KR20180079218A - Coating composition and film manufactured therefrom - Google Patents
Coating composition and film manufactured therefrom Download PDFInfo
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- KR20180079218A KR20180079218A KR1020170184763A KR20170184763A KR20180079218A KR 20180079218 A KR20180079218 A KR 20180079218A KR 1020170184763 A KR1020170184763 A KR 1020170184763A KR 20170184763 A KR20170184763 A KR 20170184763A KR 20180079218 A KR20180079218 A KR 20180079218A
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- 239000008199 coating composition Substances 0.000 title claims abstract description 34
- 229920002284 Cellulose triacetate Polymers 0.000 claims abstract description 37
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims abstract description 37
- 230000035699 permeability Effects 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 42
- 238000000576 coating method Methods 0.000 abstract description 22
- 230000003287 optical effect Effects 0.000 abstract description 7
- 239000010985 leather Substances 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 70
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 45
- 239000003054 catalyst Substances 0.000 description 32
- 239000000654 additive Substances 0.000 description 29
- 230000000996 additive effect Effects 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 17
- 239000011342 resin composition Substances 0.000 description 17
- -1 aconitril Chemical compound 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 15
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 15
- 239000010931 gold Substances 0.000 description 15
- 229910052737 gold Inorganic materials 0.000 description 15
- 239000012535 impurity Substances 0.000 description 15
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 229920001296 polysiloxane Polymers 0.000 description 13
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 11
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 10
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012788 optical film Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012994 photoredox catalyst Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/12—Cellulose acetate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Polarising Elements (AREA)
- Silicon Polymers (AREA)
Abstract
Description
본 발명은 코팅 조성물에 관한 것으로서, 특히 트리아세틸 셀룰로오스 필름 위에 코팅 조성물을 이용하여 간단한 코팅 공정만으로 트리아세틸 셀룰로오스 필름의 광학적 물성을 해치지 않으면서, 내투습성 및 표면경도를 개선할 수 있는 코팅 조성물에 관한 것이다.The present invention relates to a coating composition, and more particularly, to a coating composition capable of improving moisture permeability and surface hardness without damaging the optical properties of a triacetyl cellulose film by a simple coating process using a coating composition on a triacetylcellulose film will be.
이하에 기술되는 내용은 단순히 본 발명과 관련되는 배경 정보만을 제공할 뿐 종래기술을 구성하는 것이 아니다.The following description merely provides background information related to the present invention and does not constitute the prior art.
트리아세틸 셀룰로오스 필름은 사진 필름으로 반세기 이상 사용되어 온 천연소재 플라스틱 필름이며, 독특한 비정질 구조를 갖고 있어서 그로 인해 독특한 기계적, 광학적 물성을 발현한다. 특히 복굴절이 매우 낮은 수준으로 광학적 등방성이 뛰어난 특성을 갖는다. 이러한 특성을 바탕으로 트리아세틸 셀룰로오스 필름은 편광판용 보호필름, 시야각 확대 필름의 지지체 등의 광학필름 용으로 널리 사용되고 있다. 특히 편광판용 보호필름으로 사용되는 트리아세틸 셀룰로오스 필름은 순도가 높고 투명성과 광학적 등방성이 양호하여 위상차가 없어 폴리비닐알콜 필름의 양면에 접착하여 강도를 향상하고 폴리비닐알콜 기재를 열이나 습도로부터 보호하는 역할을 한다. 또한, 폴리비닐알콜 기재와 트리아세틸 셀룰로오스 필름을 접착시킬 때 수용성 접착제를 이용하므로, 이에 이용되는 트리아세틸 세룰로오스 필름은 접착 이후 수분이 빠져나갈 수 있도록 적절한 투습 특성이 필수적으로 요구되었다. 그러나 최근의 편광판 제작 동향을 살펴보면, 기존의 수계 접착제를 이용하던 것이, 반응성 접착제로 급격히 변화되고 있어 더 이상 트리아세틸 셀룰로오스 필름의 투습 특성이 필요치 않도록 공정과정 또한 함께 변화되고 있다.Triacetylcellulose film is a natural plastic film that has been used as a photographic film for more than half a century. It has a unique amorphous structure and thus exhibits unique mechanical and optical properties. In particular, the birefringence is extremely low and the optical isotropy is excellent. Based on these properties, triacetyl cellulose films are widely used for optical films such as protective films for polarizing plates, supports for viewing angle enlargement films, and the like. In particular, the triacetyl cellulose film used as a protective film for a polarizing plate has high purity and good transparency and optical isotropy because it has no phase difference, so that the triacetyl cellulose film is bonded to both sides of the polyvinyl alcohol film to improve the strength and protect the polyvinyl alcohol substrate from heat and humidity It plays a role. Further, since a water-soluble adhesive is used for bonding the polyvinyl alcohol base material and the triacetyl cellulose film, the triacetyl cellulose film used therefor is required to have proper moisture permeability so that moisture can escape after bonding. However, recent trends in polarizer production show that the use of conventional water-based adhesives is rapidly changing with reactive adhesives, and the process is also changing so that the moisture-permeability characteristics of triacetyl cellulose films are no longer required.
또한, 트리아세틸 셀룰오로스 필름은 수분투과도가 타 필름 류에 비해 높은 편으로 고온, 다습한 환경에서는 내구성이 저하되기 쉬워 편광자의 불량을 야기시키며, 스크래치에 취약한 표면의 경도는 해결되어야 하는 궁극의 과제로 지적되고 있다.In addition, triacetylcellulose films have higher water permeability than other types of films, so that durability tends to be lowered in a high-temperature and high-humidity environment, leading to defective polarizers, and the hardness of the surface, which is vulnerable to scratches, It is pointed out as an issue.
위와 같은 문제점을 극복하고자 산업계에서는 많은 시도들이 이어져 왔다. 예를 들어 한국공개특허 10-2016-0080656호에서는 트리아세틸 셀룰로오스 필름 위에 실록산올리고머를 포함한 코팅층을 형성하여 트리아세틸 셀룰로오스 필름의 투습도 및 표면경도를 극복하려고 하였다. 그러나, 상기 기술들에는 표면경도가 3H의 한계를 보이며, 높은 투습율을 나타내어 내구성이 떨어지는 문제점이 여전히 존재하였다.Many attempts have been made in the industry to overcome these problems. For example, in Korean Patent Laid-Open No. 10-2016-0080656, a coating layer containing a siloxane oligomer is formed on a triacetylcellulose film to overcome the moisture permeability and surface hardness of the triacetylcellulose film. However, the above-mentioned techniques have a problem that the surface hardness shows a limit of 3H and a high moisture permeability is exhibited and the durability is poor.
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 간단한 코팅 공정만으로 필름의 광학적 물성을 해치지 않으면서, 내투습성 및 표면경도를 현저히 개선할 수 있는 코팅 조성물을 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a coating composition capable of remarkably improving moisture permeability and surface hardness without deteriorating the optical properties of the film by a simple coating process.
또한 본 발명은 상기 코팅 조성물을 이용하여 투습성 및 표면경도가 향상된 필름 및 이를 포함하는 광학필름을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide a film having improved moisture permeability and surface hardness by using the coating composition and an optical film containing the same.
상기 목적을 달성하기 위하여 본 발명은 In order to achieve the above object,
케이지형실세스퀴옥산 수지와 레더형실세스퀴옥산 수지의 중량비가 10 중량% : 90 중량% 내지 80 중량% : 20 중량%인 실세스퀴옥산올리고머를 포함하는 코팅 조성물을 제공한다.A silsesquioxane oligomer having a weight ratio of cage-type silsesquioxane resin to a leather-type silsesquioxane resin of 10 wt%: 90 wt% to 80 wt%: 20 wt%.
또한 본 발명은 코팅 조성물이 기재 상에 코팅되어 경화된 필름을 제공한다.The present invention also provides a cured film wherein the coating composition is coated on a substrate.
본 발명에 따른 코팅 조성물은 간단한 코팅 공정만으로 필름의 우수한 광학적 물성을 해치지 않으면서, 내투습성 및 표면경도를 개선할 수 있다. The coating composition according to the present invention can improve moisture permeability and surface hardness without impairing the excellent optical properties of the film by a simple coating process.
도 1은 본 발명의 일 실시예에 따른 코팅된 필름을 나타낸 도면이며, 코팅층은 실제보다 두껍게 표시되어 있다.
도 2는 본 발명의 일 실시예에 따른 하드코팅된 트리아세틸 셀룰로오스 필름의 결합구조를 나타낸 도면이다.
도 3은 본 발명의 실시예 1에 따른 코팅된 트리아세틸 셀룰로오스 필름의 코팅단면 SEM 사진이다.1 is a view showing a coated film according to an embodiment of the present invention, wherein the coating layer is thicker than actual.
2 is a view showing a bonding structure of a hard coated triacetyl cellulose film according to an embodiment of the present invention.
3 is a SEM photograph of a coated cross-section of the coated triacetylcellulose film according to Example 1 of the present invention.
아래에서는 첨부한 도면을 참고로 하여 본 발명의 실시예에 대하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
명세서 전체에서, 어떤 부분이 어떤 구성요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다.Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise.
본 발명의 코팅조성물은 케이지형실세스퀴옥산 수지와 레더형실세스퀴옥산 수지의 중량비가 10 중량% : 90 중량% 내지 80 중량% : 20 중량%인 실세스퀴옥산올리고머를 포함한다.The coating composition of the present invention comprises a silsesquioxane oligomer having a weight ratio of cage silsesquioxane resin to ladder type silsesquioxane resin of 10 wt%: 90 wt% to 80 wt%: 20 wt%.
구체적으로 본 발명의 코팅 조성물은 상기 실세스퀴옥산올리고머; 개시제; 및 용매를 포함할 수 있다.Specifically, the coating composition of the present invention comprises the silsesquioxane oligomer; Initiator; And a solvent.
상기 실세스퀴옥산올리고머는 케이지 구조와 레더 구조를 함께 가질 수 있으며, 구체적으로 화학식 1로 표시되는 레더형실세스퀴옥산 수지에 화학식 2로 표시되는 케이지형실세스퀴옥산 수지가 결합된 것일 수 있다.The silsesquioxane oligomer may have both a cage structure and a ladder structure. Specifically, the silsesquioxane oligomer may include a cage silsesquioxane resin represented by the following formula (2) bonded to a lether-type silsesquioxane resin represented by formula .
상기 화학식 1에서,In Formula 1,
R1, R2, R3, R4는 각각 독립적으로 치환기로 치환되거나 치환되지 않은 메틸기; 페닐기; 아미노기; (메타)아크릴기; 비닐기; 에폭시기; 사이올기; 또는 자외선흡수체이며, n은 1 내지 100의 정수이고,R 1 , R 2 , R 3 and R 4 each independently represent a methyl group, which is optionally substituted with a substituent; A phenyl group; An amino group; (Meth) acrylic group; Vinyl group; An epoxy group; A diazo group; Or an ultraviolet absorber, n is an integer of 1 to 100,
R5, R6, R7, R8은 각각 독립적으로, 수소; 치환기로 치환되거나 치환되지 않은 C1~C10의 알킬기; 또는 하기 화학식 2로 표시되는 연결기이며, R5, R6, R7, R8 중 적어도 하나는 하기 화학식 2와 연결되며,R 5 , R 6 , R 7 , and R 8 are each independently hydrogen; A C 1 to C 10 alkyl group which is unsubstituted or substituted with a substituent group; Or a linking group represented by the following formula (2), and at least one of R 5 , R 6 , R 7 and R 8 is connected to the following formula (2)
상기 화학식 2에서,In Formula 2,
R은 각각 독립적으로 치환기로 치환되거나 치환되지 않은 메틸기, 페닐기, 아미노기, (메타)아크릴기, 비닐기, 에폭시기, 사이올기 또는 자외선흡수제이며, R0은 각각 독립적으로 수소 또는 치환기로 치환되거나 치환되지 않은 C1~C10의 알킬기이며,R is each independently substituted with a substituent or unsubstituted methyl group, a phenyl group, an amino group, a (meth) olgi between the acrylic group, a vinyl group, an epoxy group, or an ultraviolet absorber, R 0 is unsubstituted or substituted with hydrogen or a substituent, each independently C 1 -C 10 alkyl group,
n은 3 내지 6의 정수이며,n is an integer from 3 to 6,
상기 화학식 1 또는 2에서 치환기는 각각 독립적으로 중수소, 할로겐, 아민기, 에폭시기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기 또는 페닐기이다.In the above general formula (1) or (2), the substituents are each independently a deuterium, a halogen, an amine group, an epoxy group, a (meth) acrylic group, a silyl group, an isocyanate group, a nitrile group, a nitro group or a phenyl group.
상기 자외선 흡수체는 200 ㎚ 내지 400 ㎚의 파장 범위를 갖는 자외선을 흡수하는 구조체이며, 범용적으로 사용되어지고 있는 자외선흡수체로는 benzophenone계(자외선 흡수범위 300~380nm), benzotriazole계(흡수범위 300 ~385nm), salicylic acid계(흡수범위 260~340nm), acrylonitrile계(흡수범위 290~400nm) 등이 있다.The ultraviolet absorber is a structure that absorbs ultraviolet rays having a wavelength range of 200 to 400 nm. Examples of the ultraviolet absorber generally used include benzophenone (ultraviolet absorption range 300 to 380 nm), benzotriazole series (absorption range 300 to 300 nm) 385 nm), salicylic acid (absorption range 260 to 340 nm), and acrylonitrile (absorption range 290 to 400 nm).
본 발명에 사용되는 상기 실세스퀴옥산올리고머는 올리고머 내의 케이지 구조의 비율이 10 내지 80 중량%를 가짐으로써 TAC 필름의 수분투과도는 100 g/m2.day이하인 우수한 내투습성을 만족시킬 수 있으며, 구체적으로 실세스퀴옥산올리고머는 올리고머 내의 케이지 구조의 비율이 20 내지 50 중량%를 가짐으로써 TAC 필름의 수분투과도는 85 g/m2.day이하인 우수한 내투습성 및 동시에 만족시킬 수 있으며, 더욱 구체적으로 실세스퀴옥산올리고머는 올리고머 내의 케이지 구조의 비율이 25 내지 35 중량%를 가짐으로써 TAC 필름의 수분투과도는 70 g/m2.day이하인 우수한 내투습성 만족시킬 수 있다.Since the silsesquioxane oligomer used in the present invention has a cage structure ratio of 10 to 80% by weight in the oligomer, the water permeability of the TAC film can satisfy an excellent moisture permeability of 100 g / m 2 .day or less, Specifically, the silsesquioxane oligomer has a cage structure ratio of 20 to 50% by weight in the oligomer, so that the moisture permeability of the TAC film is 85 g / m < 2 >.day or less, The silsesquioxane oligomer has a cage structure ratio of 25 to 35% by weight in the oligomer so that the moisture permeability of the TAC film can satisfy an excellent moisture permeability of 70 g / m 2 .day or less.
또한 구체적으로 화학식 2로 표시되는 연결기는 n이 4인 경우 하기 화학식 3과 같은 구조일 수 있다.More specifically, the linking group represented by the formula (2) may have a structure represented by the following formula (3) when n is 4.
상기 화학식 3에서 *는 연결부위이며, R 및 R0는 화학식 2에서 정의한 바와 같다.In the above formula (3), * is a linking site, and R and R 0 are as defined in formula (2).
본 발명의 코팅 조성물에서 상기 실세스퀴옥산올리고머의 함량은 20 내지 60 중량%인 것이 좋다. 상기 범위 내인 경우 TAC 필름의 우수한 내투습성 및 우수한 표면경도를 동시에 만족시킬 수 있다.The content of the silsesquioxane oligomer in the coating composition of the present invention is preferably 20 to 60% by weight. Within the above range, excellent moisture permeability and excellent surface hardness of the TAC film can be satisfied at the same time.
트리아세틸 셀룰로오스 필름은 높은 수분투과도로 인하여 다습한 환경에서는 내구성이 저하되기 쉬우며, 특히 이를 이용한 편광판의 편광자의 불량을 야기시키는 원인이 된다. 이에 본 발명에서는 트리아세틸 셀룰로오스 필름 위에 실세스퀴옥산을 포함한 조성물을 코팅함으로써 트리아세틸 셀룰로오스 필름의 수분투과도를 현저하게 낮추면서 표면경도 또한 월등히 향상시켜 내구성이 향상된 트리아세틸 셀룰로오스 필름을 제공하는 것이다. The triacetyl cellulose film has a high water permeability and therefore tends to lower its durability in a high humidity environment. In particular, the triacetyl cellulose film causes a defective polarizer of the polarizing plate. Accordingly, the present invention provides a triacetylcellulose film having a triacetylcellulose film which is coated with a composition containing silsesquioxane on the triacetylcellulose film, thereby significantly improving the water permeability of the triacetylcellulose film and greatly improving the surface hardness thereof.
레더형 단독의 실세스퀴옥산은 취성이 높아, 코팅 시에 코팅막이 갈라지며 부서지기 쉬워 코팅막으로는 용이하지 못하다. 또한 케이지형 단독의 실세스퀴옥산은 코팅 후 시간이 지남에 따라서 재배열을 일으켜 초기의 성능을 유지하지 못하며, 케이지 구조자체가 갖는 공극으로 인하여 투습율을 저하시키는 것에 한계가 있다.The silsesquioxane of the leather type alone has high brittleness, and the coating film is cracked at the time of coating and is easily broken, which is not easy for the coating film. In addition, the cage-type silsesquioxane does not maintain its initial performance due to rearrangement over time after coating, and there is a limit to lowering the moisture permeability due to the pores of the cage structure itself.
이에, 본 발명자들은 한 분자내 케이지형 구조와 레더형 구조를 동시에 갖는 실세스퀴옥산을 제조하였다. 또한 케이지형 구조와 레더형 구조의 비율을 조절함으로써 투습율 및 표면경도를 향상시켰다. 특히 케이지형 구조와 레더형 구조의 비율이 10 중량% : 90 중량% 내지 80 중량% : 20 중량%을 갖는 코팅 조성물을 코팅 시에 형성 된 네트워크 구조사이의 공극의 크기를 줄여 투습율을 현저하게 저하시켰으며, 표면경도 또한 월등히 향상시켰다.Thus, the present inventors prepared silsesquioxane having both a cage-type structure and a ladder-type structure in a molecule. In addition, the moisture permeability and surface hardness were improved by controlling the ratio of the cage type structure to the ladder type structure. In particular, the coating composition having a cage-type structure and a ladder-like structure in a ratio of 10 wt%: 90 wt% to 80 wt%: 20 wt% is reduced in size of pores between the network structures formed at the time of coating, And the surface hardness was also improved remarkably.
또한 본 발명의 코팅 조성물에 포함되는 개시제는 특별히 한정되지 않으며, 구체적으로 광 라디칼개시제, 광 양이온 개시제, 열 라디칼개시제 또는 열 양이온 개시제 등을 사용할 수 있다. 본 발명의 코팅 조성물에서 상기 개시제의 함량은 0.1 내지 10 중량%인 것이 좋다. 상기 범위 내인 경우 TAC 필름의 우수한 내투습성 및 우수한 표면경도를 동시에 만족시킬 수 있다.The initiator contained in the coating composition of the present invention is not particularly limited, and specifically, a photo radical initiator, a photo cation initiator, a thermal radical initiator, or a thermal cation initiator may be used. The content of the initiator in the coating composition of the present invention is preferably 0.1 to 10% by weight. Within the above range, excellent moisture permeability and excellent surface hardness of the TAC film can be satisfied at the same time.
또한 본 발명에서 사용 가능한 용매는 용해성이 있으며 반응에 영향을 미치지 않는 용매라면 특별히 한정되지 않으며, 구체적으로는 상기 유기용매로는 알코올류, 케톤류, 글리콜류, 퓨란계, 디메틸포름아미드, 디메틸아세트아미드, N-메틸-2-피롤리돈 등의 극성용매 뿐 아니라, 헥산, 사이클로헥산, 사이클로헥사논, 톨루엔, 자일렌, 크레졸, 클로로포름, 디클로로벤젠, 디메틸벤젠, 트리메틸벤젠, 피리딘, 메틸나프탈렌, 니트로메탄, 아크로니트릴, 메틸렌클로라이드, 옥타데실아민, 아닐린, 디메틸설폭사이드, 벤질알콜 등 다양한 용매를 이용할 수 있으나, 이에 제한되지는 않는다. 본 발명에서 상기 용매는 실세스퀴옥산올리고머, 개시제 및 선택적으로 추가되는 첨가제를 제외한 잔량으로 포함될 수 있다.The solvent usable in the present invention is not particularly limited as long as it is soluble and does not affect the reaction. Specifically, the organic solvent includes alcohols, ketones, glycols, furans, dimethylformamide, dimethylacetamide , And N-methyl-2-pyrrolidone as well as polar solvents such as hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, Methane, aconitril, methylene chloride, octadecylamine, aniline, dimethylsulfoxide, benzyl alcohol, and the like, but the present invention is not limited thereto. In the present invention, the solvent may be included in the balance excluding the silsesquioxane oligomer, the initiator and optionally the additive.
본 발명의 코팅 조성물은 필요에 따라 실리콘계 첨가제 또는 아크릴계 첨가제를 더욱 포함할 수 있다.The coating composition of the present invention may further include a silicone-based additive or an acrylic-based additive as needed.
상기 코팅 조성물의 실리콘계 첨가제는 BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310가 있으며, 아크릴계 첨가제는 BYK-340, BYK-350, BYK-352, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-359, BYK-361N, BYK-380N, BYK-381, BYK-388, BYK-390, BYK-392, BYK-394가 있다. 상기 첨가제는 각각 독립적으로 0.01 내지 5 중량%의 함량으로 첨가될 수 있다. 상기 실리콘계 첨가제를 포함할 경우 하드코팅층의 표면슬립성과 코팅의 평탄성을 더욱 향상시킬 수 있으며, 내투습성을 더욱 향상시킬 수 있다. 또한 아크릴계 첨가제를 사용할 경우 하드코팅층의 레벨링성 및 내투습성을 더욱 향상시킬 수 있다. 또한 본 발명의 하드코팅 조성물은 필요에 따라 산화방지제, 레벨링제 등 하드코팅 조성물에 첨가될 수 있는 공지의 첨가제를 더욱 포함할 수 있다.The silicone additive of the coating composition may be selected from the group consisting of BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK- BYK-310 and BYK-340, BYK-350, BYK-352, BYK-355, BYK-356, BYK-358, BYK- BYK-381, BYK-388, BYK-390, BYK-392 and BYK-394. The additive may be added independently in an amount of 0.01 to 5% by weight. When the silicone additive is included, the surface slip of the hard coat layer and the flatness of the coating can be further improved, and the moisture permeability can be further improved. When the acrylic additive is used, the leveling property and moisture permeability of the hard coat layer can be further improved. In addition, the hard coating composition of the present invention may further include known additives which may be added to the hard coating composition such as an antioxidant, a leveling agent and the like if necessary.
또한 본 발명은 상기 코팅 조성물이 기재 상에 코팅되어 경화된 필름을 제공한다.The present invention also provides a cured film wherein the coating composition is coated on a substrate.
본 발명에 따른 코팅 조성물은 4 g/m2.day이상의 수분투과도를 갖는 필름에서 내투습성을 향상시키는 효과를 가져온다. 자세하게, 상기 코팅 조성물은 PMMA, PET, PC, PES, PVA, PI, COC 등의 필름에 코팅 가능하며, 특히, 트리아세틸 셀룰로오스 필름에 코팅하였을 경우, 투습력 향상의 효과가 가장 효과적으로 일어난다.The coating composition according to the present invention has an effect of improving the moisture permeability in a film having a water permeability of 4 g / m 2 .day or more. In detail, the coating composition can be coated on films such as PMMA, PET, PC, PES, PVA, PI, and COC. Particularly, when the coating composition is coated on a triacetyl cellulose film, the effect of improving the moisture permeability is most effective.
도 1은 본 발명의 일 실시예에 따른 코팅된 필름(100)을 나타낸 것이다.Figure 1 shows a
본 발명의 코팅된 필름(100)은 필름층(101) 위에 상기 코팅 조성물의 경화층(102)이 결합된 구조를 가진다. 구체적으로 상기 코팅 조성물의 경화층(102)의 두께는 10 내지 60 um일 수 있다. 상기 필름은 PMMA, PET, PC, PES, PVA, PI, COC 등의 필름일 수 있으며, 특히, 트리아세틸 셀룰로오스 필름일 수 있다. 상기 범위 내인 경우 코팅된 필름(100)의 내투습성과 표면경도를 더욱 향상시킬 수 있다. The
상기 코팅 조성물의 경화층(102)를 형성하는 방법은 상기 코팅 조성물을 필름층(101) 표면 위에 코팅한 후 건조 또는 경화시켜 형성할 수 있으며, 코팅방법은 스핀코팅, 바코팅, 슬릿코팅, 딥 코팅, 내츄럴 코팅, 리버스 코팅, 롤 코팅, 스핀코팅, 커텐코팅, 스프레이 코팅, 침지법, 함침법, 그라비어 코팅 등 공지된 방법 중에서 당업자가 임의로 선택하여 적용할 수 있다.The method of forming the cured
구체적으로 상기 코팅 조성물의 경화층(102)은 실리콘계 첨가제 및 아크릴계 첨가제를 더욱 포함할 수 있으며, 이 경우 코팅된 필름(100)의 내투습성과 표면경도를 더욱 향상시킬 수 있다.Specifically, the cured
도 2는 본 발명의 코팅된 트리아세틸 셀룰로오스 필름(100)의 코팅단면의 결합구조를 나타낸 것이다. 도 2에 나타나는 바와 같이 필름층(101)과 코팅 조성물의 경화층(102)이 수소결합 및/또는 반데르발스 결합을 통하여 강하게 결합됨으로써 전체 코팅된 트리아세틸 셀룰로오스 필름(100)이 내투습성과 표면경도에 내구성이 뛰어난 장점이 있다.Fig. 2 shows the bonding structure of the coated cross-section of the
본 발명에 따른 코팅된 필름(100)은 종래 필름의 고질적 문제인 내투습성 및 표면경도를 현저히 개선하여 편광판용 보호필름, 시야각확대 필름의 지지체 등 광학필름에 유용하게 적용할 수 있다. The
이하, 본 발명의 이해를 돕기 위하여 구체적인 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.
[촉매 제조][Catalyst preparation]
염기도 조절을 위하여, 테트라메틸암모늄하이드록사이드 25 중량% 수용액에 10% 포타슘하이드록사이드 수용액을 혼합하여 촉매를 제조하였다.For controlling the basicity, a 25% by weight aqueous solution of tetramethylammonium hydroxide and a 10% aqueous solution of potassium hydroxide were mixed to prepare a catalyst.
[합성예 1][Synthesis Example 1]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 20중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 10 : 90의 비율을 갖는 실세스퀴옥산올리고머를 얻었다. 10 parts by weight of distilled water, 20 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer, stirred for 1 hour at room temperature, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice. Finally, a silsesquioxane oligomer having a cage-type silsesquioxane and a leather-like silsesquioxane ratio of 10: 90 was obtained.
[합성예 2][Synthesis Example 2]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 50 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 30 : 70의 비율을 갖는 실세스퀴옥산올리고머를 얻었다. 10 parts by weight of distilled water, 50 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer, stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice. Finally, a silsesquioxane oligomer having a cage-type silsesquioxane and a leather-like silsesquioxane ratio of 30:70 was obtained.
[합성예 3][Synthesis Example 3]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 90 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 50 : 50의 비율을 갖는 실세스퀴옥산올리고머를 얻었다.10 parts by weight of distilled water, 90 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer, stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice. Finally, a silsesquioxane oligomer having a cage-type silsesquioxane and a leather-like silsesquioxane ratio of 50:50 was finally obtained.
[합성예 4][Synthesis Example 4]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 220 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 80 : 20의 비율을 갖는 실세스퀴옥산올리고머를 얻었다.10 parts by weight of distilled water, 220 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer, stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice. Finally, a silsesquioxane oligomer having a cage-type silsesquioxane and a leather-like silsesquioxane ratio of 80:20 was obtained.
[합성예 5][Synthesis Example 5]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 7 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 3 : 97의 비율을 갖는 실세스퀴옥산올리고머를 얻었다.10 parts by weight of distilled water, 7 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer and stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice to obtain a silsesquioxane oligomer having a cage type silsesquioxane and a leather type silsesquioxane ratio of 3: 97.
[합성예 6][Synthesis Example 6]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 10 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 5 : 95의 비율을 갖는 실세스퀴옥산올리고머를 얻었다.10 parts by weight of distilled water, 10 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer, stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice. Finally, a silsesquioxane oligomer having a cage-type silsesquioxane and a leather-like silsesquioxane ratio of 5: 95 was obtained.
[합성예 7][Synthesis Example 7]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 260 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 85 : 15의 비율을 갖는 실세스퀴옥산올리고머를 얻었다.10 parts by weight of distilled water, 260 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer, stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice. Finally, a silsesquioxane oligomer having a cage-type silsesquioxane and a leather-like silsesquioxane ratio of 85: 15 was obtained.
[합성예 8][Synthesis Example 8]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 280 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 90 : 10의 비율을 갖는 실세스퀴옥산올리고머를 얻었다.10 parts by weight of distilled water, 280 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer and stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice. Finally, a silsesquioxane oligomer having a cage-type silsesquioxane and a leather-like sesquioxane ratio of 90:10 was obtained.
[실시예 1][Example 1]
상기 합성예 1에서 얻어진 실세스퀴옥산올리고머를 50 g을 메틸아이소부틸케톤에 50 중량%로 녹여 100 g의 조성물을 제조하였다. 이후, 준비된 조성물 100 중량부에 클로로아세토페논 5 중량부, 실리콘계 첨가제 BYK-302 1 중량부 및 아크릴계 첨가제 BYK-359 1 중량부를 첨가하고 10분간 교반하여 케이지형 구조와 레더형 구조의 비율이 10 중량% : 90 중량% 인 광경화형 수지 조성물을 제조하였다. 제조된 광경화형 수지 조성물을 80 ㎛ 트리아세틸 셀룰로오스 필름(FUJIFILM) 위에 도포하고 85의 건조오븐에서 용매를 증발시킨 후 UV 장비를 이용하여 1 J/cm2의 UV를 조사하여 결과물을 수득하였다.50 g of the silsesquioxane oligomer obtained in Synthesis Example 1 was dissolved in 50% by weight of methyl isobutyl ketone to prepare 100 g of a composition. Then, 5 parts by weight of chloroacetophenone, 1 part by weight of silicone additive BYK-302 and 1 part by weight of acrylic additive BYK-359 were added to 100 parts by weight of the prepared composition and stirred for 10 minutes to obtain a cage-type structure and a ladder- %: 90% by weight based on the total weight of the photocurable resin composition. The photocurable resin composition thus prepared was applied on an 80 탆 triacetyl cellulose film (FUJIFILM), and the solvent was evaporated in a drying oven of 85, followed by UV irradiation at 1 J / cm 2 using UV equipment.
[실시예 2][Example 2]
상기 합성예 2에서 얻어진 실세스퀴옥산올리고머를 50 g을 메틸아이소부틸케톤에 50 중량%로 녹여 100 g의 조성물을 제조하였다. 이후, 준비된 조성물 100 중량부에 클로로아세토페논 5 중량부, 실리콘계 첨가제 BYK-302 1 중량부 및 아크릴계 첨가옥산 및 레더형실세스퀴옥산이 10 : 90의 비율을 갖는 실세스퀴옥산올리고머를 얻었다. 50 g of the silsesquioxane oligomer obtained in Synthesis Example 2 was dissolved in 50% by weight of methyl isobutyl ketone to prepare 100 g of a composition. Thereafter, 5 parts by weight of chloroacetophenone, 1 part by weight of silicone additive BYK-302, and a silsesquioxane oligomer having a ratio of acrylic addoxane and leather-like sesquioxane of 10:90 were obtained in 100 parts by weight of the prepared composition.
[합성예 2][Synthesis Example 2]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 50 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 30 : 70의 비율을 갖는 실세스퀴옥산올리고머를 얻었다. 10 parts by weight of distilled water, 50 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer, stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice. Finally, a silsesquioxane oligomer having a cage-type silsesquioxane and a leather-like silsesquioxane ratio of 30:70 was obtained.
[합성예 3][Synthesis Example 3]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 90 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 50 : 50의 비율을 갖는 실세스퀴옥산올리고머를 얻었다.10 parts by weight of distilled water, 90 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer, stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice. Finally, a silsesquioxane oligomer having a cage-type silsesquioxane and a leather-like silsesquioxane ratio of 50:50 was finally obtained.
[합성예 4][Synthesis Example 4]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 220 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 80 : 20의 비율을 갖는 실세스퀴옥산올리고머를 얻었다.10 parts by weight of distilled water, 220 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer, stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice. Finally, a silsesquioxane oligomer having a cage-type silsesquioxane and a leather-like silsesquioxane ratio of 80:20 was obtained.
[합성예 5][Synthesis Example 5]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 7 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 3 : 97의 비율을 갖는 실세스퀴옥산올리고머를 얻었다.10 parts by weight of distilled water, 7 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer and stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice to obtain a silsesquioxane oligomer having a cage type silsesquioxane and a leather type silsesquioxane ratio of 3: 97.
[합성예 6][Synthesis Example 6]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 10 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 5 : 95의 비율을 갖는 실세스퀴옥산올리고머를 얻었다.10 parts by weight of distilled water, 10 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer, stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice. Finally, a silsesquioxane oligomer having a cage-type silsesquioxane and a leather-like silsesquioxane ratio of 5: 95 was obtained.
[합성예 7][Synthesis Example 7]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 260 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 85 : 15의 비율을 갖는 실세스퀴옥산올리고머를 얻었다.10 parts by weight of distilled water, 260 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer, stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice. Finally, a silsesquioxane oligomer having a cage-type silsesquioxane and a leather-like silsesquioxane ratio of 85: 15 was obtained.
[합성예 8][Synthesis Example 8]
냉각관과 교반기를 구비한 건조된 플라스크에, 증류수 10 중량부, 아세토니트릴(대정화금) 280 중량부, 제조된 촉매 2 중량부를 적가하고, 1시간 동안 상온에서 교반한 후, 2-(3,4 에폭시사이클로헥실) 에틸트리메톡시실란(신에츠, 상품명 KBM-303) 20 중량부를 적가하여 6시간을 추가 교반하였다. 반응 완료 후 두 차례 세정하여 촉매와 불순물을 추출하였으며, 최종적으로 케이지형실세스퀴옥산 및 레더형실세스퀴옥산이 90 : 10의 비율을 갖는 실세스퀴옥산올리고머를 얻었다.10 parts by weight of distilled water, 280 parts by weight of acetonitrile (purified gold) and 2 parts by weight of the prepared catalyst were added dropwise to a dried flask equipped with a cooling tube and a stirrer and stirred at room temperature for 1 hour, , 4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu, product name: KBM-303) were added dropwise, and the mixture was further stirred for 6 hours. After completion of the reaction, the catalyst and impurities were extracted twice by washing twice. Finally, a silsesquioxane oligomer having a cage-type silsesquioxane and a leather-like sesquioxane ratio of 90:10 was obtained.
[실시예 1][Example 1]
상기 합성예 1에서 얻어진 실세스퀴옥산올리고머를 50 g을 메틸아이소부틸케톤에 50 중량%로 녹여 100 g의 조성물을 제조하였다. 이후, 준비된 조성물 100 중량부에 클로로아세토페논 5 중량부, 실리콘계 첨가제 BYK-302 1 중량부 및 아크릴계 첨가제 BYK-359 1 중량부를 첨가하고 10분간 교반하여 케이지형 구조와 레더형 구조의 비율이 10 중량% : 90 중량% 인 광경화형 수지 조성물을 제조하였다. 제조된 광경화형 수지 조성물을 80 ㎛ 트리아세틸 셀룰로오스 필름(FUJIFILM) 위에 도포하고 85의 건조오븐에서 용매를 증발시킨 후 UV 장비를 이용하여 1 J/cm2의 UV를 조사하여 결과물을 수득하였다.50 g of the silsesquioxane oligomer obtained in Synthesis Example 1 was dissolved in 50% by weight of methyl isobutyl ketone to prepare 100 g of a composition. Then, 5 parts by weight of chloroacetophenone, 1 part by weight of silicone additive BYK-302 and 1 part by weight of acrylic additive BYK-359 were added to 100 parts by weight of the prepared composition and stirred for 10 minutes to obtain a cage-type structure and a ladder- %: 90% by weight based on the total weight of the photocurable resin composition. The photocurable resin composition thus prepared was applied on an 80 탆 triacetyl cellulose film (FUJIFILM), and the solvent was evaporated in a drying oven of 85, followed by UV irradiation at 1 J / cm 2 using UV equipment.
[실시예 2][Example 2]
상기 합성예 2에서 얻어진 실세스퀴옥산올리고머를 50 g을 메틸아이소부틸케톤에 50 중량%로 녹여 100 g의 조성물을 제조하였다. 이후, 준비된 조성물 100 중량부에 클 BYK-359 1 중량부를 첨가하고 10분간 교반하여 케이지형 구조와 레더형 구조의 비율이 30 중량% : 70 중량% 인 광경화형 수지 조성물을 제조하였다. 제조된 광경화형 수지 조성물을 80 ㎛ 트리아세틸 셀룰로오스 필름(FUJIFILM) 위에 도포하고 85 의 건조오븐에서 용매를 증발시킨 후 UV 장비를 이용하여 1 J/cm2의 UV를 조사하여 결과물을 수득하였다.50 g of the silsesquioxane oligomer obtained in Synthesis Example 2 was dissolved in 50% by weight of methyl isobutyl ketone to prepare 100 g of a composition. 1 part by weight of BYK-359 was added to 100 parts by weight of the prepared composition and stirred for 10 minutes to prepare a photocurable resin composition having a cage-type structure and a ladder-type structure in a ratio of 30% by weight to 70% by weight. The photocurable resin composition thus prepared was applied on an 80 탆 triacetyl cellulose film (FUJIFILM), and the solvent was evaporated in a drying oven of 85, followed by UV irradiation at 1 J / cm 2 using UV equipment.
[실시예 3][Example 3]
상기 합성예 3에서 얻어진 실세스퀴옥산올리고머를 50 g을 메틸아이소부틸케톤에 50 중량%로 녹여 100 g의 조성물을 제조하였다. 이후, 준비된 조성물 100 중량부에클로로아세토페논 5 중량부, 실리콘계 첨가제 BYK-302 1 중량부 및 아크릴계 첨가제 BYK-359 1 중량부를 첨가하고 10분간 교반하여 케이지형 구조와 레더형 구조의 비율이 50 중량% : 50 중량% 인 광경화형 수지 조성물을 제조하였다. 제조된 광경화형 수지 조성물을 80 ㎛ 트리아세틸 셀룰로오스 필름(FUJIFILM) 위에 도포하고 85의 건조오븐에서 용매를 증발시킨 후 UV 장비를 이용하여 1 J/cm2의 UV를 조사하여 결과물을 수득하였다.50 g of the silsesquioxane oligomer obtained in Synthesis Example 3 was dissolved in 50% by weight of methyl isobutyl ketone to prepare 100 g of a composition. Then, 5 parts by weight of chloroacetophenone, 1 part by weight of silicone additive BYK-302 and 1 part by weight of acrylic additive BYK-359 were added to 100 parts by weight of the prepared composition and stirred for 10 minutes to obtain a mixture of cage- %: 50% by weight based on the total weight of the photocurable resin composition. The photocurable resin composition thus prepared was applied on an 80 탆 triacetyl cellulose film (FUJIFILM), and the solvent was evaporated in a drying oven of 85, followed by UV irradiation at 1 J / cm 2 using UV equipment.
[실시예 4][Example 4]
상기 합성예 4에서 얻어진 실세스퀴옥산올리고머를 50 g을 메틸아이소부틸케톤에 50 중량%로 녹여 100 g의 조성물을 제조하였다. 이후, 준비된 조성물 100 중량부에 클로로아세토페논 5 중량부, 실리콘계 첨가제 BYK-302 1 중량부 및 아크릴계 첨가제 BYK-359 1 중량부를 첨가하고 10분간 교반하여 케이지형 구조와 레더형 구조의 비율이 80 중량% : 20 중량% 인 광경화형 수지 조성물을 제조하였다. 제조된 광경화형 수지 조성물을 80 ㎛ 트리아세틸 셀룰로오스 필름(FUJIFILM) 위에 도포하고 85의 건조오븐에서 용매를 증발시킨 후 UV 장비를 이용하여 1 J/cm2의 UV를 조사하여 결과물을 수득하였다.50 g of the silsesquioxane oligomer obtained in Synthesis Example 4 was dissolved in 50% by weight of methyl isobutyl ketone to prepare 100 g of a composition. Then, 5 parts by weight of chloroacetophenone, 1 part by weight of silicone additive BYK-302 and 1 part by weight of acrylic additive BYK-359 were added to 100 parts by weight of the prepared composition and stirred for 10 minutes so that the ratio of the cage- %: 20% by weight based on the total weight of the photocurable resin composition. The photocurable resin composition thus prepared was applied on an 80 탆 triacetyl cellulose film (FUJIFILM), and the solvent was evaporated in a drying oven of 85, followed by UV irradiation at 1 J / cm 2 using UV equipment.
[실시예 5][Example 5]
상기 합성예 2에서 얻어진 실세스퀴옥산올리고머를 50 g을 메틸아이소부틸케톤에 50 중량%로 녹여 100 g의 조성물을 제조하였다. 이후, 준비된 조성물 100 중량부에 클로로아세토페논 5 중량부, 실리콘계 첨가제 BYK-302 1 중량부 및 아크릴계 첨가제 BYK-359 1 중량부를 첨가하고 10분간 교반하여 케이지형 구조와 레더형 구조의 비율이 30 중량% : 70 중량% 인 광경화형 수지 조성물을 제조하였다. 제조된 광경화형 수지 조성물을 80 ㎛ 트리아세틸 셀룰로오스 필름(FUJIFILM) 위에 도포하고 85의 건조오븐에서 용매를 증발시킨 후 UV 장비를 이용하여 1 J/cm2의 UV를 조사하였으며, 반대면에도 똑같은 공정을 통해 양면 코팅하여 결과물을 수득하였다.50 g of the silsesquioxane oligomer obtained in Synthesis Example 2 was dissolved in 50% by weight of methyl isobutyl ketone to prepare 100 g of a composition. Then, 5 parts by weight of chloroacetophenone, 1 part by weight of silicone additive BYK-302 and 1 part by weight of acrylic additive BYK-359 were added to 100 parts by weight of the prepared composition and stirred for 10 minutes to obtain a mixture of cage- %: 70% by weight. The photocurable resin composition thus prepared was applied on an 80 탆 triacetylcellulose film (FUJIFILM), and the solvent was evaporated in a drying oven of 85, followed by UV irradiation at 1 J / cm 2 using UV equipment, and the same process To obtain a resultant product.
[비교예 1][Comparative Example 1]
실시예 및 비교예의 코팅기재로 사용한 80 ㎛ 트리아세틸 셀룰로오스 필름(FUJIFILM) 단독으로 하기 실험을 진행하였다.The following experiment was carried out on an 80 占 퐉 triacetyl cellulose film (FUJIFILM) alone used as a coating base material in Examples and Comparative Examples.
[비교예 2][Comparative Example 2]
상기 합성예 5에서 얻어진 실세스퀴옥산올리고머를 50 g을 메틸아이소부틸케톤에 50 중량%로 녹여 100 g의 조성물을 제조하였다. 이후, 준비된 조성물 100 중량부에 클로로아세토페논 5 중량부, 실리콘계 첨가제 BYK-302 1 중량부 및 아크릴계 첨가제 BYK-359 1 중량부를 첨가하고 10분간 교반하여 케이지형 구조와 레더형 구조의 비율이 3 중량% : 97 중량% 인 광경화형 수지 조성물을 제조하였다.제조된 광경화형 수지 조성물을 80 ㎛ 트리아세틸 셀룰로오스 필름(FUJIFILM) 위에 도포하고 85 의 건조오븐에서 용매를 증발시킨 후 UV 장비를 이용하여 1 J/cm2의 UV를 조사하여 결과물을 수득하였다.50 g of the silsesquioxane oligomer obtained in Synthesis Example 5 was dissolved in 50% by weight of methyl isobutyl ketone to prepare 100 g of a composition. Then, 5 parts by weight of chloroacetophenone, 1 part by weight of silicone additive BYK-302 and 1 part by weight of acrylic additive BYK-359 were added to 100 parts by weight of the prepared composition and stirred for 10 minutes to obtain a cage-type structure and a ladder- The photo-curable resin composition thus prepared was applied on an 80 탆 triacetyl cellulose film (FUJIFILM), the solvent was evaporated in a drying oven of 85, / cm < 2 > was irradiated to obtain a resultant product.
[비교예 3][Comparative Example 3]
상기 합성예 6에서 얻어진 실세스퀴옥산올리고머를 50 g을 메틸아이소부틸케톤에 50 중량%로 녹여 100 g의 조성물을 제조하였다. 이후, 준비된 조성물 100 중량부에 클로로아세토페논 5 중량부, 실리콘계 첨가제 BYK-302 1 중량부 및 아크릴계 첨가제 BYK-359 1 중량부를 첨가하고 10분간 교반하여 케이지형 구조와 레더형 구조의 비율이 5 중량% : 95 중량% 인 광경화형 수지 조성물을 제조하였다. 50 g of the silsesquioxane oligomer obtained in Synthesis Example 6 was dissolved in 50% by weight of methyl isobutyl ketone to prepare 100 g of a composition. Then, 5 parts by weight of chloroacetophenone, 1 part by weight of silicone additive BYK-302 and 1 part by weight of acrylic additive BYK-359 were added to 100 parts by weight of the prepared composition and stirred for 10 minutes to obtain a cage- %: 95% by weight of a photocurable resin composition.
제조된 광경화형 수지 조성물을 80 ㎛ 트리아세틸 셀룰로오스 필름(FUJIFILM) 위에 도포하고 85 의 건조오븐에서 용매를 증발시킨 후 UV 장비를 이용하여 1 J/cm2의 UV를 조사하여 결과물을 수득하였다.The photocurable resin composition thus prepared was applied on an 80 탆 triacetyl cellulose film (FUJIFILM), and the solvent was evaporated in a drying oven of 85, followed by UV irradiation at 1 J / cm 2 using UV equipment.
[비교예 4][Comparative Example 4]
상기 합성예 7에서 얻어진 실세스퀴옥산올리고머를 50 g을 메틸아이소부틸케톤에 50 중량%로 녹여 100 g의 조성물을 제조하였다. 이후, 준비된 조성물 100 중량부에 클로로아세토페논 5 중량부, 실리콘계 첨가제 BYK-302 1 중량부 및 아크릴계 첨가제 BYK-359 1 중량부를 첨가하고 10분간 교반하여 케이지형 구조와 레더형 구조의 비율이 85 중량% : 15 중량% 인 광경화형 수지 조성물을 제조하였다. 50 g of the silsesquioxane oligomer obtained in Synthesis Example 7 was dissolved in 50% by weight of methyl isobutyl ketone to prepare 100 g of a composition. Then, 5 parts by weight of chloroacetophenone, 1 part by weight of silicone additive BYK-302 and 1 part by weight of acrylic additive BYK-359 were added to 100 parts by weight of the prepared composition and stirred for 10 minutes to obtain a mixture of cage- %: 15% by weight based on the total weight of the photocurable resin composition.
제조된 광경화형 수지 조성물을 80 ㎛ 트리아세틸 셀룰로오스 필름(FUJIFILM) 위에 도포하고 85 의 건조오븐에서 용매를 증발시킨 후 UV 장비를 이용하여 1 J/cm2의 UV를 조사하여 결과물을 수득하였다.The photocurable resin composition thus prepared was applied on an 80 탆 triacetyl cellulose film (FUJIFILM), and the solvent was evaporated in a drying oven of 85, followed by UV irradiation at 1 J / cm 2 using UV equipment.
[비교예 5][Comparative Example 5]
상기 합성예 8에서 얻어진 실세스퀴옥산올리고머를 50 g을 메틸아이소부틸케톤에 50 중량%로 녹여 100 g의 조성물을 제조하였다. 이후, 준비된 조성물 100 중량부에 클로로아세토페논 5 중량부, 실리콘계 첨가제 BYK-302 1 중량부 및 아크릴계 첨가제 BYK-359 1 중량부를 첨가하고 10분간 교반하여 케이지형 구조와 레더형 구조의 비율이 90 중량% : 10 중량% 인 광경화형 수지 조성물을 제조하였다. 50 g of the silsesquioxane oligomer obtained in Synthesis Example 8 was dissolved in 50% by weight of methyl isobutyl ketone to prepare 100 g of a composition. Then, 5 parts by weight of chloroacetophenone, 1 part by weight of silicone additive BYK-302 and 1 part by weight of acrylic additive BYK-359 were added to 100 parts by weight of the prepared composition and stirred for 10 minutes to obtain a cage- %: 10% by weight.
제조된 광경화형 수지 조성물을 80 ㎛ 트리아세틸 셀룰로오스 필름(FUJIFILM) 위에 도포하고 85 의 건조오븐에서 용매를 증발시킨 후 UV 장비를 이용하여 1 J/cm2의 UV를 조사하여 결과물을 수득하였다.The photocurable resin composition thus prepared was applied on an 80 탆 triacetyl cellulose film (FUJIFILM), and the solvent was evaporated in a drying oven of 85, followed by UV irradiation at 1 J / cm 2 using UV equipment.
[실험][Experiment]
상기 실시예 1, 실시예 2, 실시예 3, 실시예 4, 실시예5, 비교예 1, 비교예 2, 비교예 3, 비교예 4 및 비교예 5에서 수득한 결과물을 대상으로 코팅 전후에 대하여 연필경도, 접착력, 투과도, 헤이즈, 수분투과도를 측정하여 하기 표 1에 나타내었다.The results obtained in Example 1, Example 2, Example 3, Example 4, Example 5, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4 and Comparative Example 5 were measured before and after coating The pencil hardness, adhesive strength, permeability, haze, and water permeability were measured and are shown in Table 1 below.
- 연필경도: JIS 5600-5-4에 의거하여 500 g 하중으로 평가하였다. 연필은 미쯔비시 제품을 사용하고 한 연필 경도당 5회 실시하여 2개 이상 스크래치가 발생하면 불량으로 판정하였다. 측정경도와 스크래치 미발생 횟수/실시 횟수로 표기하였다. - Pencil hardness: Evaluated according to JIS 5600-5-4 at 500 g load. The pencil was made five times per pencil hardness using Mitsubishi products and judged to be defective when two or more scratches occurred. The measured hardness and the number of incidence / non-scratch occurrence of the scratches.
- 접착력 평가: JIS K5600-5-6에 의거하여 1mm 간격으로 컷터날로 긁어서 격자무늬로 100개의 흠집을 내고, 점착테이프를 그 위에 저 붙였다가 900 방향으로 떼어내어 코팅층 표면이 점착테이프에 붙어서 떨어지는지를 육안으로 확인하였다. 표기는 100개중 떨어지지 않은 개수로 표기하였다.- Adhesive strength evaluation: According to JIS K5600-5-6, it was scratched with a cutter blade at intervals of 1 mm and 100 scratches were formed in a grid pattern. The adhesive tape was stuck on the adhesive tape and peeled off in 90 0 direction, . The notation is expressed in a number that is not out of 100.
(예: 떨어지지 않은 개수/100으로 표기, 100개가 떨어지지 않으면 100/100으로 표기 함.)(Example: number not falling / 100, 100 if not falling.)
- 투과도 및 헤이즈: ISO 14782에 의거하여, COH-400 (Nippon Denshoku)를 이용해 측정하였다. 샘플 당 5회씩 측정하여 평균값을 기재하였다.- Transmittance and haze: measured according to ISO 14782 using COH-400 (Nippon Denshoku). Five times per sample were measured and the average value was described.
- 수분투과도: MOCON 장비를 이용하여 37.8°C, 100% RH(Relative Humidity) 항온 항습 조건에서 측정하였다.- Water Permeability: Measured at 37.8 ° C and 100% RH (relative humidity) using MOCON equipment.
(500gf)Pencil hardness
(500 g f )
상기 표 1에 나타나는 바와 같이 본 발명의 실시예 2, 실시예 3, 실시예 5는 실시예 1, 실시예 4, 비교예 1, 비교예 2, 비교예 3, 비교예 4 및 비교예 5와 비교하여 현저히 우수한 물성을 나타내었다. 특히 실시예 2와 이의 양면코팅인 실시예 5의 경우 더욱 우수한 TAC 필름의 수분투과도와 연필경도를 가짐을 확인 할 수 있다.Example 1, Example 4, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, and Comparative Example 5, Example 2, Example 3 and Example 5 of the present invention, And exhibited remarkably excellent physical properties. In particular, in Example 2 and Example 5, which is a double-sided coating thereof, it can be confirmed that the TAC film has better water permeability and pencil hardness.
Claims (7)
상기 실세스퀴옥산올리고머는 화학식 1로 표시되는 레더형실세스퀴옥산 수지에 화학식 2로 표시되는 케이지형실세스퀴옥산 수지가 결합된 것인 코팅 조성물.
[화학식 1]
상기 화학식 1에서,
R1,R2,R3,R4는 각각 독립적으로 치환기로 치환되거나 치환되지 않은 메틸기; 페닐기; 아미노기; (메타)아크릴기; 비닐기; 에폭시기; 사이올기; 또는 자외선흡수체이며, n은 1 내지 100의 정수이고,
R5,R6,R7,R8은 각각 독립적으로, 수소; 치환기로 치환되거나 치환되지 않은 C1~C10의 알킬기; 또는 하기 화학식 2로 표시되는 연결기이며, R5,R6,R7,R8중 적어도 하나는 하기 화학식 2와 연결되며,
[화학식 2]
상기 화학식 2에서,
R은 각각 독립적으로 치환기로 치환되거나 치환되지 않은 메틸기, 페닐기, 아미노기, (메타)아크릴기, 비닐기, 에폭시기, 사이올기 또는 자외선차단제이며,
R0는 각각 독립적으로 수소 또는 치환되거나 치환되지 않은 C1~C10의 알킬기이며,
n은 3 내지 6의 정수이며
상기 화학식 1 또는 2에서 치환기는 각각 독립적으로 중수소, 할로겐, 아민기, 에폭시기, (메타)아크릴기, 사이올기, 이소시아네이트기, 니트릴기, 니트로기 또는 페닐기이다.The method according to claim 1,
Wherein the silsesquioxane oligomer comprises a cage silsesquioxane resin represented by formula (2) bonded to a ladder-type silsesquioxane resin represented by formula (1).
[Chemical Formula 1]
In Formula 1,
R1, R2, R3 and R4 each independently represent a methyl group, which is optionally substituted with a substituent; A phenyl group; An amino group; (Meth) acrylic group; Vinyl group; An epoxy group; A diazo group; Or an ultraviolet absorber, n is an integer of 1 to 100,
R5, R6, R7 and R8 are each independently hydrogen; A C1 to C10 alkyl group which is unsubstituted or substituted with a substituent group; Or at least one of R5, R6, R7 and R8 is connected to the following formula (2)
(2)
In Formula 2,
R is independently a methyl group, a phenyl group, an amino group, a (meth) acrylic group, a vinyl group, an epoxy group, a silyl group or an ultraviolet ray blocking agent,
R0 are each independently hydrogen or a substituted or unsubstituted C1-C10 alkyl group,
n is an integer from 3 to 6
In the above general formula (1) or (2), the substituents are each independently a deuterium, a halogen, an amine group, an epoxy group, a (meth) acrylic group, a silyl group, an isocyanate group, a nitrile group, a nitro group or a phenyl group.
상기 코팅 조성물은 광 또는 열로 개시되는 양이온 개시제, 라디칼개시제 또는 용매 중 하나 이상을 더 포함하는 코팅 조성물.The method according to claim 1,
Wherein the coating composition further comprises at least one of a cationic initiator initiated with light or heat, a radical initiator or a solvent.
상기 기재의 수분투과도는 4 g/m2.day 이상인 필름.5. The method of claim 4,
Wherein the substrate has a water permeability of 4 g / m 2 .day or more.
상기 기재는 트리아세틸 셀룰로오스인 필름.5. The method of claim 4,
Wherein the substrate is triacetylcellulose.
상기 필름은 100 g/m2.day 이하의 수분투과도를 갖는 필름.
The method according to claim 6,
Wherein the film has a water permeability of 100 g / m < 2 > .day or less.
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| KR102587608B1 (en) * | 2022-08-02 | 2023-10-12 | 주식회사 크레파머티리얼즈 | High hardness coating composition with excellent scratch resistance |
| KR102587607B1 (en) * | 2022-08-02 | 2023-10-12 | 주식회사 크레파머티리얼즈 | High hardness coating composition with excellent bendability |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60258517A (en) * | 1984-06-06 | 1985-12-20 | Dainippon Ink & Chem Inc | Liquid crystal display element |
| JPH1140554A (en) * | 1997-07-22 | 1999-02-12 | Fujitsu Ltd | Insulating film forming material, and method for forming insulating film and semiconductor device using it |
| US7344783B2 (en) * | 2003-07-09 | 2008-03-18 | Shell Oil Company | Durable hydrophobic surface coatings using silicone resins |
| CN101003712A (en) * | 2006-01-19 | 2007-07-25 | 达信科技股份有限公司 | Pre-processing method for composition of binder, support sheet material, and polarized light plate of using the composition and the plate |
| JP5158739B2 (en) * | 2006-06-13 | 2013-03-06 | 学校法人 関西大学 | Thermosetting polymer composition and cured product thereof |
| KR101249798B1 (en) * | 2010-08-18 | 2013-04-03 | 한국과학기술연구원 | A Method for Preparing a Controlled Structure of Polysilsesquioxane and Polysilsesquioxane Prepared by the Same |
| KR102004493B1 (en) * | 2012-03-27 | 2019-07-26 | 주식회사 동진쎄미켐 | Ladder-like silsesquioxane polymer and resin composition for optical film comprising the same |
| JP5954257B2 (en) * | 2012-05-23 | 2016-07-20 | マツダ株式会社 | Vehicle window material |
| JP2014102492A (en) * | 2012-10-04 | 2014-06-05 | Fujifilm Corp | Optical film and method for manufacturing the same, polarizing plate and liquid crystal display device |
| JP6021605B2 (en) * | 2012-11-19 | 2016-11-09 | 新日鉄住金化学株式会社 | Cage type silsesquioxane compound, curable resin composition and resin cured product using the same |
| CN103102467B (en) * | 2013-02-26 | 2014-06-25 | 中国科学院合肥物质科学研究院 | Preparation method of halogen-free flame retardant polyurethane-cage type silsesquioxane nanocomposite |
| WO2014193177A2 (en) * | 2013-05-31 | 2014-12-04 | 주식회사 동진쎄미켐 | Open-structure polyhedral oligomeric silsesquioxane and composition comprising same |
| US9006355B1 (en) * | 2013-10-04 | 2015-04-14 | Burning Bush Group, Llc | High performance silicon-based compositions |
| KR102170818B1 (en) * | 2013-12-26 | 2020-10-28 | 주식회사 동진쎄미켐 | Sisesquioxane which can be molded by hot melt-extrusion, highly transparent and highly heat resistant plastic transparent substrate, and method for manufacturing thereof |
| CN106062053B (en) * | 2014-02-28 | 2019-07-19 | 株式会社东进世美肯 | Surface-enhanced transparent substrate and method for manufacturing same |
| KR20150102860A (en) * | 2014-02-28 | 2015-09-08 | 주식회사 동진쎄미켐 | Silsesquioxane composite polymer and method for manufacturing thereof |
| KR102363820B1 (en) * | 2014-02-28 | 2022-02-17 | 주식회사 동진쎄미켐 | Silsesquioxane composite polymer and method for manufacturing thereof |
| JP6313137B2 (en) * | 2014-06-27 | 2018-04-18 | 株式会社日本触媒 | Polysiloxane compound, process for producing the same, and polysiloxane-containing inorganic composition |
| AU2015293085A1 (en) * | 2014-07-22 | 2017-01-19 | Tokuyama Corporation | Curable composition and photochromic composition |
| CN105778429B (en) * | 2016-04-01 | 2017-10-20 | 厦门大学 | A kind of agent of low hygroscopicity epoxy resin and preparation method thereof |
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| KR102587608B1 (en) * | 2022-08-02 | 2023-10-12 | 주식회사 크레파머티리얼즈 | High hardness coating composition with excellent scratch resistance |
| KR102587607B1 (en) * | 2022-08-02 | 2023-10-12 | 주식회사 크레파머티리얼즈 | High hardness coating composition with excellent bendability |
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