KR101291722B1 - Composite of anti-fouling paint and manufacturing process of the same - Google Patents
Composite of anti-fouling paint and manufacturing process of the same Download PDFInfo
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- KR101291722B1 KR101291722B1 KR1020120008753A KR20120008753A KR101291722B1 KR 101291722 B1 KR101291722 B1 KR 101291722B1 KR 1020120008753 A KR1020120008753 A KR 1020120008753A KR 20120008753 A KR20120008753 A KR 20120008753A KR 101291722 B1 KR101291722 B1 KR 101291722B1
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
Abstract
Description
본 발명은 방오도료 조성물 및 그 제조방법에 관한 것으로, 더욱 상세하게는 수용성의 무기염을 방오제로 사용하여 방오능력을 현저히 향상시킬 수 있도록 함과 동시에 종래의 유기주석계 화합물(TBT::Tributyltin)이 함유된 방오도료가 초래하는 해양생태계의 파괴 같은 심각한 환경오염의 문제를 방지 또는 완화시킬 수 있도록 하는 한편, 선체의 표면에 대한 접착력과 방수성을 향상시킬 수 있도록 하고, 색상을 창출할 수 있도록 한 방오도료 조성물 및 그 제조방법에 관한 것이다.The present invention relates to an antifouling coating composition and a method of manufacturing the same, and more particularly, by using a water-soluble inorganic salt as an antifouling agent, to significantly improve the antifouling ability, and at the same time, a conventional organotin compound (TBT :: Tributyltin) Antifouling to prevent or mitigate serious environmental pollution problems such as destruction of marine ecosystems caused by contained antifouling paints, improve adhesion and waterproofness of the hull surface, and create color A coating composition and its manufacturing method.
일반적으로, 방오도료는 선저부(船底部) 같은 선체의 외표면이나 수중 구조물 또는 어구(漁具)의 외부 표면에 도포하여 해수의 침적 및 도막의 표면 오염을 유발하는 해양 생물의 부착과 증식 및 성장을 방지하거나 제어하는 것이다.In general, antifouling paints are applied to the outer surface of a hull, such as the bottom of a ship, or to the outer surface of an underwater structure or fishing gear, causing the deposition, proliferation, and growth of marine organisms that cause seawater deposition and surface contamination of coatings. To prevent or control.
선체의 바닥부분((船底部)이나 수중 구조물 등이 장기간 수중에 잠겨 있는 경우, 따개비, 홍합, 조개, 굴, 갑각홍합 및 삿갓조개와 같은 동물류, 파래와 같은 해초류 및 수중 박테리아와 같은 각종 해양 생물이 표면에 부착·증식하게 되어 외관이 불량해지는 것은 물론, 심한 경우 그 기능이 저하되거나 상실된다. When the bottom part of the hull or underwater structure is immersed in water for a long time, various marine life such as seaweeds such as sea shells and underwater bacteria, animals such as barnacles, mussels, shellfish, oysters, shellfish mussels and shellfish It adheres to and proliferates on this surface, which not only deteriorates the appearance, but also worsens or loses its function in severe cases.
특히, 선저부에 이러한 해양 생물이 부착하여 증식하면 선박 외판 전체의 표면 조도가 증가하여 선속(船速)이 현저히 저하되면서 연료 소비가 증가할 수 있는데, 실제 연구결과에 따르면 선체 표면이 0.01mm 거칠어질 때마다 연료소모가 0.3∼1%씩 증가되는 것으로 알려진다.In particular, when these marine organisms adhere to and propagate on the bottom, the surface roughness of the entire ship's outer shell increases, which leads to a significant decrease in ship speed, which increases fuel consumption. It is known that fuel consumption increases by 0.3 to 1% each time it loses.
또, 선저부에 이미 해양 생물이 부착·증식되어 있는 경우, 해양 생물을 선저부로부터 제거하기 위해서는 필요 이상의 노력과 오랜 작업 시간이 필요하며, 수중 구조물에 부착하여 번식하는 박테리아 위에 점액성의 진흙 물질(Slime) 등이 부착하여 박테리아를 부패시키는 경우나, 점착성을 갖는 대형 생물이 철강재로 이루어진 수중 구조물에 부착, 번식하여 수중 구조물의 부식방지 도막(途膜)을 손상시키는 경우, 수중 구조물의 강도나 기능을 저하시켜 수명을 현저히 단축시키게 된다는 심각한 문제점이 있다.In addition, when marine life is already attached to and propagated at the bottom, more effort and longer working time are required to remove the marine life from the bottom. In the case of attaching slime, etc., to rot bacteria, or when large organisms with tackiness adhere to and propagate to the steel structure, damage to the corrosion-resistant coating film of the underwater structure. There is a serious problem that the reduction in life is significantly shortened.
이러한 문제를 미연에 방지하기 위하여, 통상 선저부에는 트리부틸주석메타크릴레이트, 메틸메타크릴레이트 등의 공중합체 및 아산화구리(Cu2O)를 함유하는 방오도료가 도장(塗裝)되고 있다.In order to prevent such a problem in advance, the bottom part is usually coated with a copolymer such as tributyltin methacrylate and methyl methacrylate and an antifouling paint containing copper nitrous oxide (Cu 2 O).
이러한 방오도료 조성물을 구성하는 상기 트리부틸주석메타크릴레이트, 메틸메타크릴레이트의 공중합체는 해수중에서 가수분해되어, 비스트리부틸주석옥사이드(Bu3Sn-OSnBu3:Bu는 부틸기) 또는 트리부틸주석할로겐화물(Bu3SnX:X는 할로겐 원자)과 같은 유기주석 화합물(TBT:Tributyltin)을 방출하여 방오효과를 나타낸다. The copolymer of tributyltin methacrylate and methyl methacrylate constituting the antifouling coating composition is hydrolyzed in seawater, thereby forming bistributyltin oxide (Bu 3 Sn-OSnBu 3 : Bu is a butyl group) or tributyl It releases an organotin compound (TBT: Tributyltin) such as tin halide (Bu 3 SnX: X is a halogen atom) to exhibit an antifouling effect.
상기 공중합체는 가수분해성 자기연마형(Self-polishing type)이기 때문에, 가수분해된 공중합체 자체도 수용성으로 바뀌어 해수중에 용해되므로써, 선저부 도막 표면에는 수지 잔류물이 남지 않고 지속적으로 활성을 갖는 표면을 유지한다.Since the copolymer is a hydrolyzable self-polishing type, the hydrolyzed copolymer itself is also changed to water solubility and dissolved in seawater, so that the surface of the bottom coating film is continuously active without remaining resin residue. Keep it.
그러나, 전술한 공중합체의 가수분해과정에서 방출되는 유기주석 화합물은 방오효과가 탁월한 반면에 그 독성 또한 매우 강하여 소라 등 복족류의 임포섹스(암컷의 수컷화)를 유발하는 등 기형 조개 또는 기형 어류의 발생을 초래하거나 먹이사슬을 통하여 해양생태계를 교란시키거나 심각한 피해를 야기시킬 수 있는 환경호르몬 물질인 것으로 밝혀져 2001년 국제해사기구(IMO)에서 채택된 "선박용 유해 방오시스템 규제협약"에 의하여 2005년부터 그 사용이 규제되고 있다. However, the organotin compound released during the hydrolysis of the above copolymer has excellent antifouling effect, while its toxicity is also very strong, causing the imposition of the gastrointestinal species such as conch (male male). In 2005, the Marine Harmful Antifouling System Regulatory Convention, adopted by the International Maritime Organization (IMO), was found to be an environmental hormone substance that could cause outbreaks or disrupt marine ecosystems or cause serious damage through the food chain. Its use has been regulated since.
이에 따라 종래의 유기주석계 화합물(TBT)을 함유하는 방오도료를 대체할 수 있는 비주석계(Tin free) 방오도료의 개발이 절실히 요구되고 있다.Accordingly, there is an urgent need to develop a tin free antifouling paint that can replace the antifouling paint containing a conventional organotin compound (TBT).
본 발명은 이와 같은 종래의 문제점을 해결하기 위한 것으로, 그 목적은 수용성의 무기염을 방오제로 사용하여 방오능력을 현저히 향상시킬 수 있도록 함과 동시에 종래의 유기주석 화합물(TBT::Tributyltin)이 함유된 방오도료가 초래하는 해양생태계의 교란이나 파괴 같은 심각한 환경오염의 문제를 방지 또는 완화시킬 수 있도록 한 새로운 방오도료 조성물을 제공하는 것이다.The present invention is to solve such a conventional problem, the object is to use a water-soluble inorganic salt as an antifouling agent to significantly improve the antifouling ability and at the same time contains a conventional organotin compound (TBT :: Tributyltin) It is to provide a new antifouling coating composition that can prevent or alleviate the problem of serious environmental pollution such as disturbance or destruction of the marine ecosystem caused by the old antifouling paint.
본 발명의 다른 목적은 선체의 표면에 대한 접착력과 방수성을 향상시킬 수 있도록 하고, 색상을 창출할 수 있도록 한 새로운 방오도료 조성물을 제공하는 것이다.Another object of the present invention is to provide a new antifouling coating composition to improve the adhesion and waterproofness to the surface of the hull, and to create a color.
본 발명의 또 다른 목적은 상기의 향상된 기능을 갖는 새로운 방오도료 조성물의 제조방법을 제공하는 것이다.Still another object of the present invention is to provide a method for preparing a new antifouling coating composition having the above improved function.
상기의 목적을 달성하기 위하여, 본 발명에 따른 방오도료 조성물은 증류수 48중량%, 불화마그네슘(MgF2:Sellaite) 10중량%, 이산화규소(SiO2) 5중량%, 수산화알루미늄(Al(OH)3) 10중량%, 폴리메틸메타크릴레이트(PMMA:Poly Methylmetacrylate) 20중량%, 옻엑기스 5중량% 및 알킬암모늄염계 분산제 2중량%로 이루어진 특징을 갖는다.In order to achieve the above object, the antifouling coating composition according to the present invention is 48% by weight of distilled water, magnesium fluoride (MgF 2 : Sellaite) 10% by weight, silicon dioxide (SiO 2 ) 5% by weight, aluminum hydroxide (Al (OH)) 3 ) 10% by weight, polymethyl methacrylate (PMMA: Poly Methyl methacrylate) 20% by weight, lacquer extract 5% by weight and alkylammonium salt-based dispersant 2% by weight.
본 발명에 따른 방오도료 조성물의 제조방법은 증류수 48중량%에 불화마그네슘(MgF2) 10중량%, 이산화규소(SiO2) 5중량%, 수산화알루미늄(Al(OH)3) 10중량%를 첨가하고, 호모믹서기에서 4,500∼6,000rpm으로 20∼40분 동안 교반하는 1차 교반단계와; 상기 1차 교반단계의 종료 후 상기 호모믹서기에 폴리메틸메타크릴레이트(PMMA:Poly Methylmetacrylate) 20중량%를 투입하고, 1,500∼2,500rpm으로 20∼40분 동안 교반하는 2차 교반단계와; 상기 2차 교반단계의 종료 후 상기 호모믹서기에 옻엑기스 5중량% 및 알킬암모늄염계 분산제 2중량%를 투입하고, 700∼1,200rpm으로 50분∼1시간 10분 동안 교반하는 3차 교반단계를 포함하여 구성된다. Method for preparing an antifouling coating composition according to the present invention is added to 48% by weight of distilled water 10% by weight of magnesium fluoride (MgF 2 ), 5% by weight of silicon dioxide (SiO 2 ), 10% by weight of aluminum hydroxide (Al (OH) 3 ) And a first stirring step of stirring at 4,500 to 6,000 rpm for 20 to 40 minutes in a homo mixer; A second stirring step of adding 20% by weight of polymethyl methacrylate (PMMA) to the homomixer after the completion of the first stirring step, and stirring at 1,500 to 2500 rpm for 20 to 40 minutes; After the completion of the second agitation step, 5% by weight of lacquer extract and 2% by weight of an alkylammonium salt-based dispersant are added to the homomixer, and includes a third agitation step of stirring at 700 to 1200 rpm for 50 minutes to 1 hour 10 minutes. It is configured by.
본 발명을 적용하면, 불화마그네슘(MgF2:Sellaite), 수산화알루미늄(Al(OH)3) 같은 수용성 무기질 성분의 방오제가 함유되기 때문에 뛰어난 방오효과를 발휘함과 동시에 장기간 바닷물에 노출되는 경우에도 종래의 유기주석 화합물(TBT)에 의하여 초래되었던 해양생태계의 교란이나 파괴 같은 환경오염을 유발시키지 않는다는 효과가 있다. According to the present invention, since an antifouling agent containing a water-soluble inorganic component such as magnesium fluoride (MgF 2 : Sellaite) and aluminum hydroxide (Al (OH) 3 ) is contained, it exhibits excellent antifouling effect and is exposed to seawater for a long time. It is effective in not causing environmental pollution such as disturbance or destruction of marine ecosystem caused by TBT.
또, 본 발명을 적용하면 수용성이기 때문에 선박표면에의 도포작업시 접착력이 뛰어나고 방수성이 크게 향상되며, 무기질이면서도 탄성율을 가지고 있고, 색상을 창출할 수 있다는 효과가 있다. In addition, since the present invention is water-soluble, it has excellent adhesive strength and greatly improves waterproofness when applied to a ship surface, and has an effect of being inorganic and elastic, and creating color.
이하, 본 발명의 바람직한 실시예를 보다 상세하게 설명한다.Hereinafter, preferred embodiments of the present invention will be described in more detail.
본 발명에 따른 방오도료 조성물은 증류수 48중량%, 불화마그네슘(MgF2:Sellaite) 10중량%, 이산화규소(SiO2) 5중량%, 수산화알루미늄(Al(OH)3) 10중량%, 폴리메틸메타크릴레이트(PMMA) 20중량%, 옻엑기스 5중량%, 알킬암모늄염계 분산제2중량%로 이루어진 특징을 갖는다.The antifouling coating composition according to the present invention is 48% by weight of distilled water, 10% by weight of magnesium fluoride (MgF 2 : Sellaite), 5% by weight of silicon dioxide (SiO 2 ), 10% by weight of aluminum hydroxide (Al (OH) 3 ), polymethyl 20 wt% of methacrylate (PMMA), 5 wt% of lacquer extract, and 2 wt% of an alkylammonium salt-based dispersant.
셀라이트라 불리우는 상기 불화마그네슘(MgF2)은 무색 또는 흰색을 띠는 주상 또는 침상의 정방정계 광물질로서, 본 발명에서는 방오제로 적용된다.The magnesium fluoride (MgF 2 ), called celite, is a colorless or white columnar or acicular tetragonal mineral, and is applied as an antifouling agent in the present invention.
상기 SiO2(Silica)는 화학적으로 비활성이고, 보통 고온에서 안정하므로 윤활제, 수압용 유체, 방수제, 광택제, 에나멜 등에 쓰이는데, 본 발명에서는 방수용으로 적용된다.The SiO 2 (Silica) is chemically inert and is usually stable at high temperatures, so that it is used in lubricants, hydraulic fluids, waterproofing agents, varnishes, enamels, and the like.
또, 상기 수산화알루미늄(Al(OH)3)은 알루미늄염의 수용액에 암모니아수를 가하면 겔(Gel)과 같이 가라앉는 흰색의 물질로서 산화 알루미늄의 제조 원료, 흡착제, 제산제(制酸劑) 등으로 사용되는데, 본 발명에서는 흡착제(Binder)로 사용된다.In addition, the aluminum hydroxide (Al (OH) 3 ) is a white substance that sinks like a gel when ammonia water is added to an aqueous solution of aluminum salt, and is used as a raw material for producing aluminum oxide, an adsorbent, an antacid, and the like. In this invention, it is used as a binder.
한편, 상기의 폴리메틸메타크릴레이트(PMMA:polymethyl methacrylate)는 공중합체로 사용되는 것으로, 플라스틱 중에서도 내후성 및 광학적성질, 특히 투명성이 대단히 우수한 수지이며, 내약품성에 대해서는 황산, 염산, 잘산, 가성소오다, 가성칼리등과 같은 무기 약품에는 실온에서 강한 저항성을 갖는 특성을 보인다.On the other hand, the polymethyl methacrylate (PMMA: polymethyl methacrylate) is used as a copolymer, a resin excellent in weatherability and optical properties, especially transparency among plastics, sulfuric acid, hydrochloric acid, zalic acid, caustic for the chemical resistance Inorganic chemicals such as Oda and Caustic exhibit strong resistance at room temperature.
상기 옻엑기스는 고형분이 10% 함유된 것으로, 본 발명에서는 방청 및 방수제로 적용되고, 상기 알킬암모늄염계 분산제는 지방아민을 염산이나 초산에서 중화하여 수용성을 갖도록 하며 방청제로 사용되는데, 친수기를 금속이나 철광석에 흡착시켜 물과의 접촉이 차단되도록 함으로써 방청기능을 갖게 되는 것이다.The lacquer extract is a solid content of 10%, is applied as a rust preventive and waterproofing agent in the present invention, the alkyl ammonium salt-based dispersant to neutralize the fatty amines in hydrochloric acid or acetic acid to be water-soluble and used as a rust inhibitor, By adsorbing on the iron ore to prevent contact with water will have a rust preventive function.
이와 같이 이루어지는 본 발명에 따른 방오도료는 다음과 같은 공정에 의하여 제조된다. Thus, the antifouling paint according to the present invention is produced by the following process.
즉, 증류수 48중량%에 불화마그네슘(MgF2) 10중량%, 이산화규소(SiO2) 5중량%, 수산화알루미늄(Al(OH)3) 10중량%를 첨가하고, 호모믹서기에서 4,500∼6,000rpm으로 20∼40분 동안 1차로 교반한다(1차교반단계). That is, 10% by weight of magnesium fluoride (MgF 2 ), 5% by weight of silicon dioxide (SiO 2 ) and 10% by weight of aluminum hydroxide (Al (OH) 3 ) are added to 48% by weight of distilled water, and 4,500 to 6,000 rpm in a homomixer. Stir for 20-40 minutes first (first stirring step).
상기 1차 교반단계의 종료 후 상기 호모믹서기에 폴리메틸메타크릴레이트(PMMA:Poly Methylmetacrylate) 20중량%를 투입하고, 1,500∼2,500rpm으로 20∼40분 동안 2차로 교반한다(2차 교반단계). After the completion of the first stirring step, 20% by weight of polymethyl methacrylate (PMMA: Poly Methylmetacrylate) was added to the homomixer and stirred for 2 to 20 minutes at 1,500 to 2500 rpm (secondary stirring step). .
상기 2차 교반단계의 종료 후 상기 호모믹서기에 옻엑기스 5중량% 및 알킬암모늄염계 분산제 2중량%를 투입하고, 700∼1,200rpm으로 50분∼1시간 10분 동안 3차 교반하면, 본 발명에 따른 방오도료 조성물이 얻어지는 것이다.After the completion of the second stirring step, 5% by weight of lacquer extract and 2% by weight of an alkylammonium salt-based dispersant were added to the homomixer, and the mixture was stirred for 3 minutes at 700 to 1,200 rpm for 50 minutes to 1 hour and 10 minutes. The antifouling coating composition according to this invention is obtained.
이와 같이 제조된 방오도료는 무광(無光)이고, 백색으로부터 파스텔톤 색상에 이르기 까지 다양한 색상을 창출할 수 있으며, 선박은 물론, 각종 해상 구조물, 발전소 같이 해양생물의 부착에 따른 설비의 효율저하가 예상되는 모든 부위에 적용될 수 있다.
The antifouling paints manufactured in this way are matt, and can produce various colors ranging from white to pastel colors, and deteriorate the efficiency of equipment due to the attachment of marine life such as ships, various offshore structures and power plants. Can be applied to all sites expected.
Claims (2)
상기 1차 교반단계의 종료 후 상기 호모믹서기에 폴리메틸메타크릴레이트(PMMA:Poly Methylmetacrylate) 20중량%를 투입하고, 1,500∼2,500rpm으로 20∼40분 동안 교반하는 2차 교반단계와;
상기 2차 교반단계의 종료 후 상기 호모믹서기에 옻엑기스 5중량% 및 알킬암모늄염계 분산제 2중량%를 투입하고, 700∼1,200rpm으로 50분∼1시간 10분 동안 교반하는 3차 교반단계를 포함하여 구성되는 것을 특징으로 하는 방오도료 조성물의 제조방법.10% by weight of magnesium fluoride (MgF 2 ), 5% by weight of silicon dioxide (SiO 2 ), and 10% by weight of aluminum hydroxide (Al (OH) 3 ) are added to 48% by weight of distilled water, and 20 to 4,500 to 6,000 rpm in a homomixer. A first stirring step of stirring for 40 minutes;
A second stirring step of adding 20% by weight of polymethyl methacrylate (PMMA) to the homomixer after the completion of the first stirring step, and stirring at 1,500 to 2500 rpm for 20 to 40 minutes;
After the completion of the second agitation step, 5% by weight of lacquer extract and 2% by weight of an alkylammonium salt-based dispersant are added to the homomixer, and includes a third agitation step of stirring at 700 to 1200 rpm for 50 minutes to 1 hour 10 minutes. Method for producing an antifouling paint composition, characterized in that configured.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3154301B2 (en) * | 1991-12-18 | 2001-04-09 | 日本化学工業株式会社 | Antifouling paints against marine fouling organisms. |
| JP2005255858A (en) * | 2004-03-11 | 2005-09-22 | Nara Institute Of Science & Technology | Antifouling resin and method for producing the same, and antifouling coating material |
| US20060204766A1 (en) * | 2005-03-14 | 2006-09-14 | Jds Uniphase Corporation | Anti-moisture and soil-repellent coatings |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3154301B2 (en) * | 1991-12-18 | 2001-04-09 | 日本化学工業株式会社 | Antifouling paints against marine fouling organisms. |
| JP2005255858A (en) * | 2004-03-11 | 2005-09-22 | Nara Institute Of Science & Technology | Antifouling resin and method for producing the same, and antifouling coating material |
| US20060204766A1 (en) * | 2005-03-14 | 2006-09-14 | Jds Uniphase Corporation | Anti-moisture and soil-repellent coatings |
| JP2006255694A (en) * | 2005-03-14 | 2006-09-28 | Jds Uniphase Corp | Water repellent and antifouling coating |
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