 부위에 박리 테이프(NB-1, Ichiban사(제))를 부착한 후 떼어내면서 에릭슨 부분이 박리되는지 여부를 관찰하였다.
The prepared steel sheet was cut into a size of 150 cm x 75 cm (width x length) to prepare specimens. The surfaces of the specimens were cut into 100 squares (width: 100 squares) at intervals of 1 mm using a cross cut guide And then a portion of the 100 columns was pushed up to a height of 6 mm using an erichsen tester and peeling tape (NB-1, manufactured by Ichiban Co., Ltd.) was applied to the pushed portion After attaching and detaching, it was observed whether or not the Ericsson part was peeled off.
<도막밀착성의 평가 기준>≪ Evaluation Criteria of Coating Film Adhesion &
○: 표면의 박리가 없는 경우○: When there is no peeling of the surface
△: 표면의 박리가 100 개 중 1개 내지 3개인 경우?: 1 to 3 of 100 peelings on the surface
×: 표면의 박리가 100 개 중 3개를 초과한 경우
X: When the peeling of the surface exceeds 3 out of 100
3) 밴딩성 측정3) Bending property measurement
제조된 강판의 밴딩성 측정은 자기치유 코팅 조성물의 피막 및 경화 후 0T 밴딩을 하고 접힌 면을 확대 관찰하여 다음과 같은 기준에 의하여 평가하였다.
The bending properties of the prepared steel sheet were evaluated by coating the self-healing coating composition and 0 T banding after curing and observing the folded surface enlarged and evaluated according to the following criteria.
<밴딩성 평가 기준>≪ Bending property evaluation standard &
○: 0%, 10%, 20% 인장 후 0T 밴딩 및 테이핑 박리를 하였을 때 모두 크랙의 흔적 없이 깨끗한 경우○: 0%, 10%, 20% 0T banding and taping peeling after stretching are all clean without any cracks
△: 0% 인장 후 0T 밴딩 및 테이핑 박리 시에는 크랙의 흔적이 없으나 10%, 20% 인장 후 0T 밴딩 및 테이핑 박리 시에는 부분 크랙의 흔적이 보일 경우△: There is no cracking at 0 T banding and taping peeling after 0% tensile, but 0 T after tensile and 20% tensile peeling, and partial cracking is visible at taping peeling.
×: 0%, 10%, 20% 인장 후 0T 밴딩 및 테이핑 박리를 하였을 때 부분 크랙 혹은 도막 전체 박리가 일어날 경우
X: 0%, 10%, 20% When 0T banding or taping peeling is performed after tensile, a partial crack or peeling of the entire film occurs
4) 의장성 측정4) designability measurement
제조된 강판의 경화 후에 표면 결함은 육안 및 현미경으로 관찰하여 다음 기준에 의하여 평가하였다.
After curing of the prepared steel sheet, surface defects were visually observed with a microscope and evaluated according to the following criteria.
<의장성 평가 기준><Evaluation criteria for design>
○: 육안 및 현미경으로 10배 확대하여 관찰 시 뚜렷한 결함이 없는 경우○: When there is no obvious defect when observing 10 times magnification with naked eye and microscope
△: 육안으로 관찰 시에는 뚜렷한 결함이 없으나 현미경으로 10배 확대하여 관찰할 경우 색의 변화나 부분박리가 보일 경우△: There is no obvious defect when observing with the naked eye, but when observed with magnification 10 times under a microscope, when color change or partial peeling is observed
×: 육안으로 관찰 시에 뚜렷한 결함이 보일 경우
X: When a clear defect is observed when observing with the naked eye
상기 표 3에 나타난 바와 같이, 발명예 1 내지 15는 본 발명의 흑색안료 분산체 조건에 해당하는 경우 흑색도, 도막밀착성, 밴딩성 및 의장성이 모두 우수함을 확인할 수 있다.
As shown in Table 3, Inventive Examples 1 to 15 can be confirmed that all of the blackness, coating adhesion, bending and designability when the black pigment dispersion conditions of the present invention.
반면에, 상기 표 4에 기재된 바와 같이, 비교예 1 내지 12는 본 발명이 제안한 범위를 만족하는 않는 흑색안료 분산체를 가짐으로써, 흑색도, 도막밀착성, 밴딩성 및 의장성 중 적어도 2개 이상의 물성이 불량한 것을 확인할 수 있다.
On the other hand, as shown in Table 4, Comparative Examples 1 to 12 have a black pigment dispersion that does not satisfy the range proposed by the present invention, at least two or more of blackness, coating adhesion, banding and design It can be confirmed that the physical properties are poor.
(실시예 2)(Example 2)
다른 조건은 상기 실시예 1의 발명예 1과 동일하되 표 5 및 6에 나타난 자기첨가제의 구성만 변경하여 자기치유 코팅 조성물을 제조하였다.
Other conditions were the same as Inventive Example 1 of Example 1, but changed only the configuration of the magnetic additive shown in Table 5 and 6 to prepare a self-healing coating composition.
division
함량(%)Polymer capsules
content(%)
크기 (um)Self-Healing Additives
Size (um)
division
크기 (um)Self-Healing Additives
Size (um)
상기와 같이 제조된 자기치유 코팅 조성물을 아연 부착량이 각각 20 g/m2인 전기아연도금 강판(강판 두께: 0.45 mm)에 롤 코터를 이용하여 코팅 후 180℃에서 건조 및 경화하여 건조 후 두께가 12 ㎛가 되도록 강판을 제조하였다. 상기와 같이 제조된 강판을 하기 기재한 평가 기준에 의하여 의장성, 자기치유성, 용액안정성 및 밴딩성을 측정한 후, 그 결과를 하기 표 7 및 8에 나타내었다.
The self-healing coating composition prepared as described above was coated on an electrogalvanized steel sheet (steel sheet thickness: 0.45 mm) having a zinc adhesion amount of 20 g / m 2 , respectively, using a roll coater, dried and cured at 180 ° C., and then dried. Steel sheet was prepared to be 12 μm. After measuring the design, self-healing, solution stability and bending properties of the steel sheet prepared as described above by the evaluation criteria described below, the results are shown in Tables 7 and 8.
5)자기치유성 5) Self-healing
제조된 강판을 150cm×75cm(가로×세로)의 크기로 재단하여 시편을 제조하고, 상기 시편의 표면에 대각선으로 5cm의 스크래치를 형성한 후 5%의 염수 용액에 상온에서 120 시간 침지 후 스크래치 부위에서 적청의 발생 여부를 관찰하여 다음의 기준에 의하여 평가하였다.
The prepared steel sheet was cut to a size of 150 cm × 75 cm (width × length) to prepare a specimen, and a 5-cm scratch was formed diagonally on the surface of the specimen and then immersed in 5% saline solution at room temperature for 120 hours at the scratch portion. We observed the occurrence of red blue at, and evaluated according to the following criteria.
<자기치유성 평가기준><Self-Healing Evaluation Criteria>
○: 적청 1% 미만○: less than 1% red blue
△: 백청 1% 이상 5% 미만△: less than 5% of white rust 1%
×: 백청 5% 이상
×: 5% of white blue
6) 용액안정성6) Solution stability
상기에 방법에 의해 제조된 자기치유 코팅 조성물을 제조한 직후, 각각 초기 점도(Vi)를 측정하고, 25℃로 냉각시킨 후, 25℃에서의 나중 점도(Vl)를 측정한 후, 하기의 수학식 1에 대입하였으며, 그 결과를 하기의 평가 기준에 따라 평가하였다. Immediately after the self-healing coating composition prepared by the above method was prepared, the initial viscosity (Vi) was measured, and after cooling to 25 ° C, the late viscosity (Vl) at 25 ° C was measured, And the results were evaluated according to the following evaluation criteria.
[수학식 1][Equation 1]
△V = (Vl - Vi)/ Vi × 100 (%)
? V = (Vi-Vi) / Vi x 100 (%)
<용액 안정성의 평가 기준><Evaluation Criteria for Solution Stability>
○: △V가 20(%) 미만이거나 육안 관찰시 겔화 현상이 보이지 않음∘: ΔV is less than 20 (%) or gelation phenomenon is not observed by visual observation
×: △V가 20(%) 이상이거나 육안 관찰시 겔화 현상이 보임
占 V: ΔV is 20 (%) or more, or gelation phenomenon is observed upon visual observation
나머지, 의장성 및 밴딩성은 상기 실시예 1에 기재한 평가방법을 이용한다.
The remaining designability and banding property use the evaluation method described in Example 1 above.
상기 표 7에 기재된 바와 같이, 발명예 16 내지 28은 본 발명이 제안한 범위를 만족하는 자기치유 첨가제를 가짐으로써, 의장성, 자기치유성, 용액안정성 및 밴딩성이 모두 우수함을 확인할 수 있다.
As shown in Table 7, Inventive Examples 16 to 28 have a self-healing additive that satisfies the range proposed by the present invention, it can be confirmed that the design, self-healing, solution stability and banding are all excellent.
반면에, 상기 표 8에 기재된 바와 같이, 비교예 13 내지 25는 본 발명이 제안한 범위를 만족하는 않는 자기치유 첨가제를 가짐으로써, 의장성, 자기치유성, 용액안정성 및 밴딩성 중 적어도 2개 이상의 물성이 불량한 것을 확인할 수 있다.
On the other hand, as shown in Table 8, Comparative Examples 13 to 25 have a self-healing additive that does not satisfy the range proposed by the present invention, at least two or more of designability, self-healing, solution stability and banding It can be confirmed that the physical properties are poor.
(실시예 3)(Example 3)
하기 표 9 및 10에 기재된 성분을 만족하는 코팅 조성물을 제조하였다.
To prepare a coating composition that satisfies the components described in Tables 9 and 10.
다른 조건은 상기 실시예 1의 발명예 1과 동일하되 표 9 및 표 10에 나타난 수성유기수지, 흑색안료 분산체, 무기금속 졸, 방청제, 부착증진제, 레벨링제, 왁스, 가교제, 자기치유 첨가제 및 촉매의 함량만 변경하여 자기치유 코팅 조성물을 제조하였다. The other conditions are the same as those of Inventive Example 1 of Example 1, but the aqueous organic resins, black pigment dispersions, inorganic metal sols, rust inhibitors, adhesion promoters, leveling agents, waxes, crosslinking agents, self-healing additives shown in Tables 9 and 10, and Only the content of the catalyst was changed to prepare a self-healing coating composition.
함량
(%)A
content
(%)
함량(%)B
content(%)
함량(%)C
content(%)
함량(%)D
content(%)
함량(%)E
content(%)
함량(%)F
content(%)
함량(%)G
content(%)
함량(%)H
content(%)
함량(%)I
content(%)
함량(%)J
content(%)
함량
(%)A
content
(%)
함량(%)B
content(%)
함량(%)C
content(%)
함량(%)D
content(%)
함량(%)E
content(%)
함량(%)F
content(%)
함량(%)G
content(%)
함량(%)H
content(%)
함량(%)I
content(%)
함량(%)J
content(%)
상기와 같은 자기치유 코팅 조성물을 아연 부착량이 각각 20 g/m2인 전기아연도금 강판(강판 두께: 0.45 mm)에 롤 코터를 이용하여 코팅 후 180℃에서 건조 및 경화하여 건조 후 두께가 12 ㎛가 되도록 강판을 제조하였다. 상기와 같이 제조된 강판을 하기 기재한 평가 기준에 의하여 흑색도, 도막밀착성, 용액안정성, 밴딩성, 윤활성, 내식성, 의장성 및 자기치유성, 용액안정성 및 밴딩성을 측정한 후, 그 결과를 하기 표 11 및 12에 나타내었다.
The self-healing coating composition was coated on an electrogalvanized steel sheet (steel sheet thickness: 0.45 mm) having a zinc adhesion amount of 20 g / m 2 , respectively, using a roll coater, dried and cured at 180 ° C., and then dried to a thickness of 12 μm. Steel sheet was prepared to be. After measuring the blackness, coating film adhesion, solution stability, banding, lubrication, corrosion resistance, design and self-healing, solution stability and banding of the steel sheet prepared as described above according to the evaluation criteria, Tables 11 and 12 are shown below.
7) 윤활성7) Lubricity
CETR (Center for Tribology Inc.) USA의 UMT-2MT를 이용하여 표면 마찰계수를 측정하여 다음 기준에 의하여 평가하였다.
The surface friction coefficient was measured using a UMT-2MT from CETR (Center for Tribology Inc.) USA and evaluated according to the following criteria.
<윤활성 평가기준><Lubricity Evaluation Standard>
○: 마찰계수 (㎛) 0.25 미만?: Friction coefficient (占 퐉) Less than 0.25
△: 마찰계수 (㎛) 0.25 이상 0.4 미만?: Friction coefficient (占 퐉)? 0.25 or more and less than 0.4
×: 마찰계수 (㎛) 0.4 이상
X: Friction coefficient (占 퐉) 0.4 or more
8) 내식성8) Corrosion Resistance
제조된 강판을 JIS-Z2371에 준한 염수분무시험을 144시간 행하여, 발청 정도를 다음 기준에 의하여 평가하였다.
The prepared steel sheet was subjected to a salt water spray test according to JIS-Z2371 for 144 hours, and the degree of smell was evaluated according to the following criteria.
<내식성 평가기준><Evaluation Criteria for Corrosion Resistance>
○: 백청 5% 미만○: less than 5% of white rye
△: 백청 5% 이상 20% 미만△: White rice 5% or more and less than 20%
×: 백청 20% 이상
×: 20% or more of white rust
나머지, 흑색도, 도막밀착성, 용액안정성, 밴딩성, 의장성 및 자기치유성은 상기 전술한 실시예 1 및 실시예 2에 기재한 평가방법을 이용한다.
The remaining blackness, film adhesion, solution stability, bending property, designability, and self-healing use the evaluation methods described in Examples 1 and 2 described above.
상기 표 11에 기재된 바와 같이, 발명예 29 내지 47은 본 발명이 제안한 범위를 만족하는 자기치유 코팅 조성물을 피복한 강판에 관한 것으로써, 흑색도, 도막밀착성, 용액안정성, 밴딩성, 윤활성, 내식성, 의장성 및 자기치유성, 용액안정성 및 밴딩성이 모두 우수함을 확인할 수 있다.
As shown in Table 11, Inventive Examples 29 to 47 relate to a steel sheet coated with a self-healing coating composition satisfying the range proposed by the present invention. The blackness, coating film adhesion, solution stability, banding property, lubricity and corrosion resistance , Design and self-healing, solution stability and banding are all excellent.
반면에, 상기 표 12에 기재된 바와 같이, 비교예 26 내지 44는 본 발명이 제안한 범위를 만족하지 않는 자기치유 코팅 조성물을 강판에 피복시킨 것으로써, 흑색도, 도막밀착성, 용액안정성, 밴딩성, 윤활성, 내식성, 의장성 및 자기치유성자기치유성, 용액안정성 및 밴딩성 중 적어도 2개 이상의 물성이 불량한 것을 확인할 수 있다.
On the other hand, as shown in Table 12, Comparative Examples 26 to 44 by coating the steel sheet with a self-healing coating composition that does not satisfy the range proposed by the present invention, blackness, coating film adhesion, solution stability, banding, Lubricity, corrosion resistance, design and self-healing Self-healing, solution stability and bending properties of at least two or more can be confirmed that the poor.
(실시예 4)(Example 4)
다른 조건은 실시예 1의 발명예 1과 동일한 자기치유 코팅 조성물을 제조하였다.
Other conditions produced the same self-healing coating composition as Example 1 of Example 1.
그 후, 상기 자기치유 코팅 조성물을 아연 부착량이 각각 20 g/m2인 전기아연도금 강판(강판 두께: 0.45 mm)에 롤 코터를 이용하여 코팅 후 180℃에서 건조 및 경화하여 건조 후 두께가 하기 표 13이 되도록 강판을 제작하였다. 상기와 같이 제조된 강판의 흑색도, 도막밀착성, 밴딩성, 내식성 및 의장성을 측정한 후, 그 결과를 하기 표 14에 나타내었다. 상기 특성들은 상기 실시예 1 내지 3에 기재한 평가방법을 이용하여 평가한다.
Thereafter, the self-healing coating composition was coated on an electrogalvanized steel sheet (steel sheet thickness: 0.45 mm) having a zinc adhesion amount of 20 g / m 2 , respectively, using a roll coater, dried and cured at 180 ° C., and then dried. The steel plate was produced so that Table 13 may be carried out. After measuring the blackness, coating film adhesion, bending properties, corrosion resistance and design of the steel sheet prepared as described above, the results are shown in Table 14 below. The properties are evaluated using the evaluation method described in Examples 1 to 3.
상기 표 14에 기재된 바와 같이, 발명예 48 내지 53은 본 발명이 제안한 범위를 만족하는 코팅 조성물의 두께를 가짐으로써, 흑색도, 도막밀착성, 밴딩성, 내식성 및 의장성이 모두 우수한 것을 확인할 수 있다.
As shown in Table 14, Inventive Examples 48 to 53 have a thickness of the coating composition that satisfies the range proposed by the present invention, it can be confirmed that the blackness, coating film adhesion, banding, corrosion resistance and design all excellent. .
반면에, 상기 표 14에 기재된 바와 같이, 비교예 45 내지 50은 본 발명이 제안한 범위를 만족하지 않는 코팅 조성물의 두께를 가짐으로써, 흑색도, 도막밀착성, 밴딩성, 내식성 및 의장성 중 적어도 2개 이상의 물성이 불량한 것을 확인할 수 있다.
On the other hand, as shown in Table 14, Comparative Examples 45 to 50 have a thickness of the coating composition does not satisfy the range proposed by the present invention, at least 2 of blackness, coating adhesion, banding, corrosion resistance and design It can be seen that more than one property is poor.
이상 실시예를 참조하여 설명하였지만, 해당 기술 분야의 숙련된 당업자는 하기의 특허 청구의 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims. It will be possible.
1: 상도층
2: 소지강판
3: 하도층1: upper layer
2: Substrate steel
3: Lower layer
Claims (21)
Corrosion inhibitor penetrates the polymer seed and the shell surrounding the polymer seed, wherein the corrosion inhibitor is contained in 30 to 60% by weight of the total self-healing agent, the average particle diameter of the self-healing agent is magnetic Healing agent.
상기 쉘의 두께는 쉘 전체 직경의 30% 미만인 자기치유제.
The method of claim 1,
Self-healing agent having a thickness of less than 30% of the total diameter of the shell.
상기 고분자 시드 또는 쉘은 폴리메틸메타크릴레이트, 폴리스타이렌 및 폴리아크릴레이트로 중 1종 이상인 자기치유제.
The method of claim 1,
The polymer seed or shell is a self-healing agent of at least one of polymethyl methacrylate, polystyrene and polyacrylate.
상기 부식억제제는 염기성 부식억제제 또는 이온계 부식억제제 중 1종 이상인 자기치유제.
The method of claim 1,
The corrosion inhibitor is a self-healing agent of at least one of basic corrosion inhibitors or ionic corrosion inhibitors.
상기 고분자 시드의 직경은 자기치유 첨가제 직경의 90% 미만인 자기치유제.
The method of claim 1,
Wherein the diameter of the polymer seed is less than 90% of the diameter of the self healing additive.
400~500g의 증류수에 고분자 시드를 첨가하여 70~90℃로 온도를 유지하고, 새로운 증류수 5~25g에 소듐퍼설페이트 0.3~0.7g을 녹여 중탕액을 준비하는 단계;
부틸아크릴레이트 3~5g, 메틸메타크릴레이트 40~60g, 메타크릴릭애시드 0.5~2.5g을 혼합하여 제 1 혼합액을 준비하는 단계;
40~60g의 증류수에 계면활성제 소듐도데실설페이트 0.3~0.5g과 소듐퍼설페이트 0.5~0.7g, 스타이렌 100~120g을 넣고 혼합하여 제 2 혼합액을 준비하는 단계;
농도가 각각 0.1~0.3M인 트리에탄올아민과 칼슘클로라이드을 혼합하여 제 3 혼합액을 준비하는 단계;
상기 준비된 제 1 내지 제 3 혼합액을 순서대로 상기 준비된 중탕액에 첨가하여 최종 중탕액을 제조하는 단계; 및
상기 최종 중탕액을 건조하는 단계를 포함하는 자기치유제의 제조방법.
The method of producing a self-healing agent produced by the emulsion neutralization method,
Adding a polymer seed to 400 to 500 g of distilled water to maintain a temperature at 70 to 90 ° C., preparing 0.3 to 0.7 g of sodium persulfate in 5 to 25 g of fresh distilled water to prepare a hot water solution;
Preparing a first mixed solution by mixing 3-5 g of butyl acrylate, 40-60 g of methyl methacrylate, and 0.5-2.5 g of methacrylic acid;
Preparing a second mixture by mixing 0.3-0.5 g of sodium dodecyl sulfate, 0.5-0.7 g of sodium persulfate, and 100-120 g of styrene in 40-60 g of distilled water;
Preparing a third liquid mixture by mixing triethanolamine and calcium chloride each having a concentration of 0.1 to 0.3 M;
Preparing the final heated liquid by adding the prepared first to third mixed liquids in order to the prepared heated liquid; And
Method of producing a self-healing agent comprising the step of drying the final bath liquid.
상기 중탕액에 상기 제 1 내지 제 3 혼합액을 첨가할 때, 50~70분간 1300~1700rpm에서 교반하며 유지하는 것을 특징으로 하는 자기치유제의 제조방법.
The method according to claim 6,
When the first to third liquid mixture is added to the bath liquid, the method of producing a self-healing agent, characterized in that the stirring is maintained at 1300 ~ 1700rpm for 50 to 70 minutes.
상기 최종 중탕액의 pH가 9.5~11.5인 자기치유제의 제조방법.
The method according to claim 6,
PH of the final bath liquid is a method of producing a self-healing agent.
Black pigment dispersion: 1 to 45% by weight, self-healing additive: 0.1 to 20% by weight, aqueous organic resin: 20 to 80% by weight, inorganic metal sol: 1 to 10% by weight, rust inhibitor: 1 to 10% by weight, adhesion Enhancer: 0.1 to 5% by weight, leveling agent: 0.01 to 5% by weight, wax: 0.1 to 5% by weight, crosslinking agent: 5 to 50% by weight and catalyst: 3% by weight or less, the self-healing additive is a corrosion inhibitor Self-healing coating composition comprising a polymer seed penetrated and a shell surrounding the polymer seed.
상기 흑색안료 분산체는 수성유기수지: 10~85중량%, 흑색안료: 5~60중량%. 분산안정제: 0.5~10중량% 및 물: 5~40중량%인 자기치유 코팅 조성물.
The method of claim 9,
The black pigment dispersion is an aqueous organic resin: 10 to 85% by weight, black pigment: 5 to 60% by weight. Dispersion stabilizer: 0.5 to 10% by weight and water: 5 to 40% by weight self-healing coating composition.
상기 흑색안료 분산체의 평균 입경은 2~10000㎚인 자기치유 코팅 조성물.
The method of claim 9,
The black pigment dispersion has a mean particle diameter of 2 ~ 10000nm self-healing coating composition.
상기 수성유기수지는 수분산 우레탄 수지, 수분산 아크릴 수지, 수용성 에폭시, 수용성 폴리에스테르 수지 및 수용성 아미노 수지 중 1종 이상인 자기치유 코팅 조성물.
The method according to any one of claims 9 to 10,
The aqueous organic resin is a self-healing coating composition of at least one of water-dispersed urethane resin, water-dispersible acrylic resin, water-soluble epoxy, water-soluble polyester resin and water-soluble amino resin.
상기 흑색안료는 우수한 탄소 나노튜브, 탄소 섬유, 카본 블랙, 그래파이트 및 그래핀 중 1종 이상인 자기치유 코팅 조성물.
The method of claim 10,
The black pigment is a self-healing coating composition of at least one of excellent carbon nanotubes, carbon fibers, carbon black, graphite and graphene.
상기 무기금속 졸은 실리카 졸, 알루미나 졸, 티타니아 졸 및 지르코니아 졸 중 1종 이상인 자기치유 코팅 조성물.
The method of claim 9,
The inorganic metal sol is a self-healing coating composition of at least one of silica sol, alumina sol, titania sol and zirconia sol.
방청제는 금속 화합물, 인산 수용액, 아연, 몰리브덴, 불소 및 붕산 중 1종 이상인 자기치유 코팅 조성물.
The method of claim 9,
A rust inhibitor is a self-healing coating composition of at least one of a metal compound, an aqueous solution of phosphoric acid, zinc, molybdenum, fluorine and boric acid.
상기 부착증진제는 티타늄계 커플링제 및 지르코늄계 커플링제 중 1종 이상인 자기치유 코팅 조성물.
The method of claim 9,
The adhesion promoter is a self-healing coating composition of at least one of a titanium-based coupling agent and a zirconium-based coupling agent.
상기 레벨링제는 폴리실록산, 폴리아크릴레이트, 플루오르카본 폴리실록산, 플루오르카본 폴리아크릴레이트, 디메틸폴리실록산, 폴리메틸 알킬실록산, 실리콘 오일 및 메틸페닐폴리실록산 중 1종 이상인 자기치유 코팅 조성물.
The method of claim 9,
The leveling agent is a self-healing coating composition of at least one of polysiloxane, polyacrylate, fluorocarbon polysiloxane, fluorocarbon polyacrylate, dimethylpolysiloxane, polymethyl alkylsiloxane, silicone oil and methylphenylpolysiloxane.
상기 왁스는 식물성 왁스군 및 합성수지 왁스 중 1종 이상인 자기치유 코팅 조성물.
The method of claim 9,
The wax is a self-healing coating composition of at least one of vegetable wax groups and synthetic waxes.
상기 가교제는 멜라민계 가교제, 이소시아네이트계 가교제 및 아지리딘계 가교제 중 1종 이상인 자기치유 코팅 조성물.
The method of claim 9,
The crosslinking agent is at least one of a melamine crosslinking agent, an isocyanate crosslinking agent and an aziridine crosslinking agent.
상기 촉매는 파라톨루엔 설포닉애시드, 알키드벤젠 설포닉애시드, 아세틸아세톤 및 벤질 알코올 중 1종 이상인 자기치유 코팅 조성물.
The method of claim 9,
The catalyst is self-healing coating composition of at least one of paratoluene sulfonic acid, alkydbenzene sulfonic acid, acetylacetone and benzyl alcohol.
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