KR101201387B1 - Cyclic olefin resins flexible substrates with low coefficient of thermal expansion - Google Patents
Cyclic olefin resins flexible substrates with low coefficient of thermal expansion Download PDFInfo
- Publication number
- KR101201387B1 KR101201387B1 KR1020110078437A KR20110078437A KR101201387B1 KR 101201387 B1 KR101201387 B1 KR 101201387B1 KR 1020110078437 A KR1020110078437 A KR 1020110078437A KR 20110078437 A KR20110078437 A KR 20110078437A KR 101201387 B1 KR101201387 B1 KR 101201387B1
- Authority
- KR
- South Korea
- Prior art keywords
- group
- cyclic olefin
- flexible substrate
- norbornene
- olefin resin
- Prior art date
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- 239000000758 substrate Substances 0.000 title claims abstract description 66
- 125000004122 cyclic group Chemical group 0.000 title claims description 75
- 229920005672 polyolefin resin Polymers 0.000 title claims description 69
- 230000009477 glass transition Effects 0.000 claims abstract description 44
- -1 cyclic olefin Chemical class 0.000 claims abstract description 41
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000001678 irradiating effect Effects 0.000 claims abstract description 15
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 12
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 10
- 229920001519 homopolymer Polymers 0.000 claims abstract description 9
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 3
- YSWATWCBYRBYBO-UHFFFAOYSA-N 5-butylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCC)CC1C=C2 YSWATWCBYRBYBO-UHFFFAOYSA-N 0.000 claims abstract description 3
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims abstract description 3
- WMWDGZLDLRCDRG-UHFFFAOYSA-N 5-hexylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCC)CC1C=C2 WMWDGZLDLRCDRG-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 31
- 238000004132 cross linking Methods 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 27
- 230000005855 radiation Effects 0.000 claims description 22
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 15
- 150000007524 organic acids Chemical group 0.000 claims description 15
- 239000011342 resin composition Substances 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 13
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000010954 inorganic particle Substances 0.000 claims description 9
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052705 radium Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001336 alkenes Chemical group 0.000 claims description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 2
- NQSHHIILMFAZCA-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)CO.O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 NQSHHIILMFAZCA-UHFFFAOYSA-N 0.000 claims description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- WMVSVUVZSYRWIY-UHFFFAOYSA-N [(4-benzoyloxyiminocyclohexa-2,5-dien-1-ylidene)amino] benzoate Chemical compound C=1C=CC=CC=1C(=O)ON=C(C=C1)C=CC1=NOC(=O)C1=CC=CC=C1 WMVSVUVZSYRWIY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000008064 anhydrides Chemical group 0.000 claims description 2
- 239000010425 asbestos Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 claims description 2
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910052895 riebeckite Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- XBYNNYGGLWJASC-UHFFFAOYSA-N barium titanium Chemical compound [Ti].[Ba] XBYNNYGGLWJASC-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- UJDNPQZXKMGSEX-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hepta-1(6),2-diene Chemical compound C1=CC2C(C)C=C1C2 UJDNPQZXKMGSEX-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 68
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 229920001577 copolymer Polymers 0.000 description 33
- 238000002834 transmittance Methods 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000807 solvent casting Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000003254 radicals Chemical group 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 238000012644 addition polymerization Methods 0.000 description 3
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical group CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 150000007942 carboxylates Chemical group 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- AQVXMEQFGRWGIN-UHFFFAOYSA-N hex-1-enyl-bis(2-methylpropyl)alumane Chemical compound CCCC\C=C\[Al](CC(C)C)CC(C)C AQVXMEQFGRWGIN-UHFFFAOYSA-N 0.000 description 3
- 150000002848 norbornenes Chemical class 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- DZBOAIYHPIPCBP-UHFFFAOYSA-L magnesium;2-methylprop-2-enoate Chemical compound [Mg+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O DZBOAIYHPIPCBP-UHFFFAOYSA-L 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- DQWHUTSNDKBDFC-UHFFFAOYSA-N C(=CCCC)[Al](CC)CC Chemical compound C(=CCCC)[Al](CC)CC DQWHUTSNDKBDFC-UHFFFAOYSA-N 0.000 description 1
- HBUVSWQQISQBQM-UHFFFAOYSA-N C(=CCCCC)[Al](CC)CC Chemical compound C(=CCCCC)[Al](CC)CC HBUVSWQQISQBQM-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- GJHRXVLRWDGVRA-UHFFFAOYSA-N bis(2-methylpropyl)-pent-1-enylalumane Chemical compound CCCC=C[Al](CC(C)C)CC(C)C GJHRXVLRWDGVRA-UHFFFAOYSA-N 0.000 description 1
- ZXBWVTLNSZUGSL-UHFFFAOYSA-N bis(2-methylpropyl)-prop-1-enylalumane Chemical compound CC=C[Al](CC(C)C)CC(C)C ZXBWVTLNSZUGSL-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 1
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- 230000005251 gamma ray Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
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- 239000007924 injection Substances 0.000 description 1
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- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- DWLAVVBOGOXHNH-UHFFFAOYSA-L magnesium;prop-2-enoate Chemical compound [Mg+2].[O-]C(=O)C=C.[O-]C(=O)C=C DWLAVVBOGOXHNH-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N methyl heptene Natural products CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical group [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- GNWCEVOXWDZRJH-UHFFFAOYSA-N repin Natural products CC1(CO1)C(=O)OC2CC3C(OC(=O)C3=C)C4C(CC(O)C45CO5)C2=C GNWCEVOXWDZRJH-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003460 sulfonic acids Chemical group 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
Description
본 발명은 낮은 열팽창계수를 갖는 환형올레핀계 수지 플렉시블 기판, 보다 상세하게는 극히 낮은 열팽창계수를 가질 뿐만 아니라 우수한 유연성, 투명성, 등방성 및 높은 유리전이온도를 가지는 플렉시블 디스플레이, 태양전지 등 용도에 적합한 신규의 환형올레핀계 수지 플렉시블 기판에 관한 것이다.The present invention is a novel cyclic olefin resin flexible substrate having a low coefficient of thermal expansion, more particularly, a novel display suitable for applications such as flexible displays, solar cells and the like having not only extremely low coefficient of thermal expansion but also excellent flexibility, transparency, isotropy and high glass transition temperature. It relates to a cyclic olefin resin flexible substrate.
플렉시블 디스플레이, 플렉시블 태양전지 등은 기존의 유리 기반 평판형 제품에 비해서 박형 및 경량이고 충격에 강하며 휴대가 간편하다는 장점이외에 공간상, 형태상의 제약에서 상대적으로 자유로워 다양한 응용성을 확보할 수 있다는 점에서 더욱더 그 수요가 급증하고 있다.Flexible displays, flexible solar cells, etc. are thinner, lighter, more impact-resistant, and easier to carry than conventional glass-based flat panel products. In that respect, the demand is increasing rapidly.
이러한 플렉시블 디스플레이, 플렉시블 태양전지 등을 구현하기 위해서는 투명 고내열성 플렉시블 기판 제조기술, 수분 및 산소에 대한 고차단성 부여기술, 투명전극 형성기술 등 많은 기술들이 복합적으로 필요하다. 대표적으로 고차단성을 부여하는 방법으로서는 가령 실리카계 산화물, 알루미늄계 산화물 등을 플렉시블 기판위에 진공증착, 스퍼터링 등 방법을 통해 박막으로 형성하고 다시 열경화성 수지를 코팅하는 작업을 반복함으로써 다층구조의 고차단성층을 형성시키는 방법이 있으며 투명전극 경우는 통상 인튬 틴 옥사이드, 인튬 징크 옥사이드 등 산화물을 진공증착, 스퍼터링 방법 등에 의해 박막으로 형성시키고 있다. In order to implement such a flexible display and a flexible solar cell, many technologies such as a transparent high heat-resistant flexible substrate manufacturing technology, a high blocking property for moisture and oxygen, and a transparent electrode forming technology are required in combination. Representative methods for providing high barrier properties include, for example, forming a thin layer of silica oxide, aluminum oxide, etc. on a flexible substrate by vacuum deposition, sputtering, or the like, and coating the thermosetting resin again, thereby repeating a high barrier layer having a multilayer structure. In the case of a transparent electrode, oxides such as indium tin oxide and indium zinc oxide are usually formed into thin films by vacuum deposition, sputtering, or the like.
고차단성 부여 및 투명전극을 형성시키는 공정에 필수적인 진공증착, 스퍼터링 등 공정은 통상 높은 온도에서 실행되어야 하므로 자연 플렉시블 기판의 내열성이 요구되고 있으며 특히 플렉시블 기판의 주요 용도중 하나인 박막트랜지스터-액정디스플레이(TFT-LCD) 생산시 박막트랜지스터 어레이를 플렉시블 기판위에 구현하는 공정온도가 200～300℃ 수준이고 유기발광다이오드(OLED)경우는 350℃ 이상 극히 고온 조건하에서 처리하는 공정도 있어 이러한 온도 조건하에서 치수안정성 측면에서 플렉시블 기판의 내열성이 더욱더 중요하게 요청되고 있다. 이러한 내열성은 현재 유리전이온도 및 치수안정성의 척도인 열팽창계수로서 이를 평가하고 있는데, 고내열성 플렉시블 기판을 제조하기 위해서는 최소 200℃이상, 좋기로는 250℃이상, 더욱 좋기로는 350℃이상의 높은 유리전이온도 및 20ppm/℃이하, 좋기로는 10ppm/℃이하의 극히 낮은 열팽창계수를 가진 플라스틱 소재가 필요하다. Processes such as vacuum deposition and sputtering, which are essential for the process of imparting high barrier properties and forming transparent electrodes, are generally required to be performed at a high temperature, and thus, heat resistance of a natural flexible substrate is required. In the production of TFT-LCD, the process temperature to implement the thin film transistor array on the flexible substrate is 200 ~ 300 ℃, and in the case of organic light emitting diode (OLED), the process is processed under extremely high temperature of 350 ℃ or above. In terms of heat resistance of the flexible substrate is increasingly important. This heat resistance is evaluated as a coefficient of thermal expansion, which is currently a measure of glass transition temperature and dimensional stability. To manufacture a high heat resistant flexible substrate, at least 200 ° C, preferably 250 ° C, and more preferably 350 ° C or higher What is needed is a plastic material with a transition temperature and an extremely low coefficient of thermal expansion of 20 ppm / ° C. or less, preferably 10 ppm / ° C. or less.
또한 이러한 플렉시블 기판에 적합한 플라스틱 소재는 상기 높은 유리전이온도 및 낮은 열팽창계수를 가지는 내열성뿐만 아니라 광투과도 기준 90% 이상 우수한 투명성, 복굴절 기준 10nm이하의 등방성 등 여러 물성이 요구되고 있다. 대한민국 공개특허 제2011-0064206호, 제2005-0113383호, 제2002-0082893호와 같이, 지금까지 연구개발의 유력한 대상이 되어온 플렉시블 기판용 플라스틱 소재로서는 폴리에틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리카보네이트, 폴리에테르설폰, 폴리이미드, 폴리노르보르넨 등이 있다. In addition, a plastic material suitable for such a flexible substrate is required to have various physical properties such as heat resistance having a high glass transition temperature and a low coefficient of thermal expansion, excellent transparency over 90% based on light transmittance, and isotropy below 10 nm based on birefringence. As the Republic of Korea Patent Publication No. 2011-0064206, No. 2005-0113383, No. 2002-0082893, plastic materials for flexible substrates that have been a strong target of research and development so far, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, poly Ethersulfone, polyimide, polynorbornene and the like.
이중 폴리에틸렌테레프탈레이트, 폴리에틸렌나프탈레이트 등 폴리에스터 수지는 열팽창계수는 13～15ppm/℃로서 비교적 낮은 편이나 유리전이온도가 80～ 120℃ 수준으로 매우 낮고, 150nm이상 높은 복굴절을 가지기 때문에 결국 플렉시블 기판에 적합한 플라스틱 소재 대상에서 제외되고 있는 실정이다. 폴리카보네이트 경우 광투과도 90%의 투명성, 10nm이하 낮은 복굴절 측면에선 긍정적이나 유리전이온도가 150～200℃ 수준으로 매우 낮아 역시 바람직하지 않으며, 폴리에테르설폰 경우 가령 스미토모배이크라이트사의 폴리에테르설폰 기판(상품명 Sumilite FS-1300)은 광투과도 89%의 투명성, 10nm이하의 낮은 복굴절을 가지는 장점이 있으며 유리전이온도가 223℃로서 폴리카보네이트 대비 우수하지만 역시 요구되는 유리전이온도 조건에는 다소 부족한 단점이 있다. 또한 폴리이미드는 300℃ 이상의 높은 유리전이온도 및 17ppm/℃ 수준의 낮은 열팽창계수를 가지므로 내열성 측면에서 큰 장점을 가지고 있으나 원료 및 제조원가가 높고 노란색을 띄고 있으며 투명성 이 떨어진다는 측면에서 바람직하지 않다. Among them, polyester resins such as polyethylene terephthalate and polyethylene naphthalate have relatively low thermal expansion coefficients of 13 to 15 ppm / ℃, but have a very low glass transition temperature of 80 to 120 degrees Celsius and have a birefringence higher than 150 nm. Excluded from the subject of suitable plastic materials. In the case of polycarbonate, the transparency of light transmittance of 90% and the low birefringence side of 10 nm or less are positive, but the glass transition temperature is very low, which is very low at the level of 150-200 ° C. In the case of polyether sulfone, for example, the polyether sulfone substrate of Sumitomo Bakelite ( Sumilite FS-1300) has the advantage of having 89% transparency of light transmittance and low birefringence of less than 10nm, and has a glass transition temperature of 223 ° C, which is superior to polycarbonate, but also has a disadvantage of being somewhat insufficient in the required glass transition temperature conditions. In addition, polyimide has a high glass transition temperature of more than 300 ℃ and a low coefficient of thermal expansion of 17ppm / ℃ level has a great advantage in terms of heat resistance, but it is not preferable in terms of high raw materials and manufacturing cost, yellow color and poor transparency.
반면 프로메러스사의 폴리노르보르넨 기판(상품명 Appear 3000)과 같은 환형올레핀계 수지 기판 경우 광투과도 92%의 우수한 투명성, 복굴절 10nm이하의 우수한 등방성, 유리전이온도 330℃의 높은 내열성을 가지고 있어 플렉시블 기판에 적합한 가장 강력한 후보 소재로서 큰 기대를 모으고 있다. 그러나 불행히도 이러한 환형올레핀계 수지 기판 경우 열팽창계수가 110～190ppm/℃수준으로 매우 높아 그 해결이 매우 절실히 요청되고 있다. On the other hand, cyclic olefin resin substrates such as Pronorus' polynorbornene substrate (trade name Appear 3000) have excellent transparency of 92%, excellent isotropy of less than 10nm of birefringence, and high heat resistance of 330 ℃ for glass transition temperature. It is expected to be the strongest candidate material suitable for the substrate. Unfortunately, however, the cyclic olefin resin substrate has a high thermal expansion coefficient of 110 to 190 ppm / ° C., which is highly urgently required to solve the problem.
상기와 같은 문제점을 해결하기 위하여 본 발명자는 예의 연구를 거듭한 결과 본 발명에 이르게 되었다. In order to solve the above problems, the inventor of the present invention has made intensive studies and has come to the present invention.
본 발명은 구체적으로 플렉시블 기판에 적합한 극히 낮은 열팽창계수를 가질 뿐만 아니라 우수한 유연성, 투명성, 등방성 및 높은 유리전이온도를 가지는 신규의 환형올레핀계 수지 플렉시블 기판을 제공하는 것을 그 목적으로 한다.It is an object of the present invention to provide a novel cyclic olefin resin flexible substrate having not only an extremely low coefficient of thermal expansion suitable for a flexible substrate, but also an excellent flexibility, transparency, isotropy and high glass transition temperature.
상기 과제를 해결하기 위하여, 본 발명은 환형올레핀계 수지로 성형된 필름에 방사선을 조사하여 얻어진 것을 특징으로 하는 낮은 열팽창계수를 갖는 플렉시블 기판에 관한 것이다.In order to solve the said subject, this invention relates to the flexible substrate which has a low coefficient of thermal expansion characterized by irradiating the film shape | molded with cyclic olefin resin.
본 발명의 제 1양태는 환형올레핀계 수지로 제조된 기판에 방사선(감마선, 전자선, X-선 등)을 조사하여 가교함으로써, 극히 낮은 열팽창계수를 가지는 신규의 기판을 제공하는 것이다.A first aspect of the present invention is to provide a novel substrate having an extremely low coefficient of thermal expansion by irradiating and crosslinking a substrate made of a cyclic olefin resin with radiation (gamma rays, electron beams, X-rays, and the like).
본 발명의 상기 환형올레핀계 수지가 수산기, 아민기, 암모늄기, 에폭시기, 할로겐기, 시아노기, 아세테이트기, 에스테르기, 유기산기, 유기산무수물기, 및 유기산염기로 구성된 군에서 선택된 극성기를 함유하는 환형올레핀계 수지로 제조한 기판에 방사선을 조사하여 가교함으로써 더욱 낮은 열팽창계수를 가지는 신규의 기판을 제공하는 것이다.The cyclic olefin resin of the present invention contains a cyclic group containing a polar group selected from the group consisting of hydroxyl group, amine group, ammonium group, epoxy group, halogen group, cyano group, acetate group, ester group, organic acid group, organic acid anhydride group, and organic acid salt group It is to provide a novel substrate having a lower coefficient of thermal expansion by irradiating and crosslinking a substrate made of an olefinic resin.
본 발명의 또 다른 양태는 라디칼 반응성기를 함유하는 환형올레핀계 수지의 기판에 방사선을 조사함으로써 더욱 낮은 열팽창계수를 가지는 신규한 기판을 제공하는 것이다.Another aspect of the present invention is to provide a novel substrate having a lower coefficient of thermal expansion by irradiating a substrate of a cyclic olefin resin containing a radical reactive group with radiation.
본 발명의 또 다른 양태는 상기의 다양한 형태의 환형올레핀계 수지에 가교조제를 첨가한 환형올레핀계 수지조성물을 이용하여 제조한 기판에 방사선을 조사함으로써 더욱 낮은 열팽창계수를 가지는 신규의 기판을 제공하는 것이다.Another aspect of the present invention is to provide a novel substrate having a lower coefficient of thermal expansion by irradiating a substrate prepared by using a cyclic olefin resin composition having a crosslinking aid added to the cyclic olefin resin of the various forms described above. will be.
본 발명의 또 다른 양태는 상기의 다양한 환형올레핀계 수지 또는 수지조성물에 무기입자를 추가하여 제조한 수지조성물을 이용하여 제조한 기판에 방사선을 조사하여 더욱 낮은 열팽창계수를 갖는 플렉시블 기판을 제공하는 것이다.Another aspect of the present invention is to provide a flexible substrate having a lower coefficient of thermal expansion by irradiating a substrate prepared by using a resin composition prepared by adding inorganic particles to the various cyclic olefin resins or resin compositions described above. .
이하 본 발명에 대하여 상세히 살펴본다.Hereinafter, the present invention will be described in detail.
본 발명에 있어 극히 낮은 열팽창계수를 가질 뿐만 아니라 동시에 우수한 유연성, 투명성, 등방성 및 높은 유리전이온도를 가지는 신규의 플렉시블 기판을 얻기 위해 도입한 기술의 핵심은, 먼저 유연성, 투명성, 등방성 및 높은 유리전이온도를 가지는 환형올레핀계 수지를 기본수지로 하여 기판을 성형하는 것이고, 또한 종래 환형올레핀계 수지가 구조적으로 자유부피(free volume)가 매우 큰 구조를 가지고 있기 때문에 높은 열팽창계수를 가질 수 밖에 없지만 만일 성형된 필름을 손쉽게 3차원적인 망상구조를 가질 수 있도록 유도할 수 있다면 획기적으로 열팽창계수가 낮아질 수 있다는데 착안하여 연구를 거듭한 결과 환형올레핀계 수지로 성형된 필름에 방사선을 조사한 결과 놀랍게도 환형올레핀계 수지의 유연성, 투명성, 등방성 및 높은 유리전이온도를 그대로 유지하면서 동시에 가교반응에 의한 3차원적 망상구조의 형성으로 극히 낮은 열팽창계수가 발현된다는 것을 발견하게 되어 본 발명을 완성하게 되었다.In the present invention, the core of the technology introduced to obtain a novel flexible substrate having not only an extremely low coefficient of thermal expansion but also excellent flexibility, transparency, isotropy and high glass transition temperature is, firstly, flexibility, transparency, isotropy and high glass transition. The substrate is molded using a cyclic olefin resin having a temperature as a basic resin, and since the conventional cyclic olefin resin has a structure with a very large free volume, it has a high coefficient of thermal expansion. When the molded film can be easily induced to have a three-dimensional network structure, the thermal expansion coefficient can be significantly lowered, and as a result of repeated studies, the film formed from the cyclic olefin resin was irradiated with a surprisingly cyclic olefin type. Flexibility, transparency, isotropy and high glass transition of resin Been found that, while maintaining the same degree at the same time an extremely low coefficient of thermal expansion expressed by the formation of three-dimensional network structure by the crosslinking reaction, thereby completing the present invention.
본 발명에 있어서 환형올레핀은 환형구조를 가지는 올레핀계 화합물로서 특별히 제한되지 않지만, 구체적인 예로서 노르보르넨, 5-메틸-2-노르보르넨, 5-에틸-2-노르보르넨, 5,6-디메틸-2-노르보르넨, 5-부틸-2-노르보르넨 등의 알킬기를 갖는 노르보르넨류, 5-바이닐-2-노르보르넨 등의 알켄일기를 갖는 노르보르넨류, 5-메틸리덴-2-노르보르넨, 5-에틸리덴-2-노르보르넨 등의 알킬리덴기를 갖는 노르보르넨류, 디시클로 펜타디엔, 시클로펜타디엔, 펜던트 관능기(pendant functional group)로서 산소, 염소, 질소, 브롬, 불소 등의 극성기를 가지는 각종 노르보르넨 유도체 등을 들 수 있다. In the present invention, the cyclic olefin is not particularly limited as an olefin compound having a cyclic structure, but specific examples thereof include norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5,6 Norbornenes having alkyl groups such as -dimethyl-2-norbornene and 5-butyl-2-norbornene, norbornenes having alkenyl groups such as 5-vinyl-2-norbornene and 5-methylidene Norbornenes having an alkylidene group, such as 2-norbornene and 5-ethylidene-2-norbornene, dicyclo pentadiene, cyclopentadiene, and pendant functional groups such as oxygen, chlorine, nitrogen, And various norbornene derivatives having polar groups such as bromine and fluorine.
본 발명에 있어서 환형올레핀계 수지는 상기 환형올레핀만을 단량체로 하여 중합하여 얻어진 단독중합체 또는 환형올레핀을 단량체로 50몰% 이상 함유하도록 하여 얻어지는 공중합체로서 통상 개환 복분해중합, 부가중합 등에 의해 얻어질 수 있다. In the present invention, the cyclic olefin resin is a homopolymer obtained by polymerizing only the cyclic olefin as a monomer or a copolymer obtained by containing 50 mol% or more of the cyclic olefin as a monomer, and can be usually obtained by ring-opening metathesis polymerization, addition polymerization or the like. have.
개환 복분해중합에 의해 얻어지는 환형올레핀계 수지는 가령 대한민국 등록특허 제10-2009-0883765호, Bielawski CW, Grubbs RH. Living Ring-opening metathesis polymerization. Prog Polym Sci, Vol. 32, 1 (2007), Trimmer, MS. Commercial Applications of Ruthenium Olefin Metathesis Catalysts in Polymer Synthesis. In Handbook of Metathesis; Grubbs, R. H., Ed. Wiley-VCH, Vol. 3, 407-418 (2003) 등에 기재된 바와 같이 환형올레핀계 단량체를 루테늄, 로듐, 팔라듐, 오스뮴, 인듐, 백금 등으로부터 선택되는 금속의 할로겐화물, 질산염 또는 아세틸아세톤 화합물과 환원제로 이루어지는 촉매, 또는 티타늄, 팔라듐, 지르코늄, 몰리브덴 등으로부터 선택되는 금속의 할로겐화물 또는 아세틸아세톤 화합물과 유기 알루미늄 화합물 등 촉매 존재하에 개환 복분해 중합시키고, 경우에 따라 추가로 수소화시킴으로써 얻어지는 것으로서 대표적인 화학적 구조로서는 하기 화학식 (1)을 들 수 있다. The cyclic olefin resin obtained by ring-opening metathesis polymerization is described in, for example, Korean Patent No. 10-2009-0883765, Bielawski CW, Grubbs RH. Living Ring-opening metathesis polymerization. Prog Polym Sci, Vol. 32 , 1 (2007), Trimmer, MS. Commercial Applications of Ruthenium Olefin Metathesis Catalysts in Polymer Synthesis. In Handbook of Metathesis; Grubbs, RH, Ed. Wiley-VCH, Vol. 3 , 407-418 (2003) and the like, or a catalyst consisting of a halide, nitrate or acetylacetone compound and a reducing agent of a metal selected from ruthenium, rhodium, palladium, osmium, indium, platinum and the like, or titanium Ring-opening metathesis polymerization in the presence of a catalyst such as a halide or acetylacetone compound of an metal selected from palladium, zirconium, molybdenum, and an organoaluminum compound, and optionally further hydrogenation. Can be mentioned.
(화학식 (1))(Formula (1))
상기 화학식 (1)에서, Ra 및 Rb는 동일하거나 상이하며, 수소, 알킬기 또는 수산기, 아민기, 암모늄기, 에폭시기, 할로겐기, 시아노기, 아세테이트기, 에스테르기, 유기산기, 유기산무수물기, 유기산염기 등의 극성기를 나타낸다. Ra 및 Rb는 서로 결합하여 고리를 형성하여도 좋다. ℓ은 0 또는 1 이상의 정수, m은 1 이상의 정수이다.In the formula (1), Ra and Rb are the same or different, hydrogen, alkyl or hydroxyl group, amine group, ammonium group, epoxy group, halogen group, cyano group, acetate group, ester group, organic acid group, organic acid anhydride group, organic acid salt group Polar groups such as these. Ra and Rb may combine with each other to form a ring. L is 0 or an integer of 1 or more, m is an integer of 1 or more.
부가중합에 의해 얻어지는 환형올레핀계 수지는 가령 대한민국 등록특허 제10-1999-0231173호, 일본 공개특허 소61-221206호, 일본 공개특허 소64-106호, 일본 공개특허 평2-173112호, 일본 공개특허 평3-234716호, 일본 공개 특허 평5-320258호, 일본 공개특허 평7－145213호 등에 기재된 바와 같이 환형올레핀계 단량체를 지르코늄, 티탄, 하프늄 등 전이금속계 촉매, 시클로펜타다이엔일 골격을 갖는 리간드를 포함하는 전이금속 화합물과 유기 알루미늄옥시화합물, 필요에 따라 배합되는 유기 알루미늄 화합물로 이루어지는 촉매인 메타로센계 촉매 존재하에 부가중합시켜 환형올레핀 단독중합체로서 얻어지거나 또한 50몰% 이상의 환형올레핀 단량체와 에틸렌, 프로필렌, 부텐 등과 같은 선형올레핀계 단량체를 상기 전이금속계 촉매, 메타로센계 촉매 등 존재하에 부가중합시켜 환형올레핀계 공중합체로서 얻어지는 것으로 이중 환형올레핀계 공중합체의 대표적인 화학적 구조로서는 하기 화학식 (2)를 들 수 있다.
The cyclic olefin resin obtained by addition polymerization is, for example, Korean Patent No. 10-1999-0231173, Japanese Patent Laid-Open No. 61-221206, Japanese Patent Laid-Open No. 64-106, Japanese Patent Laid-Open No. 2-173112, Japan As described in JP-A-234716, JP-A 5-320258, JP-A-7-145213 and the like, the cyclic olefin monomers include a transition metal catalyst such as zirconium, titanium and hafnium, and a cyclopentadienyl skeleton. It is obtained as a cyclic olefin homopolymer by addition polymerization in the presence of a metallocene catalyst, which is a catalyst composed of a transition metal compound containing a ligand having a ligand and an organoaluminum oxy compound and an organoaluminum compound to be blended, if necessary. Add monomer and linear olefin monomers such as ethylene, propylene, butene, etc. in the presence of the transition metal catalyst, metalocene catalyst and the like. The following general formula (2) is mentioned as a typical chemical structure of a bicyclic olefin type copolymer by superposing | polymerizing and obtaining as a cyclic olefin type copolymer.
(화학식 (2))(Formula (2))
상기 화학식(2)중에서, Rc 및 Rd는 동일하거나 상이하며, 수소, 알킬기 또는 수산기, 아민기, 암모늄기, 에폭시기, 할로겐기, 시아노기, 아세테이트기, 에스테르기, 유기산기, 유기산무수물기, 유기산염기 등의 극성기를 나타낸다. 또 Rc 및 Rd는 서로 결합하여 고리를 형성하여도 좋다. p는 0 또는 1 이상의 정수, q 및 r은 1 이상의 정수이다.In the formula (2), Rc and Rd are the same or different, hydrogen, alkyl or hydroxyl group, amine group, ammonium group, epoxy group, halogen group, cyano group, acetate group, ester group, organic acid group, organic acid anhydride group, organic acid salt group Polar groups such as these. Rc and Rd may combine with each other to form a ring. p is 0 or an integer of 1 or more, q and r are an integer of 1 or more.
또한 본 발명에 의한 환형올레핀계 공중합체를 얻는 다른 예로서는 가령 일본특허출원 2004-138946호, 대한민국 특허출원 제10-2011-0017531호 등에 상세히 기재된 바와 같이 50몰% 이상의 상기 환형올레핀과 프로페닐디에틸알루미늄, 프로페닐디이소부틸알루미늄, 펜테닐디에틸알루미늄, 펜테닐디이소부틸알루미늄, 헥세닐디이소부틸알루미늄, 헥세닐디에틸알루미늄, 옥테닐디이소부틸알루미늄, 옥테닐디에틸알루미늄, 데케닐디이소부틸알루미늄, 도데케닐디이소부틸알루미늄, 운데케닐디이소부틸알루미늄 등 알케닐디알킬알루미늄 화합물을 메타로센 촉매, 하프메타로센 촉매 등 촉매 존재하에서 공중합시킴에 따라 얻어지는 환형올레핀-알케닐디알킬알루미늄 공중합체를 수분, 산소, 과산화물, 이산화탄소, 삼산화황 등과 접촉시켜 함유된 디알킬알루미늄기의 가수분해반응에 의해 환형올레핀 단위와 화학식(3)으로 표시되는 단위로 구성된 공중합체로서 얻어질 수 있다. In addition, as another example of obtaining the cyclic olefin copolymer according to the present invention, for example, as described in detail in Japanese Patent Application No. 2004-138946, Korean Patent Application No. 10-2011-0017531, and the like, the cyclic olefin and propenyldiethyl at least 50 mol% Aluminum, propenyldiisobutylaluminum, pentenyldiethylaluminum, pentenyldiisobutylaluminum, hexenyldiisobutylaluminum, hexenyldiethylaluminum, octenyldiisobutylaluminum, octenyldiethylaluminum, dekenyldiisobutylaluminum, The cyclic olefin-alkenyldialkylaluminum copolymer obtained by copolymerizing alkenyldialkylaluminum compounds such as dodekenyldiisobutylaluminum and undekenyldiisobutylaluminum in the presence of a catalyst such as a metalocene catalyst and a half-methlocene catalyst , Containing dialkylaluminum in contact with oxygen, peroxides, carbon dioxide, sulfur trioxide, etc. By hydrolysis of nyumgi cyclic olefin units and a copolymer consisting of a unit represented by General Formula (3) can be obtained.
(화학식 (3))(Formula (3))
상기 화학식(3)중에서, n은 1～20의 정수이고, X는 수소 또는 수산기, 카르복실산기, 술폰산기 등 극성기를 나타낸다.In said General formula (3), n is an integer of 1-20, X represents a polar group, such as hydrogen or a hydroxyl group, a carboxylic acid group, a sulfonic acid group.
보다 구체적으로 상기 환형올레핀-알케닐디알킬알루미늄 공중합체를 수분과 접촉시키면 디알킬알루미늄기가 수소로 전환되어 긴 사슬 구조를 가진 선형올레핀 함유 환형올레핀계 공중합체가 얻어질 수 있고, 산소 또는 과산화물과 접촉시키면 디알킬알루미늄기가 수산기로 전환되어 수산기 함유 환형올레핀계 공중합체가 얻어질 수 있고, 이산화탄소와 접촉시키면 디알킬알루미늄기가 카르복실산기로 전환되어 카르복실기 함유 환형올레핀계 공중합체가 얻어질 수 있고(참고문헌: K.Zieglar, F.Krupp, K.Weyer and W.Larbig, Ann.Chem., 629, 251 (1960), 삼산화황과 접촉시키면 디알킬알루미늄기가 설폰산기로 전환되어 설폰산기 함유 환형올레핀계 공중합체가 얻어질 수 있다(참고문헌: 미국 특허 제3,121,737호). 또한 가령 상기 카르복실산기 또는 설폰산기 함유 환형올레핀계 공중합체를 중화반응시키면 상기 카르복실산염기 또는 설폰산염기 함유 환형올레핀계 공중합체가 얻어질 수 있다. More specifically, when the cyclic olefin-alkenyldialkylaluminum copolymer is contacted with water, the dialkylaluminum group is converted into hydrogen to obtain a linear olefin-containing cyclic olefin copolymer having a long chain structure, and contacted with oxygen or peroxide. The dialkylaluminum group may then be converted to a hydroxyl group to obtain a hydroxyl group-containing cyclic olefin copolymer, and when contacted with carbon dioxide, the dialkylaluminum group may be converted to a carboxylic acid group to obtain a carboxyl group-containing cyclic olefin copolymer (see Literature: K.Zieglar, F.Krupp, K.Weyer and W. Larbig, Ann. Chem., 629, 251 (1960), When contacted with sulfur trioxide, the dialkylaluminum group is converted to a sulfonic acid group to form a sulfonic acid group-containing cyclic olefin-based air. Coalescing can be obtained (see US Pat. No. 3,121,737) and also cyclic containing carboxylic or sulfonic acid groups. When repin based neutralize the copolymer reaction is the acid base or acid base-containing cyclic olefin copolymer can be obtained.
본 발명에 있어 상기 환형올레핀계 공중합체는 내열성을 올리기 위해서는 환형올레핀 단위가 50몰% 내지 99.9몰%, 좋기로는 70몰% 이상, 더욱 바람직하게는 90몰% 이상 함유하도록 하는 것이 좋고 50몰% 미만일 경우 유연성은 우수하지만 유리전이온도가 너무 낮아질 우려가 있다. In the present invention, the cyclic olefin copolymer is preferably 50 mol% to 99.9 mol%, preferably 70 mol% or more, more preferably 90 mol% or more, in order to increase heat resistance. If less than%, flexibility is excellent, but there is a fear that the glass transition temperature is too low.
본 발명에 의한 환형올레핀계 수지는 극성기간의 강한 2차결합력, 특히 유기산기간의 수소결합, 유기산염기간의 이온성 결합 등 2차결합력에 의해 3차원적 망상구조 형성에 도움이 되어 보다 낮은 열팽창계수 발현이 용이해 질 수 있다는 측면에서 가령 수산기, 아민기, 암모늄기, 에폭시기, 할로겐기, 시아노기, 아세테이트기, 에스테르기, 카르복실산기, 술폰산기, 인산기 등 유기산기, 카르복실산무수물기, 술폰산무수물기, 인산무수물기 등 유기산무수물기, 카르복실산염기, 술폰산염기, 인산염기 등 유기산염기 등과 같은 극성기를 일부 함유하는 것이 바람직하고, 이중에서 유기산기 및 유기산염기가 더욱 바람직하다. The cyclic olefin resin according to the present invention helps to form a three-dimensional network structure by a secondary bonding force such as a strong secondary bonding force in the polar period, especially a hydrogen bond in the organic acid period and an ionic bond in the organic acid salt period, and thus has a lower coefficient of thermal expansion. In terms of ease of expression, for example, hydroxyl groups, amine groups, ammonium groups, epoxy groups, halogen groups, cyano groups, acetate groups, ester groups, organic acid groups such as carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, carboxylic acid anhydride groups, and sulfonic acids It is preferable to contain some polar groups, such as organic acid anhydride groups, such as an anhydride group and an phosphate anhydride group, organic acid groups, such as a carboxylate group, a sulfonate group, and a phosphate group, among which an organic acid group and an organic acid salt group are more preferable.
상기 극성기의 함유량은 0.001～20중량%, 좋기로는 0.01～10중량%가 기판의 낮은 열팽창계수의 발현이 더욱 좋다. The content of the polar group is 0.001 to 20% by weight, preferably 0.01 to 10% by weight, the lower the coefficient of thermal expansion of the substrate is more preferable.
본 발명에 의한 환형올레핀계 수지의 유리전이온도는 200～450℃ 범위의 것, 좋기로는 250～400℃ 범위의 것이 바람직하다. 특히 환형올레핀계 수지의 유리전이온도가 200℃ 미만의 것을 사용할 경우 내열성이 낮아 가령 박막트랜지스터-액정디스플레이(TFT-LCD) 생산시 박막트랜지스터 어레이를 플렉시블 기판위에 구현하는 공정중 치수가 크게 변할 우려가 있어 바람직하지 않고 450℃를 초과한 것을 사용할 경우 내열성은 우수하나 유연성이 부족해질 우려가 있다.The glass transition temperature of the cyclic olefin resin according to the present invention is preferably in the range of 200 to 450 ° C, preferably 250 to 400 ° C. In particular, when the glass transition temperature of the cyclic olefin resin is less than 200 ° C., the heat resistance is low. For example, when producing a thin film transistor-liquid crystal display (TFT-LCD), the size of the thin film transistor array on the flexible substrate may change significantly during the process. There is a possibility that the use of more than 450 ℃ is not preferable because of excellent heat resistance but lack of flexibility.
본 발명에 의한 상기 환형올레핀계 수지의 중량평균분자량은 1,000～1,000,000, 좋기로는 10,000～500,000, 더욱 좋기로는 50,000～300,000이 필름 물성 및 성형성에 있어 바람직하다. The weight average molecular weight of the cyclic olefin resin according to the present invention is preferably 1,000 to 1,000,000, preferably 10,000 to 500,000, more preferably 50,000 to 300,000 in terms of film properties and moldability.
본 발명에 의한 상기 환형올레핀계 수지는 투명성이 필요하지 않는 플렉시블 기판 용도로서도 사용가능하나 대부분의 플렉시블 기판 경우 투명성이 우수한 것이 요구되고 있기 때문에 광투과도는 90% 이상의 것이 좋고 92% 이상의 것이 더욱 바람직하다. 광투과도가 90% 미만일 경우 매우 한정적인 플렉시블 기판 용도로만 사용이 가능하다.The cyclic olefin resin according to the present invention can be used as a flexible substrate that does not require transparency, but since most flexible substrates are required to have excellent transparency, the light transmittance is preferably 90% or more and more preferably 92% or more. . If the light transmittance is less than 90%, it can be used only for very limited flexible substrate applications.
본 발명에 의한 상기 필름은 통상의 용융압출법, 용매케스팅법, 함침법 등에 의해 성형될 수 있는데 제조원가 측면에서 용융압출법이 바람직하다. 얻어진 상기 필름을 통상의 방사선 발생장치를 통해 조사하면 대표적으로 탄소-수소간 결합이 절단되면서 분자사슬내 라디칼이 형성되고 이러한 라디칼간의 결합에 의한 가교반응으로 궁극적으로 3차원적 망상구조를 형성해 본 발명에서 노리는 낮은 열팽창계수를 갖는 최종 플렉시블 기판을 얻을 수 있다. 방사선 조사방법은 뱃치 형태로 조사할 수도 있고 롤투롤 연속상에서 조사할 수도 있는데 제조원가 측면에서 연속상 조사처리가 바람직하다.The film according to the present invention may be molded by a conventional melt extrusion method, a solvent casting method, an impregnation method, etc. The melt extrusion method is preferable in terms of manufacturing cost. When the obtained film is irradiated through a conventional radiation generator, radicals in the molecular chain are typically formed while the carbon-hydrogen bonds are cleaved, and a three-dimensional network structure is ultimately formed by a crosslinking reaction by the bonds between these radicals. Nori can obtain a final flexible substrate having a low coefficient of thermal expansion. Irradiation may be carried out in a batch or roll-to-roll continuous phase. In terms of manufacturing cost, the continuous phase irradiation treatment is preferable.
본 발명에 의한 상기 방사선으로서는 감마선, 전자선, X-선 등을 들 수 있으며 이중 전자선이 바람직하다. 또한 상기 방사선의 조사선량은 1～500kGy, 좋기로는 50～300kGy 범위가 바람직하다. 조사선량이 1kGy 미만일 경우 원하는 가교반응에 의한 3차원적 망상구조 형성 효과가 적어 원하는 낮은 열팽창계수 확보가 곤란하고 조사선량이 500kGy를 초과할 경우 가교반응이 일어날 뿐만 아니라 환형올레핀계 수지의 탄소-탄소간 결합이 절단되어 분자사슬이 과도하게 분해되어 분자량저하에 의한 기계적물성이 떨어지고 황변이 일어날 우려가 있다. As said radiation by this invention, a gamma ray, an electron beam, an X-ray, etc. are mentioned, A double electron beam is preferable. In addition, the radiation dose of the radiation is preferably 1 to 500 kGy, preferably 50 to 300 kGy. If the irradiation dose is less than 1 kGy, it is difficult to secure the desired three-dimensional network structure due to the desired crosslinking reaction, and it is difficult to secure the desired low coefficient of thermal expansion. There is a fear that the bond between the liver is cleaved and the molecular chain is excessively decomposed to deteriorate the mechanical properties due to molecular weight decrease and yellowing occurs.
본 발명에서 목표로 하는 극히 낮은 열팽창계수를 가질 뿐만 아니라 우수한 유연성, 투명성, 등방성 및 높은 유리전이온도를 가지는 플렉시블 기판을 얻기 위해서는 상기 환형올레핀계 수지만을 사용하여 필름을 성형한 후 방사선을 조사시킴으로써 가교반응을 일으킬 수 있다. In order to obtain a flexible substrate having not only an extremely low coefficient of thermal expansion, but also excellent flexibility, transparency, isotropy, and high glass transition temperature aimed at by the present invention, by irradiating radiation after forming a film using only the cyclic olefin resin, May cause crosslinking reaction.
또 다른 방법으로는 가교반응성을 보다 높여 생산성을 높이기 위하여 p-퀴논 다이옥심, p, p'-다이벤조일퀴논 다이옥심, N-메틸-N-4-디니트로소아닐린, 니트로소벤젠, 디페닐구아니딘, 트리메틸올프로페인-N, N'-m-페닐렌디말레이미드, 디비닐벤젠, 트리알릴시아누레이트, 트리알릴이소시아누레이트, 에틸렌글리콜 디메타크릴레이트, 디에틸렌글리콜 디메타크릴레이트, 폴리에틸렌글리콜 디메타크릴레이트, 트리메틸올프로판 트리메타크릴레이트, 알릴메타크릴레이트 등 다작용성 메타크릴레이트 모노머, 비닐뷰틸레이트, 비닐스테아레이트 등 다작용성 비닐 모노머, 아크릴산아연, 아크릴산마그네슘 등 금속아크릴레이트, 메타크릴산아연, 메타크릴산마그네슘 등 금속메타크릴레이트 등과 같은 가교조제를 환형올레핀계 수지에 일부 혼합한 환형올레핀계 수지조성물을 이용하여 기판을 성형하고 방사선을 조사하는 것이다.Another method is p-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenyl Guanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, divinylbenzene, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate , Polyfunctional methacrylate monomers such as polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, polyfunctional vinyl monomers such as vinyl butylate and vinyl stearate, metal acrylates such as zinc acrylate and magnesium acrylate And cyclic olefins in which some crosslinking aids such as metal methacrylates such as zinc methacrylate and magnesium methacrylate are mixed with the cyclic olefin resin. The substrate is molded using a resin composition and irradiated with radiation.
즉 상기 환형올레핀계 수지 100중량부에 대해 가교조제 0.001～20중량부, 좋기로는 0.01～10중량부, 더욱 좋기로는 0.05～5중량부를 혼합한 환형올레핀계 수지조성물을 사용하면 방사선 조사 시 빠른 가교반응 유도 및 높은 가교량에 의해 낮은 열팽창계수 확보가 보다 용이해 질 수 있다. 상기 범위의 가교조제 함량이 원하는 빠르고 충분한 가교반응 촉진효과를 얻을 수 있으며 잉여 미반응된 가교조제가 표면으로 전이되어 고차단성 코팅 등 후공정시 악영향을 끼칠 우려가 없어서 좋다. That is, when using a cyclic olefin resin composition mixed with 0.001 to 20 parts by weight, preferably 0.01 to 10 parts by weight, and more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the cyclic olefin resin, Fast induction of crosslinking reaction and high crosslinking amount make it easier to secure a low coefficient of thermal expansion. The content of the crosslinking aid in the above range can achieve the desired fast and sufficient crosslinking reaction promoting effect, and the excess unreacted crosslinking aid is transferred to the surface so that there is no risk of adverse effects during the post-processing such as high barrier coating.
본 발명에서 라디칼 반응성기가 함유된 환상올레핀계 수지에 대하여 설명하면 다음과 같다. 본 발명에서 목표로 하는 극히 낮은 열팽창계수를 가질 뿐만 아니라 동시에 우수한 유연성, 투명성, 등방성 및 높은 유리전이온도를 가지는 플렉시블 기판을 얻기 위해서는 상기 환형올레핀계 수지와 가교조제와의 수지조성물을 사용하여 필름을 성형한 후 방사선을 조사하여 가교반응성을 보다 높여 생산성을 높일 수 있지만, 또 다른 방법으로서는 상기 환형올레핀계 수지가 아크릴레이트기, 메타아크릴레이트기, 비닐기, 알릴기 등의 라디칼 반응성기가 함유되어 있는 환형올레핀계 수지를 사용하여 필름을 성형한 후 방사선을 조사함으로써 원하는 낮은 열팽창계수를 갖는 플렉시블 기판을 얻을 수 있다.Referring to the cyclic olefin resin containing a radical reactive group in the present invention is as follows. In order to obtain a flexible substrate having not only an extremely low coefficient of thermal expansion, but also excellent flexibility, transparency, isotropy, and high glass transition temperature aimed at by the present invention, a film is prepared using a resin composition of the cyclic olefin resin and a crosslinking aid. After molding, radiation can be irradiated to increase crosslinking reactivity, thereby increasing productivity. As another method, the cyclic olefin resin may contain radical reactive groups such as acrylate, methacrylate, vinyl and allyl groups. By forming a film using a cyclic olefin resin and irradiating with radiation, a flexible substrate having a desired low coefficient of thermal expansion can be obtained.
예를 들어, 아크릴레이트기 또는 메타아크릴레이트기를 함유하는 환형올레핀계 수지를 얻는 방법으로서는 가령 상기 50몰% 이상 환형올레핀 단위와 카르복실산기를 함유하는 화학식(3)으로 표시되는 단위로 구성된 공중합체와 수산기 또는 에폭시기 함유 아크릴레이트계 또는 메타크릴레이트계 화합물을 테트라메틸암모니윰브로마이드, 테트라에틸암모니윰브로마이드 등 4차암모늄염 촉매, 또는 테트라부틸포스포니움브로마이드, 에틸트리페닐포스포니움브로마이드 등 4차포스포니윰염 촉매 존재하에서 반응시킴으로써 얻어질 수 있다. 수산기 함유 아크릴레이트계 또는 메타크릴레이트계 화합물로서는 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 글리세롤(메타)아크릴레이트, 3-클로로-2-히드록시프로필(메타)아크릴레이트, ω-히드록시폴리알킬렌글리콜(메타)아크릴레이트, ω-히드록시폴리카프로락톤(메타)아크릴레이트 등과 같은 수산기 함유 (메타)아크릴산에스테르류를 들 수 있고 이중에서 반응성이 우수하고 가격이 비교적 저렴한 2-히드록시에틸(메타)아크릴레이트가 바람직하며, 에폭시기 함유 아크릴레이트계 또는 메타크릴레이트계 화합물로서는 글리시딜(메타)아크릴레이트, 메틸글리시딜(메타)아크릴레이트, 3,4-에폭시시클로헥실메틸(메타)아크릴레이트, 아지리디닐(메타)아크릴레이트 등과 같은 에폭시기 함유 (메타)아크릴산에스테르류를 들 수 있고 이중에서 반응성이 우수하고 가격이 비교적 저렴한 글리시딜(메타)아크릴레이트가 바람직하다.For example, as a method of obtaining cyclic olefin resin containing an acrylate group or a methacrylate group, the copolymer comprised from the unit represented by General formula (3) containing the said cyclic olefin unit and a carboxylic acid group more than 50 mol%, for example. And hydroxyl or epoxy group-containing acrylate- or methacrylate-based compounds such as quaternary ammonium salt catalysts such as tetramethylammonium bromide and tetraethylammonium bromide, or quaternary compounds such as tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide. It can be obtained by reacting in the presence of a phosphonidium salt catalyst. As hydroxyl-containing acrylate type or methacrylate type compound, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acryl Containing hydroxyl groups such as latex, 3-chloro-2-hydroxypropyl (meth) acrylate, ω-hydroxypolyalkylene glycol (meth) acrylate, ω-hydroxypolycaprolactone (meth) acrylate, and the like (meth) 2-hydroxyethyl (meth) acrylate is preferred among which acrylic acid esters are excellent, and the reactivity is relatively low and the price is relatively low. As the epoxy group-containing acrylate or methacrylate compound, glycidyl (meth) acryl Epoxy groups such as acrylate, methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, aziridinyl (meth) acrylate, and the like The containing (meth) acrylic acid ester is mentioned, The glycidyl (meth) acrylate which is excellent in reactivity and comparatively low in price is preferable.
상기 비교적 저분자인 가교조제를 환형올레핀계 수지에 첨가하여 가교하는 경우에는 방법적으로는 간단하지만 방사선 조사 후 잉여 미반응 가교조제가 존재할 가능성이 있어 표면전이 등 여러 품질적 문제가 우려되지만 반면 상기 아크릴레이트기, 메타아크릴레이트기 등과 같은 치환체를 가지는 환형올레핀계 수지를 사용할 경우에는 가교조제의 역할을 할 수 있는 아크릴레이트기, 메타아크릴레이트기 등이 분자사슬내 고정되어 함유된 형태인 관계로 표면전이 등 문제가 전혀 발생하지 않은 우수한 효과를 얻을 수 있어서 더욱 바람직한 방법이라 할 수 있다. In the case of crosslinking by adding the relatively low molecular weight crosslinking aid to the cyclic olefin resin, there is a possibility that a surplus unreacted crosslinking aid may exist after irradiation, which may cause various quality problems such as surface transition. When using a cyclic olefin resin having a substituent such as a acrylate group or a methacrylate group, the acrylate group and the methacrylate group, which may serve as a crosslinking aid, are fixed and contained in the molecular chain. It can be said to be a more preferable method since it can obtain the outstanding effect that the problem, such as a transition, does not occur at all.
상기 환형올레핀계 수지 내 함유된 아크릴레이트기, 메타아크릴레이트기, 비닐기, 알릴기 등의 라디칼 반응성기의 함유량은 0.001～20중량%, 좋기로는 0.01～10중량%가 바람직하다. 0.001중량% 미만일 경우 원하는 빠르고 충분한 가교반응 촉진효과를 기대하기 어렵고 20중량부를 초과할 경우 가교밀도가 너무 높아져 필름수축이 과도해지고 유연성이 손상될 우려가 있다. The content of radical reactive groups such as acrylate group, methacrylate group, vinyl group and allyl group contained in the cyclic olefin resin is preferably 0.001 to 20% by weight, preferably 0.01 to 10% by weight. If it is less than 0.001% by weight, it is difficult to expect the desired fast and sufficient crosslinking reaction promoting effect. If it exceeds 20 parts by weight, the crosslinking density may be too high, resulting in excessive film shrinkage and impaired flexibility.
한편 플렉시블 기판의 내열성을 보다 올리는 또 다른 방법으로써 상기 다양한 양태의 환형올레핀계 수지 및 상기 환형올레핀계 수지조성물에 무기입자를 일부 혼합한 복합 수지조성물을 사용하여 필름을 성형한 후 방사선을 조사시킴으로써 가교반응을 일으킬 수도 있다. 무기입자로서는 탄산칼슘, 탈크, 클레이, 카올린, 실리카, 규조토, 탄산마그네슘, 염화칼슘, 황산칼슘, 수산화알미늄, 산화아연, 수산화마그네슘, 산화티탄, 알루미나, 마이카, 아스베스토스, 제오라이트, 규산백토, 바륨티타네이트, 유리섬유 등을 들 수 있고 구형, 판형, 섬유형, 휘스커형, 무정형 어느 형상의 것도 가능하고, 무기입자의 첨가량은 상기 환상올레핀계 수지 100중량부에 대해 0.001～20중량부, 좋기로는 0.01～5중량부 첨가하는 것이 바람직하다. 무기입자의 첨가량이 20중량부를 초과할 경우는 내열성은 우수해지나 투명성이 매우 나빠질 우려가 있다. 무기입자의 평균입경(섬유상은 단축)은 10nm～1,000nm, 좋기로는 20nm～500nm의 것이 바람직하며 10nm 미만일 경우는 분산이 어렵고 1,000nm를 초과할 경우 투명성을 손상할 우려가 있다. On the other hand, as another method of further increasing the heat resistance of the flexible substrate, the film is formed using a cyclic olefin resin of various embodiments and a composite resin composition in which inorganic particles are partially mixed with the cyclic olefin resin composition and then crosslinked by irradiating with radiation. It may cause a reaction. As inorganic particles, calcium carbonate, talc, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, calcium chloride, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, titanium oxide, alumina, mica, asbestos, zeolite, white silicate, barium titanate And glass fibers and the like, and may be any of spherical, plate, fibrous, whisker and amorphous forms, and the amount of inorganic particles added is 0.001 to 20 parts by weight, preferably 100 parts by weight of the cyclic olefin resin. It is preferable to add 0.01-5 weight part. When the amount of the inorganic particles added exceeds 20 parts by weight, the heat resistance may be excellent, but the transparency may be very poor. The average particle diameter (shorter fiber phase) of the inorganic particles is preferably 10 nm to 1,000 nm, preferably 20 nm to 500 nm. If it is less than 10 nm, dispersion is difficult and if it exceeds 1,000 nm, transparency may be impaired.
본 발명에 의한 환형올레핀계 수지로 성형된 필름의 두께는 용도별 그 두께를 달리할 수 있는데 10～300μm 범위의 것이 바람직하다. 10μm 미만일 경우 기계적 물성이 취약해질 우려가 있고 300μm를 초과할 경우 경량 박막 플렉시블 디스플레이 소재라는 취지에 맞지 않고 경제성이 나빠질 우려가 있다. The thickness of the film molded from the cyclic olefin resin according to the present invention may vary in thickness depending on the use, but is preferably in the range of 10 to 300 μm. If it is less than 10μm, mechanical properties may be weak, and if it is more than 300μm, it is not suitable for the purpose of a lightweight thin film flexible display material and the economy may be deteriorated.
또한 본 발명의 목적을 손상시키지 않는 범위에서 환형올레핀계 수지내에 산화방지제, 자외선차단제, 윤활제 등 통상의 첨가제를 처방할 수 있다. In addition, conventional additives such as antioxidants, sunscreens, lubricants, and the like can be prescribed in the cyclic olefin resin within the scope of not impairing the object of the present invention.
전술한 바와 같이 본 발명에 의한 환형올레핀계 수지 또는 환형올레핀계 수지조성물로 성형된 필름에 방사선을 조사하여 얻어진 필름 경우 3차원적 망상구조를 형성하여 극히 낮은 열팽창계수를 발휘함은 물론 종래 환형올레핀계 수지의 장점인 우수한 유연성, 투명성, 등방성 및 높은 유리전이온도를 동시에 가지는 실로 획기적인 것으로 이렇게 얻어진 플렉시블 기판은 플렉시블 디스플레이, 플렉시블 태양전지 등 여러 분야에 유용하게 사용될 수 있다.
As described above, in the case of a film obtained by irradiating a film formed of the cyclic olefin resin or the cyclic olefin resin composition according to the present invention with a radiation, a three-dimensional network structure forms an extremely low coefficient of thermal expansion, as well as a conventional cyclic olefin. It is a breakthrough that has excellent flexibility, transparency, isotropy, and high glass transition temperature, which are advantages of the resin, and thus the flexible substrate can be usefully used in various fields such as a flexible display and a flexible solar cell.
본 발명에 의한 환형올레핀계 수지 또는 환형올레핀계 수지조성물로 성형된 필름에 방사선을 조사하여 얻어진 필름 경우 3차원적 망상구조를 형성하여 극히 낮은 열팽창계수를 발휘함은 물론 종래 환형올레핀계 수지의 장점인 우수한 유연성, 투명성, 등방성 및 높은 유리전이온도를 동시에 가지는 실로 획기적인 것으로 이렇게 얻어진 플렉시블 기판은 플렉시블 디스플레이, 플렉시블 태양전지 등 여러 분야에 유용하게 사용될 것으로 전망된다.
In the case of a film obtained by irradiating a film formed from a cyclic olefin resin or a cyclic olefin resin composition according to the present invention, a three-dimensional network structure is formed to exhibit an extremely low coefficient of thermal expansion, as well as advantages of conventional cyclic olefin resins. It is a breakthrough that has excellent flexibility, transparency, isotropy, and high glass transition temperature. The flexible substrate thus obtained is expected to be useful in various fields such as flexible displays and flexible solar cells.
이하 실시예를 통하여 본 발명을 보다 자세히 설명하고자 한다. 하기의 실시예는 하나의 예시일 뿐 실시예에 한정하지 않는다.Through the following examples will be described in more detail the present invention. The following examples are merely examples and are not limited to the examples.
하기 실시예 및 비교예에 따라 제조된 환형올레핀계 수지 또는 환형올레핀계 수지조성물로부터 얻어진 필름 시편에 대한 열팽창계수, 유연성, 투명성, 등방성 및 유리전이온도를 다음과 같이 측정하였다.
The coefficient of thermal expansion, flexibility, transparency, isotropy and glass transition temperature of the film specimens obtained from the cyclic olefin resins or the cyclic olefin resin compositions prepared according to the following Examples and Comparative Examples were measured as follows.
(열팽창계수)(Coefficient of Thermal Expansion)
내열성에 대한 척도로서 TMA(Thermomechanical analyzer)에서 필름 시편에 대한 열팽창계수(ppm/℃)를 측정하였다.As a measure of heat resistance, the coefficient of thermal expansion (ppm / ° C.) of the film specimens was measured by a TMA (Thermomechanical Analyzer).
(유연성)(flexibility)
유연성의 척도로서 두께 100μm의 필름 시편을 굴곡시험기에 장착한 후 10,000회 반복 일정 직경으로 굴곡시킨 후에도 손상이 없을 때의 최대 직경(mm)을 기준하여 하기와 같이 평가였다.
As a measure of flexibility, the film specimens having a thickness of 100 μm were mounted on the flexure tester, and then evaluated as follows based on the maximum diameter (mm) when no damage was observed even after bending to 10,000 repeated constant diameters.
(표 1)유연성의 평가 기준 Table 1 Evaluation criteria of flexibility
(투명성)(Transparency)
투명성에 대한 척도로서 ASTM D1003에 준하여 Hazemeter를 이용하여 필름 시편에 대한 광투과도(%)를 측정하였다.As a measure of transparency, the light transmittance (%) of the film specimens was measured using a Hazemeter according to ASTM D1003.
(등방성)(Isotropic)
등방성에 대한 척도로서 위상차측정장치(OJI계측기기, KOBRA-WR)을 이용해 필름 시편에 대한 복굴절(nm)을 평가하였다. As a measure for isotropy, birefringence (nm) for film specimens was evaluated using a retardation measuring device (OJI measuring instrument, KOBRA-WR).
(유리전이온도)(Glass transition temperature)
내열성에 대한 척도로서 DSC(Differential Scanning Calorimeter)에서 필름 시편에 대한 유리전이온도(℃)를 측정하였다. The glass transition temperature (° C.) for the film specimens was measured on a differential scanning calorimeter (DSC) as a measure for heat resistance.
(실시예 1)(Example 1)
먼저 단량체로서 노르보르넨과 헥세닐디이소부틸알루미늄을 준비하였다. 교반기가 장착된 50L의 반응기에 톨루엔을 25L 넣은 다음 촉매인 [Ph3C][B(C6F5)4]를 25mmol, [t-BuNSiMe2Flu] 25mmol과 단량체인 노르보르넨 90몰%와 공단량체인 헥세닐디이소부틸알루미늄 10몰%의 조성비로서 반응기에 넣고 반응온도를 40℃로 유지하면서 40분간 중합반응을 실시하여 노르보르넨-헥세닐디이소부틸알루미늄 공중합체(A1)를 얻었다. 얻어진 노르보르넨-헥세닐디이소부틸알루미늄 공중합체(A1)를 염산과 메탄올과의 혼합물에 침전시키고 여과한 후 몇회 적당히 메탄올로 세척한 다음 60℃에서 8시간 감압건조하여 환형올레핀계 수지중 하나인 중량평균분자량 125,000의 노르보르넨-1-헥센 공중합체(A)를 얻었다. 얻어진 노르보르넨-1-헥센 공중합체(A)를 용매 클로로벤젠에 20중량% 농도로 녹인 용액을 글래스 위에 캐스팅하고 용매를 건조함으로서 두께 100μm의 필름(FA)을 성형하였다. 얻어진 필름(FA)에 0.8～1.5MeV의 전자가속기(이비테크, ELV-2)에서 50kGy로 조사하여 최종 필름(FA-1) 시편을 얻었고 이 필름(FA-1) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다.First, norbornene and hexenyldiisobutylaluminum were prepared as monomers. 25 L of toluene was added to a 50 L reactor equipped with a stirrer, and then 25 mmol of [Ph 3 C] [B (C 6 F 5 ) 4 ], a catalyst, 25 mmol of [t-BuNSiMe 2 Flu], and 90 mol% of norbornene as a monomer. And a normoene-hexenyldiisobutylaluminum copolymer (A1) was added to the reactor at a composition ratio of 10 mol% of hexenyldiisobutylaluminum as a comonomer, and the polymerization reaction was carried out for 40 minutes while maintaining the reaction temperature at 40 ° C. Got it. The obtained norbornene-hexenyldiisobutylaluminum copolymer (A1) was precipitated in a mixture of hydrochloric acid and methanol, filtered and washed several times with methanol, and then dried under reduced pressure at 60 ° C. for 8 hours to form one of the cyclic olefin resins. The norbornene-1-hexene copolymer (A) of phosphorus weight average molecular weight 125,000 was obtained. The solution (N) obtained by dissolving the obtained norbornene-1-hexene copolymer (A) in 20 wt% concentration in solvent chlorobenzene was cast on glass and dried to form a film (FA) having a thickness of 100 μm. The resulting film (FA) was irradiated with 50 kGy at 0.8 to 1.5 MeV electron accelerator (Ebi-Tech, ELV-2) to obtain the final film (FA-1) specimen, and the coefficient of thermal expansion and flexibility for the film (FA-1) specimen , Light transmittance, birefringence and glass transition temperature were evaluated and the results are shown in Table 2.
(실시예 2)(Example 2)
실시예 1에서 얻어진 필름(FA)에 120kGy로 조사한 것외에는 실시예 1과 같은 방법으로 실시하여 최종 필름(FA-2)시편을 얻었고 이 필름(FA-2) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다.Except that the film FA obtained in Example 1 was irradiated at 120 kGy, the same procedure as in Example 1 was carried out to obtain a final film FA-2 specimen, and the coefficient of thermal expansion, flexibility, and light for this film FA-2 specimen. Permeability, birefringence and glass transition temperature were evaluated and the results are shown in Table 2.
(실시예 3)(Example 3)
실시예 1에서 얻어진 필름(FA)에 200kGy로 조사한 것외에는 실시예 1과 같은 방법으로 실시하여 최종 필름(FA-3) 시편을 얻었고 이 필름(FA-3) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다.Except that the film FA obtained in Example 1 was irradiated at 200 kGy, the same procedure as in Example 1 was carried out to obtain a final film (FA-3) specimen, and the coefficient of thermal expansion, flexibility, and light for this film (FA-3) specimen. Permeability, birefringence and glass transition temperature were evaluated and the results are shown in Table 2.
(실시예 4)(Example 4)
실시예 1에서 얻어진 노르보르넨-헥세닐디이소부틸알루미늄 공중합체(A1)에 건조 산소 1.5L를 상온에서 2시간동안 서서히 주입하여 헥세닐디이소부틸알루미늄 화합물 단위에 함유된 디이소부틸알루미늄기의 완전한 가수분해반응을 진행시킨 뒤 메탄올에 침전시키고 여과한 후 몇회 적당히 메탄올로 세척한 다음 60℃에서 8시간 감압건조하여 환형올레핀계 수지중 하나인 중량평균분자량 127,000의 수산기 1.1중량% 함유 노르보르넨-1-헥센 공중합체(B)를 얻었다. 얻어진 수산기 함유 노르보르넨-1-헥센 공중합체(B)를 용매 클로로벤젠에 20중량% 농도로 녹인 용액을 글래스 위에 캐스팅하고 용매를 건조함으로서 두께 100μm의 필름을 성형하였다. 얻어진 필름에 0.8～1.5MeV의 전자가속기(이비테크, ELV-2)에서 120KGy로 조사하여 최종 필름(FB-1) 시편을 얻었고 이 필름(FB-1) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다. The diisobutyl aluminum group contained in the hexenyl diisobutyl aluminum compound unit by gradually injecting 1.5 L of dry oxygen at room temperature for 2 hours into the norbornene-hexenyl diisobutyl aluminum copolymer (A1) obtained in Example 1 at room temperature. After the complete hydrolysis reaction, precipitated in methanol, filtered and washed several times with methanol, and then dried under reduced pressure at 60 ° C. for 8 hours under a weight-average molecular weight of 127,000, which is one of the cyclic olefin resins, containing 1.1% by weight of hydroxyl group Norbor Nene-1-hexene copolymer (B) was obtained. A film having a thickness of 100 μm was formed by casting a solution obtained by dissolving the obtained hydroxyl group-containing norbornene-1-hexene copolymer (B) in a solvent chlorobenzene at a concentration of 20% by weight on glass and drying the solvent. The resulting film was irradiated with 120KGy in 0.8 ~ 1.5MeV electron accelerator (EBTECH, ELV-2) to obtain the final film (FB-1) specimen, and the coefficient of thermal expansion, flexibility, and light transmittance of this film (FB-1) specimen , Birefringence and glass transition temperature were evaluated and the results are shown in Table 2.
(실시예 5)(Example 5)
먼저 단량체로서 노르보르넨과 옥테닐디이소부틸알루미늄을 준비하였다. 교반기가 장착된 50L의 반응기에 톨루엔을 25L 넣은 다음 촉매인 [Ph3C][B(C6F5)4]를 23mmol, [t-BuNSiMe2Flu] 23mmol과 단량체인 노르보르넨 92몰%와 공단량체인 옥테닐디이소부틸알루미늄 8몰%의 조성비로서 반응기에 넣고 반응온도를 40℃로 유지하면서 50분간 중합반응을 실시하여 노르보르넨-옥테닐디이소부틸알루미늄 공중합체 수지(C1)를 얻었다. 다음 이어서 반응기내에 과량의 10L 이산화탄소를 서서히 주입하여 옥테닐디이소부틸알루미늄 화합물 단위에 함유된 디이소부틸알루미늄기의 완전한 가수분해반응을 진행시킨 뒤 메탄올에 침전시키고 여과한 후 몇회 적당히 메탄올로 세척한 다음 60℃에서 8시간 감압건조하여 중량평균분자량 129,000의 카르복실산기 2.6중량% 함유 노르보르넨-1-옥텐 공중합체(C)를 얻었다. 얻어진 카르복실산기 함유 환형올레핀계 공중합체(C)를 실시예 4와 같은 방법으로 용매캐스팅으로 필름을 제조하고 전자가속기에서 120kGy로 조사하여 최종 두께 100μm의 필름(FC-1) 시편을 얻었고 이 필름(FC-1) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다. First, norbornene and octenyldiisobutylaluminum were prepared as monomers. 25 L of toluene was added to a 50 L reactor equipped with a stirrer, followed by 23 mmol of [Ph 3 C] [B (C 6 F 5 ) 4 ] as a catalyst, 23 mmol of [t-BuNSiMe 2 Flu] and 92 mol% of norbornene as a monomer. And 8% by mole of octenyldiisobutylaluminum as a comonomer was added to the reactor and polymerization was carried out for 50 minutes while maintaining the reaction temperature at 40 ° C. to obtain norbornene-octenyldiisobutylaluminum copolymer resin (C1). . Subsequently, an excess of 10L carbon dioxide was slowly injected into the reactor to proceed with complete hydrolysis of the diisobutylaluminum group contained in the octenyldiisobutylaluminum compound unit, precipitated in methanol, filtered and washed with methanol several times. It dried under reduced pressure at 60 degreeC for 8 hours, and obtained the norbornene-1-octene copolymer (C) containing 2.6 weight% of carboxylic acid groups of the weight average molecular weight 129,000. The obtained carboxylic acid group-containing cyclic olefin copolymer (C) was prepared by solvent casting in the same manner as in Example 4 and irradiated with 120 kGy in an electron accelerator to obtain a film (FC-1) specimen having a final thickness of 100 μm. The coefficient of thermal expansion, flexibility, light transmittance, birefringence and glass transition temperature for (FC-1) specimens were evaluated and the results are shown in Table 2.
(실시예 6)(Example 6)
실시예 5에서 얻어진 노르보르넨-옥테닐디이소부틸알루미늄 공중합체 수지(C1)에 과량의 삼산화황을 상온에서 1.7시간동안 서서히 주입하여 옥테닐디이소부틸알루미늄 화합물 단위에 함유된 디이소부틸알루미늄기의 완전한 가수분해반응을 진행시킨 뒤 메탄올에 침전시키고 여과한 후 몇회 적당히 메탄올로 세척한 다음 60℃에서 8시간 감압건조하여 환형올레핀계 수지중 하나인 중량평균분자량 131,000의 설폰산기 4.6중량% 함유 노르보르넨-1-옥텐 공중합체(D)를 얻었다. 얻어진 설폰산기 함유 환형올레핀계 공중합체(D)를 실시예 4와 같은 방법으로 용매캐스팅으로 필름을 제조하고 전자가속기에서 100kGy로 조사하여 최종 두께 100μm의 필름(FD-1) 시편을 얻었고 이 필름(FD-1) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다. The norbornene-octenyldiisobutylaluminum copolymer resin (C1) obtained in Example 5 was slowly injected with an excess of sulfur trioxide at room temperature for 1.7 hours to complete the diisobutylaluminum group contained in the octenyldiisobutylaluminum compound unit. After the hydrolysis reaction was carried out, precipitated in methanol, filtered, washed several times with methanol, and then dried under reduced pressure at 60 ° C. for 8 hours under reduced pressure for 8 hours, containing 4.6% by weight of a sulfonic acid group having a weight average molecular weight of 131,000, which is one of the cyclic olefin resins, norbornene The 1-octene copolymer (D) was obtained. The obtained sulfonic acid group-containing cyclic olefin copolymer (D) was prepared by solvent casting in the same manner as in Example 4 and irradiated at 100 kGy in an electron accelerator to obtain a film (FD-1) specimen having a final thickness of 100 μm. FD-1) The coefficient of thermal expansion, flexibility, light transmittance, birefringence and glass transition temperature for the specimens were evaluated and the results are shown in Table 2.
(실시예 7)(Example 7)
실시예 5에서 얻어진 카르복실산기 함유 노르보르넨-1-옥텐 공중합체(C) 90중량부와 산화아연 10중량부로 혼합한 조성물을 L/D 70인 이축압출기에서 혼련시켜 산화아연 마스터뱃치를 준비하였다. 이어서 상기 카르복실산기 2.6중량% 함유 노르보르넨-1-옥텐 공중합체(C) 100중량부에 대해 산화아연 마스터뱃치 10중량부를 혼합한 조성물을 호퍼에 투입하여 스크류 직경 70mm이고, L/D 70인 이축 압출기에 주입하고 용융 압출 중화반응을 시켜 중화도 65%의 카르복실산아연염기 함유 노르보르넨-1-옥텐 공중합체(E)를 제조하였다. 얻어진 중화도 65%의 카르복실산아연염기 함유 노르보르넨-1-옥텐 공중합체(E) 펠렛을 호퍼에 투입하여 스크류 직경 70mm이고, L/D 36인 압출기에 주입하고 용융 압출시켜 티다이를 통해 필름을 제조하고 전자가속기에서 90kGy로 조사하여 최종 두께 100μm의 필름(FE-1) 시편을 얻었고 이 필름(FE-1) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다. 90 parts by weight of the carboxylic acid group-containing norbornene-1-octene copolymer (C) obtained in Example 5 and 10 parts by weight of zinc oxide were kneaded in a twin screw extruder of L / D 70 to prepare a zinc oxide masterbatch. It was. Subsequently, a composition in which 10 parts by weight of a zinc oxide masterbatch was mixed with respect to 100 parts by weight of the norbornene-1-octene copolymer (C) containing 2.6% by weight of the carboxylic acid group was introduced into a hopper to have a screw diameter of 70 mm, and an L / D 70 ratio. The norbornene-1-octene copolymer (E) containing zinc carboxylate having a degree of neutralization of 65% was prepared by injection into a phosphorus twin screw extruder and subjected to melt extrusion neutralization. The obtained carboxylic acid zinc-base containing norbornene-1-octene copolymer (E) pellet having a degree of neutralization of 65% was introduced into a hopper, injected into an extruder having a screw diameter of 70 mm and L / D 36, melt-extruded, and passed through a T-die. A film was prepared and irradiated with 90 kGy in an electron accelerator to obtain a film (FE-1) specimen having a final thickness of 100 μm. The thermal expansion coefficient, flexibility, light transmittance, birefringence and glass transition temperature for the film (FE-1) specimens were evaluated. The results are shown in Table 2.
(실시예 8)(Example 8)
실시예 5에서 얻어진 카르복실산기 2.6중량% 함유 노르보르넨-1-옥텐 공중합체(C) 100중량부에 대해 가교조제로서 메타크릴산마그네슘 1중량부로 혼합한 수지조성물을 호퍼에 투입하여 스크류 직경 70mm이고, L/D 36인 압출기에 주입하고 용융 압출시켜 티다이를 통해 필름을 제조하고 전자가속기에서 80kGy로 조사하여 최종 두께 100μm의 필름(FF-1) 시편을 얻었고 이 필름(FF-1) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다. The resin composition mixed with 1 weight part of magnesium methacrylate as a crosslinking aid with respect to 100 weight part of 2.6 weight% containing carboxylic acid groups containing 2.6 weight% of carboxylic acid groups obtained in Example 5 was put into a hopper, and screw diameter 70 mm, L / D 36 was injected into an extruder and melt-extruded to prepare a film through a T-die and irradiated at 80 kGy in an electron accelerator to obtain a film (FF-1) specimen having a final thickness of 100 μm. The coefficient of thermal expansion, flexibility, light transmittance, birefringence, and glass transition temperature were evaluated for the results. Table 2 shows the results.
(실시예 9)(Example 9)
실시예 5에서 얻어진 카르복실산기 2.6중량% 함유 노르보르넨-1-옥텐 공중합체(C) 100중량부에 대해 가교조제로서 아크릴산아연 0.5중량부로 혼합한 수지조성물을 호퍼에 투입하여 스크류 직경 70mm이고, L/D 36인 압출기에 주입하고 용융 압출시켜 티다이를 통해 필름을 제조하고 전자가속기에서 50kGy로 조사하여 최종 두께 100 μm의 필름(FG-1) 시편을 얻었고 이 필름(FG-1) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다. A resin composition mixed with 0.5 parts by weight of zinc acrylate as a crosslinking aid with respect to 100 parts by weight of a 2.6 wt% carboxylic acid group-containing norbornene-1-octene copolymer (C) obtained in Example 5 was introduced into a hopper with a screw diameter of 70 mm. , L / D 36 was injected into an extruder and melt-extruded to prepare a film through a T-die and irradiated at 50 kGy in an electron accelerator to obtain a film (FG-1) specimen having a final thickness of 100 μm. The coefficient of thermal expansion, flexibility, light transmittance, birefringence and glass transition temperature were evaluated. The results are shown in Table 2.
(실시예 10)(Example 10)
교반기가 장착된 10L의 반응기에 상기 실시예 5에서 얻어진 카르복실산기 2.6중량% 함유 노르보르넨-1-옥텐 공중합체(C) 1kg를 넣고 테트라히드로푸란 4L를 첨가하고 교반하여 용해시켰다. 여기에 글리시딜메타크릴레이트 12g, 테트라에틸암모니윰브로마이드 0.02g을 투입하고 50℃, 40시간 반응시킨 뒤 메탄올에 침전시키고 여과한 후 몇회 적당히 메탄올로 세척한 다음 60℃에서 8시간 감압건조하여 중량평균분자량 135,000의 메타크릴레이트기 2.5중량% 함유 노르보르넨-1-옥텐 공중합체(F)를 얻었다. 얻어진 메타크릴레이트기 함유 노르보르넨-1-옥텐 공중합체(F) 펠렛을 호퍼에 투입하여 스크류 직경 70mm이고, L/D 36인 압출기에 주입하고 용융 압출시켜 티다이를 통해 필름을 제조하고 전자가속기에서 50kGy로 조사하여 최종 두께 100μm의 필름(FH-1) 시편을 얻었고 이 필름(FH-1) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다. 1 kg of the norbornene-1-octene copolymer (C) containing 2.6 wt% of the carboxylic acid group obtained in Example 5 was added to a 10 L reactor equipped with a stirrer, and 4 L of tetrahydrofuran was added and stirred to dissolve. 12 g of glycidyl methacrylate and 0.02 g of tetraethylammonium bromide were added thereto, reacted at 50 ° C. for 40 hours, precipitated in methanol, filtered, washed several times with methanol, and then dried under reduced pressure at 60 ° C. for 8 hours. The norbornene-1-octene copolymer (F) containing 2.5 weight% of methacrylate groups of the weight average molecular weight 135,000 was obtained. The obtained methacrylate group-containing norbornene-1-octene copolymer (F) pellets were introduced into a hopper, injected into an extruder having a screw diameter of 70 mm and L / D 36, melt-extruded to prepare a film through a Ti-die, and an electron accelerator. The film (FH-1) specimen with final thickness of 100μm was obtained by irradiating at 50kGy at, and the coefficient of thermal expansion, flexibility, light transmittance, birefringence and glass transition temperature for the film (FH-1) specimens were evaluated. Indicated.
(실시예 11)(Example 11)
교반기가 장착된 10L의 반응기에 상기 실시예 5에서 얻어진 카르복실산기 함유 노르보르넨-1-옥텐 공중합체(C) 1kg, 2-히드록시에틸아크릴레이트 20g, 테트라부틸포스포니움브로마이드 0.05g의 조성으로 조정한 것외에는 실시예 9와 동일하게 실시하여 중량평균분자량 133,000의 아크릴레이트기 1.8중량% 함유 노르보르넨-1-옥텐 공중합체(G)를 얻었다. 얻어진 아크릴레이트기 함유 노르보르넨-1-옥텐 공중합체(G)를 실시예 4와 같은 방법으로 용매캐스팅으로 필름을 제조하고 전자가속기에서 40kGy로 조사하여 최종 두께 100μm의 필름(FI-1) 시편을 얻었고 이 필름(FI-1) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다. 1 kg of carboxylic acid group-containing norbornene-1-octene copolymer (C) obtained in Example 5, 20 g of 2-hydroxyethyl acrylate, and 0.05 g of tetrabutylphosphonium bromide were added to a 10 L reactor equipped with a stirrer. Except having adjusted to the composition, it carried out similarly to Example 9 and obtained the 1.8 weight% containing norbornene-1-octene copolymer (G) of the acrylate group of the weight average molecular weight 133,000. The obtained acrylate group-containing norbornene-1-octene copolymer (G) was prepared by solvent casting in the same manner as in Example 4 and irradiated with 40 kGy in an electron accelerator to film (FI-1) specimen having a final thickness of 100 μm. The coefficient of thermal expansion, flexibility, light transmittance, birefringence and glass transition temperature for the film (FI-1) specimens were evaluated and the results are shown in Table 2.
(실시예 12)(Example 12)
교반기가 장착된 10L의 반응기에 상기 실시예 7에서 얻어진 중화도 65%의 카르복실산아연염기 함유 노르보르넨-1-옥텐 공중합체(E) 1kg, 2-히드록시에틸아크릴레이트 7g, 테트라부틸포스포니움브로마이드 0.02g의 조성으로 조정한 것외에는 실시예 9와 동일하게 실시하여 카르복실산아염염기 및 아크릴레이트기 함유 노르보르넨-1-옥텐 공중합체(H)를 얻었다. 얻어진 카르복실산아염염기 및 아크릴레이트기 함유 노르보르넨-1-옥텐 공중합체(H)를 실시예 4와 같은 방법으로 용매캐스팅으로 필름을 제조하고 전자가속기에서 25kGy로 조사하여 최종 두께 100μm의 필름(FJ-1) 시편을 얻었고 이 필름(FJ-1) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다. In a 10 L reactor equipped with a stirrer, 1 kg of a norbornene-1-octene copolymer (E) containing zinc carboxylate having a neutralization degree of 65% obtained in Example 7, 7 g of 2-hydroxyethyl acrylate, and tetrabutyl Except having adjusted to the composition of phosphonium bromide 0.02g, it carried out similarly to Example 9, and obtained the carboxylate salt group and the acrylate group containing norbornene-1-octene copolymer (H). The obtained carboxylic acid salt base and the acrylate group-containing norbornene-1-octene copolymer (H) were prepared by solvent casting in the same manner as in Example 4 and irradiated with 25 kGy in an electron accelerator to obtain a film having a final thickness of 100 μm. (FJ-1) specimens were obtained, and the coefficient of thermal expansion, flexibility, light transmittance, birefringence and glass transition temperature for the film (FJ-1) specimens were evaluated and the results are shown in Table 2.
(실시예 13)(Example 13)
먼저 단량체로서 5-노르보르넨-2-카복실릭산 메틸에스테르를 준비하였다. 교반기가 장착된 250L의 반응기에 상기 5-노르보르넨-2-카복실릭산 메틸에스테르(10L)와 톨루엔 20L를 상온에서 넣고 반응 온도를 80℃로 올렸다. 80℃에서 Pd(acetylacetonate)2/디메틸아닐리늄 테트라키스(펜타플루오로페닐)보레이트/트리시클로헥실포스핀(몰비, 1/2/1) 혼합촉매를 단량체용액에 투입하고 18시간동안 반응시켰다. 18시간 반응 후에 50L 톨루엔을 넣어 굳어진 중합체를 녹인 후, 과량의 메탄올에 투입하여 침전시키고 여과한 후 몇회 적당히 메탄올로 세척한 다음 60℃에서 8시간 감압건조하여 환형올레핀계 수지중 하나인 중량평균분자량 275,000의 5-노르보르넨-2-카르복실릭산 메틸에스테르 단독중합체(I)를 얻었다. 얻어진 5-노르보르넨-2-카르복실릭산 메틸에스테르 단독중합체(I))를 실시예 1과 같은 방법으로 용매캐스팅으로 필름을 제조하고 전자가속기에서 50kGy로 조사하여 최종 두께 100μm의 필름(FK-1) 시편을 얻었고 이 필름(FK-1) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다. First, 5-norbornene-2-carboxylic acid methyl ester was prepared as a monomer. The 5-norbornene-2-carboxylic acid methyl ester (10L) and toluene 20L were put in a 250L reactor equipped with a stirrer at room temperature, and the reaction temperature was raised to 80 ° C. Pd (acetylacetonate) 2 / dimethylanilinium tetrakis (pentafluorophenyl) borate / tricyclohexylphosphine (molar ratio, 1/2/1) mixed catalyst was added to the monomer solution at 80 ° C. and reacted for 18 hours. After 18 hours of reaction, 50L toluene was added to dissolve the solidified polymer, and the precipitate was added to excess methanol, precipitated, filtered, washed several times with methanol, and then dried under reduced pressure at 60 ° C for 8 hours to obtain one of the cyclic olefin resins. 275,000 5-norbornene-2-carboxylic acid methyl ester homopolymer (I) was obtained. The obtained 5-norbornene-2-carboxylic acid methyl ester homopolymer (I)) was prepared by solvent casting in the same manner as in Example 1 and irradiated with 50 kGy in an electron accelerator to obtain a film having a final thickness of 100 μm (FK- 1) Specimens were obtained and the coefficient of thermal expansion, flexibility, light transmittance, birefringence and glass transition temperature for this film (FK-1) specimens were evaluated and the results are shown in Table 2.
(실시예 14)(Example 14)
상기 실시예 13에서 얻어진 5-노르보르넨-2-카르복실릭산 메틸에스테르 단독중합체(I)) 100중량부에 대해 무기입자로서 평균입경 20nm의 실리카 4.5중량부로 혼합한 수지조성물을 호퍼에 투입하여 스크류 직경 70mm이고, L/D 50인 이축압출기에서 컴파운딩하여 복합수지조성물 펠렛을 얻었다. 얻어진 펠렛을 스크류 직경 70mm이고, L/D 36인 압출기에 주입하고 용융 압출시켜 티다이를 통해 필름을 제조하고 전자가속기에서 50kGy로 조사하여 최종 두께 100 μm의 필름(FL-1) 시편을 얻었고 이 필름(FL-1) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다. Resin composition mixed with 4.5 parts by weight of silica having an average particle diameter of 20 nm as an inorganic particle was added to 100 parts by weight of 5-norbornene-2-carboxylic acid methyl ester homopolymer (I) obtained in Example 13. Compound resin pellets were obtained by compounding in a twin screw extruder having a screw diameter of 70 mm and L / D 50. The obtained pellet was injected into an extruder with a screw diameter of 70 mm and L / D 36 and melt-extruded to prepare a film through a T-die and irradiated with 50 kGy in an electron accelerator to obtain a film (FL-1) specimen having a final thickness of 100 μm. The coefficient of thermal expansion, flexibility, light transmittance, birefringence and glass transition temperature for (FL-1) specimens were evaluated and the results are shown in Table 2.
(비교예 1)(Comparative Example 1)
실시예 1에서 얻어진 노르보르넨-1-헥센 공중합체(A)를 용매 클로로벤젠에 20중량% 농도로 녹인 용액을 글래스 위에 캐스팅하고 용매를 건조함으로서 두께 100μm의 필름(FC-1) 시편을 얻었고 이 필름(FC-1) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다.The norbornene-1-hexene copolymer (A) obtained in Example 1 was dissolved in solvent chlorobenzene at a concentration of 20% by weight on a glass, and the solvent was dried to obtain a film (FC-1) specimen having a thickness of 100 μm. The coefficient of thermal expansion, flexibility, light transmittance, birefringence and glass transition temperature for the film (FC-1) specimens were evaluated and the results are shown in Table 2.
(비교예 2)(Comparative Example 2)
실시예 4에서 얻어진 수산기 함유 노르보르넨-1-헥센 공중합체(B)를 용매 클로로벤젠에 20중량% 농도로 녹인 용액을 글래스 위에 캐스팅하고 용매를 건조함으로서 두께 100μm의 필름(FC-2) 시편을 얻었고 이 필름(FC-2) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다.A film (FC-2) having a thickness of 100 μm by casting a solution of the hydroxyl group-containing norbornene-1-hexene copolymer (B) obtained in Example 4 in a solvent chlorobenzene at a concentration of 20% by weight on a glass and drying the solvent. The coefficient of thermal expansion, flexibility, light transmittance, birefringence and glass transition temperature for the film (FC-2) specimens were evaluated and the results are shown in Table 2.
(비교예 3)(Comparative Example 3)
실시예 5에서 얻어진 카르복실산기 함유 환형올레핀계 공중합체(C)를 실시예 4와 같은 방법으로 용매캐스팅으로 필름을 제조하고 전자가속기에서 500kGy로 조사하여 최종 두께 100μm의 필름(FC-3) 시편을 얻었고 이 필름(FC-3) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다. The carboxylic acid group-containing cyclic olefin copolymer (C) obtained in Example 5 was prepared by solvent casting in the same manner as in Example 4, and was irradiated with 500 kGy in an electron accelerator to produce a film (FC-3) having a final thickness of 100 μm. The coefficient of thermal expansion, flexibility, light transmittance, birefringence and glass transition temperature for this film (FC-3) specimens were evaluated and the results are shown in Table 2.
(비교예 4)(Comparative Example 4)
실시예 13에서 얻어진 5-노르보르넨-2-카르복실릭산 메틸에스테르 단독중합체(I)를 용매 테트라히드로푸란에 20중량% 농도로 녹인 용액을 글래스 위에 캐스팅하고 용매를 건조함으로서 두께 100μm의 필름(FC-4) 시편을 얻었고 이 필름(FC-4) 시편에 대한 열팽창계수, 유연성, 광투과도, 복굴절 및 유리전이온도를 평가하였고 그 결과를 표 2에 나타내었다.A film having a thickness of 100 μm by casting a solution obtained by dissolving 5-norbornene-2-carboxylic acid methyl ester homopolymer (I) obtained in Example 13 in a solvent tetrahydrofuran at a concentration of 20% by weight on glass and drying the solvent ( FC-4) specimens were obtained and the coefficient of thermal expansion, flexibility, light transmittance, birefringence and glass transition temperature for the film (FC-4) specimens were evaluated and the results are shown in Table 2.
(표 2) 실시예 1～14 및 비교예 1～4에 따라 얻어진 기판의 물성 Table 2 Physical properties of the substrates obtained according to Examples 1 to 14 and Comparative Examples 1 to 4
실시예 1 내지 실시예 3과 비교예 1을 비교해 보면 방사선(전자선) 조사 유무에 따라 열팽창계수가 획기적으로 차이가 남을 알 수 있고 방사선의 조사량 증가에 따라 열팽창계수 개선효과가 증가됨을 알 수 있는데, 다만 조사도가 너무 크면 가교도 증가폭이 커서 유연성이 다소 떨어짐을 알 수 있다. 이는 방사선을 조사한 실시예 4와 조사하지 않은 비교예 2와의 비교에서도 방사선 조사 유무에 따라 열팽창계수 차이를 극명하게 알 수 있다. 또한 극성기가 함유되지 않은 환형올레핀계 수지가 사용된 실시예 2와 수산기, 카르복실산기, 설폰산기, 카르복실산염기 등 극성기가 함유된 환형올레핀계 수지가 사용된 실시예 4 내지 실시예 7을 비교해 보면 극성기가 함유된 환형올레핀계 수지를 사용한 경우가 훨씬 열팽창계수 개선효과가 큼을 알 수 있다. 이는 극성기간의 강한 2차결합력에 기인한 것으로 추정된다. 실시예 8과 실시예 9에서 볼 수 있듯이 환형올레핀계 수지에 가교조제가 일부 첨가된 경우 제조원가 측면에서 유리한 낮은 방사선 조사조건에서도 가교가 효과적으로 진행되어 열팽창계수 개선효과가 큼을 알 수 있다. 이는 아크릴레이트기 또는 메타크릴레이트기가 함유된 환형올레핀계 수지가 사용된 실시예 10과 실시예 11에서도 이런 현상을 엿볼 수 있다. 특히 카르복실산염기와 아크릴레이트기가 동시에 함유된 환형올레핀계 수지를 사용한 실시예 12 경우 유연성, 투명성, 등방성 및 높은 유리전이온도를 보유하면서 실로 획기적으로 낮은 열팽창계수를 가짐을 알 수 있다. 한편 너무나 방사선 조사량이 큰 비교예 3을 보면 열팽창계수 개선효과는 탁월하나 유연성이 극히 나빠지고 투명성 저하가 뚜렷하고 황변현상도 나타났다. 또한 실시예 13와 비교예 14에서와 같이 환형올레핀계 단독중합체의 경우에도 방사선 조사 유무에 따라 열팽창계수가 획기적으로 차이가 남을 알 수 있다. 또한 실시예 14에서 볼 수 있듯이 환형올레핀계 수지에 나노입자를 적정량 첨가할 경우 투명도는 약간 떨어지지만 열팽창계수가 효과적으로 개선됨을 알 수 있다. Comparing Examples 1 to 3 and Comparative Example 1, it can be seen that the thermal expansion coefficient is significantly different depending on the presence or absence of radiation (electron beam) irradiation, and the effect of improving the coefficient of thermal expansion increases as the radiation dose is increased. However, if the degree of irradiation is too large, the increase in crosslinking degree is large, indicating that the flexibility is somewhat inferior. This can be clearly seen in the thermal expansion coefficient difference according to the presence or absence of radiation even in comparison with Example 4 irradiated with Comparative Example 2 not irradiated. In addition, Example 2 in which cyclic olefin resins containing no polar group are used and Examples 4 to 7 in which cyclic olefin resins containing polar groups such as hydroxyl group, carboxylic acid group, sulfonic acid group and carboxylate group are used are used. In comparison, it can be seen that the use of a cyclic olefin resin containing a polar group is much more effective in improving the coefficient of thermal expansion. This is presumably due to the strong secondary binding force of the polar period. As can be seen in Examples 8 and 9, when a part of the crosslinking aid is added to the cyclic olefin resin, crosslinking proceeds effectively even under low irradiation conditions, which are advantageous in terms of manufacturing cost, and thus, the effect of improving the coefficient of thermal expansion is high. This can be seen in Examples 10 and 11 in which cyclic olefin resins containing acrylate or methacrylate groups are used. In particular, in the case of Example 12 using a cyclic olefin resin containing a carboxylate group and an acrylate group at the same time it can be seen that it has a significantly low coefficient of thermal expansion while retaining flexibility, transparency, isotropy and high glass transition temperature. On the other hand, Comparative Example 3, in which the radiation dose is too large, is excellent in improving the coefficient of thermal expansion, but the flexibility is extremely poor, the transparency is clearly deteriorated, and yellowing is also observed. In addition, in the case of the cyclic olefin homopolymer as in Example 13 and Comparative Example 14, it can be seen that the thermal expansion coefficient is significantly different depending on the presence or absence of radiation. In addition, as can be seen in Example 14, when the appropriate amount of nanoparticles are added to the cyclic olefin resin, the transparency is slightly reduced, but it can be seen that the coefficient of thermal expansion is effectively improved.
Claims (21)
(화학식 1)
(상기 화학식 1에서 Ra 및 Rb는 동일 또는 상이하며, 수소, 알킬기 또는 수산기, 아민기, 암모늄기, 에폭시기, 할로겐기, 시아노기, 아세테이트기, 에스테르기, 유기산기, 유기산무수물기 및 유기산염기 중 어느 하나이며, Ra 및 Rb는 서로 결합하여 고리를 형성할 수 있다. l은 0 또는 1 이상의 정수, m은 1 이상의 정수이다.)
(화학식 2)
(상기 화학식 2에서 Rc 및 Rd는 동일 또는 상이하며, 수소, 알킬기 또는 수산기, 아민기, 암모늄기, 에폭시기, 할로겐기, 시아노기, 아세테이트기, 에스테르기, 유기산기, 유기산무수물기 및 유기산염기 중 어느 하나이며, Rc 및 Rd는 서로 결합하여 고리를 형성할 수 있다. p는 0 또는 1 이상의 정수, q 및 r은 1 이상의 정수이다.
(화학식 3)
(상기 화학식 3에서 n은 1~20의 정수이고, X는 수소 또는 수산기, 카르복실산기 또는 술폰산기 중 어느 하나이다.)50 to 99 mol% of a cyclic olefin homopolymer or cyclic olefin-linear olefin copolymer selected from Chemical Formulas 1 or 2 and 1 to 50 mol% of units satisfying the following Chemical Formula 3 are irradiated with radiation. Flexible substrate.
(Formula 1)
(Ra and Rb in the formula (1) is the same or different, hydrogen, alkyl group or hydroxyl group, amine group, ammonium group, epoxy group, halogen group, cyano group, acetate group, ester group, organic acid group, organic acid anhydride group and organic acid acid group And Ra and Rb may combine with each other to form a ring, where l is 0 or an integer of 1 or more, and m is an integer of 1 or more.)
(2)
(In Formula 2, Rc and Rd are the same or different, and any one of hydrogen, an alkyl group or a hydroxyl group, an amine group, an ammonium group, an epoxy group, a halogen group, a cyano group, an acetate group, an ester group, an organic acid group, an organic anhydride group, and an organic acid salt group) And Rc and Rd may be bonded to each other to form a ring, p is an integer of 0 or 1 or more, q and r are integers of 1 or more.
(Formula 3)
(In Formula 3, n is an integer of 1 to 20, X is hydrogen or any one of a hydroxyl group, a carboxylic acid group or a sulfonic acid group.)
상기 환형올레핀은 노르보르넨, 5-비닐-2-노르보르넨, 5-부틸-2-노르보르넨, 5-메틸-2-노르보르넨, 5-헥실-2-노르보르넨, 5-디메틸메톡시 노르보르넨, 디시클로 펜타디엔, 시클로펜타디엔 또는 이들의 유도체에서 선택되는 것인 플렉시블 기판.The method of claim 1,
The cyclic olefins are norbornene, 5-vinyl-2-norbornene, 5-butyl-2-norbornene, 5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5- Flexible substrate selected from dimethylmethoxy norbornene, dicyclo pentadiene, cyclopentadiene or derivatives thereof.
상기 환형올레핀계 수지가 라디칼 반응성기를 함유하는 것인 플렉시블 기판.The method of claim 1,
The flexible substrate, wherein the cyclic olefin resin contains a radical reactive group.
상기 환형올레핀계 수지가 환형올레핀 단위와 극성기 함유 올레핀 단위로 구성된 환형올레핀계 공중합체인 플렉시블 기판.The method of claim 1,
A flexible substrate, wherein the cyclic olefin resin is a cyclic olefin copolymer composed of a cyclic olefin unit and a polar group-containing olefin unit.
상기 환형올레핀계 수지 내 극성기의 함유량이 0.001～10중량%인 플렉시블 기판.The method of claim 4, wherein
The flexible substrate whose content of the polar group in the said cyclic olefin resin is 0.001 to 10 weight%.
상기 환형올레핀계 수지의 유리전이온도가 200～450℃ 범위인 플렉시블 기판.The method of claim 1,
The flexible substrate whose glass transition temperature of the said cyclic olefin resin is 200-450 degreeC.
상기 방사선은 감마선, 전자선 및 X-선으로 이루어진 군에서 선택된 것인 플렉시블 기판.The method of claim 1,
The radiation is selected from the group consisting of gamma rays, electron beams and X-rays.
상기 방사선은 전자선인 플렉시블 기판.The method of claim 1,
The radiation is an electron beam flexible substrate.
상기 방사선의 조사선량은 1～500kGy인 플렉시블 기판.The method of claim 1,
The radiation dose of the radiation is 1 to 500kGy flexible substrate.
상기 환형올레핀계 수지 100중량부에 대해 가교조제가 0.001～20중량부로 더 첨가된 환형올레핀계 수지조성물로 형성된 필름에 방사선을 조사하여 얻어진 플렉시블 기판.The method of claim 1,
A flexible substrate obtained by irradiating a film formed of a cyclic olefin resin composition with a crosslinking aid added to 0.001 to 20 parts by weight based on 100 parts by weight of the cyclic olefin resin.
상기 가교조제는 p-퀴논 다이옥심, p, p'-다이벤조일퀴논 다이옥심, N-메틸-N-4-디니트로소아닐린, 니트로소벤젠, 디페닐구아니딘, 트리메틸올프로페인-N, N'-m-페닐렌디말레이미드, 디비닐벤젠, 트리알릴시아누레이트, 트리알릴이소시아누레이트, 에틸렌글리콜 디메타크릴레이트, 디에틸렌글리콜 디메타크릴레이트, 폴리에틸렌글리콜 디메타크릴레이트, 다작용성 메타크릴레이트 모노머, 다작용성 비닐 모노머, 금속아크릴레이트, 금속메타크릴레이트로 구성된 군에서 선택된 어느 하나 이상의 것인 플렉시블 기판.13. The method of claim 12,
The crosslinking aid is p-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N, N '-m-phenylenedimaleimide, divinylbenzene, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, multifunctional At least one flexible substrate selected from the group consisting of methacrylate monomers, polyfunctional vinyl monomers, metal acrylates, metal methacrylates.
상기 라디칼 반응성기가 아크릴레이트기, 메타아크릴레이트기, 비닐기, 알릴기로 구성된 군에서 선택된 어느 하나 이상의 것인 플렉시블 기판.The method of claim 4, wherein
The radical substrate is any one or more selected from the group consisting of acrylate group, methacrylate group, vinyl group, allyl group.
상기 라디칼 반응성기가 아크릴레이트기 또는 메타아크릴레이트기인 플렉시블 기판.The method of claim 4, wherein
A flexible substrate, wherein the radical reactive group is an acrylate group or a methacrylate group.
상기 환형올레핀계 수지내 라디칼 반응성기의 함유량이 0.001～20중량%인 플렉시블 기판.The method of claim 4, wherein
The flexible substrate whose content of the radical reactive group in the said cyclic olefin resin is 0.001 to 20 weight%.
상기 환형올레핀계 수지 100중량부에 대해 무기입자가 0.001～20중량부로 더 첨가된 환형올레핀계 수지조성물로 형성된 필름에 방사선을 조사하여 얻어진 플렉시블 기판.The method according to any one of claims 1, 3 to 6, 8 to 16,
A flexible substrate obtained by irradiating a film formed of a cyclic olefin resin composition in which inorganic particles are further added in an amount of 0.001 to 20 parts by weight based on 100 parts by weight of the cyclic olefin resin.
상기 무기입자가 탄산칼슘, 탈크, 클레이, 카올린, 실리카, 규조토, 탄산마그네슘, 염화칼슘, 황산칼슘, 수산화알미늄, 산화아연, 수산화마그네슘, 산화티탄, 알루미나, 마이카, 아스베스토스, 제오라이트, 규산백토, 바륨티타네이트, 유리섬유로 구성된 군에서 선택된 어느 하나 이상인 플렉시블 기판.18. The method of claim 17,
The inorganic particles are calcium carbonate, talc, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, calcium chloride, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, titanium oxide, alumina, mica, asbestos, zeolite, white silicate, barium titanium Nate, a glass substrate of any one or more selected from the group consisting of glass fibers.
상기 환형올레핀계 수지로 성형된 필름의 두께는 10～300μm인 것을 특징으로 하는 낮은 열팽창계수를 갖는 플렉시블 기판.The method of claim 1,
A flexible substrate having a low coefficient of thermal expansion, characterized in that the thickness of the film molded from the cyclic olefin resin is 10 ~ 300μm.
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| PCT/KR2012/006272 WO2013022263A2 (en) | 2011-08-08 | 2012-08-08 | Cyclic olefin copolymer resin flexible board having a low thermal expansion coefficient |
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| WO2017119645A1 (en) * | 2016-01-08 | 2017-07-13 | 동우화인켐 주식회사 | Film touch sensor and method for manufacturing same |
| WO2017171272A1 (en) * | 2016-03-31 | 2017-10-05 | 동우화인켐 주식회사 | Color filter and image display device comprising same |
| WO2020153655A1 (en) * | 2019-01-22 | 2020-07-30 | 동우 화인켐 주식회사 | Film touch sensor and manufacturing method therefor |
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| DE102005036520A1 (en) * | 2005-04-26 | 2006-11-09 | Osram Opto Semiconductors Gmbh | Optical component, optoelectronic component with the component and its manufacture |
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| JP2005320420A (en) | 2004-05-07 | 2005-11-17 | Takeshi Shiono | Cycloolefin/alkenyldialkyl aluminum copolymer |
| JP2008044971A (en) | 2006-08-10 | 2008-02-28 | Sumitomo Electric Fine Polymer Inc | Resin composition and manufacturing method of molded product |
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| WO2017119645A1 (en) * | 2016-01-08 | 2017-07-13 | 동우화인켐 주식회사 | Film touch sensor and method for manufacturing same |
| KR20170083286A (en) * | 2016-01-08 | 2017-07-18 | 동우 화인켐 주식회사 | Film Touch Sensor and Method for Fabricating the Same |
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| US10894390B2 (en) | 2016-01-08 | 2021-01-19 | Dongwoo Fine-Chem Co., Ltd. | Film touch sensor and method for fabricating the same |
| TWI726960B (en) * | 2016-01-08 | 2021-05-11 | 南韓商東友精細化工有限公司 | Film touch sensor and method for fabricating the same |
| TWI739787B (en) * | 2016-01-08 | 2021-09-21 | 南韓商東友精細化工有限公司 | Film touch sensor and method for fabricating the same |
| WO2017171272A1 (en) * | 2016-03-31 | 2017-10-05 | 동우화인켐 주식회사 | Color filter and image display device comprising same |
| WO2020153655A1 (en) * | 2019-01-22 | 2020-07-30 | 동우 화인켐 주식회사 | Film touch sensor and manufacturing method therefor |
| CN114920866A (en) * | 2022-05-23 | 2022-08-19 | 万华化学集团股份有限公司 | Preparation method of polyolefin thermoplastic elastomer |
| CN114920866B (en) * | 2022-05-23 | 2023-07-14 | 万华化学集团股份有限公司 | Preparation method of polyolefin thermoplastic elastomer |
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