KR101752182B1 - Fluoropro polyhedral oligomeric silsesquioxane-silanes for glass-coating agent and manufacturing method of it - Google Patents
Fluoropro polyhedral oligomeric silsesquioxane-silanes for glass-coating agent and manufacturing method of it Download PDFInfo
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- KR101752182B1 KR101752182B1 KR1020150100348A KR20150100348A KR101752182B1 KR 101752182 B1 KR101752182 B1 KR 101752182B1 KR 1020150100348 A KR1020150100348 A KR 1020150100348A KR 20150100348 A KR20150100348 A KR 20150100348A KR 101752182 B1 KR101752182 B1 KR 101752182B1
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- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910000077 silane Inorganic materials 0.000 claims abstract description 51
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 125000000524 functional group Chemical group 0.000 claims abstract description 27
- 239000005871 repellent Substances 0.000 claims abstract description 22
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000008199 coating composition Substances 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 56
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000011521 glass Substances 0.000 claims description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 34
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000006184 cosolvent Substances 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 239000005047 Allyltrichlorosilane Substances 0.000 claims description 13
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 claims description 13
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- -1 3,3,3-trifluoropropyl- Chemical group 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- NYIKUOULKCEZDO-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F NYIKUOULKCEZDO-UHFFFAOYSA-N 0.000 claims description 3
- MLXDKRSDUJLNAB-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F MLXDKRSDUJLNAB-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims 4
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 239000010703 silicon Substances 0.000 claims 2
- WSFGXCFQMASFNR-UHFFFAOYSA-N C(C)O[SiH](OCC)OCC.[Si] Chemical compound C(C)O[SiH](OCC)OCC.[Si] WSFGXCFQMASFNR-UHFFFAOYSA-N 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- RNFNDJAIBTYOQL-UHFFFAOYSA-N chloral hydrate Chemical compound OC(O)C(Cl)(Cl)Cl RNFNDJAIBTYOQL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 28
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 14
- 230000003373 anti-fouling effect Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000010702 perfluoropolyether Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 125000006162 fluoroaliphatic group Chemical group 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000000015 trinitrotoluene Substances 0.000 description 1
Images
Classifications
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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
-
- 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
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
-
- 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
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
본 발명은 불소 사슬과 반응성이 있는 실란 작용기를 가지는 폴리히드랄 올리고머릭 실세스퀴옥산(POSS)을 합성하고 이를 기재의 표면에 코팅함으로써 발수성과 발유성을 가지는 표면을 형성하는 법에 관한 것이다.
이에, 본 발명은 발수 및 발유성 코팅을 위한 코팅제 조성물에 있어서, 실란 작용기계와 불소계 작용기들이 도입된 불소계 폴리히드랄 올리고머릭 실세스퀴옥산(POSS)을 포함하여 구성되는 것을 특징으로 하는 불소계 폴리히드랄 올리고머릭 실세스퀴옥산을 포함하는 발수 및 발유성 코팅을 위한 코팅제 조성물을 제공한다.The present invention relates to a method for synthesizing a polyhydral oligomeric silsesquioxane (POSS) having a silane functional group reactive with a fluorine chain and coating the surface with a substrate to form a surface having water repellency and oil repellency.
Accordingly, the present invention provides a coating composition for water-repellent and oil-repellent coating, which comprises a fluorine-based polyhydral oligomeric silsesquioxane (POSS) to which a silane action machine and fluorine-based functional groups are introduced, A coating composition for a water- and oil-repellent coating comprising a hydral oligomeric silsesquioxane is provided.
Description
본 발명은 불소 사슬과 반응성이 있는 실란 작용기를 가지는 폴리히드랄 올리고머릭 실세스퀴옥산(POSS)을 합성하고 이를 기재의 표면에 코팅함으로써 발수성과 발유성을 가지는 표면을 형성하는 법에 관한 것이다.
The present invention relates to a method for synthesizing a polyhydral oligomeric silsesquioxane (POSS) having a silane functional group reactive with a fluorine chain and coating the surface with a substrate to form a surface having water repellency and oil repellency.
최근 통신, 전기, 전자 산업분야에서 작고 가벼우면서도 고성능을 갖고 또한 내열 기능을 갖는 수지에 대한 필요성이 점차 증대되고 있다. 그러나, 탄소 골격의 플라스틱(plastics)은 내열성 면에서 한계가 있는 반면에, 규소골격의 플라스틱 재료는 한층 더 고도의 성능을 실현할 수 있는 가능성을 가지고 있는 것으로 알려져 있다. 실세스퀴옥산(silsesquioxane)은 규소원자에 대한 산소원자의 비율이 1.5 인 실리콘)silicone) 화합물로 실험식이 RSiO3/2 (여기서, R은 수소 또는 알킬, 알켄, 알릴, 알릴렌 기)이다. 실세스퀴옥산은 내열성이 우수하기 때문에, 반도체의 절연 보호막이나 층간절연막 등의 내열재료로서 널리 이용되고 있으며, 실세스퀴옥산은 일반 고분자들과의 공중합이 가능한 합성의 편이성 및 열적, 기계적, 전기적 특성이 우수하며, 항공우주, 살균제, 광학 재료, 미소전자 공학재료, 반도체 재료, 화장품, 촉매과학 물질 등 다양한 분야에서 활용되고 있는 물질이다.In recent years, there has been a growing need for a resin which is small, light, high in performance, and has a heat-resistant function in the fields of communication, electric and electronic industries. However, while the plastic skeleton plastics have a limit in heat resistance, the plastic skeleton material has the possibility of achieving even higher performance. Silsesquioxane is a silicone silicone compound having a ratio of oxygen atoms to silicon atoms of 1.5. The empirical formula is RSiO 3/2 , wherein R is hydrogen or an alkyl, alkene, allyl, or allylene group. Silsesquioxane is widely used as a heat-resistant material for insulating films and interlayer insulating films of semiconductors because of its excellent heat resistance. The silsesquioxane has a simplicity of synthesis capable of copolymerization with general polymers and thermal, mechanical and electrical And is used in various fields such as aerospace, bactericide, optical materials, microelectronic materials, semiconductor materials, cosmetics, and catalyst science materials.
통상, [RSiO3/2]n으로 나타내어지는 폴리실세스퀴옥산 (Polysilsequioxane, PSSQ)은 크게 나누어 바스켓형, 사다리형, 랜덤형의 3종류로 분류될 수 있다. 그 중에서도, 바스켓형 폴리실세스퀴옥산은 (완전 축합형 POSS)은 분자구조가 명확하고, 구조적 특징으로 골격이 단단한 무기입자의 성질을 가짐과 동시에 나노 사이즈 크기로 유기 용매와 친화력을 가지고 있어 고분자 복합소재 및 무기 첨가제등으로도 사용이 가능하다.Generally, polysilsesquioxane (PSSQ) represented by [RSiO 3/2 ] n can be broadly divided into three types, namely, a basket type, a ladder type, and a random type. Among them, the basket-type polysilsesquioxane (full condensation type POSS) has a clear molecular structure, an inorganic particle nature of a skeleton with a structural characteristic, and an affinity with an organic solvent at a nano size size. It can also be used for composite materials and inorganic additives.
최근 스마트폰, 테블릿 PC 등과 같이 손가락을 사용하는 터치패널이 일상생활 및 산업분야에서 널리 사용되고 있다. 이들 기기의 터치패널의 표면은 손, 손가락 등과 같은 피부와의 접촉시 지문 및 얼룩이 남게 되는데 이는 체내에서 분비되는 지질성분에 의한 것이다. 이러한 지질(기름성분)이 터치패널의 표면에 쉽게 부착되는 이유는 터치패널에 사용되는 강화글래스의 표면에너지가 높아 발생하는 현상이다. 이러한 오염은 디스플레이의 시인성을 저하시켜 사용자의 사용상 불편함을 발현시키고 뿐만아니라 터치스크린상에 입력하는 지문, 보안 패턴등이 노출될 수 있는 보안상의 문제도 발생한다. 이러한 문제를 해결하기 위해 내지문 필름, 내지문 코팅, 방오코팅 등 다양한 기술이 개발되고 있다. Recently, finger-like touch panels such as smart phones and tablet PCs are widely used in everyday life and industrial fields. The surface of the touch panel of these devices is left with fingerprints and smudges when they come into contact with the skin such as hands, fingers, etc., due to lipid components secreted from the body. This lipid (oil component) easily adheres to the surface of the touch panel because the surface energy of the reinforcing glass used in the touch panel is high. Such contamination lowers the visibility of the display, thereby causing inconveniences in the use of the user, as well as security problems such as fingerprints and security patterns input on the touch screen. To solve these problems, various technologies such as my fingerprint film, fingerprint coating and antifouling coating have been developed.
본원 발명에서는 불소계 POSS-실란을 합성하고 이를 강화글래스 표면에 공유결합을 형성시켜 코팅함으로써 투명도는 유지되고 고내구성을 지니며 120°에 가까운 수접촉각과 70°가 넘는 오일 접촉각을 가진 발수-발유 표면을 형성시키는 내용에 관한 것이다.
In the present invention, fluorosurfactant POSS-silane is synthesized and coated by forming a covalent bond on the surface of the reinforcing glass, whereby transparency is maintained and high durability and a water-repellent surface having a water contact angle close to 120 ° and an oil contact angle exceeding 70 ° And the like.
발수, 발유 코팅조성물에 관한 선행기술로서 공개특허 제2003-0045191호 '발수, 발유 및 내오염성 코팅 조성물'은 플루오로지방족기 함유 불포화 에스테르 단량체 및 불포화 실란 단량체를 포함하는 단량체를 공중합시켜 얻은 공중합체를 포함하는 코팅 조성물을 개시한 바 있다.
As a prior art relating to a water-repellent and oil-repellent coating composition, the 'water-repellent, oil-repellent and oil-repellent coating composition' of Patent Publication No. 2003-0045191 relates to a copolymer obtained by copolymerizing a monomer containing a fluoroaliphatic group-containing unsaturated ester monomer and an unsaturated silane monomer ≪ / RTI >
등록특허 제10-1436018호 '과불소 폴리에테르 변성 화합물을 포함하는 방오성 광경화 수지 조성물 및 이를 이용한 하드코트용 방오성 투명 박막'은 과불소 폴리에테르 변성 화합물을 포함하는 방오성 광경화 수지 조성물 및 이를 이용하여 제조되는 하드코트용 방오성 투명 박막에 관한 것으로, 본 발명에 따른 화학식 1로 표시되는 광경화형 과불소 폴리에테르 변성 화합물을 포함하는 방오성 광경화 수지 조성물은 고분자와 같이 유기 재료에 적용이 가능하고, 타 유기약제와 병용성이 뛰어나며, 롤투롤(roll to roll, R2R) 공정의 적용이 가능한 기술을 개시한 바 있다. 또한, 제10-1436018호에 따른 광경화형 과불소 폴리에테르 변성 화합물은 종래의 탄화수소계 이중결합을 보유한 광경화형 화합물과 비교하여, 추가적인 라디칼 개시제 필요없이 자외선 경화 가능하며, 모든 탄화수소 화합물과 반응에 의해 화학적 결합을 이룰 수 있으므로, 이를 포함하는 광경화 수지 조성물은 반응율이 높아 미반응물이 없으며, 그에 따른 기재와의 밀착성 및 피막 형성성이 우수하며나아가, 과불소 폴리에테르 화합물으로 인한 방오성이 상당히 우수하여 하드코트 용 방오성 투명 박막의 제조가 가능하므로, 디스플레이용 기능성 코팅막, 광학 필터, 전자제품의 프레임 또는 표면 코팅, 섬유 발수 코팅, 광학제품 코팅 또는 생활용품, 건축, 조선 토목 분야에 사용되는 방수용 도료 등의 분야에 적용 가능하다. Patent No. 10-1436018 'Antifouling photocurable resin composition containing a perfluoropolyether-modified compound and antifouling transparent film for hard coat using the same is an antifouling photocurable resin composition containing a perfluoropolyether-modified compound and use thereof The antifouling photocurable resin composition containing the photocurable perfluoropolyether-modified compound represented by the general formula (1) according to the present invention can be applied to an organic material such as a polymer, The present invention discloses a technique capable of applying a roll to roll (R2R) process with excellent compatibility with other organic chemicals. In addition, the photo-curable perfluoropolyether modified compound according to the 10-1436018 is capable of ultraviolet curing without the need for an additional radical initiator, as compared to a photo-curable compound having a conventional hydrocarbon-based double bond, The photocurable resin composition containing the photocurable resin composition of the present invention has high reactivity and thus has no unreacted material and is thus excellent in adhesiveness to a base material and film forming property and further has excellent antifouling property due to a perfluoropolyether compound Since it is possible to produce an antifouling transparent thin film for hard coat, a functional coating film for display, an optical filter, a frame or a surface coating of an electronic product, a water repellent coating, an optical product coating or a waterproof paint used in a household product, . ≪ / RTI >
그러나 공개특허 제2003-0045191호나 등록특허 제10-1436018호 등의 기술은 기계적 강도가 기대에 미치지 못하는 문제점이 있었다.
However, the techniques disclosed in Japanese Patent Application Laid-Open No. 2003-0045191 and No. 10-1436018 have a problem in that the mechanical strength is less than expected.
이에, 본 발명은 불소계 POSS 실란을 제조하고 이를 글래스등의 표면에 코팅하여 가시광에 대한 투과도가 우수하고, 기계적 성질이 우수하고 고내구성을 가지며, 발수/발유성을 크게 향상 시켜주는 방법을 제공하는데 그 목적이 있다.
Accordingly, the present invention provides a method for producing a fluorine-based POSS silane and coating it on the surface of a glass or the like to improve transparency to visible light, excellent mechanical properties, high durability, and water / oil repellency It has its purpose.
이에, 본 발명은 발수 및 발유성 코팅을 위한 코팅제 조성물에 있어서, 실란 작용기계와 불소계 작용기들이 도입된 불소계 폴리히드랄 올리고머릭 실세스퀴옥산(POSS)을 포함하여 구성되는 것을 특징으로 하는 불소계 폴리히드랄 올리고머릭 실세스퀴옥산을 포함하는 발수 및 발유성 코팅을 위한 코팅제 조성물을 제공함으로써 상기의 과제를 해결하고자 한다.
Accordingly, the present invention provides a coating composition for water-repellent and oil-repellent coating, which comprises a fluorine-based polyhydral oligomeric silsesquioxane (POSS) to which a silane action machine and fluorine-based functional groups are introduced, And to provide a coating composition for water- and oil-repellent coatings containing hydral oligomeric silsesquioxane.
본 발명은 글래스등의 표면에 코팅하여 가시광에 대한 투과도가 우수하고, 고내구성을 가지며, 발수/발유성을 크게 향상 시켜주는 코팅조성물을 제공한다. The present invention provides a coating composition which is coated on the surface of a glass or the like to provide excellent transmittance to visible light, high durability, and greatly improved water repellency / oil repellency.
본 발명에 따른 불소계 폴리히드랄 올리고머릭 실세스퀴옥산을 포함하는 발수 및 발유성 코팅을 위한 코팅제 조성물을 코팅한 유리는 수접촉각(Water CA)이 91.6~120°이며, 기름(hexadecane) 접촉각(Oil CA)은 19.5~74°의 양호한 측정치를 얻었으며, 모든 실시예에서 9H의 경도를 확인할 수 있었다. The glass coated with a coating composition for a water- and oil-repellent coating comprising a fluorinated polyhydronic oligomeric silsesquioxane according to the present invention has a water CA of 91.6 to 120 ° and a hexadecane contact angle Oil CA) gave good readings of 19.5 to 74 °, and in all the examples the hardness of 9H was verified.
특히, 헵타데카플루오로-1,1,2,2-테트라하이드로데실-POSS-실란의 경우 수접촉각 120°기름접촉각 74°의 효과를 확인할 수 있었다.
Particularly, in the case of heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS-silane, the effect of
도1은 불소계 POSS 실란의 합성 반응식의 설명도이다.
도2는 알릴(Allyl) 작용기가 도입된 불소계 POSS의 (A)구조식 (B) 1H NMR (C)13C NMR (D) 29Si NMR 결과이다.
도3은 3,3,3-트리플루오로프로필-POSS-실란의 구조식이다.
도4는 노나플루오로헥실-POSS-실란의 구조식이다.
도5는 트리데카플루오로-1,1,2,2-테트라하이드로옥틸-POSS-실란의 구조식이다.
도6은 헵타데카플루오로-1,1,2,2-테트라하이드로데실-POSS-실란의 구조식이다.
도7은 에칭 글래스 표면의 (A) 수접촉각 (B) 기름 접촉각의 측정결과를 나타낸 사진이다.
도8은 3,3,3-트리플루오로프로필-POSS-실란으로 표면개질된 글래스 표면의 (A)수접촉각 및 (B) 기름 접촉각의 측정결과를 나타낸 사진이다.
도9는 노나플루오로헥실-POSS-실란으로 표면개질된 글래스 표면의 (A)수접촉각 및 (B) 기름 접촉각의 측정결과를 나타낸 사진이다.
도10은 트리데카플루오로-1,1,2,2-테트라하이드로옥틸-POSS-실란으로 표면개질된 글래스 표면의 (A)수접촉각 및 (B) 기름 접촉각의 측정결과를 나타낸 사진이다.
도11은 헵타데카플루오로-1,1,2,2-테트라하이드로데실-POSS-실란으로 표면개질된 글래스 표면의 (A)수접촉각 및 (B) 기름 접촉각의 측정결과를 나타낸 사진이다.1 is an explanatory diagram of a synthesis reaction formula of a fluorine-based POSS silane.
2 shows the (A) structural formula (B) 1 H NMR (C) 13 C NMR (D) 29 Si NMR results of the fluorinated POSS into which the Allyl functional group is introduced.
3 is a structural formula of 3,3,3-trifluoropropyl-POSS-silane.
4 is a structural formula of nonafluorohexyl-POSS-silane.
5 is a structural formula of tridecafluoro-1,1,2,2-tetrahydrooctyl-POSS-silane.
6 is a structural formula of heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS-silane.
7 is a photograph showing measurement results of (A) water contact angle (B) oil contact angle on the surface of the etching glass.
8 is a photograph showing measurement results of the water contact angle (A) and the oil contact angle (B) of the glass surface surface-modified with 3,3,3-trifluoropropyl-POSS-silane.
9 is a photograph showing measurement results of the water contact angle (A) and the oil contact angle (B) of the glass surface surface-modified with nonafluorohexyl-POSS-silane.
10 is a photograph showing measurement results of the water contact angle (A) and the oil contact angle (B) of the glass surface surface-modified with tridecafluoro-1,1,2,2-tetrahydrooctyl-POSS-silane.
11 is a photograph showing measurement results of the water contact angle (A) and the oil contact angle (B) on the surface of the glass surface-modified with heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS-silane.
이하 첨부된 발명을 참조하여 본 발명을 상세히 설명한다. 본 발명은 불소 사슬과 반응성이 있는 실란 작용기를 가지는 폴리히드랄 올리고머릭 실세스퀴옥산(POSS)을 합성하고 이를 기재의 표면에 코팅함으로써 발수성과 발유성을 가지는 표면을 형성하는 법에 관한 것이다. DETAILED DESCRIPTION OF THE INVENTION The present invention will now be described in detail with reference to the accompanying drawings. The present invention relates to a method for synthesizing a polyhydral oligomeric silsesquioxane (POSS) having a silane functional group reactive with a fluorine chain and coating the surface with a substrate to form a surface having water repellency and oil repellency.
도1은 불소계 POSS 실란의 기본이 되는 합성 반응식의 설명도이다. 도1과 같은 반응을거쳐 불소계 POSS 실란을 합성한다. 상기 합성반응식에서 R은 Cl, O-CH3, O-CH2-CH3 중에서 선택되며, Rf는 (^CF2)n-CF3 (n=0~9)이다. 이하 각 실시예별로 도1의 반응식 설명도를 참조하여 상세히 설명한다.
1 is an explanatory diagram of a synthetic reaction formula which is a basis of a fluorine-based POSS silane. The fluorosurfactant POSS silane is synthesized through the reaction shown in FIG. In the above reaction scheme, R is selected from Cl, O-CH 3 , O-CH 2 -CH 3 , and Rf is (CF 2 ) n-CF 3 (n = 0 to 9). Hereinafter, each embodiment will be described in detail with reference to the explanatory diagram of the reaction formula of FIG.
<실시예1>≪ Example 1 >
먼저, 트리에톡시실란 (Tiethoxy silane) 작용기가 도입된 3,3,3-트리플루오로프로필-POSS(3,3,3-trifluoropropyl-POSS)의 합성은 하기의 단계로 제조된다. First, the synthesis of 3,3,3-trifluoropropyl-POSS (3,3,3-trifluoropropyl-POSS) into which a functional group of triethoxysilane is introduced is prepared by the following steps.
트리메톡시(3,3,3-트리플루오로프로필)-실란(Trimethoxy(3,3,3-trifluoropropyl)-silane)를 THF에 녹이는 단계;Dissolving trimethoxy (3,3,3-trifluoropropyl) -silane in THF;
수산화나트륨(NaOH)을 물에 녹인 후 상기 테트라하이드로퓨란(이하 THF라 칭함) 용액에 넣고 교반하고 40-90℃ 온도에서 2-7시간 동안 반응시키고 상온에서 10-20시간 동안 추가로 반응을 더 진행하는 단계;Sodium hydroxide (NaOH) was dissolved in water, and the solution was added to the above tetrahydrofuran (hereinafter referred to as THF) solution. The mixture was stirred at 40-90 ° C for 2-7 hours and further reacted at room temperature for 10-20 hours An advancing step;
반응을 종료 시킨후 THF 및 미반응 트리메톡시(3,3,3-트리플루오로프로필)-실란 등을 고진공하에서 제거하여. 흰색 파우더 생성물을 얻는 단계;After completion of the reaction, THF and unreacted trimethoxy (3,3,3-trifluoropropyl) -silane were removed under high vacuum. Obtaining a white powder product;
상기 생성물과 트리에틸아민을 THF에 녹인후 알릴트리클로로실란(Allyltrichlorosilane)을 주입하고 교반하여 반응시키는 단계;Dissolving the product and triethylamine in THF, injecting allyltrichlorosilane, and stirring to react;
반응에 의해 생성된 침전물은 필터링 하여 제거하고 남은 용액은 진공건조하는 단계;Filtering the precipitate produced by the reaction and vacuum drying the remaining solution;
진공건조로 얻어진 흰색 파우더를 디클로로메탄(Dichloromethane)에 다시 녹이고 증류수로 수차례 수세하는 단계;White powder obtained by vacuum drying is redissolved in dichloromethane and washed several times with distilled water;
수세 후 물과 분리된 디클로로메탄(Dichloronethane) 용액에 MgSO4를 넣고 수분을 제거한 후 필터링하여 진공건조하여 흰색 파우더 성상의 알릴(Allyl) 작용기가 도입된 불소계 POSS를 회수하는 단계;After washing with water, MgSO 4 is put into a dichloromethane solution, and after removing moisture, it is filtered and vacuum dried to recover a fluorinated POSS into which an allyl functional group of white powder phase is introduced.
알릴 작용기가 도입된 POSS와 트리에톡시실란(triethoxysilane)을 톨루엔에 녹인 후 테트라메틸디비닐디실록산-백금(tetramethyldivinyldisiloxan-platinum) 촉매를 상기 용액에 주입하고 교반하여 반응시키는 단계;POSS and triethoxysilane having an allyl functional group introduced therein are dissolved in toluene, and tetramethyldivinyldisiloxane-platinum catalyst is injected into the solution, followed by stirring and reacting.
용매와 미반응 트리에톡시실란(triethoxysilane)을 진공으로 제거하고 활성탄소를 이용하여 백금 촉매를 제거하는 단계;
Removing the solvent and unreacted triethoxysilane in a vacuum and removing the platinum catalyst using activated carbon;
본 발명의 3,3,3-트리플루오로프로필-POSS 실란은 상기의 제조단계를 거치는 것이 바람직하나, 균등범위의 안에서의 변형된 적용이 가능하다, 예로서, '상기 생성물과 트리에틸아민을 THF에 녹인후 알릴트리클로로실란(Allyltrichlorosilane)을 주입하고 교반하여 반응시키는 단계'에 의하여 형성되는 알릴기의 단일결합 탄소사슬의 수는 더 증가될 수 있다.
The 3,3,3-trifluoropropyl-POSS silane of the present invention is preferably subjected to the above-described preparation steps, but it is possible to apply the modified application within an even range, for example, by reacting the product with triethylamine The number of single bond carbon chains of the allyl group formed by the step of dissolving in THF and then injecting allyltrichlorosilane and stirring and reacting can be further increased.
상기의 제조단계에 따른 바람직한 실시예는 다음과 같다. A preferred embodiment according to the above manufacturing steps is as follows.
트리메톡시(3,3,3-트리플루오로프로필)-실란(Trimethoxy(3,3,3-trifluoropropyl)-silane) (10.05g)을 THF (50mL)에 녹인다. 수산화나트륨(NaOH) (0.8g)를 물(1.044g)에 녹인 후 상기 THF 용액에 넣고 강하게 교반하고 70℃ 온도에서 5시간 동안 반응시키고 상온에서 15시간 동안 추가로 반응을 더 진행한다. 반응을 종료 시킨후 THF 및 미반응 트리메톡시(3,3,3-트리플루오로프로필)-실란 등을 고진공하에서 제거한다. 7.4g의 흰색 파우더 타입의 생성물이 얻어졌다. 이 생성물 2.27g과 트리에틸아민(0.2g)을 THF(45mL)에 녹인후 알릴트리클로로실란(Allyltrichlorosilane) (0.56g)을 이 용액에 주입한하고 교반한다. 4시간 동안 반응을 진행하고 반응에 의해 생성된 침전물은 필터링 하여 제거하고 남은 용액은 진공건조하였다. 진공건조로 얻어진 흰색 파우더를 디클로로메탄(Dichloromethane)에 다시 녹이고 증류수로 수차례 수세하였다. 수세 후 물과 분리된 디클로로메탄(Dichloronethane) 용액에 MgSO4를 넣고 수분을 제거한 후 필터링하여 진공건조하였으며 2g의 흰색 파우더 타입의 알릴(Allyl) 작용기가 도입된 불소계 POSS를 회수하였다. 알릴(Allyl) 작용기가 도입된 불소계 POSS 구조식은 도1(A)와 같으며 이에 대해 1H, 13C, 29Si NMR 분석을 수행하였으며 그 결과는 다음과 같다.Trimethoxy (3,3,3-trifluoropropyl) -silane (10.05 g) was dissolved in THF (50 mL). Sodium hydroxide (NaOH) (0.8 g) was dissolved in water (1.044 g), and the solution was added to the THF solution. The mixture was stirred at 70 ° C for 5 hours and further reacted at room temperature for 15 hours. After completion of the reaction, THF and unreacted trimethoxy (3,3,3-trifluoropropyl) -silane are removed under high vacuum. 7.4 g of a white powder type product was obtained. 2.27 g of the product and 0.2 g of triethylamine are dissolved in 45 ml of THF, and then 0.56 g of allyltrichlorosilane is poured into the solution and stirred. The reaction was carried out for 4 hours. The precipitate produced by the reaction was filtered off and the remaining solution was vacuum dried. The white powder obtained by vacuum drying was redissolved in dichloromethane and washed several times with distilled water. After washing with water, MgSO4 was added to the dichloromethane solution, which was then filtered to remove moisture, followed by vacuum drying, and 2 g of a white powder type of Allyl-functional POSS was recovered. The fluorinated POSS structure having the Allyl functional group is shown in FIG. 1 (A), and 1 H, 13 C and 29 Si NMR analyzes were carried out. The results are as follows.
; 1H NMR (CDCl3, 400MHz) δ 5.77 (m, 1H, Si-CH2-CH=CH2), 5.00 (m, 2H, Si-CH2-CH=CH2), 2.14 (m, 14H, -CH2-CF3), 1.7 (t, 2H, -CH2-Si), 0.95 (m, 14H, Si-CH2-CH2-CF3). (도1(B)); 1 H NMR (CDCl 3, 400MHz ) δ 5.77 (m, 1H, Si-CH 2 -CH = CH 2), 5.00 (m, 2H, Si-CH 2 -CH = CH 2), 2.14 (m, 14H, -CH 2 -CF 3 ), 1.7 (t, 2H, -CH 2 -Si), 0.95 (m, 14H, Si-CH 2 -CH 2 -CF 3 ). (Fig. 1 (B)).
; 13C NMR (CDCl3, 100 MHz) δ 131.41, 128.68, 125.92, and 116.20 (-CF3), 28.17, 27.85, 27.55, and 27.25 (-CH2-CF3), 19.73 (Si-CH2-CH=CH2), 4.03 (Si-CH2-CH2-CF3). (도1(C)); 13 C NMR (CDC l3, 100 MHz) δ 131.41, 128.68, 125.92, and 116.20 (-CF 3), 28.17, 27.85, 27.55, and 27.25 (-CH 2 -CF 3), 19.73 (Si-CH 2 -CH = CH 2 ), 4.03 (Si-CH 2 -CH 2 -CF 3 ). (Fig. 1 (C)).
; 29Si NMR (CDCl3, 79 MHz):- δ -67.75 and -68.45 (CF3-CH2-CH2-SiO1.5), -70.6 (Si-CH2-CH=CH2).(도1(D))
; 29 Si NMR (CDCl 3, 79 MHz): -? -67.75 and -68.45 (CF 3 -CH 2 -CH 2 -SiO 1.5 ), -70.6 (Si-CH 2 -CH = CH 2 ) ))
알릴 작용기가 도입된 POSS 1.92g과 트리에톡시실란(triethoxysilane) 2.5mL을 톨루엔 (5mL)에 녹인 후 테트라메틸디비닐디실록산-백금(tetramethyldivinyldisiloxan-platinum) 촉매 (5 drop)를 상기 용액에 주입하고 교반하였다. 60℃에서 12시간 반응을 진행하고 용매와 미반응 트리에톡시실란(triethoxysilane)은 진공으로 제거하였으며 활성탄소를 이용하여 백금 촉매를 제거하였다. 1.8g의 3,3,3-트리플루오로프로필-POSS-실란을 얻었으며 그 구조는 도3과 같다. 1H NMR을 확인한 결과 Allyl 작용기의 특성 피크인 δ 5.77 (m, 1H, Si-CH2-CH=CH2), 5.00 (m, 2H, Si-CH2-CH=CH2) 가 사라지고 트리에톡시실란(triethoxysilane)의 특성 피크가 생성되었다. ; 1H NMR (CDCl3, 400MHz) δ 3.82 (m, 2H, Si-O-CH2-CH3), 1.22 (t, 3H, Si-O-CH2-CH3).
1.92 g of POSS to which an allyl functional group was introduced and 2.5 mL of triethoxysilane were dissolved in toluene (5 mL), tetramethyldivinyldisiloxane-platinum catalyst (5 drop) was injected into the solution Lt; / RTI > The reaction was carried out at 60 ° C for 12 hours. The solvent and unreacted triethoxysilane were removed in vacuo and the platinum catalyst was removed using activated carbon. 1.8 g of 3,3,3-trifluoropropyl-POSS-silane was obtained and its structure is shown in Fig. The characteristic peaks of the Allyl functional group, δ 5.77 (m, 1H, Si-CH 2 -CH═CH 2) and 5.00 (m, 2H, Si-CH 2 -CH═CH 2) disappeared, and triethoxysilane Lt; / RTI >; 1 H NMR (CDCl 3, 400 MHz)? 3.82 (m, 2H, Si-O-CH2-CH3), 1.22 (t, 3H, Si-O-CH2-CH3).
<실시예2>≪ Example 2 >
트리에톡시실란기를 도입한 노나플루오로헥실-POSS(Triethoxy silane functionalized Nonafluorohexyl-POSS (7Rf4-T8-Triethoxy silane))의 합성은 하기의 단계로 제조될 수 있다. Synthesis of triethoxy silane functionalized Nonafluorohexyl-POSS (7Rf4-T8-Triethoxy silane) in which a triethoxysilane group is introduced can be prepared by the following steps.
노나플루오로헥실 트리에톡시실란(Nonafluorohexyl triethoxysilane)을 트리플루오로톨루엔(Trifluorotoluene)과 THF의 공용매에녹이는 단계;Dissolving Nonafluorohexyl triethoxysilane in a co-solvent of Trifluorotoluene and THF;
상기 용액에 NaOH를 물에 녹인 용액을 넣고 40-90℃에서 2-7시간 동안 반응시킨 후 상온에서 10-20시간 동안 추가반응을 진행한 후 반응을 종료하는 단계; Adding a solution prepared by dissolving NaOH in water to the solution, reacting the mixture at 40-90 ° C for 2-7 hours, further reaction for 10-20 hours at room temperature, and terminating the reaction;
용매와 미반응 트리메톡시(3,3,3-트리플루오로프로필)-실란(Trimethoxy(3,3,3-trifluoropropyl)-silane)등을 고진공하에서 제거하여 흰색 파우더 성상의 생성물을 얻는 단계;Removing a solvent and unreacted trimethoxy (3,3,3-trifluoropropyl) -silane under high vacuum to obtain a white powdery product;
상기 생성물과 트리에틸아민(triethylamine)을 트리플루오로톨루엔과 THF의 공용매에 녹인 후 알릴트리클로로실란(Allyltrichlorosilane)을 이 용액에 주입하여 반응을 진행하는 단계;Dissolving the product and triethylamine in a co-solvent of trifluoro toluene and THF, and injecting allyltrichlorosilane into the solution to proceed the reaction;
반응 종료후 수세하고 건조하여 알릴(Allyl) 작용기가 도입된 노나플루우로헥실-POSS(Nonafluorohexyl-POSS)를 얻는 단계;After completion of the reaction, the reaction mixture is washed with water and dried to obtain nonafluorohexyl-POSS having an Allyl functional group introduced therein;
얻어진 생성물과 트리에톡시실란(triethoxysilane)을 트리플루우로톨루엔과 THF의 공용매에 녹이고 테트라메틸디비닐디실록산-백금(tetramethyldivinyldisiloxan-platinum) 촉매(10 drop)를 주입한 후 반응시키는 단계;Dissolving the obtained product and triethoxysilane in a co-solvent of trifluthrotoluene and THF, injecting tetramethyldivinyldisiloxane-platinum catalyst (10 drop), and reacting;
반응 종료후 미반응물을 제거하고 촉매는 활성탄소를 이용하여 제거하여 노나프루오로헥실-POSS-실란을 얻는 단계;
Removing unreacted materials after completion of the reaction and removing the catalyst using activated carbon to obtain nonafluorohexyl-POSS-silane;
상기의 제조방법에 따른 바람직한 실시예는 아래와 같다. Preferred embodiments according to the above manufacturing method are as follows.
노나플루오로헥실 트리에톡시실란(Nonafluorohexyl triethoxysilane) (15g)을 트리플루오로톨루엔(Trifluorotoluene)과 THF의 공용매(120mL)에녹인다. 상기 용액에 NaOH (0.42g)을 물 (0.55g)에 녹인 용액을 넣고 강하게 교반한다. 70℃에서 5시간 동안 반응시킨 후 상온에서 16시간 동안 추가반응을 진행한 후 반응을 종료하고 용매와 미반응 트리메톡시(3,3,3-트리플루오로프로필)-실란(Trimethoxy(3,3,3-trifluoropropyl)-silane)등을 고진공하에서 제거하였다. 12g의 흰색 파우더 타입의 물질이 생성되었다. 12g의 생성물과 트리에틸아민(triethylamine) 1g을 트리플루오로톨루엔과 THF의 공용매 120mL에 녹인 후 알릴트리클로로실란(Allyltrichlorosilane)(2.5g)을 이 용액에 주입하여 5시간 동안 반응을 진행하였다. 반응 종료후 수세하고 건조하였으며 10g의 알릴(Allyl) 작용기가 도입된 노나플루우로헥실-POSS(Nonafluorohexyl-POSS)를 얻었다. 얻어진 생성물 10g과 트리에톡시실란(triethoxysilane)을 트리플루우로톨루엔과 THF의 공용매 100mL에 녹이고 테트라메틸디비닐디실록산-백금(tetramethyldivinyldisiloxan-platinum) 촉매(10 drop)를 주입한다. 60℃에서 12시간 동안 반응을 진행하였으며 반응 종료후 미반응물을 제거하고 촉매는 활성탄소를 이용하여 제거하였다. 9.8g의 노나프루오로헥실-POSS-실란을 성공적으로 합성하였으며 그 구조식은 도4와 같다.
Nonafluorohexyl triethoxysilane (15 g) is dissolved in 120 mL of a co-solvent of trifluoro toluene and THF. To this solution is added a solution of NaOH (0.42 g) in water (0.55 g) and stirred vigorously. After reacting at 70 ° C for 5 hours, the reaction was allowed to proceed at room temperature for 16 hours. The reaction was terminated and the reaction was terminated by addition of a solvent and unreacted trimethoxy (3,3,3-trifluoropropyl) 3,3-trifluoropropyl) -silane) was removed under high vacuum. 12 g of a white powder type material was produced. 12 g of product and 1 g of triethylamine were dissolved in 120 ml of a co-solvent of trifluorotoluene and THF, and then 2.5 g of allyltrichlorosilane was introduced into the solution, and the reaction was carried out for 5 hours. After completion of the reaction, the reaction mixture was washed with water and dried to obtain 10 g of nonafluorohexyl-POSS having an Allyl functional group introduced therein. 10 g of the obtained product and triethoxysilane are dissolved in 100 ml of a common solvent of triflouro toluene and THF, and tetramethyldivinyldisiloxane-platinum catalyst (10 drop) is introduced. The reaction was carried out at 60 ° C for 12 hours. After completion of the reaction, unreacted material was removed and the catalyst was removed using activated carbon. 9.8 g of nonafluorohexyl-POSS-silane was successfully synthesized and its structural formula is shown in FIG.
<실시예3>≪ Example 3 >
트리에톡시실란 작용기를 도입한 트리데카플루오로-1,1,2,2-에트라하이드로옥틸-POSS(Triethoxy silane functionalized Tridecafluoro-1,1,2,2-tetrahydrooctyl-POSS)의 합성은 하기의 제조단계를 거친다. Synthesis of tridecafluoro-1,1,2,2-etrahydrooctyl-POSS (triethoxy silane functionalized tridecafluoro-1,1,2,2-tetrahydrooctyl-POSS) having a triethoxysilane functional group was carried out by the following method It goes through a manufacturing step.
1H,1H,2H,2H-퍼플루오로옥틸트리에톡시실란(1H,1H,2H,2H-Perfluorooctyltriethoxysilane)을 트리플루오로톨루엔(Trifluorotoluene)과 THF의 공용매에녹이는 단계;1H, 1H, 2H, 2H-Perfluorooctyltriethoxysilane (1H, 1H, 2H, 2H-Perfluorooctyltriethoxysilane) in a co-solvent of Trifluorotoluene and THF;
상기 용액에 NaOH를 물에 녹인 용액을 넣고 40-90℃에서 2-7시간 동안 반응시킨 후 상온에서 10-20시간 동안 추가반응을 진행한 후 반응을 종료하는 단계; Adding a solution prepared by dissolving NaOH in water to the solution, reacting the mixture at 40-90 ° C for 2-7 hours, further reaction for 10-20 hours at room temperature, and terminating the reaction;
용매와 미반응 트리메톡시(3,3,3-트리플루오로프로필)-실란(Trimethoxy(3,3,3-trifluoropropyl)-silane)등을 고진공하에서 제거하여 흰색 파우더 성상의 생성물을 얻는 단계;Removing a solvent and unreacted trimethoxy (3,3,3-trifluoropropyl) -silane under high vacuum to obtain a white powdery product;
상기 생성물과 트리에틸아민(triethylamine)을 트리플루오로톨루엔과 THF의 공용매에 녹인 후 알릴트리클로로실란(Allyltrichlorosilane)을 이 용액에 주입하여 반응을 진행하는 단계;Dissolving the product and triethylamine in a co-solvent of trifluoro toluene and THF, and injecting allyltrichlorosilane into the solution to proceed the reaction;
반응 종료후 수세하고 건조하여 알릴(Allyl) 작용기가 도입된 노나플루우로헥실-POSS(Nonafluorohexyl-POSS)를 얻는 단계;After completion of the reaction, the reaction mixture is washed with water and dried to obtain nonafluorohexyl-POSS having an Allyl functional group introduced therein;
얻어진 생성물과 트리에톡시실란(triethoxysilane)을 트리플루우로톨루엔과 THF의 공용매에 녹이고 테트라메틸디비닐디실록산-백금(tetramethyldivinyldisiloxan-platinum) 촉매를 주입한 후 반응시키는 단계;Dissolving the obtained product and triethoxysilane in a co-solvent of triflouro toluene and THF, injecting a tetramethyldivinyldisiloxane-platinum catalyst, and reacting;
반응 종료후 미반응물을 제거하고 촉매는 활성탄소를 이용하여 제거하여 After completion of the reaction, unreacted materials were removed and the catalyst was removed using activated carbon
트리데카플루오로-1,1,2,2-테트라하이드로옥틸-POSS-실란을 얻는 단계;
To obtain tridecafluoro-1,1,2,2-tetrahydrooctyl-POSS-silane;
상기와 같은 제조단계에 따른 바람직한 실시예는 아래와 같다. A preferred embodiment according to the above manufacturing steps is as follows.
1H,1H,2H,2H-퍼플루오로옥틸트리에톡시실란(1H,1H,2H,2H-Perfluorooctyltriethoxysilane) 20g, H2O 0.89g, NaOH 0.68g, 용매 120 ml를 사용하였으며 16.43g의 생성물을 얻었다. 얻어진 생성물 16.43g, 트리에틸아민(triethylamine) 0.574 g, 알릴트리클로로실란(Allyltrichlorosilane) 1.59 g, 공용매 120 ml를 사용하여 반응을 진행하였으며 7.9g의 알릴작용기가 도입된 POSS 생성물을 얻었다. 반응 생성물 6.1g, 트리에톡시실란(triethoxysilane) 3.1 ml, 테트라메틸디비닐디실록산-백금(tetramethyldivinyldisiloxan-platinum)(7 drop), 용매 12ml을 이용하여 실란화 반응을 진행하였으며 최종적으로 6 g의 트리데카플루오로-1,1,2,2-테트라하이드로옥틸-POSS-실란(Tridecafluoro-1,1,2,2-tetrahydrooctyl-POSS-실란)을 얻었으며 그 구조는 도5와 같다.
(1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane), 0.89 g of H2O, 0.68 g of NaOH and 120 ml of a solvent were used to obtain 16.43 g of a product. The reaction was carried out using 16.43 g of the obtained product, 0.574 g of triethylamine, 1.59 g of allyltrichlorosilane and 120 ml of a co-solvent to obtain 7.9 g of the POSS product into which the allyl functional group was introduced. Silanization reaction was carried out using 6.1 g of the reaction product, 3.1 ml of triethoxysilane, 7 ml of tetramethyldivinyldisiloxane-platinum and 12 ml of solvent, and finally, 6 g of tri Decafluoro-1,1,2,2-tetrahydrooctyl-POSS-silane (Tridecafluoro-1,1,2,2-tetrahydrooctyl-POSS-silane).
<실시예4><Example 4>
트리에톡시실란기가 도입된 헵타데카플루오로-1,1,2,2-테트라하이드로데실-POSS( Triethoxy silane functionalized Heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS) (7Rf8-T8-Triethoxy silane)의 합성은 하기의 단계로 제조된다.Triethoxysilane functionalized Heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS (7Rf8-T8-Triethoxysilane-POSS) in which a triethoxysilane group is introduced ) Is prepared by the following steps.
(헵타데카플루오로-1,1,2,2-테트라하이드로데실)트리에톡시실란 ((Heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane)을 트리플루오로톨루엔(Trifluorotoluene)과 THF의 공용매에녹이는 단계;(Heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane) was prepared by a common use of Trifluorotoluene and THF Dissolving in a medium;
상기 용액에 NaOH를 물에 녹인 용액을 넣고 40-90℃에서 2-7시간 동안 반응시킨 후 상온에서 10-20시간 동안 추가반응을 진행한 후 반응을 종료하는 단계; Adding a solution prepared by dissolving NaOH in water to the solution, reacting the mixture at 40-90 ° C for 2-7 hours, further reaction for 10-20 hours at room temperature, and terminating the reaction;
용매와 미반응 트리메톡시(3,3,3-트리플루오로프로필)-실란(Trimethoxy(3,3,3-trifluoropropyl)-silane)등을 고진공하에서 제거하여 흰색 파우더 성상의 생성물을 얻는 단계;Removing a solvent and unreacted trimethoxy (3,3,3-trifluoropropyl) -silane under high vacuum to obtain a white powdery product;
상기 생성물과 트리에틸아민(triethylamine)을 트리플루오로톨루엔과 THF의 공용매에 녹인 후 알릴트리클로로실란(Allyltrichlorosilane)을 이 용액에 주입하여 반응을 진행하는 단계;Dissolving the product and triethylamine in a co-solvent of trifluoro toluene and THF, and injecting allyltrichlorosilane into the solution to proceed the reaction;
반응 종료후 수세하고 건조하여 알릴(Allyl) 작용기가 도입된 노나플루우로헥실-POSS(Nonafluorohexyl-POSS)를 얻는 단계;After completion of the reaction, the reaction mixture is washed with water and dried to obtain nonafluorohexyl-POSS having an Allyl functional group introduced therein;
얻어진 생성물과 트리에톡시실란(triethoxysilane)을 트리플루우로톨루엔과 THF의 공용매에 녹이고 테트라메틸디비닐디실록산-백금(tetramethyldivinyldisiloxan-platinum) 촉매를 주입한 후 반응시키는 단계;Dissolving the obtained product and triethoxysilane in a co-solvent of triflouro toluene and THF, injecting a tetramethyldivinyldisiloxane-platinum catalyst, and reacting;
반응 종료후 미반응물을 제거하고 촉매는 활성탄소를 이용하여 제거하여 After completion of the reaction, unreacted materials were removed and the catalyst was removed using activated carbon
트리에톡시실란기가 도입된 헵타데카플루오로-1,1,2,2-테트라하이드로데실-POSS을 얻는 단계;
Obtaining heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS having a triethoxysilane group introduced therein;
상기와 같은 제조단계에 따른 바람직한 실시예는 아래와 같다. 같다. A preferred embodiment according to the above manufacturing steps is as follows. same.
(헵타데카플루오로-1,1,2,2-테트라하이드로데실)트리에톡시실란) ((Heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane) 6g, H2O 0.22g, NaOH 0.168g, 공용매 50 ml를 사용하였으며 5g의 생성물을 얻었다. 반응 생성물 5g, 트리에틸아민(triethylamine) 0.5 ml, 알릴트리클로로실란(Allyltrichlorosilane) 0.32 ml, 공용매 50 ml를 사용하여 합성을 진행하여 3.85g의 반응 생성물을 얻었다. 3.85 g의 반응생성물과 트리에톡시실란(triethoxysilane) 3.1 ml, 테트라에틸디비닐디실록산-백금(tetramethyldivinyldisiloxan-platinum)(7 drop), 용매 30 ml를 사용하여 반응을 진행하였고 최종적으로 헵타데카플루오로-1,1,2,2-테트라하이드로데실-POSS(Heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS-실란) 3.8g을 얻었으며 그 구조식은 도6과 같다.
(Heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane), 0.22 g of H 2 O, 0.168 g of NaOH, Each 50 ml was used and 5 g of product was obtained. Synthesis was carried out using 5 g of the reaction product, 0.5 ml of triethylamine, 0.32 ml of allyltrichlorosilane, and 50 ml of a cosolvent to obtain 3.85 g of a reaction product. 3.85 g of the reaction product was reacted with 3.1 ml of triethoxysilane, tetramethyldivinyldisiloxane-platinum (7 drop) and 30 ml of a solvent. Finally, heptadecafluoro 3.8 g of heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS-silane was obtained and its structural formula is shown in FIG.
상기와 같은 방법으로 제조된 불소계-POSS-실란을 이용한 글래스 표면 코팅하고 합성된 불소계-POSS-실란의 물과 기름에 대한 접촉각을 확인하기 위한 실험을 실시하였다. 코팅하기전 글래스 표면을 깨끗하게 하기 위해 KOH 10% 수용액으로 30분간 에칭하였으며 에칭된 표면의 물과 기름에 대한 접촉각을 도7에 도시하였다. 도7에서 도시된 바와 같이 에칭된 표면의 수접촉각(Water CA)은 0° 기름(hexadecane) 접촉각(Oil CA)은 17.5°로 확인되었다.
An experiment was conducted to confirm the contact angle of the fluorinated-POSS-silane with respect to water and oil by coating the glass surface with the fluorinated-POSS-silane prepared as described above. Before coating, the glass surface was etched with
<실험1><Experiment 1>
3,3,3-트리플루오로프로필-POSS-실란(3,3,3-trifluoropropyl-POSS)란의 글래스 코팅.Glass coating of 3,3,3-trifluoropropyl-POSS-silane.
트리플루오로톨루엔(Trifluorotoluene)에 1%의 농도로 3,3,3-트리플루오로프로필-POSS-실란란을 녹인후 이 용액에 에칭된 글래스를 30분간 담지하여 코팅반응을 진행하였다. 이후 깨끗한 트리플루오로톨루엔 용액에 코팅된 글래스를 담지하여 글래스와 반응하지 않은 3,3,3-트리플루오로프로필-POSS-실란을 완전히 제거한 후 물과 기름에 대한 접촉각을 측정하였으며 그 결과를 도8에 도시하였다. 도8에 도시된 바와 같이 수접촉각(Water CA)은 91.6° 기름(hexadecane) 접촉각(Oil CA)은 19.5°로 확인되었다. 또한 코팅면의 연필경도 테스트를 수행하였으며 9H의 경도를 나타내었다.
After dissolving 3,3,3-trifluoropropyl-POSS-silanane in a concentration of 1% in trifluorotoluene, the etched glass was carried on this solution for 30 minutes to carry out the coating reaction. Then, the coated glass was loaded on a clean trifluoro-toluene solution to completely remove 3,3,3-trifluoropropyl-POSS-silane which had not reacted with the glass, and then the contact angle with respect to water and oil was measured. 8. As shown in FIG. 8, the water contact angle (Water CA) was 91.6 ° and the hexadecane contact angle (Oil CA) was 19.5 °. Also, pencil hardness test of the coated surface was carried out and the hardness of 9H was shown.
<실험2><
노나플루오로헥실-POSS-실란의 글래스 코팅.Glass coating of nonafluorohexyl-POSS-silane.
트리플루오로톨루엔에 2%의 농도로 노나플루오로헥실-POSS-실란을 녹인 후 이 용액에 에칭된 글래스를 30분간 담지하여 코팅반응을 진행하였다. 이후 깨끗한 트리니트로톨루엔 용액에 코팅된 글래스를 담지하여 글래스와 반응하지 않은 노나플루오로헥실-POSS-실란을 완전히 제거한 후 물과 기름에 대한 접촉각을 측정하였으며 그 결과를 도9에 나타내었다. 도9에서 보는 바와 같이 수접촉각(Water CA)은 100.1° 기름(hexadecane) 접촉각(Oil CA)은 51.2°로 확인되었다. 또한 코팅면의 연필경도 테스트를 수행하였으며 9H의 경도를 나타내었다. The nonafluorohexyl-POSS-silane was dissolved in trifluoro toluene at a concentration of 2%, and then the etched glass was immersed in this solution for 30 minutes to carry out the coating reaction. Thereafter, the coated glass was loaded on a clean trinitrotoluene solution to completely remove the nonafluorohexyl-POSS-silane which had not reacted with the glass, and the contact angle to water and oil was measured. The results are shown in FIG. As shown in FIG. 9, the water contact angle (Water CA) was 100.1 ° and the hexadecane contact angle (Oil CA) was 51.2 °. Also, pencil hardness test of the coated surface was performed and the hardness of 9H was shown.
<실험3><Experiment 3>
트리데카플루오로-1,1,2,2-에트라하이드로옥틸-POSS-실란의 글래스 코팅.Glass coating of tridecafluoro-1,1,2,2-etrahydrooctyl-POSS-silane.
트리플루오로톨루엔에 2%의 농도로 트리데카플루오로-1,1,2,2-에트라하이드로옥틸-POSS-실란을 녹인 후 이 용액에 에칭된 글래스를 30분간 담지하여 코팅반응을 진행하였다. 이후 깨끗한 트리플루오로톨루엔 용액에 코팅된 글래스를 담지하여 글래스와 반응하지 않은 트리데카플루오로-1,1,2,2-에트라하이드로옥틸-POSS-실란을 완전히 제거한 후 물과 기름에 대한 접촉각을 측정하였으며 그 결과를 도10에 나타내었다. 도10에서 나타난 바와 같이 수접촉각(Water CA)은 110.1°기름(hexadecane) 접촉각(Oil CA)은 62.2°로 확인되었다. 또한 코팅면의 연필경도 테스트를 수행하였으며 9H의 경도를 나타내었다. After dissolving tridecafluoro-1,1,2,2-etrahydrooctyl-POSS-silane in trifluoro toluene at a concentration of 2%, the etched glass was carried on this solution for 30 minutes to carry out the coating reaction . Then, the coated glass was loaded on a clean trifluoro-toluene solution to completely remove tridecafluoro-1,1,2,2-etrahydrooctyl-POSS-silane which had not reacted with the glass, and then contact angle of water and oil And the results are shown in FIG. As shown in FIG. 10, the water contact angle (Water CA) was 110.1 ° and the hexadecane contact angle (Oil CA) was 62.2 °. Also, pencil hardness test of the coated surface was performed and the hardness of 9H was shown.
<실험4><Experiment 4>
헵타데카플루오로-1,1,2,2-테트라하이드로데실-POSS-실란의 글래스 코팅.Glass coating of heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS-silane.
트리플루오로톨루엔에 2%의 농도로 헵타데카플루오로-1,1,2,2-테트라하이드로데실-POSS-실란을 녹인 후 이 용액에 에칭된 글래스를 30분간 담지하여 코팅반응을 진행하였다. 이후 깨끗한 트리플루오로톨루엔 용액에 코팅된 글래스를 담지하여 글래스와 반응하지 않은 헵타데카플루오로-1,1,2,2-테트라하이드로데실-POSS-실란을 완전히 제거한 후 물과 기름에 대한 접촉각을 측정하였으며 그 결과를 그림 10에 나타내었다. 그림에서 보는 바와 같이 수접촉각(Water CA)은 120°, 기름(hexadecane) 접촉각(Oil CA)은 74°로 확인되었다. 코팅면의 연필경도 테스트를 수행하였으며 9H의 경도를 나타내었다.
Heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS-silane was dissolved in trifluoro toluene at a concentration of 2%, and the etched glass was supported on this solution for 30 minutes to carry out the coating reaction. Then, the coated glass was loaded on a clean trifluoro-toluene solution to completely remove heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS-silane which did not react with the glass, and contact angle against water and oil The results are shown in Fig. As shown in the figure, the water contact angle (Water CA) was 120 ° and the hexadecane contact angle (Oil CA) was 74 °. The pencil hardness test of the coated side was carried out and showed a hardness of 9H.
상술한 바와 같이 본 발명은 글래스등의 표면에 코팅하여 가시광에 대한 투과도가 우수하고, 고내구성을 가지며, 발수/발유성을 크게 향상 시켜주는 코팅조성물을 제공한다. INDUSTRIAL APPLICABILITY As described above, the present invention provides a coating composition which is coated on the surface of a glass or the like to provide excellent transparency to visible light, high durability, and greatly improved water repellency / oil repellency.
본 발명에 따른 불소계 폴리히드랄 올리고머릭 실세스퀴옥산을 포함하는 발수 및 발유성 코팅을 위한 코팅제 조성물을 코팅한 유리는 수접촉각(Water CA)이 91.6~120°이며, 기름(hexadecane) 접촉각(Oil CA)은 19.5~74°의 양호한 측정치를 얻었으며, 모든 실시예에서 9H의 경도를 확인할 수 있었다. The glass coated with a coating composition for a water- and oil-repellent coating comprising a fluorinated polyhydronic oligomeric silsesquioxane according to the present invention has a water CA of 91.6 to 120 ° and a hexadecane contact angle Oil CA) gave good readings of 19.5 to 74 °, and in all the examples the hardness of 9H was verified.
특히, 헵타데카플루오로-1,1,2,2-테트라하이드로데실-POSS-실란의 경우 수접촉각 120°기름접촉각 74°의 효과를 확인할 수 있었다.
Particularly, in the case of heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS-silane, the effect of
본 발명을 첨부된 도면과 함께 설명하였으나, 이는 본 발명의 요지를 포함하는 다양한 실시 형태 중의 하나의 실시예에 불과하며, 당업계에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 하는 데에 그 목적이 있는 것으로, 본 발명은 상기 설명된 실시예에만 국한되는 것이 아님은 명확하다. 따라서, 본 발명의 보호범위는 하기의 청구범위에 의해 해석되어야 하며, 본 발명의 요지를 벗어나지 않는 범위 내에서의 변경, 치환, 대체 등에 의해 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리범위에 포함될 것이다. 또한, 도면의 일부 구성은 구성을 보다 명확하게 설명하기 위한 것으로 실제보다 과장되거나 축소되어 제공된 것임을 명확히 한다.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it should be understood that various changes and modifications will be apparent to those skilled in the art. It is to be understood that the present invention is not limited to the above-described embodiments. Accordingly, the scope of protection of the present invention should be construed according to the following claims, and all technical ideas which fall within the scope of equivalence by alteration, substitution, substitution and the like within the scope of the present invention, Range. In addition, it should be clarified that some configurations of the drawings are intended to explain the configuration more clearly and are provided in an exaggerated or reduced size than the actual configuration.
Claims (11)
상기 불소계 폴리히드랄 올리고머릭 실세스퀴옥산의 골격을 형성하는 규소 중 상기 불소계 작용기가 치환되어 있지 않은 나머지 규소에 치환된 실란 작용기는 에틸 트리에톡시실란(Ethyl triethoxy silane)이며,
하기 화학식 2로 표현되고, 상기 실란 작용기는 알릴 작용기가 먼저 도입된 이후에 트리에톡시실란(Triethoxy silane)을 반응시켜 형성되는 3,3,3-트리플루오로프로필-POSS(3,3,3-trifluoropropyl-POSS)-실란을 포함하는 것을 특징으로 하는 발수 및 발유성 코팅을 위한 코팅제 조성물.
[화학식2]
The fluorine-based functional group substituted on the silicon forming the skeleton of the fluorinated polyhydral oligomeric silsesquioxane (POSS) is 3,3,3-trifluoropropyl- (3,3,3-trifluoropropyl-)
The silane functional group substituted with the remaining silicon in which the fluorine-based functional group is not substituted is silicon triethoxy silane,
And the silane functional group is represented by the following formula (2): 3,3,3-trifluoropropyl-POSS (3,3,3-trifluoropropyl) -POSS formed by reacting triethoxy silane after the allyl functional group is first introduced -trifluoropropyl-POSS) -silane. < / RTI >
(2)
상기 불소계 작용기는 노나플루오로헥실-(Nonafluorohexyl)이며,
상기 실란 작용기는 에틸 트리에톡시실란(Ethyl triethoxy silane)이고,
하기의 화학식3 으로 표현되는 노나플루오로헥실-POSS(Ethyl triethoxy silane functionalized Nonafluorohexyl-POSS-실란을 포함하는 것을 특징으로 하는 발수 및 발유성 코팅을 위한 코팅제 조성물.
[화학식3]
3. The method of claim 2,
The fluorine-based functional group is nonafluorohexyl,
The silane functional group is ethyl triethoxy silane,
A coating composition for water- and oil-repellent coating, characterized in that it comprises Ethyl triethoxy silane functionalized Nonafluorohexyl-POSS-silane represented by the following formula (3).
(3)
상기 불소계 작용기는 트리데카플루오로-1,1,2,2-테트라하이드로옥틸-(Tridecafluoro-1,1,2,2-tetrahydrooctyl)이고,
상기 실란 작용기는 에틸 트리에톡시실란(Ethyl triethoxy silane)이고,
하기의 화학식4로 표현되고, 상기 실란 작용기는 알릴 작용기가 먼저 도입된 이후에 트리에톡시실란(Triethoxy silane)을 반응시켜 형성되는 트리데카플루오로-1,1,2,2-에트라하이드로옥틸-POSS-실란을 포함하는 것을 특징으로 하는 발수 및 발유성 코팅을 위한 코팅제 조성물.
[화학식4]
3. The method of claim 2,
The fluorine-based functional group is tridecafluoro-1,1,2,2-tetrahydrooctyl,
The silane functional group Ethyl triethoxy silane,
The silane functional group is represented by the following formula (4), and the silane functional group is represented by the following formula (4): tridecafluoro-1,1,2,2-etrahydrooctyl group formed by reacting triethoxy silane after the allyl functional group is first introduced -POSS-silane. ≪ RTI ID = 0.0 > 11. < / RTI >
[Chemical Formula 4]
상기 불소계 작용기는 헵타데카플루오로-1,1,2,2-테트라하이드로데실-(Heptadecafluoro-1,1,2,2-tetrahydrodecyl)이며,
상기 실란 작용기는 에틸 트리에톡시실란(Ethyl triethoxy silane)이고,
하기의 화학식5로 표현되고, 상기 실란 작용기는 알릴 작용기가 먼저 도입된 이후에 트리에톡시실란(Triethoxy silane)을 반응시켜 형성되는 헵타데카플루오로-1,1,2,2-테트라하이드로데실-POSS-실란을 포함하는 것을 특징으로 하는 발수 및 발유성 코팅을 위한 코팅제 조성물.
[화학식5]
3. The method of claim 2,
The fluorine-based functional group is heptadecafluoro-1,1,2,2-tetrahydrodecyl,
The silane functional group Ethyl triethoxy silane,
Wherein the silane functional group is represented by the following formula (5), wherein the silane functional group is a heptadecafluoro-1,1,2,2-tetrahydrodecyl-1,1,2,2-tetrahydro-naphthyl group formed by reacting triethoxy silane after the allyl functional group is first introduced, A coating composition for water- and oil-repellent coating, characterized in that it comprises POSS-silane.
[Chemical Formula 5]
트리메톡시(3,3,3-트리플루오로프로필)-실란(Trimethoxy(3,3,3-trifluoropropyl)-silane)를 THF에 녹이는 단계;
수산화나트륨(NaOH)을 물에 녹인 후 상기 THF 용액에 넣고 교반하고 40-90℃ 온도에서 2-7시간 동안 반응시키고 상온에서 10-20시간 동안 추가로 반응을 더 진행하는 단계;
반응을 종료 시킨후 THF 및 미반응 트리메톡시(3,3,3-트리플루오로프로필)-실란 등을 고진공하에서 제거하여. 흰색 파우더 생성물을 얻는 단계;
상기 생성물과 트리에틸아민을 THF에 녹인후 알릴트리클로로실란(Allyltrichlorosilane)을 주입하고 교반하여 반응시키는 단계;
반응에 의해 생성된 침전물은 필터링 하여 제거하고 남은 용액은 진공건조하는 단계;
진공건조로 얻어진 흰색 파우더를 디클로로메탄(Dichloromethane)에 다시 녹이고 증류수로 수차례 수세하는 단계;
수세 후 물과 분리된 디클로로메탄(Dichloronethane) 용액에 MgSO4를 넣고 수분을 제거한 후 필터링하여 진공건조하여 흰색 파우더 성상의 알릴(Allyl) 작용기가 도입된 불소계 POSS를 회수하는 단계;
알릴 작용기가 도입된 POSS와 트리에톡시실란(triethoxysilane)을 톨루엔에 녹인 후 테트라메틸디비닐디실록산-백금(tetramethyldivinyldisiloxan-platinum) 촉매를 상기 용액에 주입하고 교반하여 반응시키는 단계;
용매와 미반응 트리에톡시실란(triethoxysilane)을 진공으로 제거하고 활성탄소를 이용하여 백금 촉매를 제거하는 단계;
를 포함하는 것을 특징으로 하는 불소계 폴리히드랄 올리고머릭 실세스퀴옥산을 포함하는 발수 및 발유성 코팅을 위한 코팅제 조성물의 제조방법.
A process for producing the fluorinated polyhydral oligomeric silsesquioxane of claim 2,
Dissolving trimethoxy (3,3,3-trifluoropropyl) -silane in THF;
Sodium hydroxide (NaOH) is dissolved in water, and the solution is added to the THF solution, stirred, reacted at 40-90 ° C for 2-7 hours, and further reacted at room temperature for 10-20 hours.
After completion of the reaction, THF and unreacted trimethoxy (3,3,3-trifluoropropyl) -silane were removed under high vacuum. Obtaining a white powder product;
Dissolving the product and triethylamine in THF, injecting allyltrichlorosilane, and stirring to react;
Filtering the precipitate produced by the reaction and vacuum drying the remaining solution;
White powder obtained by vacuum drying is redissolved in dichloromethane and washed several times with distilled water;
After washing with water, MgSO 4 is put into a dichloromethane solution, and after removing moisture, it is filtered and vacuum dried to recover a fluorinated POSS into which an allyl functional group of white powder phase is introduced.
POSS and triethoxysilane having an allyl functional group introduced therein are dissolved in toluene, and tetramethyldivinyldisiloxane-platinum catalyst is injected into the solution and stirred to react.
Removing the solvent and unreacted triethoxysilane in a vacuum and removing the platinum catalyst using activated carbon;
Wherein the fluorinated polyhydric oligomeric silsesquioxane is a fluorinated polyhydric oligomeric silsesquioxane.
노나플루오로헥실 트리에톡시실란(Nonafluorohexyl triethoxysilane)을 트리플루오로톨루엔(Trifluorotoluene)과 THF의 공용매에녹이는 단계;
상기 용액에 NaOH를 물에 녹인 용액을 넣고 40-90℃에서 2-7시간 동안 반응시킨 후 상온에서 10-20시간 동안 추가반응을 진행한 후 반응을 종료하는 단계;
용매와 미반응 트리메톡시(3,3,3-트리플루오로프로필)-실란(Trimethoxy(3,3,3-trifluoropropyl)-silane)등을 고진공하에서 제거하여 흰색 파우더 성상의 생성물을 얻는 단계;
상기 생성물과 트리에틸아민(triethylamine)을 트리플루오로톨루엔과 THF의 공용매에 녹인 후 알릴트리클로로실란(Allyltrichlorosilane)을 이 용액에 주입하여 반응을 진행하는 단계;
반응 종료후 수세하고 건조하여 알릴(Allyl) 작용기가 도입된 노나플루우로헥실-POSS(Nonafluorohexyl-POSS)를 얻는 단계;
얻어진 생성물과 트리에톡시실란(triethoxysilane)을 트리플루우로톨루엔과 THF의 공용매에 녹이고 테트라메틸디비닐디실록산-백금(tetramethyldivinyldisiloxan-platinum) 촉매를 주입한 후 반응시키는 단계;
반응 종료후 미반응물을 제거하고 촉매는 활성탄소를 이용하여 제거하여 노나프루오로헥실-POSS-실란을 얻는 단계;
를 포함하는 것을 특징으로 하는 불소계 폴리히드랄 올리고머릭 실세스퀴옥산을 포함하는 발수 및 발유성 코팅을 위한 코팅제 조성물의 제조방법.
A process for producing the fluorinated polyhydral oligomeric silsesquioxane of claim 3,
Dissolving Nonafluorohexyl triethoxysilane in a co-solvent of Trifluorotoluene and THF;
Adding a solution prepared by dissolving NaOH in water to the solution, reacting the mixture at 40-90 ° C for 2-7 hours, further reaction for 10-20 hours at room temperature, and terminating the reaction;
Removing a solvent and unreacted trimethoxy (3,3,3-trifluoropropyl) -silane under high vacuum to obtain a white powdery product;
Dissolving the product and triethylamine in a co-solvent of trifluoro toluene and THF, and injecting allyltrichlorosilane into the solution to proceed the reaction;
After completion of the reaction, the reaction mixture is washed with water and dried to obtain nonafluorohexyl-POSS having an Allyl functional group introduced therein;
Dissolving the obtained product and triethoxysilane in a co-solvent of triflouro toluene and THF, injecting a tetramethyldivinyldisiloxane-platinum catalyst, and reacting;
Removing unreacted materials after completion of the reaction and removing the catalyst using activated carbon to obtain nonafluorohexyl-POSS-silane;
Wherein the fluorinated polyhydric oligomeric silsesquioxane is a fluorinated polyhydric oligomeric silsesquioxane.
1H,1H,2H,2H-퍼플루오로옥틸트리에톡시실란(1H,1H,2H,2H-Perfluorooctyltriethoxysilane)을 트리플루오로톨루엔(Trifluorotoluene)과 THF의 공용매에녹이는 단계;
상기 용액에 NaOH를 물에 녹인 용액을 넣고 40-90℃에서 2-7시간 동안 반응시킨 후 상온에서 10-20시간 동안 추가반응을 진행한 후 반응을 종료하는 단계;
용매와 미반응 트리메톡시(3,3,3-트리플루오로프로필)-실란(Trimethoxy(3,3,3-trifluoropropyl)-silane)등을 고진공하에서 제거하여 흰색 파우더 성상의 생성물을 얻는 단계;
상기 생성물과 트리에틸아민(triethylamine)을 트리플루오로톨루엔과 THF의 공용매에 녹인 후 알릴트리클로로실란(Allyltrichlorosilane)을 이 용액에 주입하여 반응을 진행하는 단계;
반응 종료후 수세하고 건조하여 알릴(Allyl) 작용기가 도입된 노나플루우로헥실-POSS(Nonafluorohexyl-POSS)를 얻는 단계;
얻어진 생성물과 트리에톡시실란(triethoxysilane)을 트리플루우로톨루엔과 THF의 공용매에 녹이고 테트라메틸디비닐디실록산-백금(tetramethyldivinyldisiloxan-platinum) 촉매를 주입한 후 반응시키는 단계;
반응 종료후 미반응물을 제거하고 촉매는 활성탄소를 이용하여 제거하여
트리데카플루오로-1,1,2,2-테트라하이드로옥틸-POSS-실란을 얻는 단계;
를 포함하는 것을 특징으로 하는 불소계 폴리히드랄 올리고머릭 실세스퀴옥산을 포함하는 발수 및 발유성 코팅을 위한 코팅제 조성물의 제조방법.
A process for producing the fluorinated polyhydral oligomeric silsesquioxane of claim 4,
1H, 1H, 2H, 2H-Perfluorooctyltriethoxysilane (1H, 1H, 2H, 2H-Perfluorooctyltriethoxysilane) in a co-solvent of Trifluorotoluene and THF;
Adding a solution prepared by dissolving NaOH in water to the solution, reacting the mixture at 40-90 ° C for 2-7 hours, further reaction for 10-20 hours at room temperature, and terminating the reaction;
Removing a solvent and unreacted trimethoxy (3,3,3-trifluoropropyl) -silane under high vacuum to obtain a white powdery product;
Dissolving the product and triethylamine in a co-solvent of trifluoro toluene and THF, and injecting allyltrichlorosilane into the solution to proceed the reaction;
After completion of the reaction, the reaction mixture is washed with water and dried to obtain nonafluorohexyl-POSS having an Allyl functional group introduced therein;
Dissolving the obtained product and triethoxysilane in a co-solvent of triflouro toluene and THF, injecting a tetramethyldivinyldisiloxane-platinum catalyst, and reacting;
After completion of the reaction, unreacted materials were removed and the catalyst was removed using activated carbon
To obtain tridecafluoro-1,1,2,2-tetrahydrooctyl-POSS-silane;
Wherein the fluorinated polyhydric oligomeric silsesquioxane is a fluorinated polyhydric oligomeric silsesquioxane.
트리에톡시실란기가 도입된 헵타데카플루오로-1,1,2,2-테트라하이드로데실-POSS( Triethoxy silane functionalized Heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS) (7Rf8-T8-Triethoxy silane)의 합성은 하기의 단계로 제조된다.
(헵타데카플루오로-1,1,2,2-테트라하이드로데실)트리에톡시실란 ((Heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane)을 트리플루오로톨루엔(Trifluorotoluene)과 THF의 공용매에 녹이는 단계;
상기 용액에 NaOH를 물에 녹인 용액을 넣고 40-90℃에서 2-7시간 동안 반응시킨 후 상온에서 10-20시간 동안 추가반응을 진행한 후 반응을 종료하는 단계;
용매와 미반응 트리메톡시(3,3,3-트리플루오로프로필)-실란(Trimethoxy(3,3,3-trifluoropropyl)-silane)등을 고진공하에서 제거하여 흰색 파우더 성상의 생성물을 얻는 단계;
상기 생성물과 트리에틸아민(triethylamine)을 트리플루오로톨루엔과 THF의 공용매에 녹인 후 알릴트리클로로실란(Allyltrichlorosilane)을 이 용액에 주입하여 반응을 진행하는 단계;
반응 종료후 수세하고 건조하여 알릴(Allyl) 작용기가 도입된 노나플루우로헥실-POSS(Nonafluorohexyl-POSS)를 얻는 단계;
얻어진 생성물과 트리에톡시실란(triethoxysilane)을 트리플루우로톨루엔과 THF의 공용매에 녹이고 테트라메틸디비닐디실록산-백금(tetramethyldivinyldisiloxan-platinum) 촉매를 주입한 후 반응시키는 단계;
반응 종료후 미반응물을 제거하고 촉매는 활성탄소를 이용하여 제거하여
트리에톡시실란기가 도입된 헵타데카플루오로-1,1,2,2-테트라하이드로데실-POSS을 얻는 단계;
를 포함하는 것을 특징으로 하는 불소계 폴리히드랄 올리고머릭 실세스퀴옥산을 포함하는 발수 및 발유성 코팅을 위한 코팅제 조성물의 제조방법.
A process for producing the fluorinated polyhydral oligomeric silsesquioxane of claim 5,
Triethoxysilane functionalized Heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS (7Rf8-T8-Triethoxysilane-POSS) in which a triethoxysilane group is introduced ) Is prepared by the following steps.
(Heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane) was prepared by a common use of Trifluorotoluene and THF Dissolving in a medium;
Adding a solution prepared by dissolving NaOH in water to the solution, reacting the mixture at 40-90 ° C for 2-7 hours, further reaction for 10-20 hours at room temperature, and terminating the reaction;
Removing a solvent and unreacted trimethoxy (3,3,3-trifluoropropyl) -silane under high vacuum to obtain a white powdery product;
Dissolving the product and triethylamine in a co-solvent of trifluoro toluene and THF, and injecting allyltrichlorosilane into the solution to proceed the reaction;
After completion of the reaction, the reaction mixture is washed with water and dried to obtain nonafluorohexyl-POSS having an Allyl functional group introduced therein;
Dissolving the obtained product and triethoxysilane in a co-solvent of triflouro toluene and THF, injecting a tetramethyldivinyldisiloxane-platinum catalyst, and reacting;
After completion of the reaction, unreacted materials were removed and the catalyst was removed using activated carbon
Obtaining heptadecafluoro-1,1,2,2-tetrahydrodecyl-POSS having a triethoxysilane group introduced therein;
Wherein the fluorinated polyhydric oligomeric silsesquioxane is a fluorinated polyhydric oligomeric silsesquioxane.
글래스 표면을 깨끗하게 하기 위해 KOH 수용액으로 에칭하는 단계;
트리플루오로톨루엔에 제2항 내지 제5항 중 선택되는 어느 한 항의 불소계 폴리히드랄 올리고머릭 실세스퀴옥산-실란을 녹이는 단계;
트리플루오로톨루엔에 상기 불소계 폴리히드랄 올리고머릭 실세스퀴옥산-실란을 녹인 용액에 에칭된 글래스를 30분간 담지하여 코팅반응을 진행시키는 단계;
깨끗한 트리플루오로톨루엔 용액에 코팅된 글래스를 담지하여 글래스와 반응하지 않은 상기 불소계 폴리히드랄 올리고머릭 실세스퀴옥산-실란을 완전히 제거하는 단계;
를 포함하는 것을 특징으로 하는 불소계 폴리히드랄 올리고머릭 실세스퀴옥산-실란을 코팅한 유리판의 제조방법.
A method for producing a glass plate with water-repellent and oil-repellent coating,
Etching with a KOH aqueous solution to clean the glass surface;
Dissolving the fluorinated polyhydral oligomeric silsesquioxane-silane of any one of claims 2 to 5 in trifluorotoluene;
A step of supporting the etched glass in a solution of the fluorinated polyhydral oligomeric silsesquioxane-silane dissolved in trifluorotoluene for 30 minutes to allow the coating reaction to proceed;
Carrying a coated glass on a clean trifluorotoluene solution to completely remove the fluorinated polyhydral oligomeric silsesquioxane-silane that has not reacted with the glass;
Wherein the fluorinated polyhydric oligomeric silsesquioxane-silane is coated on the glass substrate.
제10항의 불소계 폴리히드랄 올리고머릭 실세스퀴옥산-실란을 코팅한 유리판의 제조방법으로 제조된 것을 특징으로 하는 불소계 폴리히드랄 올리고머릭 실세스퀴옥산-실란을 코팅한 유리판.
A glass plate coated with a water-repellent and oil-repellent coating,
A glass plate coated with a fluorinated polyhydral oligomeric silsesquioxane-silane according to claim 10, which is produced by the process for producing a fluorinated polyhydral oligomeric silsesquioxane-silane coated glass sheet.
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| KR102234674B1 (en) | 2019-11-13 | 2021-03-31 | 계명대학교 산학협력단 | A manufacturing method for anti―smudge coating and ladder type polysilsesquioxanes with the fluorine group |
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