KR102174467B1 - a coating composition for anti-reflection - Google Patents
a coating composition for anti-reflection Download PDFInfo
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- KR102174467B1 KR102174467B1 KR1020180007413A KR20180007413A KR102174467B1 KR 102174467 B1 KR102174467 B1 KR 102174467B1 KR 1020180007413 A KR1020180007413 A KR 1020180007413A KR 20180007413 A KR20180007413 A KR 20180007413A KR 102174467 B1 KR102174467 B1 KR 102174467B1
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- 239000008199 coating composition Substances 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 229920001709 polysilazane Polymers 0.000 claims abstract description 32
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 239000004094 surface-active agent Substances 0.000 claims description 21
- -1 titanium halide Chemical class 0.000 claims description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 239000006184 cosolvent Substances 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 8
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 6
- ZMTWFOKZRDNMEJ-SUKNRPLKSA-L (z)-4-oxopent-2-en-2-olate;oxotitanium(2+) Chemical compound [Ti+2]=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZMTWFOKZRDNMEJ-SUKNRPLKSA-L 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical group [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- SNOJPWLNAMAYSX-UHFFFAOYSA-N 2-methylpropan-1-ol;titanium Chemical compound [Ti].CC(C)CO.CC(C)CO.CC(C)CO.CC(C)CO SNOJPWLNAMAYSX-UHFFFAOYSA-N 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 33
- 238000013035 low temperature curing Methods 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 description 14
- 239000011148 porous material Substances 0.000 description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910000077 silane Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000001593 sorbitan monooleate Substances 0.000 description 3
- 235000011069 sorbitan monooleate Nutrition 0.000 description 3
- 229940035049 sorbitan monooleate Drugs 0.000 description 3
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 description 2
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000006117 anti-reflective coating Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229940100608 glycol distearate Drugs 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 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 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/006—Anti-reflective coatings
-
- 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
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Paints Or Removers (AREA)
Abstract
본 발명은 반사방지용 코팅 조성물 및 기공성 반사방지막의 제조방법에 관한 것으로, 더욱 상세하게는 폴리실라잔, 이산화티탄 전구체 및 용매를 포함하는 반사방지용 코팅 조성물 및 이로부터 기공성 반사방지막을 제조하는 방법에 관한 것이다.
본 발명은 기공성 실리카 막의 굴절율과 반사율을 낮추고 투과율을 증가시킬 수 있으며, 저온 경화 특성, 친수성 및 내구성이 우수한 반사방지용 코팅 조성물을 제공할 수 있다.
또한 본 발명은 저온 경화특성이 우수한 폴리실라잔을 사용함으로써 경도, 친수성, 내구성, 접착력, 투과율 등이 우수하여 태양전지, 편광판, 액정표시장치, 렌즈 등에 장기간 안정적으로 사용될 수 있는 기공성 반사방지막의 제조방법을 제공할 수 있다.The present invention relates to an antireflection coating composition and a method for preparing a porous antireflection film, and more particularly, to a antireflection coating composition comprising polysilazane, a titanium dioxide precursor, and a solvent, and a method for producing a porous antireflection film therefrom It is about.
The present invention can lower the refractive index and reflectance of the porous silica film and increase the transmittance, and can provide an antireflection coating composition having excellent low-temperature curing properties, hydrophilicity, and durability.
In addition, the present invention uses polysilazane, which has excellent low-temperature curing properties, so that it has excellent hardness, hydrophilicity, durability, adhesion, and transmittance. A manufacturing method can be provided.
Description
본 발명은 반사방지용 코팅 조성물 및 기공성 반사방지막의 제조방법에 관한 것으로, 더욱 상세하게는 폴리실라잔, 이산화티탄 전구체 및 용매를 포함하는 반사방지용 코팅 조성물 및 이로부터 기공성 반사방지막을 제조하는 방법에 관한 것이다. The present invention relates to an antireflection coating composition and a method for preparing a porous antireflection film, and more particularly, to a antireflection coating composition comprising polysilazane, a titanium dioxide precursor and a solvent, and a method for producing a porous antireflection film therefrom It is about.
최근 환경 문제의 중요성이 부각되면서 청정에너지로 수력 발전, 풍력 발전 및 태양광 발전이 각광을 받고 있다.As the importance of environmental issues has recently emerged, hydroelectric power generation, wind power generation, and solar power generation are in the spotlight as clean energy.
그 중에서도 태양 에너지를 이용한 태양광 발전은 무한한 에너지원인 태양을 이용하고 지구 온난화 방지에 유용하기 때문에 다양한 연구가 이루어지고 있다. Among them, solar power generation using solar energy uses the sun, which is an infinite energy source, and is useful for preventing global warming, so various studies have been conducted.
단결정 실리콘, 다결정 실리콘, 아모퍼스 실리콘 등의 반도체를 사용한 태양전지는 반도체에 태양광이 조사되면 전류를 방출시키는 원리를 실용화한 것이다.A solar cell using a semiconductor such as monocrystalline silicon, polycrystalline silicon, or amorphous silicon is a practical application of the principle of emitting current when the semiconductor is irradiated with sunlight.
태양전지는 일반적으로 실리콘, 갈륨-비소, 구리-인듐-셀렌 등의 태양전지 소자를 상부 투명 보호재와 하부 기판 보호재로 보호하고, 태양전지 소자와 보호재를 접착제로 고정하여 제조되는 태양전지 모듈을 포함한다.Solar cells generally include solar cell modules manufactured by protecting solar cell elements such as silicon, gallium-arsenic, copper-indium-selenium, etc. with an upper transparent protective material and a lower substrate protective material, and fixing the solar cell element and the protective material with an adhesive. do.
태양전지 모듈에서 상부 보호재는 통상적으로 유리를 사용하는데, 유리는 태양광을 반사하기 때문에 태양전지 모듈의 발전 효율이 떨어지는 단점이 있다. In the solar cell module, glass is generally used as the upper protective material, but since the glass reflects sunlight, there is a disadvantage in that the power generation efficiency of the solar cell module is lowered.
이를 해결하기 위하여 반사방지막을 사용하는 등의 다양한 연구가 수행되고 있다. In order to solve this problem, various studies such as using an antireflection film have been conducted.
이와 관련하여 한국공개특허 제10-2013-0015935호는 (메타)아크릴레이트 모노머(A), 나노실리카 입자(B), 4급 암모늄염(C), 알코올계 용제(D) 및 케톤계 용제(E)를 포함하여 이루어지는 것을 특징으로 하는 방현성 반사방지 코팅 조성물을 개시하고 있다.In this regard, Korean Patent Laid-Open Publication No. 10-2013-0015935 describes (meth)acrylate monomer (A), nano silica particles (B), quaternary ammonium salt (C), alcohol-based solvent (D), and ketone-based solvent (E ) Disclosed is an anti-glare anti-reflective coating composition comprising:
한국공개특허 제10-2013-0021182호는 (메타)아크릴레이트 단량체; 중공 실리카 나노입자; 4급 암모늄염; 알코올계 용매와 케톤계 용매의 혼합 용매; 및 광중합 개시제를 포함하는 방현성 반사방지 코팅 조성물을 개시하고 있다. Korean Patent Publication No. 10-2013-0021182 discloses a (meth)acrylate monomer; Hollow silica nanoparticles; Quaternary ammonium salt; A mixed solvent of an alcohol-based solvent and a ketone-based solvent; And it discloses an anti-glare anti-reflection coating composition comprising a photopolymerization initiator.
또한 한국등록특허 제10-1205477호는 제1분자량을 갖는 (메트)아크릴레이트계 화합물; 제1분자량보다 큰 제2분자량을 갖는 (메트)아크릴레이트계 화합물; 무기 미립자; 및 중공 입자를 포함하며, 상기 제2분자량을 갖는 (메트)아크릴레이트계 화합물은 제1분자량을 갖는 (메트)아크릴레이트계 화합물의 2 분자 이상이 링커에 의해 연결된 구조의 화합물을 포함하는 반사 방지 코팅용 조성물을 개시하고 있다. In addition, Korean Patent Registration No. 10-1205477 discloses a (meth)acrylate-based compound having a first molecular weight; A (meth)acrylate-based compound having a second molecular weight greater than the first molecular weight; Inorganic fine particles; And hollow particles, wherein the (meth)acrylate-based compound having the second molecular weight prevents reflection including a compound having a structure in which two or more molecules of the (meth)acrylate-based compound having a first molecular weight are connected by a linker Disclosed is a composition for coating.
그러나 상기 문헌에 개시된 기술은 반사방지막의 굴절율과 반사율이 높고 투과율이 저하되며, 저온 경화 특성이 불량하여 태양전지 모듈에 장기간 안정적으로 사용될 수 없다. However, the technology disclosed in the above document cannot be stably used for a long period of time in a solar cell module due to high refractive index and reflectance of the antireflection film and low transmittance, and poor low-temperature curing properties.
본 발명은 상기 종래 기술의 문제점을 해결하기 위한 것으로서, 기공성 실리카 막의 굴절율과 반사율을 낮추고 투과율을 증가시킬 수 있으며, 저온 경화 특성, 친수성 및 내구성이 우수한 반사방지용 코팅 조성물을 제공하는 데 그 목적이 있다.The present invention is to solve the problems of the prior art, it is possible to lower the refractive index and reflectance of the porous silica film and increase the transmittance, and to provide an antireflection coating composition excellent in low temperature curing properties, hydrophilicity and durability. have.
또한 본 발명은 저온 경화특성이 우수한 폴리실라잔을 사용함으로써 경도, 친수성, 내구성, 접착력, 투과율 등이 우수하여 태양전지, 편광판, 액정표시장치, 렌즈 등에 장기간 안정적으로 사용될 수 있는 기공성 반사방지막의 제조방법을 제공하는 것을 목적으로 한다.In addition, the present invention uses polysilazane, which has excellent low-temperature curing properties, so that it has excellent hardness, hydrophilicity, durability, adhesion, and transmittance. It aims to provide a manufacturing method.
상기와 같은 목적을 달성하기 위하여 본 발명은 폴리실라잔; 이산화티탄 전구체; 계면활성제; 및 용매를 포함하는 반사방지용 코팅 조성물을 제공한다.In order to achieve the above object, the present invention is polysilazane; Titanium dioxide precursor; Surfactants; And it provides an anti-reflective coating composition containing a solvent.
본 발명의 일실시예에 있어서, 상기 조성물은 용매 100중량부에 대하여 폴리실라잔 3~15중량부, 이산화티탄 전구체 1~10중량부 및 계면활성제 1~5중량부를 포함하는 것을 특징으로 한다. In one embodiment of the present invention, the composition is characterized in that it comprises 3 to 15 parts by weight of polysilazane, 1 to 10 parts by weight of a titanium dioxide precursor, and 1 to 5 parts by weight of a surfactant based on 100 parts by weight of a solvent.
본 발명의 일실시예에 있어서, 상기 이산화티탄 전구체는 티타늄 테트라메톡사이드, 티타늄 테트라에톡사이드, 티타늄 테트라 n-프로폭사이드, 티타늄 테트라이소프로폭사이드, 티타늄 테트라 n-부톡사이드, 티타늄 테트라이소부톡사이드, 티타늄 할라이드, 티타닐설페이트 및 티타닐비스(아세틸아세토네이트)에서 선택되는 하나 이상인 것을 특징으로 한다.In one embodiment of the present invention, the titanium dioxide precursor is titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetraisobu It is characterized in that at least one selected from oxide, titanium halide, titanyl sulfate and titanyl bis (acetylacetonate).
본 발명의 일실시예에 있어서, 상기 용매는 디에틸 에테르, 디프로필 에테르, 디부틸 에테르, 벤젠, 톨루엔 및 자일렌에서 선택되는 하나 이상인 것을 특징으로 한다.In one embodiment of the present invention, the solvent is characterized in that at least one selected from diethyl ether, dipropyl ether, dibutyl ether, benzene, toluene, and xylene.
본 발명의 일실시예에 있어서, 상기 조성물은 공용매를 추가로 포함하는 것을 특징으로 한다. In one embodiment of the present invention, the composition is characterized in that it further comprises a co-solvent.
본 발명의 일실시예에 있어서, 상기 조성물은 용매 100중량부에 대하여 폴리실라잔 3~15중량부, 이산화티탄 전구체 1~10중량부, 계면활성제 1~5중량부 및 공용매 1~10중량부를 포함하는 것을 특징으로 한다. In one embodiment of the present invention, the composition comprises 3 to 15 parts by weight of polysilazane, 1 to 10 parts by weight of a titanium dioxide precursor, 1 to 5 parts by weight of a surfactant, and 1 to 10 parts by weight of a co-solvent based on 100 parts by weight of the solvent. It is characterized by including wealth.
본 발명의 일실시예에 있어서, 상기 공용매는 메탄올, 에탄올, 미네랄 스피릿, 등유, 에틸 아세테이트, 디메틸 카보네이트 및 디아세톤 알코올에서 선택되는 하나 이상인 것을 특징으로 한다. In one embodiment of the present invention, the co-solvent is characterized in that at least one selected from methanol, ethanol, mineral spirit, kerosene, ethyl acetate, dimethyl carbonate and diacetone alcohol.
또한 본 발명은 (a) 기재를 세척하는 단계; (b) 폴리실라잔; 이산화티탄 전구체; 계면활성제; 및 용매를 포함하는 반사방지용 코팅 조성물을 준비하는 단계; (c) 상기 기재의 적어도 한 면에 상기 코팅 조성물을 코팅하여 반사방지층을 형성하는 단계; 및 (d) 상기 반사방지층을 열처리하여 기공성 실리카 막을 제조하는 단계를 포함하는 기공성 반사방지막의 제조방법을 제공한다. In addition, the present invention comprises the steps of (a) washing the substrate; (b) polysilazane; Titanium dioxide precursor; Surfactants; And preparing an antireflection coating composition comprising a solvent; (c) forming an antireflection layer by coating the coating composition on at least one surface of the substrate; And (d) heat treating the antireflection layer to prepare a porous silica film.
본 발명의 일실시예에 있어서, 상기 (b) 단계의 조성물은 용매 100중량부에 대하여 폴리실라잔 3~15중량부, 이산화티탄 전구체 1~10중량부 및 계면활성제 1~5중량부를 포함하는 것을 특징으로 것을 특징으로 한다.In one embodiment of the present invention, the composition of step (b) comprises 3 to 15 parts by weight of polysilazane, 1 to 10 parts by weight of a titanium dioxide precursor, and 1 to 5 parts by weight of a surfactant based on 100 parts by weight of the solvent. It is characterized by that.
본 발명의 일실시예에 있어서, 상기 이산화티탄 전구체는 티타늄 테트라메톡사이드, 티타늄 테트라에톡사이드, 티타늄 테트라 n-프로폭사이드, 티타늄 테트라이소프로폭사이드, 티타늄 테트라 n-부톡사이드, 티타늄 테트라이소부톡사이드, 티타늄 할라이드, 티타닐설페이트 및 티타닐비스(아세틸아세토네이트)에서 선택되는 하나 이상인 것을 특징으로 한다.In one embodiment of the present invention, the titanium dioxide precursor is titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetraisobu It is characterized in that at least one selected from oxide, titanium halide, titanyl sulfate and titanyl bis (acetylacetonate).
본 발명의 일실시예에 있어서, 상기 용매는 디에틸 에테르, 디프로필 에테르, 디부틸 에테르, 벤젠, 톨루엔 및 자일렌에서 선택되는 하나 이상인 것을 특징으로 한다.In one embodiment of the present invention, the solvent is characterized in that at least one selected from diethyl ether, dipropyl ether, dibutyl ether, benzene, toluene, and xylene.
본 발명의 일실시예에 있어서, 상기 (b) 단계의 조성물은 공용매를 추가로 포함하는 것을 특징으로 한다.In one embodiment of the present invention, the composition of step (b) is characterized in that it further comprises a co-solvent.
본 발명의 일실시예에 있어서, 상기 (b) 단계의 조성물은 용매 100중량부에 대하여 폴리실라잔 3~15중량부, 이산화티탄 전구체 1~10중량부, 계면활성제 1~5중량부 및 공용매 1~10중량부를 포함하는 것을 특징으로 한다.In an embodiment of the present invention, the composition of step (b) includes 3 to 15 parts by weight of polysilazane, 1 to 10 parts by weight of a titanium dioxide precursor, 1 to 5 parts by weight of a surfactant and common It characterized in that it contains every 1 to 10 parts by weight.
본 발명의 일실시예에 있어서, 상기 공용매는 메탄올, 에탄올, 미네랄 스피릿, 등유, 에틸 아세테이트, 디메틸 카보네이트 및 디아세톤 알코올에서 선택되는 하나 이상인 것을 특징으로 한다. In one embodiment of the present invention, the co-solvent is characterized in that at least one selected from methanol, ethanol, mineral spirit, kerosene, ethyl acetate, dimethyl carbonate and diacetone alcohol.
본 발명은 기공성 실리카 막의 굴절율과 반사율을 낮추고 투과율을 증가시킬 수 있으며, 저온 경화 특성, 친수성 및 내구성이 우수한 반사방지용 코팅 조성물을 제공할 수 있다.The present invention can lower the refractive index and reflectance of the porous silica film and increase the transmittance, and can provide an antireflection coating composition having excellent low-temperature curing properties, hydrophilicity, and durability.
또한 본 발명은 저온 경화특성이 우수한 폴리실라잔을 사용함으로써 경도, 친수성, 내구성, 접착력, 투과율 등이 우수하여 태양전지, 편광판, 액정표시장치, 렌즈 등에 장기간 안정적으로 사용될 수 있는 기공성 반사방지막의 제조방법을 제공할 수 있다.In addition, the present invention uses polysilazane, which has excellent low-temperature curing properties, so that it has excellent hardness, hydrophilicity, durability, adhesion, and transmittance. A manufacturing method can be provided.
이하 실시예를 바탕으로 본 발명을 상세히 설명한다. 본 발명에 사용된 용어, 실시예 등은 본 발명을 보다 구체적으로 설명하고 통상의 기술자의 이해를 돕기 위하여 예시된 것에 불과할 뿐이며, 본 발명의 권리범위 등이 이에 한정되어 해석되어서는 안 된다.The present invention will be described in detail based on the following examples. The terms, examples, etc. used in the present invention are merely exemplified to describe the present invention in more detail and to aid understanding of those skilled in the art, and the scope of the present invention should not be interpreted as being limited thereto.
본 발명에 사용되는 기술 용어 및 과학 용어는 다른 정의가 없다면 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 나타낸다.Technical terms and scientific terms used in the present invention represent the meanings commonly understood by those of ordinary skill in the art, unless otherwise defined.
본 발명은 폴리실라잔, 이산화티탄 전구체, 계면활성제 및 용매를 포함하는 반사방지용 코팅 조성물에 관한 것이다. The present invention relates to an antireflection coating composition comprising polysilazane, a titanium dioxide precursor, a surfactant, and a solvent.
상기 코팅 조성물은 용매 100중량부에 대하여 폴리실라잔 3~15중량부, 이산화티탄 전구체 1~10중량부 및 계면활성제 1~5중량부를 포함할 수 있다. The coating composition may include 3 to 15 parts by weight of polysilazane, 1 to 10 parts by weight of a titanium dioxide precursor, and 1 to 5 parts by weight of a surfactant based on 100 parts by weight of a solvent.
상기 폴리실라잔은 Si-N-Si- 결합을 갖는 고분자 화합물로서 열처리를 통하여 폴리실라잔이 실리카로 전화되면서 실리카 막이 형성된다. The polysilazane is a polymer compound having a Si-N-Si- bond, and a silica film is formed by converting the polysilazane to silica through heat treatment.
열처리에 의하여 폴리실라잔으로부터 실리카 막이 제조되고, 이 과정에서 용매 및 계면활성제가 제거되면서 실리카 막 내부에 다수의 기공을 형성한다. A silica film is prepared from polysilazane by heat treatment, and a number of pores are formed inside the silica film while the solvent and surfactant are removed during this process.
막 내부에 형성된 기공은 막의 굴절율과 반사율을 낮추고 투과율을 증가시키는 역할을 수행한다. The pores formed inside the film serve to lower the refractive index and reflectance of the film and increase the transmittance.
폴리실라잔은 다른 실라카 전구체 대비 수분과의 반응성이 매우 뛰어나 경도, 친수성, 내구성, 접착력 등이 우수한 반사 방지막 제조가 용이하다. Polysilazane has excellent reactivity with moisture compared to other silica precursors, so it is easy to manufacture an antireflection film having excellent hardness, hydrophilicity, durability, and adhesion.
폴리실라잔의 중량평균분자량은 1,000~30,000g/mol인 것이 바람직하고, 5,000~20,000g/mol인 것이 더욱 바람직하다. 중량평균분자량이 1,000g/mol 미만인 경우 경도 및 내구성이 저하되고, 30,000g/mol를 초과하는 경우 가공성 및 코팅성이 오히려 저하된다. The weight average molecular weight of polysilazane is preferably 1,000 to 30,000 g/mol, and more preferably 5,000 to 20,000 g/mol. When the weight average molecular weight is less than 1,000 g/mol, hardness and durability are deteriorated, and when it exceeds 30,000 g/mol, workability and coating properties are rather deteriorated.
상기 폴리실라잔은 용매 100중량부에 대하여 3~15중량부 사용되며, 함량이 3중량부 미만인 경우 막의 강도와 내구성이 저하되고, 15중량부를 초과하는 경우 균일한 코팅층을 형성할 수 없어 막의 투과율 및 내구성이 오히려 저하된다. The polysilazane is used in 3 to 15 parts by weight based on 100 parts by weight of the solvent, and if the content is less than 3 parts by weight, the strength and durability of the film decrease, and if it exceeds 15 parts by weight, a uniform coating layer cannot be formed, and thus the transmittance of the film. And durability is rather lowered.
상기 이산화티탄 전구체는 폴리실라잔의 저온 경화를 촉진시키며, 열처리 과정 중에 가수분해 되면서 이산화티탄으로 변환되어 반사방지막에 친수성을 부여하는 역할을 동시에 수행한다. The titanium dioxide precursor promotes low-temperature curing of polysilazane, and is converted into titanium dioxide while being hydrolyzed during the heat treatment process, thereby simultaneously serving to impart hydrophilicity to the antireflection film.
이산화티탄 전구체로는 티타늄 알콕사이드, 티타늄 테트라클로라이드와 같은 티타늄 할라이드, 티타닐설페이트 및 티타닐비스(아세틸아세토네이트)에서 선택되는 하나 이상이 사용될 수 있다. As the titanium dioxide precursor, at least one selected from titanium alkoxide, titanium halide such as titanium tetrachloride, titanyl sulfate, and titanyl bis (acetylacetonate) may be used.
상기 티타늄 알콕사이드는 Ti(OR)4 화합물이며, 여기서 R은 C1~C6 알킬인 것이 바람직하다. The titanium alkoxide is a Ti(OR) 4 compound, wherein R is preferably C1~C6 alkyl.
상기 티타늄 알콕사이드로는 티타늄 테트라메톡사이드, 티타늄 테트라에톡사이드, 티타늄 테트라 n-프로폭사이드, 티타늄 테트라이소프로폭사이드, 티타늄 테트라 n-부톡사이드, 티타늄 테트라이소부톡사이드 등이 사용될 수 있다. As the titanium alkoxide, titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetraisobutoxide, and the like may be used.
반사방지막의 저온 경화 특성, 친수성, 경도 및 내구성의 측면에서 이산화티탄 전구체로 티타늄 테트라이소프로폭사이드가 사용되는 것이 바람직하다.It is preferable that titanium tetraisopropoxide is used as the titanium dioxide precursor in terms of low temperature curing properties, hydrophilicity, hardness and durability of the antireflection film.
상기 이산화티탄 전구체는 용매 100중량부에 대하여 1~10중량부 사용되며, 3~7중량부 사용되는 것이 바람직하다. 함량이 1중량부 미만인 경우 첨가의 효과가 미미하고, 10중량부를 초과하는 경우 균일한 기공을 형성할 수 없어 막의 투과율 및 내구성이 오히려 저하된다. The titanium dioxide precursor is used in 1 to 10 parts by weight based on 100 parts by weight of the solvent, and it is preferable to use 3 to 7 parts by weight. If the content is less than 1 part by weight, the effect of the addition is insignificant, and if it exceeds 10 parts by weight, uniform pores cannot be formed, so that the transmittance and durability of the membrane are rather lowered.
상기 용매는 조성물의 점도를 조절하며, 디에틸 에테르, 디프로필 에테르, 디부틸 에테르, 벤젠, 톨루엔 및 자일렌에서 선택되는 하나 이상이 사용될 수 있다. The solvent controls the viscosity of the composition, and at least one selected from diethyl ether, dipropyl ether, dibutyl ether, benzene, toluene, and xylene may be used.
반사방지막의 투과율, 경도 및 내구성의 측면에서 용매로 디부틸 에테르가 사용되는 것이 바람직하다. It is preferable to use dibutyl ether as a solvent in terms of transmittance, hardness and durability of the antireflection film.
상기 계면활성제는 조성물의 균일성 및 코팅성을 향상시키며, 열처리에 의하여 제거되어 실리카 막 내부에 다수의 기공을 형성시키는 역할을 한다. The surfactant improves the uniformity and coating properties of the composition, and is removed by heat treatment to form a plurality of pores in the silica film.
계면활성제로는 폴리옥시에틸렌 알킬에테르, 폴리옥시에틸렌 옥틸페닐에테르, 폴리옥시에틸렌 노닐페닐에테르, 폴리옥시에틸렌 알킬알릴에테르, 폴리옥시에틸렌-폴리옥시프로필렌 블록 코폴리머, 소르비탄 지방산 에스테르, 폴리옥시에틸렌 소르비탄 지방산 에스테르, 폴리에틸렌글리콜, 폴리에틸렌글리콜 모노올리에이트, 폴리에틸렌글리콜 디스테아레이트, 소르비탄 모노올리에이트, 소르비탄 모노스테아레이트, 소르비탄 모노라우레이트, 폴리옥시에틸렌 알킬페닐에테르, 올레산, 옥탄산, 리놀레산, 스테아르산 및 라우르산에서 선택되는 하나 이상이 사용될 수 있다. Surfactants include polyoxyethylene alkyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene-polyoxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene. Sorbitan fatty acid ester, polyethylene glycol, polyethylene glycol monooleate, polyethylene glycol distearate, sorbitan monooleate, sorbitan monostearate, sorbitan monolaurate, polyoxyethylene alkylphenyl ether, oleic acid, octanoic acid, One or more selected from linoleic acid, stearic acid and lauric acid may be used.
반사방지막의 투과율, 경도 및 내구성의 측면에서 계면활성제로 폴리에틸렌글리콜 모노올리에이트, 폴리에틸렌글리콜 디스테아레이트, 소르비탄 모노올리에이트 및 폴리옥시에틸렌 노닐페닐에테르가 사용되는 것이 바람직하다.Polyethylene glycol monooleate, polyethylene glycol distearate, sorbitan monooleate, and polyoxyethylene nonylphenyl ether are preferably used as surfactants in terms of transmittance, hardness and durability of the antireflection film.
상기 계면활성제는 용매 100중량부에 대하여 1~5중량부 사용되며, 함량이 1중량부 미만인 경우 첨가의 효과가 미미하고, 5중량부를 초과하는 경우 균일한 기공을 형성할 수 없어 막의 투과율 및 내구성이 오히려 저하된다. The surfactant is used in an amount of 1 to 5 parts by weight based on 100 parts by weight of the solvent, and when the content is less than 1 part by weight, the effect of addition is insignificant, and when it exceeds 5 parts by weight, uniform pores cannot be formed, so the transmittance and durability of the membrane This is rather degraded.
본 발명의 조성물은 공용매를 추가로 포함할 수 있으며, 상기 공용매는 조성물의 코팅성을 향상시키고 막 내부의 기공도를 증가시켜 막의 투과율을 향상시키는 역할을 한다.The composition of the present invention may further include a co-solvent, and the co-solvent serves to improve the coating property of the composition and increase the porosity inside the membrane to improve the transmittance of the membrane.
상기 공용매로는 메탄올, 에탄올, 미네랄 스피릿, 등유, 에틸 아세테이트, 디메틸 카보네이트 및 디아세톤 알코올에서 선택되는 하나 이상이 사용될 수 있으며, 막의 투과율 및 내구성의 측면에서 메탄올이 바람직하다. As the co-solvent, at least one selected from methanol, ethanol, mineral spirit, kerosene, ethyl acetate, dimethyl carbonate and diacetone alcohol may be used, and methanol is preferable in terms of permeability and durability of the membrane.
상기 조성물은 용매 100중량부에 대하여 폴리실라잔 3~15중량부, 이산화티탄 전구체 1~10중량부, 계면활성제 1~5중량부 및 공용매 1~10중량부를 포함할 수 있다. The composition may include 3 to 15 parts by weight of polysilazane, 1 to 10 parts by weight of a titanium dioxide precursor, 1 to 5 parts by weight of a surfactant, and 1 to 10 parts by weight of a co-solvent based on 100 parts by weight of the solvent.
상기 공용매는 용매 100중량부에 대하여 1~10중량부 사용되는 것이 바람직하며, 함량이 1중량부 미만인 경우 가공성 및 코팅성이 저하되고, 10중량부를 초과하는 경우 막의 투과율 및 내구성이 오히려 저하된다. The co-solvent is preferably used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the solvent, and when the content is less than 1 part by weight, processability and coating properties are deteriorated, and when it exceeds 10 parts by weight, the transmittance and durability of the membrane are rather lowered.
상기 조성물은 용매 100중량부에 대하여 실리카 전구체 1~5중량부를 추가로 포함할 수 있으며, 실리카 전구체는 열처리에 의하여 실리카 막을 형성하여 막의 강도와 내구성을 개선할 수 있다.The composition may further contain 1 to 5 parts by weight of a silica precursor based on 100 parts by weight of the solvent, and the silica precursor may improve the strength and durability of the film by forming a silica film by heat treatment.
실리카 전구체로는 테트라메톡시실란(TMOS), 테트라에톡시실란(TEOS) 등의 알콕시실란, 소듐 실리케이트(sodium silicate), 포타슘 실리케이트(potassium silicate), 실리콘 테트라클로라이드 등이 제한 없이 사용될 수 있으며, 테트라에톡시실란이 사용되는 것이 바람직하다. As the silica precursor, alkoxysilanes such as tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), sodium silicate, potassium silicate, silicon tetrachloride, etc. may be used without limitation. It is preferred that ethoxysilane is used.
상기 실리카 전구체는 1~5중량부 사용되며, 함량이 1중량부 미만인 경우 첨가의 효과가 미미하고, 5중량부를 초과하는 경우 막의 투과율이 오히려 저하된다.1 to 5 parts by weight of the silica precursor is used, and when the content is less than 1 part by weight, the effect of the addition is insignificant, and when it exceeds 5 parts by weight, the transmittance of the film is rather lowered.
폴리실라잔 및 실리카 전구체의 가수분해를 촉진하기 위하여 염산, 질산, 아세트산, 수산화암모늄, 암모니아수, 수산화나트륨, 수산화칼륨 등이 제한 없이 사용될 수 있으며, 암모니아수가 사용되는 것이 바람직하다. Hydrochloric acid, nitric acid, acetic acid, ammonium hydroxide, aqueous ammonia, sodium hydroxide, potassium hydroxide, etc. may be used without limitation in order to accelerate the hydrolysis of the polysilazane and silica precursor, and aqueous ammonia is preferably used.
상기 조성물은 용매 100중량부에 대하여 실리카 나노입자 1~5중량부를 추가로 포함할 수 있으며, 실리카 나노입자는 막의 강도 및 내구성을 향상시킬 수 있다. The composition may further include 1 to 5 parts by weight of silica nanoparticles based on 100 parts by weight of the solvent, and the silica nanoparticles may improve the strength and durability of the film.
실리카 나노입자의 함량이 1중량부 미만인 경우 첨가의 효과가 미미하고, 5중량부를 초과하는 경우 막의 투과율이 저하된다. When the content of the silica nanoparticles is less than 1 part by weight, the effect of the addition is insignificant, and when it exceeds 5 parts by weight, the transmittance of the membrane decreases.
실리카 나노입자의 직경은 20~100nm인 것이 바람직하고, 더 바람직하게는 50~80nm이다. 직경이 상기 수치 범위를 만족하는 경우 막의 투과율을 저하시키지 않으면서 경도 및 내구성을 향상시킬 수 있다. The diameter of the silica nanoparticles is preferably 20 to 100 nm, more preferably 50 to 80 nm. When the diameter satisfies the above numerical range, hardness and durability can be improved without lowering the transmittance of the film.
상기 실리카 나노입자는 실란 커플링제로 표면 처리될 수 있다. The silica nanoparticles may be surface-treated with a silane coupling agent.
실란 커플링제는 유기 화합물과 결합할 수 있는 유기 관능기 및 무기물과 반응할 수 있는 가수분해기를 가지며, 기재와 코팅 조성물 사이의 계면 접착력 및 실리카 막을 구성하는 성분 사이의 계면 접착력을 증가시켜 실리카 막의 반사방지 특성, 투과율, 친수성, 경도, 내구성 등을 향상시킬 수 있다. The silane coupling agent has an organic functional group capable of binding to an organic compound and a hydrolyzable group capable of reacting with an inorganic substance, and increases the interface adhesion between the substrate and the coating composition and the components constituting the silica film to prevent reflection of the silica film. Properties, transmittance, hydrophilicity, hardness, durability, etc. can be improved.
실란 커플링제로는 알킬기 함유 실란, 아미노기 함유 실란, 에폭시기 함유 실란, 아크릴레이트기 함유 실란, 이소시아네이트기 함유 실란, 메르캅토기 함유 실란, 불소기 함유 실란, 비닐기 함유 실란 등이 사용된다. As the silane coupling agent, an alkyl group-containing silane, an amino group-containing silane, an epoxy group-containing silane, an acrylate group-containing silane, an isocyanate group-containing silane, a mercapto group-containing silane, a fluorine group-containing silane, a vinyl group-containing silane, and the like are used.
실란 커플링제의 함량은 나노입자 100중량부에 대하여 1~10중량부인 것이 바람직하며, 함량이 1중량부 미만인 경우 접착력 향상을 기대하기 어렵고, 10중량부를 초과하는 경우 과다한 실란 커플링제의 사용으로 오히려 계면 접착 특성, 투과율 및 내구성이 저하된다.The content of the silane coupling agent is preferably 1 to 10 parts by weight based on 100 parts by weight of the nanoparticles, and if the content is less than 1 part by weight, it is difficult to expect improved adhesion, and if it exceeds 10 parts by weight, the use of excessive silane coupling agent is rather The interfacial adhesion properties, transmittance and durability are deteriorated.
특히 이소시아네이트기 함유 실란 커플링제 60~90중량% 및 아크릴레이트기 함유 실란 커플링제 10~40중량%로 구성되는 실란 커플링제 혼합물이 사용되는 것이 바람직하다.In particular, it is preferable to use a silane coupling agent mixture composed of 60 to 90% by weight of an isocyanate group-containing silane coupling agent and 10 to 40% by weight of an acrylate group-containing silane coupling agent.
또한 본 발명의 조성물은 용매 100중량부에 대하여 이소시아네이트기 함유 실란 커플링제와 아크릴레이트기 함유 실란 커플링제를 미리 반응시켜 제조한 실란 커플링제 올리고머 1~5중량부를 추가로 포함할 수 있다. In addition, the composition of the present invention may further include 1 to 5 parts by weight of a silane coupling agent oligomer prepared by reacting in advance a silane coupling agent containing an isocyanate group and a silane coupling agent containing an acrylate group based on 100 parts by weight of a solvent.
상기 실란 커플링제 올리고머를 사용함으로써 실리카 막의 접착력, 가공성, 투과율, 내구성 등이 향상될 수 있다. By using the silane coupling agent oligomer, adhesion, processability, transmittance, and durability of the silica film may be improved.
실란 커플링제 올리고머의 중량평균분자량은 1,000~5,000g/mol이 바람직하며, 실란 커플링제 올리고머의 함량이 1중량부 미만인 경우 첨가의 효과가 미미하고, 5중량부를 초과하는 경우 가공성 및 투과율이 저하된다. The weight average molecular weight of the silane coupling agent oligomer is preferably 1,000 to 5,000 g/mol, and when the content of the silane coupling agent oligomer is less than 1 part by weight, the effect of the addition is insignificant, and when it exceeds 5 parts by weight, processability and transmittance are lowered. .
또한 본 발명은 (a) 기재를 세척하는 단계; (b) 폴리실라잔; 이산화티탄 전구체; 계면활성제; 및 용매를 포함하는 반사방지용 코팅 조성물을 준비하는 단계; (c) 상기 기재의 적어도 한 면에 상기 코팅 조성물을 코팅하여 반사방지층을 형성하는 단계; 및 (d) 상기 반사방지층을 열처리하여 기공성 실리카 막을 제조하는 단계를 포함하는 기공성 반사방지막의 제조방법에 관한 것이다. In addition, the present invention comprises the steps of: (a) washing the substrate; (b) polysilazane; Titanium dioxide precursor; Surfactants; And preparing an antireflection coating composition comprising a solvent; (c) forming an antireflection layer by coating the coating composition on at least one surface of the substrate; And (d) heat-treating the antireflection layer to prepare a porous silica film.
상기 (a) 단계는 먼지, 오일, 유기 화합물, 오염물 등을 제거하는 단계로서, 기재를 600~700℃로 가열하거나 탈염수, 알코올, 산성 또는 염기성의 세정액으로 기재를 세척할 수 있다. The step (a) is a step of removing dust, oil, organic compounds, contaminants, and the like, and the substrate may be heated to 600 to 700°C, or the substrate may be washed with demineralized water, alcohol, acidic or basic washing liquid.
상기 기재는 유리, 석영, 폴리에틸렌테레프탈레이트, 폴리에틸렌나프탈레이트 등의 폴리에스테르, 폴리아미드, 폴리카보네이트, 폴리메틸메타크릴레이트, 폴리스티렌 등의 필름, 시트 또는 기판이 제한 없이 사용될 수 있다. The substrate may be a film, sheet, or substrate such as glass, quartz, polyethylene terephthalate, polyester such as polyethylene naphthalate, polyamide, polycarbonate, polymethyl methacrylate, and polystyrene, without limitation.
상기 (b) 단계의 조성물은 용매 100중량부에 대하여 폴리실라잔 3~15중량부, 이산화티탄 전구체 1~10중량부 및 계면활성제 1~5중량부를 포함할 수 있다. The composition of step (b) may include 3 to 15 parts by weight of polysilazane, 1 to 10 parts by weight of a titanium dioxide precursor, and 1 to 5 parts by weight of a surfactant based on 100 parts by weight of the solvent.
또한 상기 (b) 단계의 조성물은 용매 100중량부에 대하여 폴리실라잔 3~15중량부, 이산화티탄 전구체 1~10중량부, 계면활성제 1~5중량부 및 공용매 1~10중량부를 포함할 수 있다. In addition, the composition of step (b) includes 3 to 15 parts by weight of polysilazane, 1 to 10 parts by weight of a titanium dioxide precursor, 1 to 5 parts by weight of a surfactant, and 1 to 10 parts by weight of a co-solvent based on 100 parts by weight of the solvent. I can.
상기 (c) 단계는 기재의 적어도 한 면에 상기 코팅 조성물을 코팅하는 단계로서, 공지의 코팅 방법을 사용할 수 있다. The step (c) is a step of coating the coating composition on at least one side of a substrate, and a known coating method may be used.
코팅 방법은 바 코팅, 메니스커스 코팅, 분무 코팅, 롤 코팅, 스핀 코팅 및 침지 코팅을 포함한다. Coating methods include bar coating, meniscus coating, spray coating, roll coating, spin coating and dip coating.
상기 (c) 단계의 코팅 속도는 30~70mm/s 인 것이 바람직하며, 코팅 속도가 상기 수치 범위를 만족하는 경우 제조된 막의 기공이 균일하게 형성되고 내구성 및 투과율이 극대화될 수 있다The coating speed in step (c) is preferably 30 to 70 mm/s, and when the coating speed satisfies the above numerical range, the pores of the prepared membrane are uniformly formed, and durability and transmittance can be maximized.
상기 (d) 단계는 반사방지층을 열처리하여 기공성 실리카 막을 제조하는 단계로서, 열처리는 25~800℃에서 수행될 수 있다. The step (d) is a step of heat-treating the antireflection layer to prepare a porous silica film, and the heat treatment may be performed at 25 to 800°C.
열처리 온도가 상기 수치 범위를 만족하는 경우 제조된 막의 기공이 균일하게 형성되고 내구성, 친수성 및 투과율이 극대화될 수 있다.When the heat treatment temperature satisfies the above numerical range, pores of the prepared membrane are uniformly formed, and durability, hydrophilicity, and transmittance may be maximized.
열처리에 의하여 폴리실라잔으로부터 실리카 막이 제조되고, 계면활성제, 용매, 분해물질 등이 제거되면서 실리카 막 내부에 다수의 기공을 형성한다. A silica film is prepared from polysilazane by heat treatment, and a number of pores are formed in the silica film while surfactants, solvents, and decomposition substances are removed.
막 내부에 형성된 기공은 막의 굴절율과 반사율을 낮추고 투과율을 증가시키는 역할을 수행한다. The pores formed inside the film serve to lower the refractive index and reflectance of the film and increase the transmittance.
상기 기공성 실리카 막의 두께는 필요에 따라 다양하게 조절될 수 있으며, 10~2,000nm인 것이 바람직하다. The thickness of the porous silica film may be variously adjusted as necessary, and is preferably 10 to 2,000 nm.
상기 반사방지막은 장기간 사용하더라도 경도, 친수성, 내구성 및 투과율이 감소되지 않아 태양전지, 편광판, 액정표시장치, 렌즈 등에 장기간 안정적으로 사용될 수 있다. Even if the anti-reflection film is used for a long period of time, hardness, hydrophilicity, durability, and transmittance are not reduced, so that it can be stably used for a long period of time in solar cells, polarizing plates, liquid crystal displays, and lenses.
특히 상기 반사방지막은 이산화티탄 전구체로부터 변환된 이산화티탄이 폴리실라잔의 저온 경화(25~400℃)를 촉진하므로, 저온 경화 특성이 매우 우수할 뿐 아니라 친수성도 증가하게 된다. In particular, since the antireflection film promotes low-temperature curing (25 to 400° C.) of polysilazane, the titanium dioxide converted from the titanium dioxide precursor has excellent low-temperature curing properties and increases hydrophilicity.
이하 실시예 및 비교예를 통해 본 발명을 상세히 설명한다. 하기 실시예는 본 발명의 실시를 위하여 예시된 것일 뿐, 본 발명의 내용이 하기 실시예에 의하여 한정되는 것은 아니다.The present invention will be described in detail through examples and comparative examples below. The following examples are only illustrated for the practice of the present invention, and the contents of the present invention are not limited by the following examples.
(반사율)(reflectivity)
분광 광도계 UV 2450에 어댑터 MPC 2200을 장착하여 380~780nm의 파장 영역에서 입사각 5°에서의 출사각 5°에 대한 경면 반사율을 측정하고, 450~650nm의 평균 반사율을 산출하였다.By attaching the adapter MPC 2200 to the spectrophotometer UV 2450, the specular reflectance was measured for the emission angle of 5° at the incident angle of 5° in the wavelength region of 380 to 780 nm, and the average reflectance of 450 to 650 nm was calculated.
(투과율)(Transmittance)
전광선 투과율은 ASTM D 1003에 의거하여 투과율 측정기(HM-150)를 사용하여 측정하였다.The total light transmittance was measured using a transmittance meter (HM-150) according to ASTM D 1003.
(표면경도)(Surface hardness)
연필경도시험기를 이용하여 500g 하중을 걸고 상기 실시예 및 비교예로부터 제조된 기공성 실리카 막의 연필경도를 측정하였다. A 500g load was applied using a pencil hardness tester, and the pencil hardness of the porous silica membranes prepared from the Examples and Comparative Examples was measured.
연필은 미쯔비시 제품을 사용하고 한 연필경도 당 5회 실시하였다.The pencil was made from Mitsubishi and was performed 5 times per pencil hardness.
(접촉각)(Contact angle)
제조된 기공성 실리카 막의 친수성 정도를 알아보기 위하여 기공성 실리카 막의 표면에 증류수를 떨어뜨린 후 접촉각을 측정하였다.In order to determine the degree of hydrophilicity of the prepared porous silica film, distilled water was dropped on the surface of the porous silica film and then the contact angle was measured.
(실시예 1)(Example 1)
유리 기판을 세정제로 세척하여 기판에 존재하는 먼지, 오일, 유기 화합물, 오염물 등을 제거하였다. The glass substrate was washed with a cleaning agent to remove dust, oil, organic compounds, and contaminants present on the substrate.
폴리실라잔 10중량부, 이산화티탄 전구체(티타늄 테트라이소프로폭사이드) 5중량부, 계면활성제(소르비탄 모노올리에이트) 3중량부 및 용매(디부틸 에테르) 100중량부를 포함하는 반사방지용 코팅 조성물을 제조하였다.Antireflection coating composition comprising 10 parts by weight of polysilazane, 5 parts by weight of a titanium dioxide precursor (titanium tetraisopropoxide), 3 parts by weight of a surfactant (sorbitan monooleate) and 100 parts by weight of a solvent (dibutyl ether) Was prepared.
상기 유리 기판에 상기 코팅 조성물을 바 코팅으로 도포하여 반사방지층을 형성하였다. The coating composition was applied to the glass substrate by bar coating to form an antireflection layer.
상기 반사방지층을 400℃에서 10분 동안 열처리하여(저온 경화) 기공성 실리카 막을 제조하였다. The antireflection layer was heat-treated at 400° C. for 10 minutes (low temperature curing) to prepare a porous silica film.
(실시예 2)(Example 2)
이산화티탄 전구체(티타늄 테트라이소프로폭사이드) 0.5중량부를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 기공성 실리카 막을 제조하였다. A porous silica film was prepared in the same manner as in Example 1, except that 0.5 parts by weight of a titanium dioxide precursor (titanium tetraisopropoxide) was used.
(실시예 3)(Example 3)
이산화티탄 전구체(티타늄 테트라이소프로폭사이드) 12중량부를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 기공성 실리카 막을 제조하였다. A porous silica film was prepared in the same manner as in Example 1, except that 12 parts by weight of a titanium dioxide precursor (titanium tetraisopropoxide) was used.
(실시예 4)(Example 4)
공용매(메탄올) 5중량부를 추가로 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 기공성 실리카 막을 제조하였다. A porous silica membrane was prepared in the same manner as in Example 1, except that 5 parts by weight of a co-solvent (methanol) was additionally used.
(실시예 5)(Example 5)
테트라에톡시실란 3중량부를 추가로 사용한 것을 제외하고는 실시예 4와 동일한 방법으로 기공성 실리카 막을 제조하였다. A porous silica membrane was prepared in the same manner as in Example 4, except that 3 parts by weight of tetraethoxysilane was additionally used.
(실시예 6)(Example 6)
3-이소시아네이트프로필트리에톡시실란 70중량% 및 3-메타크릴록시프로필트리메톡시실란 30중량%를 미리 반응시켜 제조한 실란 커플링제 올리고머 3중량부를 추가로 사용한 것을 제외하고는 실시예 5와 동일한 방법으로 기공성 실리카 막을 제조하였다. Same as in Example 5 except that 3 parts by weight of a silane coupling agent oligomer prepared by reacting in advance with 70% by weight of 3-isocyanate propyltriethoxysilane and 30% by weight of 3-methacryloxypropyltrimethoxysilane was additionally used. A porous silica membrane was prepared by the method.
(비교예 1)(Comparative Example 1)
폴리실라잔 대신에 테트라에톡시실란을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 기공성 실리카 막을 제조하였다. A porous silica membrane was prepared in the same manner as in Example 1, except that tetraethoxysilane was used instead of polysilazane.
(비교예 2)(Comparative Example 2)
이산화티탄 전구체(티타늄 테트라이소프로폭사이드)를 사용하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 기공성 실리카 막을 제조하였다. A porous silica film was prepared in the same manner as in Example 1, except that a titanium dioxide precursor (titanium tetraisopropoxide) was not used.
상기 실시예 및 비교예로부터 제조된 기공성 실리카 막의 반사율, 투과율, 표면경도(내구성) 및 접촉각을 측정하여 그 결과를 아래의 표 1에 나타내었다. The reflectance, transmittance, surface hardness (durability), and contact angle of the porous silica films prepared from the Examples and Comparative Examples were measured, and the results are shown in Table 1 below.
상기 표 1의 결과로부터, 실시예 1 내지 6은 이산화티탄이 폴리실라잔의 저온 경화를 촉진하는 역할을 수행하여 기공성 실리카 막의 굴절율과 반사율을 낮추고 투과율을 증가시키며, 저온 경화 특성이 우수하여 표면경도, 친수성 및 내구성이 우수함을 알 수 있다. From the results of Table 1, Examples 1 to 6 show that titanium dioxide plays a role in promoting low-temperature curing of polysilazane, lowering the refractive index and reflectance of the porous silica film, increasing the transmittance, It can be seen that the hardness, hydrophilicity and durability are excellent.
반면 비교예 1 및 2는 실시예 1 내지 6에 비해 투과율, 표면경도, 친수성, 내구성 및 저온 경화 특성이 열등함을 알 수 있다. On the other hand, it can be seen that Comparative Examples 1 and 2 are inferior to Examples 1 to 6 in terms of transmittance, surface hardness, hydrophilicity, durability, and low-temperature curing properties.
Claims (14)
이산화티탄 전구체;
계면활성제;
용매;
공용매; 및
이소시아네이트기 함유 실란 커플링제와 아크릴레이트기 함유 실란 커플링제를 반응시켜 제조한 실란 커플링제 올리고머;를 포함하는 반사방지용 코팅조성물에 있어서,
상기 조성물은 용매 100중량부에 대하여 폴리실라잔 3~15중량부, 이산화티탄 전구체 1~10중량부, 계면활성제 1~5중량부, 공용매 1~10중량부 및 실란 커플링제 올리고머 1~5중량부를 포함하고,
상기 이산화티탄 전구체는 티타늄 테트라메톡사이드, 티타늄 테트라에톡사이드, 티타늄 테트라 n-프로폭사이드, 티타늄 테트라이소프로폭사이드, 티타늄 테트라 n-부톡사이드, 티타늄 테트라이소부톡사이드, 티타늄 할라이드, 티타닐설페이트 및 티타닐비스(아세틸아세토네이트)에서 선택되는 하나 이상이며,
상기 용매는 디에틸 에테르, 디프로필 에테르, 디부틸 에테르, 벤젠,
톨루엔 및 자일렌에서 선택되는 하나 이상이고,
상기 공용매는 메탄올, 에탄올, 미네랄 스피릿, 등유, 에틸 아세테이트, 디메틸 카보네이트 및 디아세톤 알코올에서 선택되는 하나 이상인 것을 특징으로 하는 반사방지용 코팅조성물.
Polysilazane;
Titanium dioxide precursor;
Surfactants;
menstruum;
Common sale; And
In the antireflection coating composition comprising; a silane coupling agent oligomer prepared by reacting an isocyanate group-containing silane coupling agent and an acrylate group-containing silane coupling agent,
The composition comprises 3 to 15 parts by weight of polysilazane, 1 to 10 parts by weight of a titanium dioxide precursor, 1 to 5 parts by weight of a surfactant, 1 to 10 parts by weight of a co-solvent, and 1 to 5 parts by weight of a silane coupling agent oligomer based on 100 parts by weight of the solvent. Including parts by weight,
The titanium dioxide precursor is titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetraisobutoxide, titanium halide, titanyl sulfate And at least one selected from titanylbis (acetylacetonate),
The solvent is diethyl ether, dipropyl ether, dibutyl ether, benzene,
At least one selected from toluene and xylene,
The co-solvent is an antireflection coating composition, characterized in that at least one selected from methanol, ethanol, mineral spirit, kerosene, ethyl acetate, dimethyl carbonate and diacetone alcohol.
(b) 제1항의 반사방지용 코팅 조성물을 준비하는 단계;
(c) 상기 기재의 적어도 한 면에 상기 코팅 조성물을 코팅하여 반사방지층을 형성하는 단계; 및
(d) 상기 반사방지층을 열처리하여 기공성 실리카 막을 제조하는 단계를 포함하는 기공성 반사방지막의 제조방법.
(a) washing the substrate;
(b) preparing the antireflection coating composition of claim 1;
(c) forming an antireflection layer by coating the coating composition on at least one surface of the substrate; And
(d) a method of manufacturing a porous antireflection film comprising the step of heat-treating the antireflection layer to prepare a porous silica film.
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| JP2016047931A (en) * | 2015-10-27 | 2016-04-07 | 旭化成イーマテリアルズ株式会社 | Functional coating film |
| JP2016117881A (en) * | 2014-12-19 | 2016-06-30 | 三星エスディアイ株式会社ＳＡＭＳＵＮＧ ＳＤＩ Ｃｏ．， ＬＴＤ． | Composition for forming silica based layer, method for manufacturing silica based layer, and electronic device including said silica based layer |
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| KR20130015935A (en) | 2011-08-05 | 2013-02-14 | 동우 화인켐 주식회사 | Coating composition for anti-glare and anti-reflection, film using the same, polarizing plate, and display device |
| KR20130021182A (en) | 2011-08-22 | 2013-03-05 | 동우 화인켐 주식회사 | Anti-glare/anti-reflective coating composition and anti-glare/anti-reflective film using the same |
| KR101205477B1 (en) | 2011-08-26 | 2012-11-27 | 주식회사 엘지화학 | Composition for anti-reflective coating and anti-reflective coating film using the same |
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