KR101526003B1 - Composite sheet, method for preparing the same, flexible substrate comprising the same and display apparatus comprising the same - Google Patents
Composite sheet, method for preparing the same, flexible substrate comprising the same and display apparatus comprising the same Download PDFInfo
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- KR101526003B1 KR101526003B1 KR1020120080808A KR20120080808A KR101526003B1 KR 101526003 B1 KR101526003 B1 KR 101526003B1 KR 1020120080808 A KR1020120080808 A KR 1020120080808A KR 20120080808 A KR20120080808 A KR 20120080808A KR 101526003 B1 KR101526003 B1 KR 101526003B1
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- composite sheet
- composition
- matrix
- silicone resin
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 239000000758 substrate Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 239000011159 matrix material Substances 0.000 claims abstract description 44
- 229920002050 silicone resin Polymers 0.000 claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 239000012779 reinforcing material Substances 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims description 29
- 238000003848 UV Light-Curing Methods 0.000 claims description 26
- 230000003746 surface roughness Effects 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 229920001296 polysiloxane Polymers 0.000 claims description 17
- 239000003365 glass fiber Substances 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 15
- 239000004744 fabric Substances 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000002787 reinforcement Effects 0.000 claims description 9
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 7
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 claims description 6
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 239000008119 colloidal silica Substances 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims 1
- 238000001723 curing Methods 0.000 description 20
- -1 polyethylene terephthalate Polymers 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
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- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 6
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 6
- 239000003351 stiffener Substances 0.000 description 6
- 125000000392 cycloalkenyl group Chemical group 0.000 description 5
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
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- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920001230 polyarylate Polymers 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
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WAKHLWOJMHVUJC-FYWRMAATSA-N (2e)-2-hydroxyimino-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(=N/O)\C(O)C1=CC=CC=C1 WAKHLWOJMHVUJC-FYWRMAATSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- ZGPJPUGCDODKKH-UHFFFAOYSA-N 4-methylhept-2-yn-4-ol Chemical compound CCCC(C)(O)C#CC ZGPJPUGCDODKKH-UHFFFAOYSA-N 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- AFWTZXXDGQBIKW-UHFFFAOYSA-N C14 surfactin Natural products CCCCCCCCCCCC1CC(=O)NC(CCC(O)=O)C(=O)NC(CC(C)C)C(=O)NC(CC(C)C)C(=O)NC(C(C)C)C(=O)NC(CC(O)=O)C(=O)NC(CC(C)C)C(=O)NC(CC(C)C)C(=O)O1 AFWTZXXDGQBIKW-UHFFFAOYSA-N 0.000 description 1
- OOVLMFMECLBCJR-UHFFFAOYSA-K O[Sb](O)(Cl)=O Chemical compound O[Sb](O)(Cl)=O OOVLMFMECLBCJR-UHFFFAOYSA-K 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 description 1
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- 239000000805 composite resin Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012955 diaryliodonium Substances 0.000 description 1
- 125000005520 diaryliodonium group Chemical group 0.000 description 1
- OWZDULOODZHVCQ-UHFFFAOYSA-N diphenyl-(4-phenylsulfanylphenyl)sulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC1=CC=CC=C1 OWZDULOODZHVCQ-UHFFFAOYSA-N 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
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- 238000007373 indentation Methods 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
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- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
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- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- NJGWOFRZMQRKHT-UHFFFAOYSA-N surfactin Natural products CC(C)CCCCCCCCCC1CC(=O)NC(CCC(O)=O)C(=O)NC(CC(C)C)C(=O)NC(CC(C)C)C(=O)NC(C(C)C)C(=O)NC(CC(O)=O)C(=O)NC(CC(C)C)C(=O)NC(CC(C)C)C(=O)O1 NJGWOFRZMQRKHT-UHFFFAOYSA-N 0.000 description 1
- NJGWOFRZMQRKHT-WGVNQGGSSA-N surfactin C Chemical compound CC(C)CCCCCCCCC[C@@H]1CC(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@H](CC(C)C)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(=O)O1 NJGWOFRZMQRKHT-WGVNQGGSSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
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- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03926—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
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- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- 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
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
Abstract
본 발명은 복합시트, 그의 제조 방법, 이를 포함하는 플렉시블 기판 및 이를 포함하는 디스플레이 장치에 관한 것이다. 보다 상세하게는, 본 발명은 UV 경화형 실리콘계 수지와 개시제를 포함하는 매트릭스용 조성물과, 상기 매트릭스용 조성물에 함침된 보강재의 경화물로 이루어진 복합시트, 그의 제조 방법, 이를 포함하는 플렉시블 기판 및 이를 포함하는 장치에 관한 것이다.The present invention relates to a composite sheet, a manufacturing method thereof, a flexible substrate including the composite sheet, and a display device including the composite sheet. More particularly, the present invention relates to a composite sheet comprising a composition for matrix comprising a UV curable silicone resin and an initiator, and a cured product of a reinforcing material impregnated in the matrix composition, a process for producing the same, a flexible substrate containing the same .
Description
본 발명은 복합시트, 이의 제조 방법, 이를 포함하는 플렉시블 기판 및 이를 포함하는 디스플레이 장치에 관한 것이다. 보다 상세하게는, 본 발명은 열팽창성이 낮고 유연성, 내열성 및 투명성이 좋으며, UV 경화로 제조되어 우수한 표면 특성을 가지며, 표면 조도의 저하를 최소화할 수 있는 복합시트, 그의 제조 방법, 이를 포함하는 플렉시블 기판 및 이를 포함하는 장치에 관한 것이다.The present invention relates to a composite sheet, a method of manufacturing the same, a flexible substrate including the composite sheet, and a display device including the composite sheet. More particularly, the present invention relates to a composite sheet which is low in thermal expansion, has good flexibility, heat resistance and transparency, is manufactured by UV curing and has excellent surface properties and can minimize the decrease in surface roughness, To a flexible substrate and an apparatus including the flexible substrate.
액정 표시 소자나 유기 EL 표시 소자용 기판, 컬러 필터 기판, 태양 전지 기판 등으로 내열성 및 투명성이 우수하고, 선팽창 계수가 낮은 유리가 널리 이용되고 있다. 최근에는 표시 소자용 기판 소재로 소형화, 박형화, 경량화, 내충격성, 유연성이 요구되고 있어 유리기판을 대체하기 위한 소재로서 플라스틱 소재가 각광을 받고 있다. Glass substrates having excellent heat resistance and transparency and low coefficient of linear expansion have been widely used as substrates for liquid crystal display devices, organic EL display devices, color filter substrates, and solar cell substrates. BACKGROUND ART [0002] In recent years, as a substrate material for a display device, miniaturization, thinness, weight reduction, impact resistance, and flexibility are required, and plastic materials are attracting attention as a material for replacing glass substrates.
근래에는 플라스틱 기판으로 폴리에틸렌테레프탈레이트(PET), 폴리에테르설폰(PES), 폴리에틸렌나프탈레이트(PEN), 폴리아릴레이트(PAR), 폴리카보네이트(PC), 폴리이미드(PI) 등의 소재가 사용되고 있다. 그러나, 이들 소재들은 열팽창계수가 상당히 높아 제품의 휘어짐이나 배선의 단선 등을 일으키는 문제가 있다. 폴리이미드계 수지는 비교적 낮은 열팽창계수를 갖지만, 투명성이 매우 낮고 높은 복굴절성, 흡습성 등으로 인해 기판 소재로는 적합하지 않다는 문제가 지적되고 있다.In recent years, materials such as polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), polyarylate (PAR), polycarbonate (PC) and polyimide . However, these materials have a problem of causing warpage of the product and disconnection of the wiring due to a high thermal expansion coefficient. The polyimide-based resin has a relatively low thermal expansion coefficient, but it has been pointed out that it is not suitable as a substrate material due to its extremely low transparency, high birefringence, hygroscopicity and the like.
이와 관련하여, 일본 공개공보 2004-51960호에서는 에스테르기를 포함하는 지환식 에폭시 수지, 비스페놀 A형 에폭시 수지, 산무수물계 경화제 및 촉매와 유리섬유포(glass fiber cloth)로부터 제조되는 투명 복합 광학 시트가, 일본 공개공보 2005-146258호에서는 에스테르기를 포함하는 지환식 에폭시 수지와 디사이클로펜타디엔 골격을 가지는 에폭시 수지, 산무수물계 경화제와 유리섬유포로부터 제조되는 투명 복합 광학 시트가, 일본 공개공보 2004-233851호에서는 비스페놀 A형 에폭시 수지, 비스페놀 A 노볼락(novolac)형 에폭시 수지, 산무수물계 경화제 및 유리섬유포로 제조되는 투명 기판을 개시하고 있다. 그러나, 상기 특허들은 섬유와 수지 매트릭스간에 응력이 생기고, 그로 인해 파손이 발생하며, 광학이방성이 크기 때문에 표시성능이 저하되는 단점이 있다.In this regard, Japanese Laid-Open Publication No. 2004-51960 discloses a transparent hybrid optical sheet prepared from an alicyclic epoxy resin containing an ester group, a bisphenol A epoxy resin, an acid anhydride curing agent, a catalyst and a glass fiber cloth, Japanese Unexamined Patent Application, First Publication No. 2005-146258 discloses a transparent hybrid optical sheet prepared from an epoxy resin having an alicyclic epoxy resin containing an ester group and a dicyclopentadiene skeleton, an acid anhydride-based curing agent and a glass fiber cloth, Discloses a transparent substrate made of a bisphenol A type epoxy resin, a bisphenol A novolac type epoxy resin, an acid anhydride type curing agent, and a glass fiber cloth. However, the above patents are disadvantageous in that display performance is deteriorated because stress is generated between the fiber and the resin matrix, breakage occurs thereby, and optical anisotropy is large.
유리 섬유포-수지 복합체의 경우 유리섬유포의 낮은 표면 특성과 이를 따르는 conformal한 수지의 흐름성, 경화시의 수축 및 열에 의해 발생하는 수지와 섬유포간의 열팽창 계수의 차이 등의 요인에 의하여 복합체의 표면 조도의 저하가 일어난다.In the case of the glass fiber foam-resin composite, the surface roughness of the composite due to factors such as the low surface properties of the glass fiber cloth, the conformal resin flowability, the shrinkage upon curing, and the difference in thermal expansion coefficient between the resin and the fibril A drop occurs.
본 발명의 목적은 열팽창성이 낮고 유연성, 내열성 및 투명성이 좋은 복합시트를 제공하는 것이다.An object of the present invention is to provide a composite sheet having a low thermal expansion property and excellent flexibility, heat resistance and transparency.
본 발명의 다른 목적은 UV 경화를 적용하여 우수한 표면 특성을 갖는 복합시트를 제공하는 것이다. Another object of the present invention is to provide a composite sheet having excellent surface properties by applying UV curing.
본 발명의 또 다른 목적은 표면 조도의 저하를 최소화할 수 있는 복합시트를 제공하는 것이다.It is still another object of the present invention to provide a composite sheet capable of minimizing deterioration of surface roughness.
본 발명의 또 다른 목적은 보강재의 복합화 공정에서 발생할 수 있는 표면 조도의 저하 및 고온 경화 시에 발생되는 경화 수축에 의한 표면 조도의 저하를 최소화할 수 있는 복합시트 제조방법을 제공하는 것이다.It is still another object of the present invention to provide a composite sheet production method capable of minimizing surface roughness that may occur in a composite process of a reinforcing material and minimizing surface roughness degradation caused by shrinkage of hardening that occurs during high temperature curing.
본 발명의 또 다른 목적은 공정성 측면에서 공정 시간을 단축한 복합시트 제조방법을 제공하는 것이다. It is still another object of the present invention to provide a method for manufacturing a composite sheet in which process time is shortened in terms of processability.
본 발명의 또 다른 목적은 상기 복합시트를 포함하는 플렉시블 기판 및 디스플레이 장치를 제공하는 것이다.It is still another object of the present invention to provide a flexible substrate and a display device including the composite sheet.
본 발명의 일 관점인 복합시트는 UV 경화형 실리콘계 수지와 개시제를 포함하는 매트릭스용 조성물과, 상기 매트릭스용 조성물에 함침된 보강재의 경화물로 이루어질 수 있다.The composite sheet which is one aspect of the present invention can be composed of a composition for a matrix containing a UV curable silicone resin and an initiator and a cured product of a reinforcing material impregnated in the matrix composition.
본 발명의 다른 관점인 복합시트는 실리콘계 수지와 UV 경화형 촉매를 포함하는 매트릭스용 조성물과, 상기 매트릭스용 조성물에 함침된 보강재의 경화물로 이루어질 수 있다.Another aspect of the present invention is a composite sheet comprising a composition for a matrix comprising a silicone resin and a UV curable catalyst and a cured product of a reinforcing material impregnated in the matrix composition.
본 발명의 또 다른 관점인 복합시트 제조방법은 UV 경화형 실리콘계 수지와 개시제를 포함하는 매트릭스용 조성물을 제조하는 단계; 및 상기 조성물에 보강재를 함침하고 UV 경화시키는 단계를 포함할 수 있다.Another aspect of the present invention is a method for producing a composite sheet comprising the steps of: preparing a matrix composition comprising a UV curable silicone resin and an initiator; And impregnating and UV curing the composition with a reinforcement.
본 발명의 또 다른 관점인 복합시트 제조방법은 실리콘계 수지와 UV 경화형 촉매를 포함하는 매트릭스용 조성물을 제조하는 단계; 및 상기 조성물에 보강재를 함침하고 UV 경화시키는 단계를 포함할 수 있다.Another aspect of the present invention is a method for producing a composite sheet, comprising the steps of: preparing a matrix composition comprising a silicone resin and a UV curable catalyst; And impregnating and UV curing the composition with a reinforcement.
본 발명의 또 다른 관점인 플렉시블 기판 및 디스플레이 장치는 상기 복합시트를 포함할 수 있다.The flexible substrate and the display device according to another aspect of the present invention may include the composite sheet.
본 발명은 열팽창성이 낮고 유연성, 내열성 및 투명성이 좋으며, UV 경화를 적용하여 우수한 표면 특성을 가지며, 표면 조도의 저하를 최소화할 수 있는 복합시트를 제공하였다. 본 발명은 보강재의 복합화 공정에서 발생할 수 있는 표면 조도의 저하 및 고온 경화 시에 발생되는 경화 수축에 의한 표면 조도의 저하를 최소화할 수 있고 공정성 측면에서 공정 시간을 단축한 복합시트 제조 방법을 제공하였다. 본 발명은 상기 복합시트를 포함하는 플렉시블 기판 및 디스플레이 장치를 제공하였다.The present invention provides a composite sheet which is low in thermal expansion, has good flexibility, heat resistance and transparency, has excellent surface properties by applying UV curing, and can minimize the decrease in surface roughness. The present invention provides a composite sheet manufacturing method capable of minimizing surface roughness that may occur in the composite process of a reinforcing material and minimizing surface roughness caused by shrinkage of hardening caused at the time of high temperature curing and shortening the process time in terms of processability . The present invention provides a flexible substrate and a display device including the composite sheet.
도 1은 본 발명 일 실시예의 복합시트의 단면도를 나타낸 것이다.
10:복합시트, 1:매트릭스, 2:유리섬유1 is a cross-sectional view of a composite sheet according to an embodiment of the present invention.
10: composite sheet, 1: matrix, 2: glass fiber
본 발명의 일 관점인 복합시트는 실리콘계 수지를 포함하는 매트릭스용 조성물과, 상기 매트릭스용 조성물에 함침되는 보강재의 경화물로 이루어질 수 있다.The composite sheet according to one aspect of the present invention may be composed of a composition for a matrix containing a silicone resin and a cured product of a reinforcing material impregnated in the matrix composition.
보강재와 실리콘계 수지는 열팽창 계수의 차이가 발생한다. 그 결과, 기존에 열 경화로 제조된 복합시트는 보강재의 복합화 공정에서 발생할 수 있는 표면 조도의 저하뿐만 아니라, 고온 경화 시에 경화 수축으로 인해 표면 조도의 저하가 컸다. 반면에, 본 발명의 복합시트는 UV 경화물로서 표면 조도의 저하를 최소화할 수 있다.The difference between the thermal expansion coefficients of the stiffener and the silicone resin occurs. As a result, the conventional composite sheet produced by heat curing has a large decrease in surface roughness due to curing shrinkage at the time of high temperature curing, as well as a decrease in surface roughness that can occur in a composite process of a reinforcing material. On the other hand, the composite sheet of the present invention can minimize degradation of surface roughness as UV cured products.
상기 복합시트는 표면 조도(Ra)가 100nm 이하 바람직하게는 50nm 이하 더 바람직하게는 5nm-50nm가 될 수 있고, young,s modulus는 1-200MPa, 바람직하게는 1-150MPa가 될 수 있다.The composite sheet may have a surface roughness (Ra) of 100 nm or less, preferably 50 nm or less, more preferably 5 nm to 50 nm, and a Young's modulus of 1-200 MPa, preferably 1-150 MPa.
상기 복합시트는 열팽창계수가 0ppm/℃-400ppm/℃, 바람직하게는 0ppm/℃-10ppm/℃, 보다 바람직하게는 3ppm/℃-7ppm/℃가 될 수 있다. 상기 범위 내에서, 플렉시블 기판으로 제조시 열 변형이 억제될 수 있다.The composite sheet may have a thermal expansion coefficient of 0 ppm / ° C to -400 ppm / ° C, preferably 0 ppm / ° C to 10 ppm / ° C, more preferably 3 ppm / ° C to 7 ppm / Within this range, thermal deformation can be suppressed during production of the flexible substrate.
열팽창계수는 ASTM E 831 방법으로서, 온도에 따른 dimensional change를 Thermo-mechanical analysizer(expansion mode, force 0.05N)를 이용하여 측정한 후, 온도(30℃-250℃)에 따른 시료 길이의 변화 곡선으로부터 측정할 수 있다.The ASTM E 831 thermal expansion coefficient was measured by using a thermo-mechanical analyzer (expansion mode, force 0.05 N) for dimensional changes with temperature, and then from the curve of the sample length according to the temperature (30 ° C. to 250 ° C.) Can be measured.
상기 복합시트 두께는 15㎛-200㎛가 될 수 있다. 상기 범위에서, 플렉시블 기판 용도의 복합시트로 사용될 수 있다.The thickness of the composite sheet may be 15 탆 to 200 탆. Within this range, it can be used as a composite sheet for a flexible substrate.
상기 복합시트는 매트릭스; 및 상기 매트릭스 내에 포함된 보강재로 구성될 수 있다. 도 1은 본 발명의 복합시트의 일 실시예를 나타낸 것이다. 복합시트(10)는 매트릭스(1) 내에 보강재(2)가 포함된 구조로 되어 있다. 보강재는 분산, 단일 층 또는 복수층 구조로 포함될 수 있다.The composite sheet comprising: a matrix; And a reinforcing material contained in the matrix. 1 shows an embodiment of a composite sheet of the present invention. The
상기 복합시트에서 매트릭스:보강재는 70:30 내지 95:5의 중량비로 포함될 수 있다. 상기 범위에서, 플렉시블 기판으로 사용될 수 있는 복합시트의 물성을 가질 수 있다. 바람직하게는 80:20 내지 90:10의 중량비로 포함될 수 있다.In the composite sheet, the matrix: reinforcement may be included in a weight ratio of 70:30 to 95: 5. Within this range, the properties of the composite sheet that can be used as a flexible substrate can be obtained. Preferably in a weight ratio of 80:20 to 90:10.
일 실시예에서, 상기 복합시트는 UV 경화형 실리콘계 수지와 개시제를 포함하는 매트릭스용 조성물과, 상기 매트릭스용 조성물에 함침된 보강재의 경화물로 이루어질 수 있다.In one embodiment, the composite sheet may comprise a composition for a matrix comprising a UV curable silicone resin and an initiator, and a cured product of the reinforcement impregnated in the matrix composition.
상기 UV 경화형 실리콘계 수지는 러버 화합물로 매트릭스의 바인더로 작용한다.The UV curable silicone resin is a rubber compound and acts as a binder of the matrix.
상기 UV 경화형 실리콘계 수지는 UV 경화 작용기를 갖는 폴리오르가노실록산일 수 있다.The UV curable silicone resin may be a polyorganosiloxane having a UV curing functional group.
본 명세서에서 '*'은 연결 부위를 나타낸다.In the present specification, '*' denotes a connecting site.
일 구체예에서, 상기 UV 경화형 실리콘계 수지는 하기 화학식 1a의 단위를 포함할 수 있다:In one embodiment, the UV curable silicone based resin may comprise a unit of the formula (I)
<화학식 1a><Formula 1a>
(상기 식에서, Ra와 Rb는 동일하거나 다르고, 수소 원자, C1-C20 알킬기, C2-C20 알케닐기, C2-C20 알키닐기, C1-C20 알콕시기, C3-C30 사이클로알킬기, C3-C30 사이클로알케닐기, C3-C30 사이클로알키닐기, C6-C30 아릴기, C6-C30 아릴옥시기 또는 UV 경화 작용기이고, Ra와 Rb 중 적어도 하나 이상은 UV 경화 작용기이고, n은 2-1000의 정수이다).Ra and Rb are the same or different and each represents a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C1-C20 alkoxy group, a C3-C30 cycloalkyl group, a C3-C30 cycloalkenyl group , A C3-C30 cycloalkynyl group, a C6-C30 aryl group, a C6-C30 aryloxy group or a UV curing functional group, at least one of Ra and Rb is a UV curing functional group and n is an integer of 2-1000.
상기 UV 경화형 실리콘계 수지는 상기 화학식 1a의 단위를 포함하거나 화학식 1a의 단위로 이루어진 고리형 또는 선형 실리콘계 수지가 될 수 있다. The UV curable silicone resin may be a cyclic or linear silicone resin comprising the unit represented by the formula (1a) or the unit represented by the formula (1a).
선형 실리콘계 수지인 경우, 말단은 하기 화학식 1b 또는 화학식 1c가 될 수 있다:In the case of a linear silicone-based resin, the terminal may be represented by the following formula (1b) or (1c):
<화학식 1b>≪ EMI ID =
R1R2R3SiO-R1R2R3SiO-
<화학식 1c>≪ Formula 1c >
R4R5R6Si-R4R5R6Si-
(상기에서 R1,R2,R3,R4,R5,R6은 각각 독립적으로 수소 원자, C1-C20 알킬기, C2-C20 알케닐기, C2-C20 알키닐기, C1-C20 알콕시기, C3-C30 사이클로알킬기, C3-C30 사이클로알케닐기, C3-C30 사이클로알키닐기, C6-C30 아릴기, C6-C30 아릴옥시기 또는 UV 경화 작용기)이 될 수 있다.(Wherein R 1,
상기 UV 경화형 실리콘계 수지에서 UV 경화 작용기는 실리콘계 수지의 말단 또는 측쇄에 위치할 수 있다.In the UV curable silicone resin, the UV curable functional group may be located at the terminal or side chain of the silicone resin.
다른 구체예에서, 상기 UV 경화형 실리콘계 수지는 하기 화학식 2a, 2b 및 2c의 단위를 포함할 수 있다.In another embodiment, the UV curable silicone resin may comprise units of the following formulas (2a), (2b) and (2c).
<화학식 2a>≪ EMI ID =
(상기에서, Rc와 Rd는 동일하거나 다르고, 수소 원자, C1-C20 알킬기, C2-C20 알케닐기, C2-C20 알키닐기, C1-C20 알콕시기, C3-C30 사이클로알킬기, C3-C30 사이클로알케닐기, C3-C30 사이클로알키닐기, C6-C30 아릴기, C6-C30 아릴옥시기이고, n은 2-1000의 정수이다).(Wherein Rc and Rd are the same or different and each is a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C1-C20 alkoxy group, a C3-C30 cycloalkyl group, a C3-C30 cycloalkenyl group , A C3-C30 cycloalkynyl group, a C6-C30 aryl group, a C6-C30 aryloxy group, and n is an integer of 2-1000.
<화학식 2b>(2b)
R7R8R9SiO-R7R8R9SiO-
<화학식 2c>(2c)
R10R11R12Si-R10R11R12Si-
(상기에서 R7,R8,R9,R10,R11,R12은 각각 독립적으로 수소 원자, C1-C20 알킬기, C2-C20 알케닐기, C2-C20 알키닐기, C1-C20 알콕시기, C3-C30 사이클로알킬기, C3-C30 사이클로알케닐기, C3-C30 사이클로알키닐기, C6-C30 아릴기, C6-C30 아릴옥시기 또는 UV 경화 작용기이고, 상기 R7,R8,R9,R10,R11,R12 중 적어도 하나 이상은 UV 경화 작용기이다)이 될 수 있다.(Wherein R7, R8, R9, R10, R11 and R12 each independently represents a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C1-C20 alkoxy group, At least one or more of R7, R8, R9, R10, R11, and R12 is selected from the group consisting of a UV-C30 aryl group, a C6-C30 arylalkoxy group, It is a curing functional group).
상기 UV 경화형 실리콘계 수지는 상기 화학식 2a, 2b, 2c의 단위를 포함하거나 화학식 2a, 2b, 2c의 단위로 이루어진 고리형 또는 선형 실리콘계 수지가 될 수 있다. The UV-curable silicone resin may be a cyclic or linear silicone-based resin comprising the units of formulas (2a), (2b) and (2c) or the units of formulas (2a), (2b) and (2c).
상기 UV 경화 작용기는 (메타)아크릴레이트기, 에폭시알콕시알킬기(예:에폭시기를 갖는 탄소수 1-10의 알콕시기를 함유하는 탄소수 1-10의 알킬기), 에폭시기, 에폭시알킬기(예:에폭시기를 갖는 탄소수 1-10의 알킬기), 알릴기 또는 비닐기 중 하나 이상을 포함할 수 있다.The UV-curing functional group may be a (meth) acrylate group, an epoxyalkoxyalkyl group (e.g., an alkyl group having 1-10 carbon atoms having 1-10 carbon atoms having an epoxy group), an epoxy group, an epoxyalkyl group -10) alkyl group, an allyl group or a vinyl group.
상기 UV 경화형 실리콘계 수지는 1종 또는 2종 이상의 혼합물로 사용될 수 있다.The UV curable silicone resin may be used alone or in combination of two or more.
상기 UV 경화형 실리콘계 수지는 중량평균분자량이 350g/mol-50,000g/mol, 바람직하게는 350g/mol-30,000g/mol이 될 수 있다. 상기 범위에서, 함침 및 경화 후 유연성 및 기계적 물성을 기대할 수 있다.The UV curable silicone resin may have a weight average molecular weight of 350 g / mol-50,000 g / mol, preferably 350 g / mol-30,000 g / mol. Within this range, flexibility and mechanical properties can be expected after impregnation and curing.
상기 매트릭스용 조성물은 실리콘 우레탄 (메타)아크릴레이트(silicone urethane (meth)acrylate)를 더 포함할 수 있다. 실리콘 우레탄 (메타)아크릴레이트의 중량평균분자량은 350g/mol-50,000g/mol, 바람직하게는 350g/mol-30,000g/mol, 더 바람직하게는 350g/mol-10,000g/mol이 될 수 있다. 상기 범위에서, 높은 경화율과 UV 경화 후의 기계적 물성을 기대할 수 있다.The composition for a matrix may further comprise silicone urethane (meth) acrylate. The weight average molecular weight of the silicone urethane (meth) acrylate may be 350 g / mol-50,000 g / mol, preferably 350 g / mol-30,000 g / mol, more preferably 350 g / mol-10,000 g / mol. Within the above range, a high curing rate and mechanical properties after UV curing can be expected.
상기 매트릭스 조성물 중 UV 경화형 실리콘계 수지와 실리콘 우레탄 (메타)아크릴레이트의 합 100중량부 중 UV 경화형 실리콘계 수지는 1-99중량부, 실리콘 우레탄 (메타)아크릴레이트는 1-99중량부로 포함될 수 있다. 바람직하게는 UV 경화형 실리콘계 수지는 40-60중량부, 실리콘 우레탄 (메타)아크릴레이트는 40-60중량부로 포함될 수 있다. 상기 범위 내에서, 우수한 내열성과 높은 가교밀도를 가질 수 있다.The UV curable silicone resin and the silicone urethane (meth) acrylate may be contained in an amount of 1-99 parts by weight and 1-99 parts by weight, respectively, in 100 parts by weight of the sum of the UV curable silicone resin and the silicone urethane (meth) acrylate in the matrix composition. Preferably, the UV curable silicone resin may be contained in an amount of 40 to 60 parts by weight, and the silicone urethane (meth) acrylate may be contained in an amount of 40 to 60 parts by weight. Within the above range, excellent heat resistance and high crosslinking density can be obtained.
상기 개시제는 광중합 개시제, 광산 발생제(PAG, photo acid generator) 또는 이들의 혼합물을 포함할 수 있다.The initiator may include a photopolymerization initiator, a photo acid generator (PAG), or a mixture thereof.
개시제는 UV 경화형 실리콘계 수지(또는 UV 경화형 실리콘계 수지와 실리콘 우레탄 (메타)아크릴레이트의 합) 100중량부에 대하여 0.01-10중량부, 바람직하게는 0.1-3중량부로 포함될 수 있다. 상기 범위에서, 경화가 충분히 될 수 있고 잔량의 개시제가 남지 않는다.The initiator may be contained in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the UV curable silicone resin (or the sum of the UV curable silicone resin and the silicone urethane (meth) acrylate). Within this range, curing can be sufficient and no residual initiator remains.
광중합 개시제와 광산 발생제는 통상의 종류를 제한없이 사용할 수 있다.The photopolymerization initiator and the photoacid generator may be used in any kind without limitation.
구체예로서, 광중합 개시제는 벤조페논계, 인계, 트리아진계, 아세토페논계, 티오크산톤계, 벤조인계, 옥심계 또는 이들의 혼합물을 포함할 수 있다. 예를 들면, 1-히드록시시클로헥실 페닐 케톤 등을 포함하는 벤조페논계를 사용할 수 있다.As a specific example, the photopolymerization initiator may include benzophenone, phosphorus, triazine, acetophenone, thioxanthone, benzoin, oxime, or a mixture thereof. For example, a benzophenone system including 1-hydroxycyclohexyl phenyl ketone and the like can be used.
광산 발생제는 오늄 이온인 양이온과 음이온의 오늄염을 사용할 수 있다. 양이온의 구체예로서는 디페닐요오드늄, 4-메톡시디페닐요오드늄 등의 디아릴요오드늄, 트리페닐술포늄, 4-페닐티오페닐디페닐술포늄 등의 트리아릴술포늄 등을 들 수 있다. 음이온의 구체예로서는, 테트라플루오로보레이트(BF4-), 헥사플루오로포스페이트(PF6-), 헥사플루오로안티모네이트(SbF6-), 헥사플루오로아르세네이트(AsF6-), 헥사클로로안티모네이트(SbCl6-) 등을 들 수 있다.As the photoacid generator, an onium salt of an onium ion and an onium salt of an anion may be used. Specific examples of the cation include diaryl iodonium such as diphenyl iodonium and 4-methoxydiphenyl iodonium, triarylsulfonium such as triphenylsulfonium and 4-phenylthiophenyldiphenylsulfonium, and the like. Specific examples of the anion include tetrafluoroborate (BF 4 -), hexafluorophosphate (PF 6 -), hexafluoroantimonate (SbF 6 -), hexafluoroarsenate (AsF 6 - And chlorantimonate (SbCl 6 -).
다른 실시예에서, 상기 복합시트는 실리콘계 수지와 UV 경화형 촉매를 포함하는 매트릭스용 조성물과, 상기 매트릭스용 조성물에 함침된 보강재의 경화물로 이루어질 수 있다.In another embodiment, the composite sheet may comprise a composition for a matrix comprising a silicone resin and a UV curable catalyst, and a cured product of the reinforcement impregnated in the matrix composition.
상기 실리콘계 수지는 하기 화학식 3의 단위를 포함할 수 있다.The silicone resin may include a unit represented by the following formula (3).
<화학식 3>(3)
(상기 식에서, Re와 Rf는 동일하거나 다르고, 수소 원자, C1-C20 알킬기, C2-C20 알케닐기, C2-C20 알키닐기, C1-C20 알콕시기, C3-C30 사이클로알킬기, C3-C30 사이클로알케닐기, C3-C30 사이클로알키닐기, C6-C30 아릴기, C6-C30 아릴옥시기이고, Re and Rf are the same or different and are a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C1-C20 alkoxy group, a C3-C30 cycloalkyl group, a C3-C30 cycloalkenyl group , A C3-C30 cycloalkynyl group, a C6-C30 aryl group, a C6-C30 aryloxy group,
n은 2 내지 1000의 정수이다).and n is an integer of 2 to 1000).
상기 실리콘계 수지는 상기 화학식 3의 단위를 포함하거나 화학식 3의 단위로 이루어진 고리형 또는 선형 실리콘계 수지가 될 수 있다.The silicone-based resin may be a cyclic or linear silicone-based resin comprising the unit of the formula (3) or the unit of the formula (3).
상기 실리콘계 수지의 말단은 -OSiR13R14R15 또는 -SiR16R17R18(상기에서 R13,R14,R15,R16,R17,R18은 각각 독립적으로 수소 원자, C1-C20 알킬기, C2-C20 알케닐기, C2-C20 알키닐기, C1-C20 알콕시기, C3-C30 사이클로알킬기, C3-C30 사이클로알케닐기, C3-C30 사이클로알키닐기, C6-C30 아릴기 또는 C6-C30 아릴옥시기)가 될 수 있다.Wherein the terminal of the silicone resin is -OSiR13R14R15 or -SiR16R17R18 wherein R13, R14, R15, R16, R17 and R18 each independently represents a hydrogen atom, a C1-C20 alkyl group, a C2- C30 alkoxy group, a C3-C30 cycloalkyl group, a C3-C30 cycloalkenyl group, a C3-C30 cycloalkynyl group, a C6-C30 aryl group or a C6-C30 aryloxy group.
상기 UV 경화형 실리콘계 수지는 중량평균분자량이 350g/mol-50,000g/mol, 바람직하게는 350g/mol-30,000g/mol이 될 수 있다. 상기 범위에서, 함침 및 경화 후 유연성 및 기계적 물성을 기대할 수 있다.The UV curable silicone resin may have a weight average molecular weight of 350 g / mol-50,000 g / mol, preferably 350 g / mol-30,000 g / mol. Within this range, flexibility and mechanical properties can be expected after impregnation and curing.
상기 실리콘계 수지는 상기 UV 경화 작용기를 더 포함할 수도 있다. The silicone resin may further comprise the UV curing functional group.
상기 UV 경화형 촉매는 광에너지선 조사를 받아 활성을 띄고, 히드로실릴화 반응을 촉진시키는 화합물이기만 하면 특별히 제한되지 않는다. 이의 예로는 백금 촉매, 루테늄 촉매 및 로듐 촉매로 이루어진 군으로부터 선택될 수 있다. The UV curable catalyst is not particularly limited as long as it is a compound which is activated by irradiation with a photo energy ray and promotes the hydrosilylation reaction. Examples thereof may be selected from the group consisting of platinum catalysts, ruthenium catalysts and rhodium catalysts.
상기 UV 경화형 촉매는 디엔계 화합물이 될 수 있다.The UV curable catalyst may be a diene compound.
상기 촉매는 상기 실리콘계 수지 100중량부에 대하여 0.001~1중량부가 포함될 수 있다. 바람직하게는 0.01~0.1중량부의 양으로 포함되는데, 이 양이 0.001중량부 미만이면 경화속도가 느려지고, 1중량부를 초과하면 경화물의 장기저장성에 영향을 미칠 수 있으며, 최종 경화 필름에 황변이 올 수 있다.The catalyst may be added in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the silicone resin. If the amount is less than 0.001 part by weight, the curing rate is slowed. If the amount is more than 1 part by weight, the long-term storage stability of the cured product may be affected. If the amount is less than 0.001 part by weight, have.
상기 매트릭스용 조성물은 상술한 성분 이외에, 가교제(crosslinker), 촉매, 억제제를 더 포함할 수 있다.In addition to the components described above, the composition for a matrix may further include a crosslinker, a catalyst, and an inhibitor.
가교제는 플렉시블 기판용 복합시트 제조에서 통상적으로 사용되는 가교제를 사용할 수 있다. 예를 들면, Si-CH3와 Si-H를 갖는 폴리오르가노실록산을 사용할 수 있다. 가교제는 실리콘 수지의 C2-C20 알케닐기 예를 들면 비닐기의 몰 수에 대해 가교제의 Si-H의 몰 수의 몰 당량비가 1.0 이상, 바람직하게는 1.0-1.3이 되도록 포함될 수 있다.The cross-linking agent may be a cross-linking agent usually used in the production of a composite sheet for a flexible substrate. For example, a polyorganosiloxane having Si-CH 3 and Si-H can be used. The crosslinking agent may be contained so that the molar equivalent ratio of the number of moles of Si-H in the crosslinking agent to the number of moles of the C2-C20 alkenyl group, for example, the vinyl group of the silicone resin is 1.0 or more, preferably 1.0 to 1.3.
촉매는 플렉시블 기판용 복합시트 제조에서 통상적으로 사용되는 촉매를 사용할 수 있다. 예를 들면, 백금계 또는 로듐계 촉매로서 백금과 유기 화합물의 복합체, 백금과 비닐화된 오르가노실록산 복합체, 로듐과 올레핀 착체 등을 사용할 수 있다. 구체적으로는, Karstedt 촉매를 포함하는 비닐알킬실란 백금 착물, 백금흑(platinum black), 염화백금산, 염화백금산-올레핀 착체, 염화백금산-알코올 배위 화합물, 또는 이들의 혼합물을 사용할 수 있다. As the catalyst, a catalyst commonly used in the production of a composite sheet for a flexible substrate can be used. For example, a platinum-based or rhodium-based catalyst may be used, for example, a composite of platinum and an organic compound, a platinum-vinylated organosiloxane complex, or a rhodium-olefin complex. Specifically, a vinylalkylsilane platinum complex containing Karstedt catalyst, platinum black, chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-alcohol coordination compound, or a mixture thereof can be used.
촉매는 금속의 중량으로, 상기 실리콘계 수지에 대해 2ppm-2000ppm, 바람직하게는 5ppm-500ppm으로 포함될 수 있다.The catalyst may be contained in an amount of 2 ppm-2000 ppm, preferably 5 ppm-500 ppm, based on the metal-based resin.
억제제는 25℃에서는 촉매의 작용을 억제하고 고온의 경화 과정에서는 억제 작용을 하지 않음으로써, 고온에서 매트릭스를 경화시킬 수 있다.The inhibitor inhibits the action of the catalyst at 25 < 0 > C and does not inhibit it during the high temperature curing process, thereby allowing the matrix to cure at high temperatures.
억제제는 플렉시블 기판용 복합시트 제조에서 통상적으로 사용되는 억제제를 사용할 수 있다. 예를 들면, 억제제는 디메틸-1-헥신-3-올을 포함하는 아세틸렌성 알코올, 피리딘, 포스핀, 유기 포스파이트, 불포화아미드, 디알킬카르올실레이트, 디알킬아세틸렌디카르복실레이트, 알킬화된 말리에이트, 디알릴말리에이트, 또는 이들의 혼합물로 이루어진 군으로부터 선택될 수 있다. 억제제는 상기 실리콘계 수지에 대해 100ppm-2500ppm으로 포함될 수 있다. The inhibitor may be an inhibitor commonly used in the production of a composite sheet for a flexible substrate. For example, the inhibitor may be selected from the group consisting of acetylenic alcohols including dimethyl-1-hexyn-3-ol, pyridine, phosphine, organic phosphite, unsaturated amide, dialkylcarnosylate, dialkyl acetylenedicarboxylate, alkylated Maleic anhydride, maleic anhydride, diallyl maleate, or a mixture thereof. The inhibitor may be contained at 100 ppm to 2500 ppm with respect to the silicone-based resin.
상기 복합시트 중 매트릭스는 70-95중량%, 더 바람직하게는 80-90중량%로 포함될 수 있다. 상기 범위에서, 복합시트에 유연성을 제공할 수 있다.The matrix of the composite sheet may include 70-95 wt%, more preferably 80-90 wt%. Within this range, it is possible to provide flexibility to the composite sheet.
상기 보강재는 매트릭스 내에 포함(embedd)되어 있다. 보강재는 매트릭스와의 굴절률 차이(보강재의 굴절률-매트릭스의 굴절률의 절대값)가 0.01 이하가 될 수 있다. 상기 범위 내에서, 우수한 투명성과 투광성을 가질 수 있다. 바람직하게는 상기 굴절률 차이는 0.005 이하, 더 바람직하게는 0.0001-0.005가 될 수 있다.The stiffener is embeddable within the matrix. The stiffener may have a refractive index difference with respect to the matrix (refractive index of the stiffener - absolute value of the refractive index of the matrix) of 0.01 or less. Within the above range, it can have excellent transparency and transparency. Preferably, the refractive index difference is 0.005 or less, more preferably 0.0001-0.005.
상기 보강재는 유리섬유, 유리 섬유포(glass fiber cloth), 유리 직물(glass fibric), 유리 부직포, 유리 메쉬(glass mesh), 유리 비드, 유리 플레이크(glass flake), 실리카 입자 및 콜로이달 실리카로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있다. 바람직하게는 유리 섬유포를 사용할 수 있다.The reinforcing material may be selected from the group consisting of glass fibers, glass fiber cloth, glass fabric, glass nonwoven fabric, glass mesh, glass beads, glass flake, silica particles and colloidal silica And the like. Preferably, a glass fiber cloth can be used.
상기 복합시트 중 보강재는 5-30중량%, 바람직하게는 10-20중량%로 포함될 수 있다. 상기 범위에서, 플렉시블 기판의 고내열성 및 기계적 물성을 확보할 수 있고, 투명성, 유연성, 경량성이 좋도록 할 수 있다. The reinforcing material in the composite sheet may be contained in an amount of 5-30% by weight, preferably 10-20% by weight. Within the above range, high heat resistance and mechanical properties of the flexible substrate can be ensured, and transparency, flexibility and light weight can be improved.
본 발명의 다른 관점인 복합시트 제조방법은 실리콘계 수지를 포함하는 매트릭스용 조성물과, 상기 매트리스용 조성물에 함침된 보강재를 UV 경화시켜 제조될 수 있다.The composite sheet producing method according to another aspect of the present invention can be produced by UV curing a matrix composition comprising a silicone resin and a reinforcing material impregnated in the composition for a mattress.
일 구체예에서, UV 경화형 실리콘계 수지와 개시제를 포함하는 매트릭스용 조성물을 제조하는 단계; 및 상기 조성물에 보강재를 함침하고 UV 경화시키는 단계를 포함할 수 있다.In one embodiment, there is provided a method of preparing a composition for a matrix, comprising: preparing a composition for a matrix comprising a UV curable silicone resin and an initiator; And impregnating and UV curing the composition with a reinforcement.
다른 구체예에서, 실리콘계 수지와 UV 경화형 촉매를 포함하는 매트릭스용 조성물을 제조하는 단계; 및 상기 조성물에 보강재를 함침하고 UV 경화시키는 단계를 포함할 수 있다.In another embodiment, there is provided a method of preparing a composition for a matrix, comprising: preparing a matrix composition comprising a silicone resin and a UV curable catalyst; And impregnating and UV curing the composition with a reinforcement.
구체적으로는, 매트릭스용 조성물에 보강재를 함침하고, 라미네이션(lamination) 한 후, UV 경화시켜 제조할 수 있다. UV 경화는 500mJ/cm2-10,000mJ/cm2의 조사량, 0.01초-10분의 조사로 수행될 수 있지만, 이에 제한되지 않는다.Specifically, it can be produced by impregnating a matrix composition with a reinforcing material, lamination, and UV curing. UV curing may be performed by irradiation of the irradiation dose, 0.01 cho -10 minutes of 500mJ / cm 2 -10,000mJ / cm 2 , but is not limited thereto.
상기 제조방법은 UV 경화 후 열 처리하는 단계를 더 포함할 수 있다. 열 처리는 25℃-150℃, 0.1-5시간 동안 처리하는 단계를 포함한다. UV 경화시킨 후 열 처리는 에이징(aging) 효과를 부여할 수 있다.The manufacturing method may further include a heat treatment after UV curing. The heat treatment includes treating at 25 DEG C to 150 DEG C for 0.1 to 5 hours. After UV curing, the heat treatment can impart an aging effect.
상기 제조방법은 상기 보강재를 함침한 후 UV 경화시키기 전(즉, 보강재를 함침하는 단계와 UV 경화시키는 단계 사이)에 열 처리하는 단계를 더 포함할 수 있다. 열 처리는 25℃-150℃, 0.1-5시간 동안 처리하는 단계를 포함한다. 보강재를 함침하는 단계와 UV 경화시키는 단계 사이에 열 처리는 열 경화 효과를 부여할 수 있다.The manufacturing method may further include heat treating the reinforcing material after impregnating the reinforcing material and before UV curing (i.e., between the step of impregnating the reinforcing material and the step of UV curing). The heat treatment includes treating at 25 DEG C to 150 DEG C for 0.1 to 5 hours. Between the step of impregnating the stiffener and the step of UV curing, the heat treatment can impart a thermosetting effect.
상기 매트릭스용 조성물과 보강재에 대한 내용은 상술한 바와 같다.The composition for the matrix and the reinforcing material are as described above.
상기 제조방법으로 제조된 복합시트는 표면 조도(Ra) 100nm 이하, 바람직하게는 50nm 이하, 더 바람직하게는 5nm-50nm를 가질 수 있다.The composite sheet produced by the above production method may have a surface roughness (Ra) of 100 nm or less, preferably 50 nm or less, and more preferably 5 nm to 50 nm.
상기 제조방법으로 제조된 복합시트는 young,s modulus가 1MPa-200MPa, 바람직하게는 1MPa-150MPa가 될 수 있다.The Young's modulus of the composite sheet produced by the above-described method may be 1 MPa-200 MPa, preferably 1 MPa-150 MPa.
본 발명의 또 다른 관점인 플렉시블 기판 및 이를 포함하는 디스플레이 장치는 상기 복합시트를 포함할 수 있다. 플렉시블 기판은 액정 표시 소자(LCD)용 기판, 컬러 필터(color filter)용 기판, 유기 EL 표시소자용 기판, 태양 전지용 기판, 터치 스크린 패널(touch screen panel)용 기판 등의 디스플레이 또는 광 소자의 용도로서 이용할 수 있다. A flexible substrate and a display device including the flexible substrate according to another aspect of the present invention may include the composite sheet. The flexible substrate can be used as a display for a liquid crystal display (LCD) substrate, a substrate for a color filter, a substrate for an organic EL display device, a substrate for a solar cell, a substrate for a touch screen panel, .
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로 본 발명을 제한하는 것으로 해석되어서는 안 된다.Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
제조예Manufacturing example 1: One: D4MAD4MA 의 합성 및 제조Synthesis and Manufacture
D4silane(1,3,5,7-tetramethyl cyclotetrasiloxane)과 allyl methacrylate를 몰비 1:1.1 당량으로 넣고, Pt촉매(Karstedt catalyst)를 1중량%, 히드로퀴논 (inhibitor)을 allyl methacrylate 대비 10 mol%를 첨가한 후 톨루엔 용제 하에서 70℃에서 리플럭스(reflux)하여 반응시켰다. 그 후에 톨루엔을 제거하고 여과하여 D4MA(메타아크릴기 함유 고리형 오르가노실록산)를 얻었다.D4silane (1,3,5,7-tetramethyl cyclotetrasiloxane) and allyl methacrylate were added in a molar ratio of 1: 1.1 equivalent, 1 wt% of Pt catalyst (Karstedt catalyst), 10 mol% of hydroquinone (inhibitor) relative to allyl methacrylate And refluxed at 70 ° C in a toluene solvent. Thereafter, toluene was removed and filtered to obtain D4MA (a methacrylic group-containing cyclic organosiloxane).
제조예Manufacturing example 2:실리콘계( 2: silicon system ( PDMSPDMS ) 수지 매트릭스의 합성 및 제조) Synthesis and Preparation of Resin Matrix
페닐메틸 디메톡시 실록산(Phenylmethyl dimethoxy siloxane, PMDMS), 디메틸 디메톡시 실록산(Dimethyl dimethoxy siloxane, DMDMS), 비닐 트리메톡시 실록산(Vinyl trimethoxy siloxane, VTMS)를 사용하여 합성을 진행하였다. PDMDS, DMDMS 및 VTMS를 계량 후((PMDMS + DMDMS) : VTMS 중량비 95:5) 70℃에서 1시간 동안 탈이온수와 KOH 하에서 가수분해를 진행하였다. 90℃에서 반응을 진행한 후 톨루엔과 물을 첨가하여 25도로 낮추고 물로 세정하였다. 그 후에 Vi-MM(1,1,3,3,-tetramethyl-1,3-divinyl disiloxane)을 첨가하여 50℃에서 5hr가량 말단 캡핑(endcapping)을 진행하고, 25℃에서 물로 세정하고 용매를 제거하여 최종 PDMS 수지(페닐기, 메틸기, 비닐기 함유 폴리오르가노실록산 수지)를 합성하였다. (PMDMS + DMDMS) : VTMS를 일정비율로 하여 PMDMS과 DMDMS의 함량을 다르게 한 2종류를 합성하였으며, 유리 섬유포(D-glass cloth)와의 굴절률을 matching하기 위해 2종의 PDMS를 혼합하여 사용하였다.Synthesis was conducted using phenylmethyl dimethoxy siloxane (PMDMS), dimethyl dimethoxy siloxane (DMDMS), and vinyl trimethoxy siloxane (VTMS). PDMDS, DMDMS and VTMS were weighed ((PMDMS + DMDMS): VTMS weight ratio 95: 5) and hydrolysis was carried out at 70 ° C for 1 hour under deionized water and KOH. After the reaction was carried out at 90 ° C, toluene and water were added and the mixture was cooled to 25 ° C and washed with water. Then, Vi-MM (1,1,3,3-tetramethyl-1,3-divinyl disiloxane) was added to perform end capping at 50 ° C for about 5 hours, washed with water at 25 ° C to remove the solvent To obtain a final PDMS resin (phenyl group, methyl group, and vinyl group-containing polyorganosiloxane resin). (PMDMS + DMDMS): Two kinds of PMDMS and DMDMS were synthesized at a certain ratio of VTMS and two kinds of PDMS were mixed to match the refractive index with the D-glass cloth.
제조예Manufacturing example 3:촉매 시스템 A 제조 3: Production of catalyst system A
촉매로 Karstedt catalyst(PT-CS-1.8CS, Umicore)와 억제제 surfynol를 배합하여 사용하였다.Karstedt catalyst (PT-CS-1.8CS, Umicore) and surfactin surfynol were used as catalysts.
실시예Example 1 One
제조예 1의 D4MA와 Miramer SIU1000(미원, Mw 530g/mol, slilicone urethane acrylate)을 중량비 40wt%/60wt%로 혼합하였다. 개시제 Igacure184를 1wt% 첨가하여 매트릭스용 조성물을 제조하였다. 유리 섬유포(D-glass cloth)에 함침하고 라미네이션(Lamination)한 후, 1분 동안 UV를 조사(수은 lamp, 5000mJ/cm2)하여 복합시트를 제조하였다.D4MA of Preparation Example 1 and Miramer SIU1000 (Mwon, Mw 530 g / mol, slilicone urethane acrylate) were mixed at a weight ratio of 40 wt% / 60 wt%. 1 wt% of initiator Igacure 184 was added to prepare a composition for a matrix. The laminate was impregnated with a D-glass cloth, laminated, and irradiated with UV (mercury lamp, 5000 mJ / cm 2 ) for 1 minute to prepare a composite sheet.
실시예Example 2 2
PMS-E11(Gelest, epoxypropoxypropyl terminated polyphenylmethylsiloxane, Mn 500g/mol)과 DMS-E09(Gelest, epoxypropoxypropyl terminated polydimethylsiloxane, Mn 350g/mol)를 중량비 40wt%/60wt%로 혼합하였다. 광산 발생제 CPI-210S를 1wt% 첨가하여 실시예 1과 마찬가지로 유리 섬유포에 함침하고 라미네이션한 후, 1분 동안 UV를 조사(수은 lamp, 5000mJ/cm2)하여 경화를 진행하였다. 그 후 100℃에서 1시간 더 열처리를 진행하여 복합시트를 제조하였다.PMS-E11 (Gelest, epoxypropoxypropyl terminated polyphenylmethylsiloxane, Mn 500 g / mol) and DMS-E09 (Gelest, epoxypropoxypropyl terminated polydimethylsiloxane, Mn 350 g / mol) were mixed at a weight ratio of 40 wt% / 60 wt%. 1% by weight of photo acid generator CPI-210S was added thereto, and the resultant mixture was impregnated with a glass fiber cloth and laminated in the same manner as in Example 1, and then cured by UV irradiation (mercury lamp, 5000 mJ / cm 2 ) for 1 minute. Thereafter, heat treatment was further performed at 100 캜 for one hour to prepare a composite sheet.
실시예Example 3 3
제조예 2의 PDMS 수지에 crosslinker로 HMS-501(Gelest)를 Si-H/vinyl 몰비 1.2로 배합 후 UV 경화형 백금 촉매 0.05 wt%를 첨가하고 유리 섬유포에 함침하고 라미네이션한 후, 1분 동안 UV를 조사(수은 lamp, 5000mJ/cm2)하여 복합시트를 제조하였다. HMS-501 (Gelest) was mixed with the PDMS resin of Preparation Example 2 in a molar ratio of Si-H / vinyl of 1.2 by a crosslinker, followed by addition of 0.05 wt% of a UV-curable platinum catalyst, followed by impregnation with a glass fiber cloth and lamination. (Mercury lamp, 5000 mJ / cm 2 ) to prepare a composite sheet.
비교예Comparative Example 1 One
제조예 2의 PDMS 수지에 촉매시스템 A를 0.05wt%를 첨가하고 유리 섬유포를 함침시키고 고온 경화(80℃에서 10분)를 진행하여 복합시트를 제조하였다. 0.05% by weight of the catalyst system A was added to the PDMS resin of Production Example 2, and the glass sheet was impregnated with the glass fiber cloth, followed by curing at high temperature (80 占 폚 for 10 minutes) to prepare a composite sheet.
비교예Comparative Example 2 2
제조예 2의 PDMS 수지에 촉매시스템 A를 0.05wt%를 첨가하고 유리 섬유포를 함침시키고 상온 경화(25℃에서 10시간)를 진행하여 복합시트를 제조하였다. 0.05% by weight of Catalyst System A was added to the PDMS resin of Production Example 2, followed by impregnation with a glass fiber cloth and curing at room temperature (25 占 폚 for 10 hours) to prepare a composite sheet.
상기 제조한 복합시트에 대해 하기의 물성을 평가하고 표 1에 나타내었다.The following composite sheets were evaluated for the following physical properties and are shown in Table 1.
(1)열팽창계수(CTE)(ppm/℃): ASTM E 831 방법에 따라 온도에 따른 dimensional change를 Thermo-mechanical Aanlysizer(Expansion mode, Force 0.05N)를 이용하여 측정한 후, 온도 변화(30-250℃)에 따른 시료길이의 변화 곡선으로부터, 시료의 CTE(ppm/℃)를 구하였다.(1) Thermal expansion coefficient (CTE) (ppm / ° C): Dimensional change according to ASTM E 831 method was measured using Thermo-mechanical Aanlysizer (Expansion mode, Force 0.05N) 250 占 폚), the CTE (ppm / 占 폚) of the sample was determined.
(2)Young,s modulus(Mpa): Micro indentor(Fischer, H100)를 이용하여 indentation modulus를 측정하였다.(2) Young, s modulus (Mpa): The indentation modulus was measured using a microindenter (Fischer, H100).
(3)표면 조도(Ra, nm): Optical profiler를 이용하여 비접촉식으로 측정하였다. 복합 시트 1.2mm x 9mm의 면적에서 NT1100(Veeco사)를 사용하여 5 Point 측정하고 평균값을 취하였다.(3) Surface roughness (Ra, nm): Measured in a non-contact manner using an optical profiler. The composite sheet was measured at 5 points using an area of 1.2 mm x 9 mm using NT1100 (Veeco) and the average value was taken.
상기 표 1에서와 같이, 본 발명의 복합시트는 짧은 시간에 걸쳐 제조되었음에도 불구하고 표면 조도가 개선되었다. 반면에, 고온에서 경화시켜 제조된 비교예 1의 복합시트는 단시간에 제조되었지만 표면 조도 값이 높았다. 또한, 상온에서 경화시켜 제조된 비교예 2의 복합시트는 표면 조도 값은 낮지만 장시간에 걸쳐 제조되었다. As shown in Table 1, the composite sheet of the present invention improved surface roughness even though it was produced over a short period of time. On the other hand, the composite sheet of Comparative Example 1 prepared by curing at a high temperature was produced in a short time, but the surface roughness value was high. In addition, the composite sheet of Comparative Example 2 prepared by curing at room temperature had a surface roughness value but was produced over a long period of time.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (16)
상기 조성물은 실리콘 우레탄 (메타)아크릴레이트(silicone urethane (meth)acrylate)를 더 포함하는 복합시트.A composition for a matrix comprising a UV curable silicone resin and an initiator, and a cured product of a reinforcing material impregnated in the matrix composition,
Wherein the composition further comprises silicone urethane (meth) acrylate.
상기 조성물은 실리콘 우레탄 (메타)아크릴레이트(silicone urethane (meth)acrylate)를 더 포함하는 복합시트.A composition for a matrix comprising a silicone resin and a UV curable catalyst and a cured product of a reinforcing material impregnated in the matrix composition,
Wherein the composition further comprises silicone urethane (meth) acrylate.
[화학식 3]
(상기 식에서, Re와 Rf는 서로 동일하거나 상이하며, 수소 원자, C1-C20 알킬기, C2-C20 알케닐기, C2-C20 알키닐기, C1-C20 알콕시기, C3-C30 사이클로알킬기, C3-C30 사이클로알케닐기, C3-C30 사이클로알키닐기, C6-C30 아릴기, 또는 C6-C30 아릴옥시기이고, n은 2 내지 1000의 정수이다).The composite sheet according to claim 2, wherein the silicone resin comprises a polyorganosiloxane resin containing units of the following formula 3:
(3)
Re and Rf are the same or different and are a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C1-C20 alkoxy group, a C3-C30 cycloalkyl group, A C3-C30 cycloalkynyl group, a C6-C30 aryl group, or a C6-C30 aryloxy group, and n is an integer of 2 to 1000).
상기 조성물에 보강재를 함침하고, 그리고 UV 경화시키는 단계를 포함하고,
상기 조성물에 실리콘 우레탄 (메타)아크릴레이트(silicone urethane (meth)acrylate)를 추가하는 단계를 포함하는 복합시트 제조방법.A composition for a matrix comprising a UV curable silicone resin and an initiator is prepared,
Impregnating the composition with a reinforcement, and UV curing the composition,
And adding silicone urethane (meth) acrylate to the composition.
상기 조성물에 실리콘 우레탄 (메타)아크릴레이트(silicone urethane (meth)acrylate)를 추가하는 단계를 포함하는 복합시트 제조방법.Preparing a composition for a matrix comprising a silicone resin and a UV curable catalyst; And impregnating the composition with a reinforcement and UV curing,
And adding silicone urethane (meth) acrylate to the composition.
A display device comprising the flexible substrate of claim 15.
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| PCT/KR2013/006551 WO2014017795A1 (en) | 2012-07-24 | 2013-07-23 | Complex sheet, method for manufacturing same, flexible substrate including same, and display device including same |
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| KR101786189B1 (en) | 2015-08-07 | 2017-11-15 | 현대자동차주식회사 | Composition for lightened and transparent composite, method for preparing the composites using the same and the composites prepared thereby |
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| US9370904B2 (en) | 2013-12-19 | 2016-06-21 | Carbitex, LLC | Flexible fiber-reinforced composite material |
| WO2015094308A1 (en) * | 2013-12-19 | 2015-06-25 | Carbitex, LLC | Flexible fiber-reinforced composite material |
| KR20170110998A (en) | 2016-03-24 | 2017-10-12 | 다우 코닝 코포레이션 | Optical Silicone Double-Side Tape Comprising a Silicone Substrate Layer Having Low Storage Modulus |
| KR102568774B1 (en) * | 2018-03-14 | 2023-08-21 | 모멘티브퍼포먼스머티리얼스코리아 주식회사 | Display panel and method for manufacturing thereof |
| DE102018109411A1 (en) | 2018-04-19 | 2019-10-24 | Festool Gmbh | Connectors |
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| KR20100070349A (en) * | 2007-10-12 | 2010-06-25 | 다우 코닝 코포레이션 | Reinforced silicone resin film and nanofiber-filled silicone composition |
| KR20100083697A (en) * | 2009-01-13 | 2010-07-22 | 한국과학기술원 | Transparent composite compound |
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| EP1676937B1 (en) * | 2004-11-26 | 2016-06-01 | Rohm and Haas Electronic Materials, L.L.C. | UV curable catalyst compositions |
| JP5471180B2 (en) * | 2008-09-11 | 2014-04-16 | 信越化学工業株式会社 | Silicone laminated substrate, method for producing the same, silicone resin composition for producing silicone laminated substrate, and LED device |
| CN102869829A (en) * | 2010-04-29 | 2013-01-09 | 3M创新有限公司 | Electron beam cured siliconized fibrous webs |
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| KR20100070349A (en) * | 2007-10-12 | 2010-06-25 | 다우 코닝 코포레이션 | Reinforced silicone resin film and nanofiber-filled silicone composition |
| KR20100083697A (en) * | 2009-01-13 | 2010-07-22 | 한국과학기술원 | Transparent composite compound |
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| KR101786189B1 (en) | 2015-08-07 | 2017-11-15 | 현대자동차주식회사 | Composition for lightened and transparent composite, method for preparing the composites using the same and the composites prepared thereby |
| US10363708B2 (en) | 2015-08-07 | 2019-07-30 | Hyundai Motor Company | Composition for preparing lightweight transparent composite, method of preparing composite using the same and composite prepared thereby |
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