KR100987356B1 - Silicone Hybrid Hard Coating Composition for Platic Substrate Comprising Photocatalyst - Google Patents
Silicone Hybrid Hard Coating Composition for Platic Substrate Comprising Photocatalyst Download PDFInfo
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- KR100987356B1 KR100987356B1 KR1020080050640A KR20080050640A KR100987356B1 KR 100987356 B1 KR100987356 B1 KR 100987356B1 KR 1020080050640 A KR1020080050640 A KR 1020080050640A KR 20080050640 A KR20080050640 A KR 20080050640A KR 100987356 B1 KR100987356 B1 KR 100987356B1
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 45
- 239000008199 coating composition Substances 0.000 title claims abstract description 36
- 229920001296 polysiloxane Polymers 0.000 title abstract description 8
- 239000000758 substrate Substances 0.000 title 1
- 239000010409 thin film Substances 0.000 claims abstract description 51
- 238000000576 coating method Methods 0.000 claims abstract description 50
- 239000011248 coating agent Substances 0.000 claims abstract description 47
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004033 plastic Substances 0.000 claims abstract description 24
- 229920003023 plastic Polymers 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008119 colloidal silica Substances 0.000 claims abstract description 23
- 239000002985 plastic film Substances 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004566 building material Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- -1 titanium alkoxide Chemical class 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 33
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 abstract description 28
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 17
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 16
- 150000002484 inorganic compounds Chemical class 0.000 abstract description 14
- 239000002904 solvent Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 12
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 6
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 6
- 230000000845 anti-microbial effect Effects 0.000 abstract description 4
- 238000011109 contamination Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 9
- 238000001782 photodegradation Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000006303 photolysis reaction Methods 0.000 description 5
- 230000015843 photosynthesis, light reaction Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007542 hardness measurement Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 208000035859 Drug effect increased Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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Abstract
본 발명은 플라스틱판 코팅용 실리콘 계열 하이브리드 하드 코팅제 조성물을 제공한다. 본 발명의 조성물은 무기 화합물로서 테트라에톡시실란(tetraethoxysilane) 또는 콜로이드 실리카, 실란커플링제로서 메틸트리메톡시실란(methyltrimethoxysilane) 또는 메틸트리에톡시실란(methyltriethoxysilane) 및 광촉매가 포함되어 이루어진다. 본 발명의 코팅제 조성물을 플라스틱판에 코팅하여 박막을 형성시키면, 이 박막을 갖는 플라스틱판의 표면경도를 향상시키고, 우수한 내후성, 내용제성 및 내약품성을 부여할 수 있는 동시에, 내오염특성, 내화학성 및 항균성도 갖게 할 수 있다. The present invention provides a silicone-based hybrid hard coating composition for plastic plate coating. The composition of the present invention comprises tetraethoxysilane or colloidal silica as an inorganic compound, methyltrimethoxysilane or methyltriethoxysilane as a silane coupling agent and a photocatalyst. When the coating composition of the present invention is coated on a plastic sheet to form a thin film, the surface hardness of the plastic sheet having the thin film can be improved, and excellent weather resistance, solvent resistance, and chemical resistance can be imparted, and at the same time, contamination resistance and chemical resistance are achieved. And antimicrobial properties.
하이브리드 하드 코팅제, 광촉매, 실리콘, 메틸렌 블루 Hybrid hard coatings, photocatalysts, silicones, methylene blue
Description
본 발명은 광촉매를 포함하는 플라스틱판 코팅용 실리콘계 하이브리드 하드 코팅제 조성물 및 이 조성물에 의해 코팅된 박막을 갖는 플라스틱판에 관한 것이다. The present invention relates to a silicone-based hybrid hard coating composition for coating a plastic sheet containing a photocatalyst and a plastic sheet having a thin film coated by the composition.
일반적으로 플라스틱 소재는 타 소재에 없는 다양한 우수한 특징, 예를 들면 경량이지만 단단하고 가공하기 쉬운 성질을 갖고 있다. 이러한 특징은 생산 합리화, 에너지 절약등 사회적 요구에 부응하면서 용도는 여러 가지 분야에 확대되고 있다. 그러나 플라스틱은, 그와 같은 장점을 지닌 반면, 표면경도가 낮고, 내후성이 떨어지고 내약품성, 내용제성 등이 약하여 옥외에서 쉽게 변색하거나 균열이 생기는 등의 문제를 일으키기 때문에 용도에 따라서는 이러한 점들이 큰 장애가 되어 사용이 제한되는 경우가 적지 않다. 특히, 건축자재 및 주방용품 시장에서 플라스 틱 소재가 많이 사용되고 있는데, 이 플라스틱 소재는 표면굴곡문제, 내후성, 표면경도 및 내용제성의 단점이 지적되어 왔다. In general, plastic materials have a variety of excellent features that are not found in other materials, such as lightweight, yet hard and easy to process. These features are being extended to various fields while meeting the social needs such as rationalization of production and energy saving. However, since plastics have such advantages, they have a low surface hardness, poor weather resistance, weak chemical resistance, solvent resistance, and the like, causing problems such as discoloration and cracking outdoors. There are many cases where the use is restricted due to obstacles. In particular, plastic materials are widely used in the building materials and kitchenware market, which has been pointed out the disadvantages of surface bending problems, weather resistance, surface hardness and solvent resistance.
따라서 플라스틱 표면에 유기 또는 무기 실리콘계 내마모성 하드 코팅제를 처리하여 경도가 높은 피막을 형성시킴과 동시에 내후성, 내약품성, 내용제성 등을 향상시켜 광학재료, 자동차 부품, 전기제품 및 건축재료 등에 응용이 가능한 플라스틱 제품에 대한 연구가 진행되고 있다. 그러나, 이러한 목적으로 현재 사용되고 있는 코팅제는 대분분 수입에 의존하고 있고, 제품의 저장성이 나쁘며 상당히 고가이고, 일부는 국내 연구개발이 추진되어 제품을 출시하고 있다. 이와 같은 하드 코팅제의 제조기술 및 활용기술은 고부가가치를 창출할 수 있는 분야이지만 국내에서 생산되는 재료는 제품의 종류가 다양하지 않고 물성 개선이 필요하여 이의 활용분야 연구에 어려움이 따른다. Therefore, the plastic surface can be applied to optical materials, automobile parts, electrical appliances, and building materials by forming organic coatings with high hardness by coating organic or inorganic silicone wear-resistant hard coatings and improving weather resistance, chemical resistance, and solvent resistance. Research on the product is ongoing. However, the coating agent currently used for this purpose relies mostly on imports, the shelf life of the product is poor and quite expensive, and some of the coatings have been promoted in Korea to release the product. Such a manufacturing technology and utilization technology of the hard coating agent is a field that can create high value added, but domestically produced materials are difficult to study the field of utilization of them because there is not a variety of products and properties need to be improved.
한편, 광촉매는 선진국들에서 건축자재 제품, 이슬이 생기지 않는 유리창, 의료용품, 주방 및 주거 용품, 도로설비, 건축물, 자동차 용품 등에 사용되어 광택성 등의 표면특성을 개선시키거나, 내화학성, 내마모성, 환경오염물질 분해특성과 같은 내오염특성, 항균성을 향상시키기 위한 목적으로 응용되고 있다. 특히, 실리콘 재료에는 산화티탄과 같은 광촉매를 직접 접촉시키는 것이 가능하고, 실리콘에 결합된 광촉매는 비교적 장기간 안정하게 활성을 유지할 수 있다. 그러나 광촉매의 응용범위를 더욱 넓히기 위해서는 보다 안정성 있고 간편하게 코팅하여 중간층을 형성할 수 있는 실리콘계열 화합물의 개발이 필수적이다. On the other hand, photocatalysts are used in developed countries in building materials products, glass windows without dew, medical supplies, kitchen and residential goods, road equipment, buildings, and automobile products to improve surface characteristics such as glossiness, chemical resistance, and wear resistance. It has been applied for the purpose of improving pollution resistance and antimicrobial properties such as environmental pollutant decomposition characteristics. In particular, it is possible to bring the silicon material into direct contact with a photocatalyst such as titanium oxide, and the photocatalyst bonded to silicon can be stably maintained for a relatively long time. However, in order to further broaden the application range of the photocatalyst, it is necessary to develop a silicon-based compound that can be more stably and simply coated to form an intermediate layer.
또한, 내장재에서는 광강도 부족에 따른 광촉매 기능 발현의 어려움이 최대 의 문제로 대두된다. 따라서 미소량의 오염물질의 경우를 제외하고는 보다 감도가 높은 광촉매 재료나 가시광 응답형 광촉매 재료의 개발이 요구된다. 최근에 투명 이산화티탄(TiO2) 함유막을 코팅한 PET나 아크릴 수지, 염화비닐 등 고분자 필름의 개발도 활발하게 진행되고 있다. 기능적으로는 방오, 셀프 크리닝, 방담 효과가 기대되고 있다. 그러나, 옥외 용도로는 장기 안정성이, 옥내용도로는 감도부족이 역시 과제가 되고 있고, 저온 경화의 조건을 만족시키며, 보다 안정한 바인더 및 중간층의 개발이 요구되고 있다. In addition, in the interior material, the difficulty of expressing photocatalytic function due to the lack of light intensity is the biggest problem. Therefore, except for a small amount of contaminants, development of more sensitive photocatalyst material or visible light responsive photocatalyst material is required. Recently, the development of polymer films such as PET, acrylic resin, and vinyl chloride coated with a transparent titanium dioxide (TiO 2 ) -containing film has been actively progressed. Functionally, antifouling, self-cleaning and antifogging effects are expected. However, for outdoor use, long-term stability and lack of sensitivity in indoor roads also become a problem, satisfying the conditions of low temperature curing, and developing more stable binders and intermediate layers are required.
본 발명자들은 플라스틱 재료의 표면경도를 향상시키고, 우수한 내후성, 내용제성 및 내약품성을 부여할 수 있는 동시에, 내오염특성, 내화학성 및 항균성도 갖게 할 수 있는 기능성 하드 코팅제를 개발하기 위해 연구 노력하였다. 그 결과 무기 화합물로서 테트라에톡시실란 (TEOS, tetraethoxysilane) 또는 콜로이드 실리카 (colloidal silica)를 사용하고, 실란커플링제로서 메틸트리메톡시실란(MTMS, methyltrimethoxysilane) 또는 메틸트리에톡시실란 (MTES, methyltriethoxysilane)를 사용하여 조성물을 구성하고, 여기에 광촉매를 첨가시켜 코팅용 조성물을 제조하면, 무기물이 갖고 있는 강도, 경도 및 열적 특성과, 유기물이 갖고 있는 열가소성 및 탄성과, 광촉매 활성등에 의해 코팅용 조성물이 코팅된 박막을 갖는 플라스 틱판의 광택도와 같은 표면 특성을 개선시킬 수 있고, 표면경도, 내마모성, 내오염특성, 내화학성의 특성을 향상시킬 수 있음을 실험적으로 확인함으로써 본 발명을 완성하였다. The present inventors have made efforts to develop functional hard coatings that can improve the surface hardness of plastic materials, impart excellent weather resistance, solvent resistance and chemical resistance, and can also have pollution resistance, chemical resistance and antimicrobial properties. . As a result, tetraethoxysilane (TEOS) or colloidal silica (TEOS) is used as the inorganic compound, and methyltrimethoxysilane (MTMS) or methyltriethoxysilane (MTES) is used as the silane coupling agent. When the composition is composed of and the photocatalyst is added to prepare a coating composition, the coating composition is formed by the strength, hardness and thermal properties of the inorganic material, the thermoplastic and elasticity of the organic material, and the photocatalytic activity. The present invention was completed by experimentally confirming that surface properties such as glossiness of a plastic plate having a coated thin film can be improved, and that surface hardness, abrasion resistance, fouling resistance, and chemical resistance properties can be improved.
따라서, 본 발명은 테트라에톡시실란(TEOS) 또는 콜로이드 실리카의 무기물질을 포함하며, 메틸트리메톡시실란(MTMS) 또는 메틸트리에톡시실란(MTES)의 실란커플링제를 포함하고, 광촉매를 포함하는 플라스틱판 코팅에 사용되는 실리콘계 하이브리드 하드 코팅제 조성물을 제공하는 것을 목적으로 한다. Accordingly, the present invention includes inorganic materials of tetraethoxysilane (TEOS) or colloidal silica, includes a silane coupling agent of methyltrimethoxysilane (MTMS) or methyltriethoxysilane (MTES), and includes a photocatalyst. An object of the present invention is to provide a silicone-based hybrid hard coating composition used for coating a plastic sheet.
또한, 본 발명은 상기 코팅제 조성물로 코팅된 박막을 갖는 플라스틱판을 제공하는 것을 목적으로 한다. In addition, an object of the present invention is to provide a plastic plate having a thin film coated with the coating composition.
본 발명의 목적 및 장점은 하기의 발명의 상세한 설명, 청구의 범위 및 도면에 의해 보다 명확하게 된다. The objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.
본 발명의 일 양태에 따르면, 본 발명은 (a) 콜로이드 실리카 (colloidal silica) 100 중량부 및 메틸트리에톡시실란 (MTES, methyltriethoxysilane) 200-400 중량부를 포함하며; (b) 상기 콜로이드 실리카 및 메틸트리에톡시실란(MTES)을 합한 양을 100 중량부로 하였을 때, 1-2.5 중량부의 광촉매를 포함하는 플라스틱판의 코팅에 사용되는 실리콘계 하이브리드 하드 코팅제 조성물을 제공한다. According to one aspect of the invention, the present invention comprises (a) 100 parts by weight of colloidal silica and 200-400 parts by weight of methyltriethoxysilane (MTES); (b) when the total amount of the colloidal silica and methyltriethoxysilane (MTES) is 100 parts by weight, it provides a silicon-based hybrid hard coating composition used for coating a plastic sheet containing 1-2.5 parts by weight of a photocatalyst.
본 발명자들은 플라스틱 재료의 표면경도를 향상시키고, 우수한 내후성, 내용제성 및 내약품성을 부여할 수 있는 동시에, 내오염특성, 내화학성 및 항균성도 갖게 할 수 있는 기능성 하드 코팅제를 개발하기 위해 연구 노력하였다. 그 결과 무기화합물로서 테트라에톡시실란(TEOS) 또는 콜로이드 실리카(colloidal silica)를 사용하고, 실란커플링제로서 메틸트리메톡시실란(MTMS) 또는 메틸트리에톡시실란(MTES)를 사용하여 조성물을 구성하고, 여기에 광촉매를 첨가시켜 코팅용 조성물을 제조하면, 무기물이 갖고 있는 강도, 경도 및 열적 특성과, 유기물이 갖고 있는 열가소성 및 탄성과, 광촉매 활성 등에 의해 코팅용 조성물이 코팅된 박막을 갖는 플라스틱판의 광택도와 같은 표면 특성을 개선시킬 수 있고, 표면경도, 내마모성, 내오염특성, 내화학성의 특성을 향상시킬 수 있음을 실험적으로 확인함으로써 본 발명을 완성하였다. The present inventors have made efforts to develop functional hard coatings that can improve the surface hardness of plastic materials, impart excellent weather resistance, solvent resistance and chemical resistance, and can also have pollution resistance, chemical resistance and antimicrobial properties. . As a result, tetraethoxysilane (TEOS) or colloidal silica was used as the inorganic compound, and methyltrimethoxysilane (MTMS) or methyltriethoxysilane (MTES) was used as the silane coupling agent. When the coating composition is prepared by adding a photocatalyst, the plastic having a thin film coated with the coating composition by the strength, hardness and thermal properties of the inorganic material, the thermoplastic and elasticity of the organic material, and the photocatalytic activity, etc. The present invention was completed by experimentally confirming that surface characteristics such as glossiness of a plate can be improved, and that surface hardness, abrasion resistance, fouling resistance, and chemical resistance can be improved.
본 발명의 하드 코팅제 조성물은 구성성분으로 무기화합물과 유기화합물이 혼합되어 이루어진 실리콘 계열의 하이브리드(hybrid) 조성물이다. 본 발명의 하이브리 조성물은 무기화합물이 갖고 있는 강도, 경도, 열적 특성과, 유기화합물이 갖고 있는 열가소성 및 탄성의 장점을 동시에 가질 수 있다. The hard coating composition of the present invention is a silicon-based hybrid composition composed of an inorganic compound and an organic compound as a component. The hybrid composition of the present invention may have the strengths, hardness, and thermal properties of the inorganic compound and the advantages of thermoplastic and elasticity of the organic compound.
본 발명의 코팅제 조성물은 표면경도가 낮고 내후성과 내용제성 및 내약품성 등이 저하되는 것을 보완하기 위한 하드(hard) 코팅제이다. The coating composition of the present invention is a hard coating agent for compensating for low surface hardness and deterioration in weather resistance, solvent resistance, and chemical resistance.
본 발명의 조성물에 포함되는 무기화합물은 테트라에톡시실란(TEOS, tetraethoxysilane) 또는 콜로이드 실리카(colloidal silica)이고, 유기화합물은 실란 커플링제(silane coupling agent)로서 메틸트리메톡시실란(MTMS, methyltrimethoxysilane) 또는 메틸트리에톡시실란(MTES, methyltriethoxysilane)이다. The inorganic compound included in the composition of the present invention is tetraethoxysilane (TEOS) or colloidal silica, and the organic compound is methyltrimethoxysilane (MTMS) as a silane coupling agent. Or methyltriethoxysilane (MTES).
본 발명의 조성물에서 테트라에톡시실란(TEOS) 100 중량부에 대해 메틸트리메톡시실란(MTMS)은 200-600 중량부로 포함되며, 또는 콜로이드 실리카 100 중량부에 대해 메틸트리에톡시실란(MTES)은 200-400 중량부로 포함된다. In the composition of the present invention, methyltrimethoxysilane (MTMS) is included in an amount of 200-600 parts by weight based on 100 parts by weight of tetraethoxysilane (TEOS), or methyltriethoxysilane (MTES) is used in 100 parts by weight of colloidal silica. Is comprised in 200-400 parts by weight.
본 발명의 조성물에는 내오염성, 광택성, 내후성, 내약품성, 내용제성을 향상시키기 위해 광촉매(photocatalyst)를 포함시킨다. 본 발명의 광촉매는 특별히 한정되지 않으나, 이산화티타늄(TiO2) 또는 티타늄 알콕사이드 (TTIP-titanium tetraisopropoxide)가 바람직하다. 상기 광촉매는 바람직하게는, (i)상기 테트라에톡시실란(TEOS) 및 메틸트리메톡시실란(MTMS)의 총중량 100 중량부에 대해, 또는 (ⅱ) 상기 콜로이드 실리카 및 메틸트리에톡시실란(MTES)의 총중량 100중량부에 대해, 1-2.5 중량부의 함유량으로 포함되고, 더욱 바람직하게는 1-1.5 중량부로 함유된다. 광촉매의 함유량이 2.5 중량부를 초과하는 경우에는 코팅 박막의 투명도가 현저히 떨어지고, 1 중량부 미만으로 첨가되는 경우에는 광촉매 활성에 의한 광촉매 효과를 얻기 어렵다. The composition of the present invention includes a photocatalyst to improve stain resistance, gloss, weather resistance, chemical resistance, and solvent resistance. The photocatalyst of the present invention is not particularly limited, but titanium dioxide (TiO 2 ) or titanium alkoxide (TTIP-titanium tetraisopropoxide) is preferable. The photocatalyst is preferably (i) based on 100 parts by weight of the total weight of the tetraethoxysilane (TEOS) and methyltrimethoxysilane (MTMS), or (ii) the colloidal silica and methyltriethoxysilane (MTES). It is contained in content of 1-2.5 weight part with respect to 100 weight part of total weight of a), More preferably, it is contained in 1-1.5 weight part. When the content of the photocatalyst exceeds 2.5 parts by weight, the transparency of the coating thin film is remarkably inferior, and when it is added below 1 part by weight, it is difficult to obtain a photocatalytic effect due to the photocatalytic activity.
본 발명의 바람직한 구현예에 의하면, 본 발명의 코팅제 조성물이 적용되는 플라스틱판은 주방용품 또는 건축자재용품의 플라스틱판이다. According to a preferred embodiment of the present invention, the plastic plate to which the coating composition of the present invention is applied is a plastic plate of kitchenware or building materials.
본 발명의 다른 양태에 따르면, 본 발명은 상기 본 발명의 코팅제 조성물로 코팅된 코팅 박막을 갖는 플라스틱판을 제공한다. According to another aspect of the present invention, the present invention provides a plastic plate having a coating thin film coated with the coating composition of the present invention.
또한, 본 발명의 바람직한 구현예에 따르면, 상기 플라스틱판은 주방용품 또는 건축자재용품의 플라스틱판이다. In addition, according to a preferred embodiment of the present invention, the plastic plate is a plastic plate of kitchen or building materials.
또한, 본 발명의 다른 바람직한 구현예에 따르면, 본 발명의 상기 코팅 박막의 두께는 10-50 ㎛ 이고, 더욱 바람직하게는 10-35 ㎛이다. 코팅 박막의 두께가 10 ㎛ 보다 작은 경우 경도가 약해지며, 박막 두께가 50 ㎛를 초과하면 박막의 투명도가 떨어지는 단점이 있다. In addition, according to another preferred embodiment of the present invention, the thickness of the coating thin film of the present invention is 10-50 ㎛, more preferably 10-35 ㎛. If the thickness of the coating thin film is less than 10 ㎛ the hardness is weak, if the thickness of the thin film has a disadvantage that the transparency of the thin film falls.
본 발명의 코팅제 조성물의 제조방법은 다음과 같다. 우선 무기화합물로서 콜로이드 실리카 또는 테트라에톡시실란(TEOS)를, 실란커플링제로서 메틸트리메톡시실란(MTMS) 또는 메틸트리에톡시실란(MTES)을 용매에 녹인 후 산촉매를 사용하여 반응시킨다. 이어서, 광촉매를 초음파로 분산시키면서 혼합한다. 이 조성물은 가열하는 경우 탈수축합반응에 의해 경화되어 코팅 박막을 형성한다. 본 발명의 조성물에 형성되는 코팅막의 특성은 연필경도, 투명도 및 메틸렌블루의 분해성능 등으로 평가할 수 있다. Method for producing a coating composition of the present invention is as follows. First, colloidal silica or tetraethoxysilane (TEOS) is used as an inorganic compound, and methyltrimethoxysilane (MTMS) or methyltriethoxysilane (MTES) is dissolved in a solvent as a silane coupling agent and then reacted using an acid catalyst. Subsequently, the photocatalyst is mixed while ultrasonically dispersed. The composition, when heated, cures by dehydration condensation to form a coating thin film. The characteristics of the coating film formed in the composition of the present invention can be evaluated by the pencil hardness, transparency and the decomposition performance of methylene blue.
본 발명의 플라스틱판 코팅용 실리콘계열 하이브리드 하드 코팅제 조성물은 무기 화합물로서 테트라에톡시실란(TEOS) 또는 콜로이드 실리카, 실란커플링제로서 메틸트리메톡시실란(MTMS) 또는 메틸트리에톡시실란(MTES) 및 이산화티타늄(TiO2) 또는 티타늄 알콕사이드 (TTIP-titanium tetraisopropoxide)의 광촉매가 포함되어 이루어진다. 본 발명의 코팅제 조성물을 플라스틱판에 코팅하여 박막을 형성시키면, 이 박막을 갖는 플라스틱 재료의 표면경도를 향상시키고, 우수한 내후성, 내용제성 및 내약품성을 부여할 수 있는 동시에, 광촉매에 의해 내오염특성, 내화학성 및 항균성도 갖게 할 수 있다. The silicone-based hybrid hard coating composition for coating a plastic sheet of the present invention is tetraethoxysilane (TEOS) or colloidal silica as an inorganic compound, methyltrimethoxysilane (MTMS) or methyltriethoxysilane (MTES) as a silane coupling agent, and It comprises a photocatalyst of titanium dioxide (TiO 2 ) or titanium alkoxide (TTIP-titanium tetraisopropoxide). When the coating composition of the present invention is coated on a plastic sheet to form a thin film, the surface hardness of the plastic material having the thin film can be improved, and excellent weather resistance, solvent resistance, and chemical resistance can be imparted, and at the same time, a fouling resistance property is achieved by a photocatalyst. It can also have chemical resistance and antibacterial properties.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 당업계에서 통상의 지식을 가진 자에 있어서 자명할 것이다. Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .
실시예 Example
실험방법 Experiment method
1. 코팅제 조성물 용액의 제조 1. Preparation of Coating Composition Solution
코팅제 조성물의 무기화합물 성분으로서 테트라에톡시실란(TEOS)과 콜로이드 실리카를 사용하였다. 무기화합물 테트라에톡시실란(TEOS)에 대한 실란커플링제로는 메틸트리메톡시실란(MTMS)를 사용하였으며, 무기화합물 콜로이드 실리카에 대한 실란 커플링제로는 메틸트리에톡시실란(MTES)를 사용하였다. 코팅제 조성물의 용매로서 에탄올과 이소프로필 알코올 사용하였으며, 산 촉매로는 염산을 사용하였다. Tetraethoxysilane (TEOS) and colloidal silica were used as the inorganic compound component of the coating composition. Methyltrimethoxysilane (MTMS) was used as the silane coupling agent for the inorganic compound tetraethoxysilane (TEOS), and methyltriethoxysilane (MTES) was used as the silane coupling agent for the inorganic compound colloidal silica. . Ethanol and isopropyl alcohol were used as solvents for the coating composition, and hydrochloric acid was used as the acid catalyst.
먼저, 가수분해속도가 느린 테트라에톡시실란(TEOS)을 에탄올에 에탄올과 동일한 중량 비율로 넣은 후, 물의 첨가량 비율을 변화시키면서 실험하였다. 테트라에톡시실란(TEOS), 에탄올 및 물의 혼합물을 2 시간 동안 가수분해시킨 다음 0.1 M의 염산용액을 넣어 pH를 원하는 값으로 조절하였다. First, tetraethoxysilane (TEOS) having a slow hydrolysis rate was added to ethanol at the same weight ratio as ethanol, and then experimented with varying the amount of water added. The mixture of tetraethoxysilane (TEOS), ethanol and water was hydrolyzed for 2 hours and then the pH was adjusted to the desired value by adding 0.1 M hydrochloric acid solution.
실란커플링제 메틸트리메톡시실란(MTMS)를 TEOS:MTMS의 중량비율이 1:1, 1:2, 1:4, 1:6의 비율이 되도록 첨가량을 각각 변화시키면서 첨가하였다. 실란커플링제를 첨가한 후 24 시간 교반하면서 가수분해와 축합반응을 진행시켰다. The silane coupling agent methyltrimethoxysilane (MTMS) was added with varying amounts of addition so that the weight ratio of TEOS: MTMS was 1: 1, 1: 2, 1: 4, 1: 6. After the addition of the silane coupling agent, the hydrolysis and the condensation reaction proceeded with stirring for 24 hours.
한편, 콜로이드 실리카를 무기화합물로서 사용하는 경우 실란커플링제 메틸트리에톡시실란(MTES)을 콜로이드실리카:MTES의 중량비율이 1:1, 1:2, 1:4의 비율이 되도록 양을 변화시키면서 실험을 진행하였다. On the other hand, when colloidal silica is used as an inorganic compound, the amount of silane coupling agent methyltriethoxysilane (MTES) is changed so that the weight ratio of colloidal silica: MTES is 1: 1, 1: 2, 1: 4. The experiment was conducted.
제조된 코팅제 조성물에 광촉매로서 이산화티타늄(TiO2)을 사용하였고, 광촉매는 상기 사용된 무기화합물 및 유기 실란커플링제의 총중량 100중량부에 대해 1-2.5 중량부의 범위내에서 변화시키면서 5분 동안 초음파를 걸어주면서 첨가하여 조성물 용액내에 잘 분산시켰다. Titanium dioxide (TiO 2 ) was used as the photocatalyst in the prepared coating composition, and the photocatalyst was ultrasonic for 5 minutes while varying within the range of 1-2.5 parts by weight based on 100 parts by weight of the total weight of the inorganic compound and the organic silane coupling agent. It was added while hanging to disperse well in the composition solution.
2. 코팅제 조성물 용액을 이용한 코팅 박막의 제조 및 특성 평가 2. Preparation and Characterization of Coating Thin Film Using Coating Composition Solution
제조가 완료된 코팅제 조성물을 사용하여 플라스틱 판에 두께 10-35 ㎛의 코 팅 박막이 형성되도록 코팅하였다. 코팅 박막의 경화는 100℃ 오븐에서 1시간 동안 열경화시켜 행하였다. The coating composition was used to prepare a coating thin film having a thickness of 10-35 μm on a plastic plate. Curing of the coated thin film was carried out by thermosetting in an oven at 100 ° C. for 1 hour.
광촉매가 포함된 기능성 코팅제 조성물로 만들어진 박막의 특성을 평가하기 위해, 10 ppm의 메틸렌 블루 용액을 제조하고, 여기에 자외선을 조사하면서 코팅 박막의 시간에 따른 광분해 활성을 UV에 의한 농도 측정으로 검사하였다. In order to evaluate the properties of the thin film made of the functional coating composition containing a photocatalyst, a 10 ppm methylene blue solution was prepared, and the photodegradation activity over time of the coating thin film was examined by UV concentration measurement while irradiating UV light thereto. .
박막의 내마모성을 조사하기 위해, 연필경도 측정기(CT-PC2, Fain Auto, Pencil hardness testor)를 사용하여 일정한 하중(500g)을 가하면서 내마모성을 측정하였다. Staedtler 연필을 사용하였으며, H-8H, F, HB, B-2B등의 강도를 나타낸다. In order to investigate the wear resistance of the thin film, the wear resistance was measured while applying a constant load (500 g) using a pencil hardness tester (CT-PC2, Fain Auto, Pencil hardness testor). Staedtler pencil was used, showing the strength of H-8H, F, HB, B-2B and the like.
가시광선 영역에서 코팅 박막의 투과율을 조사하기 위해 UV visible spectrometer (UV-1601, Shimadzu)를 사용하여 400-1000nm의 파장영역에서 투과율을 측정하였다. In order to investigate the transmittance of the coating thin film in the visible region, the transmittance was measured in the wavelength region of 400-1000 nm using a UV visible spectrometer (UV-1601, Shimadzu).
실험 결과 Experiment result
1. One. TEOSTEOS 와 Wow MTMSMTMS 로 구성되는 코팅제 박막의 경도 분석 Hardness Analysis of Coating Thin Films
무기화합물인 TEOS와 실란커플링제인 MTMS를 [표 1]에서와 같은 중량 비율로 혼합하여 코팅제 조성물 용액을 제조하고, 이를 사용하여 플라스틱 판을 코팅하여 10 ㎛ 두께의 박막을 제조한 후 박막의 연필 경도를 측정하였다. 박막의 두께가 10 ㎛ 보다 작은 경우 경도 특성이 약해지는 것과 박막 두께가 50 ㎛ 이상인 경우 투명도가 떨어지는 것을 고려하여, 10 ㎛ 및 35 ㎛의 두 가지 두께로 박막을 제조 하고 이를 실험에 사용하였다. TEOS, an inorganic compound, and MTMS, a silane coupling agent, were mixed at the same weight ratio as in Table 1 to prepare a coating composition solution, and then coated with a plastic plate to prepare a thin film having a thickness of 10 μm. The hardness was measured. When the thickness of the thin film is smaller than 10 μm, the hardness characteristics are weakened, and when the thin film thickness is 50 μm or more, the transparency is deteriorated, and thus the thin film was prepared in two thicknesses of 10 μm and 35 μm and used in the experiment.
[표 1]에서 나타난 바와 같이 실란 커플링제의 함유량이 커질수록 연필 경도 높게 나타났으며, TEOS:MTMS의 중량비율이 1:1인 경우는 코팅막이 겔 형태로 되어 불량임을 알 수 있었고, 최소 1:2의 비율이 되어야 적합한 코팅막이 형성되고 연필경도가 3H가 나옴을 알 수 있었다. 또한 TEOS:MTMS의 비율이 클수록 물의 비율이 작을 경우 코팅 막의 형성이 잘 되지 않음을 알 수 있었다. As shown in [Table 1], the higher the content of the silane coupling agent, the higher the pencil hardness. When the weight ratio of TEOS: MTMS was 1: 1, it was found that the coating film was in the form of a gel, which was poor. It was found that the ratio of 2: 2 forms a suitable coating film and the pencil hardness is 3H. In addition, it was found that the larger the ratio of TEOS: MTMS, the less the formation of the coating film when the ratio of water was small.
[표 1] : TEOS/MTMS의 중량비에 따른 코팅 박막의 경도 측정 결과 [Table 1]: Hardness measurement results of the coated thin film according to the weight ratio of TEOS / MTMS
2. 2. 콜로이드실리카와Colloidal silica MTESMTES 로 구성되는 코팅제 박막의 경도 분석 Hardness Analysis of Coating Thin Films
무기물인 콜로이드 실리카와 실란 커플링제인 MTES를 [표 2]에 표시한 비율로 혼합하여 제조하고, 두께 10 ㎛의 박막을 제조하여, 박막의 연필 경도 특성을 조사하였다. [표 2]에서 나타난 바와 같이 실란 커플링제 MTES의 비율이 증가할수록 연필경도는 높게 나타났으며, 콜로이드실리카:MTES의 중량비율이 1:1인 경우는 코팅막이 겔 형태로 되어 불량임을 알 수 있었고, 또한 콜로이드실리카:MTES의 중량비율이 1:4이 되었을 때 코팅막의 연필경도가 4H가 나옴을 알 수 있었다. Colloidal silica, which is an inorganic substance, and MTES, which is a silane coupling agent, were mixed and prepared, and a thin film having a thickness of 10 μm was prepared, and the pencil hardness characteristics of the thin film were examined. As shown in [Table 2], the pencil hardness increased as the ratio of the silane coupling agent MTES was increased, and when the weight ratio of colloidal silica: MTES was 1: 1, it was found that the coating film was in the form of gel and was inferior. Also, when the weight ratio of colloidal silica: MTES was 1: 4, the pencil hardness of the coating film was found to be 4H.
[표 2] : 콜로이드실리카:MTES의 중량비율에 따른 박막의 경도 측정 결과 [Table 2]: Hardness measurement results of the thin film according to the weight ratio of colloidal silica: MTES
3. 광촉매 포함 코팅제에 의한 박막의 표면 특성 분석 3. Surface Characterization of Thin Films by Coatings with Photocatalysts
(1) 박막 표면의 전자현미경 분석 (1) Analysis of electron microscope on the surface of thin film
도 1은 광촉매를 포함한 본 발명의 코팅제 조성물을 사용하여 코팅한 박막의 표면을 SEM(Scanning Electron Microscope, 주사전자현미경)으로 관찰한 결과를 나타낸 사진이다. 코팅 박막 표면에 광촉매가 코팅되어 있는 것을 확인할 수 있었다.1 is a photograph showing the results of observing the surface of a thin film coated with a coating composition of the present invention including a photocatalyst with a scanning electron microscope (SEM). It was confirmed that the photocatalyst was coated on the surface of the coated thin film.
(2) 광택도 분석 (2) glossiness analysis
도 2는 플라스틱 표면에 광촉매가 포함된 본 발명의 코팅제 조성물 용액을 코팅하여 박막을 형성한 전과 후의 표면 변화를 나타낸 사진이다. 박막 표면의 광택도가 향상된 것을 알 수 있었다. FIG. 2 is a photograph showing surface changes before and after forming a thin film by coating a coating composition solution of the present invention including a photocatalyst on a plastic surface. It was found that the glossiness of the thin film surface was improved.
(3) 투과율 분석 (3) transmittance analysis
도 3은 가시광선 영역에서 코팅층의 투과율을 측정한 결과이다. 박막의 두 께가 커지면 투과율이 작아지는 특성을 고려하여 35 ㎛ 두께의 코팅 박막을 제조하고 파장 400-1000nm 범위에서 투과율을 측정하였다. 도 3에서 나타난 바와 같이 본 발명의 코팅제에 의해 형성된 박막은 80-92％의 투과율을 나타내고 있었다. 도 4는 제조된 열 경화된 코팅 박막을 보여주고 있다. Figure 3 is the result of measuring the transmittance of the coating layer in the visible light region. In consideration of the property that the transmittance decreases as the thickness of the thin film increases, a coated thin film having a thickness of 35 μm was prepared and the transmittance was measured in the wavelength range of 400-1000 nm. As shown in FIG. 3, the thin film formed by the coating agent of the present invention exhibited a transmittance of 80-92%. 4 shows the thermally cured coating thin film produced.
(4) 광분해 효과 분석 (4) photolysis effect analysis
광촉매의 광분해 효과를 조사하기 위해 제조한 코팅제 용액에, 광촉매인 이산화티타늄의 함유량을, 실리콘계열 코팅액 성분인 TEOS 또는 콜로이드 실리카 및 MTMS 또는 MTES의 총중량 100중량부에 대해 중량비율로 1-2.5 중량부의 범위내에서 변화시켜 첨가시키면서 5분 동안 초음파를 걸어 잘 분산시켰다. 제조한 이산화티타늄의 광촉매를 포함하는 코팅제 조성물 용액을 코팅하여 코팅 박막을 제조한 후 메틸렌 블루 용액을 10 ppm을 제조하여 광분해 효과를 측정하였다. In the coating solution prepared to investigate the photodegradation effect of the photocatalyst, the content of titanium dioxide, which is a photocatalyst, is 1-2.5 parts by weight in a weight ratio to 100 parts by weight of the total weight of TEOS or colloidal silica and MTMS or MTES, which are components of the silicone-based coating solution. Ultrasonic wave was dispersed for 5 minutes with varying addition within the range. After coating a coating composition solution containing a photocatalyst of titanium dioxide to prepare a coating thin film, 10 ppm of methylene blue solution was prepared to measure photodegradation effect.
도 5에 나타낸 바와 같이 1시간 간격으로 용액을 측정하여 얻은 결과, 광촉매양이 증가할수록 광분해 효과가 증가하고, 3시간이 지나면 메틸렌 블루 용액의 80％ 이상이 분해됨을 알 수 있었다. As shown in FIG. 5, as a result of measuring the solution at an interval of 1 hour, as the amount of photocatalyst increased, the photolysis effect increased, and after 3 hours, 80% or more of the methylene blue solution was decomposed.
광촉매양이 10g의 실란계열 코팅액 성분에 대해 0.25g 이상일 때는 투명성에 문제가 있으며, 0.1-0.15g의 광촉매를 사용한 경우에서도 0.25g에 비해 광분해 효과도 크게 차이가 나지 않기 때문에 투명도를 감안하여 광촉매의 함유량은 실리콘 코팅액 성분 100중량부에 대해 중량비율로 1-1.5 중량부가 적당한 것으로 판단하였다. When the amount of photocatalyst is 0.25g or more with respect to 10g of the silane-based coating liquid, there is a problem in transparency, and even when 0.1-0.15g of photocatalyst is used, the photodegradation effect is not significantly different from 0.25g. The content was determined to be 1-1.5 parts by weight in a weight ratio relative to 100 parts by weight of the silicone coating liquid component.
(5) 자외선 조사량에 따른 광분해 효과 분석(5) Analysis of photolysis effect according to the amount of ultraviolet radiation
자외선 조사량에 따른 광분해 효과를 살펴보기 위해 광촉매를 0.1g을 첨가한 코팅막을 제조하고 자외선 조사량을 20W 및 40 W를 사용하여 광분해 실험을 하였다. 도 6에서 보는 바와 같이 자외선 조사량이 2배로 증가하면 광분해 효과도 약 2배 증가함을 알 수 있었다. In order to examine the photodegradation effect according to the UV irradiation amount, a coating film to which 0.1g was added to the photocatalyst was prepared, and photolysis experiment was performed using 20W and 40W of UV irradiation amount. As shown in FIG. 6, when the UV irradiation amount increased by 2 times, the photolysis effect also increased by about 2 times.
(6) 에탄올 첨가량에 따른 광분해 효과 분석(6) Analysis of photodegradation effect according to ethanol addition amount
광촉매 첨가시 코팅제 용액의 용매인 에탄올의 첨가량에 따른 효과를 살펴보기 위해 광촉매 0.1g을 첨가한 후, 이를 이용하여 코팅 박막을 제조하였다. 이렇게 제조된 코팅 박막에 40W 조사량의 자외선을 사용하였다. 그 결과를 도 7에 나타내었다. 도 7 에서 나타낸 바와 같이 에탄올의 첨가량에 따른 효과는 크게 없음을 알 수 있었다. When the photocatalyst was added, 0.1 g of the photocatalyst was added to examine the effect of the amount of ethanol which is a solvent of the coating solution, and then a coating thin film was prepared. 40 W of ultraviolet light was used for the coating thin film thus prepared. The results are shown in FIG. As shown in Figure 7 it can be seen that the effect of the added amount of ethanol is not significantly.
이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현 예일 뿐이며, 이에 본 발명의 범위가 제한되는 것이 아닌 점은 명백하다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항과 그의 등가물에 의하여 정의된다고 할 것이다. Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that the specific technology is merely a preferred embodiment, and the scope of the present invention is not limited thereto. Thus, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.
도 1은 광촉매를 포함한 본 발명의 코팅제 조성물을 코팅한 박막의 표면을 SEM(Scanning Electron Microscope, 주사전자현미경)으로 관찰한 결과이다. 1 is a result of observing the surface of a thin film coated with a coating composition of the present invention including a photocatalyst with a scanning electron microscope (SEM).
도 2는 플라스틱 표면에 광촉매가 포함된 본 발명의 기능성 코팅제 조성물 용액을 사용하여 박막을 형성한 전과 후의 표면 변화를 나타낸 사진이다. 2 is a photograph showing surface changes before and after forming a thin film using the functional coating composition solution of the present invention including a photocatalyst on a plastic surface.
도 3은 가시광선 영역에서 코팅층의 투과율을 측정한 결과이다. Figure 3 is the result of measuring the transmittance of the coating layer in the visible light region.
도 4는 광촉매를 포함한 본 발명의 코팅제 조성물로 제조하여 열 경화된 코팅막 사진이다. Figure 4 is a photograph of the coating film heat-cured prepared by the coating composition of the present invention including a photocatalyst.
도 5는 본 발명의 광촉매 이산화티타늄 포함 코팅제 용액을 이용하여 코팅박막을 제조한 후 메틸렌 블루용액의 광분해 특성을 실험한 결과이다. 5 is a result of experiments on the photodegradation characteristics of the methylene blue solution after preparing a coating thin film using the photocatalyst titanium dioxide-containing coating solution of the present invention.
도 6은 본 발명의 광촉매 코팅제 용액을 이용하여 코팅박막을 제조한 후 자외선 조사량에 따른 광분해 효과를 측정한 실험 결과이다. 6 is an experimental result of measuring the photodegradation effect according to the UV irradiation amount after the production of the coating thin film using the photocatalyst coating solution of the present invention.
도 7은 광촉매 첨가시 코팅제 용액의 용매인 에탄올의 첨가량에 따른 광분해 효과를 측정한 실험 결과이다. 7 is an experimental result of measuring the photodegradation effect according to the addition amount of ethanol which is a solvent of the coating solution when the photocatalyst is added.
Claims (6)
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| CN108610919B (en) * | 2016-12-26 | 2021-03-30 | 3M创新有限公司 | Preparation method of durable and easy-to-clean antibacterial coating composition |
| KR102021420B1 (en) * | 2019-02-27 | 2019-09-16 | 우태영 | Air filter made of glass or aluminum structure using photocatalyst precoat and manufaturing method there of |
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| JP2004143452A (en) * | 2002-09-30 | 2004-05-20 | Toto Ltd | Self-cleaning aqueous coating composition and self- cleaning member |
| JP2005061156A (en) * | 2003-08-19 | 2005-03-10 | Matsushita Electric Works Ltd | Manufacturing method for functional building member |
| KR20050072928A (en) * | 2004-01-08 | 2005-07-13 | 박주민 | Non-stick and easy cleaning ceramic coating agent |
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| JP2004143452A (en) * | 2002-09-30 | 2004-05-20 | Toto Ltd | Self-cleaning aqueous coating composition and self- cleaning member |
| JP2005061156A (en) * | 2003-08-19 | 2005-03-10 | Matsushita Electric Works Ltd | Manufacturing method for functional building member |
| KR20050072928A (en) * | 2004-01-08 | 2005-07-13 | 박주민 | Non-stick and easy cleaning ceramic coating agent |
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