CN108410351B - Organic silicon/inorganic silicon hybrid barrier coating composition and preparation method and application thereof - Google Patents
Organic silicon/inorganic silicon hybrid barrier coating composition and preparation method and application thereof Download PDFInfo
- Publication number
- CN108410351B CN108410351B CN201810193900.0A CN201810193900A CN108410351B CN 108410351 B CN108410351 B CN 108410351B CN 201810193900 A CN201810193900 A CN 201810193900A CN 108410351 B CN108410351 B CN 108410351B
- Authority
- CN
- China
- Prior art keywords
- parts
- barrier coating
- coating composition
- organic silicon
- silicone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 164
- 239000010703 silicon Substances 0.000 title claims abstract description 164
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 230000004888 barrier function Effects 0.000 title claims abstract description 119
- 239000008199 coating composition Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 82
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 24
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 25
- -1 acryloyloxy groups Chemical group 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000004821 distillation Methods 0.000 claims description 19
- 229920001296 polysiloxane Polymers 0.000 claims description 19
- 229920002050 silicone resin Polymers 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical class C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000002318 adhesion promoter Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000004001 thioalkyl group Chemical group 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 26
- 238000000576 coating method Methods 0.000 abstract description 26
- 239000010410 layer Substances 0.000 abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 abstract description 22
- 239000001301 oxygen Substances 0.000 abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 12
- 229920003023 plastic Polymers 0.000 abstract description 9
- 239000004033 plastic Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000012044 organic layer Substances 0.000 abstract description 3
- 238000002834 transmittance Methods 0.000 abstract description 3
- 238000004383 yellowing Methods 0.000 abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-N 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 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
- 230000008034 disappearance Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Silicon Polymers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses an organic silicon/inorganic silicon hybrid barrier coating composition and a preparation method and application thereof, wherein the organic silicon/inorganic silicon hybrid barrier coating composition comprises the following components in parts by weight: 30-70 parts of multifunctional cage type polysilsesquioxane; 25-65 parts of organic silicon resin; 0-15 parts of silicone-modified (meth) acrylic resin; 0.2-5 parts of a photoinitiator; 5-15 parts of an auxiliary agent. The organic silicon/inorganic silicon hybrid barrier coating composition has higher water and oxygen barrier performance for common organic layer materials, excellent yellowing resistance, good glossiness, high light transmittance and better interface bonding force with inorganic layers, so that the barrier layer can reach the water and oxygen barrier performance of a multilayer common barrier layer material under the condition of reducing the number of layers to 3, the production time and cost of a plastic base material barrier layer can be greatly reduced by using the barrier coating, and the reliability of the barrier layer is improved.
Description
Technical Field
The invention relates to the field of functional polymers, in particular to an organic silicon/inorganic silicon hybrid barrier coating composition and a preparation method and application thereof.
Background
The rapid development of the optoelectronic technology in recent years makes Organic Light Emitting Devices (OLEDs), quantum dot displays (QuantumDots), organic solar cells (OPVs), flexible liquid crystal displays (flexible LCDs), electronic paper (E-paper), etc. to occupy a considerable market share in the future market. In order to meet the requirements of modern technologies for electronic products, the development of optoelectronic devices using plastic substrates as substrates instead of conventional glass substrates has been a trend. The plastic substrate not only provides thinner and more flexible characteristics, but also improves the disadvantage that the conventional glass substrate is easy to crack. However, one of the biggest disadvantages of plastic substrates relative to glass substrates is poor barrier properties against water vapor and oxygen. One of the prerequisites for ensuring reliable use of the above-mentioned OLED, quantum dot display, E-paper, and other display elements for a long time is a sealed environment with an extremely low water-oxygen content.
The water and oxygen barrier property of the plastic base material can be greatly improved by alternately forming a plurality of (generally more than 5) organic/inorganic layers with the water and oxygen barrier function on the plastic base material, and the method is a feasible water and oxygen barrier technology at present. However, multiple coating or deposition of organic-inorganic layers adds significant process complexity and production cost. In addition, the difference of the physical and chemical properties of the common organic layer material and the inorganic layer material is large, so that the interface bonding force is insufficient, and some defects are easily caused in the preparation process of the barrier layer or the long-time use process of the device, thereby reducing the water and oxygen barrier property.
Disclosure of Invention
Based on the above, the present invention provides an organosilicon/inorganic silicon hybrid barrier coating composition with a water-oxygen barrier property, which has a higher water-oxygen barrier property, excellent yellowing resistance, good glossiness, high light transmittance, and a better interface bonding force with an inorganic layer compared with a common organic layer material, so that the barrier layer can achieve the water-oxygen barrier property of a multilayer common barrier layer material under the condition of reducing the number of layers to 3, the production time and cost of a plastic substrate barrier layer can be greatly reduced by using the barrier coating, and the reliability of the barrier layer is improved.
Another object of the present invention is to provide a method for preparing the silicone/inorganic silicon hybrid barrier coating composition.
Another object of the present invention is to provide the use of the silicone/inorganic silicon hybrid barrier coating composition.
The technical scheme is as follows:
an organic silicon/inorganic silicon hybrid barrier coating composition comprises the following components in parts by weight:
30-70 parts of multifunctional cage type polysilsesquioxane;
25-65 parts of organic silicon resin;
0-15 parts of organosilicon modified (methyl) acrylic resin;
0.2-5 parts of a photoinitiator;
5-15 parts of an auxiliary agent;
wherein the structure of the multifunctional cage type polysilsesquioxane is shown as a formula I or a formula II:
in the formula I, RxComprising R1And R2Two groups, the quantitative relationship of the two groups being R1＝8-R2Said R is1Selected from the following structures having one or more (meth) acryloyloxy groups:
wherein N is selected from methyl or hydrogen atom, M is selected from one of linear or branched alkyl, side hydroxyalkyl, ether alkyl, thioalkyl and side (methyl) acrylate alkyl with the carbon number less than or equal to 4; r is an integer from 0 to 4;
R2one selected from the following groups or molecular segments:
wherein A is1Selected from the group consisting of N, P, SOne of the subgroups, p is selected from a positive integer of 2 to 5;
in formula II, Rn includes R3And R4Two groups, the quantitative relationship of the two groups being R3＝10-R4Said R is3Structural selection range of (1) and R2Same as R4Structural selection range of (1) and R1The same;
the multi-functional cage polysilsesquioxane has a functionality of greater than or equal to 3.
The cage type Polysilsesquioxane (POSS) is an inorganic core material consisting of a silicon-oxygen framework in alternating connection with Si-O, groups R connected with Si atoms on eight top corners of the cage type polysilsesquioxane can be reactive or inert groups, and different reactive R groups can be chemically bonded with different polymer matrixes. Experiments show that the organic silicon/inorganic silicon hybrid barrier coating composition with excellent water and oxygen barrier performance can be obtained by compounding the multifunctional cage type polysilsesquioxane with a specific structure with organic silicon modified (methyl) acrylic resin, organic silicon resin and the like, wherein POSS is an inorganic component, and is strongly bonded with organic phase organic silicon resin and organic silicon modified (methyl) acrylic resin, so that the problems of inorganic particle aggregation and weak two-phase interface bonding force are solved. In addition, the organic silicon/inorganic silicon hybrid barrier coating composition can be cured under the action of ultraviolet light, and is rapid and efficient in curing, energy-saving and environment-friendly.
In one embodiment, the silicone-modified (meth) acrylic resin is one or more of silicone-modified epoxy acrylate, silicone-modified urethane acrylate, and silicone-modified polyester acrylate. Preferably, the organosilicon modified (meth) acrylic resin is an organosilicon modified epoxy acrylate or an organosilicon modified urethane acrylate.
In one embodiment, the silicone resin is one or more of a T-type silicone tree, a trapezoidal silicone tree, and a hyperbranched silicone resin.
In one embodiment, the T-type silicone resin has the structure shown in formula iii:
wherein R is5、R6、R7Are respectively selected from the same or different H atoms or methyl groups, and q is a positive integer of 10-40; c is selected from methyl or phenyl; b is selected from linear or branched alkyl, side hydroxyalkyl and ether alkyl with the carbon number less than 4.
In one embodiment, the trapezoidal silicone resin has a structure represented by formula iv:
wherein R is8Selected from alkyl with less than 4 carbon atoms or alkoxy with less than 4 carbon atoms; r9Selected from saturated branched or straight-chain alkyl with less than 8 carbon atoms and blocked by (methyl) propylene acyloxy, aromatic hydrocarbon with 6-9 carbon atoms and substituted by (methyl) propylene acyloxy, alkoxy with less than 4 carbon atoms and blocked by (methyl) propylene acyloxy, siloxane chain with less than 8 siloxane chain links and the like.
In one embodiment, the hyperbranched silicone resin is of formula VI, wherein R is11The structure is shown as formula VII, A3Is a hydrogen atom or a methyl group, R10One selected from hydroxyl, methyl, methoxy and ethoxy;
in one embodiment, the photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone, 2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide, diphenyl- (4-phenyl sulfide) phenyl sulfonium hexafluorophosphate, and ethyl 2, 4, 6-trimethylbenzoyl phenyl phosphonate. The photoinitiator of the invention can also be one or more of benzil dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzophenone, methyl benzoylformate, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
In one embodiment, the auxiliary agent comprises one or more of a defoaming agent, a silane coupling agent, a leveling agent, an adhesion promoter and a nano filler.
In one embodiment, the defoaming agent used in the present invention is one or more of BYK-071, BYK-020, BYK-060N, BYK-065, BYK-067, BYK-088, BYK-051, BYK-052, BYK-053, BYK-A550, BYK-A560, BYK-057, BYK-077, BYK-354, BYK-352, BYK-322, BYK-320, BYK-359, TEGO Airex 920, TEGO Airex986, TEGO Airex 910, TEGO Airex 962, TEGO Airex900, TEGO Rad, TEGO Airex 910, TEGO Airex986, and TEGO Airex 2500. The defoaming agent can eliminate bubbles of the adhesive film in the gluing process, and avoid cavities or pits after the adhesive film is solidified. Preferably, the percentage content of the defoaming agent in the organic silicon/inorganic silicon hybrid barrier coating composition is 0.1-1%.
In one embodiment, the silane coupling agent used in the present invention is one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propylmethyldimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriethoxysilane, and vinyltrimethoxysilane. Gamma-methacryloxypropyltrimethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, is preferred. The silane coupling agent can improve the water resistance and the binding power of the barrier coating.
In one embodiment, the nano filler is an inorganic filler with a maximum particle size of less than 300nm, preferably, the nano filler is nano silica, nano alumina, titanium dioxide, talc, kaolin.
In one embodiment, the multifunctional cage polysilsesquioxane is prepared as follows: mixing 100 parts by weight of polyhedral oligomeric silsesquioxane containing multifunctional hydroxyl, 40-160 parts by weight of (methyl) acrylic acid and 50-150 parts by weight of toluene, adding 3-10 parts by weight of concentrated acid as a catalyst, heating to 120-130 ℃, carrying out reflux reaction for 2-4h, and carrying out reduced pressure distillation to remove water and toluene generated in the reaction, thereby obtaining the multifunctional polyhedral oligomeric silsesquioxane.
In one embodiment, the multifunctional cage polysilsesquioxane is prepared as follows: mixing 100 parts by weight of gamma-glycidyl ether oxygen propyl silsesquioxane, 1-3 parts by weight of polymerization inhibitor, 300 parts by weight of 200-containing acrylic acid and 400 parts by weight of 200-containing toluene, adding 2-5 parts by weight of amine catalyst, heating to 80-100 ℃, reacting for 3-5h, washing with water, and distilling under reduced pressure to obtain the multifunctional cage polysilsesquioxane.
In one embodiment, the preparation method of the organosilicon modified polyurethane acrylic resin comprises the following steps: distilling 100 parts of polysiloxane containing silicon-hydrogen bond terminal groups under reduced pressure to remove water, adding 80-120 parts of butanone and 0.05-2 parts of chloroplatinic acid catalyst, heating to 60 +/-5 ℃, dropwise adding 8-15 parts of diisocyanate, stirring to react for 4-6 h, adding 3-8 parts of a blocking agent containing acrylate groups or (methyl) acrylic acid as a blocking agent and 0.005-0.02 part of a polymerization inhibitor, continuing to react for 6-8 h at 80 +/-5 ℃, and finally performing rotary evaporation to remove the solvent to obtain the organic silicon modified polyurethane acrylate.
In one embodiment, the preparation method of the silicone modified epoxy acrylate resin comprises the following steps: adding 0.05-0.2 part by weight of chloroplatinic acid catalyst into 100 parts by weight of polysiloxane containing silicon-hydrogen bond end groups, heating to 120 +/-5 ℃, dropwise adding 100 +/-10 parts by weight of epoxy monomer containing vinyl, stirring and reacting for 4-6 h, adding 25-35 parts by weight of polyfunctional vinyl silicone oil, and continuously reacting for 4-6 h at 120 ℃ to obtain the organic silicon modified epoxy resin taking organic siloxane as a main chain. 100 parts by weight of the organosilicon modified epoxy resin, 1-5 parts by weight of p-methoxyphenol serving as a polymerization inhibitor, 1-5 parts by weight of triethylamine serving as a reaction catalyst, and 200 parts by weight of acrylic acid are added into a reaction vessel together, and the mixture is refluxed and stirred at 90 ℃ for 5 hours while introducing air, so that the organosilicon modified epoxy acrylate is obtained.
The preparation method of the organic silicon/inorganic silicon hybrid barrier coating composition comprises the following steps:
(1) placing multifunctional cage type polysilsesquioxane, organic silicon resin, organic silicon modified (methyl) acrylic resin, photoinitiator and auxiliary agent in a vacuum stirrer, and stirring at the temperature of 40-50 ℃ to obtain a mixture;
(2) filtering the mixture obtained in the step (1) to a needle cylinder by using 1500-2000-mesh nylon filter cloth, then placing the needle cylinder in an oven, and heating and defoaming at the temperature of 50-55 ℃ for 3-5h to obtain the organic silicon/inorganic silicon hybrid barrier coating composition.
An organic silicon/inorganic silicon hybrid barrier coating is formed by UV curing the organic silicon/inorganic silicon hybrid barrier coating composition.
Application of organic silicon/inorganic silicon hybrid barrier coating composition in preparation of barrier composite film
An organic/inorganic composite barrier film comprises an organic silicon/inorganic silicon hybrid barrier coating, an inorganic coating and an organic silicon/inorganic silicon hybrid barrier coating which are sequentially stacked.
A composite barrier film packaging layer comprises an organic silicon/inorganic silicon hybrid barrier coating, an inorganic coating, an organic silicon/inorganic silicon hybrid barrier coating and a PET (polyethylene terephthalate) base material which are sequentially stacked.
The invention has the beneficial effects that: the multifunctional cage polysilsesquioxane with a specific structure is compounded with organic silicon modified (methyl) acrylic resin, organic silicon resin and the like, so that the prepared organic silicon/inorganic silicon hybrid barrier coating composition has excellent water-oxygen barrier performance, and the interface bonding force between the organic silicon/inorganic silicon hybrid barrier coating and other inorganic layer materials is strong; the organic silicon/inorganic silicon hybrid barrier coating composition can be cured under the action of ultraviolet light, and compared with the traditional thermal curing mode, the curing in the photo-curing mode is rapid and efficient, and is energy-saving and environment-friendly.
Drawings
Fig. 1 is a schematic structural view of a composite barrier film encapsulation layer described in embodiment 21.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and the detailed description. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The polyfunctional cage-type polysilsesquioxane used in the following examples was prepared as follows:
multifunctional cage polysilsesquioxane a: adding 100 parts by weight of trihydroxy-containing cage polysilsesquioxane (Aldrich, product number 560391), 40 parts by weight of acrylic acid and 60 parts by weight of toluene solvent into a reactor with a stirring and reduced pressure distillation device, adding 5 parts by weight of concentrated sulfuric acid serving as a catalyst, heating to 120 ℃, carrying out reflux reaction for 3 hours, and carrying out reduced pressure distillation to remove water and the solvent generated by the reaction, thereby finally obtaining the reactive trifunctional cage polysilsesquioxane A. The structure of the multifunctional cage type polysilsesquioxane A is shown in a formula A. The multifunctional cage polysilsesquioxane A is 1642cm higher than that of the cage polysilsesquioxane containing trihydroxy through infrared test-1And 1726cm-1Characteristic peaks of a carbon-carbon double bond and a carbon-oxygen double bond appear at the position respectively, which shows that the acryloxy is successfully connected to the trihydroxy cage type polysilsesquioxane to obtain a target product, namely the multifunctional cage type polysilsesquioxane A, and the structure is shown as the formula A.
Multifunctional cage polysilsesquioxane B: 100 parts by weight of octahydroxy-containing polyhedral oligomeric silsesquioxane (Aldrich, product No. 594180), 80 parts by weight of methacrylic acid, and 120 parts by weight of a toluene solvent were added together with stirringStirring a reactor of a reduced pressure distillation device, adding 8 parts by weight of concentrated sulfuric acid as a catalyst, heating to 120 ℃, carrying out reflux reaction for 3 hours, and finally carrying out reduced pressure distillation to remove water and a solvent generated in the reaction so as to obtain the reactive octafunctional cage-type polysilsesquioxane B. The structure of the multifunctional cage type polysilsesquioxane B is shown in a formula B. The multifunctional cage polysilsesquioxane B is 1644cm higher than that of octahydroxyl cage polysilsesquioxane through infrared test-1And 1727cm-1Characteristic peaks of a carbon-carbon double bond and a carbon-oxygen double bond appear at the position respectively, which shows that methacryloxy is successfully connected to the octahydroxyl cage type polysilsesquioxane to obtain a target product, namely the multifunctional cage type polysilsesquioxane B, and the structure is shown as the formula B.
Multifunctional cage polysilsesquioxane C: adding 100 parts by weight of octavinyl POSS (Aldrich, product number 475424), 145 parts by weight of 3-mercapto-1, 2-propylene glycol and 250 parts by weight of anhydrous tetrahydrofuran into a reaction bottle, heating to a reflux state, keeping the temperature constant, dropping catalytic amount of refined AIBN, carrying out reflux reaction for 5 hours, respectively washing with anhydrous methanol and anhydrous ether after the reaction is finished, and drying to obtain the polyhydroxy cage-type polysilsesquioxane. Adding 100 parts by weight of polyhydroxy cage-type polysilsesquioxane, 160 parts by weight of methacrylic acid and 150 parts by weight of toluene solvent into a reactor with a stirring and reduced pressure distillation device, adding 10 parts by weight of concentrated sulfuric acid as a catalyst, heating to 120 ℃, carrying out reflux reaction for 3 hours, and finally carrying out reduced pressure distillation to remove water and the solvent generated by the reaction, thereby obtaining the reactive octafunctional cage-type polysilsesquioxane C. The multifunctional cage type polysilsesquioxane C has a structure shown in a formula C. The multifunctional cage polysilsesquioxane C is 1725cm relative to the octavinyl POSS through infrared test-1The characteristic peak of the carbon-oxygen double bond appears, the weak peak near 2600 is the disappearance of the S-H stretching vibration absorption peak, which indicates that the carbon-carbon double bond on the octavinyl POSS successfully sends addition reaction with the mercaptan bond, and the target product, namely the multifunctional cage type is obtainedThe polysilsesquioxane C has a structure shown as a formula C.
Multifunctional cage polysilsesquioxane D: 100 parts by weight of gamma-glycidyl ether oxypropylsilsesquioxane (aladin, product number G140436), 2 parts by weight of p-methoxyphenol serving as a polymerization inhibitor, 2 parts by weight of triethylamine serving as a reaction catalyst, 260 parts by weight of acrylic acid, and 300 parts by weight of toluene were added together to a reaction vessel, and stirred at 90 ℃ for 5 hours while introducing air, followed by washing with water, distillation under reduced pressure, and the like, to obtain polyfunctional cage-type polysilsesquioxane D. The structure of the multifunctional cage type polysilsesquioxane D is shown in a formula D. The multifunctional cage polysilsesquioxane D is 904cm relative to the gamma-glycidoxy-silicon propyl silsesquioxane by infrared test-1The epoxy group signal peak at (1) disappeared at 1725cm-1The characteristic peak of carbon-oxygen double bond appears, which shows that acryloxy is successfully connected to gamma-glycidyl ether oxygen propyl silsesquioxane to obtain the target product multifunctional cage type polysilsesquioxane D, and the structure is shown as formula D.
Multifunctional cage polysilsesquioxane E: adding 100 parts by weight of trihydroxy-containing cage type polysilsesquioxane (hybrid plastic, SO1458), 50 parts by weight of acrylic acid and 80 parts by weight of toluene solvent into a reactor with a stirring and reduced pressure distillation device, adding 8 parts by weight of concentrated sulfuric acid serving as a catalyst, heating to 120 ℃, carrying out reflux reaction for 3 hours, and finally carrying out reduced pressure distillation to remove water and the solvent generated by the reaction, thereby obtaining the reactive trifunctional cage type polysilsesquioxane E.
The structure of the multifunctional cage type polysilsesquioxane E is shown as a formula II, wherein R is1Comprises the following steps:
R1the number of R is 32Is phenyl, R2The number is 7. The multifunctional cage polysilsesquioxane E is 1642cm higher than that of the cage polysilsesquioxane containing trihydroxy through infrared test-1And 1725cm-1Characteristic peaks of a carbon-carbon double bond and a carbon-oxygen double bond appear at the position respectively, which shows that the acryloxy is successfully connected to the trihydroxy-containing cage type polysilsesquioxane, and the target product, namely the multifunctional cage type polysilsesquioxane E is obtained.
Multifunctional cage polysilsesquioxane F: adding 100 parts by weight of home-made trihydroxy-containing cage type polysilsesquioxane, 50 parts by weight of methacrylic acid and 80 parts by weight of toluene solvent into a reactor with a stirring and reduced pressure distillation device, adding 8 parts by weight of concentrated sulfuric acid as a catalyst, heating to 120 ℃, carrying out reflux reaction for 3 hours, and finally carrying out reduced pressure distillation to remove water and the solvent generated by the reaction, thereby obtaining the reactive trifunctional cage type polysilsesquioxane F.
The multifunctional cage type polysilsesquioxane F has a structure shown as a formula II, wherein R is1Comprises the following steps:
R1the number of R is 32Is composed of
R2The number is 7. The multifunctional cage polysilsesquioxane E is 1642cm higher than that of the cage polysilsesquioxane containing trihydroxy through infrared test-1And 1727cm-1Characteristic peaks of a carbon-carbon double bond and a carbon-oxygen double bond appear at the position respectively, which shows that methacryloxy is successfully connected to the trihydroxy-containing cage type polysilsesquioxane, and a target product, namely the multifunctional cage type polysilsesquioxane F is obtained.
The silicone resins used in the following examples are of the following types:
t-type silicone resin H: the structure of the T-type organic silicon resin with Gelest, MPTAM-113, 3 functions is shown as a formula III, wherein R is5、R6、R7All are methyl, q is a positive integer of 10-40, C is methyl, and B is methylene.
T-type silicone resin I: gelest, MPTA-112, having the structure shown in formula III, wherein R5、R6、R7Are all hydrogen atoms, q is a positive integer of 10 to 40, C is phenyl, B is
Trapezoidal silicone resin J: gelest, SLT-3UM3, a multifunctional ladder-shaped organic silicon resin with the structure shown in formula IV, wherein R is8Is methoxy, R9Is methacryloxy.
Trapezoidal organic silicon resin K: 100 parts by weight of trapezoidal silicone resin (Gelest, SLT-3A101) containing methoxyl, 50 parts by weight of water and 5 parts by weight of NaOH are put into a reactor, the mixture is stirred for 5 hours at 60 ℃ to ensure that the methoxyl is fully hydrolyzed into silicon hydroxyl, the temperature is raised to 90 ℃, methanol generated by hydrolysis is evaporated, and the polyhydroxy trapezoidal silicone resin is prepared by water washing, precipitation and drying. Dissolving 100 parts by weight of the prepared polyhydroxy trapezoidal silicon resin in sufficient toluene, adding 80 parts by weight of acrylic acid into a reactor with a stirring and reduced pressure distillation device, adding 8 parts by weight of concentrated sulfuric acid as a catalyst, heating to 120 ℃, carrying out reflux reaction for 3 hours, and finally carrying out reduced pressure distillation to remove water and a solvent generated in the reaction, thereby obtaining the reactive trapezoidal silicon resin K. The structure is shown as formula K:
hyperbranched silicone resin L: adding 100 parts by weight of polyhydroxy hyperbranched organic silicon resin (Wuhan hyperbranched resin science and technology Limited, HyPer HPS 601), 180 parts by weight of methacrylic acid and 80 parts by weight of toluene solvent into a reactor with a stirring and reduced pressure distillation device, adding 10 parts by weight of concentrated sulfuric acid as a catalyst, heating to 120 ℃, carrying out reflux reaction for 3 hours, and finally carrying out reduced pressure distillation to remove water and solvent generated by the reaction, thereby obtaining the hyperbranched organic silicon resin L. The structure of the hyperbranched organic silicon resin L is shown as a formula VI, wherein R9Is composed of
R10Is methoxy.
Hyperbranched silicone resin M: adding 200 parts by weight of polyhydroxy hyperbranched organic silicon resin (Wuhan hyperbranched resin science and technology Limited, HyPer HPS 8600), 180 parts by weight of acrylic acid and 80 parts by weight of toluene solvent into a reactor with a stirring and reduced pressure distillation device, adding 10 parts by weight of concentrated sulfuric acid as a catalyst, heating to 120 ℃, carrying out reflux reaction for 3 hours, and finally carrying out reduced pressure distillation to remove water and solvent generated by the reaction, thereby obtaining the hyperbranched organic silicon resin M.
The structure of the hyperbranched organic silicon resin M is shown as a formula VI, wherein R9Is composed of
R10Is methyl.
The organosilicon modified polyurethane acrylic resin O used in the following examples was prepared as follows: distilling 100 parts by weight of polysiloxane containing silicon-hydrogen bond terminal groups under reduced pressure to remove water, adding 100 parts by weight of butanone and 0.1 part by weight of chloroplatinic acid catalyst, heating to 60 ℃, dropwise adding 10 parts by weight of diisocyanate IPDI, stirring and reacting for 4-6 h, adding 5 parts by weight of end-capping reagent acrylic acid and 0.01 part by weight of polymerization inhibitor, continuing to react for 6-8 h at 80 ℃, and finally performing rotary evaporation to remove the solvent to obtain the organic silicon modified polyurethane acrylate O.
The organic silicon modified polyurethane acrylic resin P is prepared by the following method: and (2) distilling 100 parts by weight of polysiloxane containing a silicon-hydrogen bond terminal group under reduced pressure to remove water, adding 100 parts by weight of butanone and 0.1 part by weight of chloroplatinic acid catalyst, heating to 60 ℃, dropwise adding 13 parts by weight of diisocyanate HDI, stirring to react for 4-6 h, adding 5 parts by weight of end-capping reagent methacrylic acid and 0.01 part by weight of polymerization inhibitor, continuing to react for 6-8 h at 80 ℃, and finally performing rotary evaporation to remove the solvent to obtain the organic silicon modified polyurethane acrylate P.
The organic silicon modified epoxy acrylate resin Q is prepared by the following method: adding 0.1 part by weight of chloroplatinic acid catalyst into 100 parts by weight of polysiloxane containing silicon-hydrogen bond end groups, heating to 120 ℃, dropwise adding 100 parts by weight of epoxy monomer GMA containing vinyl, stirring for reaction for 4-6 h, adding 30 parts by weight of trifunctional vinyl silicone oil, and continuing to react for 4-6 h at 120 ℃ to obtain the organic silicon modified epoxy resin taking organic siloxane as a main chain.
The silicone-modified epoxy acrylate Q was obtained by adding 100 parts by weight of the above silicone-modified epoxy resin, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid together into a reaction vessel, and refluxing and stirring at 90 ℃ for 5 hours while introducing air.
The organic silicon modified epoxy acrylate resin R is prepared by the following method: 100 parts by weight of epoxy-modified silicone resin (Evonik, ALBIFLEX 296), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid were added together to a reaction vessel, and the mixture was stirred under reflux at 90 ℃ for 5 hours while introducing air, to obtain the silicone-modified epoxy acrylate R.
Other products not specifically described are all common commercial products.
Example 1
An organic silicon/inorganic silicon hybrid barrier coating composition comprises the following components in parts by weight:
the preparation method of the organic silicon/inorganic silicon hybrid barrier coating composition comprises the following steps:
(1) placing multifunctional cage type polysilsesquioxane, organic silicon resin, organic silicon modified (methyl) acrylic resin, photoinitiator and auxiliary agent in a planetary vacuum mixer, and stirring at the temperature of 40-50 ℃ to obtain a mixture;
(2) and (2) filtering the mixture obtained in the step (1) by using 1600-mesh nylon filter cloth to a needle cylinder, then placing the needle cylinder in an oven, and heating and defoaming for 4 hours at the temperature of 50 ℃ to obtain the organic silicon/inorganic silicon hybrid barrier coating composition, wherein the organic silicon/inorganic silicon hybrid barrier coating composition is UV-cured barrier coating glue.
Example 2
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are basically the same as those of example 1, except that the multifunctional cage type polysilsesquioxane used in example 2 is B.
Example 3
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are substantially the same as those of example 1, except that the multifunctional cage-type polysilsesquioxane used in this example 3 is C.
Example 4
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are substantially the same as those of example 1, except that the multifunctional cage-type polysilsesquioxane used in example 4 is D.
Example 5
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are substantially the same as those of example 1, except that the multifunctional cage-type polysilsesquioxane used in this example 5 is E.
Example 6
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are substantially the same as those of example 1, except that the multifunctional cage-type polysilsesquioxane used in this example 6 is F.
Example 7
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are substantially the same as those of example 1, except that the organosilicon resin used in this example 7 is T-type organosilicon resin H.
Example 8
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are basically the same as those of example 1, except that the organosilicon resin used in the example 8 is a T-type organosilicon resin I.
Example 9
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are substantially the same as those of example 1, except that the organosilicon resin used in this example 9 is trapezoidal organosilicon resin J.
Example 10
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are basically the same as those of example 1, except that the organosilicon resin used in this example 10 is trapezoidal organosilicon resin K.
Example 11
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are substantially the same as those of example 1, except that the organosilicon resin used in this example 11 is hyperbranched organosilicon resin M.
Example 12
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are substantially the same as those of example 1, except that the organosilicon resin used in this example 12 is hyperbranched organosilicon resin L.
Example 13
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are basically the same as those of example 1, is different from that of example 13 only in that the organosilicon-modified (meth) acrylic resin is organosilicon-modified urethane acrylic resin P.
Example 14
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are substantially the same as those of example 1, except that the organosilicon-modified (meth) acrylic resin used in this example 14 is an organosilicon-modified epoxy acrylate resin Q.
Example 15
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are basically the same as those of example 1, is different from that of example 15 only in that the organosilicon-modified (meth) acrylic resin is organosilicon-modified epoxy acrylate resin R.
Example 16
An organic silicon/inorganic silicon hybrid barrier coating composition comprises the following components in parts by weight:
the preparation method of the organic silicon/inorganic silicon hybrid barrier coating composition is the same as that of example 1.
Example 17
An organic silicon/inorganic silicon hybrid barrier coating composition comprises the following components in parts by weight:
the preparation method of the organic silicon/inorganic silicon hybrid barrier coating composition is the same as that of example 1.
Example 18
An organic silicon/inorganic silicon hybrid barrier coating composition comprises the following components in parts by weight:
the preparation method of the organic silicon/inorganic silicon hybrid barrier coating composition is the same as that of example 1.
Example 19
An organic silicon/inorganic silicon hybrid barrier coating composition comprises the following components in parts by weight:
the preparation method of the organic silicon/inorganic silicon hybrid barrier coating composition is the same as that of example 1.
Example 20
An organic silicon/inorganic silicon hybrid barrier coating composition comprises the following components in parts by weight:
the preparation method of the organic silicon/inorganic silicon hybrid barrier coating composition is the same as that of example 1.
Comparative example 1
An organic silicon/inorganic silicon hybrid barrier coating composition comprises the following components in parts by weight:
wherein the multifunctional cage polysilsesquioxane has a structure shown as a formula I (Hybirdplastic, MA0735), is an octafunctional type, and R is1、R2Are all made of
Comparative example 2
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are substantially the same as those of example 1, except that in comparative example 2, a monofunctional cage polysilsesquioxane (hybrid plastic, MA0701) is used instead of the multifunctional cage polysilsesquioxane a.
Comparative example 3
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and method of preparation of which are essentially the same as in example 1, except that this comparative example 3 replaces the multifunctional cage polysilsesquioxane a with a difunctional cage polysilsesquioxane (prepared from a dihydroxy-functional cage polysilsesquioxane a (Aldrich, product number 560308) using the same method as that used to prepare the multifunctional cage polysilsesquioxane a).
Comparative example 4
An organosilicon/inorganic silicon hybrid barrier coating composition, the composition and preparation method of which are substantially the same as those of example 1 except that a multifunctional cage polysilsesquioxane is not used.
The silicone/inorganic silicon hybrid barrier coating compositions prepared in examples 1-20 and comparative examples 1-4 were subjected to performance tests, the test results are shown in table 1, and the test methods or standards are as follows:
(1) oxygen transmission rate: GB/T19789-
(2) Water vapor transmission rate: GB/T21529-
(3) The yellowing delta b value GB/T7921-2008
(4)180 DEG peeling force GB/T2792-
(5) Haze: GB/T2410-
(6) Transmittance: GB/T2410-.
TABLE 1
From examples 1-20, it can be seen that the barrier coating prepared by the present invention has good water vapor and oxygen barrier properties, and the prepared barrier coating has excellent resistance to high and low temperatures, resistance to wet heat aging, and good adhesion to PET substrates due to the use of silicone as a main component. When the multifunctional organic silicon resin is not added into the barrier coating composition and the using amount of the components is not appropriate (comparative example 1), the oxygen and water vapor transmission rate of the prepared barrier coating is obviously increased; when the multifunctional cage-type polysilsesquioxane is not added into the barrier coating composition (comparative example 4), the water oxygen transmission rate of the prepared barrier coating is increased more obviously; when the cage polysilsesquioxane added to the barrier coating is monofunctional (comparative example 2) or difunctional (comparative example 3), the crosslink density of the resulting barrier coating decreases, resulting in a decrease in the water oxygen barrier capability.
Example 21
As shown in fig. 1The composite barrier film packaging layer comprises a first organic silicon/inorganic silicon hybrid barrier coating, an inorganic coating, a second organic silicon/inorganic silicon hybrid barrier coating and a PET (polyethylene terephthalate) base material which are sequentially stacked. More specifically, in this embodiment, the thicknesses of the first organic silicon/inorganic silicon hybrid barrier coating and the second organic silicon/inorganic silicon hybrid barrier coating are 0.6 μm, the thickness of the inorganic plating layer is 30nm, and the thickness of the PET substrate is 200 μm, and the first organic silicon/inorganic silicon hybrid barrier coating and the second organic silicon/inorganic silicon hybrid barrier coating are formed by UV curing the organic silicon/inorganic silicon hybrid barrier coating composition described in example 1. And (3) carrying out oxygen transmission rate, water vapor transmission rate and bending resistance test on the composite barrier film packaging layer (the bending resistance test is carried out for 1 ten thousand times according to the standard JIS-C-6471-19958.2, and after the test, if the composite barrier film is not layered and has no crack, the composite barrier film is judged to be passed). The test results are: oxygen transmission rate 1.40 x 10-6cm3/(m2Day), water vapor transmission rate 1.10 x 10-6g/m2Day, and passed the bend resistance test.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. An organic silicon/inorganic silicon hybrid barrier coating composition is characterized by comprising the following components in parts by weight:
30-70 parts of multifunctional cage type polysilsesquioxane;
25-65 parts of organic silicon resin;
0-15 parts of organosilicon modified (methyl) acrylic resin;
0.2-5 parts of a photoinitiator;
5-15 parts of an auxiliary agent;
wherein the structure of the multifunctional cage type polysilsesquioxane is shown as a formula I or a formula II:
in the formula I, RxComprising R1And R2Two groups, the quantitative relationship of the two groups being R1＝8-R2Said R is1Selected from the following structures having one or more (meth) acryloyloxy groups:
wherein N is selected from methyl or hydrogen atom, M is selected from one of linear or branched alkyl, side hydroxyalkyl, ether alkyl, thioalkyl and side (methyl) propylene acyloxy alkyl with the carbon number less than or equal to 4; r is an integer from 0 to 4;
R2one selected from the following groups or molecular segments:
wherein A is1One selected from N, P, S atoms, p is selected from a positive integer of 2-5;
in the formula II, RnComprising R3And R4Two groups, the quantitative relationship of the two groups being R3＝10-R4Said R is3Structural selection range of (1) and R2In the same way, R4Structural selection range of (1) and R1The same;
the multi-functional cage polysilsesquioxane functionality is greater than or equal to 3;
the organic silicon resin is one or more of T-shaped organic silicon resin, trapezoidal organic silicon resin and hyperbranched organic silicon resin.
2. The silicone/inorganic silicon hybrid barrier coating composition according to claim 1, wherein the silicone-modified (meth) acrylic resin is one or more of silicone-modified epoxy acrylate, silicone-modified urethane acrylate, silicone-modified polyester acrylate.
3. The silicone/inorganic silicon hybrid barrier coating composition according to claim 1, wherein the structure of the T-type silicone resin is shown as formula III:
wherein R is5、R6、R7Are respectively selected from the same or different H atoms or methyl groups, and q is a positive integer of 10-40; c is selected from methyl or phenyl; b is selected from linear or branched alkyl, side hydroxyalkyl and ether alkyl with the carbon number less than 4.
4. The organic silicon/inorganic silicon hybrid barrier coating composition according to claim 1, wherein the trapezoidal organic silicon resin has a structure shown in formula IV:
wherein R is8Selected from alkyl with less than 4 carbon atoms or alkoxy with less than 4 carbon atoms, R9Selected from (methyl) propylene acyloxy terminated saturated branched or straight chain alkyl with less than 8 carbon atoms, (methyl) propylene acyloxy substituted aromatic hydrocarbon with 6-9 carbon atoms, (methyl) propylene acyloxy terminated alkoxy with less than 4 carbon atoms, (methyl) propylene acyloxy terminated siliconGroups having a number of siloxane linkages of less than 8.
5. The silicone/inorganic silicon hybrid barrier coating composition of claim 1, wherein the hyperbranched silicone resin is of formula VI, wherein R is11The structure is shown as formula VII, A3Is a hydrogen atom or a methyl group, R10One selected from hydroxyl, methyl, methoxy and ethoxy;
6. the silicone/inorganic silicon hybrid barrier coating composition of claim 1, wherein the auxiliaries comprise one or more of defoamers, silane coupling agents, leveling agents, adhesion promoters, nanofillers.
7. The silicone/inorganic silicon hybrid barrier coating composition according to claim 1, wherein the multifunctional cage polysilsesquioxane is prepared as follows: mixing 100 parts by weight of polyhedral oligomeric silsesquioxane containing multifunctional hydroxyl, 40-160 parts by weight of (methyl) acrylic acid and 50-150 parts by weight of toluene, adding 3-10 parts by weight of concentrated acid as a catalyst, heating to 120-130 ℃, carrying out reflux reaction for 2-4h, and carrying out reduced pressure distillation to remove water and a solvent generated by the reaction, thereby obtaining the multifunctional polyhedral oligomeric silsesquioxane.
8. The method of preparing the silicone/inorganic silicon hybrid barrier coating composition of any one of claims 1 to 7, comprising the steps of:
(1) placing multifunctional cage type polysilsesquioxane, organic silicon resin, organic silicon modified (methyl) acrylic resin, photoinitiator and auxiliary agent in a vacuum stirrer, and stirring at the temperature of 40-50 ℃ to obtain a mixture;
(2) filtering the mixture obtained in the step (1) to a needle cylinder by using 1500-2000-mesh nylon filter cloth, then placing the needle cylinder in an oven, and heating and defoaming at the temperature of 50-55 ℃ for 3-5h to obtain the organic silicon/inorganic silicon hybrid barrier coating composition.
9. Use of the silicone/inorganic silicon hybrid barrier coating composition of any one of claims 1-7 in the preparation of a barrier composite film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810193900.0A CN108410351B (en) | 2018-03-09 | 2018-03-09 | Organic silicon/inorganic silicon hybrid barrier coating composition and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810193900.0A CN108410351B (en) | 2018-03-09 | 2018-03-09 | Organic silicon/inorganic silicon hybrid barrier coating composition and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108410351A CN108410351A (en) | 2018-08-17 |
| CN108410351B true CN108410351B (en) | 2020-06-16 |
Family
ID=63130801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810193900.0A Active CN108410351B (en) | 2018-03-09 | 2018-03-09 | Organic silicon/inorganic silicon hybrid barrier coating composition and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108410351B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111621182B (en) * | 2020-05-27 | 2021-11-16 | 中国船舶重工集团公司第七二五研究所 | Connecting coating matched with fouling release type antifouling paint and preparation method thereof |
| CN114539911B (en) * | 2022-03-02 | 2023-04-07 | 华中科技大学无锡研究院 | High-transmittance ultraviolet optical fiber internal coating with high crosslinking density and preparation method thereof |
| CN114686160B (en) * | 2022-04-28 | 2023-08-15 | 成都硅宝科技股份有限公司 | Solvent-free high-toughness organic silicon conductive adhesive for photovoltaic shingle assembly and preparation method thereof |
| CN116144284B (en) * | 2023-04-24 | 2023-08-18 | 宁波长阳科技股份有限公司 | Raw material package, integrated adhesive film backboard, preparation method of integrated adhesive film backboard and photovoltaic module |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004060330A2 (en) * | 2002-12-19 | 2004-07-22 | Kimberly-Clark Worldwide, Inc. | Multifunctional compositions for surface applications |
| CN101974227A (en) * | 2010-05-20 | 2011-02-16 | 复旦大学 | Low-stress epoxy/organic silicon/POSS nano hybrid material, and preparation method and application thereof |
| CN101985513A (en) * | 2010-05-20 | 2011-03-16 | 复旦大学 | POSS/epoxy nanometer hybrid material and preparation method and application thereof |
| CN102102007A (en) * | 2010-12-22 | 2011-06-22 | 东莞市派乐玛新材料技术开发有限公司 | Radiation cured adhesive for indium tin oxide (ITO) circuit and module protection |
| WO2012141994A2 (en) * | 2011-04-15 | 2012-10-18 | Avery Dennison Corporation | Surface treated film and/or laminate |
| CN102775567A (en) * | 2012-07-20 | 2012-11-14 | 天津大学 | POSS (polyhedral oligomeric silsesquioxane) contained polyacrylate-polysiloxane block copolymer and preparation method thereof |
| CN103435742A (en) * | 2013-08-27 | 2013-12-11 | 华南理工大学 | Hydrophobic POSS (Polyhedral Oligomeric Silsesquioxane)-based hybridization fluorinated acrylate resin as well as preparation method and application thereof |
| KR20140132573A (en) * | 2013-05-08 | 2014-11-18 | 동우 화인켐 주식회사 | Adhesive composition and method manufacturing flexible display device using the same |
| CN104592907A (en) * | 2015-02-11 | 2015-05-06 | 温州瑞阳光伏材料有限公司 | Preparation technology and product of high-performance EVA photovoltaic packaging adhesive film |
| CN105441012A (en) * | 2015-12-15 | 2016-03-30 | 东莞市派乐玛新材料技术开发有限公司 | UV adhesive for sealing quantum dot material, and preparation method thereof |
| CN105683304A (en) * | 2013-10-31 | 2016-06-15 | 埃西勒国际通用光学公司 | Article having coating on substrate, coating composition, and coating method |
| CN106221665A (en) * | 2016-07-28 | 2016-12-14 | 王烽 | A kind of LED organic silicon packaging glue of nano-cerium oxide nano aluminum nitride hybrid modification and preparation method thereof |
| CN106752628A (en) * | 2016-12-13 | 2017-05-31 | 中国人民解放军61489部队 | A kind of building water-proof paint of POSS and silicon oil modified fluorinated acrylate |
| CN106981478A (en) * | 2017-04-07 | 2017-07-25 | 京东方科技集团股份有限公司 | Top gate type thin film transistor and preparation method thereof, array base palte, display panel |
| CN107325287A (en) * | 2017-08-01 | 2017-11-07 | 西南科技大学 | The preparation method of benzocyclobutene functionalization cage modle polysilsesquioxane and its resin |
| CN107406608A (en) * | 2015-08-11 | 2017-11-28 | 株式会社Lg化学 | Photo curable coating composition, low-index layer and antireflective coating |
| CN107418420A (en) * | 2017-07-27 | 2017-12-01 | 浙江工业大学之江学院 | A kind of hydrophobic polyurethane hybrid coating and preparation method thereof |
-
2018
- 2018-03-09 CN CN201810193900.0A patent/CN108410351B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004060330A2 (en) * | 2002-12-19 | 2004-07-22 | Kimberly-Clark Worldwide, Inc. | Multifunctional compositions for surface applications |
| CN101974227A (en) * | 2010-05-20 | 2011-02-16 | 复旦大学 | Low-stress epoxy/organic silicon/POSS nano hybrid material, and preparation method and application thereof |
| CN101985513A (en) * | 2010-05-20 | 2011-03-16 | 复旦大学 | POSS/epoxy nanometer hybrid material and preparation method and application thereof |
| CN102102007A (en) * | 2010-12-22 | 2011-06-22 | 东莞市派乐玛新材料技术开发有限公司 | Radiation cured adhesive for indium tin oxide (ITO) circuit and module protection |
| WO2012141994A2 (en) * | 2011-04-15 | 2012-10-18 | Avery Dennison Corporation | Surface treated film and/or laminate |
| CN102775567A (en) * | 2012-07-20 | 2012-11-14 | 天津大学 | POSS (polyhedral oligomeric silsesquioxane) contained polyacrylate-polysiloxane block copolymer and preparation method thereof |
| KR20140132573A (en) * | 2013-05-08 | 2014-11-18 | 동우 화인켐 주식회사 | Adhesive composition and method manufacturing flexible display device using the same |
| CN103435742A (en) * | 2013-08-27 | 2013-12-11 | 华南理工大学 | Hydrophobic POSS (Polyhedral Oligomeric Silsesquioxane)-based hybridization fluorinated acrylate resin as well as preparation method and application thereof |
| CN105683304A (en) * | 2013-10-31 | 2016-06-15 | 埃西勒国际通用光学公司 | Article having coating on substrate, coating composition, and coating method |
| CN104592907A (en) * | 2015-02-11 | 2015-05-06 | 温州瑞阳光伏材料有限公司 | Preparation technology and product of high-performance EVA photovoltaic packaging adhesive film |
| CN107406608A (en) * | 2015-08-11 | 2017-11-28 | 株式会社Lg化学 | Photo curable coating composition, low-index layer and antireflective coating |
| CN105441012A (en) * | 2015-12-15 | 2016-03-30 | 东莞市派乐玛新材料技术开发有限公司 | UV adhesive for sealing quantum dot material, and preparation method thereof |
| CN106221665A (en) * | 2016-07-28 | 2016-12-14 | 王烽 | A kind of LED organic silicon packaging glue of nano-cerium oxide nano aluminum nitride hybrid modification and preparation method thereof |
| CN106752628A (en) * | 2016-12-13 | 2017-05-31 | 中国人民解放军61489部队 | A kind of building water-proof paint of POSS and silicon oil modified fluorinated acrylate |
| CN106981478A (en) * | 2017-04-07 | 2017-07-25 | 京东方科技集团股份有限公司 | Top gate type thin film transistor and preparation method thereof, array base palte, display panel |
| CN107418420A (en) * | 2017-07-27 | 2017-12-01 | 浙江工业大学之江学院 | A kind of hydrophobic polyurethane hybrid coating and preparation method thereof |
| CN107325287A (en) * | 2017-08-01 | 2017-11-07 | 西南科技大学 | The preparation method of benzocyclobutene functionalization cage modle polysilsesquioxane and its resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108410351A (en) | 2018-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108467504B (en) | Composite barrier film with water-oxygen barrier function and preparation method thereof | |
| CN108410351B (en) | Organic silicon/inorganic silicon hybrid barrier coating composition and preparation method and application thereof | |
| US9593209B2 (en) | Process for preparing clustered functional polyorganosiloxanes, and methods for their use | |
| EP2499185B1 (en) | Process for preparing clustered functional polyorganosiloxanes, and methods for their use | |
| JP6347902B1 (en) | Active energy ray-curable hot melt silicone composition, cured product thereof, and method for producing film | |
| JP2013525543A5 (en) | ||
| CN105524589A (en) | LOCA (Liquid Optical Clear Adhesive) and preparation method thereof | |
| WO2010059710A1 (en) | A silicone composition and a method for preparing the same | |
| WO2009004010A1 (en) | Coating compositions comprising organofunctional polysiloxane polymers, and use thereof | |
| CN104558501A (en) | Ultraviolet ray and moisture dual-cured modified polyurethane and preparation method thereof | |
| CN110713818B (en) | Ultraviolet/moisture dual fast-curing polysiloxane adhesive composition | |
| TWI609028B (en) | Copolymer and resin composition, packaging film and package structure including the same | |
| JP2022130696A (en) | Curable silicone optically clear adhesives and uses thereof | |
| CN104449552B (en) | Adhesion type Single-component addition-type silicone rubber adhesive and preparation method thereof | |
| CN111234136A (en) | Preparation method of photocuring organic silicon resin system and photocuring film | |
| CN103275496A (en) | Epoxy resin modified organic silicon photo-curing material and preparation method thereof | |
| KR20200079504A (en) | Silicone adhesive composition, adhesive tape, adhesive sheet and double-sided adhesive sheet | |
| CN114958295A (en) | Ultralow-adhesive-force and low-climbing organic silicon pressure-sensitive adhesive as well as preparation method and application thereof | |
| CN107118350A (en) | A kind of epoxy and phenyl silicones and preparation method and application | |
| JP6951412B2 (en) | Siloxane monomers, their polymerization and their use | |
| CN104387590A (en) | Antenna-structure cage-type organic silicon resin, and preparation method and application thereof | |
| JP5168491B2 (en) | Thermosetting resin composition | |
| CN113831536B (en) | Ester ring epoxy acrylate hybrid silicone resin, preparation method and application | |
| KR101549473B1 (en) | Modified Organic-Inorganic Hybrid Copolymer, Process of Preparing the Copolymer, Coating Composition Having the Copolymer and Application Thereof | |
| JP2010006956A (en) | Thermosetting resin composition for sealing optical semiconductor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231108 Address after: Room 101, Building 1, No. 11 Industrial West Third Road, Songshan Lake Park, Dongguan City, Guangdong Province, 523000 Patentee after: Guangdong Parma New Material Technology Co.,Ltd. Address before: 523000 Xiaohe Industrial Zone, Daojiao Town, Dongguan City, Guangdong Province (huweizhou) Patentee before: DONGGUAN POWERBOND NEW MATERIALS TECHNOLOGY DEVELOPMENT Co.,Ltd. |