KR100607716B1 - Fluorine-containing anti-fingerprint agents and preparation method thereof - Google Patents
Fluorine-containing anti-fingerprint agents and preparation method thereof Download PDFInfo
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- KR100607716B1 KR100607716B1 KR1020040027872A KR20040027872A KR100607716B1 KR 100607716 B1 KR100607716 B1 KR 100607716B1 KR 1020040027872 A KR1020040027872 A KR 1020040027872A KR 20040027872 A KR20040027872 A KR 20040027872A KR 100607716 B1 KR100607716 B1 KR 100607716B1
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- fluorine
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- 239000011737 fluorine Substances 0.000 title claims abstract description 33
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 33
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 230000003666 anti-fingerprint Effects 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title description 8
- -1 perfluorinated alkyl compound Chemical class 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 20
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 8
- 239000005052 trichlorosilane Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001263 acyl chlorides Chemical class 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 2
- 101150065749 Churc1 gene Proteins 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 102100038239 Protein Churchill Human genes 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 230000003373 anti-fouling effect Effects 0.000 abstract description 12
- 239000011521 glass Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 5
- 239000012847 fine chemical Substances 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 230000002265 prevention Effects 0.000 abstract 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000005917 acylation reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000010933 acylation Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005202 decontamination Methods 0.000 description 4
- 230000003588 decontaminative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910052990 silicon hydride Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GYXUNDYSSCDRAG-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)OC(=O)C=C GYXUNDYSSCDRAG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- KPJPHPFMCOKUMW-UHFFFAOYSA-N iodomethane Chemical compound I[CH2] KPJPHPFMCOKUMW-UHFFFAOYSA-N 0.000 description 2
- 238000006198 methoxylation reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
- H04N23/60—Control of cameras or camera modules
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
- G03B13/00—Viewfinders; Focusing aids for cameras; Means for focusing for cameras; Autofocus systems for cameras
- G03B13/32—Means for focusing
- G03B13/34—Power focusing
- G03B13/36—Autofocus systems
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
- H04N23/50—Constructional details
Abstract
본 발명은 불소계 지문방지제와 이의 제조방법에 관한 것으로서, 더욱 상세하게는 특정의 과불소알킬화합물 공중합하여 거대단량체를 형성하고, 상기 거대단량체와 실란화합물을 수소화규소첨가(Hydrosilation) 반응시켜 제조한 것으로, 발수, 발유 및 방오성과 동시에 오염 제거능 등을 우수하게 발현하여 정밀화학 제품, 생물·생화학산업 등의 각종 산업에서 다양한 용도로 활용 가능하고, 특히 자동차나 주거용 유리, 디스플레이용 유리 등의 지문과 같은 유성 오염을 방지하는데 탁월한 효과를 나타내는 불소계 지문방지제와 이의 제조방법에 관한 것이다.The present invention relates to a fluorine-based anti-fingerprint agent and a method for preparing the same, and more particularly, to copolymerize a specific perfluorinated alkyl compound to form a macromonomer, and to prepare a macromonomer and a silane compound by hydrogenation (Hydrosilation) reaction. It can be used for various purposes in various industries such as fine chemical products, biological and biochemical industries by expressing water repellency, oil repellency and antifouling at the same time, and especially in fingerprints such as automobile, residential glass, display glass, etc. The present invention relates to a fluorine-based anti-fingerprint agent and a method for producing the same, which have an excellent effect in preventing oil pollution.
과불소알킬화합물, 거대단량체, 수소화규소첨가(Hydrosilation) 반응, 지문방지Perfluoroalkyl Compounds, Macromonomers, Hydrosilation Reactions, Fingerprint Prevention
Description
본 발명은 불소계 지문방지제와 이의 제조방법에 관한 것으로서, 더욱 상세하게는 특정의 과불소알킬화합물을 공중합하여 거대단량체를 형성하고, 상기 거대단량체와 실란화합물을 수소화규소첨가(Hydrosilation) 반응시켜 제조한 것으로, 발수, 발유 및 방오성과 동시에 오염 제거능 등을 우수하게 발현하여 정밀화학 제품, 생물·생화학산업 등의 각종 산업에서 다양한 용도로 활용 가능하고, 특히 자동차나 주거용 유리, 디스플레이용 유리 등의 지문과 같은 유성 오염을 방지하는데 탁월한 효과를 나타내는 불소계 지문방지제와 이의 제조방법에 관한 것이다.The present invention relates to a fluorine-based anti-fingerprint agent and a method for preparing the same, and more particularly, to copolymerize a specific perfluorinated alkyl compound to form a macromonomer, and to prepare a macromonomer and a hydride-silicon reaction with the macromonomer. With excellent water and oil repellency and antifouling ability, it can be used for various purposes in various industries such as fine chemical products, biological and biochemical industries, and especially for fingerprints such as automobiles, residential glass and display glass. The present invention relates to a fluorine-based anti-fingerprint agent and a method for producing the same, which have an excellent effect on preventing oily contamination.
불소계 화합물은 5 ∼ 6 dyne/cm 정도의 매우 낮은 표면에너지를 가져 발수와 발유성, 내약품성, 윤활성, 이형성 및 방오성 등의 기능성을 발현한다. 이러한 기능성을 갖는 불소계 화합물은 첨단산업, 정밀화학 등의 특수 분야에서부터 일상생활에 이르기까지 광범위하게 사용될 수 있으며, 또한 그 수요도 최근 급격하게 증대되고 있다. 특히, 개인용 컴퓨터의 보급과 자동차 사용이 일반화되면서 외부 오염물로부터 물질의 표면을 보호하기 위한 소재 개발이 활발히 이루어지고 있다. 표면 보호를 위한 각종 표면코팅제의 원료로는 실리콘 화합물이나 불소화합물 등이 널리 사용되고 있다. Fluorine-based compounds have very low surface energy of about 5 to 6 dyne / cm and express functionalities such as water repellency, oil repellency, chemical resistance, lubricity, mold release property and antifouling property. Fluorine-based compounds having such functionalities can be widely used in high-tech industries, specialty fields such as fine chemistry, and everyday life, and the demand is also rapidly increasing in recent years. In particular, with the spread of personal computers and the use of automobiles, the development of materials for protecting the surface of materials from external contaminants has been actively conducted. Silicone materials, fluorine compounds, and the like are widely used as raw materials for various surface coating agents for surface protection.
그러나, 종래의 실리콘 화합물만 단독으로 사용하여 형성한 코팅제는 무기 산화물과 반응 가교성이 나빠 마찰 내구성이 불량하거나, 3차원 구조를 형성하기 위한 기능기의 수에 따라 충분한 가교결합이 이루어지지 않아 유리전이 온도(Tg)가 낮고 이로 인해 오염물이 쉽게 누적되고, 손으로 만지게 되면 지문이 잔존하게 된다. However, a coating agent formed by using only a conventional silicon compound alone has poor reaction durability with inorganic oxides and thus has poor friction durability, or sufficient crosslinking is not achieved depending on the number of functional groups for forming a three-dimensional structure. The low transition temperature (Tg) causes contaminants to accumulate easily and, if touched by hand, leaves fingerprints.
또한, 불소화합물을 단독으로 사용하여 형성한 코팅제는 오염제거성이 불량하게 되는 문제가 있어, 이러한 단점을 극복하기 위해 과불소기를 갖는 실란 화합물을 이용하여 표면개질제로 사용하고 있다. 그러나, 이들도 충분한 발수 및 발유, 방오, 오염제거 기능을 동시에 갖지 못하는 단점이 있다. In addition, the coating agent formed by using a fluorine compound alone has a problem that the decontamination property is poor, in order to overcome this disadvantage is used as a surface modifier using a silane compound having a perfluorine group. However, they also have the disadvantage of not having sufficient water repellent and oil repellent, antifouling, decontamination function at the same time.
이에 본 발명자는 종래의 표면 코팅제가 발수, 발유, 방오 효과 및 오염제거 기능을 동시에 갖지 못한다는 문제점을 가지고 있어, 신규한 지문방지제를 개발하기 위하여 연구 노력한 결과, 과불소 알킬기가 포함된 불소화합물, 헤테로글리콜 화합물 및 아실클로라이드 화합물과 일정량 혼합하여 거대단량체를 공중합하고, 상기 공중합된 거대단량체를 수소화규소첨가(Hydrosilation) 반응하면 방오, 발수 및 발유성이 월등히 향상됨과 동시에 오염제거에 우수한 효과가 있다는 것을 알게되어 본 발명을 완성하게 되었다.The present inventors have a problem that the conventional surface coating agent does not have a water repellent, oil repellent, antifouling effect and decontamination function at the same time, as a result of research efforts to develop a novel anti-fingerprint, fluorine compound containing perfluorinated alkyl group, Mixing a certain amount with a heteroglycol compound and an acyl chloride compound copolymerizes a macromonomer, and the hydrophobization reaction of the copolymerized macromonomer significantly improves antifouling, water and oil repellency, and has an excellent effect on decontamination. The present invention has been completed.
따라서, 본 발명은 방오, 발수 및 발유성이 월등히 향상됨과 동시에 오염제거에 효과가 있는 표면 코팅용 불소계 지문방지제를 제공하는데 그 목적이 있다.
Accordingly, an object of the present invention is to provide a fluorine-based fingerprint anti-fingerprint agent for surface coating which is effective in removing dirt while improving antifouling, water and oil repellency.
다음 화학식 1로 표시되는 불소계 지문방지제에 그 특징이 있다. The fluorine-based fingerprint agent represented by the following formula (1) has its characteristics.
상기 화학식 1에서, R1, R2, 및 R3은 각각 염소원자, 실릴옥시기, C1 ∼C3의 알콕시기 및 C1∼C3의 알킬기 중에서 선택되고; Q는 황원자, 산소원자 및 NR4 (이때, R4는 수소원자 또는 메틸기) 중에서 선택되고; D는 다음 화학식 2a로 표시되는 과불소알킬함유 불포화탄화수소화합물로부터 유래된 기이고; C는 탄소수 3 내지 20의 불포화탄화수소화합물로부터 유래된 기이고; B는 다음 화학식 2b로 표시되는 실리콘함유 불포화탄화수소화합물로부터 유래된 기이고; o와 p는 각각 0∼100의 정수이고; q는 1∼100의 정수이고; m은 1∼20의 정수이고, s는 0∼10의 정수이다.In Formula 1, R 1 , R 2 , and R 3 are each selected from a chlorine atom, a silyloxy group, a C 1 -C 3 alkoxy group, and a C 1 -C 3 alkyl group; Q is selected from a sulfur atom, an oxygen atom and NR 4 , wherein R 4 is a hydrogen atom or a methyl group; D is a group derived from a perfluoroalkyl-containing unsaturated hydrocarbon compound represented by the following formula (2a); C is a group derived from an unsaturated hydrocarbon compound having 3 to 20 carbon atoms; B is a group derived from a silicon-containing unsaturated hydrocarbon compound represented by the following formula (2b); o and p are each an integer from 0 to 100; q is an integer from 1 to 100; m is an integer of 1-20, s is an integer of 0-10.
상기 화학식 2a에서, X는 수소원자, 또는 할로겐원자이고; Y는 -SO2NR10-, 또는 -CH2CH(OH)-이고; R4는 수소 혹은 메틸기이고, R10은C1∼C4 의 알킬기이고, t는 1∼6의 정수이고, z는 0 또는 1의 정수이며, u는 각각 3∼21의 정수이다. In Formula 2a, X is a hydrogen atom or a halogen atom; Y is -SO 2 NR 10- , Or -CH 2 CH (OH)-; R 4 is hydrogen or a methyl group, R 10 is an alkyl group of C 1 ~C 4, t is an integer of 1~6, z is an integer of 0 or 1, u is an integer of 3-21, respectively.
상기 화학식 2b에서, R4는 수소원자 또는 메틸기이고; R5, R6, R7 , R8 및 R9는 각각 염소원자, 실릴옥시기, C1∼C3의 알콕시기 및 C1∼C3의 알킬기 중에서 선택되고; ??은 0 또는 1이고; m은 1∼20의 정수이고. r은 0∼10의 정수이다.In Formula 2b, R 4 is a hydrogen atom or a methyl group; R 5 , R 6 , R 7 , R 8 and R 9 are each selected from a chlorine atom, a silyloxy group, a C 1 -C 3 alkoxy group and a C 1 -C 3 alkyl group; ?? is 0 or 1; m is an integer of 1-20. r is an integer of 0-10.
또한, 본 발명은 상기 화학식 2a로 표시되는 과불소알킬 함유 불포화탄화수소화합물을 필수성분으로 함유하고 있고, 여기에 탄소수 3 내지 20의 불포화탄화수소화합물, 상기 화학식 2b로 표시되는 실리콘 함유 불포화탄화수소화합물, 또는 이들 화합물이 동시에 포함 또는 포함되지 않은 과불소알킬 단량체 혼합물과; 다음 화학식 3으로 표시되는 헤테로글리콜 화합물과 중합한 후 다음 화학식 4로 표시되는 아실클로라이드 화합물을 사용하여 아실레이션(Acylation)반응 한 다음, 화학식 5로 표시되는 거대단량체를 제조하는 단계와, 상기 화학식 5로 표시되는 거대단량체와 다음 화학식 6으로 표시되는 실란화합물을 수소화규소첨가(Hydrosilation) 반응하여 상기 화학식 1로 표시되는 불소계 지문방지제를 제조하는 단계를 포함하여 이루어진 불소계 지문방지제의 제조방법에 또 다른 특징이 있다.In addition, the present invention contains a perfluoroalkyl-containing unsaturated hydrocarbon compound represented by the formula (2a) as an essential component, an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, a silicon-containing unsaturated hydrocarbon compound represented by the formula (2b), or Perfluoroalkyl monomer mixtures containing or not containing these compounds simultaneously; And then polymerizing with the heteroglycol compound represented by Chemical Formula 3 and then performing acylation reaction using an acyl chloride compound represented by Chemical Formula 4, preparing a macromonomer represented by Chemical Formula 5, and Chemical Formula 5; Another characteristic of the method for preparing a fluorine-based fingerprint inhibitor comprising the step of preparing a fluorine-based fingerprint inhibitor represented by the formula (1) by reacting the macromonomer represented by the formula and the silane compound represented by the following formula (Hydrosilation) There is this.
상기 화학식에서, R1, R2, R3, R4, R5, R6 , R7, R8, R9, R10 ,X, Y, Q, ℓ, m, n, o, p, q , r, s, t, u 및 z는 각각 상기에서 정의한 바와 같다.In the above formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , X, Y, Q, l, m, n, o, p, q, r, s, t, u and z are as defined above, respectively.
이하, 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명은 상기 화학식 2a로 표시되는 화합물 중에서 선택된 과불소 알킬화합물, 화학식 3으로 표시되는 헤테로글리콜 화합물과 중합한 후 아실클로라이드 화합물로 아실레이션(Acylation)하여 거대단량체를 형성하고, 상기에서 형성된 거대단량체와 화학식 6으로 표시되는 실란화합물을 수소화규소첨가(Hydrosilation) 반응하여 화학식 1로 표시되는 불소계 지문방지제를 형성한다. 상기 형성된 불소계 지문방지제는 과불소알킬화합물을 함유하고 있으며, 이러한 과불소화합물의 긴 측쇄인 과불소알킬기는 공기쪽으로 배향하려는 특성이 강하여, 화학식 1로 표시되는 지문방지제를 이용하여 표면 코팅 처리를 수행하면 표면은 극소수성을 보이고, 발수, 발유성 및 방오성과 동시에 오염제거성에 효과적으로 향상된다. The present invention is polymerized with a perfluorinated alkyl compound selected from the compound represented by Formula 2a, a heteroglycol compound represented by Formula 3, and then acylation with an acyl chloride compound to form a macromonomer, and the macromonomer formed above. And a silane compound represented by Chemical Formula 6 to form a fluorine-based fingerprint inhibitor represented by Chemical Formula 1 by hydrolysis. The formed fluorine-based fingerprint agent contains a perfluorinated alkyl compound, and the perfluoroalkyl group, which is a long side chain of the perfluorine compound, has a strong property to be oriented toward air, and performs a surface coating process using a fingerprint agent represented by Chemical Formula 1 The lower surface is extremely hydrophobic and effectively improves water repellency, oil repellency and antifouling properties at the same time.
상기와 같은 특성을 가진 본 발명의 불소계 지문방지제는 정밀화학 제품, 생물·생화학 등의 각종 분야에서 다양한 용도로 활용 가능하며, 특히, 자동차나 주거용 유리, 디스플레이용 유리 등의 지문 등과 같은 유용성 오염 방지에 유용하게 사용될 수 있다.The fluorine-based fingerprint inhibitor of the present invention having the above characteristics can be utilized for various purposes in various fields such as fine chemical products, biological and biochemistry, and in particular, preventing useful contamination such as fingerprints, such as automobiles, residential glass, and display glass. It can be usefully used.
본 발명은 특정한 과불소알킬화합물, 헤테로글리콜 화합물과 중합한 후 아실클로라이드 화합물로 아실레이션(Acylation)하여 형성한 거대단량체를 수소화규소첨가(Hydrosilation) 반응을 수행하는 것에 기술 구성상의 특징이 있다.The present invention is characterized by a technical constitution of carrying out a hydrogenation reaction of a macromonomer formed by acylation with an acyl chloride compound after polymerization with a specific perfluorinated alkyl compound and a heteroglycol compound.
먼저, 화학식 2a의 과불소알킬화합물을 공중합하여 거대단량체를 형성하는 방법에 대하여 보다 구체적으로 살펴보면 다음과 같다.First, the method of copolymerizing the perfluorinated alkyl compound of Formula 2a to form a macromonomer will be described in more detail as follows.
상기 화학식 2a로 표시되는 과불소알킬화합물과 화학식 3으로 표시되는 헤테로글리콜 화합물을 반응시킨 후 화학식 4로 표시되는 아실클로라이드 화합물을 사용하여 아실레이션(Acylation)을 수행한다. 상기 중합방법은 당업계에서 일반적으로 수행되고 있는 고분자 중합법으로 특별히 한정을 두지 않으나, 본 발명에는 라디칼 중합법을 사용하였다. After the perfluoroalkyl compound represented by Formula 2a and the heteroglycol compound represented by Formula 3 are reacted, acylation is performed using an acyl chloride compound represented by Formula 4. The polymerization method is not particularly limited to the polymer polymerization method that is generally performed in the art, the radical polymerization method was used in the present invention.
또한, 상기 거대단량체는 과불소알킬화합물만을 단독으로 사용하여 공중합하거나, 과불소알킬화합물에 추가로 상기 화학식 2b로 표시되는 실리콘 함유 불포화탄화수소화합물 또는 불포화탄화수소화합물을 추가로 첨가하여 반응시킬 수 있고, 이렇게 형성된 거대단량체는 2 성분계 또는 3 성분계의 거대단량체를 형성하며, 이는 추가로 첨가되는 성분이 재료 표면의 비점착성 특성을 나타내어 본 발명이 목적으로 하는 지문방지의 특성과 오염물을 효과적으로 제거할 수 있는 특성을 가지게 된다. In addition, the macromonomer may be copolymerized using only a perfluoroalkyl compound alone, or may be reacted by further adding a silicon-containing unsaturated hydrocarbon compound or an unsaturated hydrocarbon compound represented by Formula 2b to the perfluoroalkyl compound. The macromonomer thus formed forms a two-component or three-component macromonomer, which additionally exhibits non-tacky properties of the material surface, which can effectively remove the anti-fingerprint properties and contaminants of the present invention. Have characteristics.
상기 실리콘 함유 화합물은 당업계에서 일반적으로 사용되는 것으로 특별히 한정하지 않으나, 예를 들면 CH2=C(CH3)CO2(CH2)3Si(OCH 3)3, CH2=CHSi(OC2H5)3, CH2=C(CH3)CO2(CH2)3Si(CH3)(OCH3 )2, CH2=CHCO2(CH2)3Si(OCH3) 3 CH2=CHSi(OCH3)3, CH2=C(CH3)CO2(CH2)3Si(CH3)(OC2 H5)2, CH2=C(CH3)CO2(CH2)3 Si(OC2H5)3 및 CH2=CHCH2Si(CH3)3, CH2=C(CH3)CO2 (CH2)3Si(CH3)2OSi(CH3)3 중에서 선택된 1 종 또는 2종 이상인 것을 사용하는 것이 좋다.The silicon-containing compound is generally used in the art and is not particularly limited. For example, CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 = CHSi (OC 2 H 5 ) 3 , CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 Si (CH 3 ) (OCH 3 ) 2 , CH 2 = CHCO 2 (CH 2 ) 3 Si (OCH 3 ) 3 CH 2 = CHSi (OCH 3 ) 3 , CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 Si (CH 3 ) (OC 2 H 5 ) 2 , CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 Si (OC 2 H 5 ) 3 and CH 2 = CHCH 2 Si (CH 3 ) 3 , CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 3 It is good to use 1 type or 2 or more types.
또한 상기 불포화탄화수소화합물도 일반적으로 당 분야에서 사용되는 화합물을 선택 사용할 수 있으나, 본 발명에서는 불포화탄화수소화합물로 예를 들면 (메타)아크릴산, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 도데실(메타)아크릴레이트, 스테아릴(메타)아크릴레이트, 벤질(메타)아크릴레이트, 사이클로헥실(메타)아크릴레이트, 스티렌, N-메틸올(메타)아크릴아미드, N-메틸올아크릴아미드부틸에테르, 2-히드록시프로필(메타)아크릴레이트 및 비닐클로로 모노머 또는 비닐리덴 클로라이드의 비닐계 화합물중에서 선택된 1종 또는 2종 이상을 사용하는 것이 좋다.In addition, the unsaturated hydrocarbon compound may be selected and used generally in the art, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl as unsaturated hydrocarbon compound in the present invention (Meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, N-methylol It is preferable to use one or two or more selected from vinyl compounds of (meth) acrylamide, N-methylolacrylamide butyl ether, 2-hydroxypropyl (meth) acrylate and vinylchloro monomer or vinylidene chloride. .
이외에, 상기 공중합시에 개시제, 촉매, 유기용매 등을 목적에 따라 추가로 첨가 사용할 수 있으며, 이들의 사용량은 일반적인 중합조건에 사용되는 것으로 특별히 한정하지 않는다.In addition, an initiator, a catalyst, an organic solvent, and the like may be additionally added and used according to the purpose during the copolymerization, and the amount thereof is not particularly limited as used in general polymerization conditions.
한편, 상기에서 공중합된 화학식 5로 표시되는 거대단량체는 화학식 6의 실란화합물과 수소화규소첨가(Hydrosilation) 반응하여 불소계 지문방지제를 제조한다. 상기 수소화규소첨가 반응에 사용되는 실란화합물은 알콕시 또는 할로실란이 사용될 수 있으며, 구체적인 예로는 트리메톡시실란(Trimethoxysilane, TMS) 또는 트리클로로실란(Trichlorosilane, TCS)을 사용하는 보다 바람직하다.On the other hand, the macromonomer represented by the formula (5) copolymerized in the above to prepare a fluorine-based fingerprint inhibitor by reacting the silane compound of the formula (6) with a hydrogenation (Hydrosilation). As the silane compound used in the silicon hydride reaction, alkoxy or halosilane may be used, and specific examples thereof include trimethoxysilane (TMS) or trichlorosilane (TCS).
상기와 같이 본 발명에 따라 제조된 불소계 지문방지제는 표면 코팅시에 오염방지 및 발수, 발유성을 발현하기 위하여 균일하게 용해시킬 수 있는 용매를 사용하여 0.1% 이상의 농도로 사용하는 것이 좋다. 이러한 불소계 지문방지제는 각종 외장제의 표면이나 액정 모니터, 자동차 유리, 정밀화학제품 등 각종 외장 보호 코팅제 등의 지문과 같은 유성 오염에 효과를 나타내어 널리 응용될 수 있다.As described above, the fluorine-based anti-fingerprint agent prepared according to the present invention may be used at a concentration of 0.1% or more using a solvent that can be uniformly dissolved in order to express anti-fouling, water repellency, and oil repellency during surface coating. Such fluorine-based anti-fingerprint agent has an effect on oily contamination, such as fingerprints, such as the surface of various exterior agents, various exterior protective coatings such as liquid crystal monitors, automobile glass, fine chemicals, etc. can be widely applied.
이상에서 설명한 바와 같이 본 발명은 다음의 실시예에 의거하여 더욱 상세하게 설명하겠는 바, 본 발명이 이에 한정되는 것은 아니다.As described above, the present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.
합성예 1 : 거대 단량체(화학식 5)의 제조Synthesis Example 1 Preparation of Macromonomer (Formula 5)
온도조절장치 및 교반장치가 부착된 1L 반응기에 과불소에틸아크릴레이트(이하 FA라 함) 100 g(0.193 mol), 테트라하이드로퓨란(이하, THF라 함) 30 g, 트리클로로트리플루오로에탄(Trichlorotrifluoroethane, 이하 F-113라 함) 120 g, 2,2'-아조비스이소부티로니트릴(이하 AIBN라 함) 0.3 g(0.0018 mol), 티오글리콜 3.02 g(0.0386 mol)을 투입하고 교반하면서 10분 동안 질소치환을 수행하였다. 100 g (0.193 mol) perfluoroethyl acrylate (hereinafter referred to as FA), 30 g of tetrahydrofuran (hereinafter referred to as THF) in a 1 L reactor equipped with a temperature controller and a stirring device, trichlorotrifluoroethane 120 g, 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN), 0.3 g (0.0018 mol), and thioglycol 3.02 g (0.0386 mol) were added thereto, followed by stirring for 10 minutes. Nitrogen substitution was performed during the process.
상기 반응물의 온도를 60 ℃로 승온하여 중합을 개시하였으며, 이때 반응중간 샘플링을 채취한 후, 기체크로마토그리피로 분석하여 FA의 전환율이 50%일 때 반응을 종료하였다. 상기 반응시간은 약 1.5시간 정도였다. The polymerization was initiated by raising the temperature of the reactant to 60 ℃, at this time, the sampling was taken during the reaction, and then analyzed by gas chromatography to terminate the reaction when the conversion of FA is 50%. The reaction time was about 1.5 hours.
상기 반응이 종료된 반응물을 메탄올에 투입하여 한쪽 말단에 하이드록시기를 갖는 불소알코올(이하 FOH라 함)을 석출하였다. 상기에서 석출된 FOH의 수율은 약 36%였다.The reaction product after completion of the reaction was introduced into methanol to precipitate fluorine alcohol (hereinafter referred to as FOH) having a hydroxyl group at one end. The yield of FOH precipitated above was about 36%.
상기에서 얻은 FOH 50 g(0.017 mol)와 F-113 50 g을 반응기에 투입하여 완전히 용해시킨 다음, 상온에서 아크릴로일 클로라이드 3.26 g(0.036 mol)를 약 30분에 걸쳐 서서히 투입하여 약 24시간 동안 교반하면서 아실화하였다. 50 g (0.017 mol) of FOH and 50 g of F-113 obtained above were completely dissolved in a reactor, and then 3.26 g (0.036 mol) of acryloyl chloride was slowly added at room temperature over about 30 minutes for about 24 hours. Acylating with stirring.
반응 혼합물에 트리에칠아민 3.64 g(0.036mol)을 투입하여 발생하는 염산을 중화한 후 셀라이트를 사용하여 염산-트리에칠아민염을 분리하였다. 분리액을 메탄올에 투입하여 거대단량체를 석출한 다음 상온에서 진공 건조하여, 불소 알킬기를 함유하는 화합물 단독의 거대단량체를 합성하였다. 3.64 g (0.036 mol) of triethylamine was added to the reaction mixture to neutralize hydrochloric acid, and then hydrochloric acid-triethylamine salt was separated using celite. The separated solution was added to methanol to precipitate the macromonomer, followed by vacuum drying at room temperature to synthesize a macromonomer of a compound alone containing a fluorine alkyl group.
합성예 2 : 거대단량체(화학식 5)의 제조Synthesis Example 2 Preparation of Macromonomer (Formula 5)
온도조절장치 및 교반장치가 부착된 1L 반응기에 메틸메타크릴레이트(이하 MMA라 함) 100 g(1 mol), 과불소에틸아크릴레이트(CF3(CF2)7CH2CH 2COOCH=CH2, 이하 FA라 함) 300 g(0.58 mol), 테트라하이드로퓨란(이하, THF라 함) 40 g, 2,2'-아조 비스이소부티로니트릴(이하, AIBN라 함) 4 g(0.024 mol), 티오글리콜 12.3 g(0.158 mol)을 투입하고 교반하면서 10분 동안 질소치환을 수행하였다. 100 g (1 mol) of methyl methacrylate (hereinafter referred to as MMA) in a 1 L reactor equipped with a thermostat and agitator, perfluoroethyl acrylate (CF 3 (CF 2 ) 7 CH 2 CH 2 COOCH = CH 2 300 g (0.58 mol), 40 g tetrahydrofuran (hereinafter referred to as THF), 4 g (0.024 mol) of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) , 12.3 g (0.158 mol) of thioglycol was added thereto, followed by nitrogen replacement for 10 minutes with stirring.
상기 반응물의 온도를 60 ℃로 승온하여 중합을 개시하였으며, 이때 반응중간 샘플링을 채취한 후, 기체크로마토그리피로 분석하여 FA의 전환율이 50%일 때 반응을 종료하였다. 상기 반응시간은 약 6시간 정도였다. The polymerization was initiated by raising the temperature of the reactant to 60 ℃, at this time, the sampling was taken during the reaction, and then analyzed by gas chromatography to terminate the reaction when the conversion of FA is 50%. The reaction time was about 6 hours.
상기 반응이 종료된 반응물을 헥산에 투입하여 한쪽 말단에 하이드록시기를 갖는 불소알코올(이하 FMOH라 함)을 석출하였다.The reaction product after completion of the reaction was introduced into hexane to precipitate fluorine alcohol (hereinafter referred to as FMOH) having a hydroxyl group at one end.
상기에서 석출된 FMOH의 수율은 약 40%였으며, 겔크로마토그래피를 사용하여 중량평균분자량을 구한 결과 분자량은 3,800이었다.The yield of the precipitated FMOH was about 40%, and the molecular weight was 3,800 as a result of obtaining the weight average molecular weight using gel chromatography.
상기에서 얻은 FMOH 50 g(0.0133 mol)와 THF 50 g을 반응기에 투입하여 완전히 용해시킨 다음, 상온에서 아크릴로일 클로라이드 3.6 g(0.0399 mol)를 약 30분에 걸쳐 서서히 투입하여 약 24시간 동안 교반하면서 아실화하였다. 50 g (0.0133 mol) of FMOH and 50 g of THF obtained above were completely dissolved in a reactor, and then 3.6 g (0.0399 mol) of acryloyl chloride was slowly added at room temperature for about 30 minutes and stirred for about 24 hours. Acylating.
반응 혼합물에 트리에칠아민 4.04 g(0.0399 mol)을 투입하여 발생하는 염산을 중화한 후 원심분리기를 사용하여 염산-트리에칠아민염을 분리하였다. Triethylamine 4.04 g (0.0399 mol) was added to the reaction mixture to neutralize the hydrochloric acid, and then hydrochloric acid-triethylamine salt was separated using a centrifuge.
분리액을 헥산에 투입하여 거대단량체를 석출한 다음 상온에서 진공건조하여, 거대단량체를 합성하였다.The separated solution was added to hexane to precipitate the macromonomer, followed by vacuum drying at room temperature to synthesize the macromonomer.
합성예 3 : 거대단량체(화학식 5)의 제조Synthesis Example 3 Preparation of Macromonomer (Formula 5)
상기 합성예 2와 동일하게 실시하되, 메틸메타크릴레이트와 함께 공단량체로 실리콘기를 함유하는 화합물인 CH2=C(CH3)CO2(CH2)3Si(OCH 3)3 100 g(0.40 gmol)을 추가하여 3 성분계 거대단량체를 합성하였다.100 g (0.40) of a compound containing CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 Si (OCH 3 ) 3 , which is a compound containing a silicon group as a comonomer together with methyl methacrylate. gmol) was added to synthesize a three-component macromonomer.
실시예 1 : 불소계 지문방지제(화학식 1) 제조Example 1: Preparation of fluorine-based fingerprint inhibitor (Formula 1)
상기 합성예 1에서 얻은 거대단량체 5 g, F-113 30 g, TCS 10 g, 백금촉매(H2PtCl6) 0.1 g을 아르곤 분위기에서 슈랭크 반응기에 넣고 50 ℃에서 환류시키며 24시간 동안 수소화규소첨가(Hydrosilation) 반응시켰다. 5 g of the macromonomer obtained in Synthesis Example 1, 30 g of F-113, 10 g of TCS, and 0.1 g of platinum catalyst (H 2 PtCl 6 ) were placed in a Schrank reactor in an argon atmosphere, refluxed at 50 ° C., and silicon hydride for 24 hours. Hydrosilation was carried out.
반응 후 촉매를 제거하고, 고진공(10-2 torr)으로 TCS를 제거한 후, 메탄올로 메톡실레이션(methoxylation)하여 불소계 지문방지제를 제조하였다. After the reaction, the catalyst was removed, TCS was removed by high vacuum (10 -2 torr), and methoxylation was performed to prepare a fluorine-based fingerprint inhibitor.
실시예 2 : 불소계 지문방지제(화학식 1) 제조Example 2 Preparation of Fluorine Fingerprint (Formula 1)
상기 합성예 2에서 얻은 거대단량체 5 g, TCS 10 g, 백금촉매(H2PtCl6) 0.1 g을 아르곤 분위기에서 슈랭크 반응기에 넣고 90 ℃에서 환류시키며 24시간 동안 수소화규소첨가(Hydrosilation) 반응을 시켰다. 5 g of the macromonomer obtained in Synthesis Example 2, 10 g of TCS, and 0.1 g of a platinum catalyst (H 2 PtCl 6 ) were placed in a Schrank reactor in an argon atmosphere, refluxed at 90 ° C., and a silicon hydride reaction was performed for 24 hours. I was.
반응 후 촉매를 제거하고, 고진공(10-2torr)으로 TCS를 제거한 후, 메탄올이나 메톡시나트륨으로 메톡실레이션(methoxylation)하여 불소계 지문방지제를 제조하였다. After the reaction, the catalyst was removed, TCS was removed with high vacuum (10 -2 torr), and methoxylation was performed with methanol or methoxy sodium to prepare a fluorine-based fingerprint inhibitor.
실시예 3 : 불소계 지문방지제(화학식 1) 제조Example 3: Preparation of fluorine-based fingerprint inhibitor (Formula 1)
상기 실시예 2와 동일하게 실시하되, 제조예 3에서 얻은 거대단량체를 사용하여 불소계 지문방지제를 제조하였다.A fluorine-based fingerprint inhibitor was prepared in the same manner as in Example 2, using the macromonomer obtained in Preparation Example 3.
실험예 Experimental Example
[시편제작][Psalm making]
실시예 1 ∼ 3 및 비교예 1에서 제조된 불소함유 지문방지제를 적당한 용매를 사용하여 0.1 중량%가 되도록 녹인다. 스핀코팅기에 유리판을 올려놓은 다음 2000 rpm으로 회전하는 유리판 위에 용액을 1 ㎖ 투입하여 약 30초간 회전시킨다. 코팅된 유리판을 160 ℃에서 5분간 경화시킨다. The fluorine-containing fingerprint inhibitors prepared in Examples 1 to 3 and Comparative Example 1 are dissolved to 0.1 wt% using a suitable solvent. Put the glass plate on the spin coater, and then add 1 ml of the solution on the glass plate rotating at 2000 rpm and rotate for about 30 seconds. The coated glass plate is cured at 160 ° C. for 5 minutes.
[물성측정][Measurement of properties]
1) 시편의 접촉각 측정 및 슬라이딩 각 측정1) Contact angle measurement and sliding angle measurement
- 접촉각 측정 : 20 ±1 ℃에서 물, 메틸렌 요오드, 헥사데칸 등의 세 종류의 접촉액을 사용하여 광조사기(illuminator)가 부착된 Goniometer(Rame-Hart 100-series)를 이용하여 측정하였다. 이때 측정은 접촉액 직경이 2 ㎜의 방울로 5개 상이한 지점에서 행했고, 평균을 기록하였다.-Contact angle measurement: Measurement was made using a Goniometer (Rame-Hart 100-series) equipped with an illuminator using three kinds of contact liquids, such as water, methylene iodine, and hexadecane, at 20 ± 1 ° C. The measurement was made at five different points with droplets of 2 mm in diameter, and the average was recorded.
- 슬라이딩 각 측정 : 화학연구원에서 자체 제작된 광학 감지식 슬라이딩 측정기를 사용하여 액적 크기 3 ㎜(용적 30 ㎕)의 액적을 전자감지기가 장착된 슬라이딩 각 측정기를 사용하여 물, 메틸렌 요오드(MI), 헥사데칸(HD)에 대해 측정하였 다. -Sliding angle measurement: Using a sliding angle measuring instrument equipped with an electron sensor, droplets of 3 mm (volume 30 μl) were dropped using an optically-sensing sliding measuring device manufactured by the Institute of Chemistry, using water, methylene iodine (MI), It was measured for hexadecane (HD).
2) 시편의 스크레치 테스트2) Scratch Test of Specimen
- 나일론 부직포(20 ×20 ㎜)를 사용하여 100 g 하중으로 20회 문질러 준다.Rub 20 times with a 100 g load using a nylon nonwoven fabric (20 x 20 mm).
3) 시편의 오염방지 측정3) Anti-fouling test of specimen
- 코팅된 표면에 유성 펜(모나미, 네임 펜)을 사용하여 X를 표시한 후, 5분 후 킴와이프스를 이용해 10 회 닦아준다. 이후 그 표면을 육안으로 관찰한다.-Mark X with oily pen (monami, naim pen) on coated surface, and wipe it 10 times with Kimwipes after 5 minutes. The surface is then visually observed.
A : X 글자가 지워짐. B : X 글자가 희미하게 보임. A: The letter X is erased. B: The letter X is blurred.
C : X 글자가 그대로 잔존함. C: X letter remains as it is.
4) 시편의 지문방지효과 측정4) Measurement of anti-fingerprint effect of specimen
- 표면처리된 기재 표면에 엄지손가락을 30초간 누른다. 5분 후 지문을 킴와이프스를 이용해 10회 문지른다. 이후 표면을 관찰한다. The thumb is pressed against the surface of the treated substrate for 30 seconds. After 5 minutes, rub your fingerprint 10 times with Kimwipes. The surface is then observed.
A : 지문이 남아있지 않음. B : 약간의 지문이 잔존A: No fingerprints remain. B: Some fingerprints remain
C : 지문이 전혀 지워지지 않음. C: Fingerprint is not erased at all.
상기 표 1에 나타낸 바와 같이, 본 발명에 따른 실시예 1 ∼ 3과 현재 시판중인 제품(Daikin사의 DSX 제품)인 비교예의 접촉각, 슬라이딩 각, 표면자유에너지, 오염방지성 및 지문방지성을 측절한 결과, 비교예에 비해 접촉각은 높게, 슬라이딩 각은 작게 나타났다. 이 같은 결과로 본 발명의 실시예가 오염방지성, 발수·발유성 및 지문방지성에 보다 효과적임을 알 수 있었다.As shown in Table 1, the contact angle, sliding angle, surface free energy, antifouling and anti-fingerprint of the Examples 1 to 3 according to the present invention and the comparative example of the currently commercially available product (DSX product of Daikin Corporation) were cut out. As a result, the contact angle was higher and the sliding angle was smaller than in the comparative example. As a result, it can be seen that the embodiment of the present invention is more effective in antifouling, water and oil repellency and anti-fingerprint.
이상에서 설명한 바와 같이, 본 발명은 특정한 과불소알킬화합물, 헤테로글리콜 화합물과 중합한 후, 아실클로라이드와 아실레이션하여 합성하여 형성된 거대단량체와 실란화합물을 수소화규소첨가(Hydrosilation) 반응하여 형성된 불소계 지문방지제로, 각종 필름이나 유리의 표면에 코팅하면 오염물 부착을 방지 및 오염물 부착시 오염물의 제거를 용이하게 하고, 표면개질성이 우수하여 정밀화학 제품, 생물·생화학 등의 각종 분야에서 다양한 용도로 활용 가능하다.As described above, the present invention is a fluorine-based fingerprint inhibitor formed by hydrogenation of a macromonomer and a silane compound formed by polymerization with a specific perfluorinated alkyl compound and a heteroglycol compound, and then acylation with an acyl chloride. By coating on the surface of various films or glass, it prevents the adhesion of contaminants and facilitates the removal of contaminants when attaching the contaminants. Do.
Claims (5)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6121113A (en) | 1984-07-09 | 1986-01-29 | Matsushita Electric Ind Co Ltd | Optical information recording medium |
| JPH09255919A (en) * | 1996-03-21 | 1997-09-30 | Sony Corp | Stainproof film forming composition and optical part |
| JP2004047040A (en) | 2002-05-16 | 2004-02-12 | Sony Corp | Optical recording medium |
| JP2004145283A (en) | 2002-08-29 | 2004-05-20 | Shin Etsu Chem Co Ltd | Lens with stainproof surface layer |
| KR20050075362A (en) * | 2002-11-18 | 2005-07-20 | 아사히 가라스 가부시키가이샤 | Optical disc having hard-coat layer to which sebum stain proofness is imparted |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6121113A (en) | 1984-07-09 | 1986-01-29 | Matsushita Electric Ind Co Ltd | Optical information recording medium |
| JPH09255919A (en) * | 1996-03-21 | 1997-09-30 | Sony Corp | Stainproof film forming composition and optical part |
| JP2004047040A (en) | 2002-05-16 | 2004-02-12 | Sony Corp | Optical recording medium |
| JP2004145283A (en) | 2002-08-29 | 2004-05-20 | Shin Etsu Chem Co Ltd | Lens with stainproof surface layer |
| KR20050075362A (en) * | 2002-11-18 | 2005-07-20 | 아사히 가라스 가부시키가이샤 | Optical disc having hard-coat layer to which sebum stain proofness is imparted |
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