KR20070004215A - Synthesis method of coating agent for antipollution and super hydrophilic - Google Patents

Synthesis method of coating agent for antipollution and super hydrophilic Download PDF

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KR20070004215A
KR20070004215A KR1020050059629A KR20050059629A KR20070004215A KR 20070004215 A KR20070004215 A KR 20070004215A KR 1020050059629 A KR1020050059629 A KR 1020050059629A KR 20050059629 A KR20050059629 A KR 20050059629A KR 20070004215 A KR20070004215 A KR 20070004215A
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titanium dioxide
coating agent
dioxide particles
titanium
sulfuric acid
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KR1020050059629A
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Korean (ko)
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서영성
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성수임
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/08—Drying; Calcining ; After treatment of titanium oxide
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic

Abstract

A method of preparing hydrophilic and anti-pollution coating agent is provided to obtain the coating agent for preventing constructional exterior material such as glass from being polluted by dust, smoke and/or exhaust gas by using titanium isopropoxide and tetraethoxysilane as starting materials and comprising optical catalyst, inorganic binder, etc. The method for producing titanium dioxide particles comprises the steps of: preparing a transparent solution by mixing titanium isopropoxide in water and sulfuric acid in a ratio of 2:1; heating the solution at 65-95deg.C to generate titanium dioxide particles; and separating the titanium dioxide particles from the solution by centrifuging, washing and drying the particles. The hydrophilic and anti-pollution coating agent preparation process includes addition of tetraethoxysilane to the prepared titanium dioxide powder and hydrolysis and peptization of the product.

Description

친수 및 오염방지를 위한 코팅제 제조방법 {Synthesis method of Coating Agent for Antipollution and Super hydrophilic}              Synthesis method of Coating Agent for Antipollution and Super hydrophilic

본 발명은 건축 외장재에 있어 특히 유리의 경우 대기중의 분진과 매연에 의The present invention relates to dust and soot in the atmosphere, especially in the case of glass in building exterior materials

해 오염되는 것을 방지하기 위한 코팅제에 관한 것으로서 광촉매제, 무기 바인더를 조성으로 하는 코팅제에 관한 것이다.The present invention relates to a coating agent for preventing contamination of the sea, and to a coating agent comprising a photocatalyst and an inorganic binder.

최근 광촉매 재료를 건물 외장에 피복함으로써 우천 시 빗물에 의해 친수화를 통한 자정기능을 갖는 재료로서 주목되고 있다. 또한 자동차 매연을 광촉매 반응에 의해 분해하여 대기정화기능을 수행할 수 있기 때문에 친환경 소재로서 각광받고 있다.Recently, the photocatalyst material has been attracting attention as a material having a self-cleaning function through hydrophilization by rainwater in rainy weather by coating the exterior of a building. In addition, since the soot can be decomposed by a photocatalytic reaction to perform an atmospheric purification function, it has been spotlighted as an environmentally friendly material.

예를 들면, 대한민국 공개특허(공개번호 : 10-2004-0097205)에 의하면 테트라 에톡시 실란을 가수분해하고 해교반응을 통하여 실리카 졸을 얻은 후 여기에 지르코늄 염, 알미늄 염, 아연 염 및 폴리아크릴산을 첨가하여 코팅액을 제조하고, 이를 코팅처리 후 300℃ 열처리를 통하여 친수성 피막을 얻는 것이 개시되어 있다.For example, according to Korean Patent Publication No. 10-2004-0097205, tetraethoxy silane is hydrolyzed to obtain silica sol through peptizing reaction, and then zirconium salt, aluminum salt, zinc salt and polyacrylic acid are added thereto. It is disclosed to prepare a coating liquid by addition, and to obtain a hydrophilic coating through a 300 ° C. heat treatment after the coating treatment.

대한민국 공개특허(공개번호 : 10-2005-0013560)에 의하면 광촉매 산화물에 실리카 졸을 첨가한 후 여기에 불소계 수지를 첨가하여 바인더로 사용하고, 조막 보조제를 첨가하여 코팅제를 제조하는 방법에 대해 개시되어 있다.Korean Patent Laid-Open Publication No. 10-2005-0013560 discloses a method of preparing a coating agent by adding a silica sol to a photocatalyst oxide, and then adding a fluorine resin to the photocatalyst oxide and adding a film-forming aid. have.

대한민국 공개특허(공개번호 : 10-2005-0039847)에 의하면 사염화티탄을 가수분해한 후 이온교환을 통하여 pH를 4로 조정하여 광촉매를 수득한 후 알루미늄 이소프로폭사이드를 아세트산과 메탄올, 아세틸아세톤 등을 첨가하여 해교반응을 통하여 바인더를 수득한 후 이를 혼합하여 코팅제를 제조하는 방법에 대하여 개시하고 있다.According to the Republic of Korea Patent Publication (Publication No .: 10-2005-0039847), after hydrolysis of titanium tetrachloride and adjusting the pH to 4 through ion exchange to obtain a photocatalyst, aluminum isopropoxide is converted into acetic acid, methanol, acetylacetone It discloses a method for producing a coating by adding a binder to obtain a binder through peptizing reaction and then mixing it.

기존 건축 외장의 오염방지를 위해서는 불소계 고분자 화합물을 처리하여 발수화하는 것이 바람직하게 생각되어 왔지만 실제 소수성 성분이 많은 분진이나 매연에서는 기재의 표면을 친수화하는 것이 더 바람직하다는 관점이 주를 이루고 있다.In order to prevent contamination of existing building exteriors, it has been considered desirable to treat water-repellent fluorine-based high molecular compounds, but in view of the fact that it is more preferable to hydrophilize the surface of the substrate in the case of dust or soot having a large number of hydrophobic components.

본 발명은 광촉매로 각광을 받고 있는 이산화티탄을 이용하여 무기 바인더와 복합화를 함으로서 광촉매성 친수 및 오염방지 코팅제를 제공한다. The present invention provides a photocatalytic hydrophilic and antifouling coating agent by complexing with an inorganic binder using titanium dioxide, which has been spotlighted as a photocatalyst.

나노크기의 이산화티탄 제조 공정에 있어, 황산법을 이용하여 균일한 입자 크기의 이산화티탄을 얻을 수 있다. 또한 무기 바인더는 기존 테트라 에톡시 실란의 가수분해 반응을 통해 제조하여 본 발명을 구성한다.In the nano-sized titanium dioxide production process, the sulfuric acid method can be used to obtain titanium dioxide having a uniform particle size. In addition, the inorganic binder is prepared through the hydrolysis reaction of the existing tetraethoxy silane to constitute the present invention.

본 발명은 광촉매 원료 물질로서 티타늄테트라이소프로폭사이드[Ti(O-iC3H7)4]를 이용하여 작용기인 -O-iC3H7를 황산기 -SO4 2 -로 치환하는 공정부터 시작된다. 티타늄 이소프로폭사이드와 황산을 1 : 2의 비율로 혼합한 후 여기에 증류수를 티타늄 이소프로폭사이드의 몰비로 1 : 50의 비율로 첨가한 후 상온에서 2시간 교반을 시키면 맑은 투명 액체가 된다. 이를 가열하여 가수분해 시키는데 일반적으로 황산기를 가진 황산티타늄의 경우 가열 온도에 따라 입자크기가 결정되며 65℃이상이면 가수분해 반응을 일으키게 된다. 본 발명에서는 이산화티탄의 수율과 광촉매로서 사용가능한 입자크기를 고려하여 70-95℃내에서 바람직하게는 75-85℃의 온도 범위내에서 교반을 통하여 이산화티탄 입자를 수득한다. 상기 명기한 온도 범위내에서 5-10시간 교반을 실시하면 백색의 미분말이 형성되는데 이렇게 수득한 이산화티탄 입자는 원심분리를 통하여 분리해 낸 다음 이를 세척하여 사용한다.The present invention starts with the process of substituting the functional group -O-iC 3 H 7 with sulfuric acid group -SO 4 2 - by using titanium tetraisopropoxide [Ti (O-iC 3 H 7 ) 4 ] as a photocatalyst raw material. do. Titanium isopropoxide and sulfuric acid are mixed at a ratio of 1: 2, and distilled water is added at a ratio of 1:50 in a molar ratio of titanium isopropoxide, followed by stirring at room temperature for 2 hours to give a clear transparent liquid. . In general, in the case of titanium sulfate having a sulfate group, the particle size is determined according to the heating temperature, and if it is 65 ° C. or more, a hydrolysis reaction is caused. In the present invention, titanium dioxide particles are obtained through stirring within the temperature range of 70-95 ° C., preferably 75-85 ° C., in consideration of the yield of titanium dioxide and the particle size usable as the photocatalyst. After stirring for 5-10 hours within the above-mentioned temperature range, white fine powder is formed. Titanium dioxide particles thus obtained are separated by centrifugation and washed.

바인더의 합성으로는 테트라에톡시실란[Si(O-C2H5)4]을 용제인 알코올과 혼합한 후 증류수를 첨가하고, 여기에 해교제를 첨가함으로서 구성할 수 있다. 테트라에톡시실란과 용제의 비율은 몰비로 1 : 100dl 바람직하며, 여기에 첨가하는 증류수의 양은 몰비로 1 : 4가 바람직하다. 또한 해교반응을 위하여 첨가하는 해교제로는 질산과 염산을 들 수 있는데, 염산을 이용하는 것이 반응속도를 빠르게 할 수 있어 바람직하다. 이때 첨가하는 염산의 양은 테트라에톡시실란 대비 몰비로 1 : 0.01이 바람직하다.In the synthesis of the binder, tetraethoxysilane [Si (OC 2 H 5 ) 4 ] is mixed with an alcohol which is a solvent, and then distilled water is added, and a peptizing agent can be added thereto. The ratio of tetraethoxysilane and the solvent is preferably 1: 100 dl in molar ratio, and the amount of distilled water added thereto is preferably 1: 4 in molar ratio. In addition, the peptizing agent added for the peptizing reaction includes nitric acid and hydrochloric acid, it is preferable to use the hydrochloric acid to speed up the reaction. At this time, the amount of hydrochloric acid added is preferably 1: 0.01 in molar ratio compared to tetraethoxysilane.

이하 제조 방법은 실시예를 통하여 상세히 설명한다. 단, 하기 실시예의 경 우 본 발명을 예시하는 것으로 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the manufacturing method will be described in detail with reference to Examples. However, in the case of the following examples to illustrate the present invention, the present invention is not limited by the examples.

< 실시예 ><Example>

우선 광촉매 입자를 수득하기 위하여 티타늄 이소프로폭사이드[Ti(O-iC3H7)4] 284g에 증류수 1800g을 첨가한 후 교반을 실시한다. 이때 흰색 분말이 생성되며 이 조성은 Ti(OH)4로 구성되어 있다. 여기에 황산 196g을 첨가하여 상온에서 4시간 교반을 실시하면 다시 맑은 투명한 액체로 변한다. 이렇게 제조된 수용액을 80℃로 가열을 하면서 8시간 교반을 실시하면 점점 뿌옇게 변하면서 TiO2입자가 생성된다. 이렇게 얻어진 수용액을 원심분리기를 이용하여 분말을 수득한 후 이를 증류수로 세척하여 황산기를 제거하고 110℃에서 건조하면 본 발명에 구성할 이산화티탄 입자를 얻을 수 있다. 이때 수득한 양은 50g이며, 수용액 중에 아직 이산화티탄 입자가 녹아 있으므로, 상기 가열공정을 반복 실시하여 총 79g의 이산화티탄 분말을 수득할 수 있다. 이때 수득한 이산화티탄의 결정은 아나타이즈 결정을 가지고 있으며, 입자크기는 1차 입경평균 30nm의 입자크기를 보이고 이다.First, 1800 g of distilled water is added to 284 g of titanium isopropoxide [Ti (O-iC 3 H 7 ) 4 ] to obtain photocatalyst particles, followed by stirring. At this time, a white powder is produced and this composition is composed of Ti (OH) 4 . 196 g of sulfuric acid was added thereto, followed by stirring at room temperature for 4 hours to change to a clear transparent liquid. When the aqueous solution thus prepared is stirred for 8 hours while heating to 80 ° C., TiO 2 particles are produced while gradually turning cloudy. The aqueous solution thus obtained was obtained by using a centrifugal separator, washed with distilled water to remove sulfuric acid, and dried at 110 ° C. to obtain titanium dioxide particles to be constituted in the present invention. In this case, the amount obtained is 50 g, and since titanium dioxide particles are still dissolved in the aqueous solution, a total of 79 g of titanium dioxide powder can be obtained by repeating the heating process. The crystal of titanium dioxide obtained at this time has an anatase crystal, and the particle size shows the particle size of the primary particle size average 30nm.

이렇게 수득한 이산화티탄 분말 중 10g을 취한 후 에탄올 400g에 넣고, 여기에 테트라에톡시실란을 18g을 첨가한 후 증류수 6g을 첨가한 후 교반을 실시한다. 여기에 염산 0.03g을 첨가한 후 상온에서 2시간 교반을 실시하여 코팅제를 제조한다. 제조된 코팅제는 TiO2 : SiO2 = 2 : 1인 친수 및 오염방지 코팅제를 얻을 수 있다.10 g of the titanium dioxide powder thus obtained is taken, and then put in 400 g of ethanol, 18 g of tetraethoxysilane is added thereto, 6 g of distilled water is added thereto, followed by stirring. After adding 0.03 g of hydrochloric acid thereto, the mixture was stirred at room temperature for 2 hours to prepare a coating agent. The prepared coating agent may obtain a hydrophilic and antifouling coating agent having TiO 2: SiO 2 = 2: 1.

본 발명을 통하여 얻어진 코팅제에 100 X 20mm의 슬라이드 글라스를 담근 후 50mm/minute의 속도로 인상하여 기재에 코팅시킨다. 코팅 후 상온에서 20분 건조 후 도막강도와 접촉각을 측정한 결과 도막강도는 연필경도 시험법으로 약 6Hv를 보이고, 물과의 접촉각은 10°로 우수한 친수 성능을 발휘하는 것으로 나타났다. 또한 코팅된 기재에 시판중인 스탬프 잉크를 묻힌 후 이를 UV Lamp(파장 : 365nm, 9W)와 10cm의 거리를 두고 빛을 조사한 결과 30분 후 잉크가 분해됨으로써 유기물 분해 기능을 확인할 수 있다. 코팅된 기재를 가시광선영역에서 투과도를 조사한 결과 98%의 양호한 투과도를 나타내어 투명기재용에 적합한 코팅제를 수득하였다.After immersing the slide glass of 100 X 20mm in the coating agent obtained through the present invention, the substrate is pulled up at a rate of 50mm / minute and coated on the substrate. After coating for 20 minutes after drying at room temperature, the coating film strength and contact angle were measured, and the coating film strength was about 6Hv by the pencil hardness test method, and the contact angle with water was 10 °. In addition, after coating the commercially available stamp ink on the coated substrate and irradiated with a UV Lamp (wavelength: 365nm, 9W) at a distance of 10cm, the ink is decomposed after 30 minutes to determine the organic decomposition function. As a result of examining the transmittance of the coated substrate in the visible region, a good transmittance of 98% was obtained to obtain a coating agent suitable for transparent substrates.

본 발명에 의하여, 친수성 및 오염분해 기능이 뛰어난 코팅 피막을 얻을 수 있었다. 본 피막은 특히 투명기재에 적용할 경우 빛의 투과도에 영향을 미치지 않고, 우천 시 오염물질을 쉽게 제거할 수 있을 뿐만 아니라 건조 속도가 빨라 작업성이 용이한 코팅제로 건물 미관보호에 바람직한 코팅제라 할 수 있다. According to the present invention, a coating film excellent in hydrophilicity and fouling decomposition function was obtained. This film is not only affecting the transmittance of light, especially when applied to transparent substrates, it is easy to remove contaminants in rainy weather, and it is a coating that is easy to work because of its fast drying speed. Can be.

Claims (3)

이산화티탄 입자 제조에 있어 티타늄 이소프로폭사이드를 물에 녹인 후 여기에 황산을 첨가하여 투명하게 제조하는 공정과 이를 가열하여 이산화티탄 입자를 생성하는 공정, 이를 분리하기 위해 원심분리 및 세척, 건조를 통하여 이산화티탄 입자를 수득하는 공정.In the production of titanium dioxide particles, a process of dissolving titanium isopropoxide in water and adding sulfuric acid to it to make it transparent and heating it to produce titanium dioxide particles, centrifugation, washing and drying to separate them Obtaining titanium dioxide particles through. 청구항 1에 있어      In claim 1 티타늄 이소프로폭사이드와 황산을 1 : 2의 비율로 혼합하여 투명한 수용액      Transparent aqueous solution by mixing titanium isopropoxide and sulfuric acid in a ratio of 1: 2 을 얻는 공정과 황산에 녹인 티타늄 이소프로폭사이드 수용액을 65-95℃, 바람직하The process for obtaining the aqueous solution of titanium isopropoxide dissolved in sulfuric acid at 65-95 ℃, preferably 게는 75-85℃로 가열하여 이산화티탄 입자를 수득하는 공정.Crab is heated to 75-85 ° C. to obtain titanium dioxide particles. 수득한 이산화티타늄 분말과 여기에 테트라에톡시 실란을 첨가하고, 가수분해 및 해교공정을 통하여 친수 및 오염방지 코팅제를 제조하는 공정     Process for preparing hydrophilic and antifouling coatings by adding titanium dioxide powder and tetraethoxy silane to it, hydrolysis and peptizing process
KR1020050059629A 2005-07-04 2005-07-04 Synthesis method of coating agent for antipollution and super hydrophilic KR20070004215A (en)

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