KR20160038256A - Anthraquinone based sol-gel compounds and organic-inorganic hydrid composition - Google Patents
Anthraquinone based sol-gel compounds and organic-inorganic hydrid composition Download PDFInfo
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- KR20160038256A KR20160038256A KR1020140130767A KR20140130767A KR20160038256A KR 20160038256 A KR20160038256 A KR 20160038256A KR 1020140130767 A KR1020140130767 A KR 1020140130767A KR 20140130767 A KR20140130767 A KR 20140130767A KR 20160038256 A KR20160038256 A KR 20160038256A
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- sol
- anthraquinone
- compound
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 50
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 239000008199 coating composition Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 238000005260 corrosion Methods 0.000 claims abstract description 21
- 230000007797 corrosion Effects 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005299 abrasion Methods 0.000 claims description 13
- -1 silane compound Chemical class 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 5
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 3
- 229940125904 compound 1 Drugs 0.000 claims description 2
- 229940125782 compound 2 Drugs 0.000 claims 1
- 229940126214 compound 3 Drugs 0.000 claims 1
- 229940125898 compound 5 Drugs 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 63
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 238000004821 distillation Methods 0.000 description 14
- 239000010408 film Substances 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 239000012267 brine Substances 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- BCLSJHWBDUYDTR-UHFFFAOYSA-N 2-(propylamino)ethanol Chemical compound CCCNCCO BCLSJHWBDUYDTR-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- JEZFASCUIZYYEV-UHFFFAOYSA-N chloro(triethoxy)silane Chemical compound CCO[Si](Cl)(OCC)OCC JEZFASCUIZYYEV-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- VGWJKDPTLUDSJT-UHFFFAOYSA-N diethyl dimethyl silicate Chemical compound CCO[Si](OC)(OC)OCC VGWJKDPTLUDSJT-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- ITAHRPSKCCPKOK-UHFFFAOYSA-N ethyl trimethyl silicate Chemical compound CCO[Si](OC)(OC)OC ITAHRPSKCCPKOK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
Description
본 발명은 신규의 안트라퀴논계 졸-겔 화합물과 이 화합물을 포함하는 유무기 하이브리드 코팅 조성물에 관한 것이다.
The present invention relates to a novel anthraquinone sol-gel compound and an organic-inorganic hybrid coating composition comprising the compound.
일반적으로 코팅은 재료의 표면에 코팅제를 도포하여 얇은 박막을 형성함으로써 재료의 표면 특성을 보완하기 위한 목적으로 이루어진다. 이러한 코팅은 선박, 자동차 외장부품, 건축자재, 종이, 목재, 가구용, 방음벽, 광학재료, 화장품 용기를 비롯하여 다양한 산업분야에서 이루어지고 있다. 최근에는 디스플레이 분야에서 플라스틱 소재의 기판 표면에 처리되는 경화형 코팅제에 대한 연구가 활발히 전개되고 있다. In general, coating is performed for the purpose of supplementing the surface characteristics of a material by applying a coating agent to the surface of the material to form a thin film. Such coatings are being made in a variety of industries, including ships, automotive exterior components, construction materials, paper, wood, furniture, soundproof walls, optical materials, and cosmetic containers. In recent years, studies have been actively conducted on curing-type coating agents that are processed on the surface of plastic substrates in the display field.
일본공개특허 제2004-117831호에는 1분자 중에 규소 원자에 결합하는 알케닐기가 0.5개 이상 함유된 오르가노폴리실록산, 1분자 중에 규소 원자에 결합하는 수소원자를 2개 이상 가지는 오르가노하이드로겐 폴리실록산 및 경화 촉매를 포함하는 실리콘 조성물이 개시되어 있다. 또한, 일본공개특허 제1997-169908호에는 분자쇄 양끝단에 알케닐기를 함유하는 디오르가노폴리실록산, 분자쇄 양끝단에 규소 원자 결합 수소원자를 함유하는 디오르가노폴리실록산, 1분자중 에 규소원자에 결합하는 수소원자를 3개 이상 가지는 오르가노폴리실록산 및 백금계 촉매를 포함하는 오르가노폴리실록산 조성물이 개시되어 있다.Japanese Patent Application Laid-Open No. 2004-117831 discloses an organopolysiloxane having at least 0.5 alkenyl groups bonded to silicon atoms in one molecule, an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule, A silicone composition comprising a curing catalyst is disclosed. Japanese Unexamined Patent Application, First Publication No. 1997-169908 discloses diorganopolysiloxanes containing an alkenyl group at both ends of a molecular chain, diorganopolysiloxanes containing a silicon atom-bonded hydrogen atom at both ends of a molecular chain, Discloses an organopolysiloxane composition comprising an organopolysiloxane having at least three hydrogen atoms and a platinum-based catalyst.
현재까지 알려진 코팅 조성물 및 이를 이용한 코팅막은 디스플레이 장치 및 휴대폰 단말기와 같은 소형화 및 고정세화 추세에 요구되는 고기능에 비교 하여 내구성 등이 요구 사양에 미치지 못하는 한계가 있다.The coating compositions known to date and the coating films using them have a limit in that the durability and the like are less than the required specifications as compared with the high performance required for the miniaturization and the high-definition trend such as the display device and the mobile phone terminal.
한편, 본 발명자들은 한국등록특허 10-1228927호 및 10-0950286호에서 졸-겔 반응이 가능한 신규 유기화합물을 합성하고, 상기 신규 유기화합물이 포함된 유-무기 하이브리드 코팅 조성물을 개시한 바 있다. 본 발명에서 제안하는 졸-겔 화합물은 선등록발명에 개시된 화합물과는 모핵 부분이 안트라퀴논으로 상이한 점에 큰 차이가 있다. 또한, 본 발명에서 제안하는 졸-겔 화합물은 모핵의 C1 및 C5 위치 관능기를 이용한 졸-겔 반응을 통하여 기재 수지에 내부식성과 내마소성을 동시에 부여하는 것이 가능할 뿐만 아니라, 유기용매 및 물에 대한 용해도가 우수하다는 장점을 가지고 있다. 따라서 본 발명에서 제안하는 졸-겔 화합물은 유기계 코팅조성물은 물론이고 수계 코팅조성물로 제조가 가능한 장점이 있다.
On the other hand, the present inventors have disclosed organic-inorganic hybrid coating compositions containing novel organic compounds by synthesizing novel organic compounds capable of sol-gel reaction in Korean Patent Nos. 10-1228927 and 10-0950286. The sol-gel compound proposed in the present invention is greatly different from the compound disclosed in the above-mentioned invention in that the ancillic acid portion is different from the anthraquinone. In addition, the sol-gel compound proposed in the present invention not only can impart corrosion resistance and resistance to abrasion to the base resin through sol-gel reaction using the C1 and C5 position functional groups of the mother nucleus, And the solubility is excellent. Therefore, the sol-gel compound proposed in the present invention has an advantage that it can be prepared with an aqueous coating composition as well as an organic coating composition.
본 발명은 신규의 안트라퀴논계 졸-겔 화합물을 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a novel anthraquinone sol-gel compound.
또한, 본 발명은 상기한 안트라퀴논계 졸-겔 화합물이 포함되어 있는 내부식성과 내마모성이 우수한 유무기 하이브리드 코팅 조성물과 이를 이용하여 제조된 코팅막을 제공하는 것을 다른 목적으로 한다.Another object of the present invention is to provide an organic-inorganic hybrid coating composition containing the anthraquinone-based sol-gel compound excellent in corrosion resistance and abrasion resistance and a coating film prepared using the same.
본 발명은 하기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물을 제공함으로써, 본 발명의 과제를 해결한다. The present invention solves the problems of the present invention by providing an anthraquinone sol-gel compound represented by the following formula (1).
[화학식 1] [Chemical Formula 1]
(상기 화학식 1에서, R은 수소원자, C1-C10 알킬기, 또는 
또한, 본 발명은 트리(C1-C6 알콕시)실릴C1-C6 알킬 그룹으로 개질된 에폭시 수지 100 중량부, 상기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물 1 내지 20 중량부, 및 하기 화학식 2로 표시되는 실란 화합물 1 내지 20 중량부를 포함하여 이루어진 내부식성 및 내마모성이 우수한 유무기 하이브리드 코팅 조성물을 제공함으로써, 본 발명의 과제를 해결한다. The present invention also relates to an epoxy resin composition comprising 100 parts by weight of an epoxy resin modified with a tri (C 1 -C 6 alkoxy) silyl C 1 -C 6 alkyl group, 1 to 20 parts by weight of an anthraquinone sol- And 1 to 20 parts by weight of a silane compound represented by the following formula (2). The present invention provides an organic-inorganic hybrid coating composition having excellent corrosion resistance and abrasion resistance.
[화학식 2] (2)
(상기 화학식 2에서, X1, X2, X3, 및 X4는 서로 같거나 다른 것으로 수소원자, 할로겐, C1-C6 알킬기, 또는 C1-C6 알콕시기를 나타내고, X1, X2, X3, 및 X4 중 하나 이상은 할로겐 또는 C1-C6 알콕시기를 나타낸다)Wherein X 1 , X 2 , X 3 and X 4 are the same or different and each represents a hydrogen atom, a halogen, a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, X 1 and X 2 , X 3 , and X 4 represents a halogen or a C 1 -C 6 alkoxy group)
또한, 본 발명은 상기한 코팅 조성물을 경화시킨 내부식성 및 내마모성이 우 수한 유무기 하이브리드 코팅막을 제공함으로써, 본 발명의 과제를 해결한다.
Further, the present invention solves the problems of the present invention by providing an organic or inorganic hybrid coating film having excellent corrosion resistance and abrasion resistance by curing the above-mentioned coating composition.
본 발명이 특징으로 하는 안트라퀴논계 졸-겔 화합물을 포함하는 코팅 조성물은 내부식성 및 내마모성을 동시에 만족하는 코팅막의 제조가 가능하다. The coating composition comprising the anthraquinone-based sol-gel compound of the present invention is capable of producing a coating film which simultaneously satisfies both corrosion resistance and wear resistance.
따라서 본 발명의 코팅 조성물은 자동차, 선박, 건축자재 등의 코팅제로 특히 유용하다. Therefore, the coating composition of the present invention is particularly useful as a coating agent for automobiles, ships, building materials and the like.
본 발명이 특징으로 하는 안트라퀴논계 졸-겔 화합물은 하기 화학식 1로 표시될 수 있다. The anthraquinone sol-gel compound characterized by the present invention can be represented by the following general formula (1).
[화학식 1] [Chemical Formula 1]
(상기 화학식 1에서, R은 수소원자, C1-C10 알킬기, 또는 
본 발명에 따른 상기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물은 신규 화합물로, 분자 구조내에 내부식성 및 내마모성을 동시에 만족시키는 관능기를 포함하고 있다. 일반적으로 내부식성 및 내마모성을 동시에 만족하는 코팅막을 형성하기 위해서는 내부식성 코팅제와 내마모성 코팅제를 각각 도포하는 다단계 코팅공정이 필요하다. 그러나 본 발명에 따른 상기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물은 내부식성 및 내마모성을 동시에 만족시키는 관능기를 포함하고 있어, 졸-겔 반응을 통하여 기재 수지에 내부식성 및 내마모성을 동시에 부여할 수 있으므로 코팅 공정을 단순화시키는 효과를 추가로 얻을 수 있다. The anthraquinone sol-gel compound represented by Formula 1 according to the present invention is a novel compound and includes a functional group simultaneously satisfying corrosion resistance and abrasion resistance in the molecular structure. In general, in order to form a coating film satisfying both corrosion resistance and wear resistance, a multi-step coating process is required in which a corrosion-resistant coating agent and a wear-resistant coating agent are respectively applied. However, the anthraquinone sol-gel compound represented by Formula 1 according to the present invention includes a functional group simultaneously satisfying corrosion resistance and abrasion resistance, so that corrosion resistance and abrasion resistance are simultaneously imparted to the base resin through sol- So that the effect of simplifying the coating process can be further obtained.
또한, 본 발명에 따른 상기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물은 물 또는 유기용매에 대한 용해도가 우수하므로 수용성(water soluble) 또는 유용성(organic solvent soluble) 하이브리드 코팅조성물 제조가 가능하고, 이로써 제조된 코팅조성물의 적용 범위가 크게 확장될 수 있다.
In addition, the anthraquinone sol-gel compound represented by Formula 1 according to the present invention has excellent solubility in water or an organic solvent, so that a water-soluble or organic solvent-soluble hybrid coating composition can be prepared, The application range of the coating composition thus produced can be greatly extended.
또한, 본 발명은 상기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물의 제조방법에도 특징이 있으며, 제조방법을 간략히 요약하면 하기 반응식 1과 같다. Also, the present invention is characterized by a process for producing an anthraquinone sol-gel compound represented by the above formula (1).
[반응식 1][Reaction Scheme 1]
(상기 반응식 1에서, R2는 수소원자, C1-C10 알킬기, 또는 
(In the above Reaction Scheme 1, R 2 represents a hydrogen atom, a C 1 -C 10 alkyl group, or
상기 반응식 1에 의하면, 상기 화학식 3으로 표시되는 1,5-다이클로로안트라퀴논 화합물과 상기 화학식 4로 표시되는 아민 화합물을 염기 존재 하에서 결합반응시켜, 히드록시 말단기를 갖는 상기 화학식 5로 표시되는 화합물을 제조한다. 그런 다음, 상기 화학식 5로 표시되는 화합물과 상기 화학식 6으로 표시되는 이소시아네이트 화합물과 반응시켜, 상기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물을 제조한다. According to Reaction Scheme 1, the 1,5-dichloroanthraquinone compound represented by Formula 3 is reacted with the amine compound represented by Formula 4 in the presence of a base to produce a compound represented by Formula 5 having a hydroxy end group ≪ / RTI > Then, an anthraquinone sol-gel compound represented by the formula (1) is prepared by reacting the compound represented by the formula (5) with the isocyanate compound represented by the formula (6).
상기 반응식 1에 따른 제조방법은 통상의 유기용매를 사용하여 40℃ 내지 용매의 환류온도범위에서 1 내지 24시간동안 교반하는 조건으로 진행한다. 이때 사용되는 통상의 유기용매는 디클로로메탄, 에틸아세테이트, 디에틸에테르, 아세토니트릴, 이소프로필알콜, 아세톤, 테트라히드로퓨란 등이 사용될 수 있다. 염기로는 당분야에서 통상적으로 사용되고 있는 통상의 유기염기 또는 무기염기일 수 있다. 상기 유기염기는 피리딘, 트리에틸아민 등의 아민염기가 포함될 수 있고, 상기 무기염기는 알칼리금속 또는 알칼리토금속의 수산화물, 탄산염, 황산염 등이 포함될 수 있다.
The production process according to the reaction scheme 1 proceeds using a conventional organic solvent at a temperature of 40 ° C to a reflux temperature of the solvent for 1 to 24 hours. Typical organic solvents used herein include dichloromethane, ethyl acetate, diethyl ether, acetonitrile, isopropyl alcohol, acetone, tetrahydrofuran, and the like. The base may be a conventional organic base or an inorganic base commonly used in the art. The organic base may include amine bases such as pyridine and triethylamine, and the inorganic base may include hydroxides, carbonates, sulfates and the like of an alkali metal or an alkaline earth metal.
또한, 본 발명은 상기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물이 포함된 코팅 조성물을 그 특징으로 한다. The present invention also provides a coating composition comprising the anthraquinone sol-gel compound represented by Formula 1 above.
본 발명의 코팅 조성물에 포함되는 기재는 상기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물과 반응하는 관능기를 포함하는 수지라면 모두 적용이 가능하다. 본 발명에서는 기재로서 트리(C1-C6 알콕시)실릴C1-C6 알킬 그룹으로 개질된 에폭시 수지를 사용하는 것을 특징으로 하며, 좀 더 구체적으로 예시하면 트리에톡시실릴프로필 그룹으로 개질된 비스페놀 A가 포함될 수 있다.The substrate included in the coating composition of the present invention is applicable to any resin containing a functional group that reacts with the anthraquinone sol-gel compound represented by the general formula (1). In the present invention, an epoxy resin modified with a tri (C 1 -C 6 alkoxy) silyl C 1 -C 6 alkyl group is used as a base material. More specifically, for example, the epoxy resin modified with triethoxysilylpropyl group Bisphenol A may be included.
본 발명의 코팅 조성물은 상기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물을 포함하는 바, 그 함량은 기재로 사용된 개질된 에폭시 수지 100 중량부를 기준으로 1 내지 20 중량부 범위, 바람직하기로는 1 내지 10 중량부 범위로 포함한다. 상기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물의 함량이 1 중량부 미만이면 내부식성 및 내마모성을 향상시키는 효과가 저조하고, 20 중량부를 초과하여 과량 포함하면 코팅 조성물 제조에 있어 용해성과 상용성이 낮아지고 균일한 코팅막을 형성하는데 어려움이 있어 바람직하지 못하다. The coating composition of the present invention comprises the anthraquinone sol-gel compound represented by the formula (1), and the content thereof is in the range of 1 to 20 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the modified epoxy resin used as the base 1 to 10 parts by weight. If the content of the anthraquinone sol-gel compound represented by the formula (1) is less than 1 part by weight, the effect of improving corrosion resistance and abrasion resistance is poor. If the content exceeds 20 parts by weight, Is lowered and it is difficult to form a uniform coating film, which is not preferable.
본 발명의 코팅 조성물은 기재 수지와 상기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물 이외에도, 하기 화학식 2로 표시되는 실란 화합물이 필수 성분으로서 함유된다. The coating composition of the present invention contains, in addition to the base resin and the anthraquinone sol-gel compound represented by the formula (1), a silane compound represented by the following formula (2) as an essential component.
[화학식 2] (2)
(상기 화학식 2에서, X1, X2, X3, 및 X4는 서로 같거나 다른 것으로 수소원자, 할로겐, C1-C6 알킬기, 또는 C1-C6 알콕시기를 나타내고, X1, X2, X3, 및 X4 중 하나 이상은 할로겐 또는 C1-C6 알콕시기를 나타낸다)Wherein X 1 , X 2 , X 3 and X 4 are the same or different and each represents a hydrogen atom, a halogen, a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, X 1 and X 2 , X 3 , and X 4 At least one represents a halogen or a C 1 -C 6 alkoxy in)
상기 화학식 2로 표시되는 실란 화합물은 기재로 사용된 개질된 에폭시 수지 100 중량부를 기준으로 1 내지 20 중량부 범위, 바람직하기로는 5 내지 15 중량부 범위로 포함한다. 상기 화학식 2로 표시되는 실란 화합물의 함량이 1 중량부 미만이면 내부식성 및 내마모성을 향상시키는 효과가 저조하고, 20 중량부를 초과하여 과량 포함하면 졸-겔 반응이 많이 일어나 코팅 조성물에서 상분리가 일어나서 균일한 코팅막을 얻기 어려우며 기재에 코팅하고 경화하였을 때 균일한 표면을 갖는 코팅막을 얻기가 어렵다. 본 발명의 코팅 조성물에 포함되는 상기 화학식 2로 표시되는 실란 화합물로서, 바람직하기로는 에톡시실란, 디에톡시실란, 에톡시트리메틸실란, 디에톡시디메틸실란, 메틸트리에톡시실란, 테트라에톡시실란, 디에톡시디메톡시실란, 에톡시트리메톡시실란, 클로로트리에톡시실란, 트리클로로메틸실란, 디클로로실란, 트리클로로실란, 디클로로디메틸실란 등으로부터 선택된 1종 또는 2종 이상을 사용할 수 있다. The silane compound represented by Formula 2 is contained in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight based on 100 parts by weight of the modified epoxy resin used as a base. If the amount of the silane compound represented by the formula (2) is less than 1 part by weight, the effect of improving the corrosion resistance and the abrasion resistance is poor. If the amount exceeds 20 parts by weight, a sol-gel reaction occurs to cause phase separation in the coating composition, It is difficult to obtain a coating film and it is difficult to obtain a coating film having a uniform surface when it is coated on a substrate and cured. Preferred examples of the silane compound represented by the above formula (2) contained in the coating composition of the present invention include ethoxysilane, diethoxysilane, ethoxytrimethylsilane, diethoxydimethylsilane, methyltriethoxysilane, tetraethoxysilane, It is possible to use one or more kinds selected from diethoxydimethoxysilane, ethoxytrimethoxysilane, chlorotriethoxysilane, trichloromethylsilane, dichlorosilane, trichlorosilane and dichlorodimethylsilane.
본 발명의 코팅 조성물은 기타 첨가제로서 통상의 경화제를 포함한다. 경화제로는 4,4'-디아미노디페닐메탄(DDM), 4,4'-디아미노디페닐설폰(DDS), 메틸렌다이아민(MDA), m-페닐렌다이아민(MPD) 등을 사용할 수 있다. The coating composition of the present invention includes conventional curing agents as other additives. As the curing agent, 4,4'-diaminodiphenylmethane (DDM), 4,4'-diaminodiphenylsulfone (DDS), methylenedianamine (MDA), m-phenylene diamine .
이상에서 설명한 바와 같은 본 발명은 하기의 합성예 및 실시예에 의거하여 더욱 상세히 설명하겠는 바, 본 발명이 이들 합성예 및 실시예에 의해 한정되는 것은 결코 아니다.
The present invention as described above will be described in more detail with reference to the following Synthesis Examples and Examples, but the present invention is by no means limited by these Synthesis Examples and Examples.
[합성예] 안트라퀴논계 졸-겔 화합물의 합성
[Synthesis Example] Synthesis of anthraquinone-based sol-gel compound
합성예 1.Synthesis Example 1
1,5-다이클로로안트라퀴논 (5.0 g, 0.0180 mol), 2-(메틸아미노)에탄올 (4.1 mL, 0.0515 mol)을 넣고 피리딘 (50 mL)을 넣은 후 질소조건하에 120℃에서 24시간동안 환류시켰다. 반응 종료 후, 에틸아세테이트 300 mL와 물 100 mL을 넣고 유기층을 추출하여 소금물로 한번 씻어준 후, 무수 황산마그네슘으로 수분을 제거하였다. 감압 증류 후 헥산:에틸아세테이트 (1:3)로 컬럼 크로마토그래피를 실시하여 적색 고체 상태의 생성물(AAQ-1) 2.5 g을 얻었다.(5.0 mL, 0.0180 mol) and 2- (methylamino) ethanol (4.1 mL, 0.0515 mol) were added and pyridine (50 mL) was added thereto. The mixture was refluxed under nitrogen at 120 ° C. for 24 hours . After completion of the reaction, 300 mL of ethyl acetate and 100 mL of water were added, and the organic layer was extracted, washed once with brine, and then dehydrated with anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was subjected to column chromatography with hexane: ethyl acetate (1: 3) to obtain 2.5 g of product (AAQ-1) in the form of a red solid.
수율 39%; 1H NMR (CDCl3, 300 MHz) δ 7.79 (d, 2H, ArH), 7.55 (t, 2H, ArH), 7.40 (d, 2H, ArH), 3.79 (m, 4H), 3.63 (m, 4H), 2.88 (s, 6H).Yield 39%; 1 H NMR (CDCl 3, 300 MHz) δ 7.79 (d, 2H, ArH), 7.55 (t, 2H, ArH), 7.40 (d, 2H, ArH), 3.79 (m, 4H), 3.63 (m, 4H ), 2.88 (s, 6H).
AAQ-1 (2.4 g, 0.0068 mol)을 테트라하이드로퓨란 50 mL에 용해시킨 후 트리에틸아민 (1.5 mL, 0.014 mol)을 넣고 45℃에서 15분간 교반한 후, 3-(트리에톡시실릴)프로필 이소시아네이트 (4.2 mL, 0.017 mol)를 천천히 적하한 후에 80℃에서 24시간동안 환류시켰다. 반응 종료 후, 감압 증류하여 용매를 제거한 다음 에틸아세테이트 150 mL와 물 50 mL을 넣고 유기층을 추출하여 소금물로 한번 씻어준 후, 무수 황산마그네슘으로 수분을 제거하였다. 감압 증류 후 헥산:에틸아세테이트 (1:1)로 컬럼 크로마토그래피를 실시하여 화합물 1의 목적 생성물 3.3 g을 얻었다.After dissolving AAQ-1 (2.4 g, 0.0068 mol) in 50 mL of tetrahydrofuran, triethylamine (1.5 mL, 0.014 mol) was added and the mixture was stirred at 45 ° C for 15 minutes. Then, 3- (triethoxysilyl) Isocyanate (4.2 mL, 0.017 mol) was slowly added dropwise and then refluxed at 80 DEG C for 24 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and 150 mL of ethyl acetate and 50 mL of water were added. The organic layer was extracted, washed once with brine, and then dehydrated with anhydrous magnesium sulfate. And then was evaporated under reduced pressure to hexane: ethyl acetate (1: 1) as the desired product of Compound 1 subjected to column chromatography 3.3 g was obtained.
수율 57%; 1H NMR (CDCl3, 300 MHz) δ 7.73 (d, 2H, ArH), 7.53 (t, 2H, Ar Hz), 7.28 (d, 2H, ArH), 4.84 (brs, 2H), 4.31 (t, 4H, J = 5.8 Hz), 3.80 (q, 12H, J = 7.0 Hz), 3.56 (t, 4H, J = 5.7 Hz), 3.10 (m, 4H), 3.00 (s, 6H), 1.58 (m, 4H), 1.21 (t, 18H, J = 7.0 Hz), 0.58 (m, 4H).
Yield 57%; 1 H NMR (CDCl 3, 300 MHz) δ 7.73 (d, 2H, ArH), 7.53 (t, 2H, Ar Hz), 7.28 (d, 2H, ArH), 4.84 (brs, 2H), 4.31 (t, 4H, J = 5.8 Hz), 3.80 (q, 12H, J = 7.0 Hz), 3.56 (t, 4H, J = 5.7 Hz), 3.10 4H), 1.21 (t, 18H, J = 7.0 Hz), 0.58 (m, 4H).
합성예 2Synthesis Example 2
1,5-다이클로로안트라퀴논 (5.0 g, 0.0180 mol), 2-(에틸아미노)에탄올 (4.6 g, 0.0515 mol)을 넣고 피리딘 (50 mL)을 넣은 후 질소조건하에 120℃에서 24시간동안 환류시켰다. 반응 종료 후, 에틸아세테이트 300 mL와 물 100 mL을 넣고 유기층을 추출하여 소금물로 한번 씻어준 후, 무수 황산마그네슘으로 수분을 제거하였다. 감압 증류 후 헥산:에틸아세테이트로 컬럼 크로마토그래피를 실시하여 적색 생성물(AAQ-2) 2.9 g을 얻었다.(5.0 g, 0.0180 mol) and 2- (ethylamino) ethanol (4.6 g, 0.0515 mol) were added and pyridine (50 mL) was added thereto. The mixture was refluxed under nitrogen at 120 ° C. for 24 hours . After completion of the reaction, 300 mL of ethyl acetate and 100 mL of water were added, and the organic layer was extracted, washed once with brine, and then dehydrated with anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was subjected to column chromatography using hexane: ethyl acetate to obtain 2.9 g of a red product (AAQ-2).
수율 42%; 1H NMR (CDCl3, 300 MHz) δ 7.78 (d, 2H, ArH), 7.54 (t, 2H, ArH), 7.41 (d, 2H, ArH), 3.79 (m, 4H), 3.63-3.45 (m, 8H), 1.12 (t, 6H).Yield 42%; 1 H NMR (CDCl 3, 300 MHz) δ 7.78 (d, 2H, ArH), 7.54 (t, 2H, ArH), 7.41 (d, 2H, ArH), 3.79 (m, 4H), 3.63-3.45 (m , 8H), 1.12 (t, 6H).
AAQ-2 (2.6 g, 0.0068 mol)을 테트라하이드로퓨란 50 mL에 용해시킨 후 트리에틸아민 (1.5 mL, 0.014 mol)을 넣고 45℃에서 15분간 교반한 후, 3-(트리에톡시실릴)프로필 이소시아네이트 (4.2 mL, 0.017 mol)을 천천히 적하한 후에 80℃에서 24시간동안 환류시켰다. 반응 종료 후, 감압 증류하여 용매를 제거한 다음 에틸아세테이트 150 mL와 물 50 mL을 넣고 유기층을 추출하여 소금물로 한번 씻어준 후, 무수 황산마그네슘으로 수분을 제거하였다. 감압 증류 후 헥산:에틸아세테이트 (1:1)로 컬럼 크로마토그래피를 실시하여 화합물 2의 목적 생성물 3.6 g을 얻었다.AAQ-2 (2.6 g, 0.0068 mol) was dissolved in tetrahydrofuran (50 mL), and then triethylamine (1.5 mL, 0.014 mol) was added thereto. The mixture was stirred at 45 캜 for 15 minutes and 3- (triethoxysilyl) Isocyanate (4.2 mL, 0.017 mol) was slowly added dropwise and then refluxed at 80 DEG C for 24 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and 150 mL of ethyl acetate and 50 mL of water were added. The organic layer was extracted, washed once with brine, and then dehydrated with anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was subjected to column chromatography with hexane: ethyl acetate (1: 1) to obtain 3.6 g of the target compound ( 2 ).
수율 61%; 1H NMR (CDCl3, 300 MHz) δ 7.74 (d, 2H, ArH), 7.53 (t, 2H, Ar Hz), 7.28 (d, 2H, ArH), 4.85 (brs, 2H), 4.31 (t, 4H), 3.80 (q, 12H, J = 7.0 Hz), 3.56(t, 4H), 3.40 (q, 4H), 3.10 (m, 4H), 1.58 (m, 4H), 1.21 (t, 18H, J = 7.0 Hz), 1.12 (t, 6H), 0.58 (m, 4H).
Yield 61%; 1 H NMR (CDCl 3, 300 MHz) δ 7.74 (d, 2H, ArH), 7.53 (t, 2H, Ar Hz), 7.28 (d, 2H, ArH), 4.85 (brs, 2H), 4.31 (t, 4H), 3.80 (q, 12H , J = 7.0 Hz), 3.56 (t, 4H), 3.40 (q, 4H), 3.10 (m, 4H), 1.58 (m, 4H), 1.21 (t, 18H, J = 7.0 Hz), 1.12 (t, 6H), 0.58 (m, 4H).
합성예 3Synthesis Example 3
1,5-다이클로로안트라퀴논 (5.0 g, 0.0180 mol), 2-(프로필아미노)에탄올 (5.3 g, 0.0515 mol)을 넣고 피리딘 (50 mL)을 넣은 후 질소조건하에 120℃에서 24시간동안 환류시켰다. 반응 종료 후, 에틸아세테이트 300 mL와 물 100 mL을 넣고 유기층을 추출하여 소금물로 한번 씻어준 후, 무수 황산마그네슘으로 수분을 제거하였다. 감압 증류 후 헥산:에틸아세테이트(1:4)로 컬럼 크로마토그래피를 실시하여 적색 생성물(AAQ-3) 2.2 g을 얻었다.(5.0 g, 0.0180 mol) and 2- (propylamino) ethanol (5.3 g, 0.0515 mol) were added and pyridine (50 mL) was added thereto. The mixture was refluxed under nitrogen at 120 ° C. for 24 hours . After completion of the reaction, 300 mL of ethyl acetate and 100 mL of water were added, and the organic layer was extracted, washed once with brine, and then dehydrated with anhydrous magnesium sulfate. After distillation under reduced pressure, column chromatography was performed with hexane: ethyl acetate (1: 4) to obtain 2.2 g of a red product (AAQ-3).
수율 30%; 1H NMR (CDCl3, 300 MHz) δ 7.79 (d, 2H, ArH), 7.55 (t, 2H, ArH), 7.40 (d, 2H, ArH), 3.79 (m, 4H), 3.73-3.60 (m, 8H), 1.57 (m, 4H), 0.87 (t, 6H).Yield 30%; 1 H NMR (CDCl 3, 300 MHz) δ 7.79 (d, 2H, ArH), 7.55 (t, 2H, ArH), 7.40 (d, 2H, ArH), 3.79 (m, 4H), 3.73-3.60 (m , 8H), 1.57 (m, 4H), 0.87 (t, 6H).
AAQ-3 (1.4 g, 0.0034 mol)을 테트라하이드로퓨란 50 mL에 용해시킨 후 트리에틸아민 (0.8 mL, 0.007 mol)을 넣고 45℃에서 15분간 교반한 후, 3-(트리에톡시실릴)프로필 이소시아네이트 (2.1 mL, 0.009 mol)을 천천히 적하한 후에 80℃에서 24시간동안 환류시켰다. 반응 종료 후, 감압 증류하여 용매를 제거한 다음 에틸아세테이트 100 mL와 물 30 mL을 넣고 유기층을 추출하여 소금물로 한번 씻어준 후, 무수 황산마그네슘으로 수분을 제거하였다. 감압 증류 후 헥산:에틸아세테이트 (1:1)로 컬럼 크로마토그래피를 실시하여 화합물 3의 목적 생성물 1.7 g을 얻었다.After dissolving AAQ-3 (1.4 g, 0.0034 mol) in 50 mL of tetrahydrofuran, triethylamine (0.8 mL, 0.007 mol) was added and the mixture was stirred at 45 ° C for 15 minutes. Isocyanate (2.1 mL, 0.009 mol) was slowly added dropwise and then refluxed at 80 DEG C for 24 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and then 100 mL of ethyl acetate and 30 mL of water were added. The organic layer was extracted, washed once with brine, and then dehydrated with anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was subjected to column chromatography with hexane: ethyl acetate (1: 1) to obtain 1.7 g of the target compound ( 3 ).
수율 54%; 1H NMR (CDCl3, 300 MHz) δ 7.73 (d, 2H, ArH), 7.53 (t, 2H, Ar Hz), 7.29 (d, 2H, ArH), 4.83 (brs, 2H), 4.31 (m, 4H, ), 3.80-3.72 (m, 16H), 3.56 (t, 4H), 3.11 (m, 4H), 1.58 (m, 8H), 1.21 (t, 18H), 0.87 (t, 6H), 0.58 (m, 4H).
Yield 54%; 1 H NMR (CDCl 3, 300 MHz) δ 7.73 (d, 2H, ArH), 7.53 (t, 2H, Ar Hz), 7.29 (d, 2H, ArH), 4.83 (brs, 2H), 4.31 (m, 4H), 1.58 (m, 8H), 1.21 (t, 18H), 0.87 (t, 6H), 0.58 m, 4H).
합성예 4Synthesis Example 4
1,5-다이클로로안트라퀴논 (5.0 g, 0.0180 mol), 2-(부틸아미노)에탄올 (6.0 g, 0.0515 mol)을 넣고 피리딘 (50 mL)을 넣은 후 질소조건하에 120℃에서 24시간동안 환류시켰다. 반응 종료 후, 에틸아세테이트 300 mL와 물 100 mL을 넣고 유기층을 추출하여 소금물로 한번 씻어준 후, 무수 황산마그네슘으로 수분을 제거하였다. 감압 증류 후 헥산:에틸아세테이트(1:3)로 컬럼 크로마토그래피를 실시하여 적색 생성물(AAQ-4) 3.9 g을 얻었다.(5.0 g, 0.0180 mol) and 2- (butylamino) ethanol (6.0 g, 0.0515 mol) were added and pyridine (50 mL) was added thereto. The mixture was refluxed under nitrogen at 120 ° C. for 24 hours . After completion of the reaction, 300 mL of ethyl acetate and 100 mL of water were added, and the organic layer was extracted, washed once with brine, and then dehydrated with anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was subjected to column chromatography with hexane: ethyl acetate (1: 3) to obtain 3.9 g of a red product (AAQ-4).
수율 50%; 1H NMR (CDCl3, 300 MHz) δ 7.79 (d, 2H, ArH), 7.55 (t, 2H, ArH), 7.40 (d, 2H, ArH), 3.79-3.53 (m, 12H), 1.56 (m, 4H), 1.35 (m, 4H), 0.93 (t, 6H). Yield 50%; 1 H NMR (CDCl 3, 300 MHz) δ 7.79 (d, 2H, ArH), 7.55 (t, 2H, ArH), 7.40 (d, 2H, ArH), 3.79-3.53 (m, 12H), 1.56 (m , 4H), 1.35 (m, 4H), 0.93 (t, 6H).
AAQ-4 (1.5 g, 0.0034 mol)을 테트라하이드로퓨란 50 mL에 용해시킨 후 트리에틸아민 (0.8 mL, 0.007 mol)을 넣고 45℃에서 15분간 교반한 후, 3-(트리에톡시실릴)프로필 이소시아네이트(2.1 mL, 0.009 mol)을 천천히 적하한 후에 80℃에서 24시간동안 환류시켰다. 반응 종료 후, 감압 증류하여 용매를 제거한 다음 에틸아세테이트 100 mL와 물 30 mL을 넣고 유기층을 추출하여 소금물로 한번 씻어준 후, 무수 황산마그네슘으로 수분을 제거하였다. 감압 증류 후 헥산:에틸아세테이트 (1:1)로 컬럼 크로마토그래피를 실시하여 화합물 4의 목적 생성물 1.7 g을 얻었다.AAQ-4 (1.5 g, 0.0034 mol) was dissolved in tetrahydrofuran (50 mL), and then triethylamine (0.8 mL, 0.007 mol) was added thereto. The mixture was stirred at 45 ° C for 15 minutes and 3- (triethoxysilyl) propyl Isocyanate (2.1 mL, 0.009 mol) was slowly added dropwise and then refluxed at 80 DEG C for 24 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and then 100 mL of ethyl acetate and 30 mL of water were added. The organic layer was extracted, washed once with brine, and then dehydrated with anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was subjected to column chromatography with hexane: ethyl acetate (1: 1) to obtain 1.7 g of the target compound ( 4 ).
수율 54%; 1H NMR (CDCl3, 300 MHz) δ 7.73 (d, 2H, ArH), 7.53 (t, 2H, Ar Hz), 7.29 (d, 2H, ArH), 4.84 (brs, 2H), 4.31 (m, 4H), 3.80-3.72 (m, 16H), 3.55 (m, 4H), 3.9 (m, 4H), 1.58 (m, 8H), 1.35 (m, 4H), 1.21 (t, 18H), 0.93 (t, 6H), 0.58 (m, 4H).
Yield 54%; 1 H NMR (CDCl 3, 300 MHz) δ 7.73 (d, 2H, ArH), 7.53 (t, 2H, Ar Hz), 7.29 (d, 2H, ArH), 4.84 (brs, 2H), 4.31 (m, 4H), 1.35 (m, 4H), 1.21 (t, 18H), 0.93 (m, , ≪ / RTI > 6H), 0.58 (m, 4H).
합성예 5Synthesis Example 5
1,5-다이클로로안트라퀴논 (5.0 g, 0.0180 mol), 다이에탄올아민 (5.4 g, 0.0515 mol)을 넣고 피리딘 (50 mL)을 넣은 후 질소조건하에 120℃에서 24시간동안 환류시켰다. 반응 종료 후, 에틸아세테이트 300 mL와 물 100 mL을 넣고 유기층을 추출하여 소금물로 한번 씻어준 후, 무수 황산마그네슘으로 수분을 제거하였다. 감압 증류 후 헥산:에틸아세테이트 (1:5)로 컬럼 크로마토그래피를 실시하여 생성물(AAQ-5) 3.9 g을 얻었다.5-Dichloroanthraquinone (5.0 g, 0.0180 mol) and diethanolamine (5.4 g, 0.0515 mol) were added, and pyridine (50 mL) was added thereto, followed by refluxing at 120 ° C for 24 hours under nitrogen. After completion of the reaction, 300 mL of ethyl acetate and 100 mL of water were added, and the organic layer was extracted, washed once with brine, and then dehydrated with anhydrous magnesium sulfate. After distillation under reduced pressure, the product was subjected to column chromatography with hexane: ethyl acetate (1: 5) to obtain 3.9 g of the product (AAQ-5).
수율 52%; 1H NMR (CDCl3, 300 MHz) δ 7.78 (d, 2H, ArH), 7.55 (t, 2H, ArH), 7.40 (d, 2H, ArH), 3.64 (t, 8H), 3.45 (t, 8H). Yield 52%; 1 H NMR (CDCl 3, 300 MHz) δ 7.78 (d, 2H, ArH), 7.55 (t, 2H, ArH), 7.40 (d, 2H, ArH), 3.64 (t, 8H), 3.45 (t, 8H ).
AAQ-5 (1.4 g, 0.0034 mol)을 테트라하이드로퓨란 50 mL에 용해시킨 후 트리에틸아민 (0.8 mL, 0.007 mol)을 넣고 45℃에서 15분간 교반한 후, 3-(트리에톡시실릴)프로필 이소시아네이트 (2.1 mL, 0.009 mol)을 천천히 적하한 후에 80℃에서 24시간동안 환류시켰다. 반응 종료 후, 감압 증류하여 용매를 제거한 다음 에틸아세테이트 100 mL와 물 30 mL을 넣고 유기층을 추출하여 소금물로 한번 씻어준 후, 무수 황산마그네슘으로 수분을 제거하였다. 감압 증류 후 헥산:에틸아세테이트 (1:1)로 컬럼 크로마토그래피를 실시하여 화합물 5의 목적 생성물 2.6 g을 얻었다.AAQ-5 (1.4 g, 0.0034 mol) was dissolved in 50 mL of tetrahydrofuran, and then triethylamine (0.8 mL, 0.007 mol) was added thereto. The mixture was stirred at 45 째 C for 15 minutes and 3- (triethoxysilyl) Isocyanate (2.1 mL, 0.009 mol) was slowly added dropwise and then refluxed at 80 DEG C for 24 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and then 100 mL of ethyl acetate and 30 mL of water were added. The organic layer was extracted, washed once with brine, and then dehydrated with anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was subjected to column chromatography with hexane: ethyl acetate (1: 1) to obtain 2.6 g of the target compound ( 5 ).
수율 55%; 1H NMR (CDCl3, 300 MHz) δ 7.74 (d, 2H, ArH), 7.52 (t, 2H, Ar Hz), 7.28 (d, 2H, ArH), 4.82 (brs, 4H), 4.32 (t, 8H), 3.80 (q, 24H, J = 7.0 Hz), 3.56 (t, 8H), 3.09 (m, 8H), 1.58 (m, 8H), 1.20 (t, 36H, J = 7.0 Hz), 0.59 (m, 8H).
Yield 55%; 1 H NMR (CDCl 3, 300 MHz) δ 7.74 (d, 2H, ArH), 7.52 (t, 2H, Ar Hz), 7.28 (d, 2H, ArH), 4.82 (brs, 4H), 4.32 (t, 8H), 3.80 (q, 24H , J = 7.0 Hz), 3.56 (t, 8H), 3.09 (m, 8H), 1.58 (m, 8H), 1.20 (t, 36H, J = 7.0 Hz), 0.59 ( m, 8H).
[참고예] 졸-겔 화합물의 용해도 비교 [Reference Example] Solubility comparison of sol-gel compound
본 참고예는 본 발명에 따른 안트라퀴논계 졸-겔 화합물의 물과 유기용매에 대한 용해도를 확인하기 위한 것이다. 비교화합물로서는 대한민국등록특허 10-0950286호에 개시된 퀴논계 졸-겔 화합물과 대한민국등록특허 10-1228927호에 개시된 트리아진계 졸-겔 화합물을 사용하였다. 용해도 시험을 위해 용매로서 수분산 우레탄 수지(보광화학사 제품, HMAR(01)), 이소프로필알콜(IPA), 물과 IPA의 혼합용매(3:1, v/v)를 사용하였다. 또한, 용해도 시험 결과는 해당 용매에서 졸-겔 화합물의 용해속도에 따라 ◎ > ○ > △ > X로 표시하였다. 그 결과는 하기 표 1에 나타내었다.This Reference Example is for confirming the solubility of anthraquinone sol-gel compound according to the present invention in water and an organic solvent. As the comparative compound, a quinone-based sol-gel compound disclosed in Korean Patent No. 10-0950286 and a triazine-based sol-gel compound disclosed in Korean Patent No. 10-1228927 were used. An aqueous dispersion urethane resin (HMAR (01)), isopropyl alcohol (IPA) and a mixed solvent of water and IPA (3: 1, v / v) were used as a solvent for the solubility test. The results of the solubility test were expressed as????>?> X according to the dissolution rate of the sol-gel compound in the solvent. The results are shown in Table 1 below.
혼합용매H 2 O / IPA
Mixed solvent
2)퀴논계: 
3)트리아진계: 
1) Anthraquinone system:
2) Quinone system:
3) Triazine:
상기 표 1로부터 확인되고 있듯이, 본 발명에 따른 상기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물은 수계 및 유기계 용매에 대한 용해도가 우수한 장점이 있다.
As shown in Table 1, the anthraquinone sol-gel compound represented by Formula 1 according to the present invention has an excellent solubility in aqueous and organic solvents.
[실시예]
[Example]
실시예 1∼15 및 비교예 1∼6. 유무기 하이브리드 코팅막의 제조 Examples 1-15 and Comparative Examples 1-6. Preparation of organic / inorganic hybrid coating film
테트라히드로퓨란(THF) (15 g)에 비스페놀 A (5 g)을 완전히 용해시킨 후, 3-이소시아네이토프로필트리에톡시실란 (2.08 g, 8.41 mmol)과 트리에틸아민 (0.150 g, 1.037 mmol)을 첨가하고 60℃에서 10시간 이상 반응하여 이소시아네이트 관능기가 사라질 때까지 교반하고, 감압 증류하여 트리에톡시실릴프로필 그룹으로 개질된 비스페놀 A를 제조하였다. After dissolving bisphenol A (5 g) completely in tetrahydrofuran (THF) (15 g), 3-isocyanatopropyltriethoxysilane (2.08 g, 8.41 mmol) and triethylamine (0.150 g, 1.037 mmol) was added thereto, and the mixture was reacted at 60 占 폚 for 10 hours or longer to stir until the isocyanate functional group disappeared. The mixture was distilled under reduced pressure to prepare bisphenol A modified with triethoxysilylpropyl group.
상기에서 제조한 개질된 비스페놀 A 100 중량부에 상기 합성예에서 제조된 안트라퀴논계 졸-겔 화합물과 테트라에톡시실란(TEOS)을 하기 표 1의 조성비로 첨가하였다. 경화제로서 4,4'-디아미노디페닐메탄(DDM) 4 중량부를 첨가하였다. 그리고, 상기에서 사용된 TEOS : 35% 염산 : 물의 중량비가 1 : 0.63 : 9를 유지하도록 염산 수용액을 첨가하고, 상온에서 1시간 교반하였다. 반응 종결 후 0.1 마이크로미터 크기의 실린더로 필터하였고, 필터 한 용액을 감압 증류하여 용매를 제거하여 코팅액을 얻었다. The anthraquinone sol-gel compound and tetraethoxysilane (TEOS) prepared in the above Synthesis Example were added to 100 parts by weight of the modified bisphenol A prepared above in the composition ratio shown in Table 1 below. And 4 parts by weight of 4,4'-diaminodiphenylmethane (DDM) as a curing agent were added. Then, an aqueous hydrochloric acid solution was added so that the weight ratio of TEOS: 35% hydrochloric acid: water used was 1: 0.63: 9, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solution was filtered through a cylinder having a size of 0.1 micrometer, and the filtered solution was distilled under reduced pressure to remove the solvent to obtain a coating solution.
기판(polish iron squares, 50mm×50mm×1.5mm, ss-41, 주식회사 젠텍)을 알루미늄옥사이드로 표면처리한 후 이소프로필알콜에 넣고 초음파 진동기계로 여러번 세척하였다. 세척된 기판은 공기로 건조한 후에, 상기에서 제조한 코팅액으로 딥 코팅하였다. 딥 코팅한 기판을 80℃에서 3시간 160℃에서 6 내지 24시간 진공오븐에서 열경화하여 코팅막을 제조하였다.
The substrate (polish iron squares, 50 mm x 50 mm x 1.5 mm, ss-41, Zentek Co., Ltd.) was surface-treated with aluminum oxide, and then put into isopropyl alcohol and washed several times with an ultrasonic vibration machine. The washed substrate was air dried and then dip coated with the coating solution prepared above. The dip-coated substrate was thermally cured at 80 DEG C for 3 hours at 160 DEG C for 6 to 24 hours in a vacuum oven to prepare a coating film.
상기와 같은 방법으로 제조된 코팅막에 대해서는, 하기의 시험방법을 통해 내부식성 및 내마모성을 확인하였다. 그 결과는 하기 표 2에 나타내었다. The corrosion resistance and abrasion resistance of the coating film prepared as described above were confirmed by the following test methods. The results are shown in Table 2 below.
1) 염수 분무 시험 방법 1) Salt water spray test method
염수 분부 장치는 (주)뉴럿핏사의 LYW-015 제품을 구입하여 사용하였다. 분무 실의 조건은 KSD9502에 의거하여 다음과 같이 하였다. 온도는 분무실의 시험편을 두는 폭로대는 35±2℃로 유지하고, 시험용 염용액 탱크의 온도 또한 35±2℃로 유지하였다. 분무는 자유낙하를 원칙으로 분무가 직접 시험편에 닿지 않는 방향으로 분무 노즐을 향함으로써 분무의 직사를 차단하여야 하였다. 시험용 염용액의 조제 방법은 염화나트륨을 증류수에 녹이고 염용액 농도 5%로 조정하고 pH 6.5∼7.2 범위에 있도록 하였다. 염수 분무 장치의 공기 공급은 염용액을 분무하기 위하여 분무 노즐로 보내는 압착 공기는 기름 및 먼지가 없고, 그 압력은 0.098±0.010 MPa로 유지하였다. 시험편의 모양은 50×50×1.5 mm의 평판으로 하였다. 시험편의 부식 확인은 1시간, 3시간, 6시간, 12시간, 24시간 간격으로 확인하였으며, 시험편 면적이 5% 이상의 부식이 발생하는 시점에 염수 분무 시험을 종결하였다. 그리고, 염수 분무 시험결과 전체 면적중 5%가 부식이 일어난 시간을 측정하였다. The salt water dispensing device was purchased from LYW-015 manufactured by New Rutledge Co., Ltd. The condition of the spray chamber was as follows according to KSD9502. The temperature was maintained at 35 ± 2 ° C in the test chamber of the spray chamber and the temperature of the test salt solution tank was maintained at 35 ± 2 ° C. Spraying was to stop direct spraying by directing the atomizing nozzle in a direction that does not touch the test specimen, in principle, free fall. The test salt solution was prepared by dissolving sodium chloride in distilled water, adjusting the salt solution concentration to 5%, and adjusting the pH to 6.5 to 7.2. The air supply of the saline sprayer was free of oil and dust, and the pressure was 0.098 ± 0.010 MPa, while the compressed air was sent to the spray nozzle to spray the salt solution. The shape of the specimen was a flat plate of 50 × 50 × 1.5 mm. The corrosion test of the test specimens was confirmed at 1 hour, 3 hours, 6 hours, 12 hours and 24 hours intervals, and the salt spray test was terminated at the time when corrosion of 5% or more of the specimen area occurred. In the salt spray test, 5% of the total area was measured for corrosion.
또한, 도 1, 2, 및 3에는 코팅도막에 대하여 염수 분무 시험을 수행한 후의 시험편 사진을 첨부하였다.
1, 2, and 3, photographs of the test pieces after the salt spray test on the coating films are shown.
2) 경도 2) Hardness
연필 경도 시험은 다음과 같이 하였다. 연필 고정부분이 테이블에 접촉 하지 않도록 상부쪽을 테이블과 수평을 이루도록 올려놓았다. 연필 고정부분 상부에 일정한 하중을 탑재하고 준비된 시험편을 시료대에 설치하여 연필이 분동하 중에 의하여 접촉하도록 핸들을 조정하였다. 시험편의 도면에 대하여 약 45ㅀ 각도로 KS G 2603 (연필)에 규정된 연필심을 대고 하중 약 1 kg·f (9.8N)로 도면에 누르면서 천천히 이동하였다. 심을 시료면에 붙이고 밀고 끝날 때까지 한 동작으로 하였다. 경도 시험이 끝나면 고정부분을 상부로 올려놓고 분동을 제거한 후 시험편을 꺼냈다. 본 실험에서 사용한 KS G 2603 (연필)은 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, HB, F, B, 2B, 3B, 4B, 5B, 6B, 7B, 8B, 9B를 사용하였다. The pencil hardness test was carried out as follows. The upper side was placed so as to be horizontal with the table so that the pencil fixing part would not touch the table. A uniform load was placed on the upper part of the pencil fixing part, and the prepared test piece was set on the sample stand, and the handle was adjusted so that the pencil came into contact with the breaking load. With reference to the drawing of the specimen, the pencil lead specified in KS G 2603 (pencil) at an angle of about 45 ° was slowly moved while pressing the drawing with a load of about 1 kg · f (9.8 N). The shim was attached to the sample surface and the operation was performed until the tip was pushed. After the hardness test was completed, the fixing part was placed on the upper side, the weight was removed, and the test piece was taken out. The KS G 2603 (pencil) used in this experiment was 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, HB, F, B, 2B, 3B, 4B, 5B, 6B, 7B, Were used.
(시간)5% corrosion time
(time)
상기 표 2의 결과에 의하면, 본 발명에 따른 상기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물을 포함하는 코팅조성물을 열경화하여 제조된 코팅막은 내부식성 및 내마모성이 우수함을 알 수 있다.
The results of Table 2 show that the coating film prepared by thermally curing the coating composition containing the anthraquinone sol-gel compound represented by Formula 1 according to the present invention has excellent corrosion resistance and abrasion resistance.
Claims (6)
[화학식 1]
(상기 화학식 1에서, R은 수소원자, C1-C10 알킬기, 또는
An anthraquinone sol-gel compound represented by the following formula (1).
[Chemical Formula 1]
(Wherein R is a hydrogen atom, a C 1 -C 10 alkyl group, or
(화합물 1)
(화합물 2)
(화합물 3)
(화합물 4)
(화합물 5)
로 이루어진 군으로부터 선택되는 것을 특징으로 하는 안트라퀴논계 졸-겔 화합물.
The method according to claim 1,
(Compound 1)
(Compound 2)
(Compound 3)
(Compound 4)
(Compound 5)
≪ / RTI > wherein the anthraquinone sol-gel compound is selected from the group consisting of:
물, 유기용매 또는 이의 혼합용매에 용해되는 특성을 가지는 것을 특징으로 하는 안트라퀴논계 졸-겔 화합물.
The method according to claim 1,
Anthraquinone sol-gel compound characterized by being soluble in water, an organic solvent or a mixed solvent thereof.
하기 화학식 1로 표시되는 안트라퀴논계 졸-겔 화합물 1 내지 20 중량부, 및
하기 화학식 2로 표시되는 실란 화합물 1 내지 20 중량부
를 포함하여 이루어진 내부식성 및 내마모성이 우수한 유무기 하이브리드 코 팅 조성물.
[화학식 1]
(상기 화학식 1에서, R은 수소원자, C1-C10 알킬기, 또는
[화학식 2]
(상기 화학식 2에서, X1, X2, X3, 및 X4는 서로 같거나 다른 것으로 수소원자, 할로겐, C1-C6 알킬기, 또는 C1-C6 알콕시기를 나타내고, X1, X2, X3, 및 X4 중 하나 이상은 할로겐 또는 C1-C6 알콕시기를 나타낸다)
100 parts by weight of an epoxy resin modified with a tri (C 1 -C 6 alkoxy) silyl C 1 -C 6 alkyl group,
1 to 20 parts by weight of an anthraquinone sol-gel compound represented by the following formula (1), and
1 to 20 parts by weight of a silane compound represented by the following formula (2)
Wherein the inorganic coating composition is excellent in corrosion resistance and abrasion resistance.
[Chemical Formula 1]
(Wherein R is a hydrogen atom, a C 1 -C 10 alkyl group, or
(2)
Wherein X 1 , X 2 , X 3 and X 4 are the same or different and each represents a hydrogen atom, a halogen, a C 1 -C 6 alkyl group or a C 1 -C 6 alkoxy group, X 1 and X 2 , X 3 , and X 4 represents a halogen or a C 1 -C 6 alkoxy group)
상기 개질된 에폭시 수지는 트리에톡시실릴프로필 그룹으로 개질된 비스페놀 A인 것을 특징으로 하는 유무기 하이브리드 코팅 조성물.
5. The method of claim 4,
Wherein the modified epoxy resin is a bisphenol A modified with a triethoxysilylpropyl group.
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| US3888891A (en) * | 1972-07-26 | 1975-06-10 | Minnesota Mining & Mfg | Silicone-compatible dyestuffs |
| JPH10279625A (en) * | 1997-04-08 | 1998-10-20 | Sekisui Finechem Co Ltd | Colored microparticle, its production, spacer for liquid crystal display and liquid crystal display element |
| WO2005010090A1 (en) * | 2003-07-15 | 2005-02-03 | General Electric Company | Colored polymeric resin composition, article made therefrom, and method for making the same |
| KR100950286B1 (en) * | 2009-05-18 | 2010-03-31 | 한국화학연구원 | Novel sol-gel compounds and organic-inorganic hydrid composition having excellent corrosion resistance and wear resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3888891A (en) * | 1972-07-26 | 1975-06-10 | Minnesota Mining & Mfg | Silicone-compatible dyestuffs |
| JPH10279625A (en) * | 1997-04-08 | 1998-10-20 | Sekisui Finechem Co Ltd | Colored microparticle, its production, spacer for liquid crystal display and liquid crystal display element |
| WO2005010090A1 (en) * | 2003-07-15 | 2005-02-03 | General Electric Company | Colored polymeric resin composition, article made therefrom, and method for making the same |
| KR100950286B1 (en) * | 2009-05-18 | 2010-03-31 | 한국화학연구원 | Novel sol-gel compounds and organic-inorganic hydrid composition having excellent corrosion resistance and wear resistance |
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| JP2017197455A (en) * | 2016-04-26 | 2017-11-02 | 信越化学工業株式会社 | Nitrogen-containing organoxysilane compound and method for producing the same |
| CN107312029A (en) * | 2016-04-26 | 2017-11-03 | 信越化学工业株式会社 | Nitrogenous polyfunctional group organic oxygen silane compound and its manufacture method |
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