KR20210065080A - Antibacterial inorganic composition, steel sheet coated antibacterial inorganic composition and manufacturing method for the same - Google Patents
Antibacterial inorganic composition, steel sheet coated antibacterial inorganic composition and manufacturing method for the same Download PDFInfo
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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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—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 by baking
- B05D3/0254—After-treatment
- B05D3/0263—After-treatment with IR heaters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—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 by baking
- B05D3/0254—After-treatment
- B05D3/0272—After-treatment with ovens
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/02—Polysilicates
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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
- C09D5/02—Emulsion paints including aerosols
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Abstract
Description
본 발명은 항균성 무기 조성물, 항균성 무기 조성물이 도포된 도금강판 및 그 제조방법에 관한 것으로서, 보다 상세하게는 크롬(Cr)을 함유하지 않아 환경 친화적이면서 항균성이 부여된 항균성 무기 조성물, 항균성 무기 조성물이 도포된 도금강판 및 그 제조방법에 관한 것이다.The present invention relates to an antimicrobial inorganic composition, a plated steel sheet coated with an antimicrobial inorganic composition, and a method for manufacturing the same, and more particularly, an antimicrobial inorganic composition that does not contain chromium (Cr) and is environmentally friendly and has antimicrobial properties, and an antimicrobial inorganic composition It relates to a coated plated steel sheet and a method for manufacturing the same.
도금강판용 후처리제는 아연이나 알루미늄 또는 아연과 알루미늄의 합금이 도금된 강판, 또는 마그네슘과 알루미늄과 아연이 혼합되어 도금된 강판 표면에 코팅되어 1차적으로 도금층을 외부로부터 보호하는 목적으로 금속 표면에서 염류에 의한 산화 방지 및 산, 염기에 의한 산화 방지를 목적으로 한다.The post-treatment agent for plated steel sheet is coated on the surface of a steel sheet plated with zinc or aluminum or an alloy of zinc and aluminum, or a mixture of magnesium, aluminum and zinc, and is coated on the surface of the plated steel sheet to primarily protect the plating layer from the outside. It aims to prevent oxidation by acid and base.
도금강판은 그 특성상 외부 요인에 의해 표면에서의 산화반응, 즉, 부식 생성물이 쉽게 발생할 수 있는데, 이러한 부식 생성물의 발생을 억제하기 위해 가장 널리 사용되고 있는 방식은 표면에 피막을 형성한다. 표면에 피막을 형성하는 방법으로, 무기 또는 유기 성분의 피막을 물리적으로 형성하는 방법과 크로메이트 처리와 같은 화학반응에 의한 피막을 생성시키는 화성피막 방법 등이 있다.Oxidation reaction, ie, corrosion products, can easily occur on the surface of plated steel sheets due to external factors due to their characteristics. The most widely used method to suppress the occurrence of such corrosion products is to form a film on the surface. As a method of forming a film on the surface, there are a method of physically forming a film of an inorganic or organic component, and a chemical conversion film method of forming a film by a chemical reaction such as chromate treatment.
이렇게 형성된 피막은 도금층을 보호하여 도금강판의 내식성, 내흑변성, 내산성 등을 향상시킬 수 있으며, 또한, 이러한 피막에 기능성을 부여하여 고가공성 또는 항균성을 향상시켜 도금강판의 사용에 특수성을 부여할 수 있다. The film thus formed protects the plating layer and can improve the corrosion resistance, blackening resistance, acid resistance, etc. of the plated steel sheet. In addition, it is possible to give a specificity to the use of the plated steel sheet by imparting functionality to this film to improve high workability or antibacterial properties. have.
일반적으로, 도금층 표면을 보호하기 위하여 많이 사용되는 방법은 크로메이트 처리를 하는 방법이 있다. 하지만, 크로메이트 처리는 독성이 강한 6가 크롬(Cr6+) 이온을 포함하고 있어, 인체에 유해한 영향을 미치며, 현재 금속산업에서는 크로메이트 처리에 대한 규제가 엄격해지고 있기에 사용상에 문제점이 많은 실정이다.In general, a method widely used to protect the surface of the plating layer is a method of chromate treatment. However, the chromate treatment contains a toxic hexavalent chromium (Cr 6+ ) ion, which has a harmful effect on the human body.
이러한 문제로 인하여 크롬이 함유되지 않은 크롬프리(Cr-free) 유기 피막 처리가 널리 사용되고 있다. 대한민국 공개특허 제10-2006-0025942호 및 제10-2006-0059012호에는 유기 수지에 항균성을 부여하는 기술이 개시되어 있다. Due to this problem, a chrome-free (Cr-free) organic coating treatment that does not contain chromium is widely used. Korean Patent Laid-Open Nos. 10-2006-0025942 and 10-2006-0059012 disclose techniques for imparting antibacterial properties to organic resins.
하지만, 이러한 기술은 유기 수지에 무기 항균제 또는 유기 항균제를 사용하는 기술로서, 성분상의 차이로 인하여 가교제(binder) 역할을 하는 유기 수지에서 항균제의 성분은 이물질 형태로 되어 피막과 그 기능을 함께하지 못하는 문제가 있다. However, this technology is a technology of using an inorganic antibacterial agent or an organic antibacterial agent in an organic resin. Due to the difference in components, the component of the antibacterial agent in the organic resin that serves as a crosslinking agent is in the form of a foreign substance, so that the film and its function cannot be combined. there is a problem.
이로 인하여, 피막 자체의 내구성은 좋을 수 있으나, 함유된 항균제의 물성이 일정 시간 후 급속도로 저하되는 문제가 있다. 또한, 유기 성분의 한계로 인하여 내열성에 취약한 문제가 있다. 즉, 일반적으로 사용되는 환경에서는 강판이나 외부에서 가해지는 열에 의한 유기 성분의 변성이 발생하지 않으나, 열에 노출되는 환경에 강판이 설치된다면, 유기 수지 내부의 유기 항균제는 변성이 일어나 그 특성이 저하되고, 무기 항균제의 경우 가교제 역할을 하는 유기 수지층이 손상되어 항균제로서의 기능이 손실되어 그 특성이 저하되는 문제가 있다.For this reason, the durability of the film itself may be good, but there is a problem in that the physical properties of the contained antimicrobial agent are rapidly reduced after a certain period of time. In addition, there is a problem in that it is vulnerable to heat resistance due to the limitation of organic components. That is, in a generally used environment, deterioration of organic components by the heat applied from the outside or steel plate does not occur, but if the steel plate is installed in an environment exposed to heat, the organic antibacterial agent inside the organic resin is denatured and its properties are deteriorated. , In the case of an inorganic antibacterial agent, the organic resin layer serving as a crosslinking agent is damaged, and the function as an antibacterial agent is lost, and there is a problem in that its properties are reduced.
본 발명은 상기와 같은 문제점을 해결하기 위해 창안된 것으로서, 크롬(Cr)을 함유하지 않아 환경 친화적이고 항균성이 부여되면서 내열성을 가지는 항균성 무기 조성물, 항균성 무기 조성물이 도포된 도금강판 및 그 제조방법을 제공하는 데에 그 목적이 있다. The present invention was devised to solve the above problems, and as it does not contain chromium (Cr), an antibacterial inorganic composition having heat resistance while being environmentally friendly and antibacterial is imparted, a plated steel sheet coated with the antibacterial inorganic composition, and a method for manufacturing the same Its purpose is to provide
상기와 같은 목적을 달성하기 위하여 본 발명의 바람직한 실시예에 따른 항균성 무기 조성물은, 도금강판에 도포되어 항균성을 가지는 크롬프리(Cr-free) 피막을 형성하는 항균성 무기 조성물에 있어서, 실란(silane)과 산촉매가 혼합되어 마련된 졸겔(sol-gel) 용액; 및 0.5중량%의 은 이온이 함유된 무기 항균 수용액;을 포함한다.In order to achieve the above object, the antimicrobial inorganic composition according to a preferred embodiment of the present invention is an antimicrobial inorganic composition that is applied to a plated steel sheet to form a Cr-free film having antibacterial properties, silane A sol-gel solution prepared by mixing an acid catalyst; and 0.5 wt% of an inorganic antibacterial aqueous solution containing silver ions.
여기서, 상기 무기 항균 수용액은, 상기 졸겔 용액의 중량 대비 0.1~5.0중량%로 마련될 수 있다.Here, the inorganic antibacterial aqueous solution may be prepared in an amount of 0.1 to 5.0% by weight based on the weight of the sol-gel solution.
그리고, 상기 실란은, 에폭시 실란, 아미노 실란, 알콕시 실란 중 어느 하나 또는 적어도 둘 이상의 조합으로 마련될 수도 있다.And, the silane, epoxy silane, amino silane, alkoxy silane any one or a combination of at least two or more may be provided.
보다 구체적으로, 상기 졸겔 용액은, 수용액에 3~40중량%의 실란(silane)과 1~5중량%의 산촉매가 혼합되어 마련될 수 있다.More specifically, the sol-gel solution may be prepared by mixing 3 to 40% by weight of silane and 1 to 5% by weight of an acid catalyst in an aqueous solution.
일 예로, 상기 실란은, 8~20중량%의 에폭시 실란, 3~7중량%의 아미노 실란, 8~12중량%의 알콕시 실란 중 어느 하나로 마련될 수 있다.For example, the silane may be prepared by any one of 8 to 20% by weight of epoxy silane, 3 to 7% by weight of amino silane, and 8 to 12% by weight of alkoxy silane.
또는, 상기 실란은, 10~15중량%의 에폭시 실란, 5중량%의 아미노 실란, 5~20중량%의 알콕시 실란 중 적어도 둘 이상의 조합으로 마련될 수도 있다.Alternatively, the silane may be provided as a combination of at least two or more of 10 to 15% by weight of epoxy silane, 5% by weight of amino silane, and 5 to 20% by weight of alkoxy silane.
그리고, 상기와 같은 목적을 달성하기 위하여 본 발명의 바람직한 실시예에 따른 항균성 무기 조성물이 도포된 도금강판의 제조방법은, 상기 어느 하나의 항균성 무기 조성물을 도금강판에 롤코팅(Roll Coating) 또는 스프레이-스퀴징(Spray-Squeezing) 방식으로 코팅하는 코팅단계; 및 상기 항균성 무기 조성물이 코팅된 도금강판의 표면온도를 100~200℃가 되도록 열풍, 유도가열, 또는 근적외선 가열에 의해 건조하는 건조단계;를 포함한다.And, in order to achieve the above object, in the method for manufacturing a plated steel sheet coated with an antimicrobial inorganic composition according to a preferred embodiment of the present invention, any one of the antimicrobial inorganic compositions is applied to the plated steel sheet by roll coating or spraying. -A coating step of coating by a squeezing (Spray-Squeezing) method; and a drying step of drying the surface temperature of the plated steel sheet coated with the antimicrobial inorganic composition by hot air, induction heating, or near-infrared heating to 100 to 200°C.
또한, 상기와 같은 목적을 달성하기 위하여 본 발명의 바람직한 실시예에 따른 항균성 무기 조성물이 도포된 도금강판은 상기 어느 하나의 항균성 무기 조성물이 0.1~1.5g/m2의 건조피막 중량으로 도포되어 마련될 수 있다.In addition, in order to achieve the above object, in the plated steel sheet coated with the antimicrobial inorganic composition according to a preferred embodiment of the present invention, any one of the antimicrobial inorganic compositions is applied with a dry film weight of 0.1 to 1.5 g/m 2 . can be
본 발명에 의한 항균성 무기 조성물, 항균성 무기 조성물이 도포된 도금강판 및 그 제조방법에 따르면, 크롬(Cr)을 함유하지 않아 환경 친화적이고, 무기계인 은 성분이 함유된 조성물을 코팅하여 항균성이 부여되면서 내열성을 가지는 효과를 얻을 수 있다.According to the antimicrobial inorganic composition, the plated steel sheet coated with the antimicrobial inorganic composition and the manufacturing method thereof according to the present invention, it is environmentally friendly because it does not contain chromium (Cr), and antibacterial properties are imparted by coating the composition containing the inorganic silver component. An effect having heat resistance can be obtained.
본 발명의 특징들에 대한 이해를 돕기 위하여, 이하 본 발명의 실시예와 관련된 항균성 무기 조성물, 항균성 무기 조성물이 도포된 도금강판 및 그 제조방법에 대하여 보다 상세하게 설명하기로 한다. In order to facilitate understanding of the features of the present invention, an antimicrobial inorganic composition related to an embodiment of the present invention, a plated steel sheet coated with an antimicrobial inorganic composition, and a manufacturing method thereof will be described in more detail below.
이하 설명되는 실시예의 이해를 돕기 위하여 첨부된 각 도면의 구성요소들에 참조부호를 부가함에 있어서, 동일한 구성요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 부호를 가지도록 하고 있음에 유의한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.Note that in adding reference numerals to the components of the accompanying drawings to help the understanding of the embodiments described below, the same components are given the same reference numerals as much as possible even though they are indicated in different drawings. . In addition, in describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.
이하, 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 도금강판에 도포되어 항균성을 가지는 크롬프리(Cr-free) 피막을 형성하는 항균성 무기 조성물에 관한 것으로, 실란(silane)과 산촉매가 혼합되어 마련된 졸겔(sol-gel) 용액에 은 이온이 함유된 무기 항균 수용액을 혼합하여 제조된다. 여기서, 상기 실란은 유기 실란으로 마련된다. 이렇게 제조된 항균성 무기 조성물을 도금강판에 피복함으로써, 도금강판의 항균성, 내열성, 내식성, 내흑변성을 개선할 수 있다. The present invention relates to an antimicrobial inorganic composition that is applied to a plated steel sheet to form a Cr-free film having antibacterial properties, wherein silver ions are added to a sol-gel solution prepared by mixing silane and an acid catalyst. It is prepared by mixing the contained inorganic antibacterial solution. Here, the silane is provided as an organic silane. By coating the thus-prepared antimicrobial inorganic composition on the plated steel sheet, the antimicrobial properties, heat resistance, corrosion resistance, and blackening resistance of the plated steel sheet can be improved.
본 발명의 실시예에 의한 항균성 무기 조성물은 실란(silane)과 산촉매가 혼합되어 마련된 졸겔 용액에 0.5중량%의 은 이온이 함유된 무기 항균 수용액을 혼합하여 마련된다. 즉, 상기 무기 항균 수용액은 수용액(물)에 0.5중량%의 은 이온이 함유되어 마련된다. 그리고, 본 발명의 항균성 무기 조성물은 졸겔 용액에 졸겔 용액의 중량 대비 0.1~5.0중량%의 항균성 수용액을 혼합하여 마련된다.The antimicrobial inorganic composition according to an embodiment of the present invention is prepared by mixing a sol-gel solution prepared by mixing silane and an acid catalyst with an inorganic antibacterial aqueous solution containing 0.5% by weight of silver ions. That is, the inorganic antibacterial aqueous solution is prepared by containing 0.5% by weight of silver ions in the aqueous solution (water). And, the antimicrobial inorganic composition of the present invention is prepared by mixing 0.1 to 5.0% by weight of an antimicrobial aqueous solution with respect to the weight of the sol-gel solution in the sol-gel solution.
나아가, 본 발명의 실시예에 의한 항균성 무기 조성물은 실란과 산촉매 이외에 용액의 작업성 향상을 위한 실리콘계 소포제가 전체 중량 대비 0.1중량% 이하로 사용될 수 있다. 또한, 항균 성분을 가지는 용액이 도포된 도금강판의 가공성 향상을 위하여 중성 타입의 PE wax가 사용될 수도 있다. 이때 사용되는 PE wax의 함량은 가공성에 따라 달라지며, 전체 용액 대비 2중량% 이하로 사용되는 것이 바람직하다.Furthermore, in the antimicrobial inorganic composition according to an embodiment of the present invention, in addition to the silane and the acid catalyst, the silicone-based antifoaming agent for improving the workability of the solution may be used in an amount of 0.1 wt% or less based on the total weight. In addition, a neutral type PE wax may be used to improve the workability of the plated steel sheet coated with a solution having an antibacterial component. The content of PE wax used at this time varies depending on processability, and it is preferable to use it in an amount of 2 wt% or less based on the total solution.
여기서, 사용되는 산촉매는 무기산 보다는 유기산을 사용하는 것이 더욱 효과적이며, 특히, 개미산, 초산이 합성 시 졸겔 화합물 형성에 안정적이다.Here, it is more effective to use an organic acid rather than an inorganic acid as the acid catalyst used, and in particular, formic acid and acetic acid are stable in forming a sol-gel compound when synthesizing.
상기 졸겔 용액은 실란과 산촉매가 혼합되어 마련된다.The sol-gel solution is prepared by mixing silane and an acid catalyst.
여기서, 상기 실란은 에폭시 실란, 아미노 실란, 알콕시 실란 중 어느 하나 또는 적어도 둘 이상의 조합으로 마련될 수 있다.Here, the silane may be provided as any one or a combination of at least two or more of epoxy silane, amino silane, and alkoxy silane.
아연, 알루미늄, 아연과 알루미늄 합금을 도금한 도금강판에 후처리제로 유기 실란 화합물을 단독으로 사용하거나 수용화하여 사용할 수 있다. 이 때 사용될 수 있는 실란은 페닐 실란, 에폭시 실란, 메틸 실란, 비닐 실란, 알킬 실란, 알콕시 실란, 아미노 실란 등이 사용될 수 있다. 이러한 실란은 단독 또는 수용화하여 사용할 시 도금강판 표면에 실란(Silane)을 주성분으로 하는 피막을 형성하기가 어렵고, 그 피막의 두께가 도금층을 보호하기 위해 요구되는 성능을 확보하기에 어려움이 있다.An organosilane compound can be used alone or water-soluble as a post-treatment agent on a plated steel sheet plated with zinc, aluminum, zinc and aluminum alloy. In this case, the silane that may be used may include phenyl silane, epoxy silane, methyl silane, vinyl silane, alkyl silane, alkoxy silane, amino silane, and the like. When such silane is used alone or in aqueous solution, it is difficult to form a film containing silane as a main component on the surface of the plated steel sheet, and the thickness of the film is difficult to secure the performance required to protect the plating layer.
이러한 단점을 보완하기 위하여, 실란을 이용한 졸겔(sol-gel) 용액을 통하여 요구되는 성능을 확보할 수 있다. 졸겔 용액은 일반적으로 산 또는 염기 촉매 하에서 금속 알콕사이드를 가수분해 및 축합, 중합시켜 제조할 수 있다. 이때, 사용되는 산촉매로는 질산, 황산, 염산, 개미산, 초산 등이 다양하게 사용 가능하다. 하지만, 보다 안정적인 반응을 위해서는 사용되는 실란의 종류에 따라 그 종류가 결정된다. 본 발명에서는 산촉매를 사용하여 실란을 가수분해하여 올리고머 형태의 졸로 합성하는 화학적 변화를 통하여 실란의 작용기에 의해 다양한 특성을 가질 수 있다. 이때, 사용되는 실란은 상기에서 언급한 실란 중 1 종만을 사용하거나, 2종 이상을 혼합하여 사용될 수도 있다. In order to compensate for this disadvantage, it is possible to secure the required performance through a sol-gel solution using silane. The sol-gel solution can be generally prepared by hydrolysis, condensation, and polymerization of a metal alkoxide under an acid or base catalyst. At this time, as the acid catalyst to be used, nitric acid, sulfuric acid, hydrochloric acid, formic acid, acetic acid, and the like can be used in various ways. However, for a more stable reaction, the type is determined according to the type of silane used. In the present invention, various properties can be obtained by the functional group of the silane through a chemical change in which silane is hydrolyzed using an acid catalyst and synthesized into an oligomeric sol. In this case, as the silane used, only one type of the above-mentioned silanes may be used, or a mixture of two or more types may be used.
여기서, 산촉매를 이용한 가수분해 시 실란의 총 중량 대비 그 사용량이 정해지는데, 졸겔 반응 시 전체 용액 대비 1~5중량%로 사용되는 것이 바람직하다. 5중량%를 초과하여 사용하게 되면 촉매로서의 역할 이외에 용액 전체의 산가(산성도)가 증가하여 도금강판의 표면에 도포 시 산에 의한 급격한 표면 반응으로 표면층을 일부 손상시킬 수 있는 문제가 있다. 그리고, 1중량% 미만으로 사용하면 촉매로서의 역할이 충분하지 않아 가수분해 반응이 느리거나, 완전히 진행되지 않아 졸겔 용액으로서의 안정성이 저하된다. 즉, 졸겔 용액 이외의 첨가물이 투입되면 안정성 등에 문제를 야기시킬 수 있게 된다. 이때 사용되는 산촉매는 무기산 보다는 유기산을 사용하는 것이 더욱 효과적이며, 특히, 개미산, 초산이 합성 시 졸겔 화합물 형성에 안정적이다.Here, the amount used relative to the total weight of the silane is determined during hydrolysis using an acid catalyst, and it is preferably used in an amount of 1 to 5% by weight relative to the total solution in the sol-gel reaction. When used in excess of 5% by weight, the acid value (acidity) of the entire solution increases in addition to the role as a catalyst, and when applied to the surface of the plated steel sheet, there is a problem that the surface layer may be partially damaged due to an abrupt surface reaction by acid. And, when used in less than 1% by weight, the role as a catalyst is not sufficient, the hydrolysis reaction is slow or does not proceed completely, the stability as a sol-gel solution is reduced. That is, when additives other than the sol-gel solution are added, problems such as stability may be caused. In this case, it is more effective to use an organic acid rather than an inorganic acid as the acid catalyst used, and in particular, formic acid and acetic acid are stable in the formation of a sol-gel compound when synthesized.
페닐 실란, 에폭시 실란, 메틸 실란, 비닐 실란, 알킬 실란, 알콕시 실란, 아미노 실란 중에서 내식성이 우수한 실란을 선정하기 위하여 ASTM-B117 조건으로 평가하여 72시간 경과 시 5% 미만 발청 발생을 가장 적합한 상태(◎)로 하여 아래 표 1 및 표 2에 상대 평가하였다.In order to select a silane with excellent corrosion resistance among phenyl silane, epoxy silane, methyl silane, vinyl silane, alkyl silane, alkoxy silane, and amino silane, it was evaluated under ASTM-B117 conditions, and less than 5% of rusting occurred after 72 hours ( (double-circle)) and relative evaluation was performed in Tables 1 and 2 below.
아래 표 1은 하나의 실란에 유기 산촉매를 1~2중량%로 사용하여 졸겔 용액으로 합성하여 내식성 테스트를 수행한 것으로, 표에 기재된 숫자는 졸겔 용액의 총 중량에 대한 실란의 중량%를 나타낸다.Table 1 below shows that the corrosion resistance test was performed by synthesizing a sol-gel solution using an organic acid catalyst in an amount of 1 to 2% by weight in one silane, and the numbers in the table indicate the weight% of the silane with respect to the total weight of the sol-gel solution.
1-1Example
1-1
1-2Example
1-2
1-3Example
1-3
1-4Example
1-4
1-5Example
1-5
1-6Example
1-6
1-7Example
1-7
1-8Example
1-8
1-9Example
1-9
1-10Example
1-10
상기 표 1에 나타난 바와 같이, 본 발명에서는 하나의 실란을 사용할 경우에는 상대적으로 내식성이 우수한(◎, ○) 에폭시 실란, 아미노 실란, 알콕시 실란을 사용하였다. As shown in Table 1, in the present invention, when a single silane was used, epoxy silane, amino silane, and alkoxy silane having relatively excellent corrosion resistance (◎, ○) were used.
또한, 실란의 중량 비율은 에폭시 실란은 8~20중량%, 아미노 실란은 3~7중량%, 알콕시 실란은 8~12중량%로 선정하여 사용하였다.In addition, as for the weight ratio of the silane, 8 to 20% by weight of the epoxy silane, 3 to 7% by weight of the amino silane, and 8 to 12% by weight of the alkoxysilane were selected and used.
아래 표 2는 둘 이상의 실란을 혼합하고 유기 산촉매를 1~2중량%로 사용하여 졸겔 용액으로 합성하여 내식성 테스트를 수행한 것으로, 표에 기재된 숫자는 졸겔 용액의 총 중량에 대한 실란의 중량%를 나타낸다.Table 2 below shows that the corrosion resistance test was performed by mixing two or more silanes and synthesizing them into a sol-gel solution using an organic acid catalyst in an amount of 1 to 2% by weight. indicates.
2-1Example
2-1
2-2Example
2-2
2-3Example
2-3
2-4Example
2-4
2-5Example
2-5
2-6Example
2-6
2-7Example
2-7
2-8Example
2-8
2-9Example
2-9
2-10Example
2-10
상기 표 2에 나타난 바와 같이, 본 발명에서는 둘 이상의 실란을 혼합하여 사용할 경우에는 상대적으로 내식성이 우수한(◎, ○) 에폭시 실란과 아미노 실란의 혼합, 에폭시 실란과 알콕시 실란의 혼합, 에폭시 실란과 아미노 실란과 알콕시 실란의 혼합을 사용하였다. As shown in Table 2 above, in the present invention, when two or more silanes are mixed and used, a mixture of an epoxy silane and an amino silane, a mixture of an epoxy silane and an alkoxy silane, and an epoxy silane and an amino silane having relatively excellent corrosion resistance A mixture of silane and alkoxy silane was used.
또한, 실란의 중량 비율은 10~15중량%의 에폭시 실란, 5중량%의 아미노 실란, 5~20중량%의 알콕시 실란 중 적어도 둘 이상의 조합으로 마련될 수도 있다. In addition, the weight ratio of the silane may be provided as a combination of at least two or more of 10 to 15% by weight of epoxy silane, 5% by weight of amino silane, and 5 to 20% by weight of alkoxy silane.
예를 들어, 10중량%의 에폭시 실란과 5중량%의 아미노 실란의 혼합(실시예 2-3), 10중량%의 에폭시 실란과 5중량%의 알콕시 실란의 혼합(실시예 2-4), 10중량%의 에폭시 실란과 5중량%의 아미노 실란과 5중량%의 알콕시 실란의 혼합(실시예 2-5), 10중량%의 에폭시 실란과 5중량%의 아미노 실란과 10중량%의 알콕시 실란의 혼합(실시예 2-6), 15중량%의 에폭시 실란과 5중량%의 아미노 실란과 10중량%의 알콕시 실란의 혼합(실시예 2-9), 그리고 15중량%의 에폭시 실란과 5중량%의 아미노 실란과 20중량%의 알콕시 실란의 혼합(실시예 2-10)을 사용할 수 있다.For example, a mixture of 10% by weight of an epoxy silane and 5% by weight of an amino silane (Example 2-3), a mixture of 10% by weight of an epoxy silane and 5% by weight of an alkoxy silane (Example 2-4), A mixture of 10 wt % epoxy silane with 5 wt % amino silane and 5 wt % alkoxy silane (Example 2-5), 10 wt % epoxy silane with 5 wt % amino silane with 10 wt % alkoxy silane of (Example 2-6), a mixture of 15 wt% epoxy silane with 5 wt% amino silane and 10 wt% alkoxy silane (Examples 2-9), and 15 wt% epoxy silane with 5 wt% A mixture of % amino silane and 20 wt % alkoxy silane (Examples 2-10) can be used.
본 발명에서는 내열성을 향상시키기 위하여 무기 성분을 선택하였고, 항균성을 향상시키기 위하여 무기 성분 중에서도 은(Ag)을 선택하였다. In the present invention, an inorganic component was selected to improve heat resistance, and silver (Ag) was selected among inorganic components to improve antibacterial properties.
은(Ag)은 항균성을 가질 뿐만 아니라 인체에 무해하여 환경 친화성을 고려해도 적합한 성분이다. Silver (Ag) not only has antibacterial properties, but is also harmless to the human body, so it is a suitable component considering environmental friendliness.
은 성분은 Ag+의 이온형태로 존재하는데, 이는 졸겔 용액에서 동일한 전하를 지닌 산촉매 성분에 영향을 받아 균일하게 분포하게 된다. 이렇게 졸겔 용액 내에 균일 분포하는 Ag+ 이온은 도금강판의 표면에 도포되어 겔화가 진행되고, 건조가 되면서 피막 내부에 균일하게 분포되어 항균 성능을 일정하게 유지할 수 있을 뿐만 아니라 내열 성능도 균일하게 가지게 된다.The silver component exists in the form of Ag + ions, which are uniformly distributed under the influence of the acid catalyst component having the same charge in the sol-gel solution. In this way, Ag + ions uniformly distributed in the sol-gel solution are applied to the surface of the plated steel sheet, gelation proceeds, and as it dries, it is uniformly distributed inside the film to maintain constant antibacterial performance and uniform heat resistance. .
그리고, 은 이온이 0.5중량% 함유된 무기 항균 수용액은 상기 졸겔 용액의 중량 대비 0.1~5.0중량%가 혼합되도록 사용된다. 즉, 도금강판의 물성인 내식성, 내흑변성 등의 저하를 초래하지 않는 범위에서 은 함유량을 조절해야 한다. And, the inorganic antibacterial aqueous solution containing 0.5 wt% of silver ions is used so that 0.1 to 5.0 wt% of the sol-gel solution is mixed. That is, it is necessary to control the silver content in a range that does not cause deterioration of the physical properties of the plated steel sheet, such as corrosion resistance and blackening resistance.
아래 표 3에는 졸겔 용액의 중량 대비하여 무기 항균 수용액의 중량을 달리하여 물성을 특정한 결과이다. 표에 기재된 숫자는 중량%를 나타낸다.Table 3 below shows the results of specific physical properties by varying the weight of the inorganic antibacterial aqueous solution compared to the weight of the sol-gel solution. Numbers in the table indicate weight percent.
3-1Example
3-1
3-2Example
3-2
3-3Example
3-3
3-4Example
3-4
상기 표 3에 나타난 바와 같이, 0.5중량%의 은 이온이 함유된 무기 항균 수용액을 혼합한 졸겔 용액, 즉, 항균성 무기 조성물을 도금강판에 도포하여 항균성 및 물성을 측정한 결과 무기 항균 수용액이 5% 미만, 바람직하게는 0.5~3중량%가 함유되었을 때 항균성을 가지면서 내식성, 내흑변성, 내열성 모두를 우수하게 유지시킬 수 있다. As shown in Table 3, a sol-gel solution mixed with an inorganic antibacterial aqueous solution containing 0.5% by weight of silver ions, that is, an antimicrobial inorganic composition was applied to a plated steel sheet to measure antibacterial properties and physical properties. As a result, the inorganic antibacterial aqueous solution was 5% When less than, preferably 0.5 to 3% by weight is contained, it is possible to maintain excellent corrosion resistance, blackening resistance, and heat resistance while having antibacterial properties.
여기서, 내식성은 ASTM-B117기준으로 평가하였으며, 내흑변성은 50℃에서 95% 상대습도 조건으로 적층하여 하중을 20kgf/cm2로 하여 평가하였으며, 내열성은 200℃, 300℃, 400℃에서 20분간 가열하여 가열 전후의 색차 ΔE≤3의 변색유무를 확인하여 가장 적합한 상태(◎)를 기준으로 상대 평가하였다.Here, the corrosion resistance was evaluated according to ASTM-B117, and the blackening resistance was evaluated by laminating at 50 ° C. under 95% relative humidity conditions and a load of 20 kgf/cm 2 After heating, the color difference of ΔE≤3 before and after heating was checked, and relative evaluation was performed based on the most suitable state (◎).
그리고, 항균성은 항균 처리된 도금강판과 항균 처리가 되지 않은 도금강판에 대한 세균 감소율을 측정하여 비교한 것으로서, 한국건설생활 환경시험연구원 KCL-FIR-1003:2018에 따른 가압밀착법을 적용하여 시험한 결과이며, 사용 균주는 대장균(Escherichia coli ATCC 8739), 녹농균(Pseudomonas aeruginosa ATCC 15442), 황색포도상구균(Staphylococcus aureus ATCC 6538P), 폐렴균(Klebsiella pneumoniae ATCC 4352), MRSA(메티실린 내성 포도상구균, Staphylococcus aureus subsp. aureus ATCC 33591) 이다. 이러한 균주를 대상으로 하여 본 발명의 항균성 무기 조성물에 의한 피막이 있는 시편과 피막이 없는 시편을 기준으로 하여, 24시간 배양 후에 세균 감소율을 확인하였다. [CFU: Colony Forming Unit, 세균 감소율[%] = (Blank - Sample) / Blank X 100, 24시간 후 농도 기준]And, the antibacterial property was compared by measuring the reduction rate of bacteria between the plated steel plate treated with antibacterial treatment and the plated steel sheet not treated with antibacterial treatment, and it was tested by applying the pressure bonding method according to KCL-FIR-1003:2018, Korea Institute of Construction and Living Environment. As a result, the strains used were Escherichia coli ATCC 8739, Pseudomonas aeruginosa ATCC 15442, Staphylococcus aureus ATCC 6538P, Klebsiella pneumoniae ATCC 4352, MRSA (methicillin-resistant Staphylococcus aureus). aureus subsp. aureus ATCC 33591). For these strains, the bacterial reduction rate was confirmed after 24 hours of incubation on the basis of the specimens with and without the coatings prepared by the antimicrobial inorganic composition of the present invention. [CFU: Colony Forming Unit, bacterial reduction rate [%] = (Blank - Sample) / Blank X 100, based on concentration after 24 hours]
여기서, 시편은 0.5중량%의 무기 항균 수용액이 혼합된 항균성 무기 조성물을 도금강판에 도포하여 건조피막을 형성한 도금강판(실시예3-1)의 항균성 평가를 진행하였다.Here, the specimen was subjected to antimicrobial evaluation of the plated steel sheet (Example 3-1) in which a dry film was formed by applying an antibacterial inorganic composition mixed with 0.5 wt% of an inorganic antibacterial aqueous solution to the plated steel sheet.
평가 결과는 아래 표 4에 기재하였고, 모두 99.9% 이상의 균 감소를 보이고 있다. 이에 따라, 무기 항균 수용액의 함량이 0.5중량% 보다 더 많이 함유된 실시예 3-2 내지 실시예 3-4의 경우에도 동등 이상의 항균성을 보여줄 것으로 판단된다.The evaluation results are shown in Table 4 below, and all of them show a bacterial reduction of 99.9% or more. Accordingly, it is judged that even in the case of Examples 3-2 to 3-4 in which the content of the inorganic antibacterial aqueous solution is greater than 0.5% by weight, it is determined that the antibacterial properties of the inorganic antibacterial solution are equal or higher.
[CFU/mL]initial concentration
[CFU/mL]
[CFU/mL]concentration after 24 hours
[CFU/mL]
[%]bacteria reduction rate
[%]
상기에서 나타난 바와 같이, 본 발명의 실시예에 의한 항균성 무기 조성물은 은 성분을 함유하고 있어 항균성 및 내열성이 우수하면서, 내식성, 내흑변성, 내열성 또한 우수하다.As shown above, the antimicrobial inorganic composition according to the embodiment of the present invention contains a silver component and thus has excellent antibacterial and heat resistance, and also excellent corrosion resistance, blackening resistance and heat resistance.
이하에서는, 본 발명의 실시예에 의한 항균성 무기 조성물을 도금강판에 코팅하여 도금강판을 제조하는 제조방법에 대하여 설명한다. Hereinafter, a manufacturing method for manufacturing a plated steel sheet by coating the plated steel sheet with the antimicrobial inorganic composition according to an embodiment of the present invention will be described.
본 발명의 실시예에 의한 도금강판의 제조방법은 상기에서 설명한 항균성 무기 조성물을 도금강판에 롤코팅(Roll Coating) 또는 스프레이-스퀴징(Spray-Squeezing) 방식으로 코팅하고, 상기 항균성 무기 조성물이 코팅된 도금강판의 표면온도를 100~200℃가 되도록 열풍, 유도가열, 또는 근적외선 가열에 의해 건조하여 제조된다. In the method for manufacturing a plated steel sheet according to an embodiment of the present invention, the above-described antimicrobial inorganic composition is coated on a plated steel sheet by a roll coating or spray-squeezing method, and the antimicrobial inorganic composition is coated. It is manufactured by drying by hot air, induction heating, or near-infrared heating so that the surface temperature of the coated steel sheet becomes 100~200℃.
무기 성분을 주성분으로 하여 도금강판 표면에서 피막을 형성하는 방법은 다양하게 존재한다. 화성처리법(Conversion coating), 침지법, 롤코팅(Roll Coating) 또는 스프레이-스퀴징(Spray-Squeezing) 방식 등 다양하게 사용되고 있다. 상기한 피막 형성 방식 중에서 롤코팅(Roll coating) 또는 스프레이-스퀴징(Spray-Squeezing) 방식은 도금강판 표면에 약 5㎛ 미만의 피막을 형성할 수 있어 널리 사용되고 있다. 즉, 상기한 두 방식은 피막 두께 관리 및 건조 등 생산에 용이한 이점이 있다. 따라서, 본 발명에서는 롤코팅(Roll Coating) 또는 스프레이-스퀴징(Spray-Squeezing) 방식으로 항균성 무기 조성물을 도금강판에 코팅하였다.There are various methods for forming a film on the surface of a plated steel sheet using an inorganic component as a main component. Conversion coating, dipping, roll coating, or spray-squeezing is used in various ways. Among the above film forming methods, roll coating or spray-squeezing is widely used because it can form a film of less than about 5 μm on the surface of the plated steel sheet. That is, the above two methods have the advantage of easy production, such as film thickness management and drying. Therefore, in the present invention, the antimicrobial inorganic composition was coated on the plated steel sheet by a roll coating or spray-squeezing method.
그리고, 본 발명의 항균성 무기 조성물이 코팅된 도금강판을 열풍, 유도가열, 또는 근적외선 등의 가열 방법을 통하여 도금강판의 표면온도를 100~200℃가 되도록 하여 건조하였다. Then, the plated steel sheet coated with the antimicrobial inorganic composition of the present invention was dried by heating the plated steel sheet with a heating method such as hot air, induction heating, or near-infrared rays so that the surface temperature of the plated steel sheet was 100 to 200°C.
여기서, 도금강판은 아연 도금강판, 55% Al-Zn계 갈바륨(Galvalume) 강판, 알루미늄 도금강판, 마그네슘을 함유하는 아연 및 알루미늄 합금 도금강판, 마그네슘 합금 도금강판으로 이루어진 군에서 선택되어 사용될 수 있다.Here, the plated steel sheet may be selected from the group consisting of a galvanized steel sheet, a 55% Al-Zn-based galvalume steel sheet, an aluminum plated steel sheet, a zinc and aluminum alloy plated steel sheet containing magnesium, and a magnesium alloy plated steel sheet.
이러한 방법을 통하여 제조된 도금강판은 항균성 무기 조성물이 0.1~1.5g/m2의 건조피막 중량으로 도포되는 것이 바람직하다. 즉, 항균성 무기 조성물이 0.1 g/m2 미만의 중량으로 도포되면 목표하는 항균성을 달성할 수 없고, 1.5 g/m2 초과하는 중량으로 도포되면 은 이온의 사용량이 증가하여 제조비용이 증가하는 문제가 있다.The plated steel sheet manufactured through this method is preferably coated with an antimicrobial inorganic composition in a dry film weight of 0.1 to 1.5 g/m 2 . That is, when the antimicrobial inorganic composition is applied at a weight of less than 0.1 g/m 2 , the target antibacterial property cannot be achieved, and when applied at a weight exceeding 1.5 g/m 2 , the amount of silver ions used increases and manufacturing cost increases. there is
이상과 같이, 본 발명은 비록 한정된 실시예와 도면에 의해 설명되었으나, 본 발명은 이것에 의해 한정되지 않으며 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 본 발명의 기술사상과 아래에 기재될 특허청구범위의 균등범위 내에서 다양한 수정 및 변형 가능함은 물론이다.As described above, although the present invention has been described with reference to limited embodiments and drawings, the present invention is not limited thereto, and the technical idea of the present invention and the following by those of ordinary skill in the art to which the present invention pertains. Of course, various modifications and variations are possible within the scope of equivalents of the claims to be described.
Claims (5)
실란(silane)과 산촉매가 혼합되어 마련된 졸겔(sol-gel) 용액; 및
0.5중량%의 은 이온이 함유된 무기 항균 수용액;
을 포함하고,
상기 실란은,
알콕시 실란을 포함하고, 상기 산촉매에 의하여 가수분해되어 올리고머 형태의 졸로 합성되고,
상기 졸겔 용액은,
내식성을 위하여 수용액에 8~40중량%의 실란(silane)과 1~5중량%의 산촉매가 혼합되어 마련되며,
상기 산촉매는,
유기산을 사용하고,
상기 도금강판은,
표면온도가 100~200℃가 되도록 가열 건조되는 것을 특징으로 하는 항균성 무기 조성물.
In the antimicrobial inorganic composition for forming a chrome-free (Cr-free) film having antibacterial properties applied to a plated steel sheet,
a sol-gel solution prepared by mixing silane and an acid catalyst; and
0.5% by weight of an inorganic antibacterial aqueous solution containing silver ions;
including,
The silane is
It contains an alkoxysilane and is hydrolyzed by the acid catalyst to synthesize an oligomeric sol,
The sol-gel solution is
For corrosion resistance, 8 to 40% by weight of silane and 1 to 5% by weight of an acid catalyst are mixed in an aqueous solution,
The acid catalyst is
organic acids are used,
The plated steel sheet,
An antibacterial inorganic composition, characterized in that the surface temperature is dried by heating to 100 ~ 200 ℃.
상기 무기 항균 수용액은,
상기 졸겔 용액의 중량 대비 0.1~5.0중량%로 마련되는 것을 특징으로 하는 항균성 무기 조성물.
According to claim 1,
The inorganic antibacterial aqueous solution,
Antimicrobial inorganic composition, characterized in that provided in 0.1 to 5.0% by weight relative to the weight of the sol-gel solution.
상기 실란은,
에폭시 실란, 아미노 실란 중 어느 하나 또는 둘을 더 조합하여 마련되는 것을 특징으로 하는 항균성 무기 조성물.
According to claim 1,
The silane is
An antimicrobial inorganic composition, characterized in that it is prepared by further combining any one or two of epoxy silane and amino silane.
상기 실란은,
10~15중량%의 에폭시 실란, 5중량%의 아미노 실란, 5~20중량%의 알콕시 실란 중 적어도 둘 이상의 조합으로 마련되는 것을 특징으로 하는 항균성 무기 조성물.
According to claim 1,
The silane is
10 to 15% by weight of epoxy silane, 5% by weight of amino silane, 5 to 20% by weight of an alkoxy silane antimicrobial inorganic composition, characterized in that provided in combination of at least two.
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