KR19990028236A - Photocatalyst Support Structure and Photocatalyst Coating Agent - Google Patents
Photocatalyst Support Structure and Photocatalyst Coating Agent Download PDFInfo
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- KR19990028236A KR19990028236A KR1019970709547A KR19970709547A KR19990028236A KR 19990028236 A KR19990028236 A KR 19990028236A KR 1019970709547 A KR1019970709547 A KR 1019970709547A KR 19970709547 A KR19970709547 A KR 19970709547A KR 19990028236 A KR19990028236 A KR 19990028236A
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- KR
- South Korea
- Prior art keywords
- photocatalyst
- adhesive layer
- layer
- weight
- resin
- Prior art date
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- CRNJBCMSTRNIOX-UHFFFAOYSA-N methanolate silicon(4+) Chemical compound [Si+4].[O-]C.[O-]C.[O-]C.[O-]C CRNJBCMSTRNIOX-UHFFFAOYSA-N 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- LIZIAPBBPRPPLV-UHFFFAOYSA-N niobium silicon Chemical compound [Si].[Nb] LIZIAPBBPRPPLV-UHFFFAOYSA-N 0.000 description 1
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
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- 229920013716 polyethylene resin Polymers 0.000 description 1
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- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- RQAGEUFKLGHJPA-UHFFFAOYSA-N prop-2-enoylsilicon Chemical compound [Si]C(=O)C=C RQAGEUFKLGHJPA-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- OEBIHOVSAMBXIB-SJKOYZFVSA-N selitrectinib Chemical compound C[C@@H]1CCC2=NC=C(F)C=C2[C@H]2CCCN2C2=NC3=C(C=NN3C=C2)C(=O)N1 OEBIHOVSAMBXIB-SJKOYZFVSA-N 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- VSSLEOGOUUKTNN-UHFFFAOYSA-N tantalum titanium Chemical compound [Ti].[Ta] VSSLEOGOUUKTNN-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B01J35/39—
-
- B01J35/30—
-
- B01J35/33—
-
- B01J35/392—
-
- 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
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
Abstract
광촉매 담지 구조체는 광촉매층, 담체, 및 광촉매층과 담체 사이에 존재하는 접착층을 포함하고, 접착층은 실리콘변성 수지, 폴리실록산함유 수지 또는 콜로이달 실리카함유 수지로 제조되고, 광촉매층은 금속산화물 또는 수산화물 겔과 광촉매로 이루어지는 복합체로 제조되며; 상기 구조체를 형성하기 위한 광촉매 코팅재료는 실리콘 화합물, 하나이상의 금속산화물 또는 금속 수산화물 졸, 및 하나이상의 광촉매 분말 또는 졸로 이루어진다.The photocatalyst support structure includes a photocatalyst layer, a carrier, and an adhesive layer present between the photocatalyst layer and the carrier, wherein the adhesive layer is made of a silicone-modified resin, a polysiloxane-containing resin, or a colloidal silica-containing resin, and the photocatalyst layer is a metal oxide or hydroxide gel. It is made of a complex consisting of and a photocatalyst; The photocatalyst coating material for forming the structure consists of a silicon compound, at least one metal oxide or metal hydroxide sol, and at least one photocatalyst powder or sol.
Description
자외선의 에너지에 의하여 물의 분해, 탈취, 살균, 물의 정화, 배수처리 등 각종 화학반응을 진행시키는 광촉매로서, n 형 반도체의 티탄이 알려져 있다. 광촉매를 분말상 혹은 용액으로 현탁시킨 형태로 사용하는 것이 일반적으로 촉매활성이 높다고 일컬어지고 있으나, 실용적으로는 얼마간의 담체상에 담지한 형태로 사용할 수밖에 없는 경우가 많다. 빛인 자외선의 에너지를 유효하게 이용하기 위해서는 담체의 형상은 빛의 조사면적을 넓게 취할 수 있는 종이상이나 시트상으로 하는 편이 유리하며, 또한 광촉매에 의하여 화합반응을 일으키고자 하는 반응물과의 접촉면적을 크게 하기 위해서는 그 표면이 다공질 구조인 편이 바람직하다.Titanium of an n-type semiconductor is known as a photocatalyst which advances various chemical reactions such as water decomposition, deodorization, sterilization, water purification, and drainage treatment by energy of ultraviolet rays. The use of the photocatalyst in powder form or in a form suspended in solution is generally said to be high in catalytic activity, but in practice, it is often used in a form supported on a carrier for some time. In order to effectively use the energy of ultraviolet light which is light, the shape of the carrier is advantageously in the form of paper or sheet which can take a large irradiation area of light, and also the contact area with the reactants to cause the compound reaction by photocatalyst is large. In order to achieve this, the surface is preferably a porous structure.
광촉매를 담지하는 담체 재질은 여러 가지가 제안되어 있으며, 예를 들면 (A) 니트로셀룰로오스, 유리, 폴리염화비닐, 플라스틱, 나일론, 메타크릴 수지, 폴리프로필렌 등 광투과성 물질 (일본 공개특허공보 소62-66861 호), (B) 폴리프로필렌 섬유, 세라믹 (일본 공개특허공보 평2-68190 호), (C) 유리, 세라믹, 나일론, 아크릴, 폴리에스테르 (일본 공개특허공보 평5-309267) 등이 있다.Various carrier materials for supporting the photocatalyst have been proposed, for example, (A) light-transmitting materials such as nitrocellulose, glass, polyvinyl chloride, plastic, nylon, methacryl resin, and polypropylene (JP-A-62) -66861), (B) polypropylene fiber, ceramics (Japanese Patent Laid-Open Publication No. Hei 2-68190), (C) glass, ceramic, nylon, acrylic, polyester (Japanese Patent Laid-Open Publication No. H5-309267), and the like. have.
그러나, 이러한 재질 중에서 유기물을 주체로 하는 것은 광촉매를 담지하면 그 촉매작용에 의하여 유기물이 분해되거나 열화된다는 사실이 보고되어 있으며, 내구성에 문제가 있었다 (다니야마분쇼, 고분자 가공 42 권, 5 호, P18 (1993), 기요노 마나부 저,“산화티탄”기보당, P165).However, it has been reported that organic materials, mainly of these materials, are decomposed or degraded by the catalytic action when supporting a photocatalyst, and there is a problem in durability (Taniyama Bunsho, Polymer Processing 42, No. 5, P18 (1993), by Kiyono Manabu, “Titanium Oxide” Gibbedang, P165).
또한, 담체 재료가 유리나 세라믹 등의 무기물인 경우라도, 광촉매를 담지하기 위하여 유기 고분자 수지를 접착제에 이용하면 광촉매 입자 표면이 수지로 피복되기 때문에 촉매활성이 저하될 뿐만 아니라, 이 수지가 광촉매 작용에 의하여 분해열화를 일으켜 광촉매가 박리되는 등, 내구성에도 문제가 발생하였다.In addition, even when the carrier material is an inorganic material such as glass or ceramic, when the organic polymer resin is used for the adhesive to support the photocatalyst, the surface of the photocatalyst particles is covered with the resin, so that the catalytic activity is lowered, and the resin is used for the photocatalytic action. As a result, decomposition deterioration caused the photocatalyst to be peeled off, which caused problems in durability.
따라서 담체재료가 내열성의 무기물인 경우에는, 유기물이 전혀 존재하지 않는 스패터링법 (일본 공개특허공보 소60-44053 호), 유기티타네이트의 도포-소성법 (일본 공개특허공보 소60-118236 호) 이나 티타니아졸의 분사-소성법 (일본 공개특허공보 평5-253544) 등의 방법이 채택되고 있다.Therefore, in the case where the carrier material is a heat resistant inorganic substance, the sputtering method in which no organic substance is present (Japanese Laid-Open Patent Publication No. 60-44053), the application-firing method of organic titanate (Japanese Laid-Open Patent Publication No. 60-118236) ) And a spray-firing method of titania sol (Japanese Patent Application Laid-open No. Hei 5-253544).
그러나, 이러한 방법은 담체상에서의 광촉매 입자의 생성, 결정화 및 담체와의 접착성을 부여하기 위하여, 고온도에서의 소성이 필요하며, 큰 면적의 담지가 어려울 뿐만 아니라 제조비용이 매우 높다는 문제가 있었다.However, this method requires the baking at a high temperature in order to produce the photocatalyst particles on the carrier, to crystallize, and to provide adhesion to the carrier, and it is difficult to support a large area, and also has a very high manufacturing cost. .
한편, 광촉매를 유리섬유 종이에 담지하기 위하여 접착제로서 금속산화물 졸을 사용하는 방법 (일본 공개특허공보 평5-309267 호) 이 제안되어 있다.On the other hand, in order to support a photocatalyst on glass fiber paper, the method of using a metal oxide sol as an adhesive agent (Unexamined-Japanese-Patent No. 5-309267) is proposed.
그러나, 실리카 졸 등의 금속산화물 졸의 접착력은 팬·데어·월스력에 의한 것이기 때문에 매우 약하고 (파인 세라믹스 제 1 권 p216 ∼ 223 1980), 접착성, 내구성이 불충분하며 또한 고온도에서의 베이킹 처리가 필요하거나 하여, 열분해를 일으키기 쉬운 범용수지를 함유하는 모든 담체에 적용할 수 있는 것은 아니었다.However, since the adhesion force of metal oxide sol such as silica sol is due to the fan-deser-wals force, it is very weak (Fine Ceramics Vol. 1, p216 to 223 1980), the adhesiveness and durability are insufficient, and the baking treatment at a high temperature is performed. It was not possible to apply it to all the carriers containing the general purpose resins, which were likely to cause thermal decomposition.
또한, 광촉매 분말을 실리카나 점토광물 등의 금속산화물 겔에 담지한 예에 있어서는, 담체의 흡착제로서의 효과에 의하여 프로피온알데히드 가스의 광촉매 분해반응이 촉진되도독 한 보고가 있다 (심포지엄“광촉매 반응의 최근 전개”예고집, 1994, 광기능 재료 연구회, 2-11, p.39).In addition, in the case where the photocatalyst powder is supported on a metal oxide gel such as silica or clay mineral, there have been reports that the photocatalytic decomposition reaction of propionaldehyde gas is promoted by the effect of the adsorbent of the carrier (symposium “the recent photocatalyst reaction”. Advancement ”, 1994, Photonics Materials Research Society, 2-11, p. 39).
그러나, 이러한 금속산화물 겔 중에 균일하게 분산시킨 광촉매를 높은 촉매활성을 유지한 채로 접착성 및 내구성이 뛰어난 담지체를 얻었다는 보고는 전혀 없었다.However, there have been no reports of obtaining a carrier having excellent adhesion and durability while maintaining a high catalytic activity of a photocatalyst uniformly dispersed in such a metal oxide gel.
그리고, 광촉매를 불소수지로 고정화하는 방법도 제안되어 있다 (일본 공개특허공보 평6-315641). 그러나, 불소수지는 고가일 뿐만 아니라 광촉매 입자를 강고하게 접착하기 위해서는 촉매입자 표면의 대부분을 불소수지로 피복해야만 하며, 그 결과 촉매활성은 분말시에 비하여 저하된다는 문제가 있었다. 광촉매를 불소수지나 폴리오르가노실록산 등의 난분해성 결착제와 혼합하여 기초체에 담지하도록 시험한 예 (EP-0633064) 가 있는데, 접착성이나 장기 내구성 등의 실용상 과제의 해결에는 불충분한 것이다.In addition, a method of immobilizing a photocatalyst with a fluorine resin is also proposed (Japanese Patent Laid-Open No. Hei 6-315641). However, in order to adhere the photocatalyst particles firmly, the fluorine resin is expensive, and most of the surface of the catalyst particles must be coated with the fluorine resin, and as a result, the catalytic activity is lowered compared with powder. There is an example in which a photocatalyst is mixed with a hardly decomposable binder such as fluororesin or polyorganosiloxane to be supported on a base material (EP-0633064), which is insufficient for solving practical problems such as adhesion and long-term durability. .
상술한 바와 같이 광촉매를 담체상에 담지하기 위하여 해결해야만 하는 과제로서, 1) 광촉매와 담체의 접착성이 양호할 것, 2) 광촉매 활성이 담체상에 담지됨으로써 저하되지 않을 것, 3) 담지한 광촉매에 의하여 담체 및 접착제가 열화되지 않으며 장기간에 걸쳐 강도를 유지하여 내구성과 촉매활성을 유지할 것, 이 3 가지 점을 들 수 있다. 그리고 고온다습한 환경에서 사용하는 경우에는, 예컨대 비등수 중에 침지한 후의 부착성이 뛰어난 것이 요구된다.As described above, the problem to be solved in order to support the photocatalyst on the carrier, 1) the adhesion between the photocatalyst and the carrier is good, 2) the photocatalytic activity is not lowered by being supported on the carrier, 3) the supported The photocatalyst does not deteriorate the carrier and the adhesive, and maintains its strength over a long period of time to maintain durability and catalytic activity. And when using in a high temperature / humidity environment, what is excellent in adhesiveness after immersion in boiling water, for example is calculated | required.
또, 광촉매를 담체에 담지하기 위한 광촉매 코팅제에 요구되는 특성으로서, 최저 1 개월 바람직하게는 3 개월 이상 보존하여도 점도증가나 입자침강이 없는 광촉매 도포액이 필요하다. 또한, 실용제품에 광촉매를 코팅하였을 때에 광촉매 작용을 저하시키지 않고 담지시키는 것도 필요하다.Moreover, as a characteristic required for a photocatalyst coating agent for supporting a photocatalyst on a carrier, a photocatalyst coating liquid without viscosity increase or particle sedimentation is required even if it is stored for at least one month and preferably three months or longer. In addition, when the photocatalyst is coated on the practical product, it is also required to be supported without degrading the photocatalytic effect.
본 발명자들은 광촉매층과 담체 사이에 특정 접착층을 형성하여 기초 담체를 광촉매 작용에 의한 열화로부터 보호하는 작용과 광촉매층을 담체에 강고하게 접착시키는 작용 및 접착층 자신이 광촉매 작용에 의한 열화를 잘 받지 않는 것으로 함으로써, 비로소 광촉매를 담체에 강고하게 접착시킬 수 있음을 발견하고 상기 과제를 해결하기에 이르렀다.The present inventors form a specific adhesive layer between the photocatalyst layer and the carrier to protect the underlying carrier from deterioration due to the photocatalytic action, to firmly adhere the photocatalyst layer to the carrier, and to prevent the adhesive layer from being deteriorated by the photocatalytic action. By doing so, the inventors have discovered that the photocatalyst can be firmly adhered to the support, thereby solving the above problems.
본 발명은 오염방지, 정수, 탈취, 살균, 배수처리, 수분해, 조류의 성육억제 및 각종 화학반응 등에 사용하는 광촉매를 담지한 구조체에 관한 것이다.The present invention relates to a structure carrying a photocatalyst for use in pollution prevention, water purification, deodorization, sterilization, drainage, hydrolysis, suppression of algae growth, and various chemical reactions.
도 1 은 본 발명의 광촉매 담지 구조체의 단면을 나타내는 모식도이다.BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the cross section of the photocatalyst support structure of this invention.
본 발명자들은 접착층의 재질로서 실리콘 함유량 2 ∼ 60 중량% 의 아크릴실리콘 수지, 에폭시-실리콘 수지 등의 실리콘 변성수지, 콜로이달 실리카를 5 ∼ 40 중량% 함유하는 수지 또는 일반식 (1)MEANS TO SOLVE THE PROBLEM The present inventors used the material of an adhesive layer as silicone modified resin, such as an acryl silicone resin of 2 to 60 weight% and an epoxy-silicone resin, resin which contains 5 to 40 weight% of colloidal silica, or General formula (1).
SiCln1(OH)n2R1n3(OR2)n4… (1)SiCln 1 (OH) n 2 R 1 n 3 (OR 2 ) n 4 . (One)
[식중, R1은 (아미노기, 카르복실기 또는 염소원자로 치환되어도 좋은) 탄소수 1 ∼ 8 의 알킬기, R2는 탄소수 1 ∼ 8 의 알킬기 혹은 알콕시기로 치환된 탄소수 1 ∼ 8 의 알킬기를 나타내고, n1은 0 내지 2 의 정수를 나타내고, n2및 n3는 0 내지 3 의 정수를 각각 나타내고, n4는 2 내지 4 의 정수를 나타내고, 또한 n1+n2+n3+n4=4 를 나타냄] 로 표시되는 화합물의 중축합반응 생성물인 폴리실록산을 3 ∼ 60 중량% 함유하는 수지가 광촉매를 강고하게 접착하여 담체를 광촉매로부터 보호하기에 적당함을 발견하여 본 발명을 완성하기에 이르렀다.[Wherein, R 1 represents an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a carboxyl group or a chlorine atom), R 2 represents an alkyl group having 1 to 8 carbon atoms substituted with an alkyl group or alkoxy group having 1 to 8 carbon atoms, and n 1 is An integer of 0 to 2, n 2 and n 3 each represent an integer of 0 to 3, n 4 represents an integer of 2 to 4, and n 1 + n 2 + n 3 + n 4 = 4; A resin containing 3 to 60% by weight of polysiloxane, which is a polycondensation reaction product of the compound, was found to be suitable for firmly adhering the photocatalyst to protect the carrier from the photocatalyst, thereby completing the present invention.
그리고, 본 발명자들은 광촉매 코팅제에 요구되는 상술한 과제를 해결하기 위하여 일반식 (2)Then, the inventors of the general formula (2) to solve the above-mentioned problems required for the photocatalyst coating agent
SiR3n5(OR4)4-n5… (2)SiR 3 n 5 (OR 4 ) 4- n 5 . (2)
[단, 식중 R3는 (아미노기, 염소원자 혹은 카르복실기로 치환되어도 좋은) 탄소수 1 ∼8 의 알킬기를 나타내고, R4는 탄소수 1 ∼ 8 의 알킬기 또는 알콕시기로 치환된 탄소수 1 ∼ 8 의 알킬기를 나타내고, n5는 0, 1, 2, 3 중 어느 한 수를 나타냄] 로 표시되는 알콕시실란류 또는 이들의 가수분해 생성물 중 1 종 또는 2 종 이상을 0.001 ∼ 5 중량%, 금속의 산화물 및/또는 수산화물의 졸을 고형분으로서 0.1 ∼ 30 중량% 및 광촉매의 분말 및/또는 졸을 고형분으로서 0.1 ∼ 30 중량% 를 함유한 광촉매 도포액이 장기간에 걸쳐 안정되고 점도증가나 입자침강이 없음을 발견하여 본 발명을 완성하였다.[Wherein, R 3 represents an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a chlorine atom or a carboxyl group), and R 4 represents an alkyl group having 1 to 8 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group , n 5 represents any one of 0, 1, 2, 3] 0.001 to 5% by weight of one or two or more of the alkoxysilanes or their hydrolysis products, oxides of metals and / or It was found that the photocatalyst coating liquid containing 0.1 to 30% by weight of a sol of hydroxide as a solid and 0.1 to 30% by weight of a photocatalyst powder and / or a sol was stable for a long time and there was no increase in viscosity or particle sedimentation. The invention has been completed.
또한, 본 발명자들은 이 광촉매 담지 구조체 및 광촉매 코팅제가 유리, 플라스틱, 금속, 직물, 목질재료 등의 담체소재에 담지가능하며, 렌즈, 점착필름, 블라인드, 부직포, 목질 도어 등에도 본 발명에 의한 광촉매 코팅제에 의한 도포가 가능함을 발견하였다.In addition, the present inventors can support the photocatalyst supporting structure and the photocatalyst coating agent on carrier materials such as glass, plastic, metal, fabric, and wood materials, and the photocatalyst according to the present invention is also applied to lenses, adhesive films, blinds, nonwoven fabrics, and wooden doors. It has been found that application with a coating is possible.
이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명에 있어서, 광촉매 담지 구조체의 접착층에 사용하는 수지는 실리콘 함유량 2 ∼ 60 중량% 의 아크릴-실리콘 수지, 에폭시-실리콘 수지 등의 실리콘 변성수지, 콜로이달 실리카를 5 ∼ 40 중량% 함유하는 수지 및 폴리실록산을 3 ∼ 60 중량% 함유하는 수지 중에서 선택된다.In this invention, resin used for the contact bonding layer of a photocatalyst carrying structure is resin containing 5-40 weight% of silicone modified resins, such as an acrylic-silicone resin of 2 to 60 weight% of silicone content, an epoxy-silicone resin, and colloidal silica. And resins containing 3 to 60% by weight of polysiloxane.
실리콘 함유량이 2 중량% 미만인 아크릴-실리콘 수지 등의 실리콘 변성수지, 폴리실록산 함유량이 3 중량% 미만인 수지나 콜로이달 실리카 함유량이 5 중량% 미만인 수지에서는 광촉매층과의 접착이 악화되며, 또한 접착층이 광촉매로 인하여 열화되어 광촉매층이 박리되기 쉬어진다. 한편, 실리콘 함유량 60 중량% 를 넘는 아크릴-실리콘 수지 등의 실리콘 변성수지에서는, 점착층과 담체의 접착이 악화되며 또한 접착층의 경도가 작아지기 때문에 내마모성이 악화된다.In silicone-modified resins such as acrylic-silicone resins having a silicon content of less than 2% by weight, resins having a polysiloxane content of less than 3% by weight or resins having a colloidal silica content of less than 5% by weight, adhesion to the photocatalytic layer is deteriorated. Due to this deterioration, the photocatalyst layer is easily peeled off. On the other hand, in silicone-modified resins such as acrylic-silicone resins having a silicon content of more than 60% by weight, the adhesion between the adhesive layer and the carrier is deteriorated, and since the hardness of the adhesive layer is reduced, the wear resistance is deteriorated.
또한, 폴리실록산 함유량이 60 중량% 를 넘는 수지나 콜로이달 실리카 함유량이 40 중량% 를 넘는 수지에서는, 접착층이 다공질로 되거나 기초 담체가 광촉매로 인하여 열화되며 또한 담체와 접착층 사이의 접착성이 악화됨과 동시에 광촉매는 담체에서 박리되기 쉬워진다.In addition, in a resin having a polysiloxane content of more than 60% by weight or a resin having a colloidal silica content of more than 40% by weight, the adhesive layer becomes porous or the underlying carrier is degraded due to the photocatalyst, and the adhesion between the carrier and the adhesive layer is deteriorated. The photocatalyst tends to peel off from the carrier.
접착층 수지가 아크릴-실리콘 수지나 에폭시-실리콘 수지 등의 실리콘 변성수지인 경우의 실리콘 수지에 대한 도입방법은 에스테르 교환반응, 실리콘매크로머나 반응성 실리콘 모너머를 사용한 그라프트 반응, 히드록실화 반응, 블록 공중합법 등 여러 가지가 있는데, 본 발명에서는 어떠한 방법으로 만들어진 것이라도 사용할 수 있다.When the adhesive layer resin is a silicone-modified resin such as an acrylic-silicone resin or an epoxy-silicone resin, a method of introducing a silicone resin includes a transesterification reaction, a graft reaction using a silicone macromer or a reactive silicone monomer, a hydroxylation reaction, and a block air. There are various kinds of legal methods, but in the present invention, anything made by any method can be used.
실리콘이 도입되는 수지로서는 아크릴수지나 에폭시수지가 성막성, 강인성, 담체와의 밀착성의 점에서 가장 뛰어나지만, 알키드수지, 우레탄수지, 폴리에스테르수지 등과 같은 것도 사용할 수 있다. 이들 수지는 용제에 녹인 타입이어도 에멀션 타입이어도 모두 사용할 수 있다. 또한, 가교제 등의 첨가물이 함유되어 있어도 전혀 문제는 없다.As the resin into which silicone is introduced, acrylic resins and epoxy resins are most excellent in terms of film formability, toughness and adhesion to carriers, but also alkyd resins, urethane resins, polyester resins and the like can be used. These resins can be used either in the type dissolved in a solvent or in an emulsion type. Moreover, even if additives, such as a crosslinking agent, are contained, there is no problem at all.
접착층 수지가 폴리실록산을 함유하며, 그 폴리실록산이 탄소수 1 ∼ 5 의 알콕시기를 가지는 실리콘알콕시드의 가수분해물 혹은 이 가수분해물로부터의 생성물인 경우에 접착성 및 내구성이 더욱 향상된 담지 구조체를 얻을 수 있다. 실리콘알콕시드의 알콕시기의 탄소수가 6 이상이면, 값이 비싸지고 또한 가수분해 속도가 매우 느리므로 수지 중에서 경화시키기가 어려워져서 접착성이나 내구성이 악화된다.When the adhesive layer resin contains polysiloxane and the polysiloxane is a hydrolyzate of a silicon alkoxide having an alkoxy group having 1 to 5 carbon atoms or a product from the hydrolyzate, a supported structure with further improved adhesion and durability can be obtained. When the number of carbon atoms of the alkoxy group of the silicon alkoxide is 6 or more, the value is expensive and the hydrolysis rate is very low, making it difficult to cure in the resin, thereby deteriorating the adhesiveness and durability.
부분적으로 염소를 함유한 실리콘알콕시드를 가수분해한 폴리실록산을 사용할 수도 있는데, 염소를 다량으로 함유한 폴리실록산을 사용하면 불순물의 염소이온으로 인하여 담체가 부식되거나 접착성을 악화시킨다.Polysiloxanes which partially hydrolyze silicon alkoxides containing chlorine may also be used, and polysiloxanes containing a large amount of chlorine deteriorate carriers or deteriorate adhesion due to chlorine ions of impurities.
폴리실록산의 수지에 대한 도입방법으로서는, 실리콘알콕시드모노머 상태로 수지용액으로 혼합하여 접착층 형성시에 공기 중의 수분으로 가수분해시키는 방법, 미리 실리콘알콕시드를 부분 가수분해한 것을 수지와 혼합하고, 다시 보호막 형성시에 공기 중의 수분으로 가수분해하는 방법 등 여러 가지가 있는데, 수지와 균일하게 혼합할 수 있는 방법이라면 어떠한 방법이어도 된다. 또한, 실리콘알콕시드의 가수분해 속도를 변경하기 위하여 산이나 염기촉매를 소량 첨가하여도 무방하다.As a method of introducing polysiloxane into the resin, a method of mixing with a resin solution in the form of a silicon alkoxide monomer and hydrolyzing it with moisture in the air at the time of forming an adhesive layer, mixing the partially hydrolyzed silicon alkoxide with a resin, and then again forming a protective film. There are various methods such as hydrolysis with moisture in the air at the time of formation, and any method may be used as long as it can be uniformly mixed with the resin. In addition, a small amount of an acid or a base catalyst may be added in order to change the hydrolysis rate of the silicon alkoxide.
폴리실록산이 도입되는 수지로서는 아크릴수지, 아크릴-실리콘수지, 에폭시-실리콘수지, 실리콘 변성수지, 우레탄수지, 에폭시수지, 폴리에스테르수지, 알키드수지 등을 사용할 수 있는데, 아크릴-실리콘수지나 에폭시-실리콘수지를 함유하는 실리콘 변성수지가 내구성의 점에서 가장 뛰어나다.Examples of the resin into which the polysiloxane is introduced include acrylic resins, acrylic silicone resins, epoxy silicone resins, silicone modified resins, urethane resins, epoxy resins, polyester resins, alkyd resins, and the like. Silicone modified resin containing the most excellent in durability.
접착층이 콜로이달 실리카를 함유하는 수지인 경우, 그 콜로이달 실리카의 입자직경은 10 ㎚ 이하가 바람직하다. 10 ㎚ 이상이 되면 접착층 중의 수지는 광촉매로 인하여 열화되기 쉬울 뿐만 아니라, 광촉매층과 접착층의 접착도 악화된다. 이 콜로이달 실리카를 수지로 도입하는 방법으로서는, 수지용액과 콜로이달 실리카 용액을 혼합한 후, 도포, 건조시켜 접착층을 형성하는 방법이 가장 간편하나, 콜로이달 실리카를 분산한 상태에서 수지를 중합하고 합성한 것을 도포, 건조시켜도 된다. 또한, 콜로이달 실리카와 수지의 접착성 및 분산성을 양호하게 하기 위하여 실란커플링제로 콜로이달 실리카를 처리하여 사용할 수도 있다.When the adhesive layer is a resin containing colloidal silica, the particle diameter of the colloidal silica is preferably 10 nm or less. When the thickness is 10 nm or more, the resin in the adhesive layer not only deteriorates easily due to the photocatalyst, but also deteriorates the adhesion between the photocatalyst layer and the adhesive layer. As a method of introducing the colloidal silica into the resin, a method of mixing the resin solution and the colloidal silica solution, then applying and drying to form an adhesive layer is the simplest method. However, the resin is polymerized in the state in which the colloidal silica is dispersed. You may apply | coat and dry what synthesize | combined. Moreover, in order to improve the adhesiveness and dispersibility of colloidal silica and resin, it can also be used by processing colloidal silica with a silane coupling agent.
콜로이달 실리카가 도입되는 수지로서는 아크릴수지, 아크릴-실리콘수지, 에폭시-실리콘수지, 실리콘 변성수지, 우레탄수지, 에폭시수지, 폴리에스테르수지, 알키드수지 등을 예시할 수 있는데, 아크릴-실리콘수지나 에폭시-실리콘수지를 함유하는 실리콘 변성수지가 내구성의 점에서 가장 뛰어나다.Examples of the resin into which colloidal silica is introduced include acrylic resins, acrylic silicone resins, epoxy silicone resins, silicone modified resins, urethane resins, epoxy resins, polyester resins, alkyd resins, and the like. -Silicone modified resin containing silicone resin is the best in terms of durability.
콜로이달 실리카는 규산나트륨 용액을 양이온 교환함으로써 만들어지는 실리카 졸이나, 실리콘알콕시드를 가수분해하여 만들어지는 실리카 졸 중 어느 것을 사용하여도 된다.Colloidal silica may use either a silica sol made by cation exchange of sodium silicate solution or a silica sol made by hydrolyzing silicon alkoxide.
또한, 접착층 수지에 광촉매 작용으로 인한 열화를 억제할 목적으로 광안정화제 및/또는 자외선 흡수제 등을 혼합함으로써 내구성을 향상시킬 수 있다. 사용할 수 있는 광안정화제로서는 힌더드 아민 (hindered amine) 계가 바람직하나, 그 외의 것도 사용할 수 있다. 자외선 흡수제로서는 트리아졸계 등을 사용할 수 있다. 첨가량은 수지에 대하여 0.005 wt% 이상 10 wt% 이하, 바람직하게는 0.01 wt% 이상 5 wt% 이하이다. 그리고, 접착층의 표면을 실란계 혹은 티탄계 커플링제로 처리하면 광촉매층과의 접착성이 향상되는 경우가 있다.In addition, durability can be improved by mixing a light stabilizer and / or an ultraviolet absorber for the purpose of suppressing deterioration due to a photocatalytic action to the adhesive layer resin. As a light stabilizer which can be used, a hindered amine system is preferable, but other things can also be used. Triazole type etc. can be used as a ultraviolet absorber. The addition amount is 0.005 wt% or more and 10 wt% or less, preferably 0.01 wt% or more and 5 wt% or less with respect to the resin. In addition, when the surface of the adhesive layer is treated with a silane or titanium coupling agent, the adhesiveness with the photocatalyst layer may be improved.
접착층을 담체에 담지하는 방법으로서는 수지용액을 인쇄법, 시트성형법, 스프레이분사법, 딥 코팅법, 스핀 코팅법 등으로 코팅하여 건조시키는 방법을 사용할 수 있다. 건조시키는 온도는 용매나 수지의 종류에 따라 다르지만, 일반적으로 150 ℃ 이하가 바람직하다. 접착층의 두께는 0.1 ㎛ 이상이면 광촉매층을 강고하게 접착하여 내구성이 높은 광촉매 담지 구조체로 할 수 있다. 또한, 그라비어 인쇄법 등의 단시간에 접착층을 건조경화시켜야 하는 도포법의 경우에는, 실리콘계 등의 경화제를 접착층 고형분에 대해 필요한 경화속도에 대응하여 0.1 ∼ 10 중량% 첨가하는 것도 바람직하게 채택된다.As a method of supporting the adhesive layer on the carrier, a method of coating and drying the resin solution by printing, sheet molding, spray spraying, dip coating, spin coating, or the like can be used. Although the temperature to dry differs according to the kind of solvent and resin, generally 150 degrees C or less is preferable. If the thickness of the adhesive layer is 0.1 µm or more, the photocatalyst layer can be firmly adhered to form a highly durable photocatalyst supported structure. In addition, in the case of the coating method which needs to dry-cure an adhesive layer in a short time, such as a gravure printing method, it is also preferable to add 0.1-10 weight% of hardening | curing agents, such as a silicone type, corresponding to the required hardening rate with respect to an adhesive layer solid content.
광촉매층 중의 금속산화물 겔 혹은 수산화물 겔은 광촉매 분말을 고착하여 접착층과 강고하게 접착시키는 효과를 가지고 있으며, 실시예에도 나타내는 바와 같이 이 광촉매 담지 구조체는 접착성, 장기 내구성이나 내후성이 뛰어난 것으로 되어 있다. 이 금속산화물 겔 혹은 수산화 겔은 다공질인 점에서 흡착성을 가지고 있으며, 광촉매 활성을 높이는 효과도 있다. 이 금속산화물 겔 혹은 금속수산화물 겔의 광촉매층 중에서의 함유량은 25 ∼ 95 중량% 가 바람직하다. 25 중량% 미만에서는 접착층과의 접착이 불충분하고, 95 중량% 를 넘으면 광촉매 활성이 불충분해진다.The metal oxide gel or the hydroxide gel in the photocatalyst layer has the effect of adhering the photocatalyst powder to firm adhesion with the adhesive layer. As shown in the examples, the photocatalyst bearing structure is excellent in adhesiveness, long-term durability and weather resistance. Since the metal oxide gel or the hydroxide gel is porous, the metal oxide gel or the hydroxide gel has adsorptive properties, and also has an effect of increasing the photocatalytic activity. As for content in the photocatalyst layer of this metal oxide gel or a metal hydroxide gel, 25 to 95 weight% is preferable. If it is less than 25 weight%, adhesion with an adhesive layer will be inadequate, and if it exceeds 95 weight%, photocatalytic activity will become inadequate.
또한, 금속산화물 겔 또는 금속수산화물 겔의 비표면적이 바람직하게는 150 ℃ 에서 건조시킨 후 50 ㎡/g 이상, 더욱 바람직하게는 100 ㎡/g 이상이면 접착성은 보다 강고해지며 촉매활성도 향상된다.In addition, the specific surface area of the metal oxide gel or the metal hydroxide gel is preferably 50 m 2 / g or more, more preferably 100 m 2 / g or more after drying at 150 ° C., and thus the adhesion becomes stronger and the catalytic activity is also improved.
금속성분으로서는 규소, 알루미늄, 티타늄, 지르코늄, 마그네슘, 니오븀, 탄탈, 텅스텐, 주석 등의 금속산화물 겔 혹은 수산화물 겔을 바람직하게 예시할 수 있다.As a metal component, metal oxide gel or hydroxide gel, such as silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, and tin, can be illustrated preferably.
또한, 금속성분으로서 규소, 알루미늄, 티타늄, 지르코늄, 니오븀 중에서 선택된 2 종 이상의 금속을 함유하는 산화물 혹은 수산화물 겔을 사용함으로써, 비등수에 침지한 후의 광촉매층의 부착성을 높일 수 있다. 내비등수성이 뛰어난 금속성분 조합의 예로서는 규소-알루미늄, 규소-티타늄, 규소-지르코늄, 규소-니오븀, 알루미늄-티타늄, 알루미늄-지르코늄, 알루미늄-니오븀, 알루미늄-탄탈, 티타늄-지르코늄, 티타늄-니오븀, 티타늄-탄탈, 규소-알루미늄-지르코늄, 규소-알루미늄-티타늄 등이 바람직하며, 더욱 바람직하게는 규소-알루미늄, 규소-티타늄, 규소-지르코늄, 규소-티타늄-알루미늄, 규소-알루미늄-지르코늄 등의 산화물 겔 혹은 수산화물 겔 등을 들 수 있다.In addition, by using an oxide or hydroxide gel containing two or more metals selected from silicon, aluminum, titanium, zirconium, and niobium as metal components, the adhesion of the photocatalyst layer after being immersed in boiling water can be improved. Examples of metal component combinations having excellent boiling resistance include silicon-aluminum, silicon-titanium, silicon-zirconium, silicon-niobium, aluminum-titanium, aluminum-zirconium, aluminum-niobium, aluminum-tantalum, titanium-zirconium, titanium-niobium, Titanium-tantalum, silicon-aluminum-zirconium, silicon-aluminum-titanium, and the like are preferable, and oxides such as silicon-aluminum, silicon-titanium, silicon-zirconium, silicon-titanium-aluminum, and silicon-aluminum-zirconium are more preferable. Gels or hydroxide gels;
이들 산화물 겔 혹은 수산화물 겔의 비표면적이 50 ㎡/g 이상이면 접착성이 높고 촉매활성도 향상되며 비등수 중에 침투한 후에도 뛰어난 접착성을 가지고 있다. 또한, 실제 사용할 때에는 겔을 형성시키기 위한 졸을 혼합하여 건조시켜 얻어지는 겔이나 공침전법 등의 방법으로 만들어지는 복합산화물 겔을 사용하여도 된다. 광촉매와의 복합화로는 겔로 되기 전의 졸 상태에서 균일 혼합하거나 혹은 졸을 조제하기 전의 원료 단계에서 혼합하는 것이 바람직하다.When the specific surface area of these oxide gels or hydroxide gels is 50 m 2 / g or more, the adhesiveness is high, the catalytic activity is improved, and the adhesive gel is excellent even after infiltration into boiling water. In addition, in actual use, you may use the composite oxide gel produced by methods, such as a gel obtained by mixing and drying a sol for forming a gel, and a co-precipitation method. As the composite with the photocatalyst, it is preferable to homogeneously mix in the sol state before forming a gel or to mix in the raw material step before preparing the sol.
겔을 조제하는 방법으로는 금속염을 가수분해하는 방법, 중화분해하는 방법, 이온교환하는 방법, 금속알콕시드를 가수분해하는 방법 등이 있는데, 겔 중으로 광촉매 분말이 균일하게 분산된 상태로 얻어지는 것이라면 어떠한 방법도 사용할 수 있다. 단, 겔 중에 다량의 불순물이 존재하면, 광촉매의 접착성이나 촉매활성에 악영향을 미치기 때문에 불순물이 적은 겔이 바람직하다.The gel may be prepared by hydrolysis of metal salts, neutralization, ion exchange, or hydrolysis of metal alkoxides. If the photocatalyst powder is uniformly dispersed in the gel, The method can also be used. However, a large amount of impurities in the gel adversely affects the adhesion and catalytic activity of the photocatalyst, so a gel having few impurities is preferable.
또한, 광촉매층 중에 실리콘 변성수지 혹은 실란커플링제를 10 ∼ 50 중량% 첨가함으로써도 높은 촉매활성을 유지한 채로 비등수 중에 15 분간 침지한 후에 JIS K5400 에서 규정된 바둑판눈금 테이프법에 의한 부착성 시험에서 평가점수가 6 점 이상인 우수한 부착성을 가지는 것을 얻을 수 있다.In addition, the adhesion test by the checkerboard tape method specified in JIS K5400 after immersion in boiling water for 15 minutes while maintaining high catalytic activity even by adding 10-50% by weight of a silicone-modified resin or a silane coupling agent to the photocatalyst layer. It is possible to obtain a good adhesiveness having an evaluation score of 6 or more.
광촉매층 중에 첨가하는 실리콘 변성수지 또는 실란커플링제는, 비등수 중에서의 광촉매층의 부착성을 높이는 효과를 가지고 있다. 실리콘 변성수지로서는 통상 시판되고 있는 실리콘-아크릴계나, 실리콘-에폭시계의 것을 사용할 수 있으며, 용제에 용해한 것이나 에멀션으로 되어 수중에 분산되어 있는 것을 모두 사용할 수 있다. 또한, 실란커플링제로서는 일반식 : RSi (Y)3나 (R)2Si(Y)2(단, R 은 유기성 관능기를, Y 는 염소원자 또는 알콕시기를 나타낸다) 등으로 표시되는 것을 사용할 수 있다. 상기 일반식에 있어서, R 로서는 메틸기, 에틸기, 비닐기, γ-글리시톡시프로필기, γ-메타크릴록시프로필기, γ-(2-아미노에틸)아미노프로필기, γ-클로로프로필기, γ-메르캅토프로필기, γ-아미노프로필기, γ-아크릴록시프로필기 등이 있고, Y 로서는 염소원자 이외에 메톡시기, 에톡시기, β-메톡시에톡시기, β-에톡시메톡시기 등의 C1∼ C5의 알콕시의 것을 모두 사용할 수 있다.The silicone modified resin or silane coupling agent added to the photocatalyst layer has the effect of improving the adhesion of the photocatalyst layer in boiling water. As silicone modified resin, the commercially available silicone-acrylic-type and silicone-epoxy clock thing can be used, and the thing melt | dissolved in the solvent and the thing disperse | distributed in water as an emulsion can be used. As the silane coupling agent, those represented by the general formula: RSi (Y) 3 or (R) 2 Si (Y) 2 (wherein R represents an organic functional group and Y represents a chlorine atom or an alkoxy group) can be used. . In the above general formula, R is a methyl group, ethyl group, vinyl group, γ-glycithoxypropyl group, γ-methacryloxypropyl group, γ- (2-aminoethyl) aminopropyl group, γ-chloropropyl group, γ -Mercaptopropyl group, γ-aminopropyl group, γ-acryloxypropyl group, and the like. As Y, C, such as methoxy group, ethoxy group, β-methoxyethoxy group, β-ethoxymethoxy group, etc. 1 and can be used to both of the C 5 alkoxy.
실리콘 변성수지 또는 실란커플링제의 첨가량은, 고형분으로서 광촉매층중에 10∼50 중량% 를 첨가하는 것이 바람직하다. 10 중량% 미만에서는 비등수 시험후의 부착성이 저하되고, 50 중량% 보다 다량의 첨가에서는 광촉매활성의 저하가 현저하다. 광촉매층 중에 대한 실리콘 변성수지 또는 실란커플링제의 첨가방법으로서는, 광촉매 분말이나 졸의 액중에 첨가하는 방법이나, 광촉매와 함께 첨가하는 금속산화물 겔을 형성하기 위한 금속의 산화물 또는 수산화물의 졸 액중에 첨가하는 방법 등 여러 가지 방법이 가능하다. 또한, 에멀션 타입의 실리콘 변성수지를 상기 졸의 액중에 첨가하는 것은, 광촉매의 활성을 거의 저하시키지 않고 비등수 중에서의 광촉매층의 부착성을 현저하게 높일 수 있으므로 특히 바람직하다.As for the addition amount of a silicone modified resin or a silane coupling agent, it is preferable to add 10-50 weight% in a photocatalyst layer as solid content. If it is less than 10 weight%, the adhesiveness after boiling water test will fall, and when a quantity of 50 weight% or more is added, the fall of photocatalytic activity is remarkable. As a method of adding a silicone-modified resin or a silane coupling agent to the photocatalyst layer, it is added to the photocatalyst powder or the sol liquid, or to the sol liquid of the metal oxide or hydroxide for forming the metal oxide gel to be added together with the photocatalyst. There are many ways to do this. In addition, it is particularly preferable to add an emulsion type silicone modified resin to the sol liquid because the adhesion of the photocatalyst layer in boiling water can be remarkably increased without substantially decreasing the activity of the photocatalyst.
또한, 가교제 등의 첨가물을 실리콘 변성수지 또는 실란커플링제에 함유시킬 수도 있다.Moreover, additives, such as a crosslinking agent, can also be contained in silicone modified resin or a silane coupling agent.
본 발명에 사용되는 광촉매는 분말상, 졸상, 용액상 등 광촉매층의 건조온도로 건조시켰을 때에 접착층과 고착하여 광촉매 활성을 나타내는 것이면 모두 사용이 가능하다. 졸상의 광촉매를 사용하는 경우, 입자직경이 20nm 이하, 바람직 하게는 10 nm 이하의 것을 사용하면, 광촉매층의 투명성이 향상되고 직선투과율이 높아지기 때문에, 투명성이 요구되는 유리기판이나 플라스틱 성형체에 도포할 경우에 특히 바람직하다. 또한 기초 담체에 색이나 모양이 인쇄된 것인 경우에 이러한 투명한 광촉매층을 도포하면 기초 색이나 무늬를 손상시키는 일이 없다.The photocatalyst used in the present invention can be used as long as it adheres to the adhesive layer and exhibits photocatalytic activity when dried at the drying temperature of the photocatalyst layer such as powder, sol, and solution. In the case of using a sol-type photocatalyst, when the particle diameter is 20 nm or less, preferably 10 nm or less, the transparency of the photocatalyst layer is improved and the linear transmittance is increased. Therefore, the photocatalyst can be applied to a glass substrate or a plastic molded article requiring transparency. It is particularly preferable in this case. If the transparent photocatalyst layer is applied when the color or shape is printed on the base carrier, the base color or pattern is not damaged.
광촉매층 중의 광촉매로서는 TiO2, ZnO, SrTiO3, CdS, GaP, InP, GaAs, BaTiO3, KNbO3, Fe2O3, Ta2O5, WO3, SnO2, Bi2O3, NiO, Cu2O, SiC, SiO2, MoS2, InPb, RuO2, CeO2등 및 이들 광촉매에 Pt, Rh, RuO2, Nb, Cu, Sn, Ni, Fe 등의 금속 및 이들 금속의 산화물을 첨가한 것을 사용할 수 있다. 또한, 이들 광촉매에 광촉매 환원작용을 이용하여 Pt, Rh, RuO2, Nb, Cu, Sn, Ni, Fe 등의 금속을 첨가한 것 등도 모두 사용할 수 있다. 광촉매층 중의 광촉매 함유량은 다량일수록 촉매의 활성이 높아지지만, 접착성의 관점에서 바람직게는 75 중량% 이하이다.Photocatalysts in the photocatalyst layer include TiO 2 , ZnO, SrTiO 3 , CdS, GaP, InP, GaAs, BaTiO 3 , KNbO 3 , Fe 2 O 3 , Ta 2 O 5 , WO 3 , SnO 2 , Bi 2 O 3 , NiO, Metals such as Pt, Rh, RuO 2 , Nb, Cu, Sn, Ni, Fe, and oxides of these metals are added to Cu 2 O, SiC, SiO 2 , MoS 2 , InPb, RuO 2 , CeO 2 and the like and these photocatalysts You can use one. In addition, all of these photocatalysts may be used by adding a metal such as Pt, Rh, RuO 2 , Nb, Cu, Sn, Ni, Fe, etc. using a photocatalytic reduction effect. The greater the amount of photocatalyst content in the photocatalyst layer, the higher the activity of the catalyst. However, from the viewpoint of adhesion, the content is preferably 75% by weight or less.
본 발명에 의한 광촉매 도포액은 실리콘 화합물을 0.001 % ∼ 5 중량%, 금속의 산화물 및/또는 수산화물의 졸을 고형분으로서 0.1 ∼ 30 중량% 및 광촉매의 분말 및/또는 졸을 고형분으로서 0.1 ∼ 30 중량% 함유하는 것을 특징으로 한다.The photocatalyst coating liquid according to the present invention contains 0.001% to 5% by weight of a silicon compound, 0.1 to 30% by weight of a sol of an oxide and / or hydroxide of a metal, and 0.1 to 30% of a powder and / or sol of a photocatalyst as a solid. It is characterized by containing%.
본 발명의 광촉매층의 도포액 중에 첨가하는 실리콘 화합물로서는 일반식 (2)As a silicone compound added in the coating liquid of the photocatalyst layer of this invention, General formula (2)
SiR3n5(OR4)4-n5… (2)SiR 3 n 5 (OR 4 ) 4- n 5 . (2)
[단, 식중 R3는 (아미노기, 염소원자 혹은 카르복실기로 치환되어도 좋은) 탄소수 1 ∼8 의 알킬기를 나타내고, R4는 탄소수 1 ∼ 8 의 알킬기 또는 알콕시기로 치환된 탄소수 1 ∼ 8 의 알킬기를 나타내고, n5는 0, 1, 2, 3 중 어느 한 수를 나타낸냄] 로 표시되는 알콕시실란류 또는 이들의 가수분해 생성물 중 1 종 또는 2 종 이상의 혼합물을 사용할 수 있다. 일반식 (2) 에 있어서, R3로서는 메틸기, 에틸기, 비닐기, γ-글리시독시프로필기, γ-메타크릴록시프로필기, γ-(2-아미노에틸)아미노프로필기, γ-클로로프로필기, γ-메르캅토프로필기, γ-아미노프로필기, γ-아크릴록시프로필기 등이 있고, -OR4로서는 메톡시기, 에톡시기, n-프로폭시기, i-프로폭시기, n-부톡시기, β-메메톡시에톡시기, β-에톡시에톡시기, 2-에틸헥시록시기 등의 C1∼ C8의 알콕시기인 것이 바람직하다. 일반식 (2) 로 표시되는 실리콘 화합물의 예로서 테트라메톡시실란, 테트라에톡시실란, 메틸트리메톡시실란, 메틸트리에톡시실란 및 이들의 가수분해 생성물 중 1 종 또는 2 종 이상의 혼합물을 바람직한 것으로 들 수 있다.[Wherein, R 3 represents an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a chlorine atom or a carboxyl group), and R 4 represents an alkyl group having 1 to 8 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group , n 5 represents any number of 0, 1, 2, 3] One or a mixture of two or more of the alkoxysilanes or their hydrolysis products can be used. In general formula (2), as R <3> , a methyl group, an ethyl group, a vinyl group, (gamma)-glycidoxy propyl group, (gamma)-methacryloxypropyl group, (gamma)-(2-aminoethyl) aminopropyl group, (gamma)-chloropropyl Group, γ-mercaptopropyl group, γ-aminopropyl group, γ-acryloxypropyl group, etc., and as -OR 4 , a methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butok group, β- selected display ethoxy Messenger group, ethoxy group Messenger to β-, 2- ethylhexyl when C 1 ~ C 8 alkoxy group of the registered time is preferred. As an example of the silicone compound represented by General formula (2), 1 type, or a mixture of 2 or more types of tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and these hydrolysis products is preferable. It can be mentioned.
광촉매층의 도포액 중에 상기 실리콘 화합물을 소량 첨가함으로써, 장기간 보존하여도 점도의 증가나 입자의 침강이 적은 안정된 광촉매 도포액을 얻을 수 있다. 실리콘 화합물의 첨가량은 고형분으로서 광촉매층의 도포액 중에 0.001 ∼ 5 중량% 를 첨가하는 것이 바람직하다. 0.001중량% 미만에서는 광촉매층 도포액의 장기보존시의 안정성이 저하되고, 5 중량% 보다 다량의 첨가에서는 광촉매 활성의 저하가 현저하다. 광촉매층의 도포액 중에의 실리콘 화합물의 첨가방법으로서는, 광촉매 분말 또는 졸의 액중에 첨가하는 방법이나, 광촉매와 함께 첨가하는 금속산화물 및/또는 수산화물의 졸의 액중에 첨가하는 방법 등 여러 가지 방법이 가능하다. 또한, 부분가수분해된 실리콘 화합물이 첨가되어 있어도 좋다. 이 광촉매층의 도포액 중에 첨가하는 실리콘 화합물은 비등수 중에서의 광촉매층의 부착성을 높이는 효과도 있기 때문에, 상술한 실란커플링제 등이 첨가되어 있는 경우에는 실리콘 화합물의 첨가량을 줄일 수 있다.By adding a small amount of the silicone compound in the coating liquid of the photocatalyst layer, it is possible to obtain a stable photocatalyst coating liquid with little increase in viscosity and sedimentation of particles even after long-term storage. It is preferable to add 0.001-5 weight% of addition amount of a silicone compound in the coating liquid of a photocatalyst layer as solid content. If it is less than 0.001 weight%, the stability at the time of long-term storage of a photocatalyst layer coating liquid will fall, and when it is added more than 5 weight%, the fall of photocatalytic activity is remarkable. As a method of adding the silicon compound to the coating liquid of the photocatalyst layer, various methods such as a method of adding to the liquid of the photocatalyst powder or the sol or a method of adding to the liquid of the sol of the metal oxide and / or hydroxide added together with the photocatalyst are It is possible. Furthermore, the partially hydrolyzed silicone compound may be added. Since the silicone compound added to the coating liquid of this photocatalyst layer also has the effect of improving the adhesiveness of the photocatalyst layer in boiling water, when the above-mentioned silane coupling agent etc. are added, the addition amount of a silicone compound can be reduced.
광촉매층의 도포액 중에 첨가하는 금속의 산화물 및/또는 수산화물의 졸은 고형분으로서 도포액에 대하여 0.1 ∼ 30 중량%, 광촉매의 분말 및/또는 졸은 고형분으로서 도포액에 대하여 0.1 ∼ 30 중량% 를 각각 첨가하는 것이 바람직하다.The sol of the oxides and / or hydroxides of the metals added in the coating liquid of the photocatalyst layer is a solid content of 0.1 to 30% by weight based on the coating liquid, and the powder and / or sol of the photocatalyst is a solid content of 0.1 to 30% by weight of the coating liquid. It is preferable to add each.
금속산화물 및/또는 수산화물의 졸은, 0.1 중량% 이하의 첨가에서는 광촉매를 기초재에 고착시키는 작용이 약하고, 30 중량% 이상의 첨가에서는 동시에 첨가되는 광촉매의 분말 및/또는 졸의 양이 적어져서 광촉매의 활성이 저하한다. 또한, 광촉매의 분말 및/또는 졸의 첨가량이 0.1 중량% 이하에서는 광촉매의 활성이 낮고, 30 중량% 이상에서는 기초재에 고착시키기 위한 금속산화물 및/또는 수산화물의 졸의 양이 적어지기 때문에 박리되기 쉬워진다.The sol of the metal oxide and / or the hydroxide has a weak effect of fixing the photocatalyst to the base material at 0.1 wt% or less, and the amount of powder and / or sol of the photocatalyst added simultaneously at a 30 wt% or more amount decreases the photocatalyst. Decreases its activity. When the amount of the photocatalyst powder and / or sol is added in an amount of 0.1 wt% or less, the activity of the photocatalyst is low, and in 30 wt% or more, the amount of the sol of the metal oxide and / or hydroxide for fixing to the base material is reduced, so that the photocatalyst is peeled off. Easier
본 발명의 광촉매 도포액은 광촉매층과 담체 사이에 접착층을 형성하기 때문에, 담체 위에 도포하는 접착층의 도포액을 병용할 수도 있다. 접착층의 도포액으로서는, 실리콘 함유량 2 ∼ 60 중량% 의 실리콘 변성수지, 폴리실록산을 3 ∼ 60 중량% 함유하는 수지나 콜로이달 실리카를 5 ∼ 40 중량% 함유하는 수지를 수지고형분으로서 1 ∼ 50 중량% 를 함유하는 용액을 사용할 수 있다.Since the photocatalyst coating liquid of this invention forms an adhesive layer between a photocatalyst layer and a support | carrier, you may use together the coating liquid of the contact bonding layer apply | coated on a support | carrier. As a coating liquid of a contact bonding layer, 1-50 weight% of resin containing 2 to 60 weight% of silicone modified resin, resin containing 3 to 60 weight% of polysiloxane, and resin which contains 5 to 40 weight% of colloidal silica as resin composition A solution containing can be used.
접착층의 도포액에 사용되는 수지로서는 상술한 접착층에 사용할 수 있는 수지를 단독 또는 혼합하여 사용하는 것이 좋고, 유기용제 용액으로서 혹은 수성 에멀션으로서 수지 고형분 1 ∼ 50 중량% 의 도포액을 사용하는 것이 바람직하다. 수지 고형분의 농도가 1 % 이하인 도포액에서는 접착층이 너무 얇아져서 광촉매층의 접착이 어려워지고, 수지 고형분이 50 중량% 이상인 도포액에서는 접착층이 너무 두꺼워져서 양호한 도포막이 이루어지지 않을 뿐만 아니라 점도가 너무 높아져서 취급이 어려워지기도 한다.As resin used for the coating liquid of an adhesive layer, it is preferable to use resin which can be used for the above-mentioned adhesive layer individually or in mixture, and to use the coating liquid of 1-50 weight% of resin solid content as an organic solvent solution or an aqueous emulsion. Do. In the coating liquid with a resin solid content of 1% or less, the adhesive layer becomes too thin to make the photocatalytic layer adhere, and in the coating liquid with a resin solid content of 50% by weight or more, the adhesive layer is too thick to obtain a good coating film and the viscosity is too high. It may become difficult to handle due to the high temperature.
광촉매층을 접착층의 위에 형성하기 위해서는 금속산화물 졸 혹은 금속수산화물의 졸액 중에 광촉매를 분산시킨 현탁액을 접착층을 형성하는 것과 동일한 코팅법으로 코팅할 수 있다. 금속산화물 졸 혹은 금속수산화물 졸의 전구체 용액 상태에서 광촉매를 분산시키고, 코팅시에 가수분해나 중화분해하여 졸화 혹은 겔화시켜도 된다. 졸을 사용하는 경우에는, 안정화를 위하여 산이나 알카리의 해교제 (解膠劑) 등이 첨가되어 있어도 좋다. 또한 졸 현탁액 중에 광촉매에 대해 5 중량% 이하의 계면활성제나 실란커플링제 등을 첨가하여 접착성이나 조작성을 좋게 할 수도 있다. 광촉매층의 형성시의 건조온도로서는 담체재질 및 접착층 중의 수지의 재질에 따라서도 달라지지만, 50 ℃ 이상 200 ℃ 이하가 바람직하다.In order to form the photocatalyst layer on the adhesive layer, a suspension obtained by dispersing the photocatalyst in the sol liquid of the metal oxide sol or the metal hydroxide may be coated by the same coating method as that of forming the adhesive layer. The photocatalyst may be dispersed in a precursor solution state of a metal oxide sol or a metal hydroxide sol, and hydrolyzed or neutralized during coating to be solvated or gelled. In the case of using a sol, an acid or alkali peptizing agent or the like may be added for stabilization. Moreover, 5 weight% or less surfactant, a silane coupling agent, etc. can be added to a photocatalyst to a sol suspension, and adhesiveness and operability can also be improved. Although the drying temperature at the time of formation of a photocatalyst layer changes also with a carrier material and the material of resin in an adhesive layer, 50 degreeC or more and 200 degrees C or less are preferable.
광촉매층의 두께는 두꺼운 쪽이 활성이 높으나, 5 ㎛ 이상이 되면 거의 변하지 않게 된다. 5 ㎛ 이하에서도 높은 촉매 활성을 나타내며 또한 투광성을 나타내게 되며, 촉매층이 눈에 띄지 않게 되어 바람직하다. 그러나, 두께가 0.1 ㎛ 미만이 되면 투광성은 좋아지지만, 광촉매가 이용하고 있는 자외선을 투과시키게 되기 때문에 높은 활성은 얻을 수 없게 된다. 광촉매층의 두께를 0.1 ㎛ 이상 5 ㎛ 이하로 하고, 또한 결정입자직경이 40 ㎜ 이하인 광촉매입자 및 비표면적 100㎡/g 이상의 금속산화물 겔 또는 금속수산화물 겔을 사용하면, 광촉매층과 접착층 합계의 파장 550 ㎚ 의 전광선 투과율은 70 % 이상이 되고, 파장 550 ㎚ 의 전광선 투과율이 70 % 이상이 되도록 담지한 구조체는, 담체가 투명한 경우에 투과된 가시광선을 조명으로서 이용할 수 있고, 또한 담체가 불투명한 경우에도 담체상의 무늬를 손상시키지 않기 때문에 장식성의 관점에서도 유용하다.The thicker the photocatalyst layer is, the higher the activity is, but it hardly changes when it is 5 µm or more. It is preferable to exhibit high catalytic activity even at 5 탆 or less and to show light transmittance, and to make the catalyst layer inconspicuous. However, when the thickness is less than 0.1 mu m, the light transmittance is improved, but high activity cannot be obtained because the ultraviolet light used by the photocatalyst is transmitted. When the photocatalyst layer has a thickness of 0.1 µm or more and 5 µm or less and a photocatalyst particle having a crystal grain diameter of 40 mm or less and a metal oxide gel or metal hydroxide gel having a specific surface area of 100 m 2 / g or more, the wavelengths of the photocatalytic layer and the adhesive layer in total The structure supported so that the total light transmittance of 550 nm becomes 70% or more and the total light transmittance of wavelength 550 nm becomes 70% or more can use visible light which permeate | transmitted when a carrier is transparent, and a carrier is opaque It is also useful in terms of decoration because it does not damage the pattern on the carrier.
담체의 형상으로서는 필름상, 판상, 관상, 섬유상, 망상 등과 같은 복잡한 형상으로 하여도 이 접착층과 광촉매층을 형성한 구조체는 얻어진다. 또한, 크기는 10 ㎛ 이상이면 강고하게 담지할 수가 있다. 담체 재질로서는 담지할 때에 열을 가할 수 없는 유기고분자체나 열이나 물 등으로 산화 부식되기 쉬운 금속으로도, 이 접착층과 광촉매층을 형성한 구조체는 얻을 수 있으므로, 고촉매활성, 고내구성을 나타낸다. 담체와 접착층의 밀착성을 좋게하기 위하여 표면을 방전처리나 프라이머 처리 등을 한 담체를 사용하여도 좋다.As the shape of the support, a structure in which the adhesive layer and the photocatalytic layer are formed can be obtained even in a complicated shape such as a film, plate, tubular, fibrous or network. If the size is 10 µm or more, it can be supported firmly. As the support material, even when the organic polymer body cannot be heated when supported, or a metal which is easily oxidatively corroded by heat or water, a structure in which the adhesive layer and the photocatalytic layer are formed can be obtained, thus exhibiting high catalytic activity and high durability. . In order to improve the adhesion between the carrier and the adhesive layer, a carrier having a surface treated with a discharge treatment or a primer may be used.
본 발명에 나타내는 광촉매를 담지한 구조체는, 실시예에 나타낸 바와 같이 건축용 도료, 벽지, 창유리, 블라인드, 커튼, 카페트, 조명기구, 조명등, 블랙 라이트, 선저 (船底), 어망 오염방지 도료, 수처리용 충전제, 농업용 비닐필름, 방초시트, 포장자재 등에 사용할 수 있다. 또한, 특히 고온고습한 환경하에서도 사용할 수 있는 광촉매 담지체로 할 수도 있다.As shown in the examples, the structure carrying the photocatalyst according to the present invention may be used for construction paints, wallpaper, window glass, blinds, curtains, carpets, lighting fixtures, lighting lamps, black lights, bottoms, fish net pollution prevention paints, and water treatment. It can be used for fillers, agricultural vinyl film, grass sheet, packaging materials and the like. Moreover, it can also be set as the photocatalyst support body which can be used especially in a high temperature, high humidity environment.
접착층과 광촉매층을 형성한 본 발명에 의한 구조체에서는, 자외선 강도 3 ㎽/㎠ 인 블랙 라이트의 빛을 온도 40℃, 상대습도 90 % 의 것으로 500 시간 조사한 후에도 JIS K5400 의 바둑판눈금 테이프법에 의한 부착성이 평가점수 6 점 이상을 유지하는 고내구성을 나타내는 것도 가능하다. 또한, 선샤인 웨더미터에 의한 촉진 내후성 시험에서도 시험시간 500 시간 후에도 JIS K5400의 바둑판눈금 테이프법에 의한 부착성이 평가점수 6 점 이상을 유지하는 뛰어난 내후성을 나타내는 것도 얻어진다. 또한, 20 ℃ 에서의 도전율이 200 ㎲/㎝ 를 나타내는 비등수 중에 15 분간 침지한 후의 JIS K5400 에 규정된 바둑판눈금 테이프법에 의한 부착성이 평가점수 6 점 이상의 높은 내비등수성을 나타내는 것도 얻어지고, 또한 모든 시료에 있어서 높은 광촉매활성을 나타내는 것으로 되는 점에서 상술한 각종 용도에 대하여 충분한 특성의 것으로 할 수 있다.In the structure according to the present invention in which the adhesive layer and the photocatalyst layer were formed, adhesion by the checkerboard scale method of JIS K5400 even after irradiating the light of black light having an ultraviolet intensity of 3 ㎽ / cm 2 for 500 hours with a temperature of 40 ° C and a relative humidity of 90% It is also possible to show the high durability that maintains a score of 6 or more. Moreover, also in the accelerated weather resistance test by a sunshine weather meter, the adhesiveness by the checkerboard scale tape method of JISK5400 which shows the outstanding weather resistance which maintains 6 or more evaluation scores is obtained even after 500 hours of test time. Moreover, the adhesiveness by the checkerboard scale method prescribed | regulated to JISK5400 after 15 minutes immersion in the boiling water which the electrical conductivity in 20 degreeC shows 200 kPa / cm is also obtained which shows the high boiling water resistance of 6 or more evaluation scores. Moreover, since it shows high photocatalytic activity in all the samples, it can be set as the thing of sufficient characteristic for the various uses mentioned above.
담체로서 사용할 수 있는 유리의 형상으로서는 판상, 관상, 구상, 섬유상 등 어떠한 복잡한 형상으로 하여도 이 접착층과 광촉매층을 형성한 유리는 얻어진다. 또한, 크기는 10 ㎛ 이상이면 강고하게 담지할 수가 있다. 또한, 시공이 끝난 창유리, 쇼 케이스, 안경 등 용도에 따라서는 가공이 끝난 유리에 처리함으로써 본 발명의 광촉매 담지유리로 할 수도 있다.As a shape of the glass which can be used as a support, the glass which provided this adhesive layer and a photocatalyst layer is obtained also in any complex shape, such as plate shape, tubular shape, spherical shape, and fibrous form. If the size is 10 µm or more, it can be supported firmly. In addition, depending on the application, such as window glass, show case, glasses, etc., which were completed, it can also be set as the photocatalyst carrying glass of this invention by processing to the processed glass.
본 발명에 나타내는 광촉매를 담지한 유리는 창유리, 계기용 커버글라스, 조명기구, 조명등, 블랙 라이트, 수처리용 충전제를 비롯하여 카메라, 안경렌즈 등 항균, 탈취, 오염방지 등의 효과를 필요로 하는 모든 사용부문에서 사용할 수 있다.The glass carrying the photocatalyst according to the present invention can be used for window glass, instrument cover glass, lighting equipment, lighting lamp, black light, filler for water treatment, camera, eyeglass lens, etc. Can be used in the sector.
본 발명에 나타내는 광촉매를 담지한 플라스틱 성형체는, 벽지, 내장용 보드, 가구, 전기기기, 차량용 부품을 비롯하여 카메라, 안경의 렌즈 등 항균, 탈취, 오염방지 등의 효과를 필요로 하는 많은 부문에서 사용할 수 있다.The plastic molded body carrying the photocatalyst according to the present invention can be used in many fields that require effects such as wallpaper, interior boards, furniture, electrical equipment, and vehicle parts, as well as antibacterial, deodorant, and pollution prevention, such as lenses of cameras and glasses. Can be.
플라스틱 성형체의 형상으로서는 필름상, 판상, 관상, 구상, 섬유상 등의 어떠한 복잡한 형상으로 하여도 이 접착층과 광촉매층을 형성한 플라스틱 성형체는 얻을 수 있다. 또한, 크기는 10 ㎛ 이상이면 강고하게 담지할 수 있다. 또한 시공이 끝난 건축자재, 가정 전화 (電化) 제품, 안경 등 용도에 따라서는 가공이 끝난 플라스틱 성형체에 처리함으로써 본 발명의 광촉매 담지 플라스틱 성형체로 할 수 있기 때문에, 그 응용범위는 매우 광범위하다고 할 수 있다.As a shape of a plastic molded object, the plastic molded object which formed this adhesive layer and a photocatalyst layer can be obtained also in any complex shape, such as film form, plate shape, tubular shape, spherical shape, and fibrous form. Further, if the size is 10 µm or more, it can be firmly supported. In addition, the application range is very broad because the photocatalyst-carrying plastic molded body of the present invention can be formed by treating the finished plastic molded body according to the application of construction materials, home telephone products, eyeglasses, etc. have.
본 발명에 사용되는 직물로서는 모, 견, 면, 마 등의 천연섬유, 레이온, 아세테이트 등의 재생섬유, 나일론, 아크릴, 폴리아미드, 폴리에스테르, 폴리아크릴로니트릴, 폴리염화비닐 등의 합성섬유, 아라미드 (aramid) 등의 내열성 섬유의 단독 혹은 혼방섬유로 된 직포, 편포, 부직포 등을 담체로서 사용할 수 있다. 또한, 실리콘계 발수제, 퍼플루오로알킬아클리레이트 등의 불소 발수제, 지르코늄염계 발수제, 에틸렌요소계 발수제 등의 발수제로 처리된 직물, 필요에 따라 내구성을 향상시키기 위하여 에틸렌이민계, 에폭시계, 멜라민계 등의 가교제를 병용하고 있는 발수가공된 직물, 폴리아미드와 폴리에스테르의 피브릴화형 복합섬유 등으로 된 의혁 (擬革), 직포, 부직포, 편포 등의 기초재에 폴리우레탄 접착제를 통하여 폴리우레탄 수지층이 형성되어 되는 합성피혁 등을 사용할 수도 있다. 또한 우산, 텐트, 가방 등, 가공이 끝난 직물에 처리함으로써 본 발명의 광촉매 담지 직물로 할 수도 있다.Examples of the fabric used in the present invention include natural fibers such as wool, silk, cotton and hemp, regenerated fibers such as rayon and acetate, synthetic fibers such as nylon, acrylic, polyamide, polyester, polyacrylonitrile and polyvinyl chloride, A woven fabric, knitted fabric, nonwoven fabric or the like made of a single or mixed fiber of heat resistant fibers such as aramid can be used as the carrier. In addition, fabrics treated with water repellents such as silicon-based water repellents, fluorine water repellents such as perfluoroalkyl acrylate, zirconium salt water repellents, and ethylene urea-based water repellents, and ethyleneimine-based, epoxy-based, and melamine-based for improving durability as necessary. Polyurethane can be applied to a base material such as leather, woven fabric, nonwoven fabric, and knitted fabric made of a water-repellent fabric using a crosslinking agent, such as a fibrillated composite fiber of polyamide and polyester. Synthetic leather, etc. in which a layer is formed can also be used. Furthermore, it can also be set as the photocatalyst support fabric of this invention by processing to processed fabrics, such as an umbrella, a tent, and a bag.
본 발명에 나타내는 광촉매를 담지한 직물은 항균, 탈취, 오염방지 등의 효과를 필요로 하는 많은 사용부문, 예를 들면 커튼, 벽지 등의 인테리어 제품, 텐트, 우산, 테이블보 등의 일용품, 식품 포장재 등으로서 또한 육묘 시트 등 농업분야에서도 사용할 수 있다.Fabrics carrying the photocatalyst of the present invention are used in many fields of use that require effects such as antibacterial, deodorant, pollution prevention, for example, interior products such as curtains, wallpaper, daily necessities such as tents, umbrellas, tablecloths, food It can also be used as a packaging material and also in agricultural fields such as seedling sheets.
본 발명에 나타내는 광촉매기능을 담지한 금속으로서는 알루미늄, 철, 구리 등의 단일체금속 외에 스테인레스, 진주, 황동, 알루미늄합금, 티탄합금 등의 각종 합금 등도 담체로서 사용할 수 있다. 또한 사용하는 금속의 형상, 재질에 따라서는 통상의 도료로 도장한 금속시트나 판, 착색한 컬러 동판이나 컬러 알루미늄 샷시 등의 위에 본 발명에 따른 접착층과 광촉매층을 형성하여 광촉매 담지체로 할 수 있다. 이 경우, 접착층 및 광촉매층의 광투과율이 높고 투명하면 기초 도료의 색조를 손상시키는 일이 없으므로 바람직하다.As the metal supporting the photocatalytic function shown in the present invention, various alloys such as stainless steel, pearl, brass, aluminum alloy, titanium alloy and the like can be used as a carrier, in addition to monolithic metals such as aluminum, iron and copper. Depending on the shape and material of the metal to be used, the adhesive layer and the photocatalyst layer according to the present invention may be formed on a metal sheet or plate coated with a conventional paint, a colored color copper plate, a color aluminum sash, or the like to form a photocatalyst carrier. . In this case, when the light transmittance of a contact bonding layer and a photocatalyst layer is high and transparent, since the color tone of a base material is not impaired, it is preferable.
금속의 형상으로서는 판상, 관상, 구상, 섬유상, 시트상 등과 같은 복잡한 형상으로 하여도 이 접착층과 광촉매층을 형성한 금속은 얻어진다. 또 크기는 10 미크론 이상이면 강고하게 담지할 수 있다. 또한 시공이 끝난 창틀, 가구, 쇼 케이스, 안경테 등 용도에 따라서는 가공이 끝난 금속에 처리함으로써 본 발명의 광촉매 담지금속으로 할 수도 있다.As a shape of a metal, even if it is complicated shapes, such as plate shape, tubular shape, spherical shape, fibrous shape, sheet shape, etc., the metal which provided this adhesive layer and the photocatalyst layer is obtained. If the size is 10 microns or more, it can be firmly supported. In addition, depending on the application, such as window frame, furniture, show case, eyeglass frame, etc., the processed metal may be used as the photocatalyst supported metal of the present invention.
본 발명에 나타내는 광촉매를 담지한 금속은 창틀, 가구, 장식품, 내장패널, 외장패널, 수처리용 충전제를 비롯하여 스트레이너, 필터 등, 항균, 탈취, 오염방지 등의 효과를 필요로 하는 많은 부문에 사용할 수 있다.The photocatalyst-carrying metal described in the present invention can be used for window frames, furniture, ornaments, interior panels, exterior panels, water treatment fillers, strainers, filters, etc., and in many fields requiring antibacterial, deodorizing, and antifouling effects. have.
본 발명에 의한 접착층과 광촉매층을 형성한 목재 및 목질재료의 형상으로서는 판상, 구상, 시트상 등과 같은 복잡한 형상도 가능하다. 또 크기는 10 ㎛ 이상이면 강고하게 담지할 수 있고, 시공이 끝난 벽, 천장판, 기둥 외에 가구, 목공세공 등의 가공이 끝난 목재 및 목질재료에 처리함으로써 본 발명의 광촉매 담지목재 및 목질재료로 할 수도 있다.As the shape of the wood and the wood material in which the adhesive layer and the photocatalyst layer are formed according to the present invention, complex shapes such as plate shape, sphere shape, sheet shape, and the like are also possible. In addition, if the size is 10 μm or more, it can be firmly supported, and the photocatalyst-supported wood and the wood material of the present invention can be treated by processing the finished wood and wood materials such as furniture, woodworking, etc. It may be.
본 발명에 나타내는 광촉매를 담지한 목재 및 목질재료는 건축용재, 가구, 목공품, 인테리어재 및 내장제 등 항균, 탈취, 오염방지 등의 효과를 필요로 하는 많은 부문에서 사용할 수 있다.The wood and wood materials carrying the photocatalyst described in the present invention can be used in many fields that require effects such as antibacterial, deodorization, pollution prevention, such as building materials, furniture, woodwork, interior materials, and interior materials.
본 발명에 의한 광촉매 담지 구조체를 설치한 플라스틱 필름은, 그 오염방지, 항균, 탈취기능을 살려서 광촉매를 담지하고 있지 않는 면에 접착제를 도포한 필름으로 함으로써, 자동차나 각종 수송기기의 창유리, 건축물의 창유리, 냉동· 냉장 쇼 케이스나 온실 등의 내측에 붙일 수 있게 되어, 내부 공간의 미량 유해물질의 분해와 유리 표면의 오염방지와 파손시의 비산방지에 유효한 투시성이 높은 필름으로 할 수 있다. 또한, 얇은 플라스틱 필름에 본 발명에 따른 광촉매 담지 구조체를 막형성한 것은 식품 포장용 랩 필름으로서도 사용할 수 있다. 이 플라스틱 필름에 사용할 수 있는 수지로서는 폴리에틸렌테레프탈레이트수지, 폴리카보네이트수지, 폴리아크릴산에스테르수지, 폴리메틸메타크릴레이트수지, 폴리에틸렌수지, 폴리프로필렌수지, 폴리아미드수지, 폴리이미드수지, 폴리스티렌수지, 폴리염화비닐수지, 폴리불소화비닐리덴수지, 불소화에틸렌-프로필렌 공중합수지, 불소화에틸렌-에틸렌 공중합수지 등의 필름상으로 성형가공하였을 때에 550 ㎚ 파장의 광의 직선투과율이 50 % 이상인 투명성이 높은 합성수지필름 또는 시트를 모두 사용할 수 있다. 또한, 벽지나 화장시트 등의 이면에 점착층과 박리필름을 형성한 표면에 모양을 인쇄한 불투명한 소재의 표면에도, 본 발명에 따른 광촉매 담지 구조체는 투명하기 때문에, 기초 벽지나 화장시트에 인쇄된 무늬나 모양을 손상시키지 않으므로 바람직하게 채택할 수 있다.The plastic film provided with the photocatalyst supporting structure according to the present invention is made of a film coated with an adhesive on a surface which does not support the photocatalyst by utilizing its antifouling, antibacterial and deodorizing function, thereby making it suitable for window panes and buildings of automobiles and various transportation equipment. It can be attached inside window panes, refrigerated or refrigerated showcases, greenhouses, etc., and can be made into a highly transparent film effective for dissolving trace harmful substances in the interior space, preventing contamination of the glass surface and scattering during breakage. Moreover, what formed the photocatalyst carrying structure which concerns on this invention on the thin plastic film can also be used as a wrap film for food packaging. Resin which can be used for this plastic film is polyethylene terephthalate resin, polycarbonate resin, polyacrylic acid ester resin, polymethyl methacrylate resin, polyethylene resin, polypropylene resin, polyamide resin, polyimide resin, polystyrene resin, polychloride When molded into a film such as vinyl resin, polyvinylidene fluoride resin, fluorinated ethylene-propylene copolymer resin, or fluorinated ethylene-ethylene copolymer resin, a highly transparent synthetic resin film or sheet having a linear transmittance of 50% or more of light having a wavelength of 550 nm is used. All can be used. In addition, since the photocatalyst supporting structure according to the present invention is transparent on the surface of an opaque material having a shape printed on the surface on which the adhesive layer and the release film are formed on the back surface of a wallpaper or a makeup sheet, the photocatalyst supporting structure is printed on a basic wallpaper or a makeup sheet. Since it does not damage the pattern or the pattern, it can be preferably adopted.
이들 합성수지 필름 또는 시트는 그 표면에 표면처리를 실시하여 광촉매 담지 구조체의 접착층의 접착성을 더욱 향상시킬 수 있으므로, 점착층을 도포하는 면을 코로나방전처리나 UV-오존처리 등에 의하여 표면을 물리적으로 극미량 산화시키거나, 실리콘계 등의 표면처리제를 얇게 도포하여 접착층과의 상호관계를 좋게 한 것이 바람직하게 사용된다. 또한, 실시예에도 나타낸 바와 같이 이들 기초재의 표면 또는 이면에 열선반사·차폐기능이나 자외선반사·차폐기능을 부여하기 위한 박막을 형성할 수 있기 때문에, 오염방지, 항균, 냄새제거기능을 모두 가진 열선반사 필름이나 자외선차단 필름으로 할 수 있을 뿐만 아니라, 본 발명에 의한 광촉매 담지 구조체는 실시예에도 나타내는 바와 같이 매우 높은 내구성과 광촉매활성을 함께 구비한 것이므로 매우 부가가치가 높은 제품으로 할 수 있다.Since these synthetic resin films or sheets can be surface treated on the surface thereof to further improve the adhesion of the adhesive layer of the photocatalyst support structure, the surface on which the adhesive layer is applied is physically treated by corona discharge treatment or UV-ozone treatment. It is preferable to use extremely small amount of oxidation or to apply a thin surface treatment agent such as silicon to improve the mutual relationship with the adhesive layer. In addition, as shown in the examples, since a thin film for imparting heat ray reflection / shielding function or ultraviolet ray reflection / shielding function can be formed on the surface or the back side of these base materials, the heating wire having all the functions of preventing pollution, antibacterial and odor removal. Not only can it be a reflective film or a sunscreen film, but also the photocatalyst carrying structure by this invention is equipped with very high durability and photocatalytic activity as shown in the Example, and can be set as a very high value-added product.
상술한 열선반사기능을 부여하기 위한 방법으로서는 A1, Ag, Cu, Cr, Ni, Ti, 스테인레스강, 알루미늄합금 등의 도전성 금속이나 산화인듐, 산화주석, 산화주석-산화인듐 화합물 등의 도전성 금속산화물을 스패터나 진공증착 등의 물리적 방법으로 필름 표면에 막형성하는 방법, 도전성 금속산화물의 용액이나 졸 용액을 도포 건조하거나, 도금법이나 CVD 법에 의하여 필름의 표면에 막형성하는 방법, 기초재의 수지 중에 그들 열선반사 특성이나 열선차폐 특성을 가진 재료를 혼합시키는 방법 등 각종 방법을 채택할 수 있다. 또한, 자외선 차폐기능을 부여하는 방법으로서는 힌더드 아민계나 산화티탄 등의 자외선 흡수제나 반사제를 필름 표면에 도포하여 막형성하는 방법, 자외선 흡수제를 미리 필름의 기초재에 첨가 혼합하여 두는 방법 등, 각종 방법을 채택할 수 있으므로 사용목적과 구조에 맞게 적당한 방법을 선택할 수 있다. 자외선 차폐제나 반사제로서 산화티탄을 사용하는 경우에는, 본 발명에도 상세하게 기술한 바와 같이 산화티탄 단독으로는 광촉매 작용에 의하여 주위의 유기물이 분해되기 때문에, 산화티탄의 표면을 물유리 등으로 얇게 코팅하여 광촉매활성을 없앤 것을 사용하는 것이 바람직하다.As a method for imparting the above-described heat ray reflection function, conductive metal oxides such as A1, Ag, Cu, Cr, Ni, Ti, stainless steel, aluminum alloys, conductive metal oxides such as indium oxide, tin oxide, tin oxide and indium oxide compounds Is formed on the surface of the film by physical methods such as spatter or vacuum deposition, the method of coating and drying a solution of a conductive metal oxide or a sol solution, or forming a film on the surface of the film by plating or CVD, or resin of the base material. Various methods, such as the method of mixing the material which has those heat ray reflection characteristics or a heat ray shielding characteristic, can be employ | adopted. As a method of imparting a UV shielding function, a method of forming a film by applying a UV absorber or reflector such as a hindered amine or titanium oxide to the surface of the film, a method of adding and mixing the UV absorber to the base material of the film in advance, etc. Since various methods can be adopted, an appropriate method can be selected according to the purpose of use and structure. In the case where titanium oxide is used as the UV shielding agent or the reflecting agent, as described in detail in the present invention, since titanium oxide alone decomposes the surrounding organic matter by photocatalytic action, the surface of titanium oxide is lightly coated with water glass or the like. It is preferable to use what removes photocatalytic activity.
또한, 이들 열선반사기능을 가진 재료나 자외선 차폐기능을 가진 재료를 필름의 이면에 형성시키는 점착제층에 첨가 혼합하여 그 효과를 발현시킬 수도 있으며, 예를 들면 컨버테크 1996 년 3 월호 pp95 에 기재되어 있는 자외선 차폐 클리어코팅제 등의 재료가 용제 분산형이며 사용가능하다. 점착제로서는 통상 아크릴계나 실리콘계 등의 점착제가 사용되는데, 각종 자외선 차폐제나 열선차폐제를 점착제에 첨가할 수 있다. 이 점착제는 교체하여 붙일 때의 점착제의 잔존부착에 의한 오염을 고려하여 강고한 접착성을 가진 점착제의 사용을 피하는 것이 바람직하다. 점착제와 박리필름을 광촉매 담지필름에 형성하는 방법으로서는, 예를 들면 용액상의 점착제를 그라비아 인쇄에 의하여 필름 이면에 코팅한 후, 건조시켜 감을 때에 박리용 폴리플로필렌필름을 라미네이트하여 감는 방법도 간편하여 바람직하게 채용할 수 있다.In addition, it is also possible to express the effect by adding and mixing these materials having a heat ray reflection function or a material having an ultraviolet shielding function to the pressure-sensitive adhesive layer formed on the back side of the film, for example, described in the March 1996 issue of Convertech. Materials such as ultraviolet ray shielding clear coating agent are solvent dispersion type and can be used. As an adhesive, although adhesives, such as an acryl type and silicone type, are used normally, various ultraviolet shielding agents and a heat ray shielding agent can be added to an adhesive. It is preferable to avoid the use of a pressure-sensitive adhesive that is firm in consideration of contamination due to the remaining adhesion of the pressure-sensitive adhesive when the pressure-sensitive adhesive is replaced and pasted. As a method of forming the pressure-sensitive adhesive and release film on the photocatalyst supporting film, for example, a solution-type pressure-sensitive adhesive is coated on the back surface of the film by gravure printing, and then a method of laminating and winding the peeling polypropylene film for drying It is preferably employable.
이하, 실시예에 의하여 본 발명을 구체적으로 설명하나, 본 발명은 이들 실시예에 한정되는 것은 아니다.Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
<평가시험법><Evaluation test method>
1) 광촉매 활성의 평가1) Evaluation of Photocatalytic Activity
크기 70 ㎜ × 70 ㎜ 의 광촉매를 담지한 시료를 용적 4ℓ 의 파이렉스제 유리용기 중에 설치하였다. 이 용기 중에 공기와 알데히드의 혼합가스를 알데히드의 농도가 500 ppm 으로 되도록 첨가하였다. 담지 시료에 자외선 강도 2 ㎽/㎠ 의 블랙 라이트 (FL 15BL-B 마쓰시다덴끼(주)제) 의 빛을 2 시간 조사한 후, 용기 내부의 알데히드 가스 농도를 가스크로마토그래프로 측정하고, 그 감소량을 통해 광촉매 활성을 평가하였다. 평가기준은 다음과 같다.A sample carrying a photocatalyst having a size of 70 mm × 70 mm was placed in a 4 L glass container made of Pyrex. In this vessel, a mixed gas of air and aldehyde was added so that the concentration of aldehyde was 500 ppm. After irradiating the supported sample with a light of black light (FL 15BL-B Matsushita Denki Co., Ltd.) having an ultraviolet intensity of 2 mW / cm 2 for 2 hours, the concentration of the aldehyde gas in the container was measured with a gas chromatograph, Photocatalytic activity was evaluated. Evaluation criteria are as follows.
2 시간 조사후의 알데히드 가스 농도 평가Aldehyde gas concentration evaluation after 2 hours irradiation
50 ppm 이하 A50 ppm or less A
50 ∼ 200 ppm B50 to 200 ppm B
200 ∼ 300 ppm C200 to 300 ppm C
300 ∼ 450 ppm D300 to 450 ppm D
450 ppm 이상 E450 ppm or more E
2)부착성 평가2) adhesion evaluation
JIS K 5400 에 규정하는 바둑판눈금 테이프법 시험으로, 부착성의 평가를 실시하였다. 잘라낸 부분의 간격을 2 ㎜ 로 하고, 눈금의 수를 25 개로 하였다. 평가점수는, JIS K 5400 에 기재된 기준으로 실시하였다.The adhesiveness was evaluated by the checkerboard scale tape method test prescribed | regulated to JISK5400. The space | interval of the part cut out was 2 mm, and the number of graduations was 25 pieces. Evaluation score was performed based on the criteria described in JIS K5400.
3) 비등수중으로의 침지시험3) Immersion test in boiling water
도전율이 170 ∼ 230 μS/㎝ 의 범위의 수돗물을 1000 ㎖ 의 파이렉스유리제 비이커에 소량의 비누와 함께 넣고, 가열비등후에 70 ㎜ × 70 ㎜ 로 잘라낸 시료전체가 수중에 가라앉도록 시판되는 클립으로 매단다. 15 분간 비등수중에 침지한 후, 실온하에서 4 시간 방치하고 건조시킨 후에 2) 에 기재한 부착성 시험을 실시하여, JIS K5400 에 기재된 기준으로 평가점수를 구하였다.Tap water in the conductivity range of 170 to 230 μS / cm was put together with a small amount of soap in a 1000 ml Pyrex glass beaker, and the entire sample cut to 70 mm × 70 mm after heating was boiled with a commercially available clip. I will. After immersion in boiling water for 15 minutes, it was left to stand at room temperature for 4 hours, and after drying, the adhesion test as described in 2) was performed, and the evaluation score was calculated | required by the criteria of JISK5400.
4) 전광선 투과율4) total light transmittance
접착층 및 광촉매층을 담지하기 전의 담체를 기준으로 하여, 담지한 시료의 파장 550 nm 의 전광선 투과율을 자기 분광광도계 (히타찌세이사꾸쇼 (日立製作所 U-4000 형) 로 측정하였다.Based on the carrier before supporting the adhesive layer and the photocatalyst layer, the total light transmittance of wavelength 550 nm of the supported sample was measured with a magnetic spectrophotometer (Hitachi Seisakusho U-4000 type).
5) 내구성 평가5) durability rating
담지한 시료에 블랙라이트로 자외선 강도 3 mW/㎠ 의 빛을 온도 40 ℃, 상대습도 90 % 의 항온 항습조내에서 500 시간 조사한 후, 2)에 기재한 부착성 시험을 실시하여, JIS K5400 에 기재된 기준으로 평가점수를 구하였다.The supported sample was irradiated with black light at a UV intensity of 3 mW / cm 2 for 500 hours in a constant temperature and humidity chamber at a temperature of 40 ° C. and a relative humidity of 90%, and then subjected to the adhesion test described in 2). The evaluation score was calculated as a standard.
6) 선샤인 카본아크 웨더미터에 의한 촉진내후성 시험6) Accelerated weathering test by sunshine carbon arc weather meter
JIS K5400 에 규정된 선샤인 카본아크 웨더미터에 의한 촉진내후성 시험을, 스가시험기 (주) 제조의 WEL-SUN-HCH 형을 사용하여, 시험시간 500 시간, 블랙패널 온도 63 ℃, 120 분 사이클, 18 분간 강우 (降雨) 의 조건에서 실시하였다. 시료 3 장을 촉진내후성 시험을 실시한 후에, 팽창, 균열, 박리, 백화의 유무 및 표면의 변화를, 촉진내후성 시험을 실시하지 않은 원상시험편과 육안으로 비교하여, 다음의 평가기준으로 표명상태를 평가하였다.The accelerated weather resistance test by the sunshine carbon arc weather meter specified in JIS K5400 was carried out using the WEL-SUN-HCH type manufactured by Suga Tester Co., Ltd., and the test time was 500 hours, the black panel temperature was 63 ° C, 120 minutes cycle, 18 It carried out on the conditions of rain for a minute. After carrying out the accelerated weathering test of three samples, the presence or absence of swelling, cracking, peeling, whitening, and surface change were compared visually with the original test piece which had not undergone the accelerated weathering test. It was.
평가 판정기준Evaluation criteria
A : 시료 3 장 모두 변화가 확인되지 않음A: No change in all three samples
B : 시료 1 ∼ 2 장에 약간의 변화가 확인됨B: slight change was observed in 1 to 2 samples.
C : 시료 3 장 모두 약간의 변화가 확인되는 것, 혹은 시료 1 ∼ 2 장에 명확하게 큰 변화가 확인되는 것C: A slight change is observed in all three samples, or a big change is clearly seen in one or two samples.
또, 시험후에 2) 에 기재된 부착성 시험을 실시하여, JIS K5400 에 기재된 기준으로 평가점수를 구하였다.Moreover, after the test, the adhesion test of 2) was performed and evaluation score was calculated | required by the criterion described in JISK5400.
7) 항균성 평가 시험 방법7) Antimicrobial Evaluation Test Method
가로 세로 5 ㎝ 로 잘라낸 시료를 80 % 에탄올로 소독하고 150 ℃ 로 건조하여 멸균한 후, 미리 전배양과 희석을 행하여 멸균도를 105개/㎖ 로 조절해둔 대장균의 균액을 0.2 ㎖ 시료면에 적하하여 인큐베이터내에 셋팅한다. 블랙라이트 (15W × 2 개, 광원과의 거리 10 ㎝) 의 빛을 조사한 것, 형광등 (15W × 2 개, 광원과의 거리 10 ㎝) 의 빛을 조사한 것, 광조사를 전혀 실시하지 않은 것, 3 종의 광조사조건으로 각각 4 개의 시료를 셋팅한다. 소정 시간후 (1, 2, 3, 4 시간후) 에 시료를 꺼내고, 멸균생리식염수에 침지한 멸균거즈로 시료상의 균액을 닦아낸다. 닦아낸 멸균거즈를 10 ㎖ 의 멸균생리식염수에 넣고 충분히 교반한다. 이 상층 균액을 오토클레이브 멸균한 95 ㎜ø 의 샤알레 한천배지에 이식하고, 36 ℃ 24 hr 배양한 후 대장균의 콜로니수를 카운트한다. 대장균의 균액을 적하하여 인큐베이터에 넣을 때까지의 조작을 완전히 동일하게 한 시료를 동일한 방법으로 처리하여 대장균의 콜로니수를 카운트하여, 그 수치를 기준으로 하여 암흑시, 블랙라이트 조사시, 형광등 조사시의 각 시료의 소정시간후에 있어서의 생존율을 산출한다. 평가 기준은 이하의 기준에 의한다.Sterilized by 80% ethanol, sterilized by drying at 150 ℃ after sterilization of the sample cut to 5 cm in width and length, pre-cultivation and dilution to the sterilization degree of E. coli bacteria was adjusted to 10 5 / ㎖ in 0.2 ml sample surface It is dripped and set in an incubator. Irradiated with light of black light (15W × 2, 10 cm from the light source), irradiated with fluorescent light (15W × 2, 10 cm from the light source), irradiated with no light at all, Four samples are set under three kinds of light irradiation conditions. After a predetermined time (1, 2, 3, 4 hours later), the sample is taken out, and the bacterial solution on the sample is wiped off with sterile gauze dipped in sterile saline solution. The wiped sterilized gauze is placed in 10 ml of sterile saline solution and stirred well. The supernatant bacteria solution is transplanted into an autoclave sterilized 95-mm-shale agar medium, incubated for 24 hours at 36 ° C, and the colony count of E. coli is counted. When the E. coli bacteria were added dropwise and placed in the incubator, the samples were treated in the same manner, and the colony count of E. coli was counted. The survival rate after a predetermined time of each sample is calculated. Evaluation criteria are based on the following criteria.
4 시간후의 대장균의 잔존율 평가Residual rate evaluation of E. coli after 4 hours
20 % 이하 A20% or less A
20 % ∼ 40 % B20% to 40% B
40 % ∼ 60 % C40% to 60% C
60 % ∼ 80 % D60% to 80% D
80 % 이상 E80% or more E
8) 오염방지성 (유지분해활성) 의 평가8) Evaluation of pollution prevention activity
오염방지기능을 평가하는 지표로서, 표면에 부착하는 유지분을 어느정도 빨리 분해하는가를 측정하기 위해 리놀산을 주성분으로 하는 시판되는 샐러드오일을 사용하여 광촉매 구조체상에서의 분해량을 정량하였다. 가로 세로 5 ㎝ 로 잘라낸 광촉매 담지구조체의 표면에 종이로 얇게 샐러드오일을 1 ㎠ 당 0.1 ∼ 0.15 ㎎ 이 되도록 도포하였다. 도포량은 도포 전후의 중량을 정밀저울로 측정하여 구하였다. 시료를 시료표면에 있어서의 자외선강도가 3 mW/㎠ 가 되는 시료와 블랙라이트의 사이의 거리를 조절하고, 블랙라이트를 점등한 후, 경과시간과 중량감소량의 관계를 구하여, 소정시간후의 샐러드오일의 분해량을 측정하여 오염방지성의 지표로 하였다.As an indicator for evaluating the antifouling function, the amount of decomposition on the photocatalyst structure was quantified using commercially available salad oil containing linoleic acid as a main component to determine how quickly the oil adhered to the surface was decomposed. On the surface of the photocatalyst support structure cut out to 5 cm in width and thinly, paper was applied so that salad oil was 0.1 to 0.15 mg per cm 2. The coating amount was determined by measuring the weight before and after coating with a precision balance. After adjusting the distance between the sample and the black light whose ultraviolet intensity is 3 mW / cm 2 on the sample surface, turning on the black light, the relationship between the elapsed time and the weight loss amount is obtained, and the salad oil after a predetermined time The amount of decomposition was measured and used as an index of pollution prevention.
24 시간 광조사후의 샐러드오일 잔존율 평가Evaluation of Salad Oil Retention Rate After 24 Hours Irradiation
10 % 이하 A10% or less A
30 % ∼ 10 % B30%-10% B
50 % ∼ 30 % C50%-30% C
80 % ∼ 50 % D80% to 50% D
80 % 이상 E80% or more E
<실시예><Example>
담체의 재료로서, 다음의 것을 사용하였다.As the material of the carrier, the followings were used.
(TA) 플라이머 처리 폴리에스테르제 필름(TA) film made of polyester
(TB) 염화비닐제 필름(TB) vinyl chloride film
(TC) 소다라임제 유리판(TC) glass plate made of soda lime
(TD) 금속 알루미늄판(TD) metal aluminum plate
(TE) 고밀도 폴리에틸렌제 강(TE) high density polyethylene steel
(실의 굵기 0.2 ㎜, 망 눈금의 크기 0.6 ㎜)(The thickness of the thread 0.2mm, the size of the mesh scale 0.6mm)
(TF) 폴리프로필렌제 관(TF) polypropylene tube
(내경 30 ㎜, 외경 36 ㎜)(30 mm inside diameter, 36 mm outside diameter)
접착층중에 함유되는 폴리실록산은, 다음의 것을 사용하였다.As the polysiloxane contained in the adhesive layer, the following were used.
(PS-1) 실리콘 테트라 메톡시드 모노머 (신에쓰화학 제조)(PS-1) Silicon Tetramethoxide Monomer (manufactured by Shin-Etsu Chemical Co., Ltd.)
(PS-2) 폴리메톡시 실록산 (콜코트 제조 상품명 메틸 실리케이트 51)(PS-2) polymethoxy siloxane (Corcote trade name methyl silicate 51)
(PS-3) 폴리에톡시 실록산 (콜코트 제조 상품명 메틸 실리케이트 40)(PS-3) Polyethoxy siloxane (Corcote brand trade name methyl silicate 40)
접착층중에 함유하는 콜로이달 실리카로서, 다음의 것을 사용하였다.As colloidal silica contained in an adhesive layer, the following was used.
(KS-1) 쇼꾸바이가세이 제조 상품명 카탈로이드 SI-350, 입자직경 7 ∼ 9 nm(KS-1) Shokubai Kasei Co., Ltd. brand name Cataloid SI-350, particle diameter 7-9 nm
(KS-2) 닛산화학 제조 상품명 스노텍스 ST-XS, 입자직경 4 ∼ 6 nm(KS-2) Nissan Chemical brand name Snortex ST-XS, particle diameter 4-6 nm
폴리실록산 혹은 콜로이달 실리카를 도입하는 수지용액으로서는 다음의 것을 사용하였다.As the resin solution into which polysiloxane or colloidal silica was introduced, the followings were used.
(J-1) 실리콘 함유량 3 중량% 의 아크릴-실리콘수지 크실렌 용액(J-1) Acrylic-silicone resin xylene solution with 3% by weight of silicone
(J-2) 실리콘 함유량 10 중량% 의 아크릴-실리콘수지 크실렌 용액(J-2) Acryl-silicon resin xylene solution with 10% by weight of silicone
(J-3) 실리콘 함유량 20 중량% 의 아크릴-실리콘수지 에멀젼 수용액(J-3) 20% by weight of silicone-acrylic resin emulsion aqueous solution
(J-4) 실리콘 함유량 50 중량% 의 아크릴-실리콘수지 에멀젼 수용액(J-4) 50% by weight of silicone-acrylic resin emulsion aqueous solution
(J-5) 실리콘 함유량 10 중량% 의 폴리에스테르-실리콘수지 크실렌 용액(J-5) Polyester-silicone resin xylene solution with 10% by weight of silicone
(J-6) 아크릴수지 크실렌 용액(J-6) Acrylic Resin Xylene Solution
(J-7) 폴리에스테르 수지 크실렌 용액(J-7) polyester resin xylene solution
(J-8) 실리콘 함유량 3 중량% 의 에폭시-실리콘수지 메틸에틸케톤 용액(J-8) Epoxy-silicone resin methyl ethyl ketone solution containing 3% by weight of silicone
폴리실록산 혹은 콜로이달 실리카를 수지용액과 혼합, 농도조제하여, 접착층 형성용 용액을 얻었다. 접착층은 두께가 2 ㎛ 이하일 때 및 평판 이외의 형상일 때에는 디핑법으로, 2 ㎛ 이상의 막두께일 때이며 평판형상일 때에는 베이커 어플리케이터로 형성하였다. 특히 담체형상이, 관상 및 망상일 때에는, 디핑법으로 실시하였다. 접착층의 건조는 담체의 재질이 (TE), (TF) 의 경우 80 ℃ 에서, (TB) 의 경우 60 ℃ 에서, 그 이외에는 120 ℃ 에서 행하였다.Polysiloxane or colloidal silica was mixed with a resin solution and concentration-concentrated to obtain a solution for forming an adhesive layer. The contact bonding layer was formed by the dipping method when the thickness was 2 micrometers or less, and when it was a shape other than a flat plate, when it was a film thickness of 2 micrometers or more, and when it was flat plate shape, it was formed by the baker applicator. In particular, when the carrier shape was tubular and network, it was carried out by the dipping method. Drying of the adhesive layer was performed at 80 ° C in the case of (TE) and (TF), at 60 ° C in the case of (TB), and at 120 ° C.
광촉매에는 다음의 것을 사용하였다.The following were used for the photocatalyst.
(C-1) 산화티탄 미립자 (니혼아에로딜사 제조 상품명 P-25, 결정입자직경 27 ㎚)(C-1) Titanium oxide fine particles (Nihon Aerodil Co., Ltd. brand name P-25, crystal grain diameter 27nm)
(C-2) 산화티탄졸 (아세트산성 졸, 결정입자직경 10 ㎚)(C-2) titanium oxide sol (acetic acid sol, crystal grain diameter 10 nm)
(C-3) 산화티탄졸 (pH 9 의 약알칼리성 졸, 결정입자직경 20 ㎚)(C-3) Titanium oxide sol (weak alkaline sol of pH 9, crystal grain diameter 20 nm)
광촉매와 동시에 담지하는 금속산화물겔 혹은 금속수산화물겔은, 다음의 졸액을 건조하여 얻었다.The metal oxide gel or metal hydroxide gel supported simultaneously with the photocatalyst was obtained by drying the following sol solution.
(Z-1) 실리카졸 : 쇼꾸바이가세이 제조 상품명 카탈로이드 SI-30, 150 ℃ 건조후의 비표면적 180 ㎡/g(Z-1) Silica sol: trade name Cataloid SI-30 manufactured by Shokubai Chemical Co., Ltd., specific surface area after drying at 150 ° C 180 m 2 / g
(Z-2) 알루미나졸 : 닛산화학 제조 알루미나졸-200, 150 ℃ 건 조후의 비표면적 400 ㎡/g(Z-2) Alumina sol: Specific surface area after drying of Alumina sol-200 manufactured by Nissan Chemical Co., Ltd.
(Z-3) 지르코니아졸 : 닛뽕소다 제조 지르코니아 테트라부톡시드 (TBZR) 를 에탄올중에서 가수분해하고, 150 ℃ 에서 건조한 후 300 ∼ 500 ℃ 에서 가열처리한 후, 희석 아세트산수용액으로 해교한 것, 해교품 (解膠品) 을 다시 150 ℃ 에서 건조한 것의 비표면적은 50 ∼ 80 ㎡/g(Z-3) Zirconia sol: Nippon Soda-made zirconia tetrabutoxide (TBZR) was hydrolyzed in ethanol, dried at 150 ° C., heated at 300 to 500 ° C., and peptized with dilute acetic acid aqueous solution. The specific surface area of the dried product at 150 ° C. was 50 to 80 m 2 / g.
(Z-4) 산화니오브졸 : CBMM 사 제조 옥살산 니오브수용액을 10 % 암모니아수로 중화하고, 150 ℃ 에서 건조한 후 희석 아세트산 수용액으로 해교한 것, 해교품을 150 ℃ 에서 건조한 것의 비표면적은 60 ㎡/g(Z-4) Niobium oxide: The aqueous solution of niobium oxalate manufactured by CBMM was neutralized with 10% ammonia water, dried at 150 ° C., and peptized with a diluted acetic acid solution. The specific surface area of the dried product at 150 ° C. was 60 m 2 /. g
(Z-5) 실리콘 함유량 20 중량% 의 아크릴실리콘 수지 에멀젼 수용액(Z-5) 20% by weight of silicone acrylic resin emulsion aqueous solution
(Z-6) 실란커플링제 니혼유니커사 제조 트리 (β-메톡시에톡시) 비닐실란 (상품명 : A-172)(Z-6) Silane coupling agent Nihon Uniker Co., Ltd. tri (β-methoxyethoxy) vinyl silane (trade name: A-172)
상기 용액중에 산화티탄 광촉매를 분산시키고, 소정량의 계면활성제를 첨가하여 광촉매층 형성용 용액으로 하였다. 광촉매층은, 두께가 2 ㎛ 이하일 때 또는 담체형상이 평판 이외일 때는 디핑법으로, 담체가 평판이고 두께가 2 ㎛ 이상일 때는 바코터로 형성하였다. 광촉매층의 건조는, 접착층을 건조하는 것과 동일한 온도로 실시하였다.The titanium oxide photocatalyst was dispersed in the solution, and a predetermined amount of surfactant was added to form a solution for forming a photocatalyst layer. The photocatalyst layer was formed by a dipping method when the thickness was 2 m or less or when the carrier shape was other than a flat plate, and a bar coater when the carrier was a flat plate and the thickness was 2 m or more. Drying of the photocatalyst layer was performed at the same temperature as drying an adhesive layer.
이하, 상기 재료의 종류 또는 양, 두께, 막형성방법 등을 변경한 실시예 및 비교예의 조성과 얻어진 광촉매담지 구조체의 성능에 대하여 표 1 ∼ 4 에 정리하여 기술한다.Hereinafter, the composition of the Example and comparative example which changed the kind or quantity of the said material, thickness, a film formation method, etc., and the performance of the obtained photocatalyst support structure are put together in Tables 1-4.
실시예 1 ∼ 18 및 비교예 1 ∼ 4 에서는, 광촉매로서 (C-1) 에서 나타낸 니혼에어로딜사의 산화티탄 (P-25) 을 사용하였다. 그 결과를 표 1 에 나타냈다.In Examples 1-18 and Comparative Examples 1-4, Nippon Aerodyl Corporation titanium oxide (P-25) shown by (C-1) was used as a photocatalyst. The results are shown in Table 1.
*1 : 건조접착층중의 SiO2로서의 중량%* 1:% by weight of SiO 2 in the dry adhesive layer
*2 : 건조 광촉매층중의 금속산화물겔 혹은 금속수산화물겔의 중량%* 2: Weight% of metal oxide gel or metal hydroxide gel in dry photocatalyst layer
*3 : 두께는 측정할 수 없음* 3 Thickness cannot be measured
*4 : 초음파세정 10 분간후 탈리 없음* 4: No detachment after 10 minutes of ultrasonic cleaning
*5: 기판형상이 복잡하고 불투명하기 때문에 측정할 수 없음* 5: Unable to measure because substrate shape is complicated and opaque
*6: 광촉매층을 형성할 때 박리되었기 때문에 측정할 수 없음.* 6: It cannot be measured because it peeled when forming a photocatalyst layer.
비교예-1 은 접착층을 형성하지 않고 광접촉층을 담지한 경우로서, 광접촉층의 부착성이 전혀 없으며, 간단히 박리되어 버리거나, 내구성 시험후의 폴리에스테르 필름의 표면은, 광촉매작용에 의해 열화되어, 구멍 또는 균열이 관찰되었다.Comparative Example-1 is a case where the optical contact layer is supported without forming an adhesive layer, and there is no adhesion of the optical contact layer, and the surface of the polyester film after peeling off or the durability test is deteriorated by photocatalytic action. , Holes or cracks were observed.
실시예-1 ∼ -2 는 접착층에 아크릴-실리콘 수지 혹은 폴리에스테르-실리콘 수지를 사용한 경우로서, 광촉매층의 부착성은 양호하고, 또, 내구성도 좋았다.Examples-1 to -2 were cases where an acrylic-silicone resin or a polyester-silicone resin was used for the adhesive layer, and the adhesion of the photocatalyst layer was good and the durability was also good.
실시예-3 ∼ -12 는 접착층에 폴리실록산을 함유한 수지를 사용한 경우로서, 촉매활성은 양호하며, 부착성 및 내구성도 양호해졌다. 폴리실록산을 도입한 수지가, 아크릴-실리콘 수지 (실시예-3, 4, 5) 혹은 폴리에스테르-실리콘 수지 (실시예-9) 인 경우에도 내구성이 좋았다. 폴리실록산을 도입한 수지가, 아크릴수지 (실시예-7) 혹은 폴리에스테르수지 (실시예-12) 이어도 양호한 것이 얻어졌다.Examples 3 to -12 were cases where a resin containing polysiloxane was used as the adhesive layer, and the catalytic activity was good, and the adhesion and durability were also good. Durability was good also when resin into which polysiloxane was introduce | transduced was acrylic-silicone resin (Example-3, 4, 5) or polyester-silicone resin (Example-9). Even if the resin into which polysiloxane was introduce | transduced was acrylic resin (Example-7) or polyester resin (Example-12), the favorable thing was obtained.
이에 대하여, 비교예-2 에 나타내는 바와 같이, 접착층에 폴리실록산을 함유한 아크릴-실리콘 수지를 사용해도, 폴리실록산의 함유량이 70 중량% 가 되면, 광촉매층이 접착되지 않게 되어, 박리되어 버렸다.On the other hand, as shown in the comparative example-2, even when using the acrylic-silicone resin containing polysiloxane for an adhesive layer, when content of polysiloxane became 70 weight%, the photocatalyst layer did not adhere and it peeled.
실시예-13 ∼ -18 은 접착층에 콜로이달 실리카를 함유한 수지를 사용한 경우로서, 촉매활성, 부착성 및 내구성이 양호하였다. 특히, 콜로이달 실리카에, 입자직경이 미세한 것 (KS-2) 을 사용하고, 또한, 콜로이달 실리카를 도입한 수지가, 아크릴-실리콘 수지인 경우 (실시예-15, 16), 매우 양호한 것이 얻어졌다.Examples -13 to -18 were cases where resin containing colloidal silica was used as the adhesive layer, and the catalytic activity, adhesion and durability were good. Particularly, in the case where a fine particle diameter (KS-2) is used for colloidal silica and the resin into which colloidal silica is introduced is an acrylic-silicone resin (Examples 15 and 16), it is very good. Obtained.
이에 대하여, 접착층중의 콜로이달 실리카의 함유량이, 50 중량% 로 많게 한 경우 (비교예-3), 부착성 및 내구성이 급격히 악화되었다.In contrast, when the content of the colloidal silica in the adhesive layer was increased to 50% by weight (Comparative Example-3), the adhesion and durability deteriorated rapidly.
실시예-1 ∼ -18 에는 광촉매로서 (C-1) 에서 나타낸 니혼에어로딜사의 산화티탄 (P-25) 을 사용하고, 광촉매층에 복합화하는 금속산화물졸 혹은 금속수산화물졸에는 그 대부분에, 실리카졸을 사용하고 있는데, 모두 양호한 것이 얻어졌다. 실시예-8 과 -9 에 폴리에틸렌제의 망 혹은 폴리프로필렌제의 관에 담지한 결과를 나타냈는데, 광촉매활성, 부착성 및 내구성이 양호한 것이 얻어졌다. 광촉매층중의 실리카졸의 함유량을 30 중량% 로 감소시켜도 (실시예-6), 양호한 것이 얻어졌으나, 20 중량% 까지 감소시키면 (비교예-4), 부착성 및 내구성은 급격하게 악화되었다.Examples 1 to -18 use titanium oxide (P-25) of Nippon Aerodyl Co., Ltd. shown in (C-1) as the photocatalyst, and most of the metal oxide sol or metal hydroxide sol compounded in the photocatalyst layer is silica. Although sol was used, all of the favorable things were obtained. In Example 8 and -9, the result which supported on the polyethylene net or the polypropylene pipe was shown, but the thing with favorable photocatalytic activity, adhesiveness, and durability was obtained. Even if the content of the silica sol in the photocatalyst layer was reduced to 30% by weight (Example-6), good results were obtained. However, when the content of silica sol was reduced to 20% by weight (Comparative Example-4), the adhesion and durability rapidly deteriorated.
실시예-11 은 실리카졸 대신에, 알루미나졸을 사용한 경우로서, 실리카졸의 경우와 동일하게 양호한 것이 얻어졌다.Example-11 was the case where alumina sol was used instead of a silica sol, and the favorable thing similar to the case of a silica sol was obtained.
실시예-17 에 접착층 및 광촉매층의 두께를 각각 0.5 ㎛, 0.1 ㎛ 로 한 경우를 나타냈는데, 부착성 및 내구성은 양호하며, 광촉매활성도 막두께가 극히 얇음에도 불구하고 높은 값을 보였다.In Example-17, the thicknesses of the adhesive layer and the photocatalyst layer were set to 0.5 µm and 0.1 µm, respectively. The adhesion and durability were good, and the photocatalytic activity was high even though the film thickness was extremely thin.
실시예-19 ∼ 23 의 데이터는 표 2 에 나타내었다.The data of Examples-19 to 23 are shown in Table 2.
*1 : 건조접착층중의 SiO2로서의 중량%* 1:% by weight of SiO 2 in the dry adhesive layer
*2 : 건조광촉매층중의 금속산화물겔 또는 금속수산화물겔의 중량%* 2: Weight% of metal oxide gel or metal hydroxide gel in the dry photocatalyst layer
*3 : 알루미나졸과 실리카졸을 1 : 1 로 혼합한 균일 용액을 사용* 3: Use a homogeneous solution in which alumina sol and silica sol are mixed 1: 1.
*4 : 실리콘 함유량 3 중량% 의 에폭시-실리콘수지의 메틸에틸케톤 용액을 사용.* 4: The methyl ethyl ketone solution of the epoxy-silicone resin of 3 weight% of silicone content is used.
실시예-19 티타니아졸의 사용Example-19 Use of Titaniaazole
니혼에어로딜사의 미립자 산화티탄 (P-25) 대신에, 질산산성 티타니아졸 (산화티탄 함유량 12 중량%) 을, 쇼꾸바이가세이 (觸媒化成) 제조 실리카졸 (상품명 카탈로이드 SI-30) 을 PH 1.5 로 조절한 것에 첨가하여 분산시키고, 계면활성제를 첨가하여 광촉매층용 도포용액으로 하였다. 실시예-10 에 사용한 수지용액에 폴리메톡시실록산 (PS-2) 을 건조접착층 중의 SiO2함유량이 35 중량% 가 되도록 첨가한 용액을 조제하여 접착층용 용액으로 하였다.Instead of Nippon Aerodyl's fine particle titanium oxide (P-25), nitrate acid titanazole (titanium oxide content 12% by weight) was manufactured by Shokubai Chemical Co., Ltd. silica sol (trade name Cataloid SI-30). In addition to the thing adjusted to PH 1.5, it disperse | distributed, and surfactant was added and it was set as the coating solution for photocatalyst layers. Example -10 to prepare a solution of a SiO 2 content is added to the medium so as to have 35% by weight resin solution methoxy poly siloxane (PS-2) was a dried adhesive layer on the adhesive solution for use in the.
7 ㎝ × 7 ㎝ 로 잘라낸 두께 1 ㎜ 의 소다라임 유리기판에 접착층을 베이커 어플리케이터로, 광촉매층을 바코터를 각각 도포하였다. 건조온도는 상기의 실시예와 동일하게 하였다.On the soda-lime glass substrate of thickness 1mm cut out to 7 cm x 7 cm, the adhesive layer was apply | coated with the baker applicator, and the photocatalyst layer was apply | coated with the bar coater, respectively. The drying temperature was the same as in the above embodiment.
얻어진 광촉매 담지체는 전광선 투과율이 매우 높은 것이었다.The obtained photocatalyst carrier had a very high total light transmittance.
실시예-20 실리카-알루미나졸의 사용Example-20 Use of Silica-Alumina Sol
실시예-19 에서 사용한 실리카졸 대신에, 닛산화학공업 (주) 제조의 알루미나졸과 실리카졸의 50 : 50 혼합졸 용액을 사용한 것 이외에는, 실시예-19 와 완전히 동일한 원료와 방법으로, 광촉매 담지체를 제조하였다.Photocatalyst immersion was carried out in exactly the same manner as in Example-19, except that a 50:50 mixed sol solution of alumina sol and silica sol manufactured by Nissan Chemical Co., Ltd. was used instead of the silica sol used in Example-19. A delay was prepared.
얻어진 광촉매 담지체는 접착성, 촉매활성이 모두 높은 것이었다.The obtained photocatalyst carrier had high adhesiveness and catalytic activity.
실시예-21 그라비아 인쇄법에 의한 도포Example-21 Application by Gravure Printing
실시예-9 에 사용한 접착층 용액과 광촉매층 용액을 사용하여, 도요보우 (東洋紡) (주) 제조의 폴리에스테르필름 (코스모샤인 A4100) 에, 각각의 건조막두께가 3 ㎛ 가 되도록, 매분 10 m 의 속도, 건조존의 온도 130 ℃ 에서 그라비아 인쇄를 실시하였다. 인쇄에는 (주) 야스이세이끼 (康井精機) 제조의 마이크로 그라비아코터 (70 ㎝ 폭) 를 사용하였다.Using the adhesive layer solution and photocatalyst layer solution used in Example-9, each polyester film (Cosmoshine A4100) manufactured by Toyobo Co., Ltd. was 10 m per minute so that each dry film thickness might be 3 micrometers. Gravure printing was performed at the speed | rate of the and the temperature of a drying zone of 130 degreeC. A micro gravure coater (70 cm width) manufactured by Yasui Seiki Co., Ltd. was used for printing.
얻어진 광촉매 담지체의 전광선 투과율은 95 % 로 매우 높은 것이었다.The total light transmittance of the obtained photocatalyst carrier was very high at 95%.
실시예-22 스프레이법에 의한 도포Example-22 Application by Spray Method
실시예-9 에 사용한 접착층 용액과 광촉매층 용액을 사용하여, 소다라임 유리기판상에, 이와다 (岩田) 도장기공업 제조의 스프레이건 WIDER88 형을 사용하여 스프레이도포하였다. 접착층, 광촉매층은 모두 120 ℃ 에서 30 분간의 건조를 실시하였다.Using the adhesive layer solution and photocatalyst layer solution used in Example-9, it spray-sprayed on the soda-lime glass board | substrate using the spray gun WIDER88 type | mold by the Iwada coating machine industry. Both the adhesive layer and the photocatalyst layer were dried at 120 ° C. for 30 minutes.
얻어진 광촉매 담지체는 접착성, 광촉매활성이 모두 양호한 것이었다.The obtained photocatalyst carrier had good adhesiveness and photocatalytic activity.
실시예-23 에폭시-실리콘 수지의 사용Example-23 Use of Epoxy-Silicone Resin
실시예-12 에 있어서, 폴리에스테르수지 크실렌용액 대신에 실리콘 함유량 3 중량% 의 에폭시 수지의 메틸에틸케톤 용액을 사용한 것 이외에는, 동일한 원료와 동일한 방법으로, 광촉매담지체를 제조하였다.In Example-12, the photocatalyst carrier was manufactured by the same method as the raw material except having used the methyl ethyl ketone solution of the epoxy resin of 3 weight% of silicone content instead of the polyester resin xylene solution.
얻어진 광촉매담지체는 접착성, 광촉매활성이 모두 양호한 것이었다.The obtained photocatalyst carrier had good adhesiveness and photocatalytic activity.
이하의 실시예 24 ∼ 35 의 조성 및 성능시험결과는 표 3 에 나타내었다.The compositions and performance test results of Examples 24 to 35 are shown in Table 3.
*1 : 건조접착층중의 SiO2로서의 중량%* 1: Weight% as SiO 2 in the dry adhesive layer
*2 : 건조광촉매층중의 산화티탄 및 금속산화물겔 혹은 금속수산화물겔의 중량%* 2: Weight% of titanium oxide and metal oxide gel or metal hydroxide gel in the dry photocatalyst layer
*3 : 바둑판눈금 테이프법을 사용할 수 없기 때문에, 점착 테이프면을 실체현미경으로 관찰하였지만 광촉매층은 부착되어 있지 않았음* 3: Since the checkerboard scale tape method cannot be used, the surface of the adhesive tape was observed with a stereomicroscope, but the photocatalyst layer was not attached.
*4 : 형상이 이형이기 때문에 측정할 수 없음* 4: Measurement is impossible because the shape is deformed
*5 : 기판이 불투명하기 때문에 측정할 수 없음* 5: Unable to measure because substrate is opaque
*6 : 실시예 35 에서는 실리카-알루미나 성분이 미리 이 비율로 복합되어 있는 졸을 사용하였음.* 6: In Example 35, a sol in which the silica-alumina component was previously mixed in this ratio was used.
실시예-24 ∼ -25 는, 접착층에 아크릴-실리콘수지를 사용하여, 광촉매층으로서 니혼 에어로딜사의 미립자 산화티탄 (P-25) (C-1) 을 50 중량%, (Z-1) 에 나타낸 실리카졸을 25 중량%, (Z-2) 에 나타낸 알루미나졸을 25 중량% 함유하는 조성이 되도록 원료분말 및 졸액을 조제하여 얻어지는 복합체를 사용한 예로, 비등수시험후의 부착성은 양호하고, 내구성, 촉진내후성도 양호하였다.Examples-24 to -25 use 50% by weight of fine particle titanium oxide (P-25) (C-1) of Nippon Aerodil Co., Ltd. as a photocatalyst layer, using acrylic-silicone resin for the adhesive layer. An example of using a composite obtained by preparing a raw material powder and a sol solution so as to have a composition containing 25 wt% of the silica sol shown and 25 wt% of the alumina sol shown in (Z-2). The accelerated weather resistance was also good.
실시예-26 ∼ -31 은, 접착층에 폴리실록산을 함유한 수지를 사용하고, 광촉매층에는 실시예-26 부터 -28 에는 (C-1) 의 미립자 산화티탄을, 실시예 -29 ∼ -31 에는 (C-2) 의 타타니아졸을 사용하고, 복합화하는 겔을 형성시키기 위한 졸액의 종류와 양을 변경한 것으로, 촉매활성은 양호하고, 비등수시험후의 부착성, 내구성, 촉진내후성이 모두 양호하였다. 폴리실록산을 도입한 수지가 아크릴-실리콘수지 (실시예-26, -27, -28), 또는 에폭시-실리콘수지 (실시예-29, -30) 의 어느 것에서나, 비등수시험후의 부착성, 내구성, 촉진내후성은 양호하였다. 폴리실록산을 도입한 수지가, 아크릴수지 (실시예-31) 에서도 양호한 것이 얻어졌다.Examples-26 to -31 use a resin containing polysiloxane in an adhesive layer, and in Example -26 to -28, fine particle titanium oxide of (C-1) is used as a photocatalyst layer, and in Examples -29 to -31, The type and amount of the sol liquid for forming the gel to be complexed by using the tartanazole of (C-2) were changed, and the catalytic activity was good, and the adhesion, durability, and accelerated weather resistance after boiling water test were all good. It was. Adhesion and durability after the boiling water test in either of the acrylic-silicone resin (Example-26, -27, -28) or the epoxy-silicone resin (Example-29, -30) in which the polysiloxane was introduced , Accelerated weather resistance was good. The resin which introduce | transduced polysiloxane also obtained favorable thing in acrylic resin (Example-31).
실시예-32, -33 에는 폴리에틸렌제의 망 또는 폴리프로필렌제의 관에 담지한 결과를 나타냈는데, 광촉매활성, 부착성 및 내구성이 양호한 것이 얻어졌다.In Examples-32 and -33, the result of being supported on a polyethylene net or a polypropylene tube was shown, but a good photocatalytic activity, adhesion and durability were obtained.
실시예-32 ∼ -35 는 접착층에 콜로이달 실리카를 함유한 수지를 사용한 것으로, 촉매활성, 비등수시험후의 부착성, 내구성, 촉진내후성은 양호하였다. 특히, 콜로이달 실리카에, 미립경이 미세한 것 (KS-2)을 사용하고, 또한, 콜로이달 실리카를 도입한 수지가, 아크릴-실리콘수지의 에멀젼인 경우 (실시예-34, 35), 매우 양호한 것이 얻어졌다.Examples-32 to -35 used a resin containing colloidal silica as the adhesive layer, and showed good catalytic activity, adhesion after boiling water test, durability, and accelerated weather resistance. In particular, when a fine particle (KS-2) is used for colloidal silica and the resin into which colloidal silica is introduced is an emulsion of acrylic-silicone resin (Examples 34 and 35), very good Was obtained.
실시예-29 에서는, 광촉매층에 질산산성 티타니아졸 (산화티탄 함유량 12 중량%) 과 쇼꾸바이가세이 제조의 실리카졸 (상품명 카타로이드 SI-30) 및 닛산화학 제조의 알루미나졸-200 을 pH 1.5 로 조절하여 분산시키고, 소정량의 계면활성제를 더하여 광촉매층용 도포용액으로 딥법으로 접착층 및 광촉매층의 두께를 각각 0.5 ㎛, 0.3 ㎛ 로 한 경우를 나타냈는데, 부착성 및 내구성은 양호하고, 광촉매활성도 박막이 얇은 것에 비해서는 높은 값을 나타냈다.In Example-29, a nitrate-acid titania sol (titanium oxide content 12% by weight), a silica sol (trade name Cataroid SI-30) manufactured by Nippon Chemical Corporation, and alumina sol-200 manufactured by Nissan Chemical Co., Ltd. were prepared in a photocatalyst layer at pH 1.5. The thickness of the adhesive layer and the photocatalyst layer was 0.5 μm and 0.3 μm, respectively, by the dip method with a coating solution for the photocatalyst layer, by adding a predetermined amount of a surfactant and dispersing it. The thin film showed a higher value than the thin film.
광촉매층 중의 실리카졸과 알루미나졸의 합계의 합유량을 30 중량% 로 줄여도 (실시예-30) 양호한 것이 얻어졌다.Even if the total amount of the silica sol and the alumina sol in the photocatalyst layer was reduced to 30% by weight (Example-30), good results were obtained.
실시예-24, -35에서 얻어진 시료로, 고온고습하의 블랙라이트에 의한 내구성시험, 비등수침지시험, 선샤인 카본아크 웨더미터에 의한 촉진내후성시험에 사용한 시료를, 다시 광촉매활성을 초기와 동일한 방법으로 아세트알데히드의 광분해량에 의해 조사한 바, 어느 시료에서나 초기의 아세트알데히드 분해량과 완전히 동일한 분해활성을 나타내어, 초기의 광촉매활성을 완전히 유지하고 있는 것을 알 수 있었다.The samples obtained in Examples-24 and -35 were used for the durability test by the black light under high temperature and high humidity, the boiling water immersion test, and the accelerated weather resistance test by the sunshine carbon arc weather meter. According to the photodegradation amount of acetaldehyde, all samples showed the same decomposition activity as the initial acetaldehyde decomposition amount, indicating that the initial photocatalytic activity was completely maintained.
이하의 실시예 36 ∼ 53 의 조성 및 성능시험결과를 표 4, 표 5 에 나타냈다.The composition and the performance test result of the following Examples 36-53 were shown to Table 4 and Table 5.
*3 : 바둑판눈금 테이프법을 사용할 수 없기 때문에, 점착 테이프면을 실체현미경으로 관찰하였지만, 광촉매층은 부착되어 있지 않았음* 3: Since the checkerboard scale tape method cannot be used, the surface of the adhesive tape was observed under a stereomicroscope, but the photocatalyst layer was not attached.
*4 : 형상이 이형이기 때문에 측정할 수 없음* 4: Measurement is impossible because the shape is deformed
*5 : 기판이 불투명하기 때문에 측정할 수 없음.* 5: Measurement is not possible because the substrate is opaque.
비교예-5 는 접착층을 형성하지 않고 광촉매층을 담지한 경우로, 광촉매층의 부착성이 전혀 없고, 간단하게 박리될 뿐만아니라, 내구성시험후의 폴리에스테르필름의 표면은, 광촉매작용에 의해 열화되어, 구멍이나 균열이 실체현미경으로 관찰되었다.Comparative Example-5 is a case where the photocatalyst layer is supported without forming an adhesive layer. The adhesion of the photocatalyst layer is completely absent, the film is easily peeled off, and the surface of the polyester film after the durability test is deteriorated by the photocatalytic action. , Holes and cracks were observed by stereomicroscope.
실시예-36 ∼ -37 은, 접착층에 아크릴-실리콘수지를 사용하여, 광촉매층으로서 니혼 에어로딜사의 미립자 산화티탄 (P-25) 을 40 ∼ 50 중량%, (Z-1) 에 나타낸 실리카졸을 40 중량%, 아크릴실리콘수지 에멀젼을 10 ∼ 20 중량% 의 조성이 되도록 원료분말 및 졸액을 조제하여 얻어지는 복합체를 사용한 예로, 비등수시험후의 부착성은 양호하고, 내구성, 촉진내후성도 양호하였다.Examples-36 to -37 are silica sol represented by 40 to 50% by weight of particulate titanium oxide (P-25) of Nippon Aerodyl Co., Ltd. as a photocatalyst layer, using an acrylic-silicone resin as an adhesive layer. Is a composite obtained by preparing a raw material powder and a sol solution so as to have a composition of 40% by weight and 10-20% by weight of an acrylic silicone resin emulsion. The adhesion after the boiling water test was good, and the durability and the accelerated weather resistance were also good.
실시예-38 ∼ -42 는, 접착층에 폴리실록산을 함유한 아크릴-실리콘수지를 사용하고, 광촉매층에는 실시예-36 과 동일한 광촉매분말을 사용하여, 복합화하는 겔을 형성시키기 위한 졸액의 종류와 양을 바꾸어 사용한 것으로, 촉매활성은 양호하고, 비등수시험후의 부착성, 내구성, 촉진내후성이 모두 양호하였다. 폴리실록산을 도입한 수지가 실리콘함유량 3 % 의 아크릴-실리콘수지 (실시예-38, 39), 또는 실리콘함유량 10 % 의 아크릴-실리콘수지 (실시예-40, 41, 42) 의 어느 것에서나, 비등수시험후의 부착성, 내구성, 촉진내후성은 양호하였다.Examples-38 to -42 used an acrylic-silicone resin containing polysiloxane in the adhesive layer and the same photocatalyst powder as in Example-36 for the photocatalyst layer, and the type and amount of the sol solution for forming a gel to be complexed. The catalyst activity was good and the adhesion after the boiling water test, the durability and the accelerated weather resistance were all good. The resin in which the polysiloxane was introduced was either boiled in acrylic-silicone resin (Example-38, 39) with 3% silicon content or acrylic-silicone resin (Examples 40, 41, 42) with 10% silicon content. Adhesion, durability, and accelerated weather resistance after water tests were good.
실시예-44, -45 에는 폴리에틸렌제의 망 또는 폴리프로필렌제의 관에 담지한 결과를 나타냈는데, 광촉매활성, 부착성 및 내구성이 양호한 것이 얻어졌다.In Examples-44 and -45, the result of being supported on a polyethylene net or a polypropylene tube was shown. However, those having good photocatalytic activity, adhesion and durability were obtained.
폴리실록산을 도입한 수지가, 에폭시-실리콘수지 (실시예-43, 46), 또는 폴리에스테르수지 (실시예-44), 아크릴수지 (실시예-47) 에서도 양호한 것이 얻어졌다.Resin which polysiloxane was introduce | transduced also obtained favorable thing also in epoxy-silicone resin (Example-43, 46), polyester resin (Example-44), and acrylic resin (Example-47).
이에 대하여, 비교예-6 에 나타낸 바와 같이, 접착층에 폴리실록산을 함유한 아크릴-실리콘수지를 사용하여도, 폴리실록산의 함유량이 70 중량% 가 되면, 광촉매층이 접착하지 않게 되어 박리되어 버렸다.In contrast, as shown in Comparative Example-6, even when an acrylic-silicon resin containing polysiloxane was used as the adhesive layer, when the content of the polysiloxane was 70% by weight, the photocatalyst layer did not adhere and peeled off.
실시예-48 ∼ -53 은, 접착층에 콜로이달 실리카를 함유한 수지를 사용한 것으로, 촉매활성, 비등수시험후의 부착성, 내구성, 촉진내후성은 양호하였다. 특히, 콜로이달 실리카에, 미립경의 미세한 것 (KS-2) 을 사용하고, 또한, 콜로이달 실리카를 도입한 수지가, 아크릴-실리콘에멀젼수지인 경우 (실시예-50, ∼53), 매우 양호한 것이 얻어졌다.In Examples-48 to -53, resin containing colloidal silica was used as the adhesive layer, and the catalytic activity, adhesion after boiling water test, durability, and accelerated weather resistance were good. In particular, when the fine particle (KS-2) of the colloidal silica is used for the colloidal silica and the resin into which the colloidal silica is introduced is an acrylic-silicone emulsion resin (Examples 50 and 53), very good Was obtained.
이에 대하여, 접착중의 콜로이달 실리카의 함유량이, 50 중량% 로 많이 된 경우 (비교예-7), 부착성 및 내구성이 급격하게 나빠졌다.On the other hand, when content of the colloidal silica in adhesion | attachment increased to 50 weight% (comparative example-7), adhesiveness and durability fell rapidly.
실시예-44 ∼ -47 에서는, 광촉매층에 니혼에어로딜사의 미립자 산화티탄 (P-25) 대신, 질산산성 티타니아졸 (산화티탄 함유량 12 중량%) 과 쇼꾸바이가세이 (觸媒化成) 제조의 실리카졸 (상품명 카타로이드 SI-30) 및 닛산화학 제조의 알루미나졸-200, 또는 닛뽕소다 제조의 지르코니아졸을 PH 1.5 로 조절하여 분산시키고, 소정량의 계면활성제를 더하여 광촉매층용 도포용액으로 하여 바코드법으로 접착층 및 광촉매층을 형성한 경우를 나타냈는데, 부착성 및 내구성은 양호하고, 광촉매활성도 막두께가 얇은 것에 비해 높은 값을 나타냈다.In Examples-44 to -47, instead of Nippon Aerodyl's fine particle titanium oxide (P-25) in the photocatalyst layer, nitrate acid titanazole (titanium oxide content 12% by weight) and Shokubai Chemical Co., Ltd. Silica sol (trade name Cataloid SI-30) and Alumina sol-200 manufactured by Nissan Chemical Co., Ltd. or zirconia sol manufactured by Nippon Soda were adjusted to pH 1.5 and dispersed, and a predetermined amount of surfactant was added to form a coating solution for the photocatalytic layer. Although the adhesive layer and the photocatalyst layer were formed by the method, the adhesiveness and durability were favorable, and the photocatalytic activity also showed high value compared with the thin film thickness.
광촉매층 중의 아크릴-실리콘수지 에멀젼과 실란커플링제의 합계의 함유량을 20 중량% 로 줄여도 (실시예-47) 양호한 것이 얻어졌지만, 5 중량% 까지 줄이면 (비교예-8), 아크릴-실리콘에멀젼수지를 첨가하여도 부착성, 내구성은 급격하게 저하되었다.Even if the total content of the acrylic-silicone resin emulsion and the silane coupling agent in the photocatalyst layer was reduced to 20% by weight (Example-47), a good one was obtained. However, when the content was reduced to 5% by weight (Comparative Example-8), the acrylic-silicone emulsion resin Adhesion and durability dropped sharply even after addition.
실시예-36 ∼ -53 에서 얻어진 시료로, 고온고습하의 블랙라이트에 의한 내구성시험, 비등수침지시험, 선샤인 카본아크 웨더미터에 의한 촉진내후성시험에 사용한 시료를, 다시 광촉매활성을 초기와 동일한 방법으로 아세트알데히드의 광분해량에 의해 조사한 바, 어느 시료에 대해서나 초기의 아세트알데히드 분해량과 완전히 동일한 값을 나타내고, 초기의 광촉매활성을 완전히 유지하고 있는 것을 알 수 있었다.The samples obtained in Examples-36 to -53 were used for the durability test by black light under high temperature and high humidity, the boiling water immersion test, and the accelerated weather resistance test by Sunshine carbon arc weather meter. According to the photodegradation amount of acetaldehyde, all samples showed the same value as the initial acetaldehyde decomposition amount, and the initial photocatalytic activity was completely maintained.
실시예 - 54Example-54
실시예 42 에 사용한 것과 동일한 방법으로 산화티탄 광촉매구조체의 시료를 제조하고, 그 시료를 사용하여 항균성의 평가를 실시하였다.A sample of the titanium oxide photocatalyst structure was produced in the same manner as used in Example 42, and the antimicrobial activity was evaluated using the sample.
그 결과, 빛을 조사하지 않은 암소에 놓은 것에서는 대장균의 생존율이 1 시간후에 92 %, 2 시간후에 91 %, 3 시간후에 91 % 이었던 것에 대하여, 블랙라이트의 빛을 조사한 것에서는 1 시간후의 생존율이 52 %, 2 시간후에 29 %, 3 시간후에 11 % 이었다. 또, 형광등의 빛을 조사한 것에서도 대장균의 생존율은, 1 시간후에 76 %, 2 시간후에 54 %, 3 시간후에 22 % 이고, 암소에 놓은 광촉매구조체의 시료에 비하여 높은 항균성을 나타냈다.As a result, the survival rate of E. coli was 92% after 1 hour, 91% after 2 hours, and 91% after 3 hours in cows that had not been irradiated with light. 52%, 29% after 2 hours, and 11% after 3 hours. In addition, even when irradiated with a fluorescent lamp, the E. coli survival rate was 76% after 1 hour, 54% after 2 hours, and 22% after 3 hours, showing higher antimicrobial activity than the samples of photocatalyst structures placed in the dark.
광촉매의 도포액에 사용하는 실리콘화합물로서는 다음의 것을 사용하였다.The following were used as the silicone compound used for the coating liquid of a photocatalyst.
(S-1) 테트라에톡시실란 (와꼬쥰야꾸 (和光純藥) 제조의 시약특급) 의 5 중량% 의 에탄올용액(S-1) 5 wt% ethanol solution of tetraethoxysilane (Reagent Express manufactured by Wako Pure Chemical Industries, Ltd.)
(S-2) 테트라메톡시실란 (신에쓰가가꾸 (信越化學) 제) 의 5 중량% 의 에탄올용액(S-2) 5 wt% ethanol solution of tetramethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
(S-3) 메틸트리에톡시실란 (와꼬쥰야꾸제조의 시약특급) 의 5 중량% 의 에탄올용액(S-3) 5% by weight of ethanol solution of methyltriethoxysilane (Reagent Express manufactured by Wako Pure Chemical Industries, Ltd.)
(S-4) 트리(β-메톡시에톡시)비닐실란 (니혼유니카사제 : 상품명 : A-172) 의 5 중량%의 에탄올용액(S-4) 5% by weight of ethanol solution of tri (β-methoxyethoxy) vinylsilane (manufactured by Nippon Unicar Company, trade name: A-172)
(Z-1) 에서 (Z-3) 에 나타낸 졸용액, 및 실리콘화합물용액 중에 산화티탄 광촉매의 분말 또는 졸액을, 사용원료나 첨가물의 종류에 따라 pH 1.5 ∼ 9 의 적당한 범위로 조절하고, 용매로서 물 또는 물 - 에탄올의 혼합용매로 분산시키고, 소정량의 계면활성제를 더하여 광촉매층 형성용 도포액으로 하였다. 얻어진 광촉매층의 도포액에 함유되는 성분의 함유량, 도포액 조제직후 및 밀봉하여 90 일 경과후의 점도, 입자의 침강상태를 정리하여 표 6 에 나타냈다.The powder or sol solution of the titanium oxide photocatalyst in the sol solution shown in (Z-1) to (Z-3) and the silicon compound solution is adjusted to a suitable range of pH 1.5 to 9 depending on the type of the raw materials or additives used, and the solvent It was dispersed in water or a mixed solvent of water and ethanol, and a predetermined amount of surfactant was added to form a coating liquid for forming a photocatalyst layer. Table 6 summarizes the content of the components contained in the coating liquid of the obtained photocatalyst layer, the viscosity immediately after preparing the coating liquid and after sealing, and the settling state of the particles after 90 days.
주) 입자의 침강은 도포액의 전체적에 차지하는 침강부분의 체적이 차지하는 비율로 나타냄.Note) The sedimentation of the particles is expressed as the ratio of the volume of the sedimentation portion to the total coating liquid.
*1 : 건조후의 도포액에 차지하는 중량 백분율로 나타냄.* 1: Shown as the weight percentage of the coating liquid after drying.
실시예-55 ∼ -57 은, 광촉매에 산화티탄분말 (p-25) 을 사용한 예로, 미량의 실리콘화합물의 첨가로 90일 경과후의 광촉매 도포액의 안정성이 매우 좋아졌다.Examples-55 to -57 used titanium oxide powder (p-25) as a photocatalyst, and the stability of the photocatalyst coating liquid after 90 days was very improved by addition of a trace amount of a silicon compound.
실시예-58 ∼ -60 은, 광촉매에 질산산성 티타니아졸을 사용하고, 또한 실시예-59, -60 에서는 복합화하는 금속산화물의 졸로서 실리카졸과 알루미나졸을 병용하여 실리콘화합물로서 메틸트리에톡시실란을 사용한 것이다. 이로써 이 도포액을 사용하여 막형성한 코팅품의 내비등수성, 특히 수돗물 중에서의 내비등수성을 훨씬 향상시키는 것이 가능해졌다. 실시예-61 ∼ -62 는, 실리콘화합물로서 테트라메톡시실란을 사용했으므로, 첨가량은 적어도 액의 안정성을 유지하는 효과를 내는 것이 가능하였다.Examples-58 to -60 use nitrate-acid titania sol as a photocatalyst, and in Examples-59 and -60, methyltriethoxy is used as a silicon compound by using a combination of silica sol and alumina sol as a sol of a metal oxide to be complexed. Silane was used. This made it possible to further improve the boiling resistance, particularly the boiling resistance in tap water, of the coating article formed using the coating liquid. Since Examples 4-61-62 used tetramethoxysilane as a silicone compound, the addition amount was able to exhibit the effect which maintains stability of a liquid at least.
실시예-63 은, 광촉매로서 분말상의 산화티탄 (P-25) 과 질산산성 티타니아졸을 병용한 것으로, 복합화화는 금속산화물졸로서는 실리카졸과 지르코니아졸을 병용하고, 테트라메톡시실란을 첨가함으로써 도포액의 안정성과 침강성이 좋은 것으로 할 수 있었다.Example-63 is a combination of powdered titanium oxide (P-25) and nitrate acid titania sol as a photocatalyst, and the compounding is performed by using a combination of silica sol and zirconia sol as a metal oxide sol, and adding tetramethoxysilane. The stability and settling property of the coating liquid were good.
실시예-64 ∼ -66 은, 실리콘화합물의 종류를 변경하여 도포액을 조제한 것으로, 모두 소정의 첨가량에 의해 안정된 도포액이 되었다.Examples-64 to -66 changed the type of silicone compound to prepare a coating liquid, and all of them became stable coating liquids by a predetermined addition amount.
이에 대하여, 비교예-9 ∼ -13 에서는, 모두 실리콘화합물을 첨가하고 있지 않기 때문에, 90 일 경과후에는 도포액의 점도가 매우 증가하거나, 입자의 침강이 반드시 일어나 도포액으로 사용하는 경우, 막형성조건의 콘트롤이 곤란하여 일정품질의 광촉매 코팅품을 얻을 수 없었다.On the other hand, in Comparative Examples 9 to -13, since no silicone compound was added, the viscosity of the coating liquid was greatly increased after 90 days, or the sedimentation of particles necessarily occurred and the film was used as a coating liquid. It was difficult to control the formation conditions, and thus a photocatalyst coating product of a certain quality could not be obtained.
<실시예 67 ∼ 71><Examples 67-71>
실시예-55 ∼ -59 에서 조제한 광촉매 도포액을 사용하여, 광촉매 코팅품을 하기의 담체를 사용하여 제조하였다. 담체의 재료로서는, 다음의 것을 사용하였다.Using the photocatalyst coating liquid prepared in Examples-55 to -59, the photocatalyst coating product was manufactured using the following carrier. As a material of a support | carrier, the following was used.
(SA) 플라즈마처리 폴리에스테르필름(SA) Plasma Treated Polyester Film
(SB) 소다라임제 유리판(SB) glass plate made of soda lime
(SC) 금속알루미늄판(SC) Metal Aluminum Plate
(SD) 고밀도 폴리에틸렌제 망(SD) High density polyethylene net
(실의 굵기 0.2 ㎜, 망 눈금의 크기 0.6 ㎜)(The thickness of the thread 0.2mm, the size of the mesh scale 0.6mm)
(SE) 폴리프로필렌제 관 (내경 30 ㎜, 외경 36 ㎜)(SE) Polypropylene tube (30 mm inner diameter, 36 mm outer diameter)
접착층은 두께를 2 미크론 이하로 할 때나 담체형상이 평판이외일 때에는 디핑법으로, 담체가 평판으로 두께를 2 미크론 이상으로 할 때에는, 베이커 어플리케이터에 의해 형성하였다. 접착층의 건조는, 담체의 재질이 (SD), (SE) 의 경우 80 ℃에서, 그 이외는 120 ℃에서 실시하였다. 광촉매층은, 두께를 2 미크론 이하로 할 때나 담체형상이 평판이외일 때에는, 디핑법으로, 담체가 평판으로 두께를 2 미크론 이상으로 할 때는, 바코더로 형성하였다. 광촉매층의 건조는, 접착층을 건조하는 것과 동일한 온도로 실시하였다. 이하, 상기 재료의 종류나 양, 도포막의 두께, 막형성방법 등을 변경한 실시예 및 비교예의 광촉매 담지구조체의 성능에 대하여 표 7 및 표 8 에 정리하여 기술한다.The adhesive layer was formed by a baker applicator when the thickness was 2 microns or less, or when the carrier was out of a flat plate by a dipping method, and when the carrier was a flat plate by 2 microns or more. Drying of the contact bonding layer was performed at 80 degreeC in the case of the material of (SD) and (SE) at 120 degreeC other than that. The photocatalyst layer was formed by a dipping method when the thickness was 2 microns or less or when the carrier shape was other than the flat plate, and when the carrier was 2 microns or more by the flat plate, the barcoder was formed. Drying of the photocatalyst layer was performed at the same temperature as drying an adhesive layer. Hereinafter, the performance of the photocatalyst support structure of the Example and the comparative example which changed the kind and quantity of the said material, the thickness of a coating film, the film formation method, etc. is put together in Table 7 and Table 8, and it describes.
*1 : 도포액중의 수지 고형분의 농도* 1: Concentration of resin solids in the coating liquid
*2 : 도포액중의 고형분으로서의 농도* 2: Concentration as a solid content in the coating liquid
*3 : 바둑판눈금 테이프법을 사용할 수 없기 때문에, 점착 테이프면을 실체현미경으로 관찰하였지만, 광촉매층은 부착되어 있지 않았음* 3: Since the checkerboard scale tape method cannot be used, the surface of the adhesive tape was observed under a stereomicroscope, but the photocatalyst layer was not attached.
*4 : 형상이 이상하기 때문에 측정할 수 없음.* 4: Measurement is impossible due to abnormal shape.
*5 : 기판이 불투명하기 때문에 측정할 수 없음.* 5: Measurement is not possible because the substrate is opaque.
*6 : 평가하지 않음.* 6: Not evaluated.
실시예-67 ∼ -71에서 얻은 시료로, 고온고습하의 블랙라이트에 의한 내구성시험, 비등수 침지시험, 선샤인 카본아크 웨더미터에 의한 촉진내후성시험에 사용한 시료를, 다시 광촉매활성을 초기와 동일한 방법으로 아세트알데히드의 광분해량에 의해 조사한 바, 어느 시료에 대해서나 초기의 아세트알데히드 분해량과 완전히 동일한 값을 나타내고, 초기의 광촉매활성을 완전히 유지하고 있는 것을 알 수 있었다.The samples obtained in Examples-67 to -71 were used for the durability test by black light under high temperature and high humidity, the boiling water immersion test, and the accelerated weather resistance test by sunshine carbon arc weather meter. According to the photodegradation amount of acetaldehyde, all samples showed the same value as the initial acetaldehyde decomposition amount, and the initial photocatalytic activity was completely maintained.
실시예-72Example-72
실시예 67 에 사용한 것과 동일한 방법으로 산화티탄 광촉매 구조체의 시료를 제조하고, 그 시료를 사용하여 상기의 방법으로 항균성의 평가를 실시하였다. 그 결과, 빛을 조사하지 않은 암소에 놓은 것에서는 대장균의 생존율이 1 시간후에 92 %, 2 시간후에 91 %, 3 시간후에 91 % 이었던 것에 대하여, 블랙라이트의 빛을 조사한 것에서는 1 시간후의 생존율이 52 %, 2 시간후에 29 %, 3 시간후에 11 % 이었다. 또, 형광등의 빛을 조사한 것에서도 대장균의 생존율은, 1 시간후에 76 %, 2 시간후에 54 %, 3 시간후에 22 % 이고, 암소에 놓은 광촉매구조체의 시료에 비하여 높은 항균성을 나타냈다.A sample of a titanium oxide photocatalyst structure was produced in the same manner as used in Example 67, and the sample was used to evaluate antimicrobial activity. As a result, the survival rate of E. coli was 92% after 1 hour, 91% after 2 hours, and 91% after 3 hours in cows that had not been irradiated with light. 52%, 29% after 2 hours, and 11% after 3 hours. In addition, even when irradiated with a fluorescent lamp, the E. coli survival rate was 76% after 1 hour, 54% after 2 hours, and 22% after 3 hours, showing higher antimicrobial activity than the samples of photocatalyst structures placed in the dark.
<실시예 73> 점착가공필름<Example 73> Adhesive processed film
실리콘함량 3 중량% 의 아크릴-실리콘수지를 25 중량% 함유하는 크실렌-이소프로판올 (50/50) 용액에, 폴리실록산 (콜코트(주) 제 메틸실리케이트 51) 을 아크릴-실리콘수지에 대하여 30 중량%, 및 경화제 (실란커플링제) 를 아크릴-실리콘수지에 대하여 5 중량% 혼합하여 얻은 접착층용액을, 메틸에틸케톤용매로 고형분함유량 10 중량% 가 되도록 희석하였다.To a solution of xylene-isopropanol (50/50) containing 25% by weight of an acrylic-silicone resin containing 3% by weight of silicone, polysiloxane (methyl silicate 51 manufactured by Colcot Co., Ltd.) was 30% by weight with respect to acrylic-silicone resin, And the adhesive layer solution obtained by mixing 5 weight% of hardening | curing agents (silane coupling agent) with respect to the acryl- silicone resin was diluted in methyl ethyl ketone solvent so that solid content might be 10 weight%.
이 희석용액을 (주) 야스이세이끼 제조의 마이크로그라비아코터 (70㎝ 폭) 에 의해, 도요보우 (주) 제조의 폴리에스테르필름 (코스모샤인 50㎛) A4100 에, 건조막두께가 1 μ 가 되도록 매분 15 m 의 속도, 건조 존의 온도 130 ℃에서 그라비아 인쇄를 실시하였다.The dilution solution was applied to a polyester film (Cosmoshine 50 µm) A4100 manufactured by Toyobo Co., Ltd. using a microgravure coater (70 cm width) manufactured by Yasui Seiki Co., Ltd., so that the dry film thickness was 1 μ. Gravure printing was performed at the speed of 15 m per minute, and the temperature of a drying zone of 130 degreeC.
다음에 이 접착층을 형성시킨 폴리에스테르필름에, 광촉매층으로서 산화티탄 함유량 20 중량% 의 질산산성 티타니아졸을, 산화규소 함유량 20 % 의 질산산성 실리카졸 중에 계면활성제의 존재하에 분산시킨 후, 이온교환수 - 에탄올 (50/50) 로 희석하고, 고형분 함유량 10 중량% 의 광촉매층의 도포액으로 한 용액을 사용하여 접착층과 동일하게 그라비아 인쇄를 실시하여, 건조막두께 1 μ 의 광촉매층을 형성시킨 폴리에스테르필름을 얻었다.Next, in the polyester film in which this adhesive layer was formed, as a photocatalyst layer, 20 weight% of titanium oxide nitrate titania sol was disperse | distributed in the presence of surfactant in silicon oxide content 20% nitrate silicate sol, and then ion-exchange Gravure printing was carried out in the same manner as the adhesive layer using a solution diluted with water-ethanol (50/50) and a coating solution of a photocatalyst layer having a solid content of 10% by weight, to form a photocatalyst layer having a dry film thickness of 1 mu. A polyester film was obtained.
이어서, 이 광촉매 담지구조체로한 폴리에스테르필름의 광촉매를 도포되어 있지 않은 면에, 동일하게 그라비아 인쇄법으로 시판의 아크릴계 점착제에, 스미또모 오오사카 시멘트(주) 제조의 열선차폐 코팅제 STS-500 을 고형분으로서 5 % 가 되도록 첨가혼합한 용액을 도포하였다. 이 점착제 도포필름은 그라비아 인쇄기의 건조존으로 건조하여 감을 때에, 도요보우 (주) 제조의 폴리프로필렌필름 (파이렌필름-OT20㎛) P-2161 를 라미네이트하여 감고, 점착가공된 부착용 필름으로 하였다.Subsequently, on the surface to which the photocatalyst of the polyester film which made this photocatalyst support structure was not apply | coated, the heat-shielding coating agent STS-500 by Sumitomo Osaka Cement Co., Ltd. made by the gravure printing method was similarly applied, and solid content The mixed solution was applied so as to be 5%. When this adhesive coating film was dried and wound by the dry zone of a gravure printing machine, it was laminated by winding the polypropylene film (Pyrene film-OT20micrometer) P-2161 by Toyobo Co., Ltd., and it was set as the adhesion film which carried out adhesive processing.
이 필름은 자동차 창유리, 일반가정의 창유리, 의료시설의 창유리등에 붙이는 점착제 부착의 필름으로서, 그의 항균, 오염방지, 냄새제거 작용을 활용할 수 있는 데다가, 유리의 파손시의 비산방지 필름으로서도 이용할 수 있었다.This film is a self-adhesive film attached to automobile window glass, general home window glass, and medical facility window glass, and its antimicrobial, antifouling, and odor removing effect can be utilized as well as shatterproof film in case of glass breakage. .
실시예 74 판유리Example 74 Plate Glass
5 ㎝ × 5 ㎝ 로 잘라낸 두께 1 ㎜ 의 소다라임 유리에, 실리콘 함량 3 중량% 의 아크릴-실리콘수지를 25 중량% 함유하는 크실렌-이소프로판올 (50/50) 용액에 폴리실록산 (콜코트(주) 제 메틸실리케이트 51) 을 아크릴-실리콘수지에 대하여 30 중량% 혼합한 용액을 No.7 의 바코더로 도포하여 100 ℃에서 60 분 건조하여 접착층으로 하였다. 실온하에서 방냉후, 광촉매층으로서 산화티탄 함유량 20 중량% 의 질산산성 티타니아졸을 산화규소 함유량 20 % 의 질산산성 실리카졸 중에, 계면활성제의 존재하에 분산시켜 광촉매층의 도포용액으로 하였다. 이 용액을 사용하여, 동일하게 No.7 의 바코더로 상기 접착층의 표면에 도포하고, 100 ℃에서 60 분 건조하여 광촉매 담지유리로 하였다. (샘플 1)Polysiloxane (Corco Co., Ltd. product) was made into the 1-mm-thick soda-lime glass cut out to 5 cm x 5 cm, and the xylene-isopropanol (50/50) solution which contains 25 weight% of acrylic-silicone resin of 3 weight% of silicone content. A solution in which 30% by weight of methyl silicate 51) was mixed with an acrylic-silicone resin was applied with a bar coder No. 7, dried at 100 ° C. for 60 minutes to obtain an adhesive layer. After allowing to cool at room temperature, a 20% by weight titanium nitrate titania sol having a titanium oxide content of 20% as a photocatalyst layer was dispersed in a 20% silicon oxide content in the presence of a surfactant to prepare a coating solution for the photocatalyst layer. Using this solution, it applied similarly to the surface of the said contact bonding layer by the bar coder of No. 7, It dried at 100 degreeC for 60 minutes, and was made into the photocatalyst carrying glass. (Sample 1)
실시예 75 유리섬유 종이Example 75 Fiberglass Paper
실시예 74 에서 사용한 접착층용액을 크실렌-이소프로판올 (50/50) 용액으로 고형분 함유량 5 중량% 가 되도록 희석하였다. 이 희석용액에 올리베스트(주) 제 E-유리제 유리섬유 종이 SAS-030 (단위면적당 중량 30 g/㎡) 을 침지하여 꺼내 정치한 후, 100 ℃에서 120 분 건조하여 유리섬유 종이의 표면에 접착층을 형성시켰다. 다음에 이 접착층을 형성시킨 유리섬유 종이를, 실시예 74 에서 사용한 광촉매층의 도포용액을 이온교환수로 10 중량% 로 희석한 용액에 침지하여 꺼내 동일하게 100 ℃에서 120 분 건조하여 광촉매 담지유리 섬유 종이로 하였다.(샘플 2)The adhesive layer solution used in Example 74 was diluted with the xylene-isopropanol (50/50) solution so that it might become 5 weight% of solid content. The dilution solution was immersed in an aliquot E-glass glass fiber paper SAS-030 (weight 30 g / m 2 per unit area), and then left to stand, and dried at 100 ° C. for 120 minutes to form an adhesive layer on the surface of the glass fiber paper. Was formed. Next, the glass fiber paper on which this adhesive layer was formed was immersed in a solution diluted with 10% by weight of ion-exchanged water in a solution of the photocatalyst layer used in Example 74, and then dried at 100 ° C. for 120 minutes to carry out the photocatalyst supported glass. Fiber paper was used. (Sample 2)
실시예 76 안경렌즈Example 76 Glasses Lens
(주)니콘제 안경용 렌즈 PC 포인탈코트 TC (+) 1.00 S 0.00 65 ㎜ψ 에, 실리콘함량 3 중량% 의 아크릴-실리콘수지를 10 중량% 함유하는 크실렌-이소프로판올 (50/50) 용액에 폴리실록산 (콜코트(주) 제 메틸실리케이트 51) 을 아크릴-실리콘수지에 대하여 20 중량% 혼합하여 조제한 용액을 사용하여, 실시예 75 와 동일한 침지법으로 접착층을 형성시키고, 100 ℃에서 20 분 건조하였다. 실온하 방냉후, 광촉매층으로서 산화티탄 함유량 5 % 의 질산산성 티타니아졸을 산화규소 함유량 5 % 의 질산산성 실리카졸 중에, 계면활성제의 존재하에서 분산시켜 광촉매층의 도포용액으로 하였다. 이 용액을 사용하여, 동일하게 침지법으로 상기 접착층의 표면에 광촉매층을 도포하고, 100 ℃에서 20 분 건조하여 광촉매 코팅 안경용 렌즈로 하였다.(샘플 3)Polysiloxane in a solution of xylene-isopropanol (50/50) containing 10 wt% of a silicone-containing 3 wt% acrylic-silicone resin in a lens PC pointal coat TC (+) 1.00 S 0.00 65 mm ψ made by Nikon Corporation Using a solution prepared by mixing 20 wt% of (Colcote Co., Ltd. methyl silicate 51) with respect to an acrylic-silicone resin, an adhesive layer was formed by the same immersion method as in Example 75, and dried at 100 ° C for 20 minutes. After cooling to room temperature, as a photocatalyst layer, a 5% nitric acid titanate containing titanium oxide was dispersed in a nitric acid silicate containing 5% silicon oxide in the presence of a surfactant to prepare a coating solution for the photocatalyst layer. Using this solution, the photocatalyst layer was applied to the surface of the adhesive layer in the same manner by dipping, and dried at 100 ° C. for 20 minutes to give a photocatalyst coated lens.
실시예 77 폴리염화비닐벽지Example 77 Polyvinyl Chloride Wallpaper
5 ㎝ × 5 ㎝ 로 잘라낸 두께 1 ㎜ 의 (주) 산게쓰제 SG5328 폴리염화비닐벽지에, 실리콘함량 3 중량% 의 아크릴-실리콘수지를 25 중량% 함유하는 크실렌-이소프로판올 (50/50) 용액에 폴리실록산 (콜코트(주) 제 메틸실리케이트 51) 을 아크릴-실리콘수지에 대하여 30 중량% 혼합한 용액을 No.7 의 바코더로 도포하여 100 ℃에서 20 분 건조하여 접착층으로 하였다. 실온하에서 방냉후, 광촉매층으로서 산화티탄 함유량 20 중량% 의 질산산성 티타니아졸을 산화규소 함유량 20 % 의 질산산성 실리카졸 중에, 계면활성제의 존재하에서 분산시켜 광촉매층의 도포용액으로 하였다. 이 용액을 사용하여, 동일하게 No.7 의 바코더로 상기 접착층의 표면에 도포하고, 100 ℃에서 20 분 건조하여 광촉매담지 벽지를 얻었다.(샘플 4)Polysiloxane in a xylene-isopropanol (50/50) solution containing 25% by weight of a silicon-containing SG5328 polyvinyl chloride wall paper cut to a size of 5 cm × 5 cm, SG5328 polyvinyl chloride, containing 25% by weight of an acrylic-silicone resin containing 3% by weight of silicon. A solution obtained by mixing 30% by weight of (Methyl Silicate 51 manufactured by Cole Coat Co., Ltd.) with respect to an acrylic-silicone resin was applied by a bar coder No. 7, dried at 100 ° C. for 20 minutes to obtain an adhesive layer. After allowing to cool at room temperature, a 20% by weight titanium nitrate titania sol having a titanium oxide content of 20% by weight was dispersed in a 20% silicon oxide nitrate-based silica sol as a photocatalyst layer to prepare a coating solution for the photocatalyst layer. Using this solution, it applied similarly to the surface of the said contact bonding layer by the bar coder of No. 7, and dried at 100 degreeC for 20 minutes, and obtained the photocatalyst supporting wallpaper. (Sample 4)
실시예 78 폴리에스테르필름Example 78 Polyester Film
실시예 77 에서 사용한 접착층용액을 크실렌-이소프로판올 (50/50) 용액으로 고형분 함유량 25 중량%가 되도록 희석하였다. 이 희석용액을 (주) 야스이세이끼 제조의 마이크로그라비아 코터 (70 ㎝ 폭) 에 의해, 도요보우 (주) 제조의 폴리에스테르필름 (코스모샤인) A4100 에, 건조막두께가 3μ 가 되도록 매분 10 m 의 속도 건조존의 온도 130 ℃에서 그라비아 인쇄를 하였다. 다음에 이 접착층을 형성시킨 폴리에스테르필름에, 실시예 77 에서 사용한 광촉매층의 도포용액을 사용하여 동일하게 그라비아 인쇄를 실시하고, 건조막두께 3μ 의 광촉매층을 형성시킨 폴리에스테르필름을 얻었다.(샘플 5)The adhesive layer solution used in Example 77 was diluted with xylene-isopropanol (50/50) solution so as to have a solid content of 25% by weight. This dilution solution was used for 10 minutes per minute with a dry film thickness of 3 μm in polyester film (Cosmo Shine) A4100 manufactured by Toyobo Co., Ltd. using a microgravure coater (70 cm width) manufactured by Yasui Seiki Co., Ltd. Gravure printing was carried out at a temperature of 130 ° C. in the drying zone. Next, the gravure printing was similarly performed to the polyester film which formed this adhesive layer using the coating solution of the photocatalyst layer used in Example 77, and the polyester film which formed the photocatalyst layer of 3 micrometers of dry film thickness was obtained. Sample 5)
실시예 79 퍼스콤 디스플레이 보호필터Example 79 Perspec Display Protection Filter
실리콘함유량 20 중량% 의 아크릴-실리콘수지를 20 중량% 함유하는 크실렌용액에 폴리실록산 (콜코드(주) 제 메틸실리케이트 51) 을 아크릴-실리콘수지에 대하여 30 중량% 혼합하고, 이소프로판올 용액으로 고형분으로서 20 중량% 가 되도록 희석한 용액에, (주)도오레 제조의 VDT 필터E-filter Ⅲ을 침지하여 꺼내 100 ℃에서 20 분간 건조하여 접착층으로 하였다, 다음에 이 접착층을 형성시킨 VDT 보호필터를, 실시예 77 에서 사용한 광촉매층의 도포용액을 이온교환수로 고형분 함유량 10 중량% 가 되도록 희석한 용액에 침지하여 꺼내 동일하게 100 ℃에서 20 분간 건조하여 광촉매 코팅 VDT 필터를 얻었다. (샘플 6)The polysiloxane (Methyl silicate 51 manufactured by Cocord Co., Ltd.) was mixed with 30% by weight with respect to the acrylic-silicone resin in a xylene solution containing 20% by weight of the acrylic-silicone resin having 20% by weight of silicon, and 20 as a solid component with an isopropanol solution. In a solution diluted to a weight%, the VDT filter E-filter III manufactured by Toray Co., Ltd. was immersed and dried for 20 minutes at 100 ° C to form an adhesive layer. Next, a VDT protective filter in which this adhesive layer was formed was carried out. The coating solution of the photocatalyst layer used in Example 77 was immersed in a solution diluted with ion-exchanged water so as to have a solids content of 10% by weight, and dried for 20 minutes at 100 ° C. to obtain a photocatalyst coated VDT filter. (Sample 6)
실시예 80 전화기 케이스Example 80 Phone Case
실시예 77 에서 사용한 접착층용액을 크실렌-이소프로판올 (50/50) 용액을 사용하여 고형분 함유량 20 중량% 가 되도록 희석하였다. 이 희석용액을 이와다 도장기공업(주) 제조의 스프레이건 WIDER88 형으로 (주)히다찌제작소 제조의 HIT-1 형 전화기의 케이스에 스프레이 도장하였다. 100 ℃에서 20 분간 건조후, 실시예 1 에서 사용한 광촉매층의 용액을 이온교환수로 고형분 함유량 8 중량% 가 되도록 희석한 용액을 사용하여, 동일하게 스프레이 도장하였다. 100 ℃ 에서 20 분간 건조하여, 광촉매를 담지한 전화기 케이스를 얻었다.(샘플 7)The adhesive layer solution used in Example 77 was diluted to a solid content of 20% by weight using a xylene-isopropanol (50/50) solution. This diluted solution was spray-coated to the case of the HIT-1 telephone made by Hitachi Co., Ltd. with a spray gun WIDER88 manufactured by Iwada Kogyo Kogyo Co., Ltd. After drying at 100 ° C. for 20 minutes, the solution of the photocatalyst layer used in Example 1 was spray-coated in the same manner using a solution diluted with ion-exchanged water to a solid content of 8% by weight. It dried for 20 minutes at 100 degreeC, and obtained the telephone case carrying the photocatalyst. (Sample 7)
실시예 81 안경렌즈Example 81 Glasses
(주)니콘제 안경용 렌즈 NL 70 HCCTc (+) 1.00S 0.00 (70 ㎜ψ) 에, 실리콘함량 3 중량% 의 아크릴-실리콘수지를 10 중량% 함유하는 크실렌-이소프로판올 (50/50) 용액에 폴리실록산 (콜코트(주) 제 메틸실리케이트 51) 을 아크릴-실리콘수지에 대하여 20 중량% 혼합하여 조제한 용액을 사용하여, 실시예 79 와 동일한 침지법으로 접착층을 형성시키고, 100 ℃에서 20 분 건조하였다. 실온하에서 방냉후, 광촉매층으로서 산화티탄 함유량 15 % 의 질산산성 티타니아졸을 산화규소 함유량 15 % 의 질산산성 실리카졸 중에, 계면활성제의 존재하에 분산시켜 광촉매층의 도포용액으로 하였다. 이 용액을 사용하여, 동일하게 침지법으로 상기 접착층의 표면에 광촉매층을 도포하고, 100 ℃에서 20 분 건조하여 광촉매 코팅 안경용 렌즈를 얻었다.(샘플 8)Polysiloxane in a solution of xylene-isopropanol (50/50) containing 10 wt% of a silicone-containing 3 wt% acrylic-silicone resin in a lens NL 70 HCCTc (+) 1.00S 0.00 (70 mmψ) manufactured by Nikon Corporation Using a solution prepared by mixing 20 wt% of (Colcote Co., Ltd. methyl silicate 51) with respect to an acrylic-silicone resin, an adhesive layer was formed by the same immersion method as in Example 79, and dried at 100 ° C for 20 minutes. After allowing to cool at room temperature, a 15% titanium oxide nitrate titania sol as a photocatalyst layer was dispersed in a silicon oxide 15% nitric acid silica sol in the presence of a surfactant to prepare a coating solution for the photocatalyst layer. Using this solution, the photocatalyst layer was apply | coated to the surface of the said contact bonding layer similarly by the immersion method, and it dried for 20 minutes at 100 degreeC, and obtained the lens for photocatalyst coating glasses. (Sample 8)
실시예 82 커튼Example 82 Curtain
가와시마직물(주) 제조의 커튼지 포스피아 (학교, 병원용) 를 7㎝ × 7㎝ 로 잘라내어, 실리콘함유량 3 중량% 의 에폭시 - 실리콘수지를 15 중량 % 크실렌-이소프로판올 (50/50) 용액에 폴리실록산 (콜코트(주) 제 메틸실리케이트 51) 을 아크릴-실리콘수지에 대하여 20 중량% 혼합한 용액에 침지하여 꺼내 80 ℃에서 120 분간 건조하였다. 실온하에서 방냉후, 광촉매층으로 산화티탄 함유량 10 중량% 의 암모니아알칼리제 티타니아졸을 산화규소 함유량 10 중량% 의 실리카졸 중에, 계면활성제의 존재하에 분산시킨 광촉매층 중에, 상기 접착층을 형성시킨 커튼지를 함침시켜 꺼내어 80 ℃ 에서 120 분간 건조하여, 광촉매 담지 커튼지로 하였다.(샘플 9)Kawashima Fabric Co., Ltd. cut curtain phosphia (for schools and hospitals) was cut into 7 cm x 7 cm, and polysiloxane was added to a 15% by weight xylene-isopropanol (50/50) solution of 3% by weight of epoxy-silicone resin. (Colcote Co., Ltd. methyl silicate 51) was immersed in the solution which mixed 20 weight% with respect to the acryl- silicone resin, and it took out and dried at 80 degreeC for 120 minutes. After cooling at room temperature, the photocatalyst layer was impregnated with the curtain paper in which the adhesive layer was formed in the photocatalyst layer in which a titanium oxide content of 10% by weight of ammonia alkali titania sol was dispersed in the presence of a surfactant in a silica sol of 10% by weight of silicon oxide. The resultant was taken out and dried at 80 ° C. for 120 minutes to obtain a photocatalyst-supported curtain paper.
실시예 83 부직포Example 83 Nonwovens
닛신(日淸)방직(주) 제조의 코튼 부직포 (상품명 오르코스) 의 미출시품 (단위면적당 중량 50 g/㎡) 을 7㎝ × 7㎝ 로 잘라내어, 실리콘함유량 3 중량% 의 아크릴-실리콘수지를 25 중량 % 크실렌-이소프로판올 (50/50) 용액에 폴리실록산 (콜코트(주) 제 메틸실리케이트 51) 을 아크릴-실리콘수지에 대하여 30 중량% 혼합한 용액을, 이와다 도장기공업(주) 제조의 스프레이건 WIDER88 형을 사용하여, 스프레이 도장하였다. 100 ℃에서 30 분 건조후, 실시예 82 에서 사용한 광촉매층의 용액을 사용하여 동일하게 도포하고, 100 ℃에서 30 분 건조하여 수술복, 테이블보, 좌변기 카바, 창호지, 육묘시트, 식품포장재 등에 적합한 광촉매담지 코튼부직포를 얻었다. (샘플 10)Unreleased product (50 g / m 2 per unit area) of a cotton nonwoven fabric (trade name Orcos) manufactured by Nisshin Textile Co., Ltd. was cut into 7 cm x 7 cm, and an acrylic-silicone resin having a silicon content of 3% by weight Iwada Kogyo Kogyo Co., Ltd. solution which mixed 30 weight% of polysiloxane (Methyl silicate 51 made from Kolkote Co., Ltd.) with 25 weight% xylene-isopropanol (50/50) solution with respect to an acrylic-silicone resin Spray coating was carried out using a spray gun WIDER88 type. After drying at 100 ° C. for 30 minutes, the same coating was applied using the solution of the photocatalytic layer used in Example 82, and dried at 100 ° C. for 30 minutes to suit photocatalysts suitable for surgical clothing, tablecloth, toilet seat cover, window paper, seedling sheet, food packaging material, and the like. Supported cotton nonwoven fabric was obtained. (Sample 10)
실시예 84 우산용 프린트 폴리에스테르 천Example 84 Print polyester cloth for umbrellas
시판되는 우산에 사용되고 있는 프린트 폴리에스테르 천을 사용하여, 실시예 83 과 동일한 방법으로, 접착층과 광촉매층을 도포하였다. 광촉매층을 담지한 프린트 폴리에스테르 천은 천의 무늬나 감촉에 거의 변화가 없었다. (샘플 11)The adhesive layer and the photocatalyst layer were apply | coated in the same way as Example 83 using the printed polyester cloth used for the commercial umbrella. The printed polyester cloth carrying the photocatalyst layer hardly changed the pattern or the texture of the cloth. (Sample 11)
실시예 85 벽지 (직물 클로스)Example 85 Wallpaper (fabric cloth)
(주)산게쓰 제조의 직물 무지벽지 (SG6758) 를 사용하여, 실시예 83 과 동일한 방법으로, 접착층과 광촉매층을 도포하였다. 광촉매층을 담지한 직물벽지는 천의 감촉을 거의 손상시키지 않는 양호한 담지체이었다. (샘플 12)The adhesive layer and the photocatalyst layer were apply | coated similarly to Example 83 using the fabric plain wallpaper (SG6758) by Sangetsu. The fabric wallpaper carrying the photocatalyst layer was a good support that hardly damaged the texture of the fabric. (Sample 12)
실시예 86 알루미늄 샷시Example 86 Aluminum Chassis
7 ㎝ × 7 ㎝ 로 잘라낸 알루미늄 샷시판에, 실리콘 함량 3 중량% 의 아크릴-실리콘수지를 25 중량% 함유하는 크실렌-이소프로판올 (50/50) 용액에 폴리실록산 (콜코트(주) 제 메틸실리케이트 51) 을 아크릴-실리콘수지에 대하여 30 중량% 혼합한 용액을 No.7 의 바코더로 도포하여 100 ℃에서 60 분 건조하여 접착층으로 하였다. 실온하에서 방냉후, 광촉매층으로서 산화티탄 함유량 20 중량% 의 질산산성 티타니아졸을 산화규소 함유량 20 % 의 질산산성 실리카졸 중에, 계면활성제의 존재하에 분산시켜 광촉매층의 도포용액으로 하였다. 이 용액을 사용하여, 동일하게 No.7 의 바코더로 상기 접착층의 표면에 도포하고, 130 ℃에서 10 분 건조하여 광촉매담지의 알루미판으로 하였다. (샘플 13)Polysiloxane (Methyl silicate 51 manufactured by Kollcote Co., Ltd.) in a xylene-isopropanol (50/50) solution containing 25% by weight of an acrylic-silicone resin having a silicon content of 3% by weight on an aluminum chassis cut out to 7 cm × 7 cm. The solution which mixed 30 weight% with respect to the acryl- silicone resin was apply | coated with the bar coder of No. 7, it dried at 100 degreeC for 60 minutes, and it was set as the contact bonding layer. After allowing to cool at room temperature, a 20% by weight titanium nitrate titania sol having a titanium oxide content of 20% as a photocatalyst layer was dispersed in a 20% silicon oxide content in the presence of a surfactant to prepare a coating solution for the photocatalyst layer. Using this solution, it applied similarly to the surface of the said contact bonding layer by the bar coder of No. 7, It dried at 130 degreeC for 10 minutes, and it was set as the photocatalyst alumina plate. (Sample 13)
실시예 87 스테인레스판Example 87 Stainless Steel Plate
실시예 86 에서 사용한 접착층용액을 크실렌-이소프로판올 (50/50) 용액으로 고형분 함유량 5 중량% 가 되도록 희석하였다. 이 희석용액에 SUS316 제 스테인레스판 (두께 0.2 ㎜) 을 7 ㎝ × 7 ㎝ 로 잘라낸 시료를 침지하여 꺼내 정치한 후, 120 ℃에서 20 분 건조하여 스테인레스판의 표면에 접착층을 형성시켰다. 다음에 이 접착층을 형성시킨 스테인레스판을, 실시예 86 에서 사용한 광촉매층의 도포용액을 이온교환수로 10 중량% 로 희석한 용액에 침지하여 꺼내 동일하게 120 ℃에서 20 분 건조하여 광촉매담지 스테인레스판으로 하였다. (샘플 14)The adhesive layer solution used in Example 86 was diluted with xylene-isopropanol (50/50) solution so as to have a solid content of 5% by weight. The sample cut out of SUS316 stainless steel plate (thickness 0.2mm) to 7 cm x 7 cm was immersed in this dilution solution, and it was left to stand still, and it dried at 120 degreeC for 20 minutes, and formed the adhesive layer on the surface of a stainless plate. Next, the stainless plate on which this adhesive layer was formed was immersed in a solution diluted with 10% by weight of ion-exchanged water in the coating solution of the photocatalyst layer used in Example 86, and dried at 120 ° C. for 20 minutes, to thereby carry a photocatalyst supported stainless plate. It was made. (Sample 14)
실시예 88 양철판Example 88 Tinplate
실리콘함유량 20 중량% 의 아크릴-실리콘수지를 20 중량% 함유하는 크실렌용액에 폴리실록산 (콜코드(주) 제 메틸실리케이트 51) 을 아크릴-실리콘수지에 대하여 30 중량% 혼합하고, 이소프로판올 용액으로 고형분으로서 20 중량% 가 되도록 희석한 용액에, 7 ㎝ × 7 ㎝ 로 잘라낸 막두께 0.1 ㎜ 의 양철판을 침지하고, 꺼내 100 ℃에서 60 분 건조하여 접착층으로 하였다. 다음에 이 접착층을 형성시킨 양철판을, 실시예 86 에서 사용한 광촉매층의 도포용액을 이온교환수로 10 중량% 로 희석한 용액에 침지하여 꺼내 동일하게 100 ℃에서 60 분 건조하여, 광촉매담지 양철판으로 하였다.(샘플 15)The polysiloxane (Methyl silicate 51 manufactured by Cocord Co., Ltd.) was mixed with 30% by weight with respect to the acrylic-silicone resin in a xylene solution containing 20% by weight of the acrylic-silicone resin having 20% by weight of silicon, and 20 as a solid component with an isopropanol solution. A tin plate having a thickness of 0.1 mm cut out at 7 cm × 7 cm was immersed in a solution diluted to a weight%, taken out and dried at 100 ° C. for 60 minutes to obtain an adhesive layer. Next, the tin plate on which this adhesive layer was formed was immersed in a solution diluted with 10% by weight of ion-exchanged water in the coating solution of the photocatalyst layer used in Example 86, and dried at 100 ° C. for 60 minutes, and the amount of the photocatalyst supported amount An iron plate was used. (Sample 15)
실시예 89 블라인드Example 89 blinds
다지가와 블라인드공업(주) 제조의 블라인드 "실키 커튼" (슬랫폭 15 ㎜ 타입) T-12 (화이트) 의 폭 800 ㎜ 높이 700 ㎜ 의 슬랫을 떼어내고, 실리콘 함유량 3 중량% 의 아크릴-실리콘수지를 25 중량% 함유하는 크실렌-이소프로판올 (50/50) 용액에 폴리실록산 (콜코트(주) 제 메틸실리케이트 51) 을 아크릴-실리콘수지에 대하여 30 중량% 혼합한 용액을, 이와다 도장기공업(주) 제조의 스프레이건 WIDER88 형으로 스프레이 도장하였다. 120 ℃에서 20 분 건조후, 실시예 86 에서 사용한 광촉매층의 용액을 이온교환수로 고형분 함유량 8 중량% 가 되도록 희석한 용액을 사용하여, 동일하게 스프레이 도장하였다. 120 ℃에서 20 분간 건조하여 광촉매를 담지한 블라인드를 얻었다. (샘플 16)Tajigawa Blind Industries Co., Ltd. blind "silky curtain" (slat width 15 mm type) T-12 (white), 800 mm wide and 700 mm high slat, removes 3% by weight of acrylic-silicone A solution obtained by mixing 30% by weight of polysiloxane (Methylsilicate 51 manufactured by Kolkote Co., Ltd.) with respect to acrylic-silicone resin in a xylene-isopropanol (50/50) solution containing 25% by weight of a resin Note) Spray coating was carried out using a manufactured spray gun WIDER88. After drying 20 minutes at 120 degreeC, it spray-coated similarly using the solution which diluted the solution of the photocatalyst layer used in Example 86 to 8 weight% of solid content with ion-exchange water. It dried for 20 minutes at 120 degreeC, and obtained the blind which supported a photocatalyst. (Sample 16)
실시예 90 프린트합판Example 90 Printed Plywood
7 ㎝ × 7 ㎝ 로 잘라낸 나가다이 (永大) 산업(주) 제조의 네오비드 (2.5 ㎜ 두께) 프린트합판에, 실리콘 함량 3 중량% 의 아크릴-실리콘수지를 25 중량% 함유하는 크실렌-이소프로판올 (50/50) 용액에 폴리실록산 (콜코트(주) 제 메틸실리케이트 51) 을 아크릴-실리콘수지에 대하여 30 중량% 혼합한 용액을 No.7 의 바코더로 도포하여 100 ℃에서 30 분 건조하여 접착층으로 하였다. 실온하에서 방냉후, 광촉매층으로서 산화티탄 함유량 20 중량% 의 질산산성 티타니아졸을 산화규소 함유량 20 % 의 질산산성 실리카졸 중에, 계면활성제의 존재하에 분산시켜 광촉매층의 도포용액으로 하였다. 이 용액을 사용하여, 동일하게 No.7 의 바코더로 상기 접착층의 표면에 도포하고, 100 ℃에서 30 분 건조하여 광촉매담지 프린트합판으로 하였다. (샘플 17)Xylene-isopropanol containing 25% by weight of a silicon-containing 3% by weight of acrylic-silicone resin in a neo-bead (2.5 mm thick) printed plywood manufactured by Nagada Industries Co., Ltd. cut out to 7 cm × 7 cm (50 (50) A solution obtained by mixing 30% by weight of polysiloxane (Methyl silicate 51 manufactured by Kollcoat Co., Ltd.) with respect to acrylic-silicone resin was applied with a barcoder of No. 7, dried at 100 ° C for 30 minutes, and used as an adhesive layer. . After allowing to cool at room temperature, a 20% by weight titanium nitrate titania sol having a titanium oxide content of 20% as a photocatalyst layer was dispersed in a 20% silicon oxide content in the presence of a surfactant to prepare a coating solution for the photocatalyst layer. Using this solution, it applied similarly to the surface of the said contact bonding layer by the bar coder of No. 7, It dried at 100 degreeC for 30 minutes, and was made into the photocatalyst carrying printed plywood. (Sample 17)
실시예 91 합성목재Example 91 Synthetic Wood
실시예 90 에서 사용한 접착층용액을 크실렌-이소프로판올 (50/50) 용액으로 고형분 함유량 5 중량% 가 되도록 희석하였다. 이 희석용액에 세끼스이 (積水) 화학공업(주) 제조의 에스론네오란바-FFU-50 을 7 ㎝ × 7 ㎝ × 7 ㎝ 로 잘라낸 목재를 침지하여 꺼내 정치한 후, 100 ℃에서 120 분 건조하여 합성목재의 표면에 접착층을 형성시켰다. 다음에 이 접착층을 형성시킨 합성목재를, 실시예 90 에서 사용한 광촉매층의 도포용액을 이온교환수로 10 중량% 로 희석한 용액에 침지하여 꺼내 동일하게 100 ℃에서 120 분 건조하여 광촉매담지 합성목재로 하였다. (샘플 18)The adhesive layer solution used in Example 90 was diluted with xylene-isopropanol (50/50) solution so as to have a solid content of 5% by weight. After dipping out the wood which cut out Eslon neolanba-FFU-50 by Sekisui Chemical Co., Ltd. in 7 cm x 7 cm x 7 cm, it was left to stand in this dilution solution, and it was left to stand 120 minutes at 100 degreeC. Drying to form an adhesive layer on the surface of the synthetic wood. Subsequently, the coating solution of the photocatalyst layer used in Example 90 was immersed in a solution diluted to 10% by weight with ion-exchanged water, and the same was dried for 120 minutes at 100 ° C. It was set as. (Sample 18)
실시예 92 목제 도어Example 92 Wood Door
다이겡 (大建) 공업(주) 제조의 옥내용 목제도어 조각도어 38 형 RC0202-IR6 (오크무늬) 를 7 ㎝ × 7 ㎝ 의 크기로 잘라내고, 실리콘 함량 3 중량% 의 아크릴-실리콘수지를 10 중량% 함유하는 크실렌-이소프로판올 (50/50) 용액에 폴리실록산 (콜코트(주) 제 메틸실리케이트 51) 을 아크릴-실리콘수지에 대하여 20 중량% 혼합하여 조제한 용액을 사용하고, 실시예 91 과 동일한 침지법으로 접착층을 형성시키고, 100 ℃에서 20 분 건조하였다. 실온하에서 방냉후, 광촉매층으로서 산화티탄 함유량 5 % 의 질산산성 티타니아졸을 산화규소 함유량 5 % 의 질산산성 실리카졸 중에, 계면활성제의 존재하에 분산시켜 광촉매층의 도포용액으로 하였다. 이 용액을 사용하여, 동일하게 침지법으로 상기 접착층의 표면에 광촉매층을 도포하고, 100 ℃에서 20 분 건조하여 광촉매코팅 목재 도어재로 하였다. (샘플 19)Indoor wooden door carved door 38 type RC0202-IR6 (oak pattern) manufactured by Daijo Industrial Co., Ltd. was cut into 7 cm x 7 cm, and acrylic-silicone resin having a silicon content of 3% by weight. A solution prepared by mixing 20% by weight of polysiloxane (Methylsilicate 51 manufactured by Colcot Co., Ltd.) with 20% by weight of a xylene-isopropanol (50/50) solution containing 10% by weight of an acrylic-silicone resin was used. An adhesive layer was formed by immersion and dried at 100 ° C. for 20 minutes. After allowing to cool at room temperature, a 5% nitric acid titanate with a titanium oxide content of 5% was dispersed in a 5% silicon oxide content with a nitric acid silicate sol as a photocatalyst layer to prepare a coating solution for the photocatalyst layer. Using this solution, the photocatalyst layer was apply | coated to the surface of the said contact bonding layer similarly by the immersion method, and it dried at 100 degreeC for 20 minutes, and used as the photocatalyst coating wooden door material. (Sample 19)
<광촉매활성의 평가> 샘플 1 ∼ 19 의 시료를 사용하여, 광촉매활성의 평가를 실시하고, 표 9 에 나타낸 결과를 얻었다.<Evaluation of Photocatalytic Activity> Photocatalytic activity was evaluated using the samples of Samples 1 to 19, and the results shown in Table 9 were obtained.
* 1 : 바둑판눈금 테이프법을 사용할 수 없기 때문에, 점착 테이프면을 주사형 전자현미경으로 관찰하였지만, 광촉매층의 부착은 없었음.* 1: Since the checkerboard scale tape method could not be used, the surface of the adhesive tape was observed with a scanning electron microscope, but there was no adhesion of the photocatalyst layer.
이상과 같이, 본 발명의 광촉매 담지구조체는, 높은 광촉매활성을 가지며, 게다가 열화되기 어렵고 내구성이 높은 광촉매를 담지한 유리, 플라스틱, 금속재료, 천, 목재 및 목질재료를, 항균, 탈취, 오염방지 등을 목적으로, 렌즈, 각종 창유리, 점착필름, 화장시트, 벽지, 커튼, 블라인드 등의 각종 건축재료나 인테리어제품 등, 폭넓은 응용분야의 제품에 적용할 수 있다.As described above, the photocatalyst supporting structure of the present invention is antibacterial, deodorant, pollution prevention of glass, plastic, metal material, cloth, wood and wood materials which have high photocatalytic activity and are hardly deteriorated and carry a high photocatalyst. For the purpose of the present invention, it can be applied to products of a wide range of applications such as lenses, various windows, adhesive films, decorative sheets, wallpaper, curtains, blinds, and various building materials and interior products.
Claims (52)
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JP96-63673 | 1996-02-26 | ||
JP6367396 | 1996-02-26 | ||
JP96-150115 | 1996-05-21 | ||
JP8150115A JPH09310039A (en) | 1996-05-21 | 1996-05-21 | Photocatalyst coating agent |
PCT/JP1996/001669 WO1997000134A1 (en) | 1995-06-19 | 1996-06-18 | Photocatalyst-carrying structure and photocatalyst coating material |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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KR20010105694A (en) * | 2000-05-17 | 2001-11-29 | 김석용 | film coated with photochemical active catalyst layer |
KR100403275B1 (en) * | 2001-03-30 | 2003-10-30 | 주식회사 매그린 | Photocatalytic Coating Composition, Preparation Method Thereof and Coated Body Using the Same |
KR100457720B1 (en) * | 1998-05-08 | 2005-01-15 | 고려화학 주식회사 | Flooring material having beneficial functions by applying a photo-catalyst to a surface processing layer |
WO2016003239A1 (en) * | 2014-07-03 | 2016-01-07 | 삼성에스디아이 주식회사 | Adhesive composition for optical film, adhesive layer, adhesive type optical film, and display device |
KR20170040170A (en) * | 2017-04-04 | 2017-04-12 | 정지희 | Visible-light responsive photocatalytic coating composition and preparation methods thereof |
US10421870B2 (en) | 2011-04-15 | 2019-09-24 | Allied Bioscience, Inc. | Composition and method to form a self decontaminating surface |
US11166458B2 (en) | 2011-04-15 | 2021-11-09 | Allied Bioscience, Inc. | Wet wipes comprising antimicrobial coating compositions |
Families Citing this family (3)
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KR20010075752A (en) * | 2000-01-17 | 2001-08-11 | 김영웅 | coating solution and its preparing method for titanium dioxide photo-catalyst |
KR100364729B1 (en) * | 2000-01-19 | 2002-12-18 | 엘지전자 주식회사 | Method for preparing Titanium dioxide film on polymer substrate |
CA2833177C (en) * | 2011-04-15 | 2019-03-05 | Craig GROSSMAN | Composition and method to form a self decontaminating surface |
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1996
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100457720B1 (en) * | 1998-05-08 | 2005-01-15 | 고려화학 주식회사 | Flooring material having beneficial functions by applying a photo-catalyst to a surface processing layer |
KR20010105694A (en) * | 2000-05-17 | 2001-11-29 | 김석용 | film coated with photochemical active catalyst layer |
KR100403275B1 (en) * | 2001-03-30 | 2003-10-30 | 주식회사 매그린 | Photocatalytic Coating Composition, Preparation Method Thereof and Coated Body Using the Same |
US10421870B2 (en) | 2011-04-15 | 2019-09-24 | Allied Bioscience, Inc. | Composition and method to form a self decontaminating surface |
US11166458B2 (en) | 2011-04-15 | 2021-11-09 | Allied Bioscience, Inc. | Wet wipes comprising antimicrobial coating compositions |
WO2016003239A1 (en) * | 2014-07-03 | 2016-01-07 | 삼성에스디아이 주식회사 | Adhesive composition for optical film, adhesive layer, adhesive type optical film, and display device |
KR20170040170A (en) * | 2017-04-04 | 2017-04-12 | 정지희 | Visible-light responsive photocatalytic coating composition and preparation methods thereof |
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