KR100308818B1 - Hydrophilic coating glass coated with porous thin layer of TiO2 - Google Patents
Hydrophilic coating glass coated with porous thin layer of TiO2 Download PDFInfo
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- KR100308818B1 KR100308818B1 KR1019990011376A KR19990011376A KR100308818B1 KR 100308818 B1 KR100308818 B1 KR 100308818B1 KR 1019990011376 A KR1019990011376 A KR 1019990011376A KR 19990011376 A KR19990011376 A KR 19990011376A KR 100308818 B1 KR100308818 B1 KR 100308818B1
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- 239000011521 glass Substances 0.000 title claims abstract description 51
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 36
- 230000004888 barrier function Effects 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 7
- -1 titanium alkoxide Chemical class 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 101150003085 Pdcl gene Proteins 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/75—Hydrophilic and oleophilic coatings
Abstract
본 발명은 유리 위에 산화티타늄(TiO2) 층 및 실리카(SiO2) 층이 복합코팅된 친수성 코팅 유리 및 그의 제조방법에 관한 것으로, 구체적으로 배리어 층 (barrier layer)인 SiO2층 및 금속 티타늄 알콕사이드에 Pd 금속, 기공 형성제 및 졸 안정제를 포함하는 TiO2층으로 구성되는 본 발명의 친수성 코팅 유리는 다공성 TiO2광촉매 친수성 코팅막을 가짐으로써 광촉매가 대기 중의 수분을 분해하는 효과를 이용하여 유리 표면의 친수성을 지속시켜 수분에 의해 유리가 흐려지는 현상을 효과적으로 방지할 수 있다.The present invention relates to a hydrophilic coated glass in which a titanium oxide (TiO 2 ) layer and a silica (SiO 2 ) layer are composite coated on a glass, and a method of manufacturing the same, and specifically, a SiO 2 layer and a metal titanium alkoxide as a barrier layer. The hydrophilic coated glass of the present invention, which comprises a TiO 2 layer comprising a Pd metal, a pore former, and a sol stabilizer, has a porous TiO 2 photocatalyst hydrophilic coating film, and thus the photocatalyst decomposes moisture in the atmosphere. The hydrophilicity can be maintained to effectively prevent the glass from being blurred by moisture.
Description
본 발명은 유리 위에 산화티타늄(TiO2) 층 및 실리카(SiO2) 층이 복합코팅된 친수성 코팅 유리 및 그의 제조방법에 관한 것으로, 보다 상세하게는 배리어 층 (barrier layer)인 SiO2층 및 금속 티타늄 알콕사이드에 Pd 금속, 기공 형성제 및 졸 안정제를 포함하는 TiO2층이 코팅된 유리를 열처리하여 제조되는 다공성 TiO2박막이 코팅된 친수성 코팅 유리에 관한 것이다.The present invention relates to a hydrophilic coated glass in which a titanium oxide (TiO 2 ) layer and a silica (SiO 2 ) layer are coated on a glass, and a method of manufacturing the same, and more particularly, an SiO 2 layer and a metal as a barrier layer. The present invention relates to a hydrophilic coated glass coated with a porous TiO 2 thin film prepared by heat treating a glass coated with a TiO 2 layer comprising a titanium alkoxide, a Pd metal, a pore former, and a sol stabilizer.
습기가 많거나 기온차가 심한 경우 차량용 유리에는 기온차에 의해 또는 강우 등의 이유로 인해 물방울 맺힘 현상이 발생되는데, 이는 운전자의 시야를 가리게 되고, 이를 해소하기 위해서 운전자가 운전 이외에 상기 물방울 맺힘 현상을 억제하기 위한 부분에 신경을 써야 하기 때문에 그로 인한 교통 안전이 문제시되고 있다. 따라서, 차량용 유리에 물방울이 맺히지 않도록 하기 위한 시도가 계속되고있는 바, 일본 특허출원공개 평 10-114,545호에는 광촉매성 TiO2에 산화 텅스텐 (WO3)을 첨가하여 표면을 극성화시켜 친수성 효과를 향상시키는 기술이 기재되어 있으며, 특허출원공개 평 10-140,046호에는 광촉매의 광여기시 표면 에너지의 수소결합성분이 증가하게 되어, Ti 원자에 결합된 OH-기의 수소원자와 물분자를 물리흡착시켜 표면을 친수화하는 방법을 기재하고 있다.When the humidity is high or the temperature difference is severe, water droplets are formed on the glass of the vehicle due to the temperature difference or because of rainfall, which obscures the driver's field of view. As a result, traffic safety is a problem. Therefore, attempts have been made to prevent water droplets from forming on vehicle glass, and Japanese Patent Application Laid-open No. Hei 10-114,545 adds tungsten oxide (WO 3 ) to photocatalytic TiO 2 to polarize the surface to provide a hydrophilic effect. improved are described technique of Patent Application Publication No. 10-140046 discloses an increase in the hydrogen bond component of the surface energy of the photocatalytic light when excited, the OH bonded to Ti atom-to-physical adsorption of hydrogen and water molecules in the group To hydrophilize a surface.
TiO2와 같은 반도성 금속의 산화물에 hν의 에너지를 갖는 광자가 조사되면 표면에서 전자의 전이가 발생된다. 이때 생성된 전자나 정공 (hole)이 재료표면으로 이동하여 반응을 일으키는데, TiO2에 흡수된 빛은 전자와 정공을 형성하며 이때 형성된 전자는 전도대 (conduction band)로 정공은 가전자대 (valence band)로 이동하게 된다. 그러나 실제로 반응물이 반도체 표면에서 분리된 전자나 정공과 반응을 시작하기 위해서는 반응물의 산화 또는 환원 전위가 중요하다. 즉 원활한 반응을 위하여는 TiO2의 가전자대 보다 반응물의 산화 전위는 높아야 하며 전도대보다 환원 전위는 낮아야 한다.When photons having an energy of hv are irradiated to oxides of semiconducting metals such as TiO 2 , electron transfer occurs on the surface. At this time, the generated electrons or holes move to the material surface to cause a reaction. Light absorbed by TiO 2 forms electrons and holes, and the formed electrons are conduction bands and holes are valence bands. Will be moved to. In practice, however, the oxidation or reduction potential of the reactants is important for the reactants to initiate reactions with electrons or holes separated from the semiconductor surface. That is, for smooth reaction, the oxidation potential of the reactants should be higher than that of the valence band of TiO 2 , and the reduction potential should be lower than that of the conduction band.
따라서 물을 분해시킬 수 있는 반도체 재료는 SrTiO3, TiO2및 CdS 등이다. 물을 분해하기 위하여는 광조사에 의하여 표면으로 이동한 전자와 정공이 물이나 분해물질에 달라붙는데, 여기서 정공은 산소에 달라붙어 결합을 끊어 산화반응을 일으키고 전자는 수소를 환원시켜 H2가 생성되어 달아나게 한다.Accordingly, semiconductor materials capable of decomposing water are SrTiO 3 , TiO 2 , CdS, and the like. In order to decompose water, electrons and holes moved to the surface by light irradiation adhere to water or decomposed substances, where holes adhere to oxygen to break bonds, causing oxidation, and electrons reduce hydrogen to generate H 2 . To run away.
하기의 반응식이 TiO2표면에서의 물 분해 반응이다.The following scheme is the water decomposition reaction on the TiO 2 surface.
TiO2상 : TiO2+ hν → TiO2+ h++ e- The TiO 2: TiO 2 + hν → TiO 2 + h + + e -
H2O + h+→ OH + H+ H 2 O + h + → OH + H +
2OH-→ H2O + O(a) 2OH - → H 2 O + O (a)
2O(a) → O2 2O (a) → O 2
Pt 상 : H++ e-→ H(a)A Pt: + H + e - → H (a)
2H(a) → H2(g)↑2H (a) → H 2 (g) ↑
상기 예에서 보듯이 물질을 분해하는 것은 주로 정공이 하게 되나 전자의 환원 반응이 일어나지 않을 경우, TiO2내에서 전하의 불균일이 일어나 전자와 정공이 더 이상 생성되지 않고 분해가 일어나지 않는다. 따라서 TiO2입자내의 전기적 중성을 유지하고 반응을 계속하기 위하여는 물질의 표면에서 전자를 포집하여 주는 기구가 필요하며 상기 반응식의 Pt가 그러한 작용을 한다.As shown in the above example, the decomposition of the material is mainly caused by holes, but when the reduction reaction of electrons does not occur, charge unevenness occurs in TiO 2 so that electrons and holes are no longer generated and decomposition does not occur. Therefore, in order to maintain the electrical neutrality in the TiO 2 particles and to continue the reaction, a mechanism for trapping electrons on the surface of the material is required, and Pt of the above scheme performs such a function.
Pt는 TiO2표면에서 전자가 빨리 표면으로 이동하여 산화되는 것을 도와주고 H+이온을 산화시켜 결국 분해 반응을 유지시키는 역할을 한다.Pt helps the electrons move quickly from the TiO 2 surface to the surface and oxidize, and oxidizes H + ions to maintain the decomposition reaction.
친수성의 발현은 이와 같은 광촉매의 물분해의 과정에서 발생하는 OH 라디칼이 표면에 존재함으로써 생기게 되는 것이다. 이 과정에서 초기에 화학적으로 즉, 광촉매 기능에 의하여 발생된 OH가 분자 단위로 표면에 존재하게 되고 결국 이들이 TiO2표면에 물리적으로 흡착하게 되어서 친수성이 계속 유지되는 것이다.Hydrophilic expression is caused by the presence of OH radicals generated on the surface of the photocatalytic hydrolysis process. In this process, OH generated by the photocatalytic function initially exists on the surface of molecules in a molecular unit, and eventually they are physically adsorbed on the TiO 2 surface to maintain hydrophilicity.
본 발명자들은 유리 위에 광촉매 기능을 이용한 친수성 코팅을 함으로써 광촉매가 대기중 수분을 분해하는 효과를 이용하여 친수성이 유지되는 친수성 코팅 유리를 개발하여 본 발명을 완성하였다.The present inventors have completed the present invention by developing a hydrophilic coating glass in which hydrophilicity is maintained by using a hydrophilic coating using a photocatalytic function on the glass to decompose moisture in the air.
본 발명의 목적은 유리 위에 광촉매 기능을 이용한 친수성 코팅을 함으로써 광촉매가 대기 중의 수분을 분해하는 효과를 이용하여 유리 표면의 친수성을 지속시켜 수분에 의해 유리가 흐려지는 현상을 효과적으로 방지할 수 있는 친수성 코팅 유리 및 그의 제조방법을 제공하는 것이다.An object of the present invention is to apply a hydrophilic coating using a photocatalytic function on the glass by using a photocatalyst to decompose moisture in the air to maintain the hydrophilicity of the glass surface to effectively prevent the phenomenon that the glass is clouded by moisture And a method for producing the same.
상기 목적을 달성하기 위하여 본 발명에서는 배리어 층 (barrier layer)인 SiO2층; 및 금속 티타늄 알콕사이드에 Pd 금속, 기공 형성제 및 졸 안정제를 포함하는 TiO2층으로 구성되는 친수성 코팅 유리 및 그의 제조방법을 제공한다.In order to achieve the above object, in the present invention, an SiO 2 layer that is a barrier layer; And a TiO 2 layer comprising a Pd metal, a pore former, and a sol stabilizer in the metal titanium alkoxide.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서는 우선, 유리 위에 산화티타늄(TiO2) 층 및 실리카(SiO2) 층이 복합코팅된 친수성 코팅 유리를 제공한다.In the present invention, first, a titanium oxide (TiO 2 ) layer and a silica (SiO 2 ) layer on the glass is provided with a hydrophilic coating glass.
상기에서, TiO2층은 TiO2층의 활성을 증가시키기 위하여 팔라듐 (Pd) 및 TiO2층을 다공질화하기 위한 기공 형성제를 포함한다.In the above, the TiO 2 layer comprises a porogen for porous palladium (Pd) and a TiO 2 layer in order to increase the activity of the TiO 2 layer.
또한 본 발명에서는 상기 친수성 코팅 유리의 제조방법을 제공한다. 본 발명의 제조방법은 :In another aspect, the present invention provides a method for producing the hydrophilic coating glass. The preparation method of the present invention is:
실리카 (SiO2) 졸을 유리에 코팅하여 약 80∼100 ℃ 사이에서 10∼20분 동안 건조시킴으로써 배리어 코팅 (barrier coating)하는 단계 (제 1단계);Coating a silica (SiO 2 ) sol on the glass and drying it between about 80 to 100 ° C. for 10 to 20 minutes (barrier coating) (first step);
제 1단계에서 배리어 코팅된 유리에 TiO2및 Pd 가 혼합된 졸을 1차 코팅한 후 100∼120 ℃의 온도에서 5∼15 분간 건조한 다음, 이러한 코팅을 2 내지 3회 반복하여 배리어 층 (barrier layer) 위에 TiO2층을 코팅하는 단계 (제 2단계); 및In the first step, the sol mixed with TiO 2 and Pd was first coated on the barrier coated glass, and then dried at a temperature of 100 to 120 ° C. for 5 to 15 minutes, and then the coating was repeated 2 to 3 times to obtain a barrier layer. coating a TiO 2 layer over a layer) (second step); And
제 2단계에서 코팅된 유리를 500∼620 ℃에서 30분∼1시간 동안 열처리하는 단계(제 3단계)로 이루어진다.The glass coated in the second step is subjected to a heat treatment at 500 to 620 ° C. for 30 minutes to 1 hour (third step).
광촉매를 Na+및 Ca+등의 양이온이 존재하는 유리 상에 직접 코팅할 경우, 이 양이온들이 표면에 광자에 의하여 발생한 정공과 먼저 반응하여 촉매의 활성을 심각하게 저하시키기 때문에 이를 방지하기 위하여 유리면 상에 우선 배리어 코팅을 한 후 TiO2코팅을 하는데, 이러한 배리어 코팅을 하는 단계가 상기 제 1단계이다.When the photocatalyst is directly coated on a glass in which cations such as Na + and Ca + exist, these cations react first with holes generated by photons on the surface to seriously degrade the activity of the catalyst. First, a barrier coating is performed, followed by a TiO 2 coating. The barrier coating is the first step.
배리어 코팅층을 이루는 SiO2졸은 실란 [Si(OR)x; R 은 C1-C4의 저급 알킬기, x는 정수]을 물과 산 촉매를 이용하여 가수분해하여 생성된 졸이며, 테트라에톡시실란 [Si(OC2H5)4]을 사용하는 것이 바람직하다. 이 때 합성되는 SiO2졸은 박막으로 코팅할 때 치밀한 막을 얻기 위하여 투입되는 물의 양을 억제하고 산 촉매의 양은 실란 투입량의 3 내지 4배 몰로 하는 것이 바람직하다. 이와 같이 합성된 SiO2졸을 디핑 (dipping) 장치에서 코팅하여 약 80∼100 ℃ 사이에서 10∼20분 동안 건조시켜서 가수분해된 실란 졸에서 축중합 반응을 일으켜 비정질의 Si-(OH) 결합을 형성시킨다.SiO 2 sol constituting the barrier coating layer is a silane [Si (OR) x ; R is a lower alkyl group of C 1 -C 4 , x is an integer, and is a sol formed by hydrolysis using water and an acid catalyst, and tetraethoxysilane [Si (OC 2 H 5 ) 4 ] is preferably used. . The SiO 2 sol synthesized at this time is preferably suppressed the amount of water added in order to obtain a dense film when coating with a thin film and the amount of the acid catalyst is 3 to 4 times mole of the silane input amount. The SiO 2 sol thus synthesized was coated in a dipping apparatus and dried at about 80 to 100 ° C. for 10 to 20 minutes to cause a polycondensation reaction in the hydrolyzed silane sol to form an amorphous Si- (OH) bond. To form.
상기에서, 제 2단계의 TiO2및 Pd 가 혼합된 졸은, 금속 티타늄의 알콕사이드에 소량의 물; 디에탄올아민 또는 아세틸 아세톤 중에서 선택되는 졸 안정제; 및 기공 형성제를 포함하는 티타늄의 졸에 Pd 화합물 용액을 티타늄 알콕사이드 양의 0.003 내지 0.007 몰배로 투입하여 혼합한 졸이다.In the above, the sol in which TiO 2 and Pd are mixed in the second step includes a small amount of water in the alkoxide of metal titanium; Sol stabilizers selected from diethanolamine or acetyl acetone; And a sol mixed with a Pd compound solution in an amount of 0.003 to 0.007 molar times the amount of titanium alkoxide to a titanium sol containing a pore-forming agent.
상기에서, 기공 형성제는 TiO2층을 다공질화시키기 위하여 200 ℃ 이상의온도로 가열할 경우 열분해되어 기공을 남길 수 있는 유기고분자 물질로서 폴리에틸렌글리콜, 하이드록시프로필 셀룰로스 및 폴리아크릴산 등을 예로 들 수 있으며, 이 중에서 폴리에틸렌글리콜이 가장 바람직하다.In the above, the pore-forming agent is an organic polymer material that can be thermally decomposed to leave pores when heated to a temperature of 200 ℃ or more in order to porousize the TiO 2 layer, and examples thereof include polyethylene glycol, hydroxypropyl cellulose and polyacrylic acid. Of these, polyethylene glycol is most preferred.
또한 상기에서, Pd 화합물은 수용성이나 유기용매에 녹는 Pd 화합물이면 무엇이나 가능하나 H2PdCl4또는 H2Pd(NH3)4Cl2등을 사용할 수 있으며 H2PdCl4가 특히 바람직하다.In addition, the Pd compound may be any water-soluble or Pd compound that is soluble in an organic solvent, but H 2 PdCl 4 or H 2 Pd (NH 3 ) 4 Cl 2 may be used, and H 2 PdCl 4 is particularly preferable.
이와 같이 얻어진 티타늄의 졸을 유리면에 코팅한 후 상기 제 3단계와 같이 열처리하면 기공형성제가 열분해되면서 티타늄 산화물의 표면에 기공을 형성시킨다.The sol of titanium thus obtained is coated on the glass surface and then heat treated as in the third step to form pores on the surface of the titanium oxide while the pore forming agent is pyrolyzed.
상기 제 3단계의 열처리는 대기중에서 수행되며, 온도는 630 ℃를 초과하지 않는 것이 바람직하다. 만약 규제 온도 이상으로 가열하는 경우에는 가열 시간을 조절하여 최적의 결정화를 얻으면서 유리의 연화점 이상 가열로 인한 변환을 방지하여야 한다.The third step of heat treatment is carried out in the air, the temperature is preferably not exceeding 630 ℃. If heating above the regulated temperature, the heating time should be adjusted to achieve optimum crystallization and to avoid conversion due to heating above the softening point of the glass.
본 발명은 전술한 바와 같이 산화티탄을 유리 표면에 투명하게 코팅된 친수성 코팅 및 이의 제조방법에 관한 것으로, 친수성 및 광촉매성의 향상을 위하여 표면을 미세한 다공질로 만들어 반응성을 높일 뿐만 아니라 물리적으로 흡착되는 OH 들이 좀 더 쉽게 TiO2표면에 흡수되고 유지 되도록 하는 방법을 제공하고 있다. 또한 촉매활성 유지를 위한 전자 포획을 위하여 Pd 를 도핑 (dopping)하고 있으며배리어 코팅을 위하여 실란 축중합체를 코팅하여 저온 열처리한 후 티타늄 금속 알콕시드의 가수분해 졸을 코팅하여 최종 소성시키는 방식을 제공하고 있다.The present invention relates to a hydrophilic coating coated with titanium oxide on a glass surface as described above, and a method for manufacturing the same, in order to improve hydrophilicity and photocatalyst, the surface is made of fine porous to increase reactivity as well as physically adsorbed OH. It provides a way for them to be more easily absorbed and retained on TiO 2 surfaces. In addition, Pd is doped to capture electrons to maintain catalytic activity, and a silane condensation polymer is coated for barrier coating, followed by low temperature heat treatment, followed by coating of hydrolytic sol of titanium metal alkoxide to provide final baking. have.
이렇게 제조된 본 발명의 유리를 일광하에서 약 5∼8 시간 방치한 후 물과의 접촉각을 측정하면 약 5°이하이며, 이 시편을 바로 일광이 조사되지 않는 암소 (暗所)에 3일간 유지시킨 후 꺼내어 물과의 접촉각을 측정하면 여전히 5°이하를 유지하고 있다. 또한 다시 이 시편을 옥외에 방치하여 6시간 동안 일광을 조사시킨 후 우천시 접촉각 및 방운 특성을 조사한 결과 약 4일간의 우천시에도 친수성을 유지하는 우수한 특성을 나타냄을 확인하였다.The glass of the present invention thus prepared is left for about 5 to 8 hours in daylight and then measured at a contact angle with water of about 5 ° or less, and the specimen is kept in a cow without direct sunlight for 3 days. After taking it out and measuring the contact angle with water, it is still kept below 5 °. In addition, the specimen was left outdoors and irradiated with sunlight for 6 hours, followed by contact angles and weatherproof characteristics during rainy weather, which showed excellent properties of maintaining hydrophilicity even in rainy weather for about 4 days.
이하 실시예에 의하여 본 발명을 보다 상세히 설명한다. 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명이 실시예에 의하여 한정되는 것을 아니다.The present invention will be described in more detail with reference to the following examples. The following examples are merely illustrative of the present invention and are not intended to limit the present invention.
실시예Example 친수성 코팅 유리의 제조Preparation of Hydrophilic Coated Glass
(단계 1)(Step 1)
테트라에톡시실란 [Si(OC2H5)4]을 에탄올 1500 ml에 용해시킨 후 촉매로 질산 (60%)을 첨가하여 약 1시간 동안 혼합하면서 가수분해 졸을 제조하였다. 유리 기판 (300×200mm)에 상기의 졸을 디핑 (Dipping) 방식에 의하여 코팅한 후 110 ℃로 가열된 건조로 내에서 약 15분간 건조시켰다.Tetraethoxysilane [Si (OC 2 H 5 ) 4 ] was dissolved in 1500 ml of ethanol and nitric acid (60%) was added as a catalyst to prepare a hydrolysis sol while mixing for about 1 hour. The sol was coated on a glass substrate (300 × 200 mm) by a dipping method, and then dried in a drying furnace heated to 110 ° C. for about 15 minutes.
(단계 2)(Step 2)
에탄올 1500 ml에 테트라 부톡시 티타네이트 (Tetrabutocxytitanate) 240 ml 와 디에탄올아민 134 ml를 투입하여 혼합(용해)한 후, 여기에 폴리에틸렌글리콜 (polyethyleneglycol; PEG) 80 g을 투입하여 용해시켰다. PEG가 용해된 시점에서 증류수 12 ml를 투입하고 다시 약 1시간 동안 혼합 용해 시켜서 가수분해 반응을 유도한 후 H2PdCl4를 1 내지 10 ml 첨가하였다.240 ml of tetrabutoxy titanate (Tetrabutocxytitanate) and 134 ml of diethanolamine were mixed and dissolved in 1500 ml of ethanol, and 80 g of polyethyleneglycol (PEG) was added thereto to dissolve it. When PEG was dissolved, 12 ml of distilled water was added and mixed and dissolved for about 1 hour to induce a hydrolysis reaction, and then 1 to 10 ml of H 2 PdCl 4 was added.
(단계 3)(Step 3)
상기 (단계 1)에 의해 제조된 졸을 유리 기판에 코팅하여 이를 100 ℃에서 건조하고, 여기에 상기 (단계 2)에 의해 제조된 졸을 수회 코팅한 후 610 ℃로 가열된 소성로에서 약 1시간 동안 가열하여 본 발명의 친수성 코팅 유리를 제조하였다.The sol prepared by (step 1) was coated on a glass substrate and dried at 100 ° C., and the sol prepared by (step 2) was coated there several times, and then about 1 hour in a calcination furnace heated to 610 ° C. Heating to prepare the hydrophilic coating glass of the present invention.
비교예 1Comparative Example 1
실시예 1의 (단계 1)의 방법으로 배리어 층 (barrier layer)용의 졸을 제조하고 (단계 2)의 TiO2용 졸을 제조함에 있어서, Pd 용액 및 기공형성제인 PEG 를 투입하지 않은 졸을 제조하여 (단계 3)과 같은 조건으로 코팅 및 열처리를 실시하여 코팅 유리를 제조하였다.In preparing the sol for the barrier layer by the method of (step 1) of Example 1 and preparing the sol for the TiO 2 in (step 2), the sol without adding PEG as a Pd solution and a pore-forming agent was prepared. To prepare a coating glass by coating and heat treatment under the same conditions as in (Step 3).
비교예 2Comparative Example 2
상기 비교예 1과 같이 배리어 층 용의 졸을 제조하고 TiO2용 졸을 제조함에 있어서, 기공형성제인 PEG 는 투입하고 Pd 용액은 투입하지 않은 졸을 제조하여 실시예의 (단계 3)과 같은 조건으로 코팅 및 열처리를 실시하여 코팅 유리를 제조하였다.In preparing the sol for the barrier layer and preparing the sol for TiO 2 as in Comparative Example 1, a sol was prepared by adding PEG as a pore-forming agent and not adding the Pd solution under the same conditions as in (Step 3) of Example. Coating and heat treatment were performed to prepare coated glass.
실험예Experimental Example
상기의 실시예와 비교예 1 및 비교예 2를 통하여 제조된 3종의 유리 시편을 일광하에서 약 3시간 동안 조사시킨 후에 증류수에 묻혀서 접촉각을 측정한 결과 3종 모두 접촉각이 5°이하이며 방운 현상을 나타내었다.After irradiating three kinds of glass specimens prepared through the above Examples and Comparative Examples 1 and 2 for about 3 hours in daylight, the contact angles were measured by dipping in distilled water. Indicated.
이후 이 3종의 유리를 빛이 조사되지 않는 암소 (暗所)에 약 3일간 보관후 꺼내어 즉시 물방울과의 접촉각을 측정한 결과 실시예에 의한 시편은 5°를 유지 하였으나, 비교예 1에 의하여 제작된 시편은 약 40°, 비교예 2에 의한 시편은 약 30°의 접촉각을 나타내어 친수특성이 없음을 알 수 있었다.Then, the three kinds of glass were stored in a cow where no light was irradiated for about 3 days, then taken out and immediately measured the contact angle with water droplets. As a result, the specimen according to the Example was kept at 5 °, but according to Comparative Example 1 The prepared specimen had a contact angle of about 40 ° and the specimen of Comparative Example 2 had a contact angle of about 30 °, indicating no hydrophilicity.
상기의 테스트 후 3종의 시편을 옥외에 방치 시켜 일광을 충분히 조사시킨 후 우천시의 친수성 유지 기간을 조사한 결과 실시예에 의한 시편은 약 4일간의 우천에도 계속적인 친수 및 방운 특성을 유지하였으나, 비교예 1의 시편은 약 18시간, 비교예 2의 시편은 약 36시간이 경과한 후부터 친수특성 및 방운 특성을 상실 하였다.After the above test, the three specimens were left in the open air and sufficiently irradiated with sunlight, and the hydrophilic retention period during rainy weather was observed. As a result, the specimens according to the examples maintained hydrophilic and weatherproof properties even in rainy weather for about 4 days. The sample of Example 1 lost about 18 hours, and the sample of Comparative Example 2 lost its hydrophilicity and weather resistance after about 36 hours.
즉, 기공형성제를 사용하여 TiO2층을 다공질화시키고, 팔라듐을 사용하여TiO2층을 활성화시킨 본 발명의 친수성 코팅 유리는, 이들을 사용하지 않은 비교예의 친수성 코팅 유리에 비하여 친수 특성 및 방운 특성이 장시간 동안 유지됨을 확인하였다.In other words, the hydrophilic coating glass of the present invention, which is made of a pore-forming agent to porous the TiO 2 layer and palladium is used to activate the TiO 2 layer, has a hydrophilic property and an ice-proof property as compared to the hydrophilic coating glass of the comparative example which does not use them. It was confirmed that this was maintained for a long time.
이상에서 살펴본 바와 같이, 본 발명에서는 광촉매성 산화티타늄을 이용한 친수성 코팅 유리를 제조함에 있어서 기공형성제를 첨가하여 표면을 다공질하게 만들어 반응성을 높이고, 팔라듐을 첨가하여 산화티타늄 층의 활성을 증가시켜 장시간 동안 친수성을 유지하여 수분에 의해 유리가 흐려지는 현상을 효과적으로 방지할 수 있다.As described above, in the present invention, in preparing a hydrophilic coated glass using photocatalytic titanium oxide, a pore forming agent is added to make the surface porous, thereby increasing the reactivity, and adding palladium to increase the activity of the titanium oxide layer for a long time. It is possible to effectively prevent the phenomenon that the glass is clouded by moisture by maintaining hydrophilicity during.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08119673A (en) * | 1994-10-21 | 1996-05-14 | Kansai Paint Co Ltd | Hydrophilization treatment of glass |
| JPH09229724A (en) * | 1995-12-22 | 1997-09-05 | Toto Ltd | Non-fogging cover for instrument panel of motorcycle, motorcycle equipped with the cover, and fogging-preventing method for the cover |
| JPH1067543A (en) * | 1996-06-18 | 1998-03-10 | Toto Ltd | Photocatalytic hydrophilic parts material |
| JPH10152350A (en) * | 1996-11-21 | 1998-06-09 | Sekisui Chem Co Ltd | Anti-fogging pair glass |
| KR100225342B1 (en) * | 1997-09-04 | 1999-10-15 | 명호근 | Method for preparing titanium oxide photocatalyst |
-
1999
- 1999-04-01 KR KR1019990011376A patent/KR100308818B1/en not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08119673A (en) * | 1994-10-21 | 1996-05-14 | Kansai Paint Co Ltd | Hydrophilization treatment of glass |
| JPH09229724A (en) * | 1995-12-22 | 1997-09-05 | Toto Ltd | Non-fogging cover for instrument panel of motorcycle, motorcycle equipped with the cover, and fogging-preventing method for the cover |
| JPH1067543A (en) * | 1996-06-18 | 1998-03-10 | Toto Ltd | Photocatalytic hydrophilic parts material |
| JPH10152350A (en) * | 1996-11-21 | 1998-06-09 | Sekisui Chem Co Ltd | Anti-fogging pair glass |
| KR100225342B1 (en) * | 1997-09-04 | 1999-10-15 | 명호근 | Method for preparing titanium oxide photocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20000065270A (en) | 2000-11-06 |
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