KR100968108B1 - The manufacturing method and composite of coating agent using oyster shells - Google Patents
The manufacturing method and composite of coating agent using oyster shells Download PDFInfo
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- KR100968108B1 KR100968108B1 KR1020090116590A KR20090116590A KR100968108B1 KR 100968108 B1 KR100968108 B1 KR 100968108B1 KR 1020090116590 A KR1020090116590 A KR 1020090116590A KR 20090116590 A KR20090116590 A KR 20090116590A KR 100968108 B1 KR100968108 B1 KR 100968108B1
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/10—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances lime
- C09D1/12—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances lime with organic additives
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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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
- C09D7/65—Additives macromolecular
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- 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
- C09D7/80—Processes for incorporating ingredients
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
Description
본 발명은 수도저장시설 콘크리트 벽면의 세라믹 코팅제에 관한 것으로 더 상세히는 남해안 일대를 중심으로 한 굴양식 산업에서 매립 및 방치되고 있는 폐자원인 굴 패각을 원료로 사용한 수용성 코팅제로써 환경호르몬인 비스페놀-A가 검출되지 않으며, 기존 코팅제에 비해 부착력이 향상된 환경 친화적인 코팅제의 조성물과 그 제조 방법에 관한 것이다.The present invention relates to a ceramic coating material for concrete walls of water storage facilities. More specifically, it is a water-soluble coating material using oyster shells, which are waste resources that are being buried and left in the oyster farming industry around the southern coast, as an environmental hormone, bisphenol-A. Is not detected and relates to a composition of an environmentally friendly coating having improved adhesion compared to a conventional coating and a method for producing the same.
본 발명은 연안지역에서 발생하는 폐자원인 굴 패각을 활용한 환경 친화적인 나노고분자세라믹 코팅제의 조성물에 관한 것이다. The present invention relates to a composition of environmentally friendly nano-polymer ceramic coatings utilizing oyster shells, which are waste resources occurring in coastal areas.
굴 패각은 남해안 일대를 중심으로 28-30만 여 톤이 매년 발생되고 있으나, 총 발생량의 약10%만이 비료 및 칼슘의 원료 등으로 재활용되고 있고, 대부분의 굴 패각은 재활용되지 않고 매립되거나 주변에 불법으로 야적 방치되어 처리곤란 및 악취발생 등으로 또 다른 해양오염원으로써 그 심각성이 대두되고 있는 실정이다. 굴 패각은 일반적으로 90%이상이 탄산칼슘(CaCO3)으로 이루어져 있으며, 인 성분이 함 유되어있어 코팅 시 인간의 뼈와 같은 인산칼슘을 생성하여 강도가 매우 높으며, 천연의 다공성 나노무기물로써 열 충격에 의한 수축팽창에 매우 안정하여 코팅 시 크랙을 방지할 수 있는 장점이 있다.Oyster shells are generated around 28-300,000 tons annually in the southern coastal area, but only about 10% of the total amount is recycled from fertilizer and calcium. Most of the oyster shells are landfilled and not recycled. It is a situation that the seriousness is emerging as another marine pollutant due to illegal disposal and illegal disposal of malaria. Oyster shells are generally made up of more than 90% of calcium carbonate (CaCO 3 ), and contain phosphorus, which produces calcium phosphate like human bones when coated, resulting in very high strength. It is very stable in shrinkage expansion due to impact and has an advantage of preventing cracks during coating.
수도저장시설은 주로 콘크리트로 설치되어 있으며 그 표면은 대부분 에폭시수지로 코팅처리 되어 있다. 이러한 수도저장시설은 정기적으로 세척을 실시하여야 하는데 세척 시 에폭시 수지의 탈리현상으로 코팅층이 박리되는 현상이 발생하게 된다. 또한, 에폭시 수지는 비스페놀-A와 에피클로로히드린을 수산화나트륨 존재 하의 반응에 의해서 만들어 지는데, 비스페놀-A는 인체에 유해를 줄 가능성이 매우 높은 것으로 보고되고 있다. 그래서 이러한 문제를 해결하고자 최근에는 위와 같은 에폭시수지 코팅에 갈음하여 콘크리트 벽면에 PE, 유리판 및 스텐레스판을 부착하는 등 음용수의 안정성을 확보하기 위해 많은 노력들을 하고 있지만, 이들 방법은 비용적인 측면에서 도포면적 1제곱미터 당 에폭시수지는 3-4만원 소요되는데 비해 PE판, 유리판 및 스텐레스판은 20-30만원이 소요되어 경제성이 매우 떨어지며, 부착방법으로는 흔히 접착제를 사용하는 방법과 천공 후 나사못 박음 방법을 이용하는데, 접착제는 유해물질로 구성되어 있어 유해물질이 용출될 우려가 있으며, 천공 처리 시 콘크리트 벽면에 금이 발생되어 물이 스며들어가 오염을 유발시킬 수 있는 단점이 있어 경제적인 측면과 실용적인 측면을 볼 때 현재 상업적으로 적용하기에는 문제점들이 많이 있다. 그리하여 현재로써는 수도저장시설의 벽면은 에폭시수지로 코팅되는 일이 일반적이지만, 에폭시수지의 제조 원료인 비스페놀-A는 환경호르몬 중에서 단일화합물로는 그 사용량이 전국적으로 61,287톤이나 되고, 비스페놀-A를 원 료로 하여 제조되는 에폭시수지는 각종 수조 및 수도관 등의 코팅제로 널리 사용되고 있는 실정에 있다. Water storage facilities are mainly installed in concrete, and most of the surface is coated with epoxy resin. Such a water storage facility should be periodically cleaned, which causes the coating layer to peel off due to desorption of epoxy resin. Epoxy resins are also produced by the reaction of bisphenol-A with epichlorohydrin in the presence of sodium hydroxide, which has been reported to have a very high risk of harm to humans. So, in order to solve this problem, in recent years, many efforts have been made to secure drinking water stability such as attaching PE, glass plates and stainless steel plates to concrete walls in place of the above epoxy resin coatings. Epoxy resin costs 3-40,000 won per square meter, while PE plate, glass plate and stainless steel plate cost 20-300,000 won, so it is very economical.Adhesive method is to use adhesive or screw after drilling. The adhesive is composed of harmful substances, which may cause the harmful substances to be eluted, and when the drilling process is carried out, gold may be generated on the concrete walls, causing water to penetrate and cause contamination. In view of this, there are many problems with the current commercial application. Thus, currently, the walls of water storage facilities are generally coated with epoxy resins. However, bisphenol-A, a raw material for the production of epoxy resins, is used as a single compound among environmental hormones, which is 61,287 tons nationwide. Epoxy resins prepared as raw materials are widely used as coating agents for various tanks and water pipes.
이에 본 발명은, 코팅제의 성분이 수중에 용출되지 않고, 수돗물이 오염되지 않아야 하며, 저장시설 세척 및 염소성분에 의해 방수층이 침식되지 않는 환경 친화적인 재료를 사용하며, 나아가 처리 곤란한 굴 패각을 이용한 수조 및 수도관 등의 코팅제를 제공하여야 한다는 과제를 해결하고자 한다.Accordingly, the present invention uses an environmentally friendly material that does not elute the components of the coating in water, the tap water should not be contaminated, and the waterproofing layer is not eroded by the washing of the storage facility and the chlorine component. To solve the problem of providing a coating such as a water tank and water pipes.
이와 같은 과제를 해결하기 위하여, 본 발명은, 해안가에 버려지는 굴 패각을 수세, 소성 및 분쇄 단계를 통해 굴 패각 분말을 얻는 단계와; 굴 패각 분말에 백시멘트, 메타카올린, Al2O3, 규사를 혼합하여 중간 조성물을 제조하는 단계와; 상기 중간 조성물에 물과 폴리아크릴릭에스테르계에멜젼을 혼합하는 단계로 되는 코팅제 제조 방법과 그에 의한 코팅제를 제공한다. 결국 이와 같은 본 발명은, 수화반응과 함께 아크릴과 겔화되지 않은 수산화칼슘과의 화학결합으로 안정화되는 구조를 갖게 하는 아크릴과 시멘트입자 표면과의 반응으로 표면을 아크릴로 둘러싸게 하는 반응을 가지게 하는 코팅제와 그 제조 방법을 제공한다.In order to solve this problem, the present invention comprises the steps of obtaining the oyster shell powder through the washing, firing and grinding step of the oyster shell discarded on the coast; Preparing an intermediate composition by mixing white cement, metakaolin, Al 2 O 3 and silica sand with oyster shell powder; It provides a coating agent manufacturing method and a coating agent which is a step of mixing water and polyacrylic ester-based emulsion in the intermediate composition. As a result, the present invention is a coating agent which has a reaction to surround the surface with acrylic by the reaction of acryl and cement particle surface having a structure which is stabilized by chemical bonding between acryl and ungelled calcium hydroxide together with a hydration reaction. The manufacturing method is provided.
즉, 본 발명은 수도저장시설 콘크리트 벽면의 코팅처리를 위한 나노고분자세라믹 코팅제 조성물로써, 그 구성은 총중량 100중량%에 대해 굴 패각 5-45wt%, 백시멘트 5∼15wt%, 메타카올린 5∼10wt%, Al2O3 5∼10wt%, 규사 10∼20wt%, 폴리아크릴릭에스테르계에멜젼 20∼40wt%, 물 10∼15wt% 인 것을 특징으로 한다.That is, the present invention is a nano-polymer ceramic coating composition for coating the concrete wall of the water storage facility, the composition is 5-45wt% oyster shell, 5-15wt% cement, 5-10wt metakaolin with respect to 100% by weight of the total weight %, Al 2 O 3 5-10wt%, silica sand 10-20wt%, polyacrylic ester emulsion 20-20wt%, water 10-15wt% It is characterized by the above-mentioned.
이상에서와 같이 본 발명은 종래의 기술에 비해 굴 패각의 폐자원을 재활용함으로서 비용측면에서 경제적으로 유리하며, 인체에 무해한 세라믹 소재를 사용함으로서 음용수로서의 안정성을 높일 수 있고 종래의 기술에 의한 코팅층의 부착력을 개선시킬 수 있는 효과가 있으며 해양오염을 줄임과 동시에 폐자원을 활용할 수 있는 용도를 확대하고 항구적인 대체 자원으로서 활용할 수 있는 효과가 있다.As described above, the present invention is economically advantageous in terms of cost by recycling waste resources of oyster shells compared to the conventional technology, and by using a ceramic material that is harmless to human body, it is possible to increase the stability as drinking water and to improve the coating layer of the conventional technology. There is an effect to improve the adhesion, and to reduce the marine pollution, and to expand the use of waste resources and to use as a permanent alternative resource.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 코팅제 조성물은 수세, 소성 및 분쇄 단계를 통해 얻은 굴 패각 분말, 백시멘트, 메타카올린, Al2O3, 규사, 폴리아크릴릭에스테르계에멜젼 및 물을 혼합하여 폴리머 기능성과 세라믹의 표면 효과를 가지게 하는 코팅제 조성물을 제공한다.The coating composition of the present invention is a mixture of oyster shell powder, white cement, metakaolin, Al 2 O 3 , silica sand, polyacrylic ester-based emulsion and water obtained through the washing, firing and grinding step of the polymer functionality and surface effect of the ceramic It provides a coating composition to have.
상기 조성물에 있어서의 조성비는, 굴 패각이 5-45wt%(총 중량비; 이하 같음), 백시멘트는 5∼15wt%, 메타카올린은 5∼10wt%, Al2O3는 5∼10wt%, 규사는 10∼20wt%, 폴리아크릴릭에스테르계에멜젼은 20∼40wt%, 물은 10∼15wt%인 것이 바람직하다.The composition ratio in the composition is 5-45wt% (total weight ratio; same as below) for oyster shell, 5-15wt% for back cement, 5-10wt% for metakaolin, 5-10wt% for Al 2 O 3 , silica sand Is preferably 10 to 20 wt%, 20 to 40 wt% of the polyacrylic ester emulsion, and 10 to 15 wt% of water.
위와 같은 조성을 가지는 코팅제의 제조 방법을 설명하면 다음과 같다. Referring to the manufacturing method of the coating agent having the composition as described above are as follows.
본 발명의 코팅제 조성물의 제조 방법은,Method for producing a coating composition of the present invention,
굴 패각을 수세하고 소성시킨 후 분쇄하는 굴 패각 분말 제조 공정과;Oyster shell powder manufacturing step of washing and crushing the oyster shell with water;
굴 패각 분말에 백시멘트, 메타카올린, Al2O3 및 규사를 건비빔으로 혼합하여 중간 조성물을 얻는 중간 조성물 제조 공정과: The intermediate composition preparation process of mixing the oyster shell powder with white cement, metakaolin, Al 2 O 3 and silica sand in a gunbibim to obtain an intermediate composition:
상기 중간 조성물에 물과 폴리아크릴릭에스테르계에멜젼을 혼합하는 공정;Mixing water and a polyacrylic ester emulsion in the intermediate composition;
으로 구성된다..
굴 패각을 수세하고 소성시킨 후 분쇄하는 굴 패각 분말 제조 공정은, 염분 및 이물질을 제거하기 위해 수세과정을 거치며, 수세 후 건조시키고, 600-800℃에서 1-4시간 소성 처리하여 2-200㎛로 분쇄하는 공정으로 구성됨이 바람직하다.The oyster shell powder manufacturing process of washing and firing oyster shells and pulverizing them, washing with water to remove salt and foreign substances, drying after washing, firing at 600-800 ° C. for 1-4 hours and then 2-200 μm It is preferably composed of a process of grinding.
중간생성물 제조 공정은, 굴 패각 분말 30g에 대하여, 백시멘트 5-10g, 메타카올린 5g, Al2O3 5g, 및 규사 10-15g을 건비빔으로 혼합하는 공정으로 구성됨이 바람직하다.The intermediate production process is preferably composed of a step of mixing 5-10 g of white cement, 5 g of metakaolin, 5 g of Al 2 O 3 , and 10-15 g of siliceous sand with respect to 30 g of oyster shell powder.
위와 같은 본 발명은, 물과 시멘트 입자가 결합하는 수화반응이 서서히 진행되어 가사시간을 늘리고, 겔화되지 않은 수산화칼슘과의 화학결합으로 안정화되는 구조를 갖게 하는 물과 시멘트 입자간의 수화반응을 얻을 수 있으며, 아크릴과 시멘트입자 표면과의 반응으로 표면을 아크릴로 둘러싸게 하는 반응을 가지게 하여, 완전히 수화된 콘크리트의 표면을 아크릴막으로 둘러싸게 함으로써, 폴리머와 세라믹 소재의 표면효과를 가진 코팅제를 제공할 수 있게 하여 수질의 안정성을 높이고, 폐자원 활용으로 인한 비용절감 효과를 가지게 하며, 수밀성이 높아 코팅되는 벽체를 보호하며, 통기성능을 갖고 있어 장시간 경과하여도 박리현상이 발생되지 않도록 하는 구성을 가지는 코팅제를 제공한다.In the present invention as described above, the hydration reaction of the water and cement particles are combined gradually to increase the pot life, it is possible to obtain a hydration reaction between the water and the cement particles to have a structure that is stabilized by chemical bonding with ungelled calcium hydroxide. The reaction between the acrylic and the cement particle surface allows the surface to be surrounded by acrylic, and the surface of the fully hydrated concrete is surrounded by the acrylic film, thereby providing a coating agent having a surface effect of polymer and ceramic material. It improves the stability of water quality, has a cost-saving effect due to the utilization of waste resources, protects the wall to be coated with high watertightness, and has a breathable performance so that the coating does not occur even after a long time. To provide.
각 구성원소의 배합내용은 표 1과 같다.The content of each component is shown in Table 1.
표 1. 사용재료의 배합비Table 1. Mixing ratio of materials used
상기 굴 패각은 점도 그리고 표면경도 및 부착력의 증진을 목적으로 사용되는데 5-45%일 때 가장 좋은 성능을 나타내었다. 하지만 상기하한수치보다 적으면 부착강도 및 코팅제의 내구성이 감소하는 문제점이 있고, 상한수치보다 클 경우는 배합 시 원료들이 균일하게 분산되지 않는 문제점이 있어 상기와 같이 수치범위를 한정하였다.The oyster shell was used for the purpose of improving viscosity, surface hardness and adhesion, and showed the best performance at 5-45%. However, less than the lower limit, there is a problem that the adhesion strength and the durability of the coating agent is reduced, if the upper limit is greater than the problem that the raw materials are not uniformly dispersed during formulation limited the numerical range as described above.
상기 풀리아크릴릭에스테르계에멜젼은 접착성, 수밀성, 방수성을 위한 목적으로 조성되는데, 20-40%일 때 가장 좋은 접착성, 수밀성, 방수성을 가지게 된다. 하지만 상기 하한 수치보다 적으면, 균열추종성과 접착력에 문제점이 있고, 상한수치보다 클 경우는 강도에 문제점이 있어 상기와 같이 수치 범위를 한정하였다.The pulley acrylic ester-based emulsion is formed for the purpose of adhesiveness, watertightness, waterproofness, when the 20-40% has the best adhesiveness, watertightness, waterproofness. However, if it is less than the lower limit value, there is a problem in crack tracking and adhesive strength, and when it is larger than the upper limit value, there is a problem in strength, thereby limiting the numerical range as described above.
상기 물은 시멘트와의 수화반응을 위한 목적으로 조성되는데, 10-15%구간 범위일 때 가장 좋은 성능을 나타낸다. 하지만, 상기 하한 수치보다 낮으면 경도가 약한 문제점이 있고, 상한수치보다 클 경우는 pH가 상당히 높은 문제점이 있어 상기와 같이 수치 범위를 한정하였다.The water is formulated for the purpose of hydration with cement, showing the best performance in the 10-15% range. However, if lower than the lower limit, the hardness is weak, and if it is larger than the upper limit, the pH is considerably high.
상기 메타카올린은 시멘트 수화반응 중 미수화된 칼슘하이드록사이드를 칼슘실리케이트하이드레이트로 변화시켜 시멘트의 강도, 밀도, 내구성을 강화시켜 주는 목적으로 조성되는데, 5-10%일 때 가장 좋은 성능을 나타내었다. 하지만 상기 하한 수치보다 적으면 내구성 강화기능이 미미한 문제점이 있고, 상한수치보다 클 경우는 가사시간이 짧은 문제점이 있어 상기와 같이 수치 범위를 한정하였다.The metakaolin is formed for the purpose of strengthening the strength, density and durability of cement by converting unhydrated calcium hydroxide into calcium silicate hydrate during cement hydration, and showed the best performance at 5-10%. . However, if it is less than the lower limit, there is a problem that the durability enhancement function is insignificant, and if it is larger than the upper limit, the pot life is short.
상기 규사는 물, 시멘트나 다른 세라믹의 보완재로서의 균열방지용을 목적으로 사용되는데, 5-10%일 때 가장 좋은 성능을 나타내었다. 하지만 상기 하한 수치보다 적으면 균열저감 효과가 미미한 문제점이 있고, 상한수치보다 클 경우는 재료분리와 분산성의 문제점이 있어 상기와 같이 수치를 한정하였다.The silica sand is used for the purpose of preventing cracks as a complement to water, cement or other ceramics, and showed the best performance at 5-10%. However, when the lower limit value is smaller than the lower limit value, there is a problem of insignificant crack reduction, and when the upper limit value is larger, there is a problem of material separation and dispersibility, and thus the numerical value is limited as described above.
이하 본 발명을 구성하는 주원료인 굴 패각과 폴리아크릴릭에스테르계에멀젼의 특징을 보다 구체적으로 설명한다.Hereinafter, the characteristics of the oyster shell and the polyacrylic ester emulsion which are the main raw materials of the present invention will be described in more detail.
가. 굴 패각end. Oyster shell
굴 패각은 염분 및 이물질을 제거하기 위해 수세과정을 거친 후 건조기로 100℃로 24시간 건조하고, 600-800℃에서 1-4시간 소성 처리하여 2-200㎛로 분쇄하여서 된 분말인 것을 특징으로 한다. 상기 굴 패각을 전기로에 넣고 소성시킨 결과 600℃에서 소성 시 표면의 기공과 유기물의 제거가 만족스러웠으며, 700℃에서 소성 시 굴 패각은 탄산칼슘의 구조와 산화칼슘(CaO)구조로 열분해 되어 있는 두가지 상태가 혼합되어있었으며, 900℃에서 소성 시 굴 패각은 완전한 산화칼슘(CaO)구조를 나타내었다. 따라서 가장 바람직한 소성 온도는 600℃로 보여 지며 2시간정도 소성시간을 취하는 것이 그 효과가 현저하게 나타났다. 굴 패각의 물리화학적 특성은 표 2와 같다.Oyster shell is a powder obtained by rinsing at 100 ℃ for 24 hours in a dryer and then calcination at 2-200 ㎛ for 1-4 hours at 600-800 ℃ after washing with water to remove salt and foreign matter do. As a result of sintering the oyster shell in an electric furnace, it was satisfactory to remove the pores and organics on the surface when fired at 600 ℃, and when fired at 700 ℃ oyster shell is pyrolyzed into a structure of calcium carbonate and calcium oxide (CaO) structure The two states were mixed, and the oyster shells on the calcination at 900 ° C showed a complete calcium oxide (CaO) structure. Therefore, the most preferable firing temperature is shown to be 600 ℃ and taking a baking time of about 2 hours the effect was remarkable. Physical and chemical properties of oyster shells are shown in Table 2.
표 2. 굴패각의 물리화학적 조성Table 2. Physicochemical Composition of Oyster Shells
(Pore Size)Pore size
(Pore Size)
(Pore Volume)Porosity
(Pore Volume)
92.08%CaCO 3 /
92.08%
나. 폴리아크릴릭에스테르계에멀젼I. Polyacrylic ester emulsion
본 발명에 사용한 에멀젼은 시멘트와 혼화성이 좋은 장점을 갖고 있으며, 물리적 특성은 다음과 같다.Emulsion used in the present invention has the advantage of good compatibility with cement, physical properties are as follows.
시멘트와 혼합할 경우 발생되는 반응 메카니즘은 크게 두가지로 분류할 수 있는데, 첫째 물과 건조한 시멘트-세라믹 입자간의 수화반응과, 둘째 아크릴과 시멘트 표면 과의 반응으로 나눌 수 있다.The reaction mechanisms generated by mixing with cement can be classified into two categories: first, hydration between water and dry cement-ceramic particles, and second, between acrylic and cement surfaces.
즉, 물과 시멘트의 수화반응에 의한 결합 시 방해되지 않고 서서히 시멘트와 결합되면서 가사시간을 늘리고, 표면을 아크릴막으로 둘러싼다. 그리고 아크릴과 겔화되지 않은 수산화칼슘과의 화학결합으로 안정화되는 구조를 갖는다. That is, when combined with water and cement by the hydration reaction of cement, it is not hindered to gradually combine with cement to increase the pot life and surround the surface with an acrylic film. And it has a structure that is stabilized by chemical bonding of acryl and calcium gel ungelled.
표 3. 폴리아크릴릭에스테르계에멀젼의 물리적 특성Table 3. Physical Properties of Polyacrylic Ester Emulsions
(폴리아크릴릭에스테르계에멀젼의 화학구조)(Chemical structure of polyacrylic ester emulsion)
이하 본 발명을 바람직한 실시 예에 따라 설명한다.Hereinafter, the present invention will be described according to preferred embodiments.
실시예1:Example 1:
제1공정; 굴 패각 분말 제조 공정First step; Oyster Shell Powder Manufacturing Process
본 발명의 목적을 달성하기 위하여 상기와 같이 굴 양식장에서 버려진 굴 패각을 채취하여 염분을 제거하기 위하여 충분히 세척한 후 세척한 굴 패각을 건조기에 100℃로 24시간 건조한 후, In order to achieve the object of the present invention, after collecting the oyster shell discarded in the oyster farm as described above sufficiently washed to remove the salt, the washed oyster shell after drying 24 hours at 100 ℃ in a dryer,
전기로에서 600℃의 온도에서 2시간 동안 소성하여 입자를 2-200㎛의 크기로 분쇄하였다. 수세하고 소성된 굴 패각의 화학적 조성을 표 4에 나타내었다. The particles were fired at a temperature of 600 ° C. for 2 hours in an electric furnace to pulverize the particles to a size of 2-200 μm. Table 4 shows the chemical composition of washed and calcined oyster shells.
표 4. 수세한 굴 패각의 화학적 조성(%)Table 4. Chemical Composition of Washed Oyster Shells (%)
제2공정; 중간 조성물(A) 제조공정Second process; Intermediate composition (A) manufacturing process
상기 제1공정에서 얻은 굴 패각 30g과 분말형태의 무기재료인 백시멘트 10g, 메타카올린 5g, Al203 5g, 규사 10g을 건조된 상태에서 건비빔으로 혼합하여 중간 조성물(A)를 제조한다.The intermediate composition (A) is prepared by mixing 30 g of the oyster shell obtained in the first step with 10 g of a white cement, 5 g of metakaolin, 5 g of
제3공정; 최종공정Third process; Final process
중간 조성물(A) 30g과, 에멜젼으로 제조된 폴리아크릴릭에스테르계에멜젼 35g과, 물 10g을 혼합한 후, 전동식 믹서기로 5분 연속해서 혼합하여 본 발명의 코팅제 조성물을 제조한다.30 g of the intermediate composition (A), 35 g of a polyacrylic ester emulsion made from an emulsion, and 10 g of water are mixed, followed by continuous mixing for 5 minutes with an electric mixer to prepare a coating composition of the present invention.
실시예2:Example 2:
제1공정; 실시예 1에 있어서의 굴 패각 소성 분쇄공정과 동일 공정으로 굴 패각 분말을 얻는 공정First step; Process of obtaining oyster shell powder by the same process as the oyster shell plastic grinding process in Example 1
제2공정; 중간 조성물(B) 제조공정Second process; Intermediate composition (B) manufacturing process
상기 제1공정에서 얻은 굴 패각 30g과 분말형태의 무기재료인 백시멘트 5g, 메타카올린 5g, Al203 5g, 규사 15g을 건조된 상태에서 건비빔으로 혼합하여 조성물(B)를 제조한다.The composition (B) is prepared by mixing 30 g of the oyster shell obtained in the first step and 5 g of the cement material in the form of powder, 5 g of metakaolin, 5 g of Al 2 O 3 , and 15 g of silica sand in a dry state.
제3공정; 최종공정Third process; Final process
중간 조성물(B) 30g과, 폴리아크릴릭에스테르계에멜젼 30g과, 물 10g을 혼합한 후, 전동식 믹서기로 5분 연속해서 혼합하여 본 발명의 코팅제 조성물을 제조한다.30 g of the intermediate composition (B), 30 g of the polyacrylic ester emulsion, and 10 g of water are mixed, followed by continuous mixing for 5 minutes with an electric mixer to prepare a coating composition of the present invention.
제조된 본 발명의 코팅제 조성물의 비스페놀-A 용출 시험, pH측정 및 부착강도 측정을 위하여 시편을 마련하였다.Specimens were prepared for the bisphenol-A elution test, pH measurement and adhesion strength of the prepared coating composition of the present invention.
코팅제 조성물의 비스페놀-A 용출 시험과 pH측정을 위해서는, 200mm(가로)× 70mm(세로)× 3mm(두께)의 유리판의 양면에 본 발명의 코팅제를 붓칠로 도포하여 시편을 마련하였으며, 부착강도 측정용 시편은, 시멘트, 모래, 물을 1:2:3으로 배합하여 15mm(가로)× 140mm(세로)× 20mm(두께)의 크기의 판체를 제작하고, 이를 28일간 양생한 후 본 발명의 코팅제를 붓칠로 도포하고, 본 발명의 코팅제를 도포 한 판체를 온도20± 3℃, 습도 80%의 조건으로 설정된 습기함에 13일간 양생한 다음 온도 20± 15℃, 상대습도 65± 20%의 실험실 내에서 24시간 건조하여 마련하였다.For the bisphenol-A elution test and pH measurement of the coating composition, a specimen was prepared by applying a coating agent of the present invention to both sides of a glass plate of 200 mm (width) x 70 mm (length) x 3 mm (thickness) by preparing a specimen, and measuring adhesion strength. For test specimens, cement, sand, and water were mixed at 1: 2: 3 to prepare a plate having a size of 15 mm (width) × 140 mm (length) × 20 mm (thickness), and after curing for 28 days, the coating agent of the present invention. Was applied by brushing, and the plate coated with the coating agent of the present invention was cured for 13 days in a humidity set at a temperature of 20 ± 3 ℃ and a humidity of 80%, and then in a laboratory at a temperature of 20 ± 15 ℃ and a relative humidity of 65 ± 20%. It was prepared by drying for 24 hours.
위와 같이 하여 마련된 시편으로 비스페놀-A 용출 시험, pH측정 및 부착강도 측정을 한 결과는 다음과 같다.Bisphenol-A dissolution test, pH measurement and adhesion strength measurement results with the specimen prepared as described above are as follows.
가. 부착강도end. Adhesion strength
일반적으로 한국산업규격에 제시된 폴리머계 방수재료의 부착강도는 약8-10(kgf/cm2)이상으로 규정하고 있는데, 본 발명의 조성물은 약22-24kgf/cm2의 높은 부착강도를 나타냈다.(도 1참조)In general, the adhesion strength of the polymer-based waterproofing material presented in the Korean Industrial Standards is defined as about 8-10 (kgf / cm 2 or more), the composition of the present invention showed a high adhesion strength of about 22-24kgf / cm 2 . (See Fig. 1)
나. pHI. pH
코팅제를 도포한 유리시편을 물에 침적하여 각 시료의 pH를 측정한 결과 초기에는 약 pH 7.9-8.5의 높은 범위를 나타냈으나 일정시간이 경과 후 측정범위가 약 pH 7.4-7.6의 낮은 수준을 나타냈다.(도 2참조)The pH of each sample was measured by immersing the glass sample coated with the coating material. Initially, it showed a high range of about pH 7.9-8.5, but after a certain time, the measurement range was low. (See Fig. 2).
다. 비스페놀-A 용출All. Bisphenol-A Elution
코팅제를 도포한 유리시편을 물에 침적하여 각 시료의 비스페놀-A 용출 농도를 측정한 결과 에폭시수지로 코팅한 시편은 2.8 ㎍/L가 용출되었으나, 본 코팅제는 검 출되지 않았다.(도 3참조)Glass samples coated with a coating agent were immersed in water to measure the bisphenol-A elution concentration of each sample. As a result, 2.8 μg / L of the sample coated with epoxy resin was eluted, but the coating agent was not detected. )
첨부된 도면에는 실시예1에 의한 코팅제는 A, 실시예2에 의한 코팅제는 B로 표시하였다.In the accompanying drawings, the coating agent according to Example 1 is represented by A, and the coating agent according to Example 2 is represented by B. FIG.
본 발명에서 얻은 코팅제는 상기 내용과 같이 폐자원인 굴 패각을 주원료로 사용하여 기존 코팅제에 비해 환경호르몬인 비스페놀-A 검출이 없으면서 콘크리트와의 부착력도 개선되어 폐자원 활용측면에서 경제적으로 유리하며, 세라믹 소재를 사용함으로써 음용수로써의 안정성을 높일 수 있는 효과가 있다. 또한, 해양오염을 줄임과 동시에 폐자원을 활용할 수 있는 용도를 확대하고 항구적인 대체 자원으로서 활용할 수 있는 점에서 우수하다고 보여 진다.The coating agent obtained in the present invention uses the oyster shell as a waste material as the main material as described above, without the detection of bisphenol-A, which is an environmental hormone, compared with the existing coating agent, it is also economically advantageous in terms of waste resource utilization by improving adhesion with concrete. Using a ceramic material has the effect of increasing the stability as drinking water. In addition, it is considered to be excellent in reducing marine pollution and at the same time expanding the use of waste resources and utilizing them as permanent alternative resources.
본 발명의 코팅제는 완성된 형태로 제공될 수 있으며, 중간조성물(A, B)과 폴리아크릴릭에스테르계에멜젼을 별도로 제공하여 시공 현장에서 제조하여 사용될 수 있다. The coating agent of the present invention may be provided in a completed form, and may be prepared and used in a construction site by separately providing an intermediate composition (A, B) and a polyacrylic ester-based emulsion.
도1은 에폭시와 본발명의 실시예1에 의한 코팅제조성물(A) 및 실시예2에 의한 코팅제조성물(B)의1 is an epoxy and a coating composition (A) according to Example 1 of the present invention and a coating composition (B) according to Example 2
부착강도 비교도Bond strength comparison
도2는 일반 수도물과 본발명의 실시예1에 의한 코팅제조성물(A) 및 실시예2에 의한 코팅제조성물(B)을 침적한 물의 산성도 비교 시험도2 is a comparison test of acidity of general tap water and water in which the coating composition (A) according to Example 1 of the present invention and the coating composition (B) according to Example 2 were deposited.
도3은 에폭시와 본발명의 실시예1에 의한 코팅제조성물(A) 및 실시예2에 의한 코팅제조성물(B)을 도포한 시편으로부터 비스페놀-A 용출 비고 시험도3 is a bisphenol-A elution from a test piece coated with epoxy and a coating composition (A) according to Example 1 of the present invention and a coating composition (B) according to Example 2
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