WO2014193177A2 - Open-structure polyhedral oligomeric silsesquioxane and composition comprising same - Google Patents
Open-structure polyhedral oligomeric silsesquioxane and composition comprising same Download PDFInfo
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- WO2014193177A2 WO2014193177A2 PCT/KR2014/004810 KR2014004810W WO2014193177A2 WO 2014193177 A2 WO2014193177 A2 WO 2014193177A2 KR 2014004810 W KR2014004810 W KR 2014004810W WO 2014193177 A2 WO2014193177 A2 WO 2014193177A2
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- WIPO (PCT)
- Prior art keywords
- formula
- composition
- polyhedral oligomeric
- poss
- oligomeric silsesquioxane
- Prior art date
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- 235000001258 Cinchona calisaya Nutrition 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical class [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical compound N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- AENNXXRRACDJAY-UHFFFAOYSA-N bis(2-dodecylphenyl)iodanium Chemical compound CCCCCCCCCCCCC1=CC=CC=C1[I+]C1=CC=CC=C1CCCCCCCCCCCC AENNXXRRACDJAY-UHFFFAOYSA-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
- 239000000872 buffer Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- MZRQZJOUYWKDNH-UHFFFAOYSA-N diphenylphosphoryl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MZRQZJOUYWKDNH-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 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
- XCGSMHBLIRBUGZ-UHFFFAOYSA-K ethyl(triphenyl)phosphanium;phosphate Chemical compound [O-]P([O-])([O-])=O.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 XCGSMHBLIRBUGZ-UHFFFAOYSA-K 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YFYSUAZHCKSLCV-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxobutan-2-yl)diazenyl]-2-methylbutanoate Chemical compound COC(=O)C(C)(CC)N=NC(C)(CC)C(=O)OC YFYSUAZHCKSLCV-UHFFFAOYSA-N 0.000 description 1
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229960000948 quinine Drugs 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- LXAWHMFHGHNIHC-UHFFFAOYSA-N sulfanyl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OS LXAWHMFHGHNIHC-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- HJBZFPLBRXFZNE-UHFFFAOYSA-M tetrabutylphosphanium fluoride hydrofluoride Chemical compound F.[F-].CCCC[P+](CCCC)(CCCC)CCCC HJBZFPLBRXFZNE-UHFFFAOYSA-M 0.000 description 1
- GFZMLBWMGBLIDI-UHFFFAOYSA-M tetrabutylphosphanium;acetate Chemical compound CC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC GFZMLBWMGBLIDI-UHFFFAOYSA-M 0.000 description 1
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
Definitions
- the present invention relates to an open structure of a polyhedral oligomeric silsesquioxane (POSS) and a composition comprising the same, more particularly cross-linking is possible to increase the compatibility with the resin, and partially open-cage (Polhedral oligomeric silsesquioxanes (POSS) with an open-cage structure and improved transparency, including them, have excellent heat resistance, flexibility, mechanical properties, and encapsulation process characteristics, and crosslink density, light transmittance, and barrier properties against gas.
- This improved open structure is directed to a composition comprising a polyhedral oligomeric silsesquioxane (POSS).
- a flexible transparent barrier film or encapsulant composition used for encapsulation of thin, light and flexible flexible OLEDs and other optical devices has been developed.
- a silicone-based polymer compound having excellent light resistance and light transmittance has been developed. It has been continuously favored and developed as the encapsulant of the device.
- compositions having improved physical properties using silsesquioxane have been disclosed, but the silsesquioxane used is a ladder structure or a mixture of a ladder structure and a cage structure.
- the powder type was poor in compatibility with the main resin, and was unsuitable for most optical element encapsulation materials requiring a solvent-free type in the process.
- the silesquioxane has a functional group of vinyl or Si-H, so that only hydrogensilylation reaction or radical polymerization of the vinyl functional group is possible. (remaining hydrosilylation platinum catalyst), the polymerization product was not very dense.
- the present invention includes the polyhedral oligomeric silsesquioxane having the open-cage structure to increase the compatibility with the resin and can be prepared in a solvent-free type, the optical can be obtained through a condensation reaction to obtain a transparent product It is an object to provide an element sealing material composition.
- the present invention provides a coating composition including the polyhedral oligomeric silsesquioxane having the open-cage structure has excellent flexibility and excellent hardness, which can be useful for buffering against external impact and strengthening durability.
- the present invention to achieve the above object
- Each R is independently a compound of Formula 2-1 or 2-2:
- R 1 to R 6 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl or aryl having 6 to 50 carbon atoms;
- Each Ra is independently hydrogen or chlorine
- z is an integer from 3 to 20 ;
- a and b are each independently an integer of 0 to 20, wherein a + b is an integer of 3 to 20,
- M, Ma and Mb are each independently methyl or phenyl.
- optical device encapsulant composition comprising the polyhedral oligomeric silsesquioxane of the open structure.
- the present invention provides a method for encapsulating an optical device using a sealing composition
- optical device encapsulation method using an optical device encapsulation material composition comprising the polyhedral oligomeric silsesquioxane of the open structure.
- the present invention also provides an optical device encapsulation film made of an optical device encapsulation material composition comprising the polyhedral oligomeric silsesquioxane having the open structure.
- the present invention also provides a coating composition comprising the polyhedral oligomeric silsesquioxane of the open structure.
- the optical element encapsulant composition of the present invention comprises a polyhedral oligomeric silsesquioxane having a partially open-cage structure with a partially open side in the form of a complete cage and capable of crosslinking to increase compatibility with the resin.
- the solubility with the siloxane resin is improved to enable a solvent-free process and to obtain a transparent product through the condensation reaction.
- the optical device encapsulation composition of the present invention has excellent solubility, heat resistance, mechanical properties and encapsulation process properties with siloxane resin, and improved crosslinking density, light transmittance and barrier properties against gas, so that various optical device encapsulation processes,
- the present invention can be applied to an optical transparent electronic device or a thick film encapsulation step.
- the coating composition of the present invention can exhibit not only excellent transparency, optical properties, light transmittance and refractive index, but also markedly improved hardness and adhesive strength with the substrate, particularly excellent flexibility.
- the present invention provides a polyhedral oligomeric silsesquioxane and an optical device encapsulant composition comprising the same, having a partially open-cage structure with a partially open ring side in the form of a complete cage, and capable of crosslinking, thereby increasing compatibility with a resin. And it is characterized by providing a coating composition.
- Cage-type polyhedral oligomeric silsesquioxanes commonly used in the art have a good compatibility with the siloxane resins used as the main resin when used in the encapsulant composition because the composite is in powder form. Therefore, it is not suitable for the encapsulant composition, and in order to increase the compatibility with the siloxane resin, it is necessary to dissolve in an organic solvent, and therefore not suitable for producing a solvent-free encapsulant composition.
- the present invention provides an open structure polyhedral oligomeric silsesquioxane represented by Formula 1-1 or 1-2 to increase compatibility with the siloxane resin:
- Each R is independently a compound of Formula 2-1 or 2-2:
- R 1 to R 6 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl or aryl having 6 to 50 carbon atoms, preferably hydrogen, methyl, ethyl, vinyl or phenyl, more preferably R 1 is Hydrogen or methyl, R 2 is methyl or phenyl, R 3 is hydrogen, methyl or phenyl, R 4 is hydrogen, methyl or vinyl, R 5 is methyl, vinyl or phenyl, R 6 is methyl, ethyl or phenyl ego;
- Each Ra is independently hydrogen or chlorine
- z is an integer of 3 to 20, preferably an integer of 5 to 20 ;
- a and b are each independently an integer of 0 to 20, wherein a + b is an integer of 3 to 20,
- M, Ma and Mb are each independently methyl or phenyl.
- R of the present invention not only has sufficient solubility with liquid siloxane resin, but also contains crosslinking sites, so that not only crosslinking density and mechanical properties but also gas barrier properties can be improved.
- the polyhedral oligomeric silsesquioxane of Formula 1-1 or 1-2 is mainly based on the compound of Formula 2-3, the compound of Formula 2-1, or the compound of Formula 2-2, or Compounds of formulas (2-4) and (2-5) can be synthesized through condensation on distilled water using the reactants as:
- R 1 to R 6 , z, a and b are as defined above;
- Ra and R 7 are each independently hydrogen or chlorine
- x and y are each independently an integer of 1-100.
- the polyhedral oligomeric silsesquioxane has a partially open-cage structure with a partially open ring in the form of a complete cage and can be crosslinked to increase compatibility with the resin, thereby allowing a solvent-free process, and condensation.
- the reaction gives a clear product. Therefore, it is possible to improve the solubility with the siloxane resin, heat resistance, mechanical properties and encapsulation process characteristics, crosslinking density, light transmittance and barrier properties against gas.
- the present invention provides an optical element encapsulant composition comprising the polyhedral oligomeric silsesquioxane of the open structure.
- the polyhedral oligomeric silsesquioxane may be used in an amount of 1 to 20% by weight based on the total composition, and when the content exceeds the content, the compatibility with the siloxane resin Can be degraded.
- the optical element encapsulant composition of the present invention may include a conventionally used siloxane resin, a crosslinked resin, a silane coupling agent, and the like in addition to the polyhedral oligomeric silsesquioxane.
- the composition may further include a catalyst or a reaction retardant.
- the composition of the present invention is 1 to 20% by weight of the polyhedral oligomeric silsesquioxane, 30 to 85% by weight of siloxane resin, 5 to 50% by weight of crosslinking resin, and It may comprise 0.05 to 10% by weight of the silane coupling agent. Also preferably the composition may further comprise 1 to 3000 ppm of catalyst or 1 to 1000 ppm of reaction retardant.
- the siloxane resins usable in the present invention include polymethylvinyl siloxane, poly (methylphenyl) siloxane, poly (phenylvinyl) -co- (methylvinyl) silsesquioxane, PDV-1635, PMV-9925, PVV-3522 from gelest
- Examples of the crosslinking resin include silsesquioxane copolymer, phenylhydrosilsesquioxane, dimethylsilylphenyl ether, and the like.
- Examples of the silane coupling agent include methacrylate-based cyclosiloxanes.
- the catalyst may include a platinum catalyst
- the reaction retardant may include, but is not limited to, ethynyltrimethylsilane or ethynyltriethylsilane, and may include one or more of them.
- the present invention also provides an optical element encapsulation method using an optical element encapsulation material composition comprising the polyhedral oligomeric silsesquioxane (POSS) of the open structure and an optical element encapsulation film made of the optical element encapsulation composition.
- an optical element encapsulation material composition comprising the polyhedral oligomeric silsesquioxane (POSS) of the open structure and an optical element encapsulation film made of the optical element encapsulation composition.
- PES polyhedral oligomeric silsesquioxane
- the optical element encapsulation method of the present invention is characterized by using the optical element encapsulation composition according to the present invention in a method of encapsulating the optical element with the optical element encapsulation composition. Processes applied to other encapsulation methods other than the use of the optical element encapsulation composition can be applied to the well-known processes, of course.
- the present invention provides an optical element encapsulation film made of the optical element encapsulation composition
- the optical element encapsulation film of the present invention not only has excellent light transmittance and refractive index, but also has significantly improved hardness, adhesive strength and elongation,
- an encapsulation thin film of the optical element is effective to extend the life of the optical element, in particular, it must be manufactured in a solvent-free process, requires transparency, can be used as an encapsulation film of the optical element that requires a thick film.
- the present invention provides a coating composition comprising the polyhedral oligomeric silsesquioxane (POSS) of the open structure of Formula 1-1 or 1-2.
- the cured product of the coating composition of the present invention has excellent flexibility and excellent hardness and can be usefully used as a buffer against external impact and durability reinforcement, and can coat and cure the coating composition to form a coating layer, or use a coating composition. It can also be used in the form of a film using a known film production process.
- the coating composition of the present invention is a specific example of a protective film of a display or a semiconductor; It can also be used as a functional interlayer material for displays, semiconductors and other industrial coatings, including automotive interior and exterior materials. It is especially useful as a protective film of the electrode or wiring of an electric element.
- the optical element encapsulation composition and the coating composition of the present invention may be usefully used as a material for encapsulation of a multilayer thin film by selectively applying the coating process and the curing process. That is, the composite layer of the organic / inorganic layer can be applied as a single layer or multilayer encapsulation film and other forms of cured products forming 1 to 5.5 dyad, in particular, the optical element encapsulation composition and coating composition of the present invention is organic / It can be used as a film-type material having excellent gas barrier properties by being formed by applying or depositing on or below the inorganic layer formed by the deposition method such as CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition) among the inorganic layers.
- CVD Chemical Vapor Deposition
- ALD Atomic Layer Deposition
- the adhesive layer (PSA) and the protective (release) film form the last auxiliary layer, and in the encapsulation process of the optical device, after removing the protective (release) film, the lamination is included in the form of an adhesive layer. By carrying out the process, more effective gas barrier performance can be realized.
- the coating composition of the present invention may include known components that are commercially applied to the coating composition in addition to the POSS, for example, in the present invention, the coating composition may include an organic solvent.
- the coating composition may further include an initiator or a curing agent.
- the optical element encapsulation composition of the present invention may be used as a coating composition.
- organic solvent examples include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol and cellosolve, ketones such as lactate, acetone and methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol,
- polar solvents such as furan-based compounds such as tetrahydrofuran, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, Dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acronitrile, methylene chloride, octadecylamine, aniline, dimethylsulfoxide, benzyl alcohol can be used, but is not limited thereto.
- the initiator and the curing agent may be appropriately selected and used depending on the organic functional groups contained in the polysiloxane composite polymer and oligomer and other monomers including POSS.
- the initiator may use various known initiators, and specific examples of the radical initiator include trichloro acetophenone, diethoxy acetophenone, and 1-phenyl-2-hydroxy.
- 2-methylpropane-1-one (1-phenyl-2-hydroxyl-2-methylpropane-1-one), 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methyl thiophenyl)- 2-morpholinopropane-1-one (2-methyl-1- (4-methyl thiophenyl) -2-morpholinopropane-1-one), 2,4,6-trimethyl benzoyl diphenylphosphine oxide (trimethyl benzoyl diphenylphosphine oxide, camphor quinine, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobis (2-methyl butyrate), 3,3-dimethyl-4 Photo-radical initiators such as -methoxy-benzophenone, p-me
- Iodonium such as iodineium or bis (dodecylphenyl) iodonium, diazonium such as phenyldiazonium, 1-benzyl-2-cyanopyridinium, 1- (naphthylmethyl) -2-cyanopridinium, etc.
- cationic or protonic acid catalysts such as triflate, boron trifluoride ether complex, boron trifluoride, etc.
- various onium salts such as ammonium salt, phosphonium salt and sulfonium salt and methyltriphenylphosphonium Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide and the like can be used without limitation, and these initiators can also be added in various mixed forms, and can be mixed with the various radical initiators specified above. Do.
- a photosensitizer may be selectively used as a raw material capable of improving the degree of curing by increasing light absorbance together with a photocurable initiator.
- a photosensitizer may have a light source and an absorption wavelength, and may activate the photoinitiator. If there is, it is not specifically limited.
- the photosensitizer include benzoin derivative compounds, benzyl ketal derivative compounds, acetophenone derivative compounds, phenone derivative compounds, phosphine oxide derivative compounds, and preferably benzophenone derivative compounds and dicarbazolyl.
- -Based compound anthracene-based compound and the like.
- a photoacid generator may be selectively used together with or alone with a photocurable initiator, and the photoacid generator is not particularly limited as long as it can generate Lewis acid or Bronsted acid by exposure.
- Onium compounds such as a sulfur salt type compound and an onium salt, can be used.
- the photoacid generator may be included in the range of 0.05 to 10 parts by weight based on 100 parts by weight of the total binder resin in the photocurable light-transparent composition. When in the above range can be satisfied at the same time the photocurability, light transparency, adhesion and moisture resistance of the coating composition.
- the curing agent may be a known curing agent, for example, amine diamine, ethylenediamine, triethylene tetramine, tetraethylene pentamine, 1,3-diaminopropane, dipropylenetriamine, 3- (2-aminoethyl) Amino-propylamine, N, N'-bis (3-aminopropyl) -ethylenediamine, 4,9-dioxadotecan-1,12-diamine, 4,7,10-trioxatridecane-1,13 -Diamine, hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisaminomethylcyclohexane, bis (4-animocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, etc. It is available.
- amine diamine ethylenediamine, triethylene tetramine, tetraethylene pentamine
- triazine-based compounds such as acetoguanamine, benzoguanamine, 2,4-diamino-6-vinyl-s-triazine, imidazole, 2-methylimidazole Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, and 1-methylimidazole, 1, 5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, diphenyl (p-tril) phosphine, tris (alkylphenyl Phosphine, tris (alkoxyphenyl) phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutyl
- phthalic anhydride trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, methylhydride anhydride, trialkyltetra Acid anhydride curing agents such as hydrophthalic anhydride, dodecenyl succinic anhydride, and 2,4-diethylglutaric anhydride can also be widely used.
- the process of coating (mounting) and coating process with UV absorbers, antioxidants, water repellents, flame retardants, adhesion improving agents and the like for the purpose of improving the hardness, strength, durability, formability, etc. of the coating material through a curing process or a post reaction.
- additives such as antifoaming agents, leveling agents, and thixotropic property improving agents may be further included.
- Such additives are not particularly limited in use, but may be appropriately added within a range that does not impair the physical properties of the coating (mounting) and coating materials.
- the POSS may be included at least 0.5 parts by weight or more based on 100 parts by weight of the coating composition, preferably 1 to 90 parts by weight, more preferably 5 to 30 parts by weight.
- the initiator is included in an amount of 0.1-10 parts by weight based on 100 parts by weight of the composition
- the curing agent is preferably included in an amount of 0.1-10 parts by weight based on 100 parts by weight of the composition, 0.01 to 10 parts by weight of an additive is included, and the remaining amount may be a stock solution (100% solids) composed of the above-mentioned components or the aforementioned organic solvents.
- the remaining amount may be a stock solution (100% solids) composed of the above-mentioned components or the aforementioned organic solvents.
- the method of coating the coating composition can be arbitrarily selected by those skilled in the art from known methods such as dispensing, screen printing, spin coating, bar coating, slit coating, spray, dipping, of course, Also in the curing method, photocuring or thermosetting can be appropriately selected and applied.
- the coating thickness of the coating composition can be arbitrarily adjusted, and in the case of a solvent type, preferably 0.01 to 500 um, more preferably 0.1 to 300 um, and even more preferably 1 to 100 um.
- a solvent type preferably 0.01 to 500 um, more preferably 0.1 to 300 um, and even more preferably 1 to 100 um.
- the composition is a solvent-free type, it is preferably 0.01 to 20 mm, more preferably 0.1 to 10 mm, even more preferably 0.5 to 5 mm range. If it is in the above range it can be secured excellent flexibility and adhesion and hardness of the coating material.
- the substrate to be coated in the present invention is not particularly limited in material, and can be applied to a film or glass or engineering plastic, and may be applied to, for example, a window substrate, a protective film, an encapsulation film, an automobile interior and exterior material, and the like.
- the coating layer formed of the coating composition of the present invention preferably has a hardness of 50 to 80 in the case of A type and 10 to 15 in the case of D type by the Shore hardness tester after curing.
- the coating composition according to the present invention can exhibit not only excellent transparency, optical properties, light transmittance and refractive index, but also significantly improved hardness and adhesive strength with the substrate, and above all, excellent flexibility.
- Octahydro POSS and vinyl terminated poly (methylphenyl) siloxane resins were synthesized at 50 ° C. under solvent via hydrogensilicon reaction under platinum catalyst.
- an optical device encapsulant composition comprising a polyhedral oligomeric silsesquioxane (POSS) of the open structure according to the composition of Table 1.
- PES polyhedral oligomeric silsesquioxane
- Siloxane Resin 1 Poly (methylphenyl) siloxane
- Siloxane resin 2 poly (phenylvinyl) -co- (methylvinyl) silsesquioxane
- Siloxane Resin 4 PVV-3522 (gelest)
- Crosslinked resin 2 dimethylsilylphenyl ether
- Silane coupling agent Methacrylate-based cyclosiloxane
- Reaction Retardant 1 Ethynyltriethylsilane (gelest)
- Reaction Retardant 2 Ethynyltrimethylsilane (gelest)
- Light transmittance The composition is applied to the surface of the glass and Teflon frame to the size of 50 mm ⁇ 50 mm ⁇ 1 mm, then 1 hour at 150 °C, 1 hour at 170 °C The specimen was prepared by curing.
- the UV-vis spectrophotometer (Mecasys) was used to measure the transmittance of five points of the prepared specimen at a wavelength of 400 to 780 nm, and the light transmittance was evaluated from the average value within the obtained wavelength range.
- Adhesive strength After applying the composition on a substrate of 100 mm ⁇ 15 mm, the two substrates were overlapped and cured for 1 hour at 150 °C, 1 hour at 170 °C to prepare a specimen, then a universal material tester ( Instron, product name: UTM-5566) was used.
- Refractive Index The composition was applied to a surface of a Teflon frame mold having a size of a cube (35 mm ⁇ 10 mm ⁇ 1 mm), and then cured for 1 hour at 150 ° C. and 1 hour at 170 ° C. to prepare a specimen. The resulting cured film was measured using an Abbe refractometer (589 nm).
- Examples 1 to 3 according to the present invention showed not only excellent light transmittance and refractive index, but also markedly improved hardness, adhesive strength and elongation.
- Siloxane Resin 1 Poly (methylphenyl) siloxane
- Siloxane resin 2 poly (phenylvinyl) -co- (methylvinyl) silsesquioxane
- Siloxane Resin 4 PVV-3522 (gelest)
- Crosslinked resin 2 dimethylsilylphenyl ether
- Silane coupling agent Methacrylate-based cyclosiloxane
- MEK Metal ethyl ketone
- MIBK methyl isobutyl ketone
- Dimethyl were mixed in a weight ratio of 3: 7, respectively.
- Light transmittance The composition is applied to the surface-treated film (plasma) to a size of 50 mm ⁇ 50 mm ⁇ 1 mm, UV irradiation (3,000 mJ), and then proceed to cure at 60 °C, 30 min Specimen was prepared.
- the UV-vis spectrophotometer (Mecasys) was used to measure the transmittance of five points of the prepared specimen at a wavelength of 400 to 780 nm, and the light transmittance was evaluated from the average value within the obtained wavelength range.
- Adhesion strength After applying the composition on a substrate of 100 mm ⁇ 15 mm, the two substrates were overlapped, UV irradiation (3,000 mJ), and then cured at 60 °C, 30 min to prepare a specimen, 180 ° Peel off test was conducted, and according to the remaining area was divided into upper (70 ⁇ 100%) / medium (40 ⁇ 69%) / lower (0 ⁇ 39%).
- the optical element encapsulant composition of the present invention comprises a polyhedral oligomeric silsesquioxane having a partially open-cage structure with a partially open side in the form of a complete cage and capable of crosslinking to increase compatibility with the resin.
- the solubility with the siloxane resin is improved to enable a solvent-free process and to obtain a transparent product through the condensation reaction.
- the optical device encapsulation composition of the present invention has excellent solubility, heat resistance, mechanical properties and encapsulation process properties with siloxane resin, and improved crosslinking density, light transmittance and barrier properties against gas, so that various optical device encapsulation processes,
- the present invention can be applied to an optical transparent electronic device or a thick film encapsulation step.
- the coating composition of the present invention can exhibit not only excellent transparency, optical properties, light transmittance and refractive index, but also markedly improved hardness and adhesive strength with the substrate, particularly excellent flexibility.
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Abstract
The present invention relates to an open-structure polyhedral oligomeric silsesquioxane (POSS) and a composition comprising the same. More specifically, the present invention relates to a POSS having increased compatibility with resin due to the POSS being cross-linkable, and having improved transparency due to the POSS having a partial open-cage structure; and a composition comprising the POSS having excellent solubility with siloxane resins, heat-resistance, mechanical properties and encapsulation properties, and an improved cross-link density, light-transmitting properties, and gas-barrier properties, thereby being usable for the encapsulation of various optical elements, especially for the encapsulation of phototransparent electronic devices or thick films. In addition, the present invention also relates to a coating composition comprising the open-cage POSS which has outstanding flexibility and excellent hardness, thereby being effectively usable for buffering against external shocks and reinforcing durability.
Description
본 발명은 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산(POSS) 및 이를 포함하는 조성물에 관한 것으로, 더욱 상세하게는 가교결합이 가능하여 수지와의 상용성이 증가되고, 부분 오픈-케이지(open-cage) 구조를 가져 투명도가 향상된 폴리헤드랄 올리고머릭 실세스퀴옥산(POSS) 및 이를 포함하여 내열성, 유연성, 기계적 특성 및 봉지 공정 특성이 우수하고 가교밀도, 광투과성 및 가스에 대한 배리어 특성이 향상된 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산(POSS)을 포함하는 조성물에 관한 것이다.The present invention relates to an open structure of a polyhedral oligomeric silsesquioxane (POSS) and a composition comprising the same, more particularly cross-linking is possible to increase the compatibility with the resin, and partially open-cage ( Polyhedral oligomeric silsesquioxanes (POSS) with an open-cage structure and improved transparency, including them, have excellent heat resistance, flexibility, mechanical properties, and encapsulation process characteristics, and crosslink density, light transmittance, and barrier properties against gas. This improved open structure is directed to a composition comprising a polyhedral oligomeric silsesquioxane (POSS).
LED, OLED, LCD 등의 광학소자에 포함되는 유기 물질은 대기 중의 산소 또는 수증기에 매우 취약하므로, 산소 또는 수증기에 노출되는 경우 출력 감소 또는 조기 성능 저하가 발생할 수 있다. 이에, 금속 및 유리를 사용하여 상기 소자들을 보호함으로써 소자의 수명을 연장시키기 위한 방법이 개발되었으나, 금속은 일반적으로 투명도가 부족하고 유리는 휨성(flexibility)이 부족한 단점이 있었다. LED, Organic materials included in optical devices such as OLEDs and LCDs are very vulnerable to oxygen or water vapor in the air, and thus, when exposed to oxygen or water vapor, output reduction or premature performance degradation may occur. Accordingly, a method for extending the life of the device by protecting the devices using metal and glass has been developed, but metals generally have a disadvantage of lack of transparency and glass lack of flexibility.
이에, 얇고 가볍고 구부러질 수 있는 플렉시블(flexible) OLED를 비롯한 기타 광학소자의 봉지화에 사용되는 휨성이 있는 투명 배리어 필름 또는 봉지재 조성물이 개발되어 왔으며, 특히 내광성 및 투광성이 우수한 실리콘계 고분자 화합물이 광학소자의 봉지재로서 지속적으로 선호 및 개발되어 왔다.Accordingly, a flexible transparent barrier film or encapsulant composition used for encapsulation of thin, light and flexible flexible OLEDs and other optical devices has been developed. In particular, a silicone-based polymer compound having excellent light resistance and light transmittance has been developed. It has been continuously favored and developed as the encapsulant of the device.
이러한 결과로서, 실세스퀴옥산(silsesquioxane)을 사용하여 물리적인 특성을 향상시킨 조성물이 개시된 바 있으나, 사용된 실세스퀴옥산은 래더(ladder) 구조이거나 래더 구조 및 케이지(cage) 구조가 혼재된 파우더(powder) 타입으로, 메인 수지와의 상용성이 좋지 않아, 공정상 무용제 타입이 필요한 대부분의 광학소자용 봉지 재료로서는 부적합하였다. As a result of this, compositions having improved physical properties using silsesquioxane have been disclosed, but the silsesquioxane used is a ladder structure or a mixture of a ladder structure and a cage structure. The powder type was poor in compatibility with the main resin, and was unsuitable for most optical element encapsulation materials requiring a solvent-free type in the process.
또한, 완전 케이지 형태의 구조를 갖는 실세스퀴옥산의 경우, 비닐 또는 Si-H의 관능기를 지님으로써 수소규소화(hydrosilylation) 반응이나 비닐 관능기에 대한 라디칼 중합만이 가능하여, 각각 색을 띄거나(hydrosilylation 백금촉매의 잔존), 중합 생성물이 치밀하지 못한 단점이 있었다.In addition, in the case of silsesquioxane having a structure of a fully caged form, the silesquioxane has a functional group of vinyl or Si-H, so that only hydrogensilylation reaction or radical polymerization of the vinyl functional group is possible. (remaining hydrosilylation platinum catalyst), the polymerization product was not very dense.
상기와 같은 문제점을 해결하기 위해, 본 발명은 완전한 케이지 형태에서 측면이 일부 개환된 부분 오픈-케이지 구조를 갖는 폴리헤드랄 올리고머릭 실세스퀴옥산을 제공하는 것을 목적으로 한다.In order to solve the above problems, it is an object of the present invention to provide a polyhedral oligomeric silsesquioxane having a partially open-cage structure with a partially open side in a complete cage form.
또한 본 발명은 상기 오픈-케이지 구조를 갖는 폴리헤드랄 올리고머릭 실세스퀴옥산을 포함하여 수지와의 상용성을 증가시키고 무용제 타입으로 제조가 가능하며, 축합반응을 통해 투명한 산물을 얻을 수 있는 광학소자 봉지재 조성물을 제공하는 것을 목적으로 한다.In addition, the present invention includes the polyhedral oligomeric silsesquioxane having the open-cage structure to increase the compatibility with the resin and can be prepared in a solvent-free type, the optical can be obtained through a condensation reaction to obtain a transparent product It is an object to provide an element sealing material composition.
또한 본 발명은 상기 오픈-케이지 구조를 갖는 폴리헤드랄 올리고머릭 실세스퀴옥산을 포함하여 뛰어난 유연성과 우수한 경도를 가져서 외부충격에 대한 완충역할 및 내구성 보강에 유용하게 사용할 수 있는 코팅 조성물을 제공하는 것을 목적으로 한다.In another aspect, the present invention provides a coating composition including the polyhedral oligomeric silsesquioxane having the open-cage structure has excellent flexibility and excellent hardness, which can be useful for buffering against external impact and strengthening durability. For the purpose of
상기 목적을 달성하기 위해 본 발명은 The present invention to achieve the above object
하기 화학식 1-1 또는 1-2의 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산(POSS)을 제공한다:To provide a polyhedral oligomeric silsesquioxane (POSS) of the open structure of formula 1-1 or 1-2:
[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
상기 식들에서,In the above formulas,
R은 각각 독립적으로 하기 화학식 2-1 또는 2-2의 화합물이고:Each R is independently a compound of Formula 2-1 or 2-2:
[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
상기 식들에서, In the above formulas,
R1 내지 R6는 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬, 알케닐 또는 탄소수 6 내지 50의 아릴이고;R 1 to R 6 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl or aryl having 6 to 50 carbon atoms;
Ra는 각각 독립적으로 수소 또는 염소 이고;Each Ra is independently hydrogen or chlorine;
z는 3 내지 20의 정수이고;
z is an integer from 3 to 20 ;
a 및 b는 각각 독립적으로 0 내지 20의 정수이며, 이때 a+b는 3 내지 20의 정수이며,a and b are each independently an integer of 0 to 20, wherein a + b is an integer of 3 to 20,
M, Ma 및 Mb는 각각 독립적으로 메틸 또는 페닐이다.M, Ma and Mb are each independently methyl or phenyl.
또한 광학소자 봉지재 조성물에 있어서,In the optical element encapsulant composition,
상기 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산을 포함하는 것을 특징으로 하는 광학소자 봉지재 조성물을 제공한다.It provides an optical device encapsulant composition comprising the polyhedral oligomeric silsesquioxane of the open structure.
또한 본 발명은 봉지 조성물을 이용하여 광학소자 봉지하는 방법에 있어서,In addition, the present invention provides a method for encapsulating an optical device using a sealing composition,
상기 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산을 포함하는 광학소자 봉지재 조성물을 사용하는 것을 특징으로 하는 광학소자 봉지방법을 제공한다.It provides an optical device encapsulation method using an optical device encapsulation material composition comprising the polyhedral oligomeric silsesquioxane of the open structure.
또한 본 발명은 상기 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산을 포함하는 광학소자 봉지재 조성물로 제조된 광학소자 봉지막을 제공한다.The present invention also provides an optical device encapsulation film made of an optical device encapsulation material composition comprising the polyhedral oligomeric silsesquioxane having the open structure.
또한 본 발명은 상기 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산을 포함하는 코팅 조성물을 제공한다.The present invention also provides a coating composition comprising the polyhedral oligomeric silsesquioxane of the open structure.
본 발명의 광학소자 봉지재 조성물은 완전한 케이지 형태에서 측면이 일부 개환된 부분 오픈-케이지 구조를 갖고 가교결합이 가능하여 수지와의 상용성이 증가된 폴리헤드랄 올리고머릭 실세스퀴옥산을 포함함으로써 실록산 수지와의 용해성이 향상되어 무용제 공정이 가능하며, 축합반응을 통해 투명한 산물을 얻을 수 있다. 따라서 본 발명의 광학소자 봉지재 조성물은 우수한 실록산 수지와의 용해성, 내열성, 기계적 특성 및 봉지 공정 특성, 및 향상된 가교밀도, 광투과성 및 가스에 대한 배리어 특성을 가지므로, 다양한 광학소자의 봉지공정, 특히 광투명성 전자소자용 또는 후막의 봉지공정에 적용할 수 있다.The optical element encapsulant composition of the present invention comprises a polyhedral oligomeric silsesquioxane having a partially open-cage structure with a partially open side in the form of a complete cage and capable of crosslinking to increase compatibility with the resin. The solubility with the siloxane resin is improved to enable a solvent-free process and to obtain a transparent product through the condensation reaction. Therefore, the optical device encapsulation composition of the present invention has excellent solubility, heat resistance, mechanical properties and encapsulation process properties with siloxane resin, and improved crosslinking density, light transmittance and barrier properties against gas, so that various optical device encapsulation processes, In particular, the present invention can be applied to an optical transparent electronic device or a thick film encapsulation step.
또한 본 발명의 코팅 조성물은 투명성, 광학성, 광투과율 및 굴절률이 우수할 뿐 아니라, 현저히 향상된 경도 및 기판과의 접착강도, 특히 뛰어난 유연성을 나타낼 수 있다.In addition, the coating composition of the present invention can exhibit not only excellent transparency, optical properties, light transmittance and refractive index, but also markedly improved hardness and adhesive strength with the substrate, particularly excellent flexibility.
본 발명은 완전한 케이지 형태에서 측면이 일부 개환된 부분 오픈-케이지 구조를 갖고 가교결합이 가능하여 수지와의 상용성이 증가된 폴리헤드랄 올리고머릭 실세스퀴옥산 및 이를 포함하는 광학소자 봉지재 조성물과 코팅 조성물을 제공하는 것을 특징으로 한다.The present invention provides a polyhedral oligomeric silsesquioxane and an optical device encapsulant composition comprising the same, having a partially open-cage structure with a partially open ring side in the form of a complete cage, and capable of crosslinking, thereby increasing compatibility with a resin. And it is characterized by providing a coating composition.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
당분야에서 통상적으로 사용되는 케이지 타입의 폴리헤드랄 올리고머릭 실세스퀴옥산(POSS)은 그 합성품이 파우더 형태이므로, 봉지재 조성물에 사용될 경우, 메인 수지로 사용되는 실록산 수지와의 상용성이 좋지 않아 봉지재 조성물에는 적합하지 않으며, 실록산 수지와의 상용성을 높이기 위해서는 유기용제에 녹이는 과정이 필요하므로, 무용제 타입의 봉지재 조성물 제조용으로는 적합하지 않다.Cage-type polyhedral oligomeric silsesquioxanes (POSS) commonly used in the art have a good compatibility with the siloxane resins used as the main resin when used in the encapsulant composition because the composite is in powder form. Therefore, it is not suitable for the encapsulant composition, and in order to increase the compatibility with the siloxane resin, it is necessary to dissolve in an organic solvent, and therefore not suitable for producing a solvent-free encapsulant composition.
이에, 본 발명은 상기 실록산 수지와의 상용성을 증가시키기 위하여 하기 화학식 1-1 또는 1-2로 표시되는 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산을 제공한다:Accordingly, the present invention provides an open structure polyhedral oligomeric silsesquioxane represented by Formula 1-1 or 1-2 to increase compatibility with the siloxane resin:
[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
상기 식들에서,In the above formulas,
R은 각각 독립적으로 하기 화학식 2-1 또는 2-2의 화합물이고:Each R is independently a compound of Formula 2-1 or 2-2:
[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
상기 식들에서, In the above formulas,
R1 내지 R6는 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬, 알케닐 또는 탄소수 6 내지 50의 아릴이고, 바람직하게는 수소, 메틸, 에틸, 비닐 또는 페닐이며, 더욱 바람직하게는 R1은 수소 또는 메틸, R2는 메틸 또는 페닐이고, R3는 수소, 메틸 또는 페닐이고, R4는 수소, 메틸 또는 비닐이고, R5는 메틸, 비닐 또는 페닐이며, R6는 메틸, 에틸 또는 페닐이고;R 1 to R 6 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl or aryl having 6 to 50 carbon atoms, preferably hydrogen, methyl, ethyl, vinyl or phenyl, more preferably R 1 is Hydrogen or methyl, R 2 is methyl or phenyl, R 3 is hydrogen, methyl or phenyl, R 4 is hydrogen, methyl or vinyl, R 5 is methyl, vinyl or phenyl, R 6 is methyl, ethyl or phenyl ego;
Ra는 각각 독립적으로 수소 또는 염소 이고;Each Ra is independently hydrogen or chlorine;
z는 3 내지 20의 정수, 바람직하게는 5 내지 20의 정수이고;
z is an integer of 3 to 20, preferably an integer of 5 to 20 ;
a 및 b는 각각 독립적으로 0 내지 20의 정수이며, 이때 a+b는 3 내지 20의 정수이며,a and b are each independently an integer of 0 to 20, wherein a + b is an integer of 3 to 20,
M, Ma 및 Mb는 각각 독립적으로 메틸 또는 페닐이다.M, Ma and Mb are each independently methyl or phenyl.
종래에는 상기 R이 탄소수 1 내지 5의 시클로실록산, 비닐 또는 수소이므로, 실록산 수지에 용해되지 않았다. 이에, 이를 용해시키기 이하여, 유기용제에 재료들을 녹임으로써 실록산 수지와의 상용성을 부여하였으나, 이는 무용제 타입의 광학소자 또는 광 반도체소자의 봉지 재료로는 부적합했다.Conventionally, since said R is C1-C5 cyclosiloxane, vinyl, or hydrogen, it did not melt | dissolve in siloxane resin. Thus, by dissolving them, the compatibility with the siloxane resin was imparted by dissolving materials in an organic solvent, but this was not suitable as a sealing material of a solvent-free optical device or an optical semiconductor device.
그러나 본 발명의 R은 액상의 실록산 수지와 충분한 용해도를 가질 뿐 아니라, 가교결합 사이트를 포함하고 있어, 가교밀도 및 기계적 특성 뿐 아니라, 가스 배리어 특성도 향상시킬 수 있다.However, R of the present invention not only has sufficient solubility with liquid siloxane resin, but also contains crosslinking sites, so that not only crosslinking density and mechanical properties but also gas barrier properties can be improved.
상기 화학식 1-1 또는 1-2의 폴리헤드랄 올리고머릭 실세스퀴옥산은 하기 화학식 2-3의 화합물을 중심으로, 하기 화학식 2-1의 화합물, 또는 하기 화학식 2-2의 화합물, 또는 하기 화학식 2-4 및 2-5의 화합물들을 반응물로 하여 증류수 상에서 축합반응을 통해 합성될 수 있다:The polyhedral oligomeric silsesquioxane of Formula 1-1 or 1-2 is mainly based on the compound of Formula 2-3, the compound of Formula 2-1, or the compound of Formula 2-2, or Compounds of formulas (2-4) and (2-5) can be synthesized through condensation on distilled water using the reactants as:
[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
[화학식 2-3][Formula 2-3]
[화학식 2-4][Formula 2-4]
[화학식 2-5][Formula 2-5]
상기 식에서,Where
R1 내지 R6, z, a 및 b는 상기에서 정의한 바와 같고;R 1 to R 6 , z, a and b are as defined above;
Ra 및 R7은 각각 독립적으로 수소 또는 염소이며;Ra and R 7 are each independently hydrogen or chlorine;
x 및 y는 각각 독립적으로 1 내지 100의 정수이다.x and y are each independently an integer of 1-100.
본 발명에서 상기 폴리헤드랄 올리고머릭 실세스퀴옥산은 완전한 케이지 형태에서 측면이 일부 개환된 부분 오픈-케이지 구조를 갖고 가교결합이 가능하여 수지와의 상용성이 증가되어 무용제 공정이 가능하며, 축합반응을 통해 투명한 산물을 얻을 수 있다. 따라서 실록산 수지와의 용해성, 내열성, 기계적 특성 및 봉지 공정 특성, 가교밀도, 광투과성 및 가스에 대한 배리어 특성 등을 향상시킬 수 있다.In the present invention, the polyhedral oligomeric silsesquioxane has a partially open-cage structure with a partially open ring in the form of a complete cage and can be crosslinked to increase compatibility with the resin, thereby allowing a solvent-free process, and condensation. The reaction gives a clear product. Therefore, it is possible to improve the solubility with the siloxane resin, heat resistance, mechanical properties and encapsulation process characteristics, crosslinking density, light transmittance and barrier properties against gas.
또한 본 발명은 상기 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산을 포함하는 것을 특징으로 하는 광학소자 봉지재 조성물을 제공한다.In another aspect, the present invention provides an optical element encapsulant composition comprising the polyhedral oligomeric silsesquioxane of the open structure.
본 발명의 광학소자 봉지재 조성물에서 상기 폴리헤드랄 올리고머릭 실세스퀴옥산은 전체 조성물에 대하여 1 내지 20 중량%의 양으로 사용할 수 있으며, 상기 함량을 초과하는 경우에는 실록산 수지와의 상용성이 저하될 수 있다.In the optical element encapsulant composition of the present invention, the polyhedral oligomeric silsesquioxane may be used in an amount of 1 to 20% by weight based on the total composition, and when the content exceeds the content, the compatibility with the siloxane resin Can be degraded.
본 발명의 광학소자 봉지재 조성물은 상기 폴리헤드랄 올리고머릭 실세스퀴옥산 외에도 통상적으로 사용되는 실록산 수지, 가교수지, 실란 커플링제 등을 통상적인 양으로 포함할 수 있다. 또한 상기 조성물은 촉매 또는 반응 지연제를 더욱 포함할 수 있다.The optical element encapsulant composition of the present invention may include a conventionally used siloxane resin, a crosslinked resin, a silane coupling agent, and the like in addition to the polyhedral oligomeric silsesquioxane. In addition, the composition may further include a catalyst or a reaction retardant.
본 발명의 일 실시양태로서, 본 발명의 조성물은 전체 조성물에 대하여 상기 폴리헤드랄 올리고머릭 실세스퀴옥산 1 내지 20 중량%, 실록산 수지 30 내지 85 중량%, 가교수지 5 내지 50 중량%, 및 실란 커플링제 0.05 내지 10 중량%를 포함할 수 있다. 또한 바람직하게는 상기 조성물은 촉매 1 내지 3000 ppm 또는 반응 지연제 1 내지 1000 ppm을 더욱 포함할 수 있다.In one embodiment of the present invention, the composition of the present invention is 1 to 20% by weight of the polyhedral oligomeric silsesquioxane, 30 to 85% by weight of siloxane resin, 5 to 50% by weight of crosslinking resin, and It may comprise 0.05 to 10% by weight of the silane coupling agent. Also preferably the composition may further comprise 1 to 3000 ppm of catalyst or 1 to 1000 ppm of reaction retardant.
본 발명에서 사용가능한 실록산 수지로는 폴리메틸비닐 실록산, 폴리(메틸페닐)실록산, 폴리(페닐비닐)-코-(메틸비닐)실세스퀴옥산, gelest사의 PDV-1635, PMV-9925, PVV-3522 등을 들 수 있고, 가교수지로는 실세스퀴옥산 공중합체, 페닐하이드로실세스퀴옥산 또는 디메틸실릴페닐에테르 등을 들 수 있고, 실란 커플링제로는 메타크릴레이트계 시클로실록산 등을 들 수 있고, 촉매로는 백금 촉매, 반응 지연제로는 에티닐트리메틸실란 또는 에티닐트리에틸실란 등을 들 수 있으나 이에 한정되는 것은 아니며, 이들을 각각 1종 이상 포함할 수 있다.The siloxane resins usable in the present invention include polymethylvinyl siloxane, poly (methylphenyl) siloxane, poly (phenylvinyl) -co- (methylvinyl) silsesquioxane, PDV-1635, PMV-9925, PVV-3522 from gelest Examples of the crosslinking resin include silsesquioxane copolymer, phenylhydrosilsesquioxane, dimethylsilylphenyl ether, and the like. Examples of the silane coupling agent include methacrylate-based cyclosiloxanes. For example, the catalyst may include a platinum catalyst, and the reaction retardant may include, but is not limited to, ethynyltrimethylsilane or ethynyltriethylsilane, and may include one or more of them.
본 발명은 또한 상기 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산(POSS)을 포함하는 광학소자 봉지재 조성물을 이용한 광학소자 봉지방법과 상기 광학소자 봉지 조성물로 제조된 광학소자 봉지막을 제공한다.The present invention also provides an optical element encapsulation method using an optical element encapsulation material composition comprising the polyhedral oligomeric silsesquioxane (POSS) of the open structure and an optical element encapsulation film made of the optical element encapsulation composition.
본 발명의 광학소자 봉지방법은 광학소자 봉지 조성물로 광학소자를 봉지하는 방법에 있어서 본 발명에 따른 상기 광학소자 봉지 조성물을 사용하는 것을 특징으로 한다. 상기 광학소자 봉지 조성물의 사용을 제외한 기타 봉지방법에 적용되는 공정은 공지의 공정들이 적용될 수 있음은 물론이다.The optical element encapsulation method of the present invention is characterized by using the optical element encapsulation composition according to the present invention in a method of encapsulating the optical element with the optical element encapsulation composition. Processes applied to other encapsulation methods other than the use of the optical element encapsulation composition can be applied to the well-known processes, of course.
또한 본 발명은 상기 광학소자 봉지 조성물로 제조된 광학소자 봉지막을 제공하는 바, 본 발명의 광학소자 봉지막은 광투과율 및 굴절률이 우수할 뿐 아니라, 현저히 향상된 경도, 접착강도 및 연신율을 가지므로, 각종 광학소자의 봉지 박막으로 사용할 경우 광학소자의 수명을 연장시키는데 효과적이며, 특히 무용제 공정으로 제조되어야 하고 투명성을 요하며, 후막이 필요한 광학소자의 봉지막으로 사용될 수 있다.In addition, the present invention provides an optical element encapsulation film made of the optical element encapsulation composition, the optical element encapsulation film of the present invention not only has excellent light transmittance and refractive index, but also has significantly improved hardness, adhesive strength and elongation, When used as an encapsulation thin film of the optical element is effective to extend the life of the optical element, in particular, it must be manufactured in a solvent-free process, requires transparency, can be used as an encapsulation film of the optical element that requires a thick film.
또한 본 발명은 상기 화학식 1-1 또는 1-2의 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산(POSS)를 포함하는 코팅 조성물을 제공한다. 본 발명의 코팅 조성물의 경화물은 뛰어난 유연성과 우수한 경도를 가져 외부충격에 대한 완충역할 및 내구성 보강에 유용하게 사용할 수 있으며, 코팅 조성물을 코팅하고 경화시켜 코팅층을 형성할 수도 있고, 코팅 조성물을 이용하고 공지의 필름제조공정을 이용하여 필름의 형태로도 이용할 수 있다. 본 발명의 코팅 조성물은 구체적인 예로 디스플레이 또는 반도체의 보호막; 디스플레이, 반도체, 자동차 내·외장재를 포함한 기타 산업용 코팅재료의 기능성 중간층 재료로도 사용될 수 있다. 특히 전기소자의 전극 또는 배선의 보호막으로 유용하다.In another aspect, the present invention provides a coating composition comprising the polyhedral oligomeric silsesquioxane (POSS) of the open structure of Formula 1-1 or 1-2. The cured product of the coating composition of the present invention has excellent flexibility and excellent hardness and can be usefully used as a buffer against external impact and durability reinforcement, and can coat and cure the coating composition to form a coating layer, or use a coating composition. It can also be used in the form of a film using a known film production process. The coating composition of the present invention is a specific example of a protective film of a display or a semiconductor; It can also be used as a functional interlayer material for displays, semiconductors and other industrial coatings, including automotive interior and exterior materials. It is especially useful as a protective film of the electrode or wiring of an electric element.
또한, 본 발명의 광학소자 봉지 조성물 및 코팅 조성물은 그 도포 공정 및 경화공정을 선택적으로 적용하여, 다층박막의 봉지용 소재로도 유용하게 사용될 수 있다. 즉, 유/무기층의 복합층을 1 내지 5.5 dyad를 이루는 단층 또는 다층구조의 봉지용 필름 및 기타 형태의 경화물로 적용할 수 있으며, 특히 본 발명의 광학소자 봉지 조성물 및 코팅 조성물은 유/무기층 중 CVD(Chemical Vapor Deposition) 또는 ALD(Atomic Layer Deposition) 등의 증착방법으로 형성된 무기층의 아래 또는 윗단에 도포 또는 증착과정을 통해 형성되어 가스배리어성이 우수한 필름형 소재로 활용할 수 있으며, 이러한 필름형 소재는 점착층(PSA)과 보호(이형)필름이 최후 보조층을 이루며, 광학소자의 봉지공정에 있어 보호(이형)필름을 제거한 후, 점착층이 포함된 형태로 라미네이션(Lamination) 공정을 수행함으로써, 더욱 효과적인 가스배리어 성능을 구현할 수 있다.In addition, the optical element encapsulation composition and the coating composition of the present invention may be usefully used as a material for encapsulation of a multilayer thin film by selectively applying the coating process and the curing process. That is, the composite layer of the organic / inorganic layer can be applied as a single layer or multilayer encapsulation film and other forms of cured products forming 1 to 5.5 dyad, in particular, the optical element encapsulation composition and coating composition of the present invention is organic / It can be used as a film-type material having excellent gas barrier properties by being formed by applying or depositing on or below the inorganic layer formed by the deposition method such as CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition) among the inorganic layers. In this film type material, the adhesive layer (PSA) and the protective (release) film form the last auxiliary layer, and in the encapsulation process of the optical device, after removing the protective (release) film, the lamination is included in the form of an adhesive layer. By carrying out the process, more effective gas barrier performance can be realized.
본 발명의 코팅 조성물은 상기 POSS 이외에 코팅 조성물에 상용적으로 적용되는 공지의 성분들이 포함될 수 있으며, 일예로 본 발명에서 상기 코팅조성물은 유기용매를 포함하여 구성될 수 있다. 또한 상기 코팅조성물은 개시제 또는 경화제를 더욱 포함할 수 있다. 또한 본 발명의 상기 광학소자 봉지 조성물을 코팅 조성물로 사용될 수도 있다.The coating composition of the present invention may include known components that are commercially applied to the coating composition in addition to the POSS, for example, in the present invention, the coating composition may include an organic solvent. In addition, the coating composition may further include an initiator or a curing agent. In addition, the optical element encapsulation composition of the present invention may be used as a coating composition.
상기 유기용매로는 메틸알콜, 에틸알콜, 이소프로필알콜, 부틸알콜, 셀로솔브계 등의 알코올류, 락테이트계, 아세톤, 메틸(아이소부틸)에틸케톤 등의 케톤류, 에틸렌글리콜 등의 글리콜 류, 테트라하이드로퓨란 등의 퓨란계, 디메틸포름아미드, 디메틸아세트아미드, N-메틸-2-피롤리돈 등의 극성용매 뿐 아니라, 헥산, 사이클로헥산, 사이클로헥사논, 톨루엔, 자일렌, 크레졸, 클로로포름, 디클로로벤젠, 디메틸벤젠, 트리메틸벤젠, 피리딘, 메틸나프탈렌, 니트로메탄, 아크로니트릴, 메틸렌클로라이드, 옥타데실아민, 아닐린, 디메틸설폭사이드, 벤질알콜 등 다양한 용매를 이용할 수 있으나, 이에 제한되지는 않는다. 상기 유기용매의 양은 POSS, 개시제, 경화제 및 선택적으로 추가되는 첨가제를 제외한 잔량으로 포함된다.Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol and cellosolve, ketones such as lactate, acetone and methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, In addition to polar solvents such as furan-based compounds such as tetrahydrofuran, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, Dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acronitrile, methylene chloride, octadecylamine, aniline, dimethylsulfoxide, benzyl alcohol can be used, but is not limited thereto. The amount of the organic solvent is included in the remaining amount excluding POSS, initiator, curing agent and optionally added additives.
또한 본 발명의 상기 코팅조성물에 있어서 상기 개시제 및 경화제는 POSS를 포함하여 폴리실록산 복합 고분자 및 올리고머, 그 밖에 모노머에 포함된 유기관능기에 따라 적절히 선택하여 사용할 수 있다.In addition, in the coating composition of the present invention, the initiator and the curing agent may be appropriately selected and used depending on the organic functional groups contained in the polysiloxane composite polymer and oligomer and other monomers including POSS.
본 발명의 코팅 조성물에서 상기 개시제는 공지의 다양한 개시제를 사용할 수 있으며, 구체적인 예로 라디칼 개시제로는 트리클로로 아세토페논(trichloro acetophenone), 디에톡시 아세토페논(diethoxy acetophenone), 1-페닐-2-히드록시-2-메틸프로판-1-온(1-phenyl-2-hydroxyl-2-methylpropane-1-one), 1-히드록시사이클로헥실페닐케톤, 2-메틸-1-(4-메틸 티오페닐)-2-모르폴리노프로판-1-온(2-methyl-1-(4-methyl thiophenyl)-2-morpholinopropane-1-one), 2,4,6-트리메틸 벤조일 디페닐포스핀 옥사이드(trimethyl benzoyl diphenylphosphine oxide), 캠퍼 퀴논(camphor quinine), 2,2’-아조비스(2-메틸부티로니트릴), 디메틸-2,2’-아조비스(2-메틸 부틸레이트), 3,3-디메틸-4-메톡시-벤조페논, p-메톡시벤조페논, 2,2-디에톡시 아세토페논, 2,2-디메톡시-1,2-디페닐 에탄-1-온 등의 광 래디컬 개시제, t-부틸파옥시 말레인산, t-부틸하이드로퍼옥사이드, 2,4-디클로로벤조일퍼옥사이드, 1,1-디(t-부틸퍼옥시)-3,3,5-트리메틸시클로헥산, N-부틸-4,4’-디(t-부틸퍼옥시)발레레이트 등의 열 레디칼 개시제 및 이들의 다양한 혼합물 등이 사용될 수 있으며, 광중합 개시제(양이온)로서 트리페닐술포늄, 디페닐-4-(페닐티오)페닐술포늄 등의 술포늄계, 디페닐요오드늄이나 비스(도데실페닐)요오드늄 등의 요오드늄, 페닐디아조늄 등의 디아조늄, 1-벤질-2-시아노피리니늄이나 1-(나프틸메틸)-2-시아노프리디늄 등의 암모늄, (4-메틸페닐)[4-(2-메틸프로필)페닐]-헥사플루오로포스페이트 요오드늄, 비스(4-t-부틸페닐)헥사플루오로포스페이트 요오드늄, 디페닐헥사플루오로포스페이트 요오드늄, 디페닐트리플루오로메탄술포네이트 요오드늄, 트리페닐술포늄 테트라풀루오로보레이트, 트리-p-토일술포늄 헥사풀루오로포스페이트, 트리-p-토일술포늄 트리풀루오로메탄술포네이트 및 (2,4-시클로펜타디엔-1-일)[(1-메틸에틸)벤젠]-Fe 등의 Fe 양이온들과 BF4
-, PF6
-, SbF6
- 등의 [BQ4]- 오늄염 조합을 이용할 수 있다(여기서, Q는 적어도 2개 이상의 불소 또는 트리플루오로메틸기로 치환된 페닐기이다.). 또한, 열에 의해 작용하는 양이온 개시제로는 트리플산염, 3불화 붕소 에테르착화합물, 3불화 붕소 등과 같은 양이온계 또는 프로톤산 촉매, 암모늄염, 포스포늄염 및 술포늄염 등의 각종 오늄염 및 메틸트리페닐포스포늄 브롬화물, 에틸트리페닐포스포늄 브롬화물, 페닐트리페닐포스포늄 브롬화물 등을 제한 없이 사용할 수 있으며, 이들 개시제 또한 다양한 혼합형태로 첨가할 수 있으며, 상기에 명시한 다양한 라디칼 개시제들과의 혼용도 가능하다.In the coating composition of the present invention, the initiator may use various known initiators, and specific examples of the radical initiator include trichloro acetophenone, diethoxy acetophenone, and 1-phenyl-2-hydroxy. 2-methylpropane-1-one (1-phenyl-2-hydroxyl-2-methylpropane-1-one), 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methyl thiophenyl)- 2-morpholinopropane-1-one (2-methyl-1- (4-methyl thiophenyl) -2-morpholinopropane-1-one), 2,4,6-trimethyl benzoyl diphenylphosphine oxide (trimethyl benzoyl diphenylphosphine oxide, camphor quinine, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobis (2-methyl butyrate), 3,3-dimethyl-4 Photo-radical initiators such as -methoxy-benzophenone, p-methoxybenzophenone, 2,2-diethoxy acetophenone, and 2,2-dimethoxy-1,2-diphenyl ethan-1-one, t-butyl Paoxymaleic acid, t-butyl high Loperoxide, 2,4-dichlorobenzoylperoxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, N-butyl-4,4'-di (t-butylper Thermal radical initiators such as oxy) valerate and various mixtures thereof may be used, and sulfonium-based and diphenyl compounds such as triphenylsulfonium and diphenyl-4- (phenylthio) phenylsulfonium as photopolymerization initiators (cations). Iodonium, such as iodineium or bis (dodecylphenyl) iodonium, diazonium such as phenyldiazonium, 1-benzyl-2-cyanopyridinium, 1- (naphthylmethyl) -2-cyanopridinium, etc. Ammonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate iodonium, bis (4-t-butylphenyl) hexafluorophosphate iodonium, diphenylhexafluorophosphate iodine , Diphenyltrifluoromethanesulfonate iodonium, triphenylsulfonium tetrafuluroborate, tri-p-toylsulfonium hexapool Fe cations and BF, such as fluorophosphate, tri-p-toylsulfonium tripulolomethanesulfonate and (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe 4 -, PF 6 -, SbF 6 - , such as [BQ 4] - can be used onium salt combinations (wherein, Q is a phenyl group substituted with at least a group of two or more fluorine or a trifluoromethyl group.). In addition, as a cationic initiator acting by heat, cationic or protonic acid catalysts such as triflate, boron trifluoride ether complex, boron trifluoride, etc., various onium salts such as ammonium salt, phosphonium salt and sulfonium salt and methyltriphenylphosphonium Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide and the like can be used without limitation, and these initiators can also be added in various mixed forms, and can be mixed with the various radical initiators specified above. Do.
본 발명에서 광경화형 개시제와 함께 광의 흡광도를 높여 경화도를 향상시킬 수 있는 원료로 광증감제를 선택적으로 사용 할 수 있으며, 이러한 광증감제는 광원과 흡수파장이 일치하고, 상기 광개시제를 활성화 시킬 수 있는 것이면, 특별히 한정지어지지 않는다. 상기 광증감제의 예로는 벤조인 유도체 화합물, 벤질케탈 유도체 화합물, 아세토페논 유도체 화합물, 페논 유도체 화합물, 포스핀 옥사이드 유도체 화합물을 사용할 수 있으며, 바람직하기로는 벤조페논 유도체 화합물, 다이카르바조릴(dicarbazolyl)계 화합물, 안트라센계 화합물 등이 좋다.In the present invention, a photosensitizer may be selectively used as a raw material capable of improving the degree of curing by increasing light absorbance together with a photocurable initiator. Such a photosensitizer may have a light source and an absorption wavelength, and may activate the photoinitiator. If there is, it is not specifically limited. Examples of the photosensitizer include benzoin derivative compounds, benzyl ketal derivative compounds, acetophenone derivative compounds, phenone derivative compounds, phosphine oxide derivative compounds, and preferably benzophenone derivative compounds and dicarbazolyl. ) -Based compound, anthracene-based compound and the like.
본 발명에서 광경화형 개시제와 함께 또는 단독으로 광산발생제를 선택적으로 사용할 수 있으며, 이러한 광산발생제로는 노광에 의해 루이스산 또는 브론스테드산을 생성시킬 수 있는 것이면 특별히 한정되지 않으며, 유기술폰산 등의 황화염계 화합물, 오니움염 등의 오니움계 화합물을 사용할 수 있다. 바람직하기로는 프탈이미도트리플루오로메탄술포네이트, 디니트로벤질토실레이트, n-데실디술폰, 나프틸이미도트리플루오로메탄술포네이트, 디페닐요도염 헥사플루오로포스페이트, 디페닐요도염 헥사플루오로아르세네이트, 디페닐요도염 헥사플루오로안티모네이트, 디페닐파라메톡시페닐설포늄 트리플레이트, 디페닐파라톨루에닐설포늄 트리플레이트, 디페닐파라이소부틸페닐설포늄 트리플레이트, 트리페닐설포늄 헥사플루오로 아르세네이트, 트리페닐설포늄 헥사플루오로 안티모네이트, 트리페닐설포늄 트리플레이트, 디부틸나프틸설포늄 트리플레이트 및 이들의 혼합물을 사용할 수 있다. 상기 광산발생제는 광경화형 광투명성 조성물에 전체 바인더 수지 100 중량부에 대하여 0.05 내지 10 중량부의 범위로 포함되는 것이 좋다. 상기 범위 내인 경우 코팅 조성물의 광경화성, 광투명성, 접착성 및 내습성을 동시에 만족시킬 수 있다. In the present invention, a photoacid generator may be selectively used together with or alone with a photocurable initiator, and the photoacid generator is not particularly limited as long as it can generate Lewis acid or Bronsted acid by exposure. Onium compounds, such as a sulfur salt type compound and an onium salt, can be used. Preferred are phthalimidotrifluoromethanesulfonate, dinitrobenzyltosylate, n-decyldisulfone, naphthylimidotrifluoromethanesulfonate, diphenylidodoxyl hexafluorophosphate, diphenylurodoxyl hexafluoroarse Nitrate, diphenyl iodo salt hexafluoroantimonate, diphenyl paramethoxyphenylsulfonium triflate, diphenyl paratoluenylsulfonium triflate, diphenyl paraisobutylphenyl sulfonium triflate, triphenylsulfonium hexafluoro Arsenate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium triflate, dibutylnaphthylsulfonium triflate and mixtures thereof can be used. The photoacid generator may be included in the range of 0.05 to 10 parts by weight based on 100 parts by weight of the total binder resin in the photocurable light-transparent composition. When in the above range can be satisfied at the same time the photocurability, light transparency, adhesion and moisture resistance of the coating composition.
또한 경화제는 공지의 경화제가 사용될 수 있으며, 일예로 아민 경화제류인 에틸렌디아민, 트리에틸렌 테트라민, 테트라에틸렌 펜타민, 1,3-디아미노프로판, 디프로필렌트리아민, 3-(2-아미노에틸)아미노-프로필아민, N,N’-비스(3-아미노프로필)-에틸렌디아민, 4,9-디옥사도테칸-1,12-디아민, 4,7,10-트리옥사트리데칸-1,13-디아민, 헥사메틸렌디아민, 2-메틸펜타메틸렌디아민, 1,3-비스아미노메틸시클로헥산, 비스(4-아니모시클로헥실)메탄, 노르보르넨디아민, 1,2-디아미노시클로헥산 등을 이용할 수 있다. In addition, the curing agent may be a known curing agent, for example, amine diamine, ethylenediamine, triethylene tetramine, tetraethylene pentamine, 1,3-diaminopropane, dipropylenetriamine, 3- (2-aminoethyl) Amino-propylamine, N, N'-bis (3-aminopropyl) -ethylenediamine, 4,9-dioxadotecan-1,12-diamine, 4,7,10-trioxatridecane-1,13 -Diamine, hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisaminomethylcyclohexane, bis (4-animocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, etc. It is available.
또한 상기 경화작용을 촉진하기 위한 경화 촉진제로, 아세토구아나민, 벤조구아나민, 2,4-디아미노-6-비닐-s-트리아진 등의 트리아진계 화합물, 이미다졸, 2-메틸이미다졸, 2-에틸-4-메틸이미다졸, 2-페닐이미다졸, 2-페닐-4-메틸이미다졸, 비닐이미다졸, 1-메틸이미다졸 등의 이미다졸계 화합물, 1,5-디아자비시클로[4.3.0]논엔-5,1,8-디아자비시클로[5.4.0]운데센-7, 트리페닐포스핀, 디페닐(p-트릴)포스핀, 트리스(알킬페닐)포스핀, 트리스(알콕시페닐)포스핀, 에틸트리페닐포스포늄포스페이트, 테트라부틸포스포늄히드록시드, 테트라부틸포스포늄아세테이트, 테트라부틸포스포늄하이드로젠디플루오라이드, 테트라부틸포스포늄디하이드로젠트리플루오르 등도 사용될 수 있다.In addition, as a curing accelerator for promoting the curing action, triazine-based compounds such as acetoguanamine, benzoguanamine, 2,4-diamino-6-vinyl-s-triazine, imidazole, 2-methylimidazole Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, and 1-methylimidazole, 1, 5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, diphenyl (p-tril) phosphine, tris (alkylphenyl Phosphine, tris (alkoxyphenyl) phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium hydrogendifluoride, tetrabutylphosphonium dihydrogen tree Fluorine and the like can also be used.
아울러, 무수프탈산, 무수트리멜리트산, 무수피로멜리트산, 무수말레산, 테트라히드로 무수프탈산, 메틸헥사히드로 무수프탈산, 메틸테트라히드로 무수프탈산, 메틸나드산 무수물, 수소화메틸나드산 무수물, 트리알킬테트라히드로 무수프탈산, 도데세닐 무수숙신산, 무수2,4-디에틸글루타르산 등의 산무수물계 경화제류도 폭넓게 사용될 수 있다.In addition, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, methylhydride anhydride, trialkyltetra Acid anhydride curing agents such as hydrophthalic anhydride, dodecenyl succinic anhydride, and 2,4-diethylglutaric anhydride can also be widely used.
본 발명에서는 또한 경화공정 또는 후반응을 통한 코팅물질의 경도, 강도, 내구성, 성형성 등을 개선하는 목적으로 자외선 흡수제, 산화 방지제, 발수제, 난연제, 접착개선제 등과 도포(실장) 및 코팅 과정의 공정특성 향상을 위하여 소포제, 레벨링제, 틱소트로픽 특성 향상제 등의 첨가제를 추가로 포함할 수 있다. 이러한 첨가제는 그 사용에 있어 특별하게 제한은 없으나 도포(실장) 및 코팅물질의 물성을 해치지 않는 범위 내에서 적절히 첨가할 수 있다.In the present invention, the process of coating (mounting) and coating process with UV absorbers, antioxidants, water repellents, flame retardants, adhesion improving agents and the like for the purpose of improving the hardness, strength, durability, formability, etc. of the coating material through a curing process or a post reaction. In order to improve properties, additives such as antifoaming agents, leveling agents, and thixotropic property improving agents may be further included. Such additives are not particularly limited in use, but may be appropriately added within a range that does not impair the physical properties of the coating (mounting) and coating materials.
바람직하기로 본 발명의 코팅조성물에 있어서 상기 POSS는 코팅조성물 100 중량부에 대하여 적어도 0.5 중량부 이상으로 포함되는 것이 좋으며, 바람직하게는 1 내지 90 중량부, 더욱 바람직하게는 5 내지 30 중량부의 양으로 포함되는 것이 바람직하며, 상기 개시제는 조성물 100 중량부에 대하여 0.1-10 중량부로 포함되는 것이 바람직하며, 상기 경화제는 조성물 100 중량부에 대하여 0.1-10 중량부로 포함되는 것이 바람직하며, 필요에 따라 0.01 내지 10 중량부의 첨가제를 포함하며, 잔량은 상기 조성성분으로 이루어진 원액(100% 고형분)이거나 앞서 언급한 기능성의 유기용매를 포함하는 것이 좋다. 상기 범위 내인 경우 코팅조성물의 경화물의 유연성(flexibility)과 기계적 물성을 더욱 향상시킬 수 있고, 경화 후 광투과도 및 코팅안정성을 동시에 만족시킬 수 있다. Preferably, in the coating composition of the present invention, the POSS may be included at least 0.5 parts by weight or more based on 100 parts by weight of the coating composition, preferably 1 to 90 parts by weight, more preferably 5 to 30 parts by weight. Preferably, the initiator is included in an amount of 0.1-10 parts by weight based on 100 parts by weight of the composition, and the curing agent is preferably included in an amount of 0.1-10 parts by weight based on 100 parts by weight of the composition, 0.01 to 10 parts by weight of an additive is included, and the remaining amount may be a stock solution (100% solids) composed of the above-mentioned components or the aforementioned organic solvents. When in the above range can further improve the flexibility (flexibility) and mechanical properties of the cured product of the coating composition, it can satisfy the light transmittance and coating stability after curing at the same time.
또한 본 발명에 있어서, 상기 코팅조성물을 코팅하는 방법은 디스펜싱, 스크린프린팅, 스핀코팅, 바코팅, 슬릿코팅, 스프레이, 침지 등 공지된 방법 중에서 당업자가 임의로 선택하여 적용할 수 있음은 물론이며, 경화방법에 있어도 광경화 또는 열경화를 적절하게 선택하여 적용할 수 있음은 물론이다.In addition, in the present invention, the method of coating the coating composition can be arbitrarily selected by those skilled in the art from known methods such as dispensing, screen printing, spin coating, bar coating, slit coating, spray, dipping, of course, Also in the curing method, photocuring or thermosetting can be appropriately selected and applied.
본 발명에서 상기 코팅조성물의 코팅 두께는 임의로 조절 가능하며, 용제형일 경우에는 바람직하게는 0.01 내지 500 um이며, 더욱 바람직하게는 0.1 내지 300 um, 더더욱 바람직하기로는 1 내지 100 um 범위가 좋다. 또한 그 조성물이 무용제형일 경우에는 바람직하게는 0.01 내지 20 mm 이며, 더욱 바람직하게는 0.1 내지 10 mm, 더더욱 바람직하기로는 0.5 내지 5 mm 범위가 좋다. 상기 범위 내인 경우 우수한 유연성과 접착성과 코팅물질의 경도를 안정적으로 확보할 수 있다.In the present invention, the coating thickness of the coating composition can be arbitrarily adjusted, and in the case of a solvent type, preferably 0.01 to 500 um, more preferably 0.1 to 300 um, and even more preferably 1 to 100 um. In addition, when the composition is a solvent-free type, it is preferably 0.01 to 20 mm, more preferably 0.1 to 10 mm, even more preferably 0.5 to 5 mm range. If it is in the above range it can be secured excellent flexibility and adhesion and hardness of the coating material.
또한 본 발명에서 코팅의 대상이 되는 기판은 재질이 특별히 한정되지 않으며, 필름 또는 유리 또는 엔지니어링 플라스틱에 적용가능하며, 일예로 윈도우 기판이나 보호필름, 봉지용 필름, 자동차 내·외장재 등에 적용될 수 있다.In addition, the substrate to be coated in the present invention is not particularly limited in material, and can be applied to a film or glass or engineering plastic, and may be applied to, for example, a window substrate, a protective film, an encapsulation film, an automobile interior and exterior material, and the like.
바람직하기로 본 발명의 상기 코팅 조성물로 형성된 코팅층은 경화 후의 도막이 Shore 경도계로 A type의 경우 50 내지 80, D type의 경우 10 내지 15의 Hardness를 가지는 것이 좋다.Preferably, the coating layer formed of the coating composition of the present invention preferably has a hardness of 50 to 80 in the case of A type and 10 to 15 in the case of D type by the Shore hardness tester after curing.
본 발명에 따른 상기 코팅 조성물은 투명성, 광학성, 광투과율 및 굴절률이 우수할 뿐 아니라, 현저히 향상된 경도 및 기판과의 접착강도, 무엇보다도 뛰어난 유연성을 나타낼 수 있다.The coating composition according to the present invention can exhibit not only excellent transparency, optical properties, light transmittance and refractive index, but also significantly improved hardness and adhesive strength with the substrate, and above all, excellent flexibility.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
합성예 1Synthesis Example 1
: 폴리헤드랄 올리고머릭 실세스퀴옥산(M-POSS)의 합성: Synthesis of polyhedral oligomeric silsesquioxane (M-POSS)
반응물로서 테트라실라노페닐 POSS 및 디클로로메틸페닐실란, 클로로디메틸비닐실란의 혼합물에 증류수를 상압 및 약 30 ℃에서 서서히 적가하면서 교반한 다음, 50 ℃에서 약 3시간 정도 추가 교반하고 용매를 제거함으로써 폴리헤드랄 올리고머릭 실세스퀴옥산을 합성하였다.To the mixture of tetrasilanophenyl POSS, dichloromethylphenylsilane and chlorodimethylvinylsilane as a reactant, distilled water was slowly added dropwise at atmospheric pressure and about 30 ° C., followed by further stirring at 50 ° C. for about 3 hours, and then the solvent was removed. Ral oligomeric silsesquioxane was synthesized.
비교합성예 1 : 폴리헤드랄 올리고머릭 실세스퀴옥산(A-POSS)의 합성Comparative Synthesis Example 1 Synthesis of Polyhedral Oligomeric Silsesquioxane (A-POSS)
옥타비닐 POSS와 수소화된 폴리(메틸페닐)실록산 수지를 백금 촉매 하에서 수소규소화(Hydrosilylation) 반응을 통해 용매하 50 ℃에서 합성하였다.Octavinyl POSS and hydrogenated poly (methylphenyl) siloxane resins were synthesized at 50 ° C. under solvent via a hydrosilylation reaction under a platinum catalyst.
비교합성예 2 : 폴리헤드랄 올리고머릭 실세스퀴옥산(B-POSS)의 합성Comparative Synthesis Example 2 Synthesis of Polyhedral Oligomeric Silsesquioxane (B-POSS)
옥타하이드로 POSS와 비닐 터미네이티드(Vinyl terminated) 폴리(메틸페닐)실록산 수지를 백금 촉매 하에서 수소규소화 반응을 통해 용매하 50 ℃에서 합성하였다.Octahydro POSS and vinyl terminated poly (methylphenyl) siloxane resins were synthesized at 50 ° C. under solvent via hydrogensilicon reaction under platinum catalyst.
실시예 1 내지 3 및 비교예 1 내지 3Examples 1 to 3 and Comparative Examples 1 to 3
하기 표 1의 조성에 따라 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산(POSS)을 포함하는 광학소자 봉지재 조성물을 제조하였다. 성분 혼합시에는 공자전 진공탈포기를 사용하였다.To prepare an optical device encapsulant composition comprising a polyhedral oligomeric silsesquioxane (POSS) of the open structure according to the composition of Table 1. In mixing the components, a vacuum deaerator was used.
표 1
Table 1
| 구분 | 실시예(단위: 중량부, ppm) | 비교예(단위: 중량부, ppm) | ||||
| 1 | 2 | 3 | 1 | 2 | 3 | |
| 실록산 수지 1 | 54 | 54 | 54 | 54 | 54 | 53 |
| 실록산 수지 2 | 22 | 27 | 22 | 22 | 27 | 22 |
| 실록산 수지 3 | 2 | |||||
| 실록산 수지 4 | 5 | |||||
| 가교수지 1 | 3 | 5 | 8 | 3 | 5 | 5 |
| 가교수지 2 | 17 | 11 | 9 | 17 | 11 | |
| 가교수지 3 | 17 | |||||
| M-POSS | 2 | 1 | 2 | |||
| A-POSS | 2 | 2 | ||||
| B-POSS | 2 | |||||
| 실란 커플링제 | 0.005 | 0.005 | 0.01 | 0.005 | 0.005 | 0.005 |
| 촉매(ppm) | 3 | 3 | 3 | 3 | 3 | 3 |
| 반응지연제 1(ppm) | 50 | 100 | 150 | 50 | 100 | |
| 반응지연제 2(ppm) | 100 | 50 | 100 | 50 | 150 | |
| division | Example (unit: parts by weight, ppm) | Comparative example (unit: parts by weight, ppm) | ||||
| One | 2 | 3 | One | 2 | 3 | |
| Siloxane Resin 1 | 54 | 54 | 54 | 54 | 54 | 53 |
| Siloxane resin 2 | 22 | 27 | 22 | 22 | 27 | 22 |
| Siloxane resin 3 | 2 | |||||
| Siloxane resin 4 | 5 | |||||
| Crosslinked Resin 1 | 3 | 5 | 8 | 3 | 5 | 5 |
| Crosslinked Resin 2 | 17 | 11 | 9 | 17 | 11 | |
| Crosslinked Resin 3 | 17 | |||||
| M-POSS | 2 | One | 2 | |||
| A-POSS | 2 | 2 | ||||
| B-POSS | 2 | |||||
| Silane coupling agent | 0.005 | 0.005 | 0.01 | 0.005 | 0.005 | 0.005 |
| Catalyst (ppm) | 3 | 3 | 3 | 3 | 3 | 3 |
| Retardant 1 (ppm) | 50 | 100 | 150 | 50 | 100 | |
| Retardant 2 (ppm) | 100 | 50 | 100 | 50 | 150 | |
실록산 수지 1 : 폴리(메틸페닐)실록산 Siloxane Resin 1: Poly (methylphenyl) siloxane
실록산 수지 2 : 폴리(페닐비닐)-코-(메틸비닐)실세스퀴옥산Siloxane resin 2: poly (phenylvinyl) -co- (methylvinyl) silsesquioxane
실록산 수지 3 : PDV-1635(gelest사)Siloxane Resin 3: PDV-1635 (gelest)
실록산 수지 4 : PVV-3522(gelest사)Siloxane Resin 4: PVV-3522 (gelest)
가교수지 1 : 페닐하이드로실세스퀴옥산Crosslinked Resin 1: Phenylhydrosilsesquioxane
가교수지 2 : 디메틸실릴페닐에테르Crosslinked resin 2: dimethylsilylphenyl ether
가교수지 3 : HPM-502(gelest사)Crosslinked resin 3: HPM-502 (gelest)
M-POSS : 상기 합성예 1에서 제조된 폴리헤드랄 올리고머릭 실세스퀴옥산M-POSS: polyhedral oligomeric silsesquioxane prepared in Synthesis Example 1
A-POSS : 상기 비교합성예 1에서 제조된 폴리헤드랄 올리고머릭 실세스퀴옥산A-POSS: polyhedral oligomeric silsesquioxane prepared in Comparative Synthesis Example 1
B-POSS : 상기 비교합성예 2에서 제조된 폴리헤드랄 올리고머릭 실세스퀴옥산B-POSS: polyhedral oligomeric silsesquioxane prepared in Comparative Synthesis Example 2
실란 커플링제 : 메타크릴레이트계 시클로실록산Silane coupling agent: Methacrylate-based cyclosiloxane
촉매 : SIP6830.3(gelest사)Catalyst: SIP6830.3 (gelest)
반응 지연제 1 : 에티닐트리에틸실란(gelest사) Reaction Retardant 1: Ethynyltriethylsilane (gelest)
반응 지연제 2 : 에티닐트리메틸실란(gelest사)Reaction Retardant 2: Ethynyltrimethylsilane (gelest)
시험예Test Example
상기 실시예 1 내지 3 및 비교예 1 내지 3에 따른 광학소자 봉지재 조성물의 물성 및 성능 평가를 하기와 같이 수행하였으며, 그 결과를 하기 표 2에 기재하였다.Evaluation of physical properties and performance of the optical device encapsulant composition according to Examples 1 to 3 and Comparative Examples 1 to 3 was performed as follows, and the results are shown in Table 2 below.
1) 광투과율: 상기 조성물을 상하 유리(glass) 및 테프론 프레임(Teflon frame) 표면에 50 mm× 50 mm× 1 mm의 크기가 되도록 도포한 후, 150 ℃에서 1시간, 170 ℃에서 1시간 동안 경화하여 시편을 제조하였다. 자외-가시선 분광광도계(메카시스(Mecasys)사)를 사용하여 400 내지 780 nm의 파장에서 상기 제조된 시편의 5 포인트별 투과율을 측정하였으며, 얻어진 파장범위 내의 평균값으로부터 광투과율을 평가하였다.1) Light transmittance: The composition is applied to the surface of the glass and Teflon frame to the size of 50 mm × 50 mm × 1 mm, then 1 hour at 150 ℃, 1 hour at 170 ℃ The specimen was prepared by curing. The UV-vis spectrophotometer (Mecasys) was used to measure the transmittance of five points of the prepared specimen at a wavelength of 400 to 780 nm, and the light transmittance was evaluated from the average value within the obtained wavelength range.
2) 경도: 20 mm× 20 mm× 15 mm 몰드 위에 상기 조성물을 도포한 후, 150 ℃에서 1시간, 170 ℃에서 1시간 동안 경화하여 시편을 제조한 다음, Shore 경도계를 사용하여 측정하였다.2) Hardness: After applying the composition on a 20 mm × 20 mm × 15 mm mold, and cured for 1 hour at 150 ℃, 1 hour at 170 ℃ to prepare a specimen, Shore It was measured using a hardness tester.
3) 접착강도: 100 mm× 15 mm의 기재 위에 상기 조성물을 도포한 후, 2개의 기판을 중첩하여 150 ℃에서 1시간, 170 ℃에서 1시간 동안 경화하여 시편을 제조한 다음, 만능재료시험기(인스트론사, 제품명 : UTM-5566)를 사용하여 측정하였다.3) Adhesive strength: After applying the composition on a substrate of 100 mm × 15 mm, the two substrates were overlapped and cured for 1 hour at 150 ℃, 1 hour at 170 ℃ to prepare a specimen, then a universal material tester ( Instron, product name: UTM-5566) was used.
4) 연신율: 상기 조성물을 직육면체의 크기(100 mm × 15 mm × 1 mm)의 테프론 몰드 표면에 도포한 후, 150 ℃에서 1시간, 170 ℃에서 1시간 동안 경화하여 시편을 제조하였다. 생성된 경화막을 능재료시험기(인스트론사, 제품명 : UTM-5566)를 사용하여 측정하였다.4) Elongation: The composition was applied to the surface of a Teflon mold having a size of a cube (100 mm × 15 mm × 1 mm), and then cured for 1 hour at 150 ° C. and 1 hour at 170 ° C. to prepare a specimen. The resulting cured film was measured using a twill material testing machine (Instron, product name: UTM-5566).
5) 굴절률: 상기 조성물을 직육면체의 크기(35 mm × 10 mm × 1 mm)의 테프론 프레임 몰드 표면에 도포한 후, 150 ℃에서 1시간, 170 ℃에서 1시간 동안 경화하여 시편을 제조하였다. 생성된 경화막을 아베 굴절계(589 nm)를 이용하여 측정하였다.5) Refractive Index: The composition was applied to a surface of a Teflon frame mold having a size of a cube (35 mm × 10 mm × 1 mm), and then cured for 1 hour at 150 ° C. and 1 hour at 170 ° C. to prepare a specimen. The resulting cured film was measured using an Abbe refractometer (589 nm).
6) 유연성 : 상기 조성물을 직육면체의 크기(50 mm × 15 mm × 1 mm)의 테프론 프레임 몰드 표면에 도포한 후, 150 ℃에서 1시간, 170 ℃에서 1시간 동안 경화하여 시편을 제조하였다. 생성된 경화막을 bending 각도를 높여가며 경화도막의 crack 또는 파단이 진행되기 직전 상황에서, 버니어 캘리퍼(vernier caliper)를 사용하여 곡률반경을 측정하였다.6) Flexibility: The composition was applied to a Teflon frame mold surface having a size of a cube (50 mm × 15 mm × 1 mm), and then cured at 150 ° C. for 1 hour and at 170 ° C. for 1 hour to prepare a specimen. The curvature radius was measured by using a vernier caliper in the situation where the resulting cured film was raised just before the crack or fracture of the cured film was increased.
표 2
TABLE 2
| 실시예 1 | 실시예 2 | 실시예 3 | 비교예 1 | 비교예 2 | 비교예3 | |
| 광투과율(%) | 98.1 | 97.5 | 97.8 | 92.5 | 91 | 92 |
| 경도(Shore A) | 70 | 72 | 75 | 65 | 55 | 50 |
| 접착강도(Kgf/cm2) | 20 | 25 | 30 | 15 | 19 | 17 |
| 연신율(%) | 35 | 33 | 34 | 15 | 11 | 12 |
| 굴절률 | 1.53 | 1.53 | 1.54 | 1.53 | 1.52 | 1.52 |
| 곡률반경(R/ mm) | 3 | 4 | 5 | 10 | 12 | 15 |
| Example 1 | Example 2 | Example 3 | Comparative Example 1 | Comparative Example 2 | Comparative Example 3 | |
| Light transmittance (%) | 98.1 | 97.5 | 97.8 | 92.5 | 91 | 92 |
| Shore A | 70 | 72 | 75 | 65 | 55 | 50 |
| Adhesive Strength (Kgf / cm 2 ) | 20 | 25 | 30 | 15 | 19 | 17 |
| Elongation (%) | 35 | 33 | 34 | 15 | 11 | 12 |
| Refractive index | 1.53 | 1.53 | 1.54 | 1.53 | 1.52 | 1.52 |
| Bending Radius (R / mm) | 3 | 4 | 5 | 10 | 12 | 15 |
상기 표 2에 나타난 바와 같이, 본 발명에 따른 실시예 1 내지 3은 광투과율 및 굴절률이 우수할 뿐 아니라, 현저히 향상된 경도, 접착강도 및 연신율을 나타내었다. As shown in Table 2, Examples 1 to 3 according to the present invention showed not only excellent light transmittance and refractive index, but also markedly improved hardness, adhesive strength and elongation.
비교예 1 내지 3에서 사용한 비교합성예 1 및 2의 POSS는 완전한 케이지형 구조를 가지고 있어 이의 산물은 엷은 갈색 또는 황색 계열을 나타내므로, 합성예 1의 부분 오픈 구조를 갖는 POSS를 포함하는 실시예 1 내지 3의 조성물에 비하여 최종 조성물 제조 후, 경화시 광투과율이 낮았다. 따라서 비교예 1 내지 3의 조성물은 광학특성이 기본이 되어야 하는 본 발명의 봉지 재료로서는 적합하지 않으며, 합성을 위해 사용하는 백금촉매가 조성물 전체의 촉매함량과 더해져 궁극적으로는 신뢰성에도 악영향을 미칠 수 있다.Since the POSS of Comparative Synthesis Examples 1 and 2 used in Comparative Examples 1 to 3 had a complete cage-like structure, and the product thereof was light brown or yellowish, the Example including the POSS having a partially open structure of Synthesis Example 1 The light transmittance at the time of curing was lower after preparation of the final composition as compared to the composition of 1 to 3. Therefore, the compositions of Comparative Examples 1 to 3 are not suitable as the encapsulation material of the present invention in which the optical properties should be the basic, and the platinum catalyst used for synthesis may be added to the catalyst content of the whole composition and ultimately may adversely affect reliability. have.
실시예 4 내지 6 및 비교예 4 내지 6Examples 4-6 and Comparative Examples 4-6
하기 표 3의 조성에 따라 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산(POSS)을 포함하는 코팅 조성물을 제조하였다.To prepare a coating composition comprising a polyhedral oligomeric silsesquioxane (POSS) of the open structure according to the composition of Table 3.
표 3
TABLE 3
| 구분 | 실시예(단위: 중량부, ppm) | 비교예(단위: 중량부, ppm) | ||||
| 4 | 5 | 6 | 4 | 5 | 6 | |
| 실록산 수지 1 | 54 | 54 | 54 | 54 | 54 | 53 |
| 실록산 수지 2 | 22 | 27 | 22 | 22 | 27 | 22 |
| 실록산 수지 3 | 2 | |||||
| 실록산 수지 4 | 5 | |||||
| 가교수지 1 | 3 | 5 | 8 | 3 | 5 | 5 |
| 가교수지 2 | 17 | 11 | 9 | 17 | 11 | |
| 가교수지 3 | 17 | |||||
| M-POSS | 4 | 2 | 4 | |||
| A-POSS | 4 | 4 | ||||
| B-POSS | 4 | |||||
| 실란 커플링제 | 2 | 2 | 4 | 2 | 2 | 2 |
| 혼합 유기용매 | 50 | 50 | 50 | 50 | 50 | 50 |
| 광 개시제 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| Leveling agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Defoaming agent | 1 | 1 | 1 | 1 | 1 | 1 |
| division | Example (unit: parts by weight, ppm) | Comparative example (unit: parts by weight, ppm) | ||||
| 4 | 5 | 6 | 4 | 5 | 6 | |
| Siloxane Resin 1 | 54 | 54 | 54 | 54 | 54 | 53 |
| Siloxane resin 2 | 22 | 27 | 22 | 22 | 27 | 22 |
| Siloxane resin 3 | 2 | |||||
| Siloxane resin 4 | 5 | |||||
| Crosslinked Resin 1 | 3 | 5 | 8 | 3 | 5 | 5 |
| Crosslinked Resin 2 | 17 | 11 | 9 | 17 | 11 | |
| Crosslinked Resin 3 | 17 | |||||
| M-POSS | 4 | 2 | 4 | |||
| A-POSS | 4 | 4 | ||||
| B-POSS | 4 | |||||
| Silane coupling agent | 2 | 2 | 4 | 2 | 2 | 2 |
| Mixed organic solvent | 50 | 50 | 50 | 50 | 50 | 50 |
| Photoinitiator | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| Leveling agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Defoaming agent | One | One | One | One | One | One |
실록산 수지 1 : 폴리(메틸페닐)실록산 Siloxane Resin 1: Poly (methylphenyl) siloxane
실록산 수지 2 : 폴리(페닐비닐)-코-(메틸비닐)실세스퀴옥산Siloxane resin 2: poly (phenylvinyl) -co- (methylvinyl) silsesquioxane
실록산 수지 3 : PDV-1635(gelest사)Siloxane Resin 3: PDV-1635 (gelest)
실록산 수지 4 : PVV-3522(gelest사)Siloxane Resin 4: PVV-3522 (gelest)
가교수지 1 : 페닐하이드로실세스퀴옥산Crosslinked Resin 1: Phenylhydrosilsesquioxane
가교수지 2 : 디메틸실릴페닐에테르Crosslinked resin 2: dimethylsilylphenyl ether
가교수지 3 : HPM-502(gelest사)Crosslinked resin 3: HPM-502 (gelest)
M-POSS : 상기 합성예 1에서 제조된 폴리헤드랄 올리고머릭 실세스퀴옥산M-POSS: polyhedral oligomeric silsesquioxane prepared in Synthesis Example 1
A-POSS : 상기 비교합성예 1에서 제조된 폴리헤드랄 올리고머릭 실세스퀴옥산A-POSS: polyhedral oligomeric silsesquioxane prepared in Comparative Synthesis Example 1
B-POSS : 상기 비교합성예 2에서 제조된 폴리헤드랄 올리고머릭 실세스퀴옥산B-POSS: polyhedral oligomeric silsesquioxane prepared in Comparative Synthesis Example 2
실란 커플링제 : 메타크릴레이트계 시클로실록산Silane coupling agent: Methacrylate-based cyclosiloxane
혼합 유기용매 : MEK(Methyl ethyl ketone)/ MIBK(methyl isobutyl ketone)/ Dimethyl를 각각 3 : 7 중량비율로 혼합하였다.Mixed organic solvents: MEK (Methyl ethyl ketone) / MIBK (methyl isobutyl ketone) / Dimethyl were mixed in a weight ratio of 3: 7, respectively.
시험예Test Example
상기 실시예 4 내지 6 및 비교예 4 내지 6에 따른 광학소자 봉지재 조성물의 물성 및 성능 평가를 하기와 같이 수행하였으며, 그 결과를 하기 표 4에 기재하였다.Evaluation of physical properties and performance of the optical device encapsulant composition according to Examples 4 to 6 and Comparative Examples 4 to 6 was performed as follows, and the results are shown in Table 4 below.
1) 광투과율: 상기 조성물을 표면처리(plasma)된 필름에 50 mm× 50 mm× 1 mm의 크기가 되도록 도포한 후, UV 조사(3,000 mJ)한 후, 60 ℃, 30 min 경화를 진행하여 시편을 제조하였다. 자외-가시선 분광광도계(메카시스(Mecasys)사)를 사용하여 400 내지 780 nm의 파장에서 상기 제조된 시편의 5 포인트별 투과율을 측정하였으며, 얻어진 파장범위 내의 평균값으로부터 광투과율을 평가하였다.1) Light transmittance: The composition is applied to the surface-treated film (plasma) to a size of 50 mm × 50 mm × 1 mm, UV irradiation (3,000 mJ), and then proceed to cure at 60 ℃, 30 min Specimen was prepared. The UV-vis spectrophotometer (Mecasys) was used to measure the transmittance of five points of the prepared specimen at a wavelength of 400 to 780 nm, and the light transmittance was evaluated from the average value within the obtained wavelength range.
2) 접착강도: 100 mm× 15 mm의 기재 위에 상기 조성물을 도포한 후, 2개의 기판을 중첩하여 UV 조사(3,000 mJ)한 후, 60 ℃, 30 min 경화하여 시편을 제조한 다음, 180°peel off 테스트를 진행하고, 그 남은 면적이 많음에 따라서 상(70~100%)/중(40~69%)/하(0~39%)로 구분하였다.2) Adhesion strength: After applying the composition on a substrate of 100 mm × 15 mm, the two substrates were overlapped, UV irradiation (3,000 mJ), and then cured at 60 ℃, 30 min to prepare a specimen, 180 ° Peel off test was conducted, and according to the remaining area was divided into upper (70 ~ 100%) / medium (40 ~ 69%) / lower (0 ~ 39%).
3) 유연성 : 상기 조성물을 직육면체의 크기(50 mm × 15 mm × 1 mm)의 표면처리(plasma)된 필름에 도포한 후, UV 조사(3,000 mJ)한 후, 60 ℃, 30 min 경화하여 시편을 제조하였다. 생성된 경화막을 bending 각도를 높여가며 경화도막의 crack 또는 파단이 진행되기 직전 상황에서, 버니어 캘리퍼(vernier caliper)를 사용하여 곡률반경을 측정하였다.3) Flexibility: The composition was applied to a plasma-treated film of the size of a rectangular parallelepiped (50 mm × 15 mm × 1 mm), UV-irradiated (3,000 mJ), and then cured at 60 ° C. for 30 min. Was prepared. The curvature radius was measured by using a vernier caliper in the situation where the resulting cured film was raised just before the crack or fracture of the cured film was increased.
표 4
Table 4
| 실시예 1 | 실시예 2 | 실시예 3 | 비교예 1 | 비교예 2 | 비교예3 | |
| 광투과율(%) | 96.5 | 95.5 | 95.8 | 90.5 | 89 | 90 |
| 접착강도 | 상 | 상 | 상 | 하 | 중 | 하 |
| 곡률반경(R/ mm) | 5 | 6 | 7 | 12 | 14 | 17 |
| Example 1 | Example 2 | Example 3 | Comparative Example 1 | Comparative Example 2 | Comparative Example 3 | |
| Light transmittance (%) | 96.5 | 95.5 | 95.8 | 90.5 | 89 | 90 |
| Adhesive strength | Prize | Prize | Prize | Ha | medium | Ha |
| Bending Radius (R / mm) | 5 | 6 | 7 | 12 | 14 | 17 |
본 발명의 광학소자 봉지재 조성물은 완전한 케이지 형태에서 측면이 일부 개환된 부분 오픈-케이지 구조를 갖고 가교결합이 가능하여 수지와의 상용성이 증가된 폴리헤드랄 올리고머릭 실세스퀴옥산을 포함함으로써 실록산 수지와의 용해성이 향상되어 무용제 공정이 가능하며, 축합반응을 통해 투명한 산물을 얻을 수 있다. 따라서 본 발명의 광학소자 봉지재 조성물은 우수한 실록산 수지와의 용해성, 내열성, 기계적 특성 및 봉지 공정 특성, 및 향상된 가교밀도, 광투과성 및 가스에 대한 배리어 특성을 가지므로, 다양한 광학소자의 봉지공정, 특히 광투명성 전자소자용 또는 후막의 봉지공정에 적용할 수 있다.The optical element encapsulant composition of the present invention comprises a polyhedral oligomeric silsesquioxane having a partially open-cage structure with a partially open side in the form of a complete cage and capable of crosslinking to increase compatibility with the resin. The solubility with the siloxane resin is improved to enable a solvent-free process and to obtain a transparent product through the condensation reaction. Therefore, the optical device encapsulation composition of the present invention has excellent solubility, heat resistance, mechanical properties and encapsulation process properties with siloxane resin, and improved crosslinking density, light transmittance and barrier properties against gas, so that various optical device encapsulation processes, In particular, the present invention can be applied to an optical transparent electronic device or a thick film encapsulation step.
또한 본 발명의 코팅 조성물은 투명성, 광학성, 광투과율 및 굴절률이 우수할 뿐 아니라, 현저히 향상된 경도 및 기판과의 접착강도, 특히 뛰어난 유연성을 나타낼 수 있다.In addition, the coating composition of the present invention can exhibit not only excellent transparency, optical properties, light transmittance and refractive index, but also markedly improved hardness and adhesive strength with the substrate, particularly excellent flexibility.
Claims (12)
- 하기 화학식 1-1 또는 1-2로 표시되는 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산(POSS):Polyhedral oligomeric silsesquioxanes (POSS) having an open structure represented by the following Chemical Formula 1-1 or 1-2:[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
상기 식들에서,In the above formulas,R은 각각 독립적으로 하기 화학식 2-1 또는 2-2의 화합물이고:Each R is independently a compound of Formula 2-1 or 2-2:[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
상기 식들에서, In the above formulas,R1 내지 R6는 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬, 알케닐 또는 탄소수 6 내지 50의 아릴이고;R 1 to R 6 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl or aryl having 6 to 50 carbon atoms;Ra는 각각 독립적으로 수소 또는 염소이고;Each Ra is independently hydrogen or chlorine;z는 3 내지 20의 정수이고; z is an integer from 3 to 20 ;a 및 b는 각각 독립적으로 0 내지 20의 정수이며, 이때 a+b는 3 내지 20의 정수이며,a and b are each independently an integer of 0 to 20, wherein a + b is an integer of 3 to 20,M, Ma 및 Mb는 각각 독립적으로 메틸 또는 페닐이다.M, Ma and Mb are each independently methyl or phenyl. - 하기 화학식 2-3의 화합물을 중심으로, 하기 화학식 2-1의 화합물, 하기 화학식 2-2의 화합물, 또는 하기 화학식 2-4 및 2-5의 화합물들을 반응물로 하여 증류수 상에서 축합반응을 통해 합성되는 것을 특징으로 하는 화학식 1-1 또는 1-2의 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산의 제조방법:Based on the compound of formula 2-3, the compound of formula 2-1, the compound of formula 2-2, or the compound of formula 2-4 and 2-5 as a reactant synthesized by condensation on distilled water Method for producing a polyhedral oligomeric silsesquioxane of the open structure of formula 1-1 or 1-2, characterized in that:[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
[화학식 2-3][Formula 2-3]
[화학식 2-4][Formula 2-4]
[화학식 2-5][Formula 2-5]
[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
상기 식들에서,In the above formulas,R은 각각 독립적으로 하기 화학식 2-1 또는 2-2의 화합물이고:Each R is independently a compound of Formula 2-1 or 2-2:[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
상기 식들에서, In the above formulas,R1 내지 R6는 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬, 알케닐 또는 탄소수 6 내지 50의 아릴이고;R 1 to R 6 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl or aryl having 6 to 50 carbon atoms;Ra 및 R7은 각각 독립적으로 수소 또는 염소이고;Ra and R 7 are each independently hydrogen or chlorine;x 및 y는 각각 독립적으로 1 내지 100의 정수이고;x and y are each independently an integer from 1 to 100;z은 3 내지 20의 정수이고;z is an integer from 3 to 20;a 및 b는 각각 독립적으로 0 내지 20의 정수이며, 이때 a+b는 3 내지 20의 정수이며,a and b are each independently an integer of 0 to 20, wherein a + b is an integer of 3 to 20,M, Ma 및 Mb는 각각 독립적으로 메틸 또는 페닐이다.M, Ma and Mb are each independently methyl or phenyl. - 제1항 기재의 폴리헤드랄 올리고머릭 실세스퀴옥산을 포함하는 것을 특징으로 하는 광학소자 봉지재 조성물.An optical element sealing material composition comprising the polyhedral oligomeric silsesquioxane according to claim 1.
- 제3항에 있어서,The method of claim 3,상기 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산이 전체 조성물에 대하여 1 내지 20 중량%의 양으로 사용되는 것을 특징으로 하는 광학소자 봉지재 조성물.The open head polyhedral oligomeric silsesquioxane is used in an amount of 1 to 20% by weight based on the total composition.
- 제3항에 있어서,The method of claim 3,상기 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산 1 내지 20 중량%, 1 to 20% by weight of the polyhedral oligomeric silsesquioxane of the open structure,실록산 수지 30 내지 85 중량%, Siloxane resin 30 to 85% by weight,가교수지 5 내지 50 중량%, 및5 to 50% by weight of crosslinked resin, and실란 커플링제 0.05 내지 10 중량%0.05 to 10% by weight of silane coupling agent를 포함하는 것을 특징으로 광학소자 봉지재 조성물.Optical device encapsulant composition comprising a.
- 제5항에 있어서,The method of claim 5,촉매 1 내지 3000 ppm 또는 반응 지연제 1 내지 1000 ppm를 더욱 포함하는 것을 특징으로 하는 광학소자 봉지재 조성물.An optical device encapsulant composition, further comprising 1 to 3000 ppm of a catalyst or 1 to 1000 ppm of a reaction retardant.
- 광학소자의 봉지방법에 있어서,In the sealing method of an optical element,제3항 기재의 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산을 포함하는 광학소자 봉지재 조성물을 이용하는 것을 특징으로 하는 광학소자의 봉지방법.A method for encapsulating an optical element, comprising using an optical element encapsulant composition comprising a polyhedral oligomeric silsesquioxane having an open structure according to claim 3.
- 제3항 기재의 오픈 구조의 폴리헤드랄 올리고머릭 실세스퀴옥산을 포함하는 광학소자 봉지재 조성물을 이용하여 제조되는 광학소자 봉지막.An optical device encapsulation film prepared using the optical device encapsulation material composition comprising the polyhedral oligomeric silsesquioxane having an open structure according to claim 3.
- 제1항 기재의 폴리헤드랄 올리고머릭 실세스퀴옥산을 포함하는 것을 특징으로 하는 코팅 조성물.A coating composition comprising the polyhedral oligomeric silsesquioxane of claim 1.
- 제3항 또는 제9항 기재의 조성물을 경화시켜 제조한 경화막.The cured film manufactured by hardening | curing the composition of Claim 3 or 9.
- 제10항에 있어서,The method of claim 10,경화막이 Shore 경도계로 A type의 경우 50 내지 80, D type의 경우 10 내지 15의 Hardness를 나타내는 것을 특징으로 하는 경화막.Cured film is a Shore hardness tester cured film, characterized in that 50 to 80 in the case of A type, Hardness of 10 to 15 in the case of D type.
- 제10항에 있어서,The method of claim 10,경화막이 전기 소자의 전극 또는 배선의 보호막인 것을 특징으로 하는 경화막.The cured film is a protective film of the electrode or wiring of an electrical element.
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| KR1020140065024A KR20140141500A (en) | 2013-05-31 | 2014-05-29 | Polyhedral olygomeric silsesquioxane(poss) having open structure and composition comprising the same |
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| WO2018124769A1 (en) * | 2016-12-30 | 2018-07-05 | 주식회사 동진쎄미켐 | Coating composition and film manufactured therefrom |
| CN111788254A (en) * | 2018-02-20 | 2020-10-16 | 捷恩智株式会社 | Liquid organosilicon compound and thermosetting resin composition containing the same |
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| WO2008065967A1 (en) * | 2006-11-27 | 2008-06-05 | Panasonic Electric Works Co., Ltd. | Semiconductor optical device and transparent optical member |
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| US8353410B2 (en) * | 2009-11-24 | 2013-01-15 | International Business Machines Corporation | Polymeric films made from polyhedral oligomeric silsesquioxane (POSS) and a hydrophilic comonomer |
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| WO2008065967A1 (en) * | 2006-11-27 | 2008-06-05 | Panasonic Electric Works Co., Ltd. | Semiconductor optical device and transparent optical member |
| US8353410B2 (en) * | 2009-11-24 | 2013-01-15 | International Business Machines Corporation | Polymeric films made from polyhedral oligomeric silsesquioxane (POSS) and a hydrophilic comonomer |
| US20120277372A1 (en) * | 2010-01-19 | 2012-11-01 | Michigan Molecular Institute | Hyperbranched Polymers Containing Polyhedral Oligosilsequioxane Branching Units |
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| WO2018124769A1 (en) * | 2016-12-30 | 2018-07-05 | 주식회사 동진쎄미켐 | Coating composition and film manufactured therefrom |
| CN111788254A (en) * | 2018-02-20 | 2020-10-16 | 捷恩智株式会社 | Liquid organosilicon compound and thermosetting resin composition containing the same |
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