WO2020153508A1 - Hydrophobic ceramic coating paint having improved miscibility - Google Patents

Hydrophobic ceramic coating paint having improved miscibility Download PDF

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Publication number
WO2020153508A1
WO2020153508A1 PCT/KR2019/000847 KR2019000847W WO2020153508A1 WO 2020153508 A1 WO2020153508 A1 WO 2020153508A1 KR 2019000847 W KR2019000847 W KR 2019000847W WO 2020153508 A1 WO2020153508 A1 WO 2020153508A1
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acid
coating
solution
pdms
alcohol
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PCT/KR2019/000847
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French (fr)
Korean (ko)
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이준성
김상목
김민희
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주식회사 네오플램
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Priority to PCT/KR2019/000847 priority Critical patent/WO2020153508A1/en
Priority to KR1020217010603A priority patent/KR102644206B1/en
Publication of WO2020153508A1 publication Critical patent/WO2020153508A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Definitions

  • the present invention is a coating material for hydrophobic ceramic coating in which a complex of colloidal silica and (C 1-4 alkyl) n (C 1-4 alkoxy) m silane and polydimethylsiloxane (PDMS) are homogeneously dispersed in a water-containing solvent, the same It relates to a manufacturing method and a non-stick cooking utensil coated thereon.
  • a complex of colloidal silica and (C 1-4 alkyl) n (C 1-4 alkoxy) m silane and polydimethylsiloxane (PDMS) are homogeneously dispersed in a water-containing solvent, the same It relates to a manufacturing method and a non-stick cooking utensil coated thereon.
  • Kitchen utensils such as frying pans and pots have been mainly produced using materials such as ordinary steel, aluminum alloy, aluminum plate, and stainless steel.
  • materials such as ordinary steel, aluminum alloy, aluminum plate, and stainless steel.
  • aluminum materials that are light yet easy to mold and are inexpensive to manufacture are often used.
  • the devices made of these materials exhibit many problems, such as repeated metal expansion and contraction due to rapid heating and rapid cooling, damage and oxidation, peeling, and corrosion of the coated surface due to consumer negligence.
  • the metal component such as aluminum is exposed due to the coating being peeled off, and the substrate is corroded due to the acid component of the cooking by sticking food and food to the portion where the coating is peeled off. It has been reported to accumulate and cause side effects such as Alzheimer's disease.
  • the kitchen tool has a high corrosion resistance and resistance to peeling and scratch resistance while being able to withstand high cooking temperatures, and does not stick to food.
  • a coating of fine ceramics is coated on the metal surface of the product using an inorganic paint and an inorganic ceramic coating composition having properties such as excellent heat resistance, weather resistance, contamination resistance, chemical resistance, and durability.
  • Technology has been used to prevent metal corrosion in household kitchen appliances.
  • ceramics traditionally use natural raw materials such as clay, and have been used as a container (porcelain). Recently, it is a term that collectively refers to products that have been heat-treated using high-purity artificial inorganic materials such as glass and metal oxide, and is called fine ceramics to distinguish them from ceramics.
  • Ceramic coating is a fine ceramic with strong corrosion resistance, heat resistance, and abrasion resistance.
  • the ceramic coating is applied to the surface of the product to prevent corrosion of metal and prevent food from sticking during cooking. have.
  • Ceramic-coated kitchen containers are capable of realizing various colors that are difficult to express with other coatings such as fluorine coatings.
  • the coatings do not peel off or burn even at temperatures above 350°C, as well as many advantages such as non-toxic, anti-bacterial, and far-infrared rays from natural minerals. In spite of this, it is being ignored by consumers in that it is relatively delaminated (peeled) due to the short persistence of food non-stick (nonstick) and the property weak to impact.
  • Thermal stability of the coating material for cooking utensils is an important performance index that can shorten the life of the cooking utensil due to thermal decomposition of the coating material that may occur during heating cooking or prevent the thermally decomposed material from migrating to food.
  • PTFE-based coatings represented by Teflon (Deflon, DuPont Co.) are most commonly used for non-stick coatings, but the thermal decomposition temperature is around 200°C, so the cooking environment using meat or oil cooked at 230 to 260°C is It can release harmful toxic substances.
  • the gel casting method is the most economical method among various methods for molding fine ceramics.
  • the organic additive in the ceramic mixed solution is maintained in a monomer state, exhibiting low viscosity, and reacting catalyst during molding. It is a method of obtaining a high-viscosity molded body according to the formation of a mold by adding a polymer network having a network structure.
  • the time to transition from the sol state to the gel state can be relatively easily controlled by adjusting the type of the monomer and/or cross-linker, the amount and type of the reaction catalyst, and the amount of distilled water.
  • the current ceramic coating method has excellent performance in all aspects, but when applied to kitchen utensils, as the number of uses increases, the persistence of non-stick performance becomes shorter and weaker to impact, resulting in relatively frequent peeling. have.
  • fluorine coating products that can generate substances harmful to the human body due to lack of non-stick performance and anti-peel function occupy 80% of the domestic cooking utensil coating market.
  • silicon having hydrophobic methyl group (-CH 3 ) is introduced on the ceramic coating to improve the non-stick performance, but it is still insufficient to replace the conventional fluorine coating (friction coefficient: Teflon 0.05 to 0.05). 0.1, silicone 0.3-0.8).
  • fluorine coating-level non-stick and anti-peel ceramic coating methods there are still no companies worldwide that have commercialized fluorine coating-level non-stick and anti-peel ceramic coating methods.
  • the present inventors provide a coating material containing a hydrophobic material in order to impart a non-stick performance to prevent pressing of the cooking utensils, in colloidal silica.
  • PDMS polydimethylsiloxane
  • MTMS methyltrimethoxysilane
  • PDMS polydimethylsiloxane
  • Another object of the present invention is It is to provide a method of manufacturing a non-stick cookware including coating the coating material for coating on the surface.
  • the coating of the present invention adds PDMS to a colloidal silica-based ceramic coating solution to impart non-stick performance, but by using the colloidal silica in the form of a complex with MTES having a hydrophobic methyl group, PDMS added thereto is another component in the coating. Since it is mixed evenly with the field and does not float or spill over time, an effective hydrophobic coating is possible, and air bubbles can be prevented from being generated on the surface of the coating layer due to the floating of the PDMS and thus loss, thereby forming an even and smooth surface. .
  • 1 is a view schematically showing a coating method using a colloidal silica-MTES composite.
  • FIG. 2 is a view showing the miscibility of PDMS in a solution according to the pH of the final solution.
  • Example 3 is a view showing the degree of separation of PDMS in the paint over time.
  • the conventional paint (Comparative Example 1) and the paint of the present invention (Example 1) are pictures taken after leaving the coating for 30 minutes, which is the time required for drying after coating.
  • FIG. 4 is a diagram showing the miscibility of PDMS in the coating material of the present invention containing a colloidal silica-MTES composite and an existing paint containing only colloidal silica.
  • Example 5 is a view showing the results of observing the morphology of the particles in the solution at each step of the coating method according to Example 1 of the present invention.
  • Example 6 is a view showing the miscibility of each component of the paint prepared according to Example 1 of the present invention by visual inspection and SEM-EDS.
  • Example 7 is a view showing the miscibility according to the ratio of PDMS in the coating material prepared according to Example 1 of the present invention, confirming the degree of precipitation.
  • the (C 1-4 alkyl) n (C 1-4 alkoxy) m silane is methyltriethoxysilane (MTES), methyltrimethoxysilane (MTMS), dimethyldimethoxysilane; DMDMS), dimethyldiethoxysilane (DMDES), trimethylethoxysilane (TMES) trimethylmethoxysilane (TMMS), or a mixture thereof, but is not limited thereto.
  • MTES can be used, but is not limited thereto.
  • the present invention is designed to discover a coating solution capable of exerting non-stick performance by imparting hydrophobicity by adding PDMS to a coating material for ceramic coating based on colloidal silica.
  • a coating solution capable of exerting non-stick performance by imparting hydrophobicity by adding PDMS to a coating material for ceramic coating based on colloidal silica.
  • it is difficult to obtain desired non-stick performance by floating and separating the PDMS to the upper layer over time during application and drying. After the bubbles are formed, oxygen, moisture, etc. penetrate to solve the problem of causing corrosion of the substrate, and then colloidal silica is mixed with ammonia water and hydrophobized alkylalkoxysilane to form a complex.
  • PDMS and MTMS improves the miscibility between these components, so that over time, the PDMS is separated from other components and is able to maintain a uniform dispersion without floating or floating on the upper layer.
  • pH adjustment must be carried out, and by optimizing these conditions, it is possible to provide a coating material containing PDMS in a ratio of up to 1:1 for the colloidal silica-MTES complex.
  • the paint of the present invention can maintain a uniformly mixed solution state without separating or separating the PDMS component even after 30 minutes.
  • the 30 minutes exemplifies the time required for drying of the coating liquid during spray coating, and indicates that a uniformly mixed solution state can be maintained for a longer period of time, that is, without phase separation during the entire drying process.
  • the content ratio of polydimethylsiloxane to colloidal silica and (C 1-4 alkyl) n (C 1-4 alkoxy) m silane complex may be 10:90 to 50:50.
  • the "polydimethylsiloxane (PDMS)" is a material having excellent physical properties such as transparency, flexibility, lubricity, and releasability as well as hydrophobicity, and is a silicone-based polymer suitable for surface modification of a hydrophilic substrate with hydrophobicity.
  • PDMS may be a material having a molecular weight of 80 to 150 cPs, but is not limited thereto.
  • the paint may be in a solution state of pH 4.5 to 5.5. If the pH is less than 4.5, the incomplete condensation reaction may cause the PDMS to not mix in the solution and sink to the bottom, whereas when the pH exceeds 5.5, the PDMS may float to the upper layer due to overparticle growth. Therefore, in order to maintain a uniformly mixed solution state without phase separation, it is preferable to maintain the pH of the solution in the range of 4.5 to 5.5.
  • a second step of dissolving to prepare a second solution A third step of slowly pouring a second solution into the first solution to react;
  • MTMS methyltrimethoxysilane
  • PDMS polydimethylsiloxane
  • the (C 1-4 alkyl) n (C 1-4 alkoxy) m silane is as defined above.
  • the production acid may be an acidic solution prepared by mixing inorganic and organic acids in a predetermined ratio.
  • the inorganic acid used in the production acid is hydrochloric acid, nitric acid, sulfuric acid or a mixture thereof, and the organic acid is formic acid, acetic acid, propionic acid, phosphoric acid, citric acid, Malic acid, fumaric acid, butyric acid, or a mixture thereof, but is not limited thereto.
  • the inorganic acid and the organic acid may be used as it is or by dilution as a mixture in a weight ratio of 8:2 to 9.5:0.5, but is not limited thereto.
  • the solvent used in the second solution may be methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, isopropyl alcohol, or mixtures thereof.
  • the C 1-4 alcohol may be isopropyl alcohol, but is not limited thereto.
  • first step and the second step are marked with an arbitrary number for convenience, and may be performed independently of each other regardless of the order.
  • the first solution may be acidic with a pH of 1 to 2.
  • the second solution may be basic with a pH of 8 to 10.
  • the prepared coating may change the miscibility of PDMS according to the pH, so the step of adjusting the pH of the solution obtained from the fourth step to 4.5 to 5.5 can be added, but is not limited thereto. Does not work.
  • the present invention is It provides a method of manufacturing a non-stick cookware comprising the step of coating the coating material on the surface.
  • the coating material for coating of the present invention contains hydrophobic PDMS in a uniformly mixed state without phase separation, it can be coated on a cooking utensil to prevent pressing, that is, to impart non-stick performance.
  • the method of coating the cooking utensils may be a spray coating method in which a coating is sprayed onto a surface to be coated in a solution state and then dried to form a coating layer, but is not limited thereto, and a coating method known in the art Can be performed without any limitation.
  • Example One Colloid Silica MTES Preparation of coatings using composites
  • MTMS methyltrimethoxysilane
  • PDMS polydimethylsiloxane
  • Comparative example 1 Conventional using colloidal silica 4 component type Preparation of paint
  • the pH of the mixed final solution of basic MTES was adjusted by adjusting the amount of acid produced in the acidic colloidal silica solution. Accordingly, the mixing degree of PDMS was changed, and the results are shown in Tables 1 and 2 below. As shown in FIG. 2, the mixing degree of PDMS was different depending on the pH, which is due to the hydrocondensation reaction. Specifically, at pH 6, the PDMS floats on the upper layer due to over-particle growth, whereas at pH 4, the condensation reaction is insufficient, and the PDMS sinks to the bottom. It was confirmed that it did not sink or float in the middle and was evenly mixed. This indicates that the pH affects the rate of particle growth, i.e., the rate of hydrocondensation reactions, and that the growth of the particles should not be too fast or too slow for the PDMS to be evenly mixed in solution.
  • Example 1 Considering that the time required for drying after applying the paint in the conventional spray coating process is about 30 minutes, in order to confirm that the PDMS in the paint component is suspended and separated in the coating solution during the corresponding time, the above Example 1 and Comparative Example 1 The coating solution prepared according to the method was left for 30 minutes, and then the layer separation was visually confirmed and the results are shown in FIG. 3. As shown in Figure 3, the conventional coating of Comparative Example 1 was PDMS was suspended and separated, but the coating of the present invention of Example 1 confirmed that even after 30 minutes, PDMS was still evenly mixed in the solution.
  • FIG. 4 schematically shows the surface properties and miscibility of each component of the conventional coating of Comparative Example 1 and the coating comprising the colloidal silica-MTES composite of Example 1.
  • the existing paint became hydrophobic through the hydrocondensation reaction of colloidal silica particles and MTMS, but due to poor miscibility with PDMS, PDMS floated and evaporated over time to generate pinholes.
  • the coating material of Example 1 using MTES as a starting material was more uniformly mixed with PDMS because it exhibits more hydrophobicity than the coating material of Comparative Example 1.
  • FIG. 5 shows uniform mixing with PDMS in the final manufactured paint, confirmed by SEM-EDS.
  • the coating solution was maintained in the form of a uniform dispersion without layer separation, it was confirmed that each component is evenly mixed in the microstructure.

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

The present invention relates to: a hydrophobic ceramic coating paint comprising a homogeneous dispersion of a composite of colloid silica and (C1-4 alkyl)n(C1-4 alkoxy)msilane, and polydimethylsiloxane (PDMS) in a water-containing solvent; a method for manufacturing same; and nonstick cookware coated with same.

Description

혼화성이 개선된 소수성 세라믹 코팅용 도료Paint for hydrophobic ceramic coating with improved miscibility
본 발명은 물 함유 용매에 콜로이드 실리카와 (C1-4 알킬)n(C1-4 알콕시)m실란의 복합체 및 폴리디메틸실록산(polydimethylsiloxane; PDMS)이 균질하게 분산된 소수성 세라믹 코팅용 도료, 이의 제조방법 및 이를 코팅한 넌스틱 조리기구에 관한 것이다.The present invention is a coating material for hydrophobic ceramic coating in which a complex of colloidal silica and (C 1-4 alkyl) n (C 1-4 alkoxy) m silane and polydimethylsiloxane (PDMS) are homogeneously dispersed in a water-containing solvent, the same It relates to a manufacturing method and a non-stick cooking utensil coated thereon.
프라이팬, 냄비 등의 주방 기구는 주로 일반 스틸, 알루미늄 합금, 알루미늄 판재, 스테인리스 스틸 등의 소재를 사용하여 제작되어 왔다. 특히, 가벼우면서도 성형이 용이하며 제작 비용이 저렴한 알루미늄 소재가 자주 사용되고 있다.Kitchen utensils such as frying pans and pots have been mainly produced using materials such as ordinary steel, aluminum alloy, aluminum plate, and stainless steel. In particular, aluminum materials that are light yet easy to mold and are inexpensive to manufacture are often used.
그러나, 이들 소재로 된 기구는 급열, 급랭의 반복에 의한 금속의 팽창 및 수축의 반복, 소비자의 과실로 인한 코팅면의 손상 및 산화, 벗겨짐, 부식 등 많은 문제점을 나타내고 있다. 특히, 전술한 이유로 코팅이 벗겨져 알루미늄 등 금속 성분이 노출되며, 코팅이 벗겨진 부위에는 음식물이 눌러 붙어 조리물의 산 성분으로 인해 기재가 부식되고, 이러한 눌러 붙은 음식물을 섭취하는 경우에는 금속 성분이 인체에 축적되어 알츠하이머 병 등의 부작용을 유발할 수 있는 것으로 보고되었다.However, the devices made of these materials exhibit many problems, such as repeated metal expansion and contraction due to rapid heating and rapid cooling, damage and oxidation, peeling, and corrosion of the coated surface due to consumer negligence. In particular, for the aforementioned reasons, the metal component such as aluminum is exposed due to the coating being peeled off, and the substrate is corroded due to the acid component of the cooking by sticking food and food to the portion where the coating is peeled off. It has been reported to accumulate and cause side effects such as Alzheimer's disease.
따라서, 주방 도구는 높은 조리 온도에서도 견딜 수 있고, 표면 마모 및 스크래치에 강한 내부식성 및 박리내구성을 갖추면서도, 음식물이 눌러 붙지 않는 비점착성을 갖는 것이 바람직하다.Therefore, it is preferable that the kitchen tool has a high corrosion resistance and resistance to peeling and scratch resistance while being able to withstand high cooking temperatures, and does not stick to food.
이를 위하여, 쿡웨어(cook-ware) 분야에서는 제품의 금속 표면에 우수한 내열성, 내후성, 내오염성, 내약품성, 내구성 등의 물성을 갖는 무기질 도료 및 무기계 세라믹 코팅 조성물을 이용하여 파인 세라믹으로 도막을 입혀 가정용 주방 기구의 금속 부식을 방지하는 기술이 사용되어 오고 있다.To this end, in the cook-ware field, a coating of fine ceramics is coated on the metal surface of the product using an inorganic paint and an inorganic ceramic coating composition having properties such as excellent heat resistance, weather resistance, contamination resistance, chemical resistance, and durability. Technology has been used to prevent metal corrosion in household kitchen appliances.
한편, 세라믹은 전통적으로 점토 등 천연의 원료를 사용하며, 용기(도자기)로 사용되어 왔다. 최근에는 유리, 금속산화물 등의 고순도 인공 무기물 원료로 사용하여 열처리한 제품을 통칭하는 용어로서 도자기와 구분하기 위하여 파인 세라믹(fine ceramics)으로 칭한다.Meanwhile, ceramics traditionally use natural raw materials such as clay, and have been used as a container (porcelain). Recently, it is a term that collectively refers to products that have been heat-treated using high-purity artificial inorganic materials such as glass and metal oxide, and is called fine ceramics to distinguish them from ceramics.
세라믹 코팅은 내식성, 내열성, 내마모성이 강한 파인 세라믹으로 제품 표면에 도막을 입히는 것으로, 가정용 주방 기구에서는 금속의 부식을 방지하고 조리 시 음식물이 들러붙지 않도록 하기 위하여 주로 조리 용기에 상기 세라믹 코팅을 적용하고 있다.Ceramic coating is a fine ceramic with strong corrosion resistance, heat resistance, and abrasion resistance. The ceramic coating is applied to the surface of the product to prevent corrosion of metal and prevent food from sticking during cooking. have.
세라믹 코팅 주방 용기는 불소 코팅과 같은 다른 코팅제로는 표현하기 어려운 다채로운 색상 구현이 가능하며, 350℃ 이상의 온도에서도 코팅이 벗겨지거나 타지 않을 뿐만 아니라 천연 무기물에서 비롯된 무독성, 내항균성, 원적외선 등 많은 장점에도 불구하고 음식물 비점착성(nonstick, 넌스틱)의 짧은 지속성과 충격에 약한 물성으로 비교적 박리(벗겨짐)가 잘 일어난다는 점에서 소비자로부터 외면당하고 있다.Ceramic-coated kitchen containers are capable of realizing various colors that are difficult to express with other coatings such as fluorine coatings.The coatings do not peel off or burn even at temperatures above 350℃, as well as many advantages such as non-toxic, anti-bacterial, and far-infrared rays from natural minerals. In spite of this, it is being ignored by consumers in that it is relatively delaminated (peeled) due to the short persistence of food non-stick (nonstick) and the property weak to impact.
음식 조리 시, 박리 내구성과 넌스틱 기능이 가장 중요한 쿡웨어 제품에 적용되는 기술로는 인체에 유해한 폴리테트라플루오로에틸렌(polytetrafluoroethylene; PTFE, Teflon) 기반의 불소 코팅 방식(미국 환경보호청 EPA, 2005년 공식 발표)과 젤 캐스팅(gel-casting) 방식의 친환경 세라믹 코팅 방식이 주로 사용되고 있다.When cooking food, the technology applied to cookware products in which peeling durability and non-stick function are the most important is polytetrafluoroethylene (PTFE, Teflon) based fluorine coating method harmful to the human body (US Environmental Protection Agency EPA, 2005) Official announcement) and gel-casting eco-friendly ceramic coating methods are mainly used.
조리 기구용 코팅 소재의 열 안정성은 가열 조리 시 발생할 수 있는 코팅 물질의 열분해에 의한 조리 기구의 수명 단축이나 열분해된 물질이 음식물로 전이(migration)되는 현상을 방지할 수 있는 중요한 성능 지표이다. 테플론(Teflon, DuPont Co.)으로 대표되는 PTFE 기반의 코팅은 넌스틱 코팅용으로 가장 많이 사용되고 있으나, 열분해 온도가 200℃ 부근이어서 230 내지 260℃에서 조리하는 육류나 오일을 이용하는 조리 환경에서는 인체에 유해한 독성 물질을 배출할 수 있다.Thermal stability of the coating material for cooking utensils is an important performance index that can shorten the life of the cooking utensil due to thermal decomposition of the coating material that may occur during heating cooking or prevent the thermally decomposed material from migrating to food. PTFE-based coatings represented by Teflon (Deflon, DuPont Co.) are most commonly used for non-stick coatings, but the thermal decomposition temperature is around 200°C, so the cooking environment using meat or oil cooked at 230 to 260°C is It can release harmful toxic substances.
한편, 젤 캐스팅 방식은 파인 세라믹을 성형하는 여러 방법 중 가장 경제적인 방법으로, 세라믹 분말과 혼합 시 세라믹 혼합 용액 내의 유기 첨가제가 단량체(monomer) 상태로 유지되어 낮은 점도를 나타내고, 성형 시 반응 촉매를 첨가하여 망상 구조의 고분자(polymer network)를 형성함으로써 몰드의 형성에 따라 고점도의 성형체를 얻는 방법이다. 이때 졸(sol) 상태에서 젤(gel) 상태로 전이되는 시간은 단량체 및/또는 가교제(cross-linker)의 종류, 반응 촉매의 양과 종류, 증류수의 양 등을 조절함으로써 비교적 쉽게 조절할 수 있다.On the other hand, the gel casting method is the most economical method among various methods for molding fine ceramics. When mixed with ceramic powder, the organic additive in the ceramic mixed solution is maintained in a monomer state, exhibiting low viscosity, and reacting catalyst during molding. It is a method of obtaining a high-viscosity molded body according to the formation of a mold by adding a polymer network having a network structure. At this time, the time to transition from the sol state to the gel state can be relatively easily controlled by adjusting the type of the monomer and/or cross-linker, the amount and type of the reaction catalyst, and the amount of distilled water.
그럼에도 불구하고, 현재의 세라믹 코팅 방식은 모든 면에서 우수한 성능을 가지고 있으나 주방 기구에 적용하는 경우, 사용 횟수가 증가할수록, 넌스틱 성능의 지속성이 짧아지고 충격에 약해 박리가 비교적 자주 발생하는 문제가 있다. 즉, 넌스틱 성능과 박리 방지 기능이 부족해 인체에 유해한 물질을 발생시킬 수 있는 불소 코팅 제품이 국내 조리 기구 코팅 시장의 80%를 점유하고 있다. 이를 극복하기 위하여, 세라믹 코팅 위에 소수성의 메틸기(-CH3)를 갖는 실리콘을 도입하여 넌스틱 성능을 개선하고 있으나, 종래 불소 코팅을 대체하기에는 여전히 미비하다(마찰 계수(friction coefficient): 테플론 0.05 내지 0.1, 실리콘 0.3 내지 0.8). 이와 같이 아직 불소 코팅 수준의 넌스틱 및 박리 방지 세라믹 코팅 방식을 상용화한 기업은 전세계적으로 아직 전무하다.Nevertheless, the current ceramic coating method has excellent performance in all aspects, but when applied to kitchen utensils, as the number of uses increases, the persistence of non-stick performance becomes shorter and weaker to impact, resulting in relatively frequent peeling. have. In other words, fluorine coating products that can generate substances harmful to the human body due to lack of non-stick performance and anti-peel function occupy 80% of the domestic cooking utensil coating market. To overcome this, silicon having hydrophobic methyl group (-CH 3 ) is introduced on the ceramic coating to improve the non-stick performance, but it is still insufficient to replace the conventional fluorine coating (friction coefficient: Teflon 0.05 to 0.05). 0.1, silicone 0.3-0.8). As such, there are still no companies worldwide that have commercialized fluorine coating-level non-stick and anti-peel ceramic coating methods.
본 발명자들은 조리기구에 눌음을 방지하기 위한 넌스틱(non-stick) 성능을 부여하기 위하여 소수성 물질을 포함하는 코팅용 도료를 제공함에 있어서, 콜로이드 실리카에 The present inventors provide a coating material containing a hydrophobic material in order to impart a non-stick performance to prevent pressing of the cooking utensils, in colloidal silica.
본 발명의 하나의 목적은 물 함유 용매에 콜로이드 실리카와 (C1-4 알킬)n(C1-4 알콕시)m실란(이때, n 및 m은 각각 독립적으로 1 내지 3의 정수이며, n+m=4임)의 복합체 및 폴리디메틸실록산(polydimethylsiloxane; PDMS)이 균질하게 분산된 소수성 세라믹 코팅용 도료를 제공하는 것이다.One object of the present invention is colloidal silica and (C 1-4 alkyl) n (C 1-4 alkoxy) m silane in the water-containing solvent ( where n and m are each independently integers of 1 to 3, n+ m = 4) to provide a coating material for a hydrophobic ceramic coating in which the composite and polydimethylsiloxane (PDMS) are homogeneously dispersed.
본 발명의 다른 하나의 목적은 콜로이드 실리카 및 제조산을 물 함유 용매에 용해시켜 제1용액을 준비하는 제1단계; (C1-4 알킬)n(C1-4 알콕시)m실란(이때, n 및 m은 각각 독립적으로 1 내지 3의 정수이며, n+m=4임) 및 암모니아수(ammonia solution)를 C1-4 알코올 용매에 용해시켜 제2용액을 준비하는 제2단계; 상기 제1용액에 제2용액을 서서히 부어 반응시키는 제3단계; 및 이전 단계로부터 수득한 반응 용액에 메틸트리메톡시실란(methyltrimethoxysilane; MTMS) 및 폴리디메틸실록산(PDMS)을 첨가하는 제4단계를 포함하는, 혼화성이 개선된 소수성 세라믹 코팅용 도료의 제조방법.Another object of the present invention is a first step of preparing a first solution by dissolving colloidal silica and production acid in a water-containing solvent; (C 1-4 alkyl) n (C 1-4 alkoxy) m silane (where n and m are each independently integers of 1 to 3, n+m=4) and ammonia solution C 1 -4 a second step of preparing a second solution by dissolving in an alcohol solvent; A third step of slowly pouring a second solution into the first solution to react; And a fourth step of adding methyltrimethoxysilane (MTMS) and polydimethylsiloxane (PDMS) to the reaction solution obtained from the previous step, a method for preparing a paint for hydrophobic ceramic coating with improved miscibility.
본 발명의 또 하나의 목적은 상기 코팅용 도료를 표면에 코팅하는 단계를 포함하는 넌스틱 조리기구(cookware)의 제조방법을 제공하는 것이다.Another object of the present invention is It is to provide a method of manufacturing a non-stick cookware including coating the coating material for coating on the surface.
본 발명의 도료는 콜로이드 실리카를 기반으로 하는 세라믹 코팅 용액에 PDMS를 첨가하여 넌스틱 성능을 부여하되 상기 콜로이드 실리카를 소수성 메틸기를 갖는 MTES와 복합체의 형태로 사용함으로써 이에 첨가되는 PDMS가 도료 내의 다른 성분들과 고르게 혼합되어 시간이 경과하여도 부유하거나 유출되지 않으므로 효과적인 소수성 코팅이 가능하며, PDMS의 부유 및 이에 따른 유실에 의해 코팅층 표면에 기포가 발생하는 것을 차단할 수 있어 고르고 매끄러운 표면을 형성할 수 있다.The coating of the present invention adds PDMS to a colloidal silica-based ceramic coating solution to impart non-stick performance, but by using the colloidal silica in the form of a complex with MTES having a hydrophobic methyl group, PDMS added thereto is another component in the coating. Since it is mixed evenly with the field and does not float or spill over time, an effective hydrophobic coating is possible, and air bubbles can be prevented from being generated on the surface of the coating layer due to the floating of the PDMS and thus loss, thereby forming an even and smooth surface. .
도 1은 콜로이드 실리카-MTES 복합체를 이용한 코팅 방법을 개략적으로 나타낸 도이다.1 is a view schematically showing a coating method using a colloidal silica-MTES composite.
도 2는 최종 용액의 pH에 따른 용액 중에서 PDMS의 혼화성을 나타낸 도이다.2 is a view showing the miscibility of PDMS in a solution according to the pH of the final solution.
도 3은 시간에 따른 도료 중 PDMS의 분리 정도를 나타낸 도이다. 구체적으로, 기존의 도료(비교예 1)와 본 발명의 도료(실시예 1)를 통상 코팅시 도료 도포 후 건조에 소요되는 시간인 30분 동안 방치한 후 찍은 사진이다.3 is a view showing the degree of separation of PDMS in the paint over time. Specifically, the conventional paint (Comparative Example 1) and the paint of the present invention (Example 1) are pictures taken after leaving the coating for 30 minutes, which is the time required for drying after coating.
도 4는 콜로이드 실리카만을 함유하는 기존 도료와 콜로이드 실리카-MTES 복합체를 함유하는 본 발명의 코팅용 도료에서 PDMS의 혼화성을 도식화하여 나타낸 도이다.FIG. 4 is a diagram showing the miscibility of PDMS in the coating material of the present invention containing a colloidal silica-MTES composite and an existing paint containing only colloidal silica.
도 5는 본 발명의 실시예 1에 따른 도료 제조방법의 각 단계에서 용액 내의 입자 형태를 TEM으로 관찰한 결과를 나타낸 도이다.5 is a view showing the results of observing the morphology of the particles in the solution at each step of the coating method according to Example 1 of the present invention.
도 6은 본 발명의 실시예 1에 따라 제조한 도료의 각 성분의 혼화성을 육안으로 및 SEM-EDS로 확인하여 나타낸 도이다.6 is a view showing the miscibility of each component of the paint prepared according to Example 1 of the present invention by visual inspection and SEM-EDS.
도 7은 본 발명의 실시예 1에 따라 제조한 도료 중의 PDMS 비율에 따른 혼화성을 침전 정도로 확인하여 나타낸 도이다.7 is a view showing the miscibility according to the ratio of PDMS in the coating material prepared according to Example 1 of the present invention, confirming the degree of precipitation.
상기 목적을 달성하기 위한 하나의 양태로서, 본 발명은 물 함유 용매에 콜로이드 실리카와 (C1-4 알킬)n(C1-4 알콕시)m실란(이때, n 및 m은 각각 독립적으로 1 내지 3의 정수이며, n+m=4임)의 복합체 및 폴리디메틸실록산(polydimethylsiloxane; PDMS)이 균질하게 분산된 소수성 세라믹 코팅용 도료를 제공한다.In one aspect for achieving the above object, the present invention is colloidal silica and (C 1-4 alkyl) n (C 1-4 alkoxy) m silane (where n and m are each independently 1 to It is an integer of 3, and provides a coating for hydrophobic ceramic coating in which a composite of n+m=4) and polydimethylsiloxane (PDMS) are homogeneously dispersed.
예컨대, 상기 (C1-4 알킬)n(C1-4 알콕시)m실란은 메틸트리에톡시실란(methyltriethoxysilane; MTES), 메틸트리메톡시실란(methyltrimethoxysilane; MTMS), 디메틸디메톡시실란(dimethyldimethoxysilane; DMDMS), 디메틸디에톡시실란(dimethyldiethoxysilane; DMDES), 트리메틸에톡시실란(trimethylethoxysilane; TMES) 트리메틸메톡시실란(trimethylmethoxysilane; TMMS) 또는 이들의 혼합물일 수 있으나, 이에 제한되지 않는다. 구체적으로 MTES를 사용할 수 있으나, 이에 제한되지 않는다.For example, the (C 1-4 alkyl) n (C 1-4 alkoxy) m silane is methyltriethoxysilane (MTES), methyltrimethoxysilane (MTMS), dimethyldimethoxysilane; DMDMS), dimethyldiethoxysilane (DMDES), trimethylethoxysilane (TMES) trimethylmethoxysilane (TMMS), or a mixture thereof, but is not limited thereto. Specifically, MTES can be used, but is not limited thereto.
본 발명은 콜로이드 실리카를 기반으로 하는 세라믹 코팅용 도료에 PDMS를 첨가하여 소수성을 부여함으로써 넌스틱 성능을 발휘할 수 있는 코팅 용액을 발굴하고자 고안된 것이다. 구체적으로, 기존의 콜로이드 실리카와 PDMS를 단순 혼합한 용액의 경우 기재에 도포하고 건조하는 동안 시간의 경과에 따라 PDMS가 상층으로 부유하여 이탈함으로써 원하는 넌스틱 성능을 얻기 어려울 뿐만 아니라 PDMS 이탈시 표면에 기포가 형성되어 이를 통해 산소, 수분 등이 침투하여 기재의 부식을 유발하는 문제를 해소하기 위하여, 콜로이드 실리카를 암모니아수와 가수 축합반응을 통해 소수성화한 알킬알콕시실란과 혼합하여 복합체를 형성한 후, PDMS 및 MTMS를 첨가함으로써 이들 성분 간의 혼화성이 향상되어 시간이 경과하여도 PDMS가 다른 성분으로부터 분리되어 상층에 부유되거나 하지 않고 균일한 분산액의 형태를 유지할 수 있음을 발견한 것이 본 발명의 특징이다. 특히, 이와 같은 균일한 혼합 용액을 형성하기 위해서는 pH 조절이 수반되어야 하며, 이러한 조건을 최적화함으로써 콜로이드 실리카-MTES 복합체에 대해 PDMS를 최대 1:1의 비율로 함유하는 도료를 제공할 수 있다.The present invention is designed to discover a coating solution capable of exerting non-stick performance by imparting hydrophobicity by adding PDMS to a coating material for ceramic coating based on colloidal silica. Specifically, in the case of a solution in which conventional colloidal silica and PDMS are simply mixed, it is difficult to obtain desired non-stick performance by floating and separating the PDMS to the upper layer over time during application and drying. After the bubbles are formed, oxygen, moisture, etc. penetrate to solve the problem of causing corrosion of the substrate, and then colloidal silica is mixed with ammonia water and hydrophobized alkylalkoxysilane to form a complex. It is a feature of the present invention that the addition of PDMS and MTMS improves the miscibility between these components, so that over time, the PDMS is separated from other components and is able to maintain a uniform dispersion without floating or floating on the upper layer. . In particular, in order to form such a uniform mixed solution, pH adjustment must be carried out, and by optimizing these conditions, it is possible to provide a coating material containing PDMS in a ratio of up to 1:1 for the colloidal silica-MTES complex.
예컨대, 본 발명의 도료는 30분 경과하여도 PDMS 성분이 침전 또는 부유하여 층분리되지 않고 균일하게 혼합된 용액 상태를 유지할 수 있다. 상기 30분은 통상적으로 스프레이 코팅시 코팅액의 건조에 소요되는 시간을 예시한 것으로 그 이상의 시간 동안 즉, 전체 건조 과정 동안 상분리 없이 균일하게 혼합된 용액 상태를 유지할 수 있음을 나타내는 것이다.For example, the paint of the present invention can maintain a uniformly mixed solution state without separating or separating the PDMS component even after 30 minutes. The 30 minutes exemplifies the time required for drying of the coating liquid during spray coating, and indicates that a uniformly mixed solution state can be maintained for a longer period of time, that is, without phase separation during the entire drying process.
예컨대, 본 발명의 도료는 콜로이드 실리카와 (C1-4 알킬)n(C1-4 알콕시)m실란 복합체에 대한 폴리디메틸실록산의 함량비는 10:90 내지 50:50일 수 있다. 상기 "폴리디메틸실록산(polydimethylsiloxane; PDMS)"은 소수성과 더불어 투명성, 유연성 윤활성 및 이형성 등의 우수한 물성을 지니는 물질로서, 친수성 기재를 소수성으로 표면 개질하기에 적합한 실리콘계 고분자이다.For example, the content ratio of polydimethylsiloxane to colloidal silica and (C 1-4 alkyl) n (C 1-4 alkoxy) m silane complex may be 10:90 to 50:50. The "polydimethylsiloxane (PDMS)" is a material having excellent physical properties such as transparency, flexibility, lubricity, and releasability as well as hydrophobicity, and is a silicone-based polymer suitable for surface modification of a hydrophilic substrate with hydrophobicity.
예컨대, PDMS는 80 내지 150 cPs의 점도를 나타내는 분자량의 물질일 있으나, 이에 제한되지 않는다.For example, PDMS may be a material having a molecular weight of 80 to 150 cPs, but is not limited thereto.
예컨대, 상기 도료는 pH 4.5 내지 5.5의 용액 상태일 수 있다. pH가 4.5 미만인 경우, 불완전한 축합 반응으로 인해 PDMS가 용액 중에 혼합되지 못하고 하부로 가라앉을 수 있는 반면, pH가 5.5 초과하는 경우에는 과입자성장으로 인해 PDMS가 상층으로 부유(floating)할 수 있다. 따라서, 상분리 없이 균일하게 혼합된 용액 상태를 유지하기 위해서는 용액의 pH를 4.5 내지 5.5 범위로 유지하는 것이 바람직하다.For example, the paint may be in a solution state of pH 4.5 to 5.5. If the pH is less than 4.5, the incomplete condensation reaction may cause the PDMS to not mix in the solution and sink to the bottom, whereas when the pH exceeds 5.5, the PDMS may float to the upper layer due to overparticle growth. Therefore, in order to maintain a uniformly mixed solution state without phase separation, it is preferable to maintain the pH of the solution in the range of 4.5 to 5.5.
다른 하나의 양태로서, 본 발명은 콜로이드 실리카 및 제조산을 물 함유 용매에 용해시켜 제1용액을 준비하는 제1단계; (C1-4 알킬)n(C1-4 알콕시)m실란(이때, n은 1 또는 2, m은 2 또는 3이며, n+m=4임) 및 암모니아수를 C1-4 알코올 용매에 용해시켜 제2용액을 준비하는 제2단계; 상기 제1용액에 제2용액을 서서히 부어 반응시키는 제3단계; 및 이전 단계로부터 수득한 반응 용액에 메틸트리메톡시실란(methyltrimethoxysilane; MTMS) 및 폴리디메틸실록산(polydimethylsiloxane; PDMS)을 첨가하는 제4단계를 포함하는, 혼화성이 개선된 소수성 세라믹 코팅용 도료의 제조방법을 제공한다.In another aspect, the present invention is a first step of preparing a first solution by dissolving colloidal silica and a production acid in a water-containing solvent; (C 1-4 alkyl) n (C 1-4 alkoxy) m silane (where n is 1 or 2, m is 2 or 3, n+m=4) and ammonia water in the C 1-4 alcohol solvent A second step of dissolving to prepare a second solution; A third step of slowly pouring a second solution into the first solution to react; And a fourth step of adding methyltrimethoxysilane (MTMS) and polydimethylsiloxane (PDMS) to the reaction solution obtained from the previous step, to prepare a paint for hydrophobic ceramic coating with improved miscibility. Provide a method.
상기 (C1-4 알킬)n(C1-4 알콕시)m실란은 이상에서 정의된 바와 같다.The (C 1-4 alkyl) n (C 1-4 alkoxy) m silane is as defined above.
예컨대, 상기 제조산은 무기산 및 유기산을 소정의 비율로 혼합하여 준비한 산성 용액일 수 있다. 상기 제조산에 사용되는 무기산은 염산, 질산, 황산 또는 이들의 혼합물, 유기산은 포름산(formic acid), 아세트산(acetic acid), 프로피온산(propionic acid), 인산(phosphoric acid), 시트르산(citric acid), 말산(malic acid), 푸마르산(fumaric acid), 부티르산(butyric acid) 또는 이들의 혼합물일 수 있으나, 이에 제한되지 않는다. 예컨대, 무기산 및 유기산을 8:2 내지 9.5:0.5의 중량비로 혼합한 것으로 그대로 또는 희석하여 사용할 수 있으나, 이에 제한되지 않는다.For example, the production acid may be an acidic solution prepared by mixing inorganic and organic acids in a predetermined ratio. The inorganic acid used in the production acid is hydrochloric acid, nitric acid, sulfuric acid or a mixture thereof, and the organic acid is formic acid, acetic acid, propionic acid, phosphoric acid, citric acid, Malic acid, fumaric acid, butyric acid, or a mixture thereof, but is not limited thereto. For example, the inorganic acid and the organic acid may be used as it is or by dilution as a mixture in a weight ratio of 8:2 to 9.5:0.5, but is not limited thereto.
예컨대, 제2용액에 사용되는 용매인 C1-4 알코올은 메틸알코올, 에틸알코올, 프로필알코올, 부틸알코올, 이소프로필알코올, 또는 이들의 혼합물일 수 있다. 구체적으로, 상기 C1-4 알코올은 이소프로필알코올일 수 있으나, 이에 제한되지 않는다.For example, the solvent used in the second solution, C 1-4 alcohol, may be methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, isopropyl alcohol, or mixtures thereof. Specifically, the C 1-4 alcohol may be isopropyl alcohol, but is not limited thereto.
예컨대, 상기 제1단계 및 제2단계는 편의상 임의의 번호를 붙여 표기한 것으로, 순서와 무관하게 상호 독립적으로 수행할 수 있다.For example, the first step and the second step are marked with an arbitrary number for convenience, and may be performed independently of each other regardless of the order.
예컨대, 상기 제1용액은 pH 1 내지 2의 산성일 수 있다.For example, the first solution may be acidic with a pH of 1 to 2.
한편, 상기 제2용액은 pH 8 내지 10의 염기성일 수 있다.Meanwhile, the second solution may be basic with a pH of 8 to 10.
한편, 전술한 바와 같이, 제조된 도료는 pH에 따라 PDMS의 혼화성이 변화할 수 있으므로, 제4단계로부터 수득한 용액의 pH를 4.5 내지 5.5로 조절하는 단계를 추가로 할 수 있으나, 이에 제한되지 않는다.On the other hand, as described above, the prepared coating may change the miscibility of PDMS according to the pH, so the step of adjusting the pH of the solution obtained from the fourth step to 4.5 to 5.5 can be added, but is not limited thereto. Does not work.
또 하나의 양태로서, 본 발명은 상기 코팅용 도료를 표면에 코팅하는 단계를 포함하는 넌스틱 조리기구(cookware)의 제조방법을 제공한다.In another aspect, the present invention is It provides a method of manufacturing a non-stick cookware comprising the step of coating the coating material on the surface.
본 발명의 코팅용 도료는 상분리 없이 소수성 PDMS를 균일하게 혼합된 상태로 함유하므로 조리기구에 코팅하여 눌음 방지 즉, 넌스틱 성능을 부여할 수 있다. 이때, 조리기구에 코팅하는 방법은 도료를 용액 상태로 피 코팅면에 스프레이로 분사한 후 건조하여 코팅층을 형성하는 스프레이 코팅법을 사용할 수 있으나, 이에 제한되는 것은 아니며, 당업계에 공지된 코팅방법을 제한없이 사용하여 수행할 수 있다.Since the coating material for coating of the present invention contains hydrophobic PDMS in a uniformly mixed state without phase separation, it can be coated on a cooking utensil to prevent pressing, that is, to impart non-stick performance. At this time, the method of coating the cooking utensils may be a spray coating method in which a coating is sprayed onto a surface to be coated in a solution state and then dried to form a coating layer, but is not limited thereto, and a coating method known in the art Can be performed without any limitation.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명하고자 한다. 이들 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이들 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. These examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by these examples.
실시예Example 1: One: 콜리이드Colloid 실리카- Silica MTESMTES 복합체를 이용한 코팅 도료의 제조 Preparation of coatings using composites
하나의 비커에 10 g의 증류수를 넣고 41.4 g의 콜로이드 실리카와 17 g의 제조산(포름산과 염산을 9:1의 중량비로 혼합한 것을 50% 희석하여 준비)을 첨가하여 pH를 1.8로 낮추었다(A1). 다른 하나의 비커에는 106.5 g의 이소프로필알코올(isopropyl alcohol; IPA)을 넣고 8 g의 MTES(methyltriethoxysilane)와 2 g의 암모니아수를 첨가하여 pH 10의 소수성 MTES 전구체를 제조하였다(A2). 상기 용액 2를 용액 1에 천천히 부어주어 상온에서 14시간 동안 가수축합 반응을 수행하여 실리카 복합체를 제조하였다(A1+A2=A). 상기 제조된 실리카 복합체에 50.1 g의 MTMS(methyltrimethoxysilane)와 18.65 g의 PDMS(polydimethylsiloxane)(B)를 첨가하여 표면의 잔여 히드록실기를 소수성으로 개질하고 최종 pH는 5가 되도록 하였다(A+B). 상기 각 용액에서의 입자 형태를 SEM로 관찰하고, 그 결과를 도 5에 나타내었다.10 g of distilled water was added to one beaker, and 41.4 g of colloidal silica and 17 g of production acid (prepared by diluting 50% of formic acid and hydrochloric acid in a weight ratio of 9:1) were lowered to 1.8. ( A1 ). In another beaker, 106.5 g of isopropyl alcohol (IPA) was added, and 8 g of methyltriethoxysilane (MTES) and 2 g of ammonia water were added to prepare a hydrophobic MTES precursor having a pH of 10 ( A2 ). The solution 2 was slowly poured into solution 1 to perform a hydrocondensation reaction at room temperature for 14 hours to prepare a silica composite ( A1+A2=A ). To the prepared silica composite, 50.1 g of methyltrimethoxysilane (MTMS) and 18.65 g of polydimethylsiloxane (PDMS) ( B ) were added to hydrophobically modify the remaining hydroxyl groups on the surface, and the final pH was 5 ( A+B ). . The particle morphology in each solution was observed by SEM, and the results are shown in FIG. 5.
비교예Comparative example 1: 콜로이드 실리카를 사용하는 기존의 1: Conventional using colloidal silica 4액형4 component type 도료의 제조 Preparation of paint
콜로이드 실리카를 물에 분산시킨 용액(A1')에 산 촉매(A2')를 첨가한 후, MTMS와 PDMS(B) 및 염기 촉매(C)를 상기 혼합 용액에 순차적으로 첨가하였다.After adding an acid catalyst ( A2' ) to a solution ( A1' ) in which colloidal silica was dispersed in water, MTMS and PDMS ( B ) and a base catalyst ( C ) were sequentially added to the mixed solution.
실험예Experimental Example 1: 콜로이드 실리카와 1: Colloidal silica MTES의MTES 혼합 비율에 따른 효과 Effect of mixing ratio
산성의 콜로이드 실리카 용액에서 제조산의 사용량을 조절하여 염기성의 MTES의 혼합된 최종 용액의 pH를 조절하였다. 이에 따라 PDMS의 혼합 정도가 변화하였으며, 이를 관찰하여 그 결과를 하기 표 1 및 도 2에 나타내었다. 도 2에 나타난 바와 같이, pH에 따라 PDMS의 혼합 정도는 상이하게 나타났으며, 이는 가수축합 반응에 기인한다. 구체적으로, pH 6에서는 과입자성장으로 인해 PDMS가 상층에 부유하는(floating) 반면, pH 4에서는 축합반응이 미비하여 PDMS가 하부에 가라앉았으며, pH 5에서는 적정 속도로 반응이 일어나 PDMS가 용액 중에 가라앉거나 부유하지 않고 고르게 혼합된 것을 확인하였다. 이는 pH가 입자 성장 속도 즉, 가수축합 반응 속도에 영향을 주며, 상기 입자의 성장이 너무 빠르거나 느리지 않아야 PDMS가 용액 중에 고르게 혼합될 수 있음을 나타낸다.The pH of the mixed final solution of basic MTES was adjusted by adjusting the amount of acid produced in the acidic colloidal silica solution. Accordingly, the mixing degree of PDMS was changed, and the results are shown in Tables 1 and 2 below. As shown in FIG. 2, the mixing degree of PDMS was different depending on the pH, which is due to the hydrocondensation reaction. Specifically, at pH 6, the PDMS floats on the upper layer due to over-particle growth, whereas at pH 4, the condensation reaction is insufficient, and the PDMS sinks to the bottom. It was confirmed that it did not sink or float in the middle and was evenly mixed. This indicates that the pH affects the rate of particle growth, i.e., the rate of hydrocondensation reactions, and that the growth of the particles should not be too fast or too slow for the PDMS to be evenly mixed in solution.
제조산 사용량Production acid consumption 최종 pHFinal pH 결과result
시료 1Sample 1 10 g10 g 66 PDMS가 위로 뜸PDMS tops
시료 2 Sample 2 17 g17 g 55 균일하게 혼합Mix evenly
시료 3 Sample 3 20 g20 g 44 PDMS가 아래로 가라앉음PDMS sinks down
실험예Experimental Example 2: 시간에 따른 도료의 2: Paint over time PDMSPDMS 분리 정도 비교 Comparison of separation
통상의 스프레이 코팅 공정에서 도료를 도포한 후 건조에 소요되는 시간이 약 30분인 것을 고려하여, 해당 시간 동안 도료 성분 중의 PDMS가 코팅액 중에서 부유하여 분리되는지 확인하기 위하여, 상기 실시예 1 및 비교예 1에 따라 준비한 도료 용액을 30분 동안 방치한 후 층 분리를 육안으로 확인하고 그 결과를 도 3에 나타내었다. 도 3에 나타난 바와 같이, 비교예 1의 기존 도료는 PDMS가 부유하여 층분리되었으나, 실시예 1의 본 발명의 도료는 30분이 경과하여도 여전히 PDMS가 용액 중에 고르게 혼합되어 있음을 확인하였다.Considering that the time required for drying after applying the paint in the conventional spray coating process is about 30 minutes, in order to confirm that the PDMS in the paint component is suspended and separated in the coating solution during the corresponding time, the above Example 1 and Comparative Example 1 The coating solution prepared according to the method was left for 30 minutes, and then the layer separation was visually confirmed and the results are shown in FIG. 3. As shown in Figure 3, the conventional coating of Comparative Example 1 was PDMS was suspended and separated, but the coating of the present invention of Example 1 confirmed that even after 30 minutes, PDMS was still evenly mixed in the solution.
실험예Experimental Example 3: 도료의 구조 및 물성 비교 3: Comparison of paint structure and properties
도 4에는 비교예 1의 기존 도료와 실시예 1의 콜로이드 실리카-MTES 복합체를 포함하는 도료의 각 성분의 표면 특성 및 이에 따른 혼화성을 도식화하여 나타내었다. 도 4에 나타난 바와 같이, 기존 도료는 콜로이드 실리카 입자와 MTMS의 가수축합 반응을 통해 소수성을 띄게 되었으나 PDMS와의 혼화성이 열악하여 시간이 경과함에 따라 PDMS가 상부로 부유하여 증발되면서 핀홀이 발생하였으나, MTES를 출발물질로 사용하는 실시예 1의 도료는 비교예 1의 도료 보다 더 소수성을 띄므로 PDMS와 균일하게 혼합되었다. 실시예 1에 따른 제조방법의 각 단계에서 용액 중 각 입자의 형태를 관찰하여 도 5에 나타내었으며, 도 6에는, SEM-EDS로 확인한, 최종 제조된 도료에서 PDMS와의 균일한 혼합을 나타내었다. 도 6에 나타난 바와 같이, 도료 용액은 층분리 없이 고른 분산액의 형태를 유지하였으며 미세구조에서도 각 성분이 균일하게 혼합되어 있음을 확인할 수 있었다.FIG. 4 schematically shows the surface properties and miscibility of each component of the conventional coating of Comparative Example 1 and the coating comprising the colloidal silica-MTES composite of Example 1. As shown in Fig. 4, the existing paint became hydrophobic through the hydrocondensation reaction of colloidal silica particles and MTMS, but due to poor miscibility with PDMS, PDMS floated and evaporated over time to generate pinholes. The coating material of Example 1 using MTES as a starting material was more uniformly mixed with PDMS because it exhibits more hydrophobicity than the coating material of Comparative Example 1. In each step of the manufacturing method according to Example 1, the shape of each particle in the solution was observed and is shown in FIG. 5, and FIG. 6 shows uniform mixing with PDMS in the final manufactured paint, confirmed by SEM-EDS. As shown in Figure 6, the coating solution was maintained in the form of a uniform dispersion without layer separation, it was confirmed that each component is evenly mixed in the microstructure.
실험예Experimental Example 4: 콜로이드 실리카- 4: Colloidal silica MTESMTES 복합체 사용에 따른 코팅 도료의 Coating coatings according to the use of composites PDMSPDMS 최대 첨가량 비교 Comparison of maximum addition amount
실험예 3에서 확인한 바와 같이, PDMS와의 혼화성이 증가된 실시예 1의 도료에서 균일 혼합이 가능한 PDMS의 최대 함량을 확인하기 위하여, 콜로이드 실리카-MTES에 대한 PDMS의 양을 증가시키면서 혼합하고, 균일한 분산액으로 유지되는지 여부를 육안으로 확인하여, 그 결과를 하기 표 2와 도 7에 나타내었다. 도 7에 나타난 바와 같이, PDMS 함량이 각각 20% 및 40%인 경우 침전없이 균일하게 혼합되어 분산된 상태를 유지하였으나, PDMS 함량이 각각 60 및 70%로 증가된 경우 서서히 침전되었으며, PDMS 80%인 경우에는 거의 혼합되지 않고 침전된 것을 확인하였다.As shown in Experimental Example 3, in order to confirm the maximum content of PDMS capable of uniform mixing in the paint of Example 1 with increased miscibility with PDMS, mixing was performed while increasing the amount of PDMS to colloidal silica-MTES, and uniform Whether it was maintained as one dispersion was visually confirmed, and the results are shown in Table 2 and FIG. 7 below. As shown in FIG. 7, when the PDMS content was 20% and 40%, respectively, it was uniformly mixed and dispersed without precipitation, but when the PDMS content was increased to 60 and 70%, respectively, it precipitated slowly, PDMS 80% In the case of, it was confirmed that it was precipitated with little mixing.
혼합비(중량비)Mixing ratio (weight ratio) 2:82:8 3:73:7 4:64:6 6:46:4 8:28:2
콜로이드 실리카-MTES:PDMSColloidal silica-MTES:PDMS 침전Sedimentation 서서히 침전Settle slowly 서서히 침전Settle slowly 균일 혼합Uniform mixing 균일 혼합Uniform mixing

Claims (14)

  1. 물 함유 용매에 콜로이드 실리카와 (C1-4 알킬)n(C1-4 알콕시)m실란(이때, n 및 m은 각각 독립적으로 1 내지 3의 정수이며, n+m=4임)의 복합체 및 폴리디메틸실록산(polydimethylsiloxane; PDMS)이 균질하게 분산된 소수성 세라믹 코팅용 도료.Complex of colloidal silica and (C 1-4 alkyl) n (C 1-4 alkoxy) m silane (where n and m are each independently integers of 1 to 3, n+m=4) in a water-containing solvent. And a coating for hydrophobic ceramic coating in which polydimethylsiloxane (PDMS) is homogeneously dispersed.
  2. 제1항에 있어서,According to claim 1,
    상기 (C1-4 알킬)n(C1-4 알콕시)m실란은 메틸트리에톡시실란(methyltriethoxysilane; MTES), 메틸트리메톡시실란(methyltrimethoxysilane; MTMS), 디메틸디메톡시실란(dimethyldimethoxysilane; DMDMS), 디메틸디에톡시실란(dimethyldiethoxysilane; DMDES), 트리메틸에톡시실란(trimethylethoxysilane; TMES) 및 트리메틸메톡시실란(trimethylmethoxysilane; TMMS)으로 구성된 군으로부터 선택되는 1종 이상의 물질인 것인, 도료.The (C 1-4 alkyl) n (C 1-4 alkoxy) m silane is methyltriethoxysilane (MTES), methyltrimethoxysilane (MTMS), dimethyldimethoxysilane (DMDMS) , Dimethyldiethoxysilane (DMDES), trimethylethoxysilane (TMES) and trimethylmethoxysilane (trimethylmethoxysilane; TMMS) is at least one material selected from the group consisting of, coating.
  3. 제1항에 있어서,According to claim 1,
    30분 경과하여도 PDMS 성분이 침전 또는 부유하여 층분리되지 않고 균일하게 혼합된 용액 상태를 유지하는 것인, 도료.Even after 30 minutes, the PDMS component is precipitated or suspended, so that the layer is not separated and maintains a uniformly mixed solution state.
  4. 제1항에 있어서,According to claim 1,
    콜로이드 실리카와 (C1-4 알킬)n(C1-4 알콕시)m실란 복합체에 대한 폴리디메틸실록산의 함량비는 10:90 내지 50:50인 것인, 도료.The content ratio of the polydimethylsiloxane to colloidal silica and (C 1-4 alkyl) n (C 1-4 alkoxy) m silane complex is 10:90 to 50:50.
  5. 제1항에 있어서,According to claim 1,
    pH는 4.5 내지 5.5인 것인, 도료.The pH is 4.5 to 5.5, the coating.
  6. 콜로이드 실리카 및 제조산을 물 함유 용매에 용해시켜 제1용액을 준비하는 제1단계;A first step of preparing a first solution by dissolving colloidal silica and a production acid in a water-containing solvent;
    (C1-4 알킬)n(C1-4 알콕시)m실란(이때, n 및 m은 각각 독립적으로 1 내지 3의 정수이며, n+m=4임) 및 암모니아수를 C1-4 알코올 용매에 용해시켜 제2용액을 준비하는 제2단계;(C 1-4 alkyl) n (C 1-4 alkoxy) m silane (where n and m are each independently integers of 1 to 3, n+m=4) and ammonia water in C 1-4 alcohol solvent A second step of dissolving in to prepare a second solution;
    상기 제1용액에 제2용액을 서서히 부어 반응시키는 제3단계; 및A third step of slowly pouring a second solution into the first solution to react; And
    이전 단계로부터 수득한 반응 용액에 메틸트리메톡시실란(methyltrimethoxysilane; MTMS) 및 폴리디메틸실록산(polydimethylsiloxane; PDMS)을 첨가하는 제4단계를 포함하는, 혼화성이 개선된 소수성 세라믹 코팅용 도료의 제조방법.Method for producing a paint for hydrophobic ceramic coating with improved miscibility, comprising a fourth step of adding methyltrimethoxysilane (MTMS) and polydimethylsiloxane (PDMS) to the reaction solution obtained from the previous step .
  7. 제6항에 있어서,The method of claim 6,
    상기 제1단계 및 제2단계는 순서와 무관하게 상호 독립적으로 수행되는 것인, 제조방법.The first and second steps are performed independently of each other, regardless of the order, the manufacturing method.
  8. 제6항에 있어서,The method of claim 6,
    상기 (C1-4 알킬)n(C1-4 알콕시)m실란은 메틸트리에톡시실란(methyltriethoxysilane; MTES), 메틸트리메톡시실란(methyltrimethoxysilane; MTMS), 디메틸디메톡시실란(dimethyldimethoxysilane; DMDMS), 디메틸디에톡시실란(dimethyldiethoxysilane; DMDES), 트리메틸에톡시실란(trimethylethoxysilane; TMES) 및 트리메틸메톡시실란(trimethylmethoxysilane; TMMS)으로 구성된 군으로부터 선택되는 1종 이상의 물질인 것인, 제조방법.The (C 1-4 alkyl) n (C 1-4 alkoxy) m silane is methyltriethoxysilane (MTES), methyltrimethoxysilane (MTMS), dimethyldimethoxysilane (DMDMS) , Dimethyldiethoxysilane (DMDES), trimethylethoxysilane (trimethylethoxysilane; TMES) and trimethylmethoxysilane (trimethylmethoxysilane; TMMS) is at least one material selected from the group consisting of.
  9. 제6항에 있어서,The method of claim 6,
    상기 제조산은 염산, 질산, 황산 또는 이들의 혼합물로 구성된 군으로부터 선택되는 무기산 및 포름산(formic acid), 아세트산(acetic acid), 프로피온산(propionic acid), 인산(phosphoric acid), 시트르산(citric acid), 말산(malic acid), 푸마르산(fumaric acid), 부티르산(butyric acid) 또는 이들의 혼합물로 구성된 군으로부터 선택되는 유기산의 혼합물인 것인, 제조방법.The production acid is selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, or mixtures thereof, formic acid, acetic acid, propionic acid, phosphoric acid, citric acid, The manufacturing method is a mixture of organic acids selected from the group consisting of malic acid, fumaric acid, butyric acid or mixtures thereof.
  10. 제6항에 있어서,The method of claim 6,
    상기 C1-4 알코올은 메틸알코올, 에틸알코올, 프로필알코올, 부틸알코올, 이소프로필알코올, 및 이들의 혼합물로 구성된 군으로부터 선택되는 것인, 제조방법.The C 1-4 alcohol is selected from the group consisting of methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, isopropyl alcohol, and mixtures thereof.
  11. 제6항에 있어서,The method of claim 6,
    상기 제1용액은 pH 1 내지 2의 산성인 것인, 제조방법.The first solution will be acidic, pH 1 to 2, the production method.
  12. 제6항에 있어서,The method of claim 6,
    상기 제2용액은 pH 8 내지 10의 염기성인 것인, 제조방법.The second solution is a basic method of pH 8 to 10, the production method.
  13. 제6항에 있어서,The method of claim 6,
    제4단계로부터 수득한 용액의 pH를 4.5 내지 5.5로 조절하는 단계를 추가로 포함하는 것인, 제조방법.The method further comprises the step of adjusting the pH of the solution obtained from the fourth step to 4.5 to 5.5.
  14. 제1항의 코팅용 도료를 표면에 코팅하는 단계를 포함하는 넌스틱 조리기구(cookware)의 제조방법.A method of manufacturing a non-stick cookware comprising the step of coating the coating material of claim 1 on a surface.
PCT/KR2019/000847 2019-01-21 2019-01-21 Hydrophobic ceramic coating paint having improved miscibility WO2020153508A1 (en)

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US5492958A (en) * 1993-03-08 1996-02-20 Dow Corning Corporation Metal containing ceramic coatings
US20070218297A1 (en) * 2006-03-14 2007-09-20 Bong Yeol Jeon Non-stick ceramic coating composition and process
JP2013060338A (en) * 2011-09-14 2013-04-04 Fuji Xerox Co Ltd Method for producing hydrophobic silica particle
KR20150114317A (en) * 2014-04-01 2015-10-12 한국과학기술원 Producing method of transparent siloxane cured material by hydrolysis-condensation reaction
KR20170100088A (en) * 2016-02-24 2017-09-04 (주)네오플램 Ceramic Coating Composition and Methode of Ceramic Coating on plastic

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