WO2015119260A1 - Modified polysilazane, coating solution containing said modified polysilazane, and gas barrier film produced using said coating solution - Google Patents
Modified polysilazane, coating solution containing said modified polysilazane, and gas barrier film produced using said coating solution Download PDFInfo
- Publication number
- WO2015119260A1 WO2015119260A1 PCT/JP2015/053435 JP2015053435W WO2015119260A1 WO 2015119260 A1 WO2015119260 A1 WO 2015119260A1 JP 2015053435 W JP2015053435 W JP 2015053435W WO 2015119260 A1 WO2015119260 A1 WO 2015119260A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sih
- barrier layer
- film
- polysilazane
- layer
- Prior art date
Links
- 230000004888 barrier function Effects 0.000 title claims abstract description 530
- 229920001709 polysilazane Polymers 0.000 title claims abstract description 211
- 238000000576 coating method Methods 0.000 title claims description 286
- 239000011248 coating agent Substances 0.000 title claims description 266
- 239000007789 gas Substances 0.000 claims description 271
- 229910052760 oxygen Inorganic materials 0.000 claims description 110
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 109
- 239000001301 oxygen Substances 0.000 claims description 109
- 229910052751 metal Inorganic materials 0.000 claims description 107
- 239000002184 metal Substances 0.000 claims description 107
- 150000001875 compounds Chemical class 0.000 claims description 91
- 239000000758 substrate Substances 0.000 claims description 80
- -1 alkoxide compound Chemical class 0.000 claims description 67
- 125000000217 alkyl group Chemical group 0.000 claims description 66
- 239000013522 chelant Substances 0.000 claims description 58
- 239000012298 atmosphere Substances 0.000 claims description 56
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 55
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 52
- 239000007788 liquid Substances 0.000 claims description 48
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 47
- 229910052757 nitrogen Inorganic materials 0.000 claims description 42
- 150000002484 inorganic compounds Chemical class 0.000 claims description 41
- 229910010272 inorganic material Inorganic materials 0.000 claims description 41
- 229910052710 silicon Inorganic materials 0.000 claims description 39
- 229910052782 aluminium Inorganic materials 0.000 claims description 34
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 30
- 238000011282 treatment Methods 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- 125000005369 trialkoxysilyl group Chemical group 0.000 claims description 26
- 125000004122 cyclic group Chemical group 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- 238000002407 reforming Methods 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 46
- 238000003860 storage Methods 0.000 abstract description 17
- 229910003828 SiH3 Inorganic materials 0.000 abstract 2
- XMIJDTGORVPYLW-UHFFFAOYSA-N [SiH2] Chemical compound [SiH2] XMIJDTGORVPYLW-UHFFFAOYSA-N 0.000 abstract 2
- OLRJXMHANKMLTD-UHFFFAOYSA-N silyl Chemical compound [SiH3] OLRJXMHANKMLTD-UHFFFAOYSA-N 0.000 abstract 2
- 238000005133 29Si NMR spectroscopy Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 472
- 239000010408 film Substances 0.000 description 389
- 239000000243 solution Substances 0.000 description 180
- 238000000034 method Methods 0.000 description 120
- 230000015572 biosynthetic process Effects 0.000 description 76
- 238000006243 chemical reaction Methods 0.000 description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 59
- 229910052799 carbon Inorganic materials 0.000 description 49
- 239000000463 material Substances 0.000 description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 48
- 238000009826 distribution Methods 0.000 description 47
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 44
- 239000002904 solvent Substances 0.000 description 40
- 150000004703 alkoxides Chemical class 0.000 description 32
- 238000005259 measurement Methods 0.000 description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 28
- 239000003054 catalyst Substances 0.000 description 28
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- 238000005481 NMR spectroscopy Methods 0.000 description 25
- 239000002994 raw material Substances 0.000 description 25
- 208000028659 discharge Diseases 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 125000004432 carbon atom Chemical group C* 0.000 description 22
- 238000007254 oxidation reaction Methods 0.000 description 22
- 150000003377 silicon compounds Chemical class 0.000 description 22
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 21
- 230000004048 modification Effects 0.000 description 21
- 238000012986 modification Methods 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 21
- 239000000523 sample Substances 0.000 description 21
- 125000003545 alkoxy group Chemical group 0.000 description 20
- 210000004027 cell Anatomy 0.000 description 19
- 238000005401 electroluminescence Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 239000010409 thin film Substances 0.000 description 18
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 17
- 125000004430 oxygen atom Chemical group O* 0.000 description 16
- 238000005229 chemical vapour deposition Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 14
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 12
- 125000005843 halogen group Chemical group 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 11
- 230000006866 deterioration Effects 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- 229910052814 silicon oxide Inorganic materials 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 10
- YNCDEEFMDXHURQ-UHFFFAOYSA-N aluminum;ethyl 3-oxobutanoate Chemical compound [Al].CCOC(=O)CC(C)=O YNCDEEFMDXHURQ-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 230000007547 defect Effects 0.000 description 10
- 238000005530 etching Methods 0.000 description 10
- 230000005525 hole transport Effects 0.000 description 10
- 229910052738 indium Inorganic materials 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- MQQXUGFEQSCYIA-OAWHIZORSA-M aluminum;(z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-] MQQXUGFEQSCYIA-OAWHIZORSA-M 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 239000004973 liquid crystal related substance Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 230000002265 prevention Effects 0.000 description 8
- 239000011241 protective layer Substances 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000012776 electronic material Substances 0.000 description 7
- 150000004767 nitrides Chemical class 0.000 description 7
- 150000002894 organic compounds Chemical class 0.000 description 7
- 150000003961 organosilicon compounds Chemical class 0.000 description 7
- 238000005240 physical vapour deposition Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000012808 vapor phase Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 6
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- 229910052711 selenium Inorganic materials 0.000 description 6
- 239000011669 selenium Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- 229920006255 plastic film Polymers 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910007991 Si-N Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910006294 Si—N Inorganic materials 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 239000002274 desiccant Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical group CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 239000000010 aprotic solvent Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 150000001983 dialkylethers Chemical class 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229940093499 ethyl acetate Drugs 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 2
- OVSGBKZKXUMMHS-VGKOASNMSA-L (z)-4-oxopent-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O OVSGBKZKXUMMHS-VGKOASNMSA-L 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical compound NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- KEBBHXFLBGHGMA-UHFFFAOYSA-K aluminum;4-ethyl-3-oxohexanoate Chemical compound [Al+3].CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O KEBBHXFLBGHGMA-UHFFFAOYSA-K 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- RPPBZEBXAAZZJH-UHFFFAOYSA-N cadmium telluride Chemical compound [Te]=[Cd] RPPBZEBXAAZZJH-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 2
- WEIQRLLXVVSKIL-UHFFFAOYSA-N ethyl 2,2-diethyl-3-oxobutanoate Chemical compound CCOC(=O)C(CC)(CC)C(C)=O WEIQRLLXVVSKIL-UHFFFAOYSA-N 0.000 description 2
- 229940093858 ethyl acetoacetate Drugs 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical class CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229960005235 piperonyl butoxide Drugs 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 125000005920 sec-butoxy group Chemical group 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 2
- OVZUSPADPSOQQN-UHFFFAOYSA-N tri(propan-2-yloxy)indigane Chemical compound [In+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] OVZUSPADPSOQQN-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- AXJAWMUPFHKOHY-UHFFFAOYSA-N trimethyl(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(C)C AXJAWMUPFHKOHY-UHFFFAOYSA-N 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- IDXCKOANSQIPGX-UHFFFAOYSA-N (acetyloxy-ethenyl-methylsilyl) acetate Chemical compound CC(=O)O[Si](C)(C=C)OC(C)=O IDXCKOANSQIPGX-UHFFFAOYSA-N 0.000 description 1
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical compound [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 description 1
- RDMHXWZYVFGYSF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RDMHXWZYVFGYSF-LNTINUHCSA-N 0.000 description 1
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- NOXQKISUYACYGB-LNTINUHCSA-K (z)-4-oxopent-2-en-2-olate;praseodymium(3+) Chemical compound [Pr+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O NOXQKISUYACYGB-LNTINUHCSA-K 0.000 description 1
- TYKCBTYOMAUNLH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;titanium(4+) Chemical compound [Ti+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O TYKCBTYOMAUNLH-MTOQALJVSA-J 0.000 description 1
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 description 1
- YQQFFTNDQFUNHB-UHFFFAOYSA-N 1,1-dimethylsiletane Chemical compound C[Si]1(C)CCC1 YQQFFTNDQFUNHB-UHFFFAOYSA-N 0.000 description 1
- GUHGBXKQVBLQGP-UHFFFAOYSA-N 1-cyclohexylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1CCCCC1 GUHGBXKQVBLQGP-UHFFFAOYSA-N 0.000 description 1
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 1
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- GOKHWHDASMAJQU-UHFFFAOYSA-N 2,2-dimethylnonane-3,5-dione Chemical compound CCCCC(=O)CC(=O)C(C)(C)C GOKHWHDASMAJQU-UHFFFAOYSA-N 0.000 description 1
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 description 1
- URZHQOCYXDNFGN-UHFFFAOYSA-N 2,4,6-trimethyl-2,4,6-tris(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[Si](C)(CCC(F)(F)F)O[Si](C)(CCC(F)(F)F)O1 URZHQOCYXDNFGN-UHFFFAOYSA-N 0.000 description 1
- BVTLTBONLZSBJC-UHFFFAOYSA-N 2,4,6-tris(ethenyl)-2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O1 BVTLTBONLZSBJC-UHFFFAOYSA-N 0.000 description 1
- KYFDXXXNUGBKLT-UHFFFAOYSA-N 2-ethoxyethynyl(dimethyl)silane Chemical compound CCOC#C[SiH](C)C KYFDXXXNUGBKLT-UHFFFAOYSA-N 0.000 description 1
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- CZMNFHBVFGQLCG-UHFFFAOYSA-N 2-methylpropan-1-ol;oxovanadium Chemical compound [V]=O.CC(C)CO.CC(C)CO.CC(C)CO CZMNFHBVFGQLCG-UHFFFAOYSA-N 0.000 description 1
- SNOJPWLNAMAYSX-UHFFFAOYSA-N 2-methylpropan-1-ol;titanium Chemical compound [Ti].CC(C)CO.CC(C)CO.CC(C)CO.CC(C)CO SNOJPWLNAMAYSX-UHFFFAOYSA-N 0.000 description 1
- ZBBMXDFMKDTJPZ-UHFFFAOYSA-N 2-methylpropan-2-olate niobium(5+) Chemical compound [Nb+5].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] ZBBMXDFMKDTJPZ-UHFFFAOYSA-N 0.000 description 1
- OSXGKVOYAKRLCS-UHFFFAOYSA-N 2-methylpropan-2-olate;tin(4+) Chemical compound CC(C)(C)O[Sn](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C OSXGKVOYAKRLCS-UHFFFAOYSA-N 0.000 description 1
- GRWPYGBKJYICOO-UHFFFAOYSA-N 2-methylpropan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] GRWPYGBKJYICOO-UHFFFAOYSA-N 0.000 description 1
- BGGIUGXMWNKMCP-UHFFFAOYSA-N 2-methylpropan-2-olate;zirconium(4+) Chemical compound CC(C)(C)O[Zr](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BGGIUGXMWNKMCP-UHFFFAOYSA-N 0.000 description 1
- GBCNIMMWOPWZEG-UHFFFAOYSA-N 3-(diethoxymethylsilyl)-n,n-dimethylpropan-1-amine Chemical compound CCOC(OCC)[SiH2]CCCN(C)C GBCNIMMWOPWZEG-UHFFFAOYSA-N 0.000 description 1
- VLZDYNDUVLBNLD-UHFFFAOYSA-N 3-(dimethoxymethylsilyl)propyl 2-methylprop-2-enoate Chemical compound COC(OC)[SiH2]CCCOC(=O)C(C)=C VLZDYNDUVLBNLD-UHFFFAOYSA-N 0.000 description 1
- HHHPYRGQUSPESB-UHFFFAOYSA-N 3-(dimethoxymethylsilyl)propyl prop-2-enoate Chemical compound COC(OC)[SiH2]CCCOC(=O)C=C HHHPYRGQUSPESB-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- GLISOBUNKGBQCL-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(C)CCCN GLISOBUNKGBQCL-UHFFFAOYSA-N 0.000 description 1
- VXOAPUIMMKQAFU-UHFFFAOYSA-N 3-ethenylsulfanylpropyl(trimethyl)silane Chemical compound C[Si](C)(C)CCCSC=C VXOAPUIMMKQAFU-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
- CCOQPNDCFRSIOZ-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2,2,2-trifluoroacetate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(F)(F)F CCOQPNDCFRSIOZ-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
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- OMAUSUKGZFZKBA-UHFFFAOYSA-N 5,5,6-trimethylheptane-1,6-diamine Chemical compound CC(C)(N)C(C)(C)CCCCN OMAUSUKGZFZKBA-UHFFFAOYSA-N 0.000 description 1
- LCLCVVVHIPPHCG-UHFFFAOYSA-N 5,5-dimethylhexane-2,4-dione Chemical compound CC(=O)CC(=O)C(C)(C)C LCLCVVVHIPPHCG-UHFFFAOYSA-N 0.000 description 1
- HRJSLUPAMXKPPM-UHFFFAOYSA-N 5-methyl-2-(3-methylphenyl)pyrazol-3-amine Chemical compound N1=C(C)C=C(N)N1C1=CC=CC(C)=C1 HRJSLUPAMXKPPM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XUHJDMGGXGKHEA-UHFFFAOYSA-N C(C)OC([O-])C.C(C)O[Mg+].[Mg+2].C(C)OC([O-])C.C(C)OC([O-])C Chemical compound C(C)OC([O-])C.C(C)O[Mg+].[Mg+2].C(C)OC([O-])C.C(C)OC([O-])C XUHJDMGGXGKHEA-UHFFFAOYSA-N 0.000 description 1
- YJIFTYXRIKMETG-UHFFFAOYSA-N C(C)OC([O-])C.[Zn+2].C(C)OC([O-])C Chemical compound C(C)OC([O-])C.[Zn+2].C(C)OC([O-])C YJIFTYXRIKMETG-UHFFFAOYSA-N 0.000 description 1
- FBXFASOKARHVAQ-UHFFFAOYSA-N CC(C)(C)[O-].[Ge+2].CC(C)(C)[O-] Chemical compound CC(C)(C)[O-].[Ge+2].CC(C)(C)[O-] FBXFASOKARHVAQ-UHFFFAOYSA-N 0.000 description 1
- QOGFQIGEQMWCJB-UHFFFAOYSA-N COC(OC)[Si]CCC(F)(F)F Chemical compound COC(OC)[Si]CCC(F)(F)F QOGFQIGEQMWCJB-UHFFFAOYSA-N 0.000 description 1
- YJOZQKPCYREOME-UHFFFAOYSA-N COC([O-])C.[Nd+3].COC([O-])C.COC([O-])C Chemical compound COC([O-])C.[Nd+3].COC([O-])C.COC([O-])C YJOZQKPCYREOME-UHFFFAOYSA-N 0.000 description 1
- CIYFDOMKPRAGBR-UHFFFAOYSA-N COC([O-])C.[Pr+3].COC([O-])C.COC([O-])C Chemical compound COC([O-])C.[Pr+3].COC([O-])C.COC([O-])C CIYFDOMKPRAGBR-UHFFFAOYSA-N 0.000 description 1
- UXVHAZNVHWLABN-UHFFFAOYSA-N C[O-].[Ta+4].C[O-].C[O-].C[O-] Chemical compound C[O-].[Ta+4].C[O-].C[O-].C[O-] UXVHAZNVHWLABN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 235000010650 Hyssopus officinalis Nutrition 0.000 description 1
- 240000001812 Hyssopus officinalis Species 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- CNNYQGIUGXJEJJ-UHFFFAOYSA-N [Ge+2].C[O-].C[O-] Chemical compound [Ge+2].C[O-].C[O-] CNNYQGIUGXJEJJ-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- QJQMCTMUAGABQR-UHFFFAOYSA-N [O-]CCCC.[Ge+2].CC([O-])C.[Ge+2] Chemical compound [O-]CCCC.[Ge+2].CC([O-])C.[Ge+2] QJQMCTMUAGABQR-UHFFFAOYSA-N 0.000 description 1
- OIIGPGKGVNSPBV-UHFFFAOYSA-N [W+4].CC[O-].CC[O-].CC[O-].CC[O-] Chemical compound [W+4].CC[O-].CC[O-].CC[O-].CC[O-] OIIGPGKGVNSPBV-UHFFFAOYSA-N 0.000 description 1
- WYUIWUCVZCRTRH-UHFFFAOYSA-N [[[ethenyl(dimethyl)silyl]amino]-dimethylsilyl]ethene Chemical compound C=C[Si](C)(C)N[Si](C)(C)C=C WYUIWUCVZCRTRH-UHFFFAOYSA-N 0.000 description 1
- RQVFGTYFBUVGOP-UHFFFAOYSA-N [acetyloxy(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)OC(C)=O RQVFGTYFBUVGOP-UHFFFAOYSA-N 0.000 description 1
- CNOSLBKTVBFPBB-UHFFFAOYSA-N [acetyloxy(diphenyl)silyl] acetate Chemical compound C=1C=CC=CC=1[Si](OC(C)=O)(OC(=O)C)C1=CC=CC=C1 CNOSLBKTVBFPBB-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- IKHOZNOYZQPPCK-UHFFFAOYSA-K aluminum;4,4-diethyl-3-oxohexanoate Chemical compound [Al+3].CCC(CC)(CC)C(=O)CC([O-])=O.CCC(CC)(CC)C(=O)CC([O-])=O.CCC(CC)(CC)C(=O)CC([O-])=O IKHOZNOYZQPPCK-UHFFFAOYSA-K 0.000 description 1
- GMARCGBNZNYETI-UHFFFAOYSA-N aluminum;oxygen(2-);propan-2-olate Chemical compound [O-2].[Al+3].CC(C)[O-] GMARCGBNZNYETI-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- SLPLCLDJTNLWPW-UHFFFAOYSA-N barium(2+);2-methylpropan-2-olate Chemical compound [Ba+2].CC(C)(C)[O-].CC(C)(C)[O-] SLPLCLDJTNLWPW-UHFFFAOYSA-N 0.000 description 1
- CPUJSIVIXCTVEI-UHFFFAOYSA-N barium(2+);propan-2-olate Chemical compound [Ba+2].CC(C)[O-].CC(C)[O-] CPUJSIVIXCTVEI-UHFFFAOYSA-N 0.000 description 1
- XRJBMOBWWDKSDQ-UHFFFAOYSA-N benzhydryl(ethenyl)silane Chemical compound C=1C=CC=CC=1C([SiH2]C=C)C1=CC=CC=C1 XRJBMOBWWDKSDQ-UHFFFAOYSA-N 0.000 description 1
- UCRXQUVKDMVBBM-UHFFFAOYSA-N benzyl 2-amino-3-(4-phenylmethoxyphenyl)propanoate Chemical compound C=1C=CC=CC=1COC(=O)C(N)CC(C=C1)=CC=C1OCC1=CC=CC=C1 UCRXQUVKDMVBBM-UHFFFAOYSA-N 0.000 description 1
- RFXODRCAZTVEOH-UHFFFAOYSA-N benzyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)CC1=CC=CC=C1 RFXODRCAZTVEOH-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- BBKXDHBLPBKCFR-FDGPNNRMSA-L beryllium;(z)-4-oxopent-2-en-2-olate Chemical compound [Be+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BBKXDHBLPBKCFR-FDGPNNRMSA-L 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- QRHCILLLMDEFSD-UHFFFAOYSA-N bis(ethenyl)-dimethylsilane Chemical compound C=C[Si](C)(C)C=C QRHCILLLMDEFSD-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- CKEGKURXFKLBDX-UHFFFAOYSA-N butan-1-ol;hafnium Chemical compound [Hf].CCCCO.CCCCO.CCCCO.CCCCO CKEGKURXFKLBDX-UHFFFAOYSA-N 0.000 description 1
- PVZMSIQWTGPSHJ-UHFFFAOYSA-N butan-1-ol;tantalum Chemical compound [Ta].CCCCO.CCCCO.CCCCO.CCCCO.CCCCO PVZMSIQWTGPSHJ-UHFFFAOYSA-N 0.000 description 1
- QFUWHTBCUVMAMS-UHFFFAOYSA-N butan-1-olate cerium(3+) Chemical compound [Ce+3].CCCC[O-].CCCC[O-].CCCC[O-] QFUWHTBCUVMAMS-UHFFFAOYSA-N 0.000 description 1
- DINQVNXOZUORJS-UHFFFAOYSA-N butan-1-olate;niobium(5+) Chemical compound [Nb+5].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] DINQVNXOZUORJS-UHFFFAOYSA-N 0.000 description 1
- QORWLRPWMJEJKP-UHFFFAOYSA-N butan-1-olate;tantalum(5+) Chemical compound [Ta+5].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] QORWLRPWMJEJKP-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- SOKKGFZWZZLHEK-UHFFFAOYSA-N butoxy(dimethyl)silane Chemical compound CCCCO[SiH](C)C SOKKGFZWZZLHEK-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- MHEVIADVQSYOSQ-UHFFFAOYSA-N butyl-ethenyl-dimethoxysilane Chemical compound CCCC[Si](OC)(OC)C=C MHEVIADVQSYOSQ-UHFFFAOYSA-N 0.000 description 1
- QAZYYQMPRQKMAC-FDGPNNRMSA-L calcium;(z)-4-oxopent-2-en-2-olate Chemical compound [Ca+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O QAZYYQMPRQKMAC-FDGPNNRMSA-L 0.000 description 1
- JHLCADGWXYCDQA-UHFFFAOYSA-N calcium;ethanolate Chemical compound [Ca+2].CC[O-].CC[O-] JHLCADGWXYCDQA-UHFFFAOYSA-N 0.000 description 1
- AMJQWGIYCROUQF-UHFFFAOYSA-N calcium;methanolate Chemical compound [Ca+2].[O-]C.[O-]C AMJQWGIYCROUQF-UHFFFAOYSA-N 0.000 description 1
- MMLSWLZTJDJYJH-UHFFFAOYSA-N calcium;propan-2-olate Chemical compound [Ca+2].CC(C)[O-].CC(C)[O-] MMLSWLZTJDJYJH-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012700 ceramic precursor Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 description 1
- BXCIHNFUIYCGKS-UHFFFAOYSA-N cerium(3+);2-methylpropan-2-olate Chemical compound [Ce+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] BXCIHNFUIYCGKS-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- JTMDFVKZKWRFNY-UHFFFAOYSA-N chromium(3+) propan-1-olate Chemical compound [Cr+3].CCC[O-].CCC[O-].CCC[O-] JTMDFVKZKWRFNY-UHFFFAOYSA-N 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- CRCKGIUJMFFISH-UHFFFAOYSA-N copper;ethanolate Chemical compound [Cu+2].CC[O-].CC[O-] CRCKGIUJMFFISH-UHFFFAOYSA-N 0.000 description 1
- AYNQPTYHFBBKFC-UHFFFAOYSA-N copper;methanolate Chemical compound [Cu+2].[O-]C.[O-]C AYNQPTYHFBBKFC-UHFFFAOYSA-N 0.000 description 1
- VNGORJHUDAPOQZ-UHFFFAOYSA-N copper;propan-2-olate Chemical compound [Cu+2].CC(C)[O-].CC(C)[O-] VNGORJHUDAPOQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
- LOGSONSNCYTHPS-UHFFFAOYSA-N cyclopentane-1,3-dione Chemical compound O=C1CCC(=O)C1 LOGSONSNCYTHPS-UHFFFAOYSA-N 0.000 description 1
- WTVNFKVGGUWHQC-UHFFFAOYSA-N decane-2,4-dione Chemical compound CCCCCCC(=O)CC(C)=O WTVNFKVGGUWHQC-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GWUJPMKBSYJFCK-UHFFFAOYSA-N decyl-dimethoxy-methylsilane Chemical compound CCCCCCCCCC[Si](C)(OC)OC GWUJPMKBSYJFCK-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- PHSNFACJRATEMO-UHFFFAOYSA-N dibenzyl(dimethyl)silane Chemical compound C=1C=CC=CC=1C[Si](C)(C)CC1=CC=CC=C1 PHSNFACJRATEMO-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- QIGCTKTXDFYSPE-UHFFFAOYSA-N diethyl-methyl-phenylsilane Chemical compound CC[Si](C)(CC)C1=CC=CC=C1 QIGCTKTXDFYSPE-UHFFFAOYSA-N 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- HQXKAHJBFCGGGP-UHFFFAOYSA-N dimethyl-[2-(3-methylbutoxy)ethenyl]silane Chemical compound CC(C)CCOC=C[SiH](C)C HQXKAHJBFCGGGP-UHFFFAOYSA-N 0.000 description 1
- HGSPSFLCJIQBDT-UHFFFAOYSA-N dimethyl-[2-(4-methylphenyl)ethenyl]silane Chemical compound C[SiH](C=CC1=CC=C(C=C1)C)C HGSPSFLCJIQBDT-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- ZHKRBCQSLSTSAO-UHFFFAOYSA-N dodecyl(trimethyl)silane Chemical compound CCCCCCCCCCCC[Si](C)(C)C ZHKRBCQSLSTSAO-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- VZLNSPSVSKXECI-UHFFFAOYSA-N ethanol;iron Chemical compound [Fe].CCO.CCO VZLNSPSVSKXECI-UHFFFAOYSA-N 0.000 description 1
- RWZKAROCZDFJEI-UHFFFAOYSA-N ethanol;zinc Chemical compound [Zn].CCO.CCO RWZKAROCZDFJEI-UHFFFAOYSA-N 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- DOGXYPDTORJOGJ-UHFFFAOYSA-N ethenyl(diethyl)silicon Chemical compound CC[Si](CC)C=C DOGXYPDTORJOGJ-UHFFFAOYSA-N 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
- VLNRSEGRGSDKLS-UHFFFAOYSA-N ethenyl-[4-[ethenyl(dimethyl)silyl]phenyl]-dimethylsilane Chemical compound C=C[Si](C)(C)C1=CC=C([Si](C)(C)C=C)C=C1 VLNRSEGRGSDKLS-UHFFFAOYSA-N 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- JEWCZPTVOYXPGG-UHFFFAOYSA-N ethenyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)C=C JEWCZPTVOYXPGG-UHFFFAOYSA-N 0.000 description 1
- NUFVQEIPPHHQCK-UHFFFAOYSA-N ethenyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)C=C NUFVQEIPPHHQCK-UHFFFAOYSA-N 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- HHBOIIOOTUCYQD-UHFFFAOYSA-N ethoxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(C)CCCOCC1CO1 HHBOIIOOTUCYQD-UHFFFAOYSA-N 0.000 description 1
- FIHCECZPYHVEJO-UHFFFAOYSA-N ethoxy-dimethyl-phenylsilane Chemical compound CCO[Si](C)(C)C1=CC=CC=C1 FIHCECZPYHVEJO-UHFFFAOYSA-N 0.000 description 1
- ADLWTVQIBZEAGJ-UHFFFAOYSA-N ethoxy-methyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C)(OCC)C1=CC=CC=C1 ADLWTVQIBZEAGJ-UHFFFAOYSA-N 0.000 description 1
- DZFYOYRNBGNPJW-UHFFFAOYSA-N ethoxythallium Chemical compound [Tl+].CC[O-] DZFYOYRNBGNPJW-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- AKYVEELUVDHHLT-UHFFFAOYSA-K europium acetylacetonate Chemical compound [Eu+3].CC([O-])=CC(C)=O.CC([O-])=CC(C)=O.CC([O-])=CC(C)=O AKYVEELUVDHHLT-UHFFFAOYSA-K 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- IQGAADOKZGEEQE-LNTINUHCSA-K gadolinium acetylacetonate Chemical compound [Gd+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O IQGAADOKZGEEQE-LNTINUHCSA-K 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- MCFIMQJAFAOJPD-MTOQALJVSA-J hafnium(4+) (Z)-4-oxopent-2-en-2-olate Chemical compound [Hf+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O MCFIMQJAFAOJPD-MTOQALJVSA-J 0.000 description 1
- AWZYJAFKVGBFEU-UHFFFAOYSA-N heptane-1,6-diamine Chemical compound CC(N)CCCCCN AWZYJAFKVGBFEU-UHFFFAOYSA-N 0.000 description 1
- DGCTVLNZTFDPDJ-UHFFFAOYSA-N heptane-3,5-dione Chemical compound CCC(=O)CC(=O)CC DGCTVLNZTFDPDJ-UHFFFAOYSA-N 0.000 description 1
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-UHFFFAOYSA-N 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- JXZRZVJOBWBSLG-UHFFFAOYSA-N indium(3+);2-methoxyethanolate Chemical compound [In+3].COCC[O-].COCC[O-].COCC[O-] JXZRZVJOBWBSLG-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XOEFHXMHZDTYQO-UHFFFAOYSA-N iron(2+);propan-1-olate Chemical compound [Fe+2].CCC[O-].CCC[O-] XOEFHXMHZDTYQO-UHFFFAOYSA-N 0.000 description 1
- QCQJPUZAVFHPMN-UHFFFAOYSA-N iron(2+);propan-2-olate Chemical compound [Fe+2].CC(C)[O-].CC(C)[O-] QCQJPUZAVFHPMN-UHFFFAOYSA-N 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- YPWKOAYHFZTKBJ-UHFFFAOYSA-N iron;methanol Chemical compound [Fe].OC.OC YPWKOAYHFZTKBJ-UHFFFAOYSA-N 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000005921 isopentoxy group Chemical group 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- UHDUMRBTZQQTHV-UHFFFAOYSA-N lanthanum(3+);1-methoxyethanolate Chemical compound [La+3].COC(C)[O-].COC(C)[O-].COC(C)[O-] UHDUMRBTZQQTHV-UHFFFAOYSA-N 0.000 description 1
- SORGMJIXNUWMMR-UHFFFAOYSA-N lanthanum(3+);propan-2-olate Chemical compound [La+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SORGMJIXNUWMMR-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AKTIAGQCYPCKFX-FDGPNNRMSA-L magnesium;(z)-4-oxopent-2-en-2-olate Chemical compound [Mg+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AKTIAGQCYPCKFX-FDGPNNRMSA-L 0.000 description 1
- YXOSSQSXCRVLJY-UHFFFAOYSA-N magnesium;2-methoxyethanolate Chemical compound COCCO[Mg]OCCOC YXOSSQSXCRVLJY-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- UQIRCVPINUNHQY-UHFFFAOYSA-N manganese(2+);methanolate Chemical compound [Mn+2].[O-]C.[O-]C UQIRCVPINUNHQY-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- LVNAMAOHFNPWJB-UHFFFAOYSA-N methanol;tantalum Chemical compound [Ta].OC.OC.OC.OC.OC LVNAMAOHFNPWJB-UHFFFAOYSA-N 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- NLSXOLJPOYUIKX-UHFFFAOYSA-N n-(3-trimethylsilylpropyl)butan-1-amine Chemical compound CCCCNCCC[Si](C)(C)C NLSXOLJPOYUIKX-UHFFFAOYSA-N 0.000 description 1
- BOYBHDHQCOROOJ-UHFFFAOYSA-N n-[butylamino(dimethyl)silyl]butan-1-amine Chemical compound CCCCN[Si](C)(C)NCCCC BOYBHDHQCOROOJ-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- QHUOBLDKFGCVCG-UHFFFAOYSA-N n-methyl-n-trimethylsilylacetamide Chemical compound CC(=O)N(C)[Si](C)(C)C QHUOBLDKFGCVCG-UHFFFAOYSA-N 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- GJYXGIIWJFZCLN-UHFFFAOYSA-N octane-2,4-dione Chemical compound CCCCC(=O)CC(C)=O GJYXGIIWJFZCLN-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- DSQPRECRRGZSCV-UHFFFAOYSA-N penta-1,4-dien-3-yl(phenyl)silane Chemical compound C=CC([SiH2]c1ccccc1)C=C DSQPRECRRGZSCV-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- XVCSANIKJQVZCJ-UHFFFAOYSA-N phenylsilylmethyl acetate Chemical compound C(C)(=O)OC[SiH2]C1=CC=CC=C1 XVCSANIKJQVZCJ-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- WUBJXWWQGDPUCE-UHFFFAOYSA-N propan-1-olate yttrium(3+) Chemical compound [Y+3].CCC[O-].CCC[O-].CCC[O-] WUBJXWWQGDPUCE-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- NREVZTYRXVBFAQ-UHFFFAOYSA-N propan-2-ol;yttrium Chemical compound [Y].CC(C)O.CC(C)O.CC(C)O NREVZTYRXVBFAQ-UHFFFAOYSA-N 0.000 description 1
- HJCRVWSKQNDSPZ-UHFFFAOYSA-N propan-2-olate;samarium(3+) Chemical compound [Sm+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] HJCRVWSKQNDSPZ-UHFFFAOYSA-N 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- UIDUKLCLJMXFEO-UHFFFAOYSA-N propylsilane Chemical compound CCC[SiH3] UIDUKLCLJMXFEO-UHFFFAOYSA-N 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CHACQUSVOVNARW-LNKPDPKZSA-M silver;(z)-4-oxopent-2-en-2-olate Chemical compound [Ag+].C\C([O-])=C\C(C)=O CHACQUSVOVNARW-LNKPDPKZSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- OHULXNKDWPTSBI-UHFFFAOYSA-N strontium;propan-2-olate Chemical compound [Sr+2].CC(C)[O-].CC(C)[O-] OHULXNKDWPTSBI-UHFFFAOYSA-N 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- PYKSLEHEVAWOTJ-UHFFFAOYSA-N tetrabutoxystannane Chemical compound CCCCO[Sn](OCCCC)(OCCCC)OCCCC PYKSLEHEVAWOTJ-UHFFFAOYSA-N 0.000 description 1
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 description 1
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- JWRQFDQQDBJDHD-UHFFFAOYSA-N tributoxyindigane Chemical compound CCCCO[In](OCCCC)OCCCC JWRQFDQQDBJDHD-UHFFFAOYSA-N 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- QAXKYAIESKANJL-UHFFFAOYSA-N tridecane-2,4-dione Chemical compound CCCCCCCCCC(=O)CC(C)=O QAXKYAIESKANJL-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- ZDYQCRCRHOQEED-UHFFFAOYSA-N triethoxy(ethyl)germane Chemical compound CCO[Ge](CC)(OCC)OCC ZDYQCRCRHOQEED-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- USLHPQORLCHMOC-UHFFFAOYSA-N triethoxygallane Chemical compound CCO[Ga](OCC)OCC USLHPQORLCHMOC-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- XIYWAPJTMIWONS-UHFFFAOYSA-N trimethoxygallane Chemical compound [Ga+3].[O-]C.[O-]C.[O-]C XIYWAPJTMIWONS-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- CDGIKLPUDRGJQN-UHFFFAOYSA-N trimethyl(octoxy)silane Chemical compound CCCCCCCCO[Si](C)(C)C CDGIKLPUDRGJQN-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- VFFKJOXNCSJSAQ-UHFFFAOYSA-N trimethylsilyl benzoate Chemical compound C[Si](C)(C)OC(=O)C1=CC=CC=C1 VFFKJOXNCSJSAQ-UHFFFAOYSA-N 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 1
- PKRKCDBTXBGLKV-UHFFFAOYSA-N tris(ethenyl)-methylsilane Chemical compound C=C[Si](C)(C=C)C=C PKRKCDBTXBGLKV-UHFFFAOYSA-N 0.000 description 1
- FUJPAQRDHMJPBB-UHFFFAOYSA-N tris(ethenyl)-phenylsilane Chemical compound C=C[Si](C=C)(C=C)C1=CC=CC=C1 FUJPAQRDHMJPBB-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- ZMCWFMOZBTXGKI-UHFFFAOYSA-N tritert-butyl borate Chemical compound CC(C)(C)OB(OC(C)(C)C)OC(C)(C)C ZMCWFMOZBTXGKI-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- WSDTWCKXZSLBGW-UHFFFAOYSA-N zinc;2-methoxyethanolate Chemical compound [Zn+2].COCC[O-].COCC[O-] WSDTWCKXZSLBGW-UHFFFAOYSA-N 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
- C09D183/16—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 in which all the silicon atoms are connected by linkages other than oxygen 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
- C08G77/60—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
Definitions
- the present invention relates to a modified polysilazane, a coating solution containing the modified polysilazane, and a gas barrier film produced using the coating solution. More specifically, the present invention is produced using a modified polysilazane used in an electronic device such as an organic electroluminescence (EL) element, a solar cell element, and a liquid crystal display, a coating solution containing the modified polysilazane, and the coating solution.
- EL organic electroluminescence
- the present invention relates to a gas barrier film.
- a gas barrier film formed by laminating a plurality of layers including thin films of metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide on the surface of a plastic substrate or film is used to block various gases such as water vapor and oxygen.
- metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide
- it is widely used in packaging applications for preventing deterioration of foods, industrial products, medicines and the like.
- a chemical deposition method in which an organic silicon compound typified by tetraethoxysilane (TEOS) is used to grow on a substrate while performing oxygen plasma oxidation under reduced pressure.
- TEOS tetraethoxysilane
- vapor phase methods such as a physical vapor deposition method (vacuum evaporation method or sputtering method) in which metal Si is evaporated using a semiconductor laser and deposited on a substrate in the presence of oxygen using a semiconductor laser.
- inorganic vapor deposition methods have been preferably applied to the formation of inorganic films such as silicon oxide, silicon nitride, and silicon oxynitride, and examination of the composition range of inorganic films for obtaining good gas barrier properties. Many studies have been made on the layer structure including these inorganic films.
- such a defect in the inorganic film causes the generation of a black spot called a dark spot that does not emit light, or the size of the dark spot grows under high temperature and high humidity. Will also affect.
- the coating of the inorganic precursor compound solution applied on the inorganic film by the above-mentioned vapor phase method and dried By modifying the layer with heat, the defect portion of the inorganic film formed by the above-mentioned vapor phase method is effectively repaired, and further, the laminated film itself has been studied to improve the gas barrier property.
- polysilazane as an inorganic precursor compound, studies have been made to develop a high gas barrier property by repairing the above-described defect portion.
- Bonding of atoms is called a photon process using light energy having a wavelength of 100 to 200 nm called vacuum ultraviolet light (hereinafter also referred to as “VUV” or “VUV light”) having an energy larger than the bonding force between each atom of polysilazane.
- VUV vacuum ultraviolet light
- a silicon oxynitride film or a silicon oxide film can be formed at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by the action of only photons.
- a first barrier layer formed by chemical vapor deposition on a substrate and a silicon compound such as polysilazane are applied.
- a gas barrier film having a second barrier layer formed by irradiating a film and irradiating energy rays (for example, vacuum ultraviolet light) is disclosed.
- the gas barrier film exhibits high barrier performance and is excellent in bending resistance, smoothness, and suitability for cutting.
- an energy beam is applied in an atmosphere substantially free of oxygen or moisture in a coating film formed by applying a polysilazane solution added with a transition metal compound on a substrate and drying it.
- a gas barrier film formed by irradiation for example, vacuum ultraviolet light
- the reforming proceeds in a short time to form a high nitrogen concentration film, and high gas barrier properties are exhibited.
- Patent Documents 1 and 2 show high gas barrier properties due to the modified surface and high gas barrier properties under general conditions, but the barrier layer by hydrolysis or the like under high temperature and high humidity. As a result, there has been a problem that the gas barrier property is rapidly lowered.
- the present invention has been made in view of the above circumstances, and provides a modified polysilazane suitable for production of a gas barrier film excellent in storage stability, particularly storage stability under severe conditions (high temperature and high humidity conditions). With the goal.
- Another object of the present invention is to provide a gas barrier film excellent in storage stability, particularly storage stability under severe conditions (high temperature and high humidity conditions).
- the present inventor has intensively studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using a modified polysilazane having a ratio of SiH 3 to the sum of SiH and SiH 2 in a specific range, and the present invention has been completed.
- a gas barrier film comprising a coating solution containing the modified polysilazane, or a substrate and a barrier layer formed using the coating solution.
- FIG. 1 It is a schematic diagram which shows an example of the vacuum plasma CVD apparatus used for formation of the inorganic compound layer (1st barrier layer) which concerns on this invention.
- 101 is a plasma CVD apparatus;
- 102 is a vacuum chamber;
- 103 is a cathode electrode;
- 105 is a susceptor;
- 106 is a heat medium circulation system;
- 107 is a vacuum exhaust system;
- 110 denotes a substrate;
- 160 denotes a heating / cooling device.
- FIG. 1 is a plasma CVD apparatus
- 102 is a vacuum chamber
- 103 is a cathode electrode
- 105 is a susceptor
- 106 is a heat medium circulation system
- 107 is a vacuum exhaust system
- 110 denotes a substrate
- 160 denotes a heating / cooling device.
- FIG. 1 is a plasma CV
- 1 is a gas barrier film
- 2 is a substrate
- 3 is a first barrier layer
- 31 is a production apparatus
- 32 is a feed roller
- 33, 34, 35, and 36 are transport rollers
- 39 and 40 are film forming rollers
- 41 is a gas supply pipe
- 42 is a power source for generating plasma
- 43 and 44 are magnetic field generators
- 45 is a winding roller.
- 21 indicates an apparatus chamber
- 22 indicates a Xe excimer lamp
- 23 indicates a holder
- 24 indicates a sample stage
- 25 indicates a sample
- 26 indicates a light shielding plate.
- the ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR [(SiH 3 ) :( SiH + SiH 2)] is 1: provide modified polysilazane 10-30.
- the coating liquid containing the modified polysilazane of this invention and the gas-barrier film manufactured using the said coating liquid are also provided.
- the perhydropolysilazane layer when the perhydropolysilazane layer is irradiated with energy rays (for example, vacuum ultraviolet light), the surface is modified to vitreous and exhibits high barrier properties. However, it deteriorates rapidly under severe conditions (high temperature and high humidity conditions).
- the barrier layer (gas barrier layer) formed using polysilazane as a precursor was significantly deteriorated under severe conditions (high-temperature and high-humidity conditions) in a configuration in which the barrier layer is in the lower layer.
- Patent Documents 1 and 2 attempts have been made to improve various characteristics including gas barrier properties of gas barrier films by various methods.
- the methods described in Patent Documents 1 and 2 only the vicinity of the surface of the polysilazane layer is modified, and an unmodified portion remains inside. It has been found that this unmodified part is one factor that causes a significant reaction under particularly severe conditions (high temperature and high humidity conditions) to lower the gas barrier property.
- the reaction proceeds due to the action of moisture in the atmosphere, the oxidation reaction has already progressed at the stage of irradiation with energy rays (for example, vacuum ultraviolet light), so the energy barrier cannot be sufficiently absorbed, and the optimum barrier film Is difficult or cannot be formed.
- energy rays for example, vacuum ultraviolet light
- modified polysilazane of the present invention is characterized by having a ratio [(SiH 3) :( SiH + SiH 2)] of the sum of SiH 3 and SiH and SiH 2 in a specific range.
- a gas barrier film excellent in storage stability, particularly storage stability under high temperature and high humidity can be provided.
- the present invention is not limited to the following.
- normally used polysilazane especially perhydropolysilazane
- has many —SiH 3 groups at the end and this —SiH 3 group becomes a reaction starting point during an operation from coating to active energy ray irradiation, and an undesirable reaction occurs. Arise.
- the gas barrier property under severe conditions is lowered.
- the highly reactive terminus of -SiH 3 group is a specific To be in the range of
- an undesirable reaction (atmosphere) generated from coating to active energy ray irradiation It is possible to preferentially and efficiently carry out a desired reforming reaction (oxidation reaction of polysilazane by irradiation with active energy rays) while suppressing the reaction with moisture and oxygen therein.
- the modified polysilazane of the present invention it is possible to produce a gas barrier film having high gas barrier properties and excellent storage stability (wet heat resistance) that suppresses / prevents deterioration of gas barrier properties particularly under high temperature and high humidity.
- the above effect can be achieved particularly remarkably when the terminal —SiH 3 group of polysilazane is modified with a metal alkoxide and / or a metal chelate compound, and a low molecular silazane and / or a low molecular siloxane.
- X to Y indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.
- the modified polysilazane has SiH and / or SiH 2 and SiH 3 , and the ratio of SiH 3 measured by 29 Si-NMR to the sum of SiH and SiH 2 [(SiH 3 ) :( SiH + SiH 2 ]] (Hereinafter also simply referred to as “SiH 3 ratio”) is 1:10 to 30 (molar ratio).
- SiH 3 ratio the ratio of SiH 3 measured by 29 Si-NMR to the sum of SiH and SiH 2 [(SiH 3 ) :( SiH + SiH 2 ]]
- the ratio of —SiH 3 groups present at the end of the modified polysilazane is the ratio [(SiH 3 ) :( SiH + SiH 2 )] of SiH 3 measured by 29 Si-NMR and the sum of SiH and SiH 2 .
- the barrier layer formed using the modified polysilazane of the present invention is excellent in gas barrier properties, particularly gas barrier properties under severe conditions (especially high temperature and high humidity).
- the ratio [(SiH 3 ) :( SiH + SiH 2 )] (SiH 3 ratio) between SiH 3 and the sum of SiH and SiH 2 is measured by 29 Si-NMR, specifically Means a value measured according to the method described in.
- the SiH 3 ratio of the modified polysilazane is 1: 10-30.
- the SiH 3 ratio exceeds the upper limit, excessively high reactive ends (SiH 3 ) are present, and thus react with moisture in the atmosphere before irradiation with active energy rays, and gas barrier properties, particularly high temperatures. Gas barrier properties under high humidity conditions are reduced.
- the SiH 3 ratio is below the lower limit, the polysilazane structure itself becomes unstable, resulting in an increase in low molecular components, liquid stagnation and coarse aggregation between molecules. Gas barrier properties under high humidity conditions are reduced.
- the SiH 3 ratio of the modified polysilazane is preferably 1:12 to 28, preferably 1:15 to 25, and 1: More preferably, it is 18-24.
- the modified polysilazane may be produced by any method as long as the polysilazane having the SiH 3 ratio as described above can be produced, but the method described in detail below can be preferably used.
- the polysilazane is reacted with at least one selected from the group consisting of low-molecular silazanes, low-molecular siloxanes, metal alkoxide compounds and metal chelate compounds to modify the SiH 3 group so as to reduce the reactivity of the SiH 3 group in the polysilazane.
- polysilazane low molecular silazanes and / or low-molecular-weight siloxane, and reacted with the metal alkoxide compound and / or a metal chelate compound, a SiH 3 group to lower the reactivity of the SiH 3 groups in the polysilazane It is more preferable to modify.
- polysilazane has a silicon atom, a hydrogen atom, and a nitrogen atom.
- the modified polysilazane of the present invention comprises (a) a polysilazane containing a silicon atom, a hydrogen atom and a nitrogen atom (hereinafter also simply referred to as “raw material polysilazane”), and (b) at least one of a low molecular silazane and a low molecular siloxane ( Hereinafter, obtained simply by reacting with at least one of “low molecular silazane / siloxane” and (c) metal alkoxide compound and metal chelate compound (hereinafter also simply referred to as “metal alkoxide / chelate compound”). Is preferred.
- (B) low molecular silazane / siloxane and (c) a metal alkoxide / chelate compound has a high reactivity with -SiH 3 group in the raw material polysilazane, the terminal -SiH 3 group in the raw material polysilazane more efficiently Can be modified.
- (c) metal alkoxide / chelate compound promotes the oxidation reaction of polysilazane by irradiation with active energy rays as compared with (b) low molecular weight silazane / siloxane, but has reactivity with water and oxygen in the atmosphere. high.
- reaction point (-SiH 3 group) at the terminal of polysilazane is modified with an amount of (c) metal alkoxide / chelate compound that exhibits the desired effect of promoting oxidation reaction, and the remaining (unreacted) reaction point (-SiH 3).
- the group) is preferably modified with (b) low molecular silazane / siloxane.
- the modified polysilazane of the present invention comprises: (a) a polysilazane containing a silicon atom, a hydrogen atom and a nitrogen atom is reacted with at least one of (c) a metal alkoxide compound and a metal chelate compound; And more preferably obtained by reacting with at least one of low molecular siloxanes.
- the polysilazane oxidation reaction (reforming treatment) proceeds more efficiently while suppressing / preventing reaction with moisture and oxygen in the atmosphere (undesirable reaction between application and irradiation of active energy rays). Can do.
- modifying the SiH 3 group means a modification / reaction to reduce the reactivity (especially the reactivity with water), and at least one hydrogen atom of the SiH 3 group is replaced with another compound (eg, low molecular silazane, low molecular siloxane, metal alkoxide compound) , A metal chelate compound), and also includes coordination of the above-mentioned other compound to terminal Si, but preferably, at least one hydrogen atom of SiH 3 group is replaced with another compound (for example, , Low molecular silazane, low molecular siloxane, metal alkoxide compound, metal chelate compound).
- (A) Polysilazane is a polymer containing at least a silicon atom, a hydrogen atom, and a nitrogen atom and having a silicon-nitrogen bond.
- the ceramic precursor inorganic polymer such as SiO 2 , Si 3 N 4 , and both intermediate solid solutions SiO x N y having bonds such as Si—N, Si—H, and N—H in the structure. is there.
- polysilazane used in the present invention are not particularly limited and include known ones. For example, those disclosed in paragraphs “0043” to “0058” of JP2013-022799A, paragraphs “0038” to “0056” of JP2013-226758A are appropriately adopted. Of these, perhydropolysilazane is most preferably used.
- Polysilazane is commercially available in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as the first barrier layer forming coating solution.
- Examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. Is mentioned.
- polysilazane examples include, but are not limited to, for example, a silicon alkoxide-added polysilazane obtained by reacting the polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-23827), and a glycidol reaction.
- a silicon alkoxide-added polysilazane obtained by reacting the polysilazane with a silicon alkoxide
- glycidol-added polysilazane Japanese Patent Laid-Open No. 6-122852
- alcohol-added polysilazane obtained by reacting alcohol
- metal carboxylate obtained by reacting metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal obtained by adding metal fine particles Fine particle added policy Zhang such (JP-A-7-196986), and a polysilazane ceramic at low temperatures.
- the low molecular silazane and the low molecular siloxane are not particularly limited, but preferably, the low molecular silazane is represented by the following general formula (I):
- X 1 , X 2 and X 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group.
- A is an integer from 1 to 10
- a cyclic low-molecular silazane (I) represented by the following general formula (II):
- X 4 is a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group
- X 5 to X 10 are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group
- a linear low molecular weight silazane (II) represented by the following general formula (III):
- X 11 and X 12 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group;
- X 13 X 16 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group.
- a low molecular weight siloxane represented by the following general formula (IV):
- Y 1 and Y 2 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group; An integer from 1 to 10, Cyclic low molecular siloxane (IV) represented by the following general formula (V):
- Y 3 to Y 14 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. It is cyclic low molecular siloxane (V) represented by these.
- X 1 , X 2 and X 3 are a hydrogen atom, a substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group. is there.
- X 1 , X 2 and X 3 may be the same or different.
- the substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (I) is the same as the definition in the general formula (1). Omitted.
- alkoxy group include linear or branched alkoxy groups having 1 to 8 carbon atoms.
- the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- X 1 , X 2 and X 3 are a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a halogen atom It is preferable that they are a hydrogen atom, a methyl group, and a methoxy group.
- the combination of X 1 , X 2 and X 3 is not particularly limited, but X 1 and X 2 are a methyl group and a hydrogen atom, respectively, and X 3 is a methyl group; X 1 and X 2 are a methyl group X 3 is preferably a hydrogen atom.
- a is an integer of 1 to 10, preferably 3 to 6.
- cyclic low-molecular silazane (I) represented by the general formula (I) include the following.
- X 4 is a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, an aryl group, a vinyl group, or a (trialkoxysilyl) alkyl group.
- X 5 to X 10 are a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group.
- X 4 and X 5 to X 10 may be the same or different.
- substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (II) is represented by the general formula (1) or (I). Since the definition is the same as that in FIG. Among these, X 4 is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a vinyl group, or an alkoxy group, and more preferably a hydrogen atom.
- X 5 to X 10 are preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a vinyl group or an alkoxy group, and more preferably a hydrogen atom, a methyl group or a vinyl group.
- X 4 or X 5 to X 10 is a hydrogen atom.
- chain low-molecular silazane (II) represented by the general formula (II) include the following.
- X 11 and X 12 are a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, an aryl group, a vinyl group, or a (trialkoxysilyl) alkyl group.
- X 13 to X 16 are a hydrogen atom, a substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group.
- X 11 and X 12 , and X 13 to X 16 may be the same or different.
- the substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (III) is represented by the general formula (1) or (I). Since the definition is the same as that in FIG. Of these, X 11 and X 12 represents a hydrogen atom, an alkyl group, a vinyl group having 1 to 3 carbon atoms, preferably an alkoxy group, and more preferably a hydrogen atom. X 13 to X 16 are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a vinyl group or an alkoxy group, and more preferably a methyl group or a t-butyl group.
- chain low-molecular silazane (III) represented by the general formula (III) include the following.
- Y 1 and Y 2 are a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, an aryl group, a vinyl group, or a (trialkoxysilyl) alkyl group.
- Y 1 and Y 2 may be the same or different.
- the substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (IV) is represented by the general formula (1) or (I). Since the definition is the same as that in FIG.
- one of Y 1 and Y 2 is a hydrogen atom and the other is an alkyl group having 1 to 3 carbon atoms, a vinyl group or an alkoxy group, or both Y 1 and Y 2 have 1 to 3 carbon atoms.
- one of Y 1 and Y 2 is a hydrogen atom and the other is an alkyl group having 1 to 3 carbon atoms, or both Y 1 and Y 2 are carbon. It is more preferably an alkyl group having 1 to 3 atoms, and one of Y 1 and Y 2 is a hydrogen atom and the other is particularly preferably an alkyl group having 1 to 3 carbon atoms.
- b is an integer of 1 to 10, preferably 3 to 6.
- cyclic low-molecular siloxane (IV) represented by the general formula (IV) include the following.
- Y 3 to Y 14 are a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, an aryl group, a vinyl group, or a (trialkoxysilyl) alkyl group.
- Y 3 to Y 14 may be the same or different.
- the substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (V) is represented by the general formula (1) or (I). Since the definition is the same as that in FIG.
- Y 3 to Y 14 are preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a vinyl group or an alkoxide group, and preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Is more preferable.
- cyclic low-molecular siloxane (V) represented by the general formula (V) include the following.
- Silazane (III) and cyclic low molecular siloxane (IV) of general formula (IV) are preferred
- cyclic low molecular silazane (I) of general formula (I) and chain low molecular silazane (II) of general formula (II) are preferred. More preferably, compounds 2 and 3 are particularly preferable.
- metal alkoxide compound and the metal chelate compound can efficiently form a high-performance barrier layer.
- the metal constituting the metal alkoxide compound and the metal chelate compound is not particularly limited.
- metal alkoxides and metal chelate compounds are beryllium (Be), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), calcium (Ca), scandium (Sc), titanium (Ti), Vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), Strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), Cadmium (Cd), Indium (
- metal alkoxides and metal chelate compounds containing aluminum (Al), titanium (Ti), iron (Fe), or copper (Cu) as a metal are more preferable in terms of high Lewis acidity.
- the metal alkoxide compound is not particularly limited, but aluminum alkoxide is preferable from the viewpoint that a high-performance barrier layer can be formed more efficiently.
- metal alkoxide compound examples include, for example, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-tert-butyl borate, magnesium ethoxy Magnesium ethoxy ethoxide, magnesium methoxy ethoxide, aluminum trimethoxide, aluminum triethoxide, aluminum tri n-propoxide, aluminum triisopropoxide, aluminum tri n-butoxide, aluminum tri sec-butoxide, aluminum tri tert -Butoxide, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monosec-butyrate, aluminum oxide isopropoxide trimer, al Nitric oxide octylate trimer, calcium methoxide, calcium ethoxide, calcium isopropoxide, titanium tetramethoxide, titanium tetraethoxide, titanium te
- Silsesquioxane can also be used as the metal alkoxide compound.
- Silsesquioxane is a siloxane-based compound whose main chain skeleton is composed of Si—O bonds, and is also called T-resin, whereas ordinary silica is represented by the general formula [SiO 2 ].
- Silsesquioxane (also referred to as polysilsesquioxane) is a compound represented by the general formula [RSiO 1.5 ].
- a (RSi (OR ') 3 ) compound in which one alkoxy group of tetraalkoxysilane (Si (OR') 4 ) represented by tetraethoxysilane is replaced with an alkyl group or an aryl group.
- the polysiloxane to be synthesized, and the molecular arrangement is typically amorphous, ladder-like, or cage-like (fully condensed cage-like).
- Silsesquioxane may be synthesized or commercially available. Specific examples of the latter include X-40-2308, X-40-9238, X-40-9225, X-40-9227, x-40-9246, KR-500, KR-510 (all of which are Shin-Etsu Chemical) SR2400, SR2402, SR2405, FOX14 (perhydrosilcelsesquioxane) (all manufactured by Toray Dow Corning), SST-H8H01 (perhydrosilcelsesquioxane) (manufactured by Gelest), etc. Is mentioned.
- a compound having a branched alkoxy group is preferable from the viewpoint of reactivity and solubility, and a compound having a 2-propoxy group or a sec-butoxy group is more preferable.
- More preferred metal alkoxide compounds are specifically aluminum trisec-butoxide, titanium tetraisopropoxide, or aluminum diisopropylate monosec-butyrate.
- the metal chelate compound is not particularly limited, but is preferably a metal chelate compound having a ⁇ -diketone as a ligand from the viewpoint that a high-performance barrier layer can be formed more efficiently. That is, it is particularly preferable that the metal alkoxide compound is an aluminum alkoxide, or the metal chelate compound is a metal chelate compound having a ⁇ -diketone as a ligand.
- Examples of ⁇ -diketone include acetylacetone, ethyl acetoacetate, 2,4-hexanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-decanedione, 2,4-tridecanedione, 5 , 5-dimethyl-2,4-hexanedione, 2,2-dimethyl-3,5-nonanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3-cyclopentanedione, Examples include 1,3-cyclohexanedione and 1-cyclohexyl-1,3-butanedione.
- metal chelate compounds having ⁇ -diketone as a ligand include, for example, beryllium acetylacetonate, magnesium acetylacetonate, aluminum acetylacetonate, aluminum ethylacetoacetate / diisopropylate, aluminum ethylacetate Acetate di n-butyrate, aluminum diethyl acetoacetate mono n-butyrate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum trisacetylacetonate, aluminum trisethylacetoacetate, bis (ethylacetoacetate) (2,4-pentane Diato) aluminum, aluminum alkyl acetoacetate diisopropylate, calcium acetylacetonate, scan Um acetylacetonate, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, tris (2,4-pentanedionato)
- metal chelate compounds having ⁇ -diketone as a ligand metal compounds having an acetylacetonate group or an ethylacetoacetate group are preferable. These groups are preferable because they have an interaction with the central element of the alkoxide compound due to the carbonyl structure, and thus handleability becomes easy. More preferably, a compound having a plurality of alkoxide groups, ethyl acetoacetate groups or acetylacetonate groups is more preferable from the viewpoints of reactivity and film composition.
- More preferable metal chelate compounds are, specifically, aluminum ethyl acetoacetate diisopropylate, aluminum ethyl acetoacetate di n-butyrate, or aluminum diethyl acetoacetate mono n-butyrate, aluminum bisethyl acetoacetate monoacetyl acetonate , Titanium diisopropoxybis (acetylacetonate), bis (2,4-pentandionato) copper (II) (copper acetylacetonate), tris (2,4-pentandionato) iron (III) (iron acetyl Acetonate).
- chelate compound having a metal alkoxide compound or ⁇ -diketone as a ligand a commercially available product or a synthesized product may be used.
- commercially available products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), Plenact (registered trademark) AL-M (acetoalkoxyaluminum) as metal alkoxide compounds.
- AMD aluminum diisopropylate monosec-butyrate
- ASBD aluminum secondary butyrate
- Plenact registered trademark
- AL-M acetoalkoxyaluminum
- Diisopropylate Ajinomoto Fine Chemical Co., Ltd.
- Olga Chix series Matsumoto Fine Chemical Co., Ltd.
- metal chelate compounds having ⁇ -diketone as a ligand include ALCH (aluminum ethyl acetoacetate diisopropylate), ALCH-TR (aluminum trisethyl acetoacetate), aluminum chelate M (aluminum alkyl acetoacetate). ⁇ Diisopropylate), aluminum chelate D (aluminum bisethyl acetoacetate monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) (above, manufactured by Kawaken Fine Chemical Co., Ltd.), ORGATIX series ( Matsumoto Fine Chemical Co., Ltd.).
- the reaction (addition) order of (a) raw material polysilazane, (b) low molecular silazane / siloxane, and (c) metal alkoxide / chelate compound is not particularly limited, and (a) (a) raw material Even if polysilazane, (b) low molecular weight silazane / siloxane, and (c) metal alkoxide / chelate compound are mixed together and reacted; (A) (a) raw material polysilazane and (c) metal alkoxide / chelate compound (B) low molecular silazane / siloxane added and reacted; (c) (a) raw material polysilazane and (b) low molecular silazane / siloxane reacted in advance; ) Metal alkoxide / chelate compound added to react; or (d) (b) low molecular silazane / siloxane and (
- the modified polysilazane is obtained by reacting (a) a polysilazane containing a silicon atom, a hydrogen atom and a nitrogen atom with at least one of (c) a metal alkoxide compound and a metal chelate compound, and (b) a low molecular silazane and a low molecular weight compound. It is particularly preferred that it is obtained by reacting with at least one of the siloxanes. By this reaction, gas barrier properties, particularly gas barrier properties under particularly severe conditions (high temperature and high humidity conditions) can be improved.
- (b) the low-molecular silazane / siloxane and (c) the metal alkoxide / chelate compound are modified from the terminal side of the —SiH 3 group of the starting polysilazane. Further, (c) modification with metal alkoxide / chelate compound promotes uptake of external oxygen (that is, when irradiated with active energy rays of modified polysilazane, as compared with modification with (b) low molecular silazane and low molecular siloxane. It promotes the oxidation reaction).
- the reactive site (-SiH 3 group) at the end of polysilazane is reacted in advance with an amount of (c) a metal alkoxide / chelate compound that exhibits a desired oxidation reaction promoting effect
- the modified polysilazane after modifying the terminal -SiH 3 group of the raw material polysilazane with a metal alkoxide / chelate compound, the unreacted (remaining) reaction point (-SiH 3 group) is modified with (b) low molecular silazane / siloxane. It is preferable to adjust the amount (number) of —SiH 3 groups in an appropriate range.
- the polysilazane oxidation reaction (reforming treatment) can proceed more efficiently while suppressing or preventing reaction with moisture and oxygen in the atmosphere.
- external oxygen uptake oxidation reaction in the modified polysilazane
- gas barrier properties particularly particularly severe conditions (high temperature and high humidity) are promoted. Under the condition), the gas barrier property can be improved more efficiently.
- reaction (a) the reaction between (b) the low molecular silazane / siloxane and (c) the metal alkoxide / chelate compound is performed by (a) the starting polysilazane and (b) the low molecular silazane / siloxane or (c). Compared to the reaction with a metal alkoxide / chelate compound, there is a possibility that the reaction proceeds with priority.
- the mixing ratio of (a) raw material polysilazane to (b) low molecular weight silazane / siloxane and (c) metal alkoxide / chelate compound is such that (a) terminal polysilazane terminal-SiH 3 group is (b)
- the ratio is not particularly limited as long as the ratio can be sufficiently modified with low molecular silazane / siloxane and (c) metal alkoxide / chelate compound.
- the total charge amount of at least one of (b) low molecular silazane and low molecular siloxane, and (c) at least one of metal alkoxide compound and metal chelate compound is (a) the number of silicon elements in the raw material polysilazane ( Si) is preferably more than 5 mol% and not more than 50 mol%, more preferably 6 to 30 mol%, more preferably 7 to 20 mol%, and more preferably 8 to 15 mol%. % Is particularly preferred. If it exceeds 5 mol%, a gas barrier film having better storage stability under high temperature and high humidity can be obtained. Moreover, if it is 50 mol% or less, the gas-barrier property of the barrier layer formed using a modified polysilazane can improve.
- the mixing ratio of (b) low-molecular silazane / siloxane and (c) metal alkoxide / chelate compound is not particularly limited, but (b) the mixing ratio (molar ratio) of low-molecular silazane / siloxane and (c) metal alkoxide / chelating compound ) Is preferably from 1: 0.1 to 10, more preferably from 1: 0.5 to 5. Within such a range, the gas barrier film formed using the modified polysilazane can exhibit better storage stability under high temperature and high humidity.
- the above reaction may be carried out in a solvent-free system, but is preferably carried out in a solvent.
- the solvent is not particularly limited as long as it can dissolve (a) raw material polysilazane, (b) low molecular silazane / siloxane, and (c) metal alkoxide / chelate compound, but it can easily react with polysilazane.
- Organic solvents that do not contain water and reactive groups (for example, hydroxyl groups or amine groups) and are inert to polysilazane are preferred, and aprotic organic solvents are more preferred.
- the solvent is an aprotic solvent; for example, pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, solvesso, terpene, aliphatic hydrocarbons, alicyclic carbonization, etc.
- Hydrocarbon solvents such as hydrogen and aromatic hydrocarbons; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Dibutyl ether, dioxane, tetrahydrofuran, mono- And aliphatic ethers such as polyalkylene glycol dialkyl ethers (diglymes) and ethers such as alicyclic ethers.
- the said solvent may be used independently or may be used with the form of a 2 or more types of mixture. Moreover, it is preferable to reduce the oxygen concentration and water content of the solvent before use.
- Means for reducing the oxygen concentration and water content in the solvent are not particularly limited, and conventionally known methods can be applied.
- the concentration of the raw material polysilazane in the reaction solution is not particularly limited.
- the modified polysilazane solution after reaction is used as it is for the production of a gas barrier film, it varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 1 to 80% by mass, more preferably 2 to 2%. It is 50% by mass, particularly preferably 10 to 40% by mass.
- the reaction conditions are not particularly limited as long as (a) the terminal-SiH 3 group of the starting polysilazane can be sufficiently modified with (b) low molecular silazane / siloxane and (c) metal alkoxide / chelate compound.
- the reaction temperature preferably 30 ° C. to 100 ° C., more preferably 40 to 90 ° C., and even more preferably 50 to 80 ° C.
- the reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 4 hours, and even more preferably 1 to 2 hours.
- the above reaction may be performed in any atmosphere, but as described above, in consideration of reactivity with water, the reaction is preferably performed in an inert environment and substantially does not contain oxygen or moisture. More preferably, it is performed under an atmosphere.
- the oxygen concentration in the reaction system is not particularly limited, but is preferably 0 to 200 ppm by volume, more preferably 0 to 100 ppm, and even more preferably 0 to 30 ppm by volume.
- the water concentration (water vapor concentration) in the reaction system is not particularly limited, but is preferably 0 to 200 ppm by volume, more preferably 0 to 100 ppm, and even more preferably 0 to 30 ppm by volume.
- the modified polysilazane of the present invention produced as described above has a small number of terminal SiH 3 groups that easily react with moisture in the atmosphere. For this reason, it is possible to preferentially advance the oxidation reaction by irradiation with active energy rays. Therefore, the modified polysilazane of the present invention is particularly useful for the production of a barrier layer excellent in gas barrier properties, particularly gas barrier properties under severe conditions (especially high temperature and high humidity), and therefore a gas barrier film.
- the present invention also provides a gas barrier film comprising a coating solution containing the modified polysilazane of the present invention, a substrate, and a barrier layer formed using the coating solution.
- the gas barrier film of the present invention includes a base material and a barrier layer formed of a coating solution containing the modified polysilazane of the present invention, but has a gas barrier property, particularly a gas barrier under severe conditions (especially high temperature and high humidity).
- a gas barrier property particularly a gas barrier under severe conditions (especially high temperature and high humidity).
- the gas barrier film comprises a substrate, an inorganic compound layer containing an inorganic compound (also referred to herein as “first barrier layer”), and the modified polysilazane of the present invention.
- a barrier layer also referred to as a “second barrier layer” in this specification
- the gas barrier film of the present invention preferably has a substrate, a first barrier layer, and a second barrier layer in this order.
- the gas barrier film may further include other members.
- the gas barrier film of the present invention is, for example, between the base material and the first barrier layer, between the first barrier layer and the second barrier layer, on the second barrier layer, or on the first barrier. You may have another member in the other surface of the base material in which the layer and the 2nd barrier layer are not formed.
- the other members are not particularly limited, and members used for conventional gas barrier films can be used similarly or appropriately modified. Specific examples include an intermediate layer, a protective layer, a smooth layer, an anchor coat layer, a bleed-out prevention layer, a desiccant layer having moisture adsorbability, and a functionalized layer of an antistatic layer.
- the gas barrier property having the first barrier layer and the second barrier layer may be formed on one surface of the substrate, or may be formed on both surfaces of the substrate.
- the gas barrier unit may include a layer that does not necessarily have a gas barrier property.
- a plastic film or a plastic sheet is preferably used as a substrate, and a film or sheet made of a colorless and transparent resin is more preferably used.
- the plastic film used is not particularly limited as long as it is a film that can hold the second barrier layer and, if necessary, the first barrier layer, etc., and can be appropriately selected according to the purpose of use. it can.
- plastic film examples include polyester resins such as polyethylene terephthalate (PET), methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, Polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene
- thermoplastic resins such as a ring-modified polycarbonate resin, an alicyclic modified polycarbonate resin, a fluorene ring-modified polyester resin, and an acryloyl compound.
- the substrates disclosed in paragraphs “0056” to “0075” of JP2012-116101A, paragraphs “0125” to “0131” of JP2013-226758A, etc. are also appropriately employed. Is done.
- the thickness of the base material used for the gas barrier film according to the present invention is not particularly limited because it is appropriately selected depending on the application, but is typically 1 to 800 ⁇ m, preferably 10 to 200 ⁇ m.
- These plastic films may have functional layers such as a transparent conductive layer, a primer layer, and a clear hard coat layer.
- As the functional layer in addition to those described above, those described in paragraph numbers “0036” to “0038” of JP-A-2006-289627 can be preferably used.
- the substrate preferably has a high surface smoothness.
- the surface smoothness those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the barrier layer is provided, may be polished to improve smoothness.
- various known treatments for improving adhesion such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, and smoothing described later. Layer stacking or the like may be performed, and it is preferable to combine the above treatments as necessary.
- the inorganic compound layer (first barrier layer) formed on the upper part of the substrate contains an inorganic compound.
- the inorganic compound is not particularly limited, and examples thereof include metal oxides, metal nitrides, metal carbides, metal oxynitrides, and metal oxycarbides.
- oxides, nitrides, carbides, oxynitrides or oxycarbides containing one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta in terms of gas barrier performance are preferably used, and an oxide, nitride or oxynitride of a metal selected from Si, Al, In, Sn, Zn and Ti is more preferable, and in particular, an oxide of at least one of Si and Al, Nitride or oxynitride is preferred.
- suitable inorganic compounds include composites such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, aluminum oxide, titanium oxide, or aluminum silicate. You may contain another element as a secondary component.
- the content of the inorganic compound contained in the first barrier layer is not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, and 95% by mass in the first barrier layer. More preferably, it is more preferably 98% by mass or more, and most preferably 100% by mass (that is, the first barrier layer is made of an inorganic compound).
- the first barrier layer contains an inorganic compound and thus has a gas barrier property.
- the gas barrier property of the first barrier layer is calculated using a laminate in which the first barrier layer is formed on the substrate, the water vapor transmission rate (WVTR) is 0.1 g / (m 2 ⁇ day). Or less, more preferably 0.01 g / (m 2 ⁇ day) or less.
- the method for forming the first barrier layer is not particularly limited, but a vacuum film-forming method such as physical vapor deposition (PVD method) or chemical vapor deposition (CVD), or a liquid containing an inorganic compound, preferably A method of modifying and forming a coating film formed by applying a liquid containing a silicon compound (hereinafter also simply referred to as a coating method) is preferred, and a physical vapor deposition method or a chemical vapor deposition method is more preferred. .
- PVD method physical vapor deposition
- CVD chemical vapor deposition
- the physical vapor deposition method is a method of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method.
- a target material for example, a thin film such as a carbon film
- Examples thereof include a DC sputtering method, an RF sputtering method, an ion beam sputtering method, and a magnetron sputtering method, a vacuum deposition method, and an ion plating method.
- Sputtering is a method in which a target is placed in a vacuum chamber, a rare gas element (usually argon) ionized by applying a high voltage is collided with the target, and atoms on the target surface are ejected and adhered to the substrate.
- a reactive sputtering method may be used in which an inorganic layer is formed by causing nitrogen and oxygen gas to flow into the chamber to react nitrogen and oxygen with an element ejected from the target by argon gas. .
- the chemical vapor deposition method (Chemical Vapor Deposition, CVD method) is a method of depositing a film by supplying a source gas containing a target thin film component onto a substrate and performing a chemical reaction on the surface of the substrate or in the gas phase. It is. In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like.
- Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The method etc. are mentioned. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of film forming speed and processing area.
- the first barrier layer preferably contains carbon, silicon, and oxygen as constituent elements.
- a more preferable form is a layer that satisfies the following requirements (i) to (iii).
- the following requirements (i) to (iii) are also referred to as “requirement (i)”, “requirement (ii)”, and “requirement (iii)”, respectively.
- the first barrier layer is based on (i) the distance (L) from the surface of the first barrier layer in the film thickness direction of the first barrier layer and the total amount of silicon atoms, oxygen atoms, and carbon atoms.
- Silicon distribution curve showing the relationship with the ratio of the amount of silicon atoms (silicon atomic ratio), the ratio of the amount of oxygen atoms to the total amount of L and silicon atoms, oxygen atoms, and carbon atoms (oxygen atomic ratio)
- the carbon distribution curve showing the relationship between the L and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon).
- the film thickness of the barrier layer In the region of 90% or more (upper limit: 100%) of the film thickness of the barrier layer, (oxygen atomic ratio), (silicon atomic ratio), (carbon atomic ratio) increase in this order (atomic ratio is O> Si> C) is preferred.
- the gas barrier property and flexibility of the obtained gas barrier film can be improved.
- the relationship among the above (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) is at least 90% or more (upper limit) of the film thickness of the first barrier layer. : 100%), and more preferably at least 93% or more (upper limit: 100%).
- at least 90% or more of the film thickness of the first barrier layer does not have to be continuous in the first barrier layer, and simply satisfies the above-described relationship at 90% or more. Good.
- the first barrier layer preferably has (ii) the carbon distribution curve has at least two extreme values.
- the first barrier layer preferably has at least three extreme values in the carbon distribution curve, and more preferably has at least four extreme values, but may have five or more extreme values.
- the extreme value of the carbon distribution curve is two or more, the gas barrier property when the obtained gas barrier film is bent can be improved.
- the upper limit of the extreme value of the carbon distribution curve is not particularly limited. For example, it is preferably 30 or less, more preferably 25 or less, but the number of extreme values is also caused by the film thickness of the first barrier layer. Therefore, it cannot be specified in general.
- the first barrier in the film thickness direction of the first barrier layer at one extreme value of the carbon distribution curve and an extreme value adjacent to the extreme value is preferably 200 nm or less, more preferably 100 nm or less, and 75 nm. It is particularly preferred that With such a distance between extreme values, a portion having a high carbon atom ratio (maximum value) exists in the first barrier layer at an appropriate period, so that appropriate flexibility is imparted to the first barrier layer. In addition, the generation of cracks when the gas barrier film is bent can be more effectively suppressed / prevented.
- extreme value means a maximum value or a minimum value of an atomic ratio of an element to a distance (L) from the surface of the first barrier layer in the film thickness direction of the first barrier layer. That means.
- maximum value means that the atomic ratio value of an element (oxygen, silicon, or carbon) changes from increasing to decreasing when the distance from the surface of the first barrier layer is changed.
- the distance from the surface of the first barrier layer in the film thickness direction of the first barrier layer from the point is further changed within the range of 4 to 20 nm, rather than the atomic ratio value of the element at that point. This is the point where the atomic ratio value of the element at the position decreases by 3 at% or more.
- the atomic ratio value of the element is reduced by 3 at% or more in any range when changing in the range of 4 to 20 nm.
- the “minimum value” means that the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from a decrease to an increase when the distance from the surface of the first barrier layer is changed. The distance from the surface of the first barrier layer in the film thickness direction of the first barrier layer from the point is further changed within the range of 4 to 20 nm, rather than the value of the atomic ratio of the element at that point. This is the point at which the value of the atomic ratio of the element at the position increases by 3 at% or more.
- the atomic ratio value of the element when changing in the range of 4 to 20 nm, the atomic ratio value of the element only needs to increase by 3 at% or more in any range.
- the lower limit of the distance between the extreme values in the case of having at least three extreme values is particularly high because the smaller the distance between the extreme values, the higher the effect of suppressing / preventing crack generation when the gas barrier film is bent.
- the thickness is preferably 10 nm or more, and more preferably 30 nm or more.
- the first barrier layer has (iii) an absolute value of a difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve (hereinafter, also simply referred to as “C max ⁇ C min difference”) of 3 at. % Or more is preferable.
- C max ⁇ C min difference an absolute value of a difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve
- the C max ⁇ C min difference is more preferably 5 at% or more, further preferably 7 at% or more, and particularly preferably 10 at% or more.
- the “maximum value” is the atomic ratio of each element that is maximum in the distribution curve of each element, and is the highest value among the maximum values.
- the “minimum value” is the atomic ratio of each element that is the minimum in the distribution curve of each element, and is the lowest value among the minimum values.
- the upper limit of the C max -C min difference is not particularly limited, but it is preferably 50 at% or less in consideration of the effect of suppressing / preventing crack generation during bending of the gas barrier film, and is preferably 40 at% or less. It is more preferable that
- the oxygen distribution curve of the first barrier layer preferably has at least one extreme value, more preferably has at least two extreme values, and further preferably has at least three extreme values.
- the oxygen distribution curve has at least one extreme value
- the gas barrier property when the obtained gas barrier film is bent is further improved as compared with a gas barrier film having no extreme value.
- the upper limit of the extreme value of the oxygen distribution curve is not particularly limited, but is preferably 20 or less, more preferably 10 or less, for example. Even in the number of extreme values of the oxygen distribution curve, there is a portion caused by the film thickness of the first barrier layer, and it cannot be defined unconditionally.
- one extreme value of the oxygen distribution curve and the first barrier layer in the thickness direction of the first barrier layer at the extreme value adjacent to the extreme value is preferably 200 nm or less, and more preferably 100 nm or less. With such a distance between extreme values, the occurrence of cracks during bending of the gas barrier film can be more effectively suppressed / prevented.
- the lower limit of the distance between the extreme values in the case of having at least three extreme values is not particularly limited, but considering the improvement effect of crack generation suppression / prevention when the gas barrier film is bent, the thermal expansion property, etc.
- the thickness is preferably 10 nm or more, and more preferably 30 nm or more.
- the silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination.
- XPS X-ray photoelectron spectroscopy
- rare gas ion sputtering such as argon in combination.
- XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample.
- a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).
- the etching time is the distance (L from the surface of the first barrier layer in the film thickness direction of the first barrier layer in the film thickness direction). ) From the relationship between the etching rate and the etching time employed in the XPS depth profile measurement as “the distance from the surface of the first barrier layer in the film thickness direction of the first barrier layer”. The calculated distance from the surface of the first barrier layer can be employed.
- the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve can be prepared under the following measurement conditions.
- Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): 10 nm
- X-ray photoelectron spectrometer Model name "VG Theta Probe", manufactured by Thermo Fisher Scientific Irradiation X-ray: Single crystal spectroscopy AlK ⁇ X-ray spot and its size: 800 ⁇ 400 ⁇ m oval.
- the film thickness (dry film thickness) of the first barrier layer formed by the plasma CVD method is not particularly limited.
- the film thickness per layer of the first barrier layer is preferably 20 to 3000 nm, more preferably 50 to 2500 nm, and particularly preferably 100 to 1000 nm.
- the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending.
- each first barrier layer has the film thickness as described above.
- the first barrier layer is in the film surface direction (parallel to the surface of the first barrier layer).
- Direction is preferably substantially uniform.
- the fact that the first barrier layer is substantially uniform in the film surface direction means that the oxygen distribution curve and the carbon are measured at any two measurement points on the film surface of the first barrier layer by XPS depth profile measurement.
- the distribution curve and the oxygen carbon distribution curve are created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the atomic ratio of carbon in each carbon distribution curve The absolute value of the difference between the maximum value and the minimum value is the same or within 5 at%.
- the carbon distribution curve is substantially continuous.
- the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously.
- the carbon distribution curve is calculated from the etching rate and the etching time. The distance (x, unit: nm) from the surface of the first barrier layer in the film thickness direction of at least one layer of the first barrier layer and the atomic ratio of carbon (C, unit: at%) ), The condition expressed by the following formula 1 is satisfied.
- the first barrier layer that satisfies all of the above conditions (i) to (iii) may include only one layer, or may include two or more layers. Further, when two or more such first barrier layers are provided, the materials of the plurality of first barrier layers may be the same or different.
- the method for forming the first barrier layer is not particularly limited, and the conventional method and the method can be applied in the same manner or appropriately modified.
- the first barrier layer is preferably a chemical vapor deposition (CVD) method, particularly a plasma chemical vapor deposition method (plasma CVD, PECVD (plasma-enhanced chemical vapor deposition), hereinafter simply referred to as “plasma CVD method”).
- CVD chemical vapor deposition
- PECVD plasma-enhanced chemical vapor deposition
- the plasma CVD method may be a Penning discharge plasma type plasma CVD method.
- plasma discharge in a space between a plurality of film forming rollers it is preferable to generate plasma discharge in a space between a plurality of film forming rollers.
- a pair of film forming rollers is used, and each of the pair of film forming rollers is used. More preferably, a substrate is placed and discharged between a pair of film forming rollers to generate plasma.
- the film formation rate can be doubled compared to the plasma CVD method without using any roller, and since it is possible to form a film having a structure that is substantially the same, it is possible to at least double the extreme value in the carbon distribution curve, It is possible to efficiently form a layer that satisfies all of the above conditions (i) to (iii).
- the film forming gas used in such a plasma CVD method preferably contains an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation.
- the first barrier layer is preferably a layer formed by a continuous film formation process.
- the gas barrier film according to the present invention preferably has the first barrier layer formed on the surface of the substrate by a roll-to-roll method from the viewpoint of productivity.
- an apparatus that can be used when the first barrier layer is manufactured by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source. It is preferable that the apparatus has a configuration capable of discharging between the film forming rollers. For example, in the case where the manufacturing apparatus shown in FIG. 2 is used, a roll-to-roll method using a plasma CVD method is used. Can also be manufactured.
- FIG. 2 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing the first barrier layer by this manufacturing method.
- the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.
- the manufacturing apparatus 31 shown in FIG. 2 includes a delivery roller 32, transport rollers 33, 34, 35, and 36, film formation rollers 39 and 40, a gas supply pipe 41, a plasma generation power source 42, and a film formation roller 39. And magnetic field generators 43 and 44 installed inside 40 and a winding roller 45.
- a vacuum chamber (not shown).
- the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.
- each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes. 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge into the space between the film forming roller 39 and the film forming roller 40 by supplying electric power from the plasma generating power source 42. Plasma can be generated in the space between the film roller 39 and the film formation roller 40. In this way, when the film forming roller 39 and the film forming roller 40 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes.
- the first barrier layer 3 can be formed on the surface of the substrate 2 by the CVD method, and the first barrier layer 3 is formed on the surface of the substrate 2 on the film formation roller 39. While the first barrier layer component is deposited, the first barrier layer component can be deposited on the surface of the substrate 2 also on the film forming roller 40, so that the first barrier is formed on the surface of the substrate 2. A layer can be formed efficiently.
- magnetic field generators 43 and 44 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.
- the magnetic field generators 43 and 44 provided on the film forming roller 39 and the film forming roller 40 are respectively a magnetic field generating device 43 provided on one film forming roller 39 and a magnetic field generating device provided on the other film forming roller 40. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between them and the magnetic field generators 43 and 44 form a substantially closed magnetic circuit. By providing such magnetic field generators 43 and 44, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell in the vicinity of the opposing surface of each film forming roller 39 and 40, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.
- the magnetic field generators 43 and 44 provided in the film forming roller 39 and the film forming roller 40 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 43 and the other magnetic field generator. It is preferable to arrange the magnetic poles so that the magnetic poles facing to 44 have the same polarity.
- By providing such magnetic field generators 43 and 44 the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force of each of the magnetic field generators 43 and 44 are opposed.
- a racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained.
- the material 2 is excellent in that the first barrier layer 3 that is a vapor deposition film can be efficiently formed.
- the film formation roller 39 and the film formation roller 40 known rollers can be used as appropriate. As such film forming rollers 39 and 40, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, the diameter of the film forming rollers 39 and 40 is preferably in the range of 300 to 1000 mm ⁇ , particularly in the range of 300 to 700 mm ⁇ , from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mm ⁇ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated and it is possible to avoid applying the total amount of heat of the plasma discharge to the substrate 2 in a short time. It is preferable because damage to the material 2 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mm ⁇ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.
- the base material 2 is disposed on a pair of film forming rollers (the film forming roller 39 and the film forming roller 40) so that the surfaces of the base material 2 face each other.
- the base material 2 By disposing the base material 2 in this manner, when the plasma is generated by performing discharge in the facing space between the film formation roller 39 and the film formation roller 40, the base existing between the pair of film formation rollers is present.
- Each surface of the material 2 can be formed simultaneously. That is, according to such a manufacturing apparatus, the first barrier layer component is deposited on the surface of the base material 2 on the film forming roller 39 by the plasma CVD method, and the first film forming roller 40 further performs the first operation. Therefore, it is possible to efficiently form the first barrier layer on the surface of the substrate 2.
- the winding roller 45 is not particularly limited as long as it can wind the gas barrier film 1 in which the first barrier layer 3 is formed on the substrate 2, and a known roller is appropriately used. Can be used.
- gas supply pipe 41 and the vacuum pump those capable of supplying or discharging the raw material gas at a predetermined speed can be appropriately used.
- the gas supply pipe 41 as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 39 and the film formation roller 40, and is a vacuum as a vacuum exhaust means.
- a pump (not shown) is preferably provided on the other side of the facing space.
- the plasma generating power source 42 a known power source of a plasma generating apparatus can be used as appropriate.
- a plasma generating power supply 42 supplies power to the film forming roller 39 and the film forming roller 40 connected thereto, and makes it possible to use these as counter electrodes for discharge.
- Such a plasma generating power source 42 can perform plasma CVD more efficiently, and can alternately reverse the polarity of the pair of film forming rollers (AC power source or the like). Is preferably used.
- the plasma generating power source 42 can perform plasma CVD more efficiently, the applied power can be set to 100 W to 10 kW, and the AC frequency can be set to 50 Hz to 500 kHz. More preferably, it is possible to do this.
- the magnetic field generators 43 and 44 known magnetic field generators can be used as appropriate.
- the base material 2 in addition to the base material used in the present invention, a material in which the first barrier layer 3 is previously formed can be used. As described above, by using the substrate 2 in which the first barrier layer 3 is formed in advance, the thickness of the first barrier layer 3 can be increased.
- the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the transport of the film (base material) By appropriately adjusting the speed, the first barrier layer according to the present invention can be produced. That is, using the manufacturing apparatus 31 shown in FIG. 2, a discharge is generated between the pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber.
- the film-forming gas (raw material gas or the like) is decomposed by plasma, and the first barrier layer 3 is formed on the surface of the base material 2 on the film-forming roller 39 and on the surface of the base material 2 on the film-forming roller 40.
- a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axes of the film forming rollers 39 and 40, and the plasma is converged on the magnetic field.
- the base material 2 passes the point A of the film forming roller 39 and the point B of the film forming roller 40 in FIG. 2, the maximum value of the carbon distribution curve is formed in the first barrier layer.
- the base material 2 passes the points C1 and C2 of the film forming roller 39 and the points C3 and C4 of the film forming roller 40 in FIG. A local minimum is formed. For this reason, five extreme values are usually generated for two film forming rollers. Further, the distance between the extreme values of the first barrier layer (the surface of the first barrier layer in the thickness direction of the first barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value) (The absolute value of the difference in distance (L) from) can be adjusted by the rotation speed of the film forming rollers 39 and 40 (the conveyance speed of the substrate). In such film formation, the substrate 2 is conveyed by the delivery roller 32, the film formation roller 39, and the like, respectively, so that the surface of the substrate 2 is formed by a roll-to-roll continuous film formation process. First barrier layer 3 is formed.
- a raw material gas, a reactive gas, a carrier gas, or a discharge gas can be used alone or in combination of two or more.
- the source gas in the film forming gas used for forming the first barrier layer 3 can be appropriately selected and used according to the material of the first barrier layer 3 to be formed.
- a source gas for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used.
- organosilicon compounds examples include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane.
- HMDSO hexamethyldisiloxane
- HMDS hexamethyldisilane
- 1,1,3,3-tetramethyldisiloxane vinyltrimethylsilane
- methyltrimethylsilane hexamethyldisilane.
- Methylsilane dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy
- TMOS tetramethoxysilane
- TEOS tetraethoxysilane
- phenyltrimethoxysilane methyltriethoxy
- Examples include silane and octamethylcyclotetrasiloxane.
- hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of the handling properties of the compound and the gas barrier properties of the obtained first barrier layer.
- organosilicon compounds can be used alone or in combination of two or more.
- organic compound gas containing carbon examples include methane, ethane, ethylene, and acetylene.
- an appropriate source gas is selected according to the type of the first barrier layer 3.
- a reactive gas may be used in addition to the raw material gas.
- a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used.
- a reaction gas for forming an oxide for example, oxygen or ozone can be used.
- a reactive gas for forming nitride nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.
- a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber.
- a discharge gas may be used as necessary in order to generate plasma discharge.
- carrier gas and discharge gas known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon; hydrogen can be used.
- the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary to completely react the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. It is excellent in that excellent barrier properties and flex resistance can be obtained by forming the first barrier layer 3 by not excessively increasing the ratio of the reaction gas. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.
- the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 Pa to 50 Pa.
- an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used.
- the power applied to the power source can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, and the like. It is preferable to be in the range. If such an applied power is 100 W or more, the generation of particles can be sufficiently suppressed. On the other hand, if the applied power is 10 kW or less, the amount of heat generated at the time of film formation can be suppressed. An increase in surface temperature can be suppressed. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.
- the conveyance speed (line speed) of the base material 2 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is in the range of 5 to 20 m / min. If the line speed is 0.25 m / min or more, generation of wrinkles due to heat in the substrate can be effectively suppressed. On the other hand, if it is 100 m / min or less, it is excellent at the point which can ensure sufficient film thickness as a 1st barrier layer, without impairing productivity.
- a plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. 2 as the first barrier layer according to the present invention.
- the film is formed by the above. This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode. This is because it is possible to efficiently manufacture the first barrier layer in which the barrier performance is compatible.
- Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.
- the first barrier layer according to the present invention is a method (coating method) formed by modifying a coating film formed by applying a liquid containing an inorganic compound, preferably a liquid containing a silicon compound, for example. It may be formed.
- a liquid containing an inorganic compound preferably a liquid containing a silicon compound, for example. It may be formed.
- the silicon compound will be described as an example of the inorganic compound, but the inorganic compound is not limited to the silicon compound.
- the silicon compound is not particularly limited as long as a coating solution containing a silicon compound can be prepared.
- perhydropolysilazane organopolysilazane, silsesquioxane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, Tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, dimethyldivinylsilane, dimethyl Ethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-
- polysilazane such as perhydropolysilazane and organopolysilazane; polysiloxane such as silsesquioxane, etc. are preferable in terms of film formation, fewer defects such as cracks, and less residual organic matter, and high gas barrier performance.
- Polysilazane is more preferable, and perhydropolysilazane is particularly preferable because the barrier performance is maintained even when bent and under high temperature and high humidity conditions.
- the polysilazane is the same as that described in the modified polysilazane, and the description thereof is omitted here.
- the content of polysilazane in the first barrier layer before the modification treatment may be 100% by mass when the total mass of the first barrier layer is 100% by mass.
- the content of polysilazane in the layer is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass or less. More preferably, it is 70 mass% or more and 95 mass% or less.
- the method for forming the first barrier layer by the application method as described above is not particularly limited, and a known method can be applied. However, the first barrier layer formation containing a silicon compound and, if necessary, a catalyst in an organic solvent is possible. It is preferable to apply the coating liquid for coating by a known wet coating method, evaporate and remove the solvent, and then perform a modification treatment.
- the solvent for preparing the first barrier layer forming coating solution is not particularly limited as long as it can dissolve the silicon compound, but water and reactive groups (for example, hydroxyl group) that easily react with the silicon compound.
- the solvent is an aprotic solvent; for example, pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, solvesso, terpene, aliphatic hydrocarbons, alicyclic carbonization, etc.
- Hydrocarbon solvents such as hydrogen and aromatic hydrocarbons; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Dibutyl ether, dioxane, tetrahydrofuran, mono- And aliphatic ethers such as polyalkylene glycol dialkyl ethers (diglymes) and ethers such as alicyclic ethers.
- the solvent is selected according to purposes such as the solubility of the silicon compound and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.
- the concentration of the silicon compound in the first barrier layer-forming coating solution is not particularly limited and varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 1 to 80% by mass, more preferably 5 to 50. % By mass, particularly preferably 10 to 40% by mass.
- the first barrier layer forming coating solution preferably contains a catalyst in order to promote reforming.
- a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, Amine catalysts such as N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds.
- the concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on the silicon compound. By setting the amount of the catalyst to be in this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.
- a sol-gel method can be used for forming the first barrier layer.
- the coating solution used when forming the modified layer by the sol-gel method preferably contains a silicon compound and at least one of a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer.
- Method for applying first barrier layer forming coating solution As a method for applying the first barrier layer forming coating solution, a conventionally known appropriate wet coating method may be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
- the coating thickness can be appropriately set according to the purpose.
- the coating thickness per first barrier layer is preferably about 10 nm to 10 ⁇ m after drying, more preferably 15 nm to 1 ⁇ m, and further preferably 20 to 500 nm. preferable. If the film thickness is 10 nm or more, sufficient barrier properties can be obtained, and if it is 10 ⁇ m or less, stable coating properties can be obtained during layer formation, and high light transmittance can be realized.
- a solvent such as an organic solvent contained in the coating film can be removed. At this time, all of the solvent contained in the coating film may be dried or may be partially left. Even when a part of the solvent is left, a suitable first barrier layer can be obtained. The remaining solvent can be removed later.
- the drying temperature of the coating film varies depending on the substrate to be applied, but is preferably 50 to 200 ° C.
- the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat.
- the temperature can be set by using a hot plate, oven, furnace or the like.
- the drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes.
- the drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.
- the modification treatment of the first barrier layer formed by the coating method in the present invention refers to a conversion reaction of a silicon compound to silicon oxide, silicon oxynitride, or the like.
- the gas barrier film as a whole has gas barrier properties. This refers to a process for forming an inorganic thin film at a level that can contribute to the expression of (water vapor permeability of 1 ⁇ 10 ⁇ 3 g / m 2 ⁇ day or less).
- the conversion reaction of the silicon compound to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method.
- Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment.
- the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment).
- the treatment by the vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds atoms with only photons called photon processes.
- This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action.
- the radiation source in the present invention may be any radiation source that emits light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator having a maximum emission at about 172 nm (eg, Xe excimer lamp), and has an emission line at about 185 nm.
- Excimer radiator having a maximum emission at about 172 nm (eg, Xe excimer lamp)
- the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.
- the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.
- ⁇ Excimer lamps have high light generation efficiency and can be lit with low power.
- light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed.
- it is suitable for flexible film materials such as PET that are easily affected by heat.
- Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of irradiation with vacuum ultraviolet rays is preferably 10 to 20,000 volume ppm, more preferably 50 to 10,000 volume ppm. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.
- the gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays is preferably a dry inert gas, and particularly preferably dry nitrogen gas from the viewpoint of cost.
- the oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.
- the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane coating is preferably 1 mW / cm 2 to 10 W / cm 2 , more preferably 30 mW / cm 2 to 200 mW / cm 2. preferably, further preferably at 50mW / cm 2 ⁇ 160mW / cm 2. If it is 1 mW / cm 2 or more, sufficient reforming efficiency is obtained, and if it is 10 W / cm 2 or less, it is difficult to cause ablation in the coating film and damage the substrate.
- Irradiation energy amount of the VUV in the coated surface it preferably from 10 ⁇ 10000mJ / cm 2, more preferably 100 ⁇ 8000mJ / cm 2, a 200 ⁇ 6000mJ / cm 2 Is more preferable. If it is 10 mJ / cm 2 or more, the modification can proceed sufficiently. If it is 10,000 mJ / cm 2 or less, cracking due to over-reformation and thermal deformation of the substrate are unlikely to occur.
- the vacuum ultraviolet light used for reforming may be generated by plasma formed in a gas containing at least one of CO 2 and CH 4.
- the gas containing at least one of CO, CO 2 and CH 4 hereinafter also referred to as carbon-containing gas
- the carbon-containing gas may be used alone, but carbon containing rare gas or H 2 as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.
- the gas barrier film obtained by the method of the present invention has a barrier layer (second barrier layer) formed using the modified polysilazane of the present invention, and preferably the modified polysilazane of the present invention on the first barrier layer.
- a barrier layer (second barrier layer) formed using hereinafter although the preferable form of this invention in which the barrier layer (2nd barrier layer) formed using the modified polysilazane of this invention is provided on the first barrier layer is described, the present invention is limited to the following form. It is not something.
- the first barrier layer may be omitted, and even in this case, the following form can be appropriately modified and applied.
- the composition of the second barrier layer provided on the first barrier layer is not particularly limited, but it contains at least silicon atoms and oxygen atoms, and the abundance ratio of oxygen atoms to silicon atoms (O / Si) is 1.
- the abundance ratio of nitrogen to silicon atoms (N / Si) is more preferably 0 to 0.4.
- the abundance ratio of oxygen atoms to silicon atoms (O / Si) is 1.4 to 2.2” means that the depth of the second barrier layer measured by the apparatus and method described later. This also means that there is no portion where O / Si shows a value less than 1.4 or more than 2.2.
- the abundance ratio of nitrogen atoms to silicon atoms (N / Si) is 0 to 0.4” means any depth of the second barrier layer measured by the apparatus and method described later. , N / Si means that there is no portion showing a value exceeding 0.4.
- the second barrier layer reacts with moisture under high temperature and high humidity, and the barrier property is greatly reduced. Highly effective in preventing On the other hand, if the ratio is 2.2 or less, the ratio of silanol groups (Si—OH) present in the molecule decreases, and thus higher barrier properties can be obtained.
- the O / Si is more preferably 1.5 to 2.1, and still more preferably 1.7 to 2.0.
- the second barrier layer reacts with moisture under high temperature and high humidity, and the barrier property decreases.
- the effect to prevent is high.
- the N / Si is more preferably 0 to 0.3, and further preferably 0 to 0.2.
- the O / Si and the N / Si can be measured by the following method. That is, the composition profile of the second barrier layer can be obtained by combining an Ar sputter etching apparatus and X-ray photoelectron spectroscopy (XPS).
- XPS X-ray photoelectron spectroscopy
- the profile distribution in the depth direction can be calculated by film processing by a FIB (focused ion beam) processing apparatus and by obtaining the actual film thickness by TEM (transmission electron microscope) and making it correspond to the XPS result.
- FIB focused ion beam
- the difference from the average value of the abundance ratio is preferably 0.4 or less.
- the average value of the abundance ratio of oxygen atoms to silicon atoms in the region from the outermost surface to a depth of 10 nm, and the average value of the abundance ratio of oxygen atoms to silicon atoms in a region where the depth from the outermost surface exceeds 10 nm are: It can be calculated by a method combining the Ar sputter etching apparatus described above and X-ray photoelectron spectroscopy (XPS).
- the second barrier layer may be formed by any method as long as it is formed using the coating solution of the modified polysilazane of the present invention, and a known method can be applied in the same manner or appropriately modified.
- the method for forming the second barrier layer is not particularly limited, but a second barrier layer forming coating solution containing a modified polysilazane, preferably a modified polysilazane, and, if necessary, a catalyst or an additive compound in an organic solvent. Is preferably applied by a known wet coating method, the solvent is evaporated and removed, and then a modification treatment is performed by irradiation with active energy rays.
- the second barrier layer is obtained by applying (i) a coating solution containing the modified polysilazane of the present invention (second coating solution for forming a barrier layer) on the inorganic compound layer (first barrier layer) and drying. It is preferable that the precursor layer be formed by further modifying (ii) the precursor layer by irradiation with active energy rays.
- a precursor layer (coating film) is formed by applying and drying a coating solution (second barrier layer forming coating solution) on the inorganic compound layer.
- the coating solution (second barrier layer forming coating solution) is prepared by dissolving modified polysilazane in a solvent.
- the solvent constituting the coating solution of the modified polysilazane is not particularly limited as long as it can dissolve the modified polysilazane, but water and a reactive group (for example, a hydroxyl group, or easily reacting with the modified polysilazane).
- An organic solvent that does not contain an amine group and is inert to polysilazane is preferable, and an aprotic organic solvent is more preferable.
- the solvent is an aprotic solvent; for example, pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, solvesso, terpene, aliphatic hydrocarbons, alicyclic carbonization, etc.
- Hydrocarbon solvents such as hydrogen and aromatic hydrocarbons; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Dibutyl ether, dioxane, tetrahydrofuran, mono- And aliphatic ethers such as polyalkylene glycol dialkyl ethers (diglymes) and ethers such as alicyclic ethers.
- the said solvent may be used independently or may be used with the form of a 2 or more types of mixture. Moreover, it is preferable to reduce the oxygen concentration and water content of the solvent before use.
- Means for reducing the oxygen concentration and water content in the solvent are not particularly limited, and conventionally known methods can be applied.
- the concentration of the modified polysilazane in the coating solution of the modified polysilazane is not particularly limited and varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 1 to 80% by mass, more preferably 2 to 50% by mass. Particularly preferred is 10 to 40% by mass.
- the modified polysilazane coating solution of the present invention may contain polysilazane as described above in addition to the modified polysilazane, but preferably contains only modified polysilazane as an active ingredient.
- the modified polysilazane of the present invention is preferably modified with a metal alkoxide / chelate compound or a low-molecular silazane / siloxane that promotes external oxygen uptake.
- the —SiH 3 group and the metal alkoxide / chelate compound in the modified polysilazane are highly reactive with moisture. For this reason, it is preferable to perform in the preparation process of a coating liquid in an environment with low oxygen and water vapor
- a coating solution by dissolving modified polysilazane in a solvent in an environment where the oxygen concentration is 200 ppm by volume or less and the water vapor concentration is 100 ppm by volume or less.
- the reaction of the modified polysilazane proceeds by absorption of vacuum ultraviolet light ( ⁇ 230 nm), and a dense barrier layer is formed.
- the modified polysilazane reacts with oxygen and moisture in the environment at the stage of preparing the coating solution, the oxidation reaction has already progressed at the stage of irradiation with vacuum ultraviolet light, so that the vacuum ultraviolet light is sufficiently absorbed. Not absorbed.
- Si—N of the modified polysilazane absorbs vacuum ultraviolet light, but when Si—N of the modified polysilazane reacts to become Si—O, it is stabilized in terms of energy, so that it does not absorb vacuum ultraviolet light. Conceivable.
- the second barrier layer forming coating solution is prepared in an environment where the oxygen concentration is 200 ppm by volume or less and the water vapor concentration is 100 ppm by volume or less, the reaction between polysilazane and oxygen or moisture during preparation is suppressed. Can do. As a result, vacuum ultraviolet light can be effectively absorbed, so that Si—N remaining in the barrier layer after irradiation with vacuum ultraviolet light can be reduced.
- the oxidation reaction of the modified polysilazane in a coating liquid may advance excessively by the oxygen in the environment at the time of liquid preparation. If the water vapor concentration exceeds 100 ppm by volume, the oxidation reaction of the modified polysilazane in the coating solution may proceed excessively due to the action of moisture.
- the coating solution is prepared in an environment where the oxygen concentration is more preferably 0 to 100 ppm by volume, and even more preferably 0 to 30 ppm by volume. Further, it is carried out in an environment where the water vapor concentration is more preferably 0 to 50 ppm by volume, and still more preferably 0 to 30 ppm by volume.
- Such an environment can be realized by preparing preparation equipment such as a glove box in which the oxygen concentration and water vapor concentration are controlled.
- a dry inert gas is preferably used as the gas that satisfies the atmosphere and is used when the second barrier layer forming coating solution is prepared.
- the inert gas include nitrogen, argon, helium and the like, but dry nitrogen gas is particularly preferable from the viewpoint of cost.
- the oxygen concentration can be adjusted by measuring the flow rates of oxygen gas and inert gas introduced into the preparation equipment such as a glove box and changing the flow rate ratio.
- the water vapor concentration in the atmosphere can be lowered by drying using a desiccant such as molecular sieves, for example. Further, the oxygen concentration in the atmosphere can be lowered by means of, for example, reacting with a metal copper catalyst or the like, or adsorbing it to an oxygen scavenger.
- the coating solution prepared in this manner is applied onto the first barrier layer to form a coating film, and the coating film is irradiated with vacuum ultraviolet rays for modification treatment to produce a gas barrier film.
- the second barrier layer forming coating solution preferably contains a catalyst in order to promote reforming.
- a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, Amine catalysts such as N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds.
- an amine catalyst it is preferable to use an amine catalyst.
- concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on the modified polysilazane. By setting the amount of the catalyst to be in this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.
- the amine catalyst can also serve as the additive compound.
- the following additives may be used as necessary.
- cellulose ethers, cellulose esters for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc.
- natural resins for example, rubber, rosin resin, etc., synthetic resins
- Aminoplasts especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.
- the coating liquid (second barrier layer forming coating liquid) obtained above is preferably applied onto the first barrier layer to form a coating film.
- a conventionally known appropriate wet coating method may be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
- the coating thickness can be appropriately set according to the purpose.
- the coating thickness (thickness after drying) per second barrier layer is preferably about 10 nm to 10 ⁇ m, more preferably 15 nm to 1 ⁇ m, and more preferably 20 to 500 nm. Further preferred. If the film thickness is 10 nm or more, sufficient barrier properties can be obtained, and if it is 10 ⁇ m or less, stable coating properties can be obtained during layer formation, and high light transmittance can be realized.
- the atmosphere for applying the coating solution may be any conditions such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, a reduced pressure atmosphere in which the oxygen concentration is controlled, etc.
- an inert gas atmosphere in which the oxygen concentration is controlled to 200 volume ppm or less and the water vapor concentration is controlled to 100 volume ppm or less.
- a solvent such as an organic solvent contained in the coating film can be removed. At this time, all of the solvent contained in the coating film may be dried or may be partially left. Even when a part of the solvent is left, a suitable second barrier layer can be obtained. The remaining solvent can be removed later.
- the drying temperature of the coating film varies depending on the substrate to be applied, but is preferably 50 to 200 ° C.
- the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat.
- the temperature can be set by using a hot plate, oven, furnace or the like.
- the drying time is preferably set to a short time.
- the drying temperature is 150 ° C.
- the drying time is preferably set within 30 minutes.
- the drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere in which the oxygen concentration is controlled.
- a coating solution is prepared. As in the step, it is preferable to carry out in an inert gas atmosphere in which the oxygen concentration is controlled to 200 volume ppm or less and the water vapor concentration is controlled to 100 volume ppm or less.
- the coating film obtained as described below is subjected to a modification treatment by irradiating it with vacuum ultraviolet rays, but the transmittance of light at 172 nm of the coating film immediately before irradiation with vacuum ultraviolet rays is preferably 20% or less, It is more preferably 15% or less, and further preferably 10% or less. This is because by having sufficient absorption with respect to vacuum ultraviolet light, modification by vacuum ultraviolet light proceeds and a dense barrier layer is formed.
- the lower limit of the transmittance of light at 172 nm of the coating film immediately before irradiation with vacuum ultraviolet rays is not particularly limited, but is substantially 0.1% or more. The value measured by the method described in the Examples is adopted as the light transmittance of 172 nm of the coating film.
- the precursor layer (coating film) obtained in the above step (i) is irradiated with active energy rays such as ultraviolet rays, electron beams, X rays, ⁇ rays, ⁇ rays, ⁇ rays, neutron rays,
- active energy rays such as ultraviolet rays, electron beams, X rays, ⁇ rays, ⁇ rays, ⁇ rays, neutron rays,
- active energy rays such as ultraviolet rays, electron beams, X rays, ⁇ rays, ⁇ rays, ⁇ rays, neutron rays.
- any commonly used active energy ray generator can be used, but a vacuum ultraviolet ray generator is preferably used.
- the method described in (ultraviolet irradiation process) in the section of the “first barrier layer” can be applied.
- the method and conditions described in the “ultraviolet irradiation treatment” section of the above “first barrier layer” can be applied also in this step (ii), and thus will be omitted.
- Vacuum ultraviolet irradiation is not particularly limited.
- the modified polysilazane of the present invention is modified with a metal alkoxide / chelate compound that promotes external oxygen uptake. For this reason, it is important to supply oxygen from the surface of the coating film, and it is preferable to carry out under conditions where oxygen is present rather than a completely inert gas atmosphere.
- vacuum ultraviolet irradiation is preferably performed in an atmosphere having an oxygen concentration of 200 to 10,000 ppm by volume. That is, in the step (ii), the modification treatment is preferably performed by irradiation with vacuum ultraviolet rays having a wavelength of 230 nm or less in an atmosphere having an oxygen concentration of 200 to 10,000 volume ppm.
- the oxygen concentration at the time of vacuum ultraviolet irradiation is 500 to 5,000 volume ppm, and more preferably 700 to 2,000 volume ppm. If the oxygen concentration is 200 ppm by volume or more, oxygen is supplied during vacuum ultraviolet irradiation, the reaction between the metal compound and polysilazane is sufficiently promoted, and as carbon dioxide derived from the metal compound, nitrogen oxide derived from polysilazane, and ammonia Released outside the system.
- the second coating liquid for forming the barrier layer contains a metal compound, if there is a large proportion of carbon atoms derived from the metal compound remaining in the barrier layer, the gas barrier property may decrease, but it reacts with oxygen.
- the gas barrier property of the barrier layer obtained by being released out of the system as carbon dioxide can be improved.
- vacuum ultraviolet rays are absorbed by oxygen, a decrease in efficiency in the vacuum ultraviolet irradiation process can be suppressed by carrying out in an atmosphere having an oxygen concentration of 10,000 ppm by volume or less.
- the irradiation with vacuum ultraviolet rays is performed in a state where the water vapor concentration is as low as possible.
- the water vapor concentration at the time of vacuum ultraviolet irradiation is preferably 1000 ppm by volume or less, and more preferably 200 ppm by volume or less.
- the vacuum ultraviolet irradiation is not particularly limited, but is preferably performed by controlling the temperature of the coating film at 50 to 120 ° C.
- the temperature of the coating film at the time of irradiation with vacuum ultraviolet rays is more preferably 60 to 100 ° C., further preferably 70 to 90 ° C.
- the reaction between the metal compound and polysilazane is sufficiently accelerated, the gas barrier property is excellent, and the gas barrier property is excellent in storage stability under high temperature and high humidity. A film can be obtained.
- the temperature of the coating film at the time of vacuum ultraviolet irradiation is 120 ° C.
- the specific means for controlling the temperature of the coating film is not particularly limited, and a conventionally known method can be appropriately used. Furthermore, it is more preferable to control the temperature of the atmosphere at the time of vacuum ultraviolet irradiation to the above range. A means for controlling the temperature of the atmosphere is not particularly limited, and a conventionally known method can be appropriately used.
- the illuminance of the vacuum ultraviolet light on the surface of the coating film formed from the second barrier layer forming coating solution is preferably 1 mW / cm 2 to 10 W / cm 2 , and 30 mW / cm 2. more preferably 2 ⁇ 200mW / cm 2, further preferably at 50mW / cm 2 ⁇ 160mW / cm 2. If it is 1 mW / cm 2 or more, sufficient reforming efficiency is obtained, and if it is 10 W / cm 2 or less, it is difficult to cause ablation in the coating film and damage the substrate.
- the amount of irradiation energy (integrated light amount) of vacuum ultraviolet rays on the coating film surface formed from the second barrier layer forming coating solution is preferably 10 to 10000 mJ / cm 2 , and preferably 100 to 8000 mJ / cm 2 . More preferably, it is 200 to 6000 mJ / cm 2 . If it is 10 mJ / cm 2 or more, the modification can proceed sufficiently. If it is 10,000 mJ / cm 2 or less, cracking due to over-reformation and thermal deformation of the substrate are unlikely to occur.
- the film density of the second barrier layer can be appropriately set according to the purpose.
- the film density of the second barrier layer is preferably in the range of 1.5 to 2.6 g / cm 3 . If it is the said range, the density of a film
- the second barrier layer may be a single layer or a laminated structure of two or more layers.
- each second barrier layer may have the same composition or a different composition.
- the gas barrier film of the present invention may have an intermediate layer between the first barrier layer and the second barrier layer for the purpose of stress relaxation and the like.
- a method of forming the intermediate layer a method of forming a polysiloxane modified layer can be applied.
- a coating liquid containing polysiloxane is applied on the first barrier layer by a wet coating method and dried, and then the coating film obtained by drying is irradiated with vacuum ultraviolet light.
- This is a method of forming an intermediate layer.
- the intermediate layer is not particularly limited, and can be applied in the same manner or appropriately modified as the intermediate layer described in, for example, Japanese Patent Application Laid-Open Nos. 2014-151571 and 2014-046272.
- the coating solution used for forming the intermediate layer preferably contains polysiloxane and an organic solvent.
- the polysiloxane applicable to the formation of the intermediate layer is not particularly limited, and conventionally known compounds such as those described in JP2014-151571A, JP2014-046272A, and the like are used. can do.
- a protective layer containing an organic compound may be provided on the second barrier layer.
- an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group is preferably used.
- the protective layer is not particularly limited, and can be applied, for example, in the same manner or appropriately modified as the protective layer described in JP2014-151571A, JP2014-046272A, and the like.
- the gas barrier film of the present invention may have a desiccant layer (moisture adsorption layer).
- the material used for the desiccant layer include calcium oxide and organometallic oxide.
- calcium oxide what was disperse
- the organic metal oxide OleDry (registered trademark) series manufactured by Futaba Electronics Co., Ltd. or the like can be used.
- the gas barrier film of the present invention may have a smooth layer (underlayer, primer layer) between the surface of the substrate having the barrier layer, preferably between the substrate and the first barrier layer.
- the smooth layer is provided in order to flatten the rough surface of the substrate on which the protrusions and the like exist, or to fill the unevenness and pinholes generated in the barrier layer with the protrusions on the substrate and to flatten the surface.
- Such a smooth layer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer. That is, it is preferable that the gas barrier film of the present invention further has a smooth layer containing a carbon-containing polymer between the substrate and the first barrier layer.
- the smooth layer also contains a carbon-containing polymer, preferably a curable resin.
- the curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material or the like with an active energy ray such as an ultraviolet ray to be cured is heated. And thermosetting resins obtained by curing. These curable resins may be used alone or in combination of two or more.
- the smooth layer is not particularly limited, and can be applied, for example, as the smooth layer described in JP-A No. 2014-151571, JP-A No. 2014-046272, or the like as appropriate.
- an anchor coat layer On the surface of the base material according to the present invention, an anchor coat layer may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion).
- the anchor coat agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene / vinyl alcohol resin, vinyl-modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. Can be used alone or in combination of two or more.
- a commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., “X-12-2400” in 3% isopropyl alcohol) can be used.
- the above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is coated by drying and removing the solvent, diluent, etc. Can do.
- the application amount of the anchor coating agent is preferably about 0.1 to 5 g / m 2 (dry state).
- a commercially available base material with an easy-adhesion layer may be used.
- the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition.
- a vapor phase method such as physical vapor deposition or chemical vapor deposition.
- an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.
- the thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 ⁇ m.
- the gas barrier film of the present invention can further have a bleed-out preventing layer.
- the bleed-out prevention layer has a smooth layer for the purpose of suppressing the phenomenon of unreacted oligomers moving from the base material to the surface when the film having the smooth layer is heated and contaminating the contact surface.
- the bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.
- Compounds that can be included in the bleed-out prevention layer include polyunsaturated organic compounds having two or more polymerizable unsaturated groups in the molecule, or one polymerizable unsaturated group in the molecule.
- Hard coat agents such as unitary unsaturated organic compounds can be mentioned.
- the bleed-out prevention layer is not particularly limited, and can be applied, for example, as the bleed-out prevention layer described in JP-A No. 2014-151571, JP-A No. 2014-046272, or the like or appropriately modified.
- the gas barrier film according to the present invention can be continuously produced and wound into a roll form (so-called roll-to-roll production). In that case, it is preferable to stick and wind up a protective sheet on the surface in which the barrier layer was formed.
- a protective sheet is applied in a place with a high degree of cleanliness. It is very effective to prevent the adhesion of dust. In addition, it is effective for preventing scratches on the surface of the barrier layer that enters during winding.
- the protective sheet is not particularly limited, and general “protective sheet” and “release sheet” having a configuration in which a weakly adhesive layer is provided on a resin substrate having a thickness of about 100 ⁇ m can be used.
- the water vapor permeability of the gas barrier film produced by the method of the present invention is preferably as low as possible. For example, it is preferably 1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 5 g / m 2 ⁇ day, and preferably 1 ⁇ 10. -4 to 1 ⁇ 10 -5 g / m 2 ⁇ day is more preferable.
- the water vapor transmission rate is a value measured by the method described in Examples described later.
- the gas barrier film produced by the method of the present invention can be preferably used for a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air.
- the device include electronic devices such as an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device. That is, the present invention also provides an organic EL device having the gas barrier film of the present invention.
- the gas barrier film produced by the method of the present invention can also be used for device film sealing. That is, it is a method of providing the gas barrier film of the present invention on the surface of the device itself as a support.
- the device may be covered with a protective layer before providing the gas barrier film.
- the gas barrier film produced by the method of the present invention can also be used as a device substrate or a film for sealing by a solid sealing method.
- the solid sealing method is a method in which after a protective layer is formed on a device, an adhesive layer and a gas barrier film are stacked and cured.
- an adhesive agent A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.
- Organic EL device Examples of organic EL elements using a gas barrier film are described in detail in JP-A-2007-30387.
- the reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a ⁇ / 4 plate, and a polarizing film in order from the bottom.
- the gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
- the transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a ⁇ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a ⁇ / 4 plate, and a polarization It has a structure consisting of a film. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
- the type of the liquid crystal cell is not particularly limited, but more preferably a TN type (Twisted Nematic), an STN type (Super Twisted Nematic), a HAN type (Hybrid Aligned Nematic), a VA type (Vertical Alignment), an EC type, a B type.
- TN type Transmission Nematic
- STN type Super Twisted Nematic
- HAN type Hybrid Aligned Nematic
- VA Very Alignment
- an EC type a B type.
- OCB type Optically Compensated Bend
- IPS type In-Plane Switching
- CPA type Continuous Pinwheel Alignment
- the gas barrier film of the present invention can also be used as a sealing film for solar cell elements.
- the gas barrier film of the present invention is preferably sealed so that the barrier layer is closer to the solar cell element.
- the solar cell element in which the gas barrier film of the present invention is preferably used is not particularly limited. For example, it is a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, or a tandem structure type.
- Amorphous silicon-based solar cell elements III-V group compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI group compound semiconductor solar cell elements such as cadmium tellurium (CdTe), I-III- such as copper / indium / selenium (so-called CIS), copper / indium / gallium / selenium (so-called CIGS), copper / indium / gallium / selenium / sulfur (so-called CIGS), etc.
- Group VI compound semiconductor solar cell element dye-sensitized solar cell element, organic solar cell element, etc. And the like.
- the solar cell element is a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur.
- CIS system copper / indium / selenium system
- CIGS system copper / indium / gallium / selenium system
- sulfur copper / indium / gallium / selenium / sulfur.
- a group I-III-VI compound semiconductor solar cell element such as a system (so-called CIGSS system) is preferable.
- the gas barrier film of the present invention can also be used as an optical member.
- the optical member include a circularly polarizing plate.
- a circularly polarizing plate can be produced by laminating a ⁇ / 4 plate and a polarizing plate using the gas barrier film in the present invention as a substrate. In this case, the lamination is performed so that the angle formed by the slow axis of the ⁇ / 4 plate and the absorption axis of the polarizing plate is 45 °.
- a polarizing plate one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used.
- MD longitudinal direction
- those described in JP-A-2002-865554 can be suitably used. .
- a film forming gas mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (which also functions as a discharge gas) as a source gas
- HMDSO hexamethyldisiloxane
- oxygen gas which also functions as a discharge gas
- a gas barrier thin film inorganic compound layer, first barrier layer
- the thickness of the inorganic compound layer was 150 nm. It was confirmed that the inorganic compound layer formed as described above contains carbon, silicon, and oxygen as constituent elements and satisfies the requirements (i) to (iii).
- PHPS non-catalytic perhydropolysilazane
- 29 Si-NMR measurement is performed as follows. Specifically, in the 29 Si-NMR measurement result, it is attributed to SiH and SiH 2 observed in the vicinity of ⁇ 35 ppm when the area of the peak attributed to SiH 3 observed in the vicinity of ⁇ 50 ppm is 1. The ratio of the peak areas is the SiH 3 ratio.
- the measurement is performed using a 500 MHz NMR apparatus manufactured by JEOL Ltd. using an NMR tube tube for 29 Si measurement and using heavy benzene as a solvent.
- the coating solution obtained above is formed on the inorganic compound layer with a spin coater so that the thickness (dry film thickness) is 80 nm, left for 2 minutes, and then heated on an 80 ° C. hot plate. Additional heat treatment was performed for 1 minute to form a polysilazane coating film (precursor layer).
- a vacuum ultraviolet ray irradiation treatment is performed so that a vacuum ultraviolet ray of 172 nm becomes 6000 mJ / cm 2 according to the following method.
- the gas barrier film 101 was produced.
- SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured in the same manner as described above, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (1) is read as SiH 3 ratio of the barrier layer (second barrier layer).
- reference numeral 21 denotes an apparatus chamber, which supplies appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) to the inside and exhausts gas from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber.
- the oxygen concentration can be maintained at a predetermined concentration.
- vacuum ultraviolet irradiation was performed with the oxygen concentration adjusted to 1,000 ppm by volume.
- the oxygen concentration in the chamber was measured using an oxygen concentration meter (zirconia oxygen concentration meter LC-450A manufactured by Toray Engineering Co., Ltd.).
- Reference numeral 22 denotes an Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm
- reference numeral 23 denotes an excimer lamp holder that also serves as an external electrode.
- Reference numeral 24 denotes a sample stage. The sample stage 24 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 21 by a moving means (not shown). The sample stage 24 can be maintained at a predetermined temperature by a heating means (not shown). Here, it was set to 100 ° C.
- Reference numeral 25 denotes a sample on which a polysilazane coating film is formed.
- Reference numeral 26 denotes a light shielding plate, which prevents the application layer of the sample from being irradiated with vacuum ultraviolet light during aging of the Xe excimer lamp 22.
- the energy irradiated to the coating film surface in the vacuum ultraviolet irradiation process was measured using a 172 nm sensor head using a UV integrating light meter: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics Co., Ltd.
- the sensor head is placed in the center of the sample stage 24 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 6 mm, and the atmosphere in the apparatus chamber 21 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as in the process, and the measurement was performed by moving the sample stage 24 at a speed of 0.5 m / min (V in FIG. 3).
- an aging time of 10 minutes was provided after the Xe excimer lamp was turned on, and then the sample stage was moved to start the measurement.
- the irradiation speed was adjusted to 6000 mJ / cm 2 by adjusting the moving speed of the sample stage.
- the vacuum ultraviolet irradiation was performed after aging for 10 minutes as in the case of irradiation energy measurement.
- Comparative Example 2 Production of gas barrier film 102
- ALCH Korean Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate
- a gas barrier film 102 was produced in the same manner as in Comparative Example 1 except that the coating liquid (2) prepared by stirring and reacting at 80 ° C. for 1 hour and then cooling was used.
- the said reaction was performed in the atmosphere whose water vapor
- the oxygen concentration in the reaction system was measured using an oxygen concentration meter (zirconia type oxygen concentration meter LC-450A manufactured by Toray Engineering Co., Ltd.).
- the water vapor concentration in the reaction system was determined by measuring the dew point using a dew point meter (manufactured by Vaisala, DMT type dew point meter), and obtaining the water vapor concentration from the measured dew point.
- Comparative Example 3 Production of gas barrier film 103
- ALCH aluminum ethyl acetoacetate diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.
- ALCH aluminum ethyl acetoacetate diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.
- a gas barrier film 103 was produced in the same manner as in Comparative Example 1 except that the coating liquid (3) prepared by stirring and reacting at 80 ° C. for 1 hour and then cooling was used. .
- the said reaction was performed in the atmosphere whose water vapor
- Example 1 Production of gas barrier film 104)
- ALCH Korean Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate
- a gas barrier film 104 was produced in the same manner as in Comparative Example 1 except that the coating liquid (4) prepared by further stirring and reacting at 80 ° C. for 1 hour and then cooling was used in addition to the liquid (1). .
- the said reaction was performed in the atmosphere whose water vapor
- Example 2 Production of gas barrier film 105)
- AMD Korean Fine Chemical Co., Ltd., aluminum diisopropylate monosecondary butyrate
- a gas barrier film 105 was produced in the same manner as in Comparative Example 1 except that the coating liquid (5) prepared by stirring and reacting at 80 ° C. for 1 hour and then cooling was used. .
- the said reaction was performed in the atmosphere whose water vapor
- Example 3 Production of gas barrier film 106
- aluminum chelate D produced by Kawaken Fine Chemical Co., Ltd., aluminum bisethyl acetoacetate / monoacetylacetonate
- the coating solution (6) prepared by further stirring and reacting at 80 ° C. for 1 hour and then cooling was used. 106 was produced.
- the said reaction was performed in the atmosphere whose water vapor
- Example 4 Production of gas barrier film 107) [Formation of inorganic compound layer (first barrier layer) (plasma CVD method)] In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
- TDAH 1,6-diaminohexane
- NAX120-20 1,6-diaminohexane
- the coating solution (7-1) thus prepared ALCH (Aluminum ethyl acetoacetate diisopropylate, manufactured by Kawaken Fine Chemical Co., Ltd.) is used in an amount of 5 mol% based on the number of Si elements in perhydropolysilazane. After that, the mixture was further reacted with stirring at 80 ° C. for 1 hour and then cooled to prepare a coating solution (7-2). Next, Compound 1 having the following structure was further added to this coating solution (7-2) in an amount of 5 mol% with respect to the number of Si elements of perhydropolysilazane, and then stirred at 80 ° C. for 1 hour. After cooling, a coating solution (7-3) was prepared.
- ALCH Aligninum ethyl acetoacetate diisopropylate, manufactured by Kawaken Fine Chemical Co., Ltd.
- a gas barrier film 107 was produced in the same manner as in Comparative Example 1, except that the coating liquid (7-3) prepared as described above was used instead of the coating liquid (1). .
- the said reaction was performed in the atmosphere whose water vapor
- the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (7) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
- Example 5 to 11 Production of gas barrier films 108 to 114
- gas barrier films 108 to 114 were produced in the same manner as in Example 4, except that compounds 2 to 8 having the following structures were used instead of compound 1, respectively.
- the said reaction was performed in the atmosphere whose water vapor
- the ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane in each coating solution was prepared in this example [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1.
- the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of each polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solutions shown in Table 1 is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
- Example 12 Production of gas barrier film 115
- a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
- a solution of 20% by mass of perhydropolysilazane containing 5% by mass of 1,6-diaminohexane (TMDAH) manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20
- TDAH 1,6-diaminohexane
- NAX120-20 1,6-diaminohexane
- the coating solution (8-1) thus prepared AMD (aluminum diisopropylate monosecondary butyrate manufactured by Kawaken Fine Chemical Co., Ltd.) is used in an amount of 5 mol% with respect to the number of Si elements in perhydropolysilazane. After further addition, the mixture was allowed to react with stirring at 80 ° C. for 1 hour and then cooled to prepare a coating solution (8-2). Next, the compound 1 is further added to the coating solution (8-2) in an amount of 5 mol% with respect to the number of Si elements of perhydropolysilazane, and then stirred at 80 ° C. for 1 hour and then cooled. Thus, a coating solution (8-3) was prepared.
- AMD aluminum diisopropylate monosecondary butyrate manufactured by Kawaken Fine Chemical Co., Ltd.
- a gas barrier film 115 was produced in the same manner as in Comparative Example 1, except that the coating liquid (8-3) prepared as described above was used instead of the coating liquid (1). .
- the said reaction was performed in the atmosphere whose water vapor
- the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (8-3) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
- Example 13 to 14 Production of gas barrier films 116 to 117
- gas barrier films 116 to 117 were produced in the same manner as in Example 12 except that the compounds 3 and 5 were used instead of the compound 1, respectively.
- the said reaction was performed in the atmosphere whose water vapor
- the ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane in each coating solution was prepared in this example [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1.
- SiH 3 ratio of the obtained barrier layer (second barrier layer) When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solutions shown in Table 1 is replaced with SiH 3 ratio of the corresponding barrier layer (second barrier layer).
- Example 15 Production of gas barrier film 118
- a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
- a solution of 20% by mass of perhydropolysilazane containing 5% by mass of 1,6-diaminohexane (TMDAH) manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20
- TDAH 1,6-diaminohexane
- NAX120-20 1,6-diaminohexane
- the coating solution (9-1) was prepared so that the ratio was 2.7% by mass.
- the coating solution (9-1) thus prepared aluminum chelate D (produced by Kawaken Fine Chemical Co., Ltd., aluminum bisethylacetoacetate / monoacetylacetonate) was added in an amount of 5 mol with respect to the number of Si elements in perhydropolysilazane. % was added, followed by stirring and reaction at 80 ° C. for 1 hour, followed by cooling to prepare a coating solution (9-2).
- the compound 1 is further added to the coating solution (9-2) in an amount of 5 mol% with respect to the number of Si elements of perhydropolysilazane, followed by stirring at 80 ° C. for 1 hour and cooling.
- a coating solution (9-3) was prepared.
- a gas barrier film 118 was produced in the same manner as in Comparative Example 1 except that the coating liquid (9-3) prepared as described above was used instead of the coating liquid (1). .
- the said reaction was performed in the atmosphere whose water vapor
- the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (9-3) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
- Example 16 to 17 Production of gas barrier films 119 to 120
- gas barrier films 119 to 120 were produced in the same manner as in Example 15 except that the compounds 3 and 5 were used instead of the compound 1, respectively.
- the said reaction was performed in the atmosphere whose water vapor
- the ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane in each coating solution was prepared in this example [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1.
- SiH 3 ratio of the obtained barrier layer (second barrier layer) When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solutions shown in Table 1 is replaced with SiH 3 ratio of the corresponding barrier layer (second barrier layer).
- Example 18 Production of gas barrier film 121) [Formation of inorganic compound layer (first barrier layer) (plasma CVD method)] In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
- TDAH 1,6-diaminohexane
- NAX120-20 1,6-diaminohexane
- the above compound 3 was further added in an amount of 5 mol% with respect to the number of Si elements of perhydropolysilazane, and then stirred at 80 ° C. for 1 hour. After cooling, a coating solution (10-2) was prepared. Next, ALCH (produced by Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate) was further added to this coating solution (10-2) in an amount of 5 mol% with respect to the number of Si elements in perhydropolysilazane. Then, the mixture was allowed to react with stirring at 80 ° C. for 1 hour and then cooled to prepare a coating solution (10-3).
- ALCH produced by Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate
- a gas barrier film 121 was produced in the same manner as in Comparative Example 1, except that the coating liquid (10-3) prepared as described above was used instead of the coating liquid (1). .
- the said reaction was performed in the atmosphere whose water vapor
- the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (10-3) is read as SiH 3 ratio of the barrier layer (second barrier layer).
- Example 19 Production of gas barrier film 122) [Formation of inorganic compound layer (first barrier layer) (plasma CVD method)] In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
- TDAH methyl-1,6-diaminohexane
- NAX120-20 methyl-1,6-diaminohexane
- the above-described coating solution was further added with each of the compound 3 and ALCH in an amount of 5 mol% based on the number of Si elements in perhydropolysilazane. After stirring and reacting at 80 ° C. for 1 hour, the mixture was cooled to prepare a coating solution (11-3). In addition, the said reaction was performed in the atmosphere whose water vapor
- a gas barrier film 122 was produced in the same manner as in Comparative Example 1 except that the coating liquid (11-3) prepared as described above was used instead of the coating liquid (1).
- the coating liquid (11-3) prepared as described above was used instead of the coating liquid (1).
- SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (11-3) is read as SiH 3 ratio of the barrier layer (second barrier layer).
- Example 20 Production of gas barrier film 123) [Formation of inorganic compound layer (first barrier layer) (plasma CVD method)] In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
- TDAH 1,6-diaminohexane
- NAX120-20 1,6-diaminohexane
- the coating liquid (12-1) thus prepared was mixed with ALCH (aluminum ethyl acetoacetate diisopropylate) manufactured by Kawaken Fine Chemical Co., Ltd. and the above compound 3 with respect to the number of Si elements in perhydropolysilazane. After further adding in an amount of 5 mol%, the mixture was reacted with stirring at 80 ° C. for 1 hour and then cooled to prepare a coating solution (12-2).
- ALCH aluminum ethyl acetoacetate diisopropylate
- a gas barrier film 123 was produced in the same manner as in Comparative Example 1, except that the coating liquid (12-2) prepared as described above was used instead of the coating liquid (1). .
- the above reaction was performed in an atmosphere having a water vapor concentration and an oxygen concentration of 10 ppm by volume or less.
- SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (12-2) is read as SiH 3 ratio of the barrier layer (second barrier layer).
- Vapor deposition device JEOL Ltd., vacuum vapor deposition device JEE-400 Constant temperature and humidity oven: Yamato Humidic Chamber IG47M (raw materials) Metal that reacts with water and corrodes: Calcium (granular) Water vapor impermeable metal: Aluminum ( ⁇ 3-5mm, granular) (Preparation of water vapor barrier property evaluation sample)
- a vacuum vapor deposition device vacuum vapor deposition device JEE-400 manufactured by JEOL Ltd.
- calcium metal was deposited on the surface of the second barrier layer of the produced gas barrier film in a size of 12 mm ⁇ 12 mm through a mask. At this time, the deposited film thickness was set to 80 nm.
- the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet and temporarily sealed.
- the vacuum state is released, and it is immediately transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum vapor-deposited surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX Corporation).
- the water vapor barrier property evaluation sample was produced by irradiating ultraviolet rays to cure and adhere the resin to perform main sealing.
- the obtained sample was stored at a high temperature and high humidity of 85 ° C. and 85% RH, and the state in which the metal calcium was corroded with respect to the storage time was observed. Observation was obtained by linearly interpolating the time when the area where metal calcium was corroded with respect to the metal calcium deposition area of 12 mm ⁇ 12 mm to 50% from the observation results, and the water vapor transmission rate WVTR (g / m 2 / g from the amount of deteriorated calcium. day).
- the gas barrier film produced according to the examples of the present invention hardly deteriorates in gas barrier property due to composition change even after being exposed to high temperature and high humidity for a long time. I understand.
- first electrode layer A 150-nm-thick ITO (indium tin oxide) film formed by sputtering on an alkali-free glass was patterned by photolithography to form a first electrode layer. The pattern was such that the light emission area was 50 mm square.
- a coating liquid for forming a hole transport layer shown below is extrusion-coated in an environment of 25 ° C. and a relative humidity of 50% RH. After coating, the substrate was dried and heated under the following conditions to form a hole transport layer. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.
- the gas barrier film was subjected to cleaning surface modification using a low-pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm 2 and a distance of 10 mm.
- the charge removal treatment was performed using a static eliminator with weak X-rays.
- PEDOT / PSS polystyrene sulfonate
- Baytron P AI 4083 manufactured by Bayer
- ⁇ Drying and heat treatment conditions After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment.
- the back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.
- the following coating solution for forming a white light emitting layer is applied by an extrusion coater under the following conditions, followed by drying and heat treatment under the following conditions to form a light emitting layer. did.
- the white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.
- ⁇ White luminescent layer forming coating solution> As a host material, 1.0 g of a compound represented by the following chemical formula HA, 100 mg of a compound represented by the following chemical formula DA as a dopant material, and 0.1 mg of a compound represented by the following chemical formula DB as a dopant material. 2 mg of a compound represented by the following chemical formula DC as a dopant material was dissolved in 0.2 mg and 100 g of toluene to prepare a white light emitting layer forming coating solution.
- the coating process is performed in an atmosphere with a nitrogen gas concentration of 99% or more, the coating temperature is 25 ° C., and the coating speed is 1 m. / Min.
- ⁇ Drying and heat treatment conditions After applying the white light emitting layer forming coating solution, the solvent was removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., and then a temperature of 130 ° C. A heat treatment was performed to form a light emitting layer.
- the following electron transport layer forming coating solution was applied by an extrusion coater under the following conditions, and then dried and heat-treated under the following conditions to form an electron transport layer.
- the coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.
- the coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.
- the electron transport layer was prepared by dissolving a compound represented by the following chemical formula EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating solution for forming an electron transport layer.
- An electron injection layer was formed on the electron transport layer formed above.
- the substrate was put into a decompression chamber and decompressed to 5 ⁇ 10 ⁇ 4 Pa.
- cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.
- Aluminum is used as the second electrode forming material on the electron injection layer formed as described above, except for the portion that becomes the extraction electrode of the first electrode 22 under a vacuum of 5 ⁇ 10 ⁇ 4 Pa, A mask pattern was formed by vapor deposition so as to have an extraction electrode so that the light emission area was 50 mm square, and a second electrode having a thickness of 100 nm was laminated.
- thermosetting adhesive containing bisphenol A diglycidyl ether (DGEBA), dicyandiamide (DICY) and an epoxy adduct curing accelerator was used as the thermosetting adhesive.
- the gas barrier film is closely attached and arranged so that the extraction electrode (including the extraction electrodes of the first electrode and the second electrode) patterned on the first electrode is exposed, and the vacuum laminator is Used tightly sealed. After sealing, post-curing treatment was performed at 110 ° C. for 15 minutes to produce an organic EL element.
- the gas barrier film produced according to the example of the present invention has the effect of reducing the occurrence of dark spots by using it as a sealing film for organic EL elements, and has a very high gas barrier property.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
- Laminated Bodies (AREA)
- Electroluminescent Light Sources (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides a method for producing a gas barrier film having exceptional storage stability, especially storage stability under rigorous conditions (high-temperature, high-humidity conditions). This modified polysilazane has a ratio ((SiH3:(SiH+SiH2)) of SiH3 and the total of SiH and SiH2 of 1:10-30 as measured by 29Si-NMR.
Description
本発明は、変性ポリシラザン、当該変性ポリシラザンを含む塗布液および当該塗布液を用いて製造されるガスバリア性フィルムに関する。より詳細には、本発明は、有機エレクトロルミネッセンス(EL)素子や太陽電池素子、液晶表示等の電子デバイスに用いられる変性ポリシラザン、当該変性ポリシラザンを含む塗布液および当該塗布液を用いて製造されるガスバリア性フィルムに関するものである。
The present invention relates to a modified polysilazane, a coating solution containing the modified polysilazane, and a gas barrier film produced using the coating solution. More specifically, the present invention is produced using a modified polysilazane used in an electronic device such as an organic electroluminescence (EL) element, a solar cell element, and a liquid crystal display, a coating solution containing the modified polysilazane, and the coating solution. The present invention relates to a gas barrier film.
従来、プラスチック基板やフィルムの表面に、酸化アルミニウム、酸化マグネシウム、酸化ケイ素等の金属酸化物の薄膜を含む複数の層を積層して形成したガスバリア性フィルムは、水蒸気や酸素等の各種ガスの遮断を必要とする物品の包装、例えば、食品や工業用品及び医薬品等の変質を防止するための包装用途に広く用いられている。
Conventionally, a gas barrier film formed by laminating a plurality of layers including thin films of metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide on the surface of a plastic substrate or film is used to block various gases such as water vapor and oxygen. For example, it is widely used in packaging applications for preventing deterioration of foods, industrial products, medicines and the like.
包装用途以外にも、フレキシブル性を有する太陽電池素子、有機エレクトロルミネッセンス(EL)素子、液晶表示素子等のフレキシブル電子デバイスへの展開が要望され、多くの検討がなされている。しかし、これらフレキシブル電子デバイスにおいては、ガラス基材レベルの非常に高いガスバリア性が要求されるため、現状では十分な性能を有するガスバリア性フィルムは未だ得られていない。
In addition to packaging applications, it has been requested to develop into flexible electronic devices such as flexible solar cell elements, organic electroluminescence (EL) elements, liquid crystal display elements, etc., and many studies have been made. However, in these flexible electronic devices, since a gas barrier property at a glass substrate level is required, a gas barrier film having sufficient performance has not been obtained yet.
このようなガスバリア性フィルムを形成する方法としては、テトラエトキシシラン(TEOS)に代表される有機ケイ素化合物を用いて、減圧下の酸素プラズマ酸化しながら基板上に成長させる化学堆積法(プラズマCVD法:Chemical Vapor Deposition)や半導体レーザーを用いて金属Siを蒸発させ酸素の存在下で基板上に堆積する物理堆積法(真空蒸着法やスパッタ法)といった気相法が知られている。
As a method for forming such a gas barrier film, a chemical deposition method (plasma CVD method) in which an organic silicon compound typified by tetraethoxysilane (TEOS) is used to grow on a substrate while performing oxygen plasma oxidation under reduced pressure. There are known vapor phase methods such as a physical vapor deposition method (vacuum evaporation method or sputtering method) in which metal Si is evaporated using a semiconductor laser and deposited on a substrate in the presence of oxygen using a semiconductor laser.
これらの気相法による無機製膜方法は、酸化ケイ素や窒化ケイ素、酸窒化ケイ素等の無機膜の形成に好ましく適用されてきており、良好なガスバリア性を得るための無機膜の組成範囲の検討、およびこれら無機膜を含む層構成の検討が多くなされている。
These inorganic vapor deposition methods have been preferably applied to the formation of inorganic films such as silicon oxide, silicon nitride, and silicon oxynitride, and examination of the composition range of inorganic films for obtaining good gas barrier properties. Many studies have been made on the layer structure including these inorganic films.
さらに、上述のような気相法では欠陥を有さない膜を形成することは非常に困難であり、例えば製膜レートを極端に低くして欠陥の生成を抑制する必要がある。このため、生産性が要求される工業的レベルにおいては、フレキシブル電子デバイスに要求されるガスバリア性は得られていない。気相法による無機膜の膜厚を単純に増加させたり、無機膜を複数層積層するといった検討もなされたが、欠陥が連続成長したり、かえってクラックが増加したりするため、ガスバリア性の向上には至っていない。
Furthermore, it is very difficult to form a film having no defects by the above-described vapor phase method. For example, it is necessary to suppress the generation of defects by extremely reducing the film forming rate. For this reason, the gas barrier property required for the flexible electronic device is not obtained at an industrial level where productivity is required. Although studies such as simply increasing the thickness of the inorganic film by the vapor phase method or stacking multiple layers of inorganic films have been made, it is possible to improve the gas barrier properties because defects grow continuously or cracks increase. It has not reached.
このような無機膜の欠陥は、例えば有機EL素子の場合、ダークスポットと呼ばれる発光しない黒点の発生を招いたり、高温高湿下においてダークスポットのサイズが成長したりと、素子自体の耐久性にも影響を与えてしまう。
For example, in the case of an organic EL element, such a defect in the inorganic film causes the generation of a black spot called a dark spot that does not emit light, or the size of the dark spot grows under high temperature and high humidity. Will also affect.
一方で、これまでの気相法による製膜に加え、ガスバリア層形成方法の一つとして、前述の気相法による無機膜上に無機前駆体化合物の溶液を塗布し、乾燥して形成した塗布層を、熱によって改質することで、上述の気相法によって製膜された無機膜の欠陥部を効果的に修復し、さらには積層した膜自体がガスバリア性を向上させる検討がなされており、特に、無機前駆体化合物としてポリシラザンを用いることで、前述した欠陥部の修復によって高度なガスバリア性を発現させようとする検討が行われている。
On the other hand, in addition to the conventional film formation by the vapor phase method, as one of the gas barrier layer formation methods, the coating of the inorganic precursor compound solution applied on the inorganic film by the above-mentioned vapor phase method and dried By modifying the layer with heat, the defect portion of the inorganic film formed by the above-mentioned vapor phase method is effectively repaired, and further, the laminated film itself has been studied to improve the gas barrier property. In particular, by using polysilazane as an inorganic precursor compound, studies have been made to develop a high gas barrier property by repairing the above-described defect portion.
しかし、ポリシラザンの熱改質または湿熱改質による緻密な酸窒化ケイ素膜あるいは酸化ケイ素膜の形成には450℃以上の高温が必要であり、プラスチック等のフレキシブル基材に適用することは不可能であった。
However, the formation of a dense silicon oxynitride film or silicon oxide film by thermal modification or wet heat modification of polysilazane requires a high temperature of 450 ° C. or higher and cannot be applied to flexible substrates such as plastics. there were.
このような問題を解決する手段として、ポリシラザン溶液から塗布形成した塗膜に真空紫外光照射を施すことにより、酸窒化ケイ素膜あるいは酸化ケイ素膜を形成する方法が提案されている。
As a means for solving such a problem, a method of forming a silicon oxynitride film or a silicon oxide film by applying vacuum ultraviolet light to a coating film formed from a polysilazane solution has been proposed.
ポリシラザンの各原子間結合力より大きいエネルギーを有する真空紫外光(以下、「VUV」、「VUV光」ともいう)と呼ばれる波長100~200nmの光エネルギーを用いて、原子の結合を光量子プロセスと呼ばれる光子のみによる作用により、直接切断しながら活性酸素やオゾンによる酸化反応を進行させることで、比較的低温で、酸窒化ケイ素膜あるいは酸化ケイ素膜の形成を行うことができる。
Bonding of atoms is called a photon process using light energy having a wavelength of 100 to 200 nm called vacuum ultraviolet light (hereinafter also referred to as “VUV” or “VUV light”) having an energy larger than the bonding force between each atom of polysilazane. A silicon oxynitride film or a silicon oxide film can be formed at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by the action of only photons.
通常、樹脂フィルム基材の上にポリシラザンを塗布し、紫外線照射を行った場合、照射した面の表面近傍が改質されバリア層(窒素高濃度層)を形成する。同時に基材側からの水分持ち込みと推定される酸化挙動が起き、バリア層下の内部は酸化膜(酸化ケイ素層)となると考えられている。
Usually, when polysilazane is applied on a resin film substrate and irradiated with ultraviolet rays, the vicinity of the surface of the irradiated surface is modified to form a barrier layer (high nitrogen concentration layer). At the same time, it is considered that an oxidation behavior presumed to be brought in moisture from the substrate side occurs, and the inside under the barrier layer becomes an oxide film (silicon oxide layer).
このようなバリア層を含むガスバリア性フィルムの製造方法において、例えば、特許文献1には、基材上に化学蒸着法で形成された第1のバリア層およびポリシラザン等の珪素化合物を塗布して製膜しエネルギー線(例えば、真空紫外光)を照射することにより形成される第2のバリア層を有するガスバリア性フィルムが開示されている。当該ガスバリア性フィルムは、高いバリア性能を示し、折り曲げ耐性、平滑性、裁断加工適性に優れる。
In a method for producing a gas barrier film including such a barrier layer, for example, in Patent Document 1, a first barrier layer formed by chemical vapor deposition on a substrate and a silicon compound such as polysilazane are applied. A gas barrier film having a second barrier layer formed by irradiating a film and irradiating energy rays (for example, vacuum ultraviolet light) is disclosed. The gas barrier film exhibits high barrier performance and is excellent in bending resistance, smoothness, and suitability for cutting.
さらに、例えば、特許文献2には、基材上に遷移金属化合物を添加したポリシラザンの溶液を塗布し、乾燥させて形成した塗膜に、酸素または水分を実質的に含まない雰囲気下でエネルギー線(例えば、真空紫外光)照射を行うことによって形成されるガスバリア性フィルムが開示されている。当該方法によると、短時間で改質が進行して窒素高濃度膜が形成され、高いガスバリア性が発現する。
Further, for example, in Patent Document 2, an energy beam is applied in an atmosphere substantially free of oxygen or moisture in a coating film formed by applying a polysilazane solution added with a transition metal compound on a substrate and drying it. A gas barrier film formed by irradiation (for example, vacuum ultraviolet light) is disclosed. According to this method, the reforming proceeds in a short time to form a high nitrogen concentration film, and high gas barrier properties are exhibited.
特許文献1~2に記載の技術では、表面が改質されていることで高いガスバリア性を示し、一般的な条件下では高いガスバリア性を示すものの、高温高湿下では加水分解等によりバリア層が変質する場合があり、その結果、ガスバリア性が急激に低下するという問題があった。
The techniques described in Patent Documents 1 and 2 show high gas barrier properties due to the modified surface and high gas barrier properties under general conditions, but the barrier layer by hydrolysis or the like under high temperature and high humidity. As a result, there has been a problem that the gas barrier property is rapidly lowered.
本発明は、上記事情を鑑みてなされたものであり、保存安定性、特に過酷な条件(高温高湿条件)下での保存安定性に優れるガスバリア性フィルムの製造に適する変性ポリシラザンを提供することを目的とする。
The present invention has been made in view of the above circumstances, and provides a modified polysilazane suitable for production of a gas barrier film excellent in storage stability, particularly storage stability under severe conditions (high temperature and high humidity conditions). With the goal.
本発明の他の目的は、保存安定性、特に過酷な条件(高温高湿条件)下での保存安定性に優れるガスバリア性フィルムを提供することである。
Another object of the present invention is to provide a gas barrier film excellent in storage stability, particularly storage stability under severe conditions (high temperature and high humidity conditions).
本発明者は、上記の問題を解決すべく、鋭意研究を行った。その結果、SiH3とSiH及びSiH2の合計との比が特定範囲にある変性ポリシラザンを使用することによって、上記課題を解決できることを見出し、本発明を完成するに至った。
The present inventor has intensively studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using a modified polysilazane having a ratio of SiH 3 to the sum of SiH and SiH 2 in a specific range, and the present invention has been completed.
すなわち、上記諸目的は、29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]が1:10~30である変性ポリシラザンによって達成されうる。
That is, the above objects are achieved by a modified polysilazane in which the ratio [(SiH 3 ) :( SiH + SiH 2 )] of SiH 3 measured by 29 Si-NMR and the sum of SiH and SiH 2 is 1: 10-30. Can be done.
上記諸目的はまた、上記変性ポリシラザンを含む塗布液、または基材および上記塗布液を用いて形成されるバリア層を含むガスバリア性フィルムによっても達成されうる。
The above-mentioned objects can also be achieved by a gas barrier film comprising a coating solution containing the modified polysilazane, or a substrate and a barrier layer formed using the coating solution.
本発明は、29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]が1:10~30である変性ポリシラザンを提供する。また、本発明の変性ポリシラザンを含む塗布液、および当該塗布液を用いて製造されるガスバリア性フィルムをも提供する。
The present invention, the ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR [(SiH 3 ) :( SiH + SiH 2)] is 1: provide modified polysilazane 10-30. Moreover, the coating liquid containing the modified polysilazane of this invention and the gas-barrier film manufactured using the said coating liquid are also provided.
このような構成とすることにより、長期の保存安定性、特に高温高湿下という過酷な条件下でもガスバリア性の低下を抑制・防止できる保存安定性に優れたガスバリア性フィルムが得られる。
By adopting such a configuration, a gas barrier film excellent in storage stability capable of suppressing / preventing deterioration of gas barrier properties even under severe conditions such as long-term storage stability, particularly under high temperature and high humidity, can be obtained.
従来、パーヒドロポリシラザン層にエネルギー線(例えば、真空紫外光)を照射すると、表面がガラス質に改質され高いバリア性を示す。しかし、過酷な条件(高温高湿条件)におかれると急激に劣化する。特にポリシラザンを前駆体として形成されたバリア層(ガスバリア層)は、下層にバリア層がある構成では過酷な条件(高温高湿条件)での劣化は顕著であった。
Conventionally, when the perhydropolysilazane layer is irradiated with energy rays (for example, vacuum ultraviolet light), the surface is modified to vitreous and exhibits high barrier properties. However, it deteriorates rapidly under severe conditions (high temperature and high humidity conditions). In particular, the barrier layer (gas barrier layer) formed using polysilazane as a precursor was significantly deteriorated under severe conditions (high-temperature and high-humidity conditions) in a configuration in which the barrier layer is in the lower layer.
また、上記特許文献1や2に記載されるように、従来、様々な方法によって、ガスバリア性フィルムのガスバリア性をはじめとする諸特性を向上させることが試みられていた。しかし、上記特許文献1や2に記載の方法では、ポリシラザン層表面付近のみが改質され、内部に未改質部が残ってしまう。この未改質部が特に過酷な条件(高温高湿条件)下で著しく反応して、ガスバリア性を低下させる一つの要因であることがわかった。また、大気中の水分による作用により反応が進むものの、エネルギー線(例えば、真空紫外光)を照射する段階で既に酸化反応が進んでいるため、エネルギー線を十分に吸収できず、最適なバリア膜を形成することが困難であるまたは形成することができない。
In addition, as described in Patent Documents 1 and 2, attempts have been made to improve various characteristics including gas barrier properties of gas barrier films by various methods. However, in the methods described in Patent Documents 1 and 2, only the vicinity of the surface of the polysilazane layer is modified, and an unmodified portion remains inside. It has been found that this unmodified part is one factor that causes a significant reaction under particularly severe conditions (high temperature and high humidity conditions) to lower the gas barrier property. In addition, although the reaction proceeds due to the action of moisture in the atmosphere, the oxidation reaction has already progressed at the stage of irradiation with energy rays (for example, vacuum ultraviolet light), so the energy barrier cannot be sufficiently absorbed, and the optimum barrier film Is difficult or cannot be formed.
これに対して、本発明の変性ポリシラザンは、特定の範囲にSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を有することを特徴とする。本発明の変性ポリシラザンを使用することによって、保存安定性、特に高温高湿下での保存安定性に優れるガスバリア性フィルムを提供できる。ここで、本発明の構成による上記作用効果の発揮のメカニズムは以下のように推測される。なお、本発明は下記に限定されるものではない。
In contrast, modified polysilazane of the present invention is characterized by having a ratio [(SiH 3) :( SiH + SiH 2)] of the sum of SiH 3 and SiH and SiH 2 in a specific range. By using the modified polysilazane of the present invention, a gas barrier film excellent in storage stability, particularly storage stability under high temperature and high humidity can be provided. Here, the mechanism for exerting the above-described effects by the configuration of the present invention is presumed as follows. The present invention is not limited to the following.
すなわち、通常使用されるポリシラザン(特にパーヒドロポリシラザン)は、末端に-SiH3基が多く存在するが、この-SiH3基が塗布から活性エネルギー線照射までの操作時に反応起点となり望ましくない反応が生じる。その結果、得られるガスバリア性フィルムでは、過酷な条件(特に高温高湿)下でのガスバリア性が低下してしまう。これに対して、本発明の変性ポリシラザンでは、この反応性の高い末端の-SiH3基を、SiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]が特定の範囲に入るように修飾する。ポリシラザン末端に存在する反応性の高い-SiH3基を修飾して、反応起点となる-SiH3基の存在量を減らすことにより、塗布から活性エネルギー線照射までの間に生じる望ましくない反応(大気中の水分や酸素との反応)を抑制して、所望とする改質反応(活性エネルギー線照射によるポリシラザンの酸化反応)を優先的にかつ効率的に行うことができる。したがって、本発明の変性ポリシラザンを用いることにより、ガスバリア性が高くかつ特に高温高湿下におけるガスバリア性の低下を抑制・防止した保存安定性(湿熱耐性)に優れるガスバリア性フィルムを作製できる。上記効果は、ポリシラザンの末端の-SiH3基を金属アルコキシドおよび/または金属キレート化合物、ならびに低分子シラザンおよび/または低分子シロキサンで修飾する際に、特に顕著に達成できる。
That is, normally used polysilazane (especially perhydropolysilazane) has many —SiH 3 groups at the end, and this —SiH 3 group becomes a reaction starting point during an operation from coating to active energy ray irradiation, and an undesirable reaction occurs. Arise. As a result, in the obtained gas barrier film, the gas barrier property under severe conditions (particularly high temperature and high humidity) is lowered. In contrast, in the modified polysilazane of the present invention, the highly reactive terminus of -SiH 3 group, the ratio of the sum of the SiH 3 and SiH and SiH 2 [(SiH 3) :( SiH + SiH 2)] is a specific To be in the range of By modifying the highly reactive —SiH 3 group present at the end of the polysilazane to reduce the abundance of the —SiH 3 group serving as a reaction starting point, an undesirable reaction (atmosphere) generated from coating to active energy ray irradiation It is possible to preferentially and efficiently carry out a desired reforming reaction (oxidation reaction of polysilazane by irradiation with active energy rays) while suppressing the reaction with moisture and oxygen therein. Therefore, by using the modified polysilazane of the present invention, it is possible to produce a gas barrier film having high gas barrier properties and excellent storage stability (wet heat resistance) that suppresses / prevents deterioration of gas barrier properties particularly under high temperature and high humidity. The above effect can be achieved particularly remarkably when the terminal —SiH 3 group of polysilazane is modified with a metal alkoxide and / or a metal chelate compound, and a low molecular silazane and / or a low molecular siloxane.
以下、本発明の好ましい実施形態を説明する。なお、本発明は、以下の実施の形態のみには限定されない。
Hereinafter, preferred embodiments of the present invention will be described. In addition, this invention is not limited only to the following embodiment.
また、本明細書において、範囲を示す「X~Y」は「X以上Y以下」を意味する。また、特記しない限り、操作および物性等の測定は室温(20~25℃)/相対湿度40~50%の条件で測定する。
In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.
<変性ポリシラザン>
変性ポリシラザンは、SiHおよび/またはSiH2ならびにSiH3を有し、この際の、29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)](以下、単に「SiH3比」とも称する)が1:10~30(モル比)である。変性ポリシラザン末端に存在する-SiH3基は、大気中の水分や酸素と反応しやすい。このため、末端の-SiH3基が多数存在する場合には、活性エネルギー照射前に大気中の水分や酸素との望ましくない反応が生じ、その結果、ガスバリア性、特に過酷な条件(特に高温高湿)下でのガスバリア性を低下させてしまう。このため、活性エネルギー線照射前の水分を減らす必要があるが、実験レベルでは水分調整は容易であるが、大量生産のレベルでは水分調整が困難である場合がある。これに対して、変性ポリシラザン末端に存在する-SiH3基の割合を29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を1:10以下にすることによって、反応性の高い-SiH3基数が少ないので、上記したような望ましくない反応自体を抑制・防止して、酸化反応を優先的に進行させることが可能である。ゆえに、本発明の変性ポリシラザンを用いて形成されるバリア層、ゆえにガスバリア性フィルムは、ガスバリア性、特に過酷な条件(特に高温高湿)下でのガスバリア性に優れる。 <Modified polysilazane>
The modified polysilazane has SiH and / or SiH 2 and SiH 3 , and the ratio of SiH 3 measured by 29 Si-NMR to the sum of SiH and SiH 2 [(SiH 3 ) :( SiH + SiH 2 ]] (Hereinafter also simply referred to as “SiH 3 ratio”) is 1:10 to 30 (molar ratio). The —SiH 3 group present at the end of the modified polysilazane tends to react with moisture and oxygen in the atmosphere. For this reason, when a large number of terminal —SiH 3 groups are present, an undesirable reaction with moisture and oxygen in the atmosphere occurs before irradiation with active energy, resulting in gas barrier properties, particularly severe conditions (especially high temperature and high temperature). Gas barrier properties under low humidity). For this reason, it is necessary to reduce the moisture before irradiation with active energy rays, but moisture adjustment is easy at the experimental level, but moisture adjustment may be difficult at the mass production level. In contrast, the ratio of —SiH 3 groups present at the end of the modified polysilazane is the ratio [(SiH 3 ) :( SiH + SiH 2 )] of SiH 3 measured by 29 Si-NMR and the sum of SiH and SiH 2 . By setting it to 1:10 or less, since the number of highly reactive —SiH 3 groups is small, it is possible to suppress / prevent the undesirable reaction itself as described above and to advance the oxidation reaction preferentially. Therefore, the barrier layer formed using the modified polysilazane of the present invention, and hence the gas barrier film, is excellent in gas barrier properties, particularly gas barrier properties under severe conditions (especially high temperature and high humidity).
変性ポリシラザンは、SiHおよび/またはSiH2ならびにSiH3を有し、この際の、29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)](以下、単に「SiH3比」とも称する)が1:10~30(モル比)である。変性ポリシラザン末端に存在する-SiH3基は、大気中の水分や酸素と反応しやすい。このため、末端の-SiH3基が多数存在する場合には、活性エネルギー照射前に大気中の水分や酸素との望ましくない反応が生じ、その結果、ガスバリア性、特に過酷な条件(特に高温高湿)下でのガスバリア性を低下させてしまう。このため、活性エネルギー線照射前の水分を減らす必要があるが、実験レベルでは水分調整は容易であるが、大量生産のレベルでは水分調整が困難である場合がある。これに対して、変性ポリシラザン末端に存在する-SiH3基の割合を29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を1:10以下にすることによって、反応性の高い-SiH3基数が少ないので、上記したような望ましくない反応自体を抑制・防止して、酸化反応を優先的に進行させることが可能である。ゆえに、本発明の変性ポリシラザンを用いて形成されるバリア層、ゆえにガスバリア性フィルムは、ガスバリア性、特に過酷な条件(特に高温高湿)下でのガスバリア性に優れる。 <Modified polysilazane>
The modified polysilazane has SiH and / or SiH 2 and SiH 3 , and the ratio of SiH 3 measured by 29 Si-NMR to the sum of SiH and SiH 2 [(SiH 3 ) :( SiH + SiH 2 ]] (Hereinafter also simply referred to as “SiH 3 ratio”) is 1:10 to 30 (molar ratio). The —SiH 3 group present at the end of the modified polysilazane tends to react with moisture and oxygen in the atmosphere. For this reason, when a large number of terminal —SiH 3 groups are present, an undesirable reaction with moisture and oxygen in the atmosphere occurs before irradiation with active energy, resulting in gas barrier properties, particularly severe conditions (especially high temperature and high temperature). Gas barrier properties under low humidity). For this reason, it is necessary to reduce the moisture before irradiation with active energy rays, but moisture adjustment is easy at the experimental level, but moisture adjustment may be difficult at the mass production level. In contrast, the ratio of —SiH 3 groups present at the end of the modified polysilazane is the ratio [(SiH 3 ) :( SiH + SiH 2 )] of SiH 3 measured by 29 Si-NMR and the sum of SiH and SiH 2 . By setting it to 1:10 or less, since the number of highly reactive —SiH 3 groups is small, it is possible to suppress / prevent the undesirable reaction itself as described above and to advance the oxidation reaction preferentially. Therefore, the barrier layer formed using the modified polysilazane of the present invention, and hence the gas barrier film, is excellent in gas barrier properties, particularly gas barrier properties under severe conditions (especially high temperature and high humidity).
本明細書において、SiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)](SiH3比)は、29Si-NMRで測定され、具体的には、実施例に記載される方法に従って測定される値を意味する。
In the present specification, the ratio [(SiH 3 ) :( SiH + SiH 2 )] (SiH 3 ratio) between SiH 3 and the sum of SiH and SiH 2 is measured by 29 Si-NMR, specifically Means a value measured according to the method described in.
変性ポリシラザンのSiH3比は、1:10~30である。ここで、上記SiH3比が上限を超えると、反応性の高い末端(SiH3)が過度に多く存在するため、活性エネルギー線照射前に大気中の水分と反応して、ガスバリア性、特に高温高湿条件下でのガスバリア性が低下する。一方、上記SiH3比が下限を下回ると、ポリシラザンの構造自体が不安定になり、低分子成分が増えたり、液停滞や分子間の粗大凝集化を引き起こしたりするため、やはりガスバリア性、特に高温高湿条件下でのガスバリア性が低下する。高温高湿条件下でのガスバリア性のより向上効果などを考慮すると、変性ポリシラザンのSiH3比は、1:12~28であることが好ましく、1:15~25であることが好ましく、1:18~24であることがより好ましい。
The SiH 3 ratio of the modified polysilazane is 1: 10-30. Here, if the SiH 3 ratio exceeds the upper limit, excessively high reactive ends (SiH 3 ) are present, and thus react with moisture in the atmosphere before irradiation with active energy rays, and gas barrier properties, particularly high temperatures. Gas barrier properties under high humidity conditions are reduced. On the other hand, if the SiH 3 ratio is below the lower limit, the polysilazane structure itself becomes unstable, resulting in an increase in low molecular components, liquid stagnation and coarse aggregation between molecules. Gas barrier properties under high humidity conditions are reduced. Considering the effect of improving the gas barrier property under high temperature and high humidity conditions, the SiH 3 ratio of the modified polysilazane is preferably 1:12 to 28, preferably 1:15 to 25, and 1: More preferably, it is 18-24.
ここで、変性ポリシラザンは、上記したようなSiH3比を有するポリシラザンが製造できれば、いずれの方法によって製造されてもよいが、好ましくは下記に詳述する方法が使用できる。ポリシラザンを、低分子シラザン、低分子シロキサン、金属アルコキシド化合物および金属キレート化合物からなる群より選択される少なくとも一種と反応させて、ポリシラザン中のSiH3基の反応性を下げるようにSiH3基を修飾することが好ましく、ポリシラザンを、低分子シラザンおよび/または低分子シロキサン、ならびに金属アルコキシド化合物および/または金属キレート化合物と反応させて、ポリシラザン中のSiH3基の反応性を下げるようにSiH3基を修飾することがより好ましい。ここで、ポリシラザンは、ケイ素原子、水素原子および窒素原子を有する。すなわち、本発明の変性ポリシラザンは、(a)ケイ素原子、水素原子および窒素原子を含むポリシラザン(以下、単に「原料ポリシラザン」とも称する)を、(b)低分子シラザンおよび低分子シロキサンの少なくとも一方(以下、単に「低分子シラザン/シロキサン」とも称する)、ならびに(c)金属アルコキシド化合物および金属キレート化合物(以下、単に「金属アルコキシド/キレート化合物」とも称する)の少なくとも一方と反応させることによって得られることが好ましい。(b)低分子シラザン/シロキサン、および(c)金属アルコキシド/キレート化合物は、原料ポリシラザン中の-SiH3基との反応性が高いため、原料ポリシラザン中の末端-SiH3基をより効率的に修飾できる。また、(c)金属アルコキシド/キレート化合物は、(b)低分子シラザン/シロキサンに比して、活性エネルギー線照射によるポリシラザンの酸化反応を促進するものの、大気中の水や酸素との反応性が高い。このため、ポリシラザンの末端の反応点(-SiH3基)を所望の酸化反応促進効果を奏する量の(c)金属アルコキシド/キレート化合物で修飾し、残り(未反応)の反応点(-SiH3基)を(b)低分子シラザン/シロキサンで修飾することが好ましい。すなわち、本発明の変性ポリシラザンは、(a)ケイ素原子、水素原子および窒素原子を含むポリシラザンを、(c)金属アルコキシド化合物および金属キレート化合物の少なくとも一方と反応させた後、(b)低分子シラザンおよび低分子シロキサンの少なくとも一方と反応させることによって得られることがより好ましい。これにより、大気中の水分や酸素との反応(塗布から活性エネルギー線照射までの間の望ましくない反応)を抑制・防止しつつ、ポリシラザンの酸化反応(改質処理)をより効率よく進行することができる。
Here, the modified polysilazane may be produced by any method as long as the polysilazane having the SiH 3 ratio as described above can be produced, but the method described in detail below can be preferably used. The polysilazane is reacted with at least one selected from the group consisting of low-molecular silazanes, low-molecular siloxanes, metal alkoxide compounds and metal chelate compounds to modify the SiH 3 group so as to reduce the reactivity of the SiH 3 group in the polysilazane. it is preferable to, polysilazane, low molecular silazanes and / or low-molecular-weight siloxane, and reacted with the metal alkoxide compound and / or a metal chelate compound, a SiH 3 group to lower the reactivity of the SiH 3 groups in the polysilazane It is more preferable to modify. Here, polysilazane has a silicon atom, a hydrogen atom, and a nitrogen atom. That is, the modified polysilazane of the present invention comprises (a) a polysilazane containing a silicon atom, a hydrogen atom and a nitrogen atom (hereinafter also simply referred to as “raw material polysilazane”), and (b) at least one of a low molecular silazane and a low molecular siloxane ( Hereinafter, obtained simply by reacting with at least one of “low molecular silazane / siloxane” and (c) metal alkoxide compound and metal chelate compound (hereinafter also simply referred to as “metal alkoxide / chelate compound”). Is preferred. (B) low molecular silazane / siloxane and (c) a metal alkoxide / chelate compound has a high reactivity with -SiH 3 group in the raw material polysilazane, the terminal -SiH 3 group in the raw material polysilazane more efficiently Can be modified. In addition, (c) metal alkoxide / chelate compound promotes the oxidation reaction of polysilazane by irradiation with active energy rays as compared with (b) low molecular weight silazane / siloxane, but has reactivity with water and oxygen in the atmosphere. high. For this reason, the reaction point (-SiH 3 group) at the terminal of polysilazane is modified with an amount of (c) metal alkoxide / chelate compound that exhibits the desired effect of promoting oxidation reaction, and the remaining (unreacted) reaction point (-SiH 3). The group) is preferably modified with (b) low molecular silazane / siloxane. That is, the modified polysilazane of the present invention comprises: (a) a polysilazane containing a silicon atom, a hydrogen atom and a nitrogen atom is reacted with at least one of (c) a metal alkoxide compound and a metal chelate compound; And more preferably obtained by reacting with at least one of low molecular siloxanes. As a result, the polysilazane oxidation reaction (reforming treatment) proceeds more efficiently while suppressing / preventing reaction with moisture and oxygen in the atmosphere (undesirable reaction between application and irradiation of active energy rays). Can do.
本明細書において、「SiH3基を修飾する」、「SiH3基の修飾」、「ポリシラザンと低分子シラザン、低分子シロキサン、金属アルコキシド化合物、金属キレート化合物との反応」とは、SiH3基の反応性(特に水との反応性)を低下させるための修飾/反応を意味し、SiH3基の少なくとも1つの水素原子を他の化合物(例えば、低分子シラザン、低分子シロキサン、金属アルコキシド化合物、金属キレート化合物)で置換することに限定されず、末端のSiに上記他の化合物が配位することをも包含するが、好ましくはSiH3基の少なくとも1つの水素原子を他の化合物(例えば、低分子シラザン、低分子シロキサン、金属アルコキシド化合物、金属キレート化合物)で置換する。
As used herein, "modifying the SiH 3 group,""modification SiH 3 group," a "polysilazane and the low molecular silazane, low molecular siloxanes, metal alkoxide compounds, reaction of the metal chelate compound", SiH 3 group Means a modification / reaction to reduce the reactivity (especially the reactivity with water), and at least one hydrogen atom of the SiH 3 group is replaced with another compound (eg, low molecular silazane, low molecular siloxane, metal alkoxide compound) , A metal chelate compound), and also includes coordination of the above-mentioned other compound to terminal Si, but preferably, at least one hydrogen atom of SiH 3 group is replaced with another compound (for example, , Low molecular silazane, low molecular siloxane, metal alkoxide compound, metal chelate compound).
以下、本発明の変性ポリシラザンの製造方法の好ましい形態を説明するが、本発明は下記形態に限定されるものではない。
Hereinafter, although the preferable form of the manufacturing method of the modified polysilazane of this invention is demonstrated, this invention is not limited to the following form.
(a)ポリシラザンは、ケイ素原子、水素原子及び窒素原子を少なくとも含み、ケイ素-窒素結合を有するポリマーである。具体的には、その構造内にSi-N、Si-H、N-H等の結合を有するSiO2、Si3N4、および両方の中間固溶体SiOxNy等のセラミック前駆体無機ポリマーである。
(A) Polysilazane is a polymer containing at least a silicon atom, a hydrogen atom, and a nitrogen atom and having a silicon-nitrogen bond. Specifically, the ceramic precursor inorganic polymer such as SiO 2 , Si 3 N 4 , and both intermediate solid solutions SiO x N y having bonds such as Si—N, Si—H, and N—H in the structure. is there.
本発明に用いられるポリシラザンの例としては、特に限定されず、公知のものが挙げられる。例えば、特開2013-022799号公報の段落「0043」~「0058」や特開2013-226758号公報の段落「0038」~「0056」などに開示されているものが適宜採用される。これらの中では、パーヒドロポリシラザンが最も好ましく用いられる。
Examples of polysilazane used in the present invention are not particularly limited and include known ones. For example, those disclosed in paragraphs “0043” to “0058” of JP2013-022799A, paragraphs “0038” to “0056” of JP2013-226758A are appropriately adopted. Of these, perhydropolysilazane is most preferably used.
また、ポリシラザンは、有機溶媒に溶解した溶液状態で市販されており、市販品をそのまま第1のバリア層形成用塗布液として使用することができる。ポリシラザン溶液の市販品としては、AZエレクトロニックマテリアルズ株式会社製のNN120-10、NN120-20、NAX120-20、NN110、NN310、NN320、NL110A、NL120A、NL120-20、NL150A、NP110、NP140、SP140等が挙げられる。
Polysilazane is commercially available in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as the first barrier layer forming coating solution. Examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. Is mentioned.
本発明で使用できるポリシラザンの別の例としては、以下に制限されないが、例えば、上記ポリシラザンにケイ素アルコキシドを反応させて得られるケイ素アルコキシド付加ポリシラザン(特開平5-238827号公報)、グリシドールを反応させて得られるグリシドール付加ポリシラザン(特開平6-122852号公報)、アルコールを反応させて得られるアルコール付加ポリシラザン(特開平6-240208号公報)、金属カルボン酸塩を反応させて得られる金属カルボン酸塩付加ポリシラザン(特開平6-299118号公報)、金属を含むアセチルアセトナート錯体を反応させて得られるアセチルアセトナート錯体付加ポリシラザン(特開平6-306329号公報)、金属微粒子を添加して得られる金属微粒子添加ポリシラザン(特開平7-196986号公報)等の、低温でセラミック化するポリシラザンが挙げられる。
Other examples of the polysilazane that can be used in the present invention include, but are not limited to, for example, a silicon alkoxide-added polysilazane obtained by reacting the polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-23827), and a glycidol reaction. Glycidol-added polysilazane (Japanese Patent Laid-Open No. 6-122852) obtained by reaction, alcohol-added polysilazane obtained by reacting alcohol (Japanese Patent Laid-Open No. 6-240208), metal carboxylate obtained by reacting metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal obtained by adding metal fine particles Fine particle added policy Zhang such (JP-A-7-196986), and a polysilazane ceramic at low temperatures.
(b)低分子シラザンおよび低分子シロキサンは、特に制限されないが、好ましくは、低分子シラザンが、下記一般式(I):
(B) The low molecular silazane and the low molecular siloxane are not particularly limited, but preferably, the low molecular silazane is represented by the following general formula (I):
上記一般式(I)において、X1、X2およびX3は、それぞれ独立して、水素原子、置換または非置換の、アルキル基、アリール基、ビニル基または(トリアルコキシシリル)アルキル基であり;aは、1~10の整数である、
で表される環状低分子シラザン(I)、下記一般式(II): In the above general formula (I), X 1 , X 2 and X 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. A is an integer from 1 to 10,
A cyclic low-molecular silazane (I) represented by the following general formula (II):
で表される環状低分子シラザン(I)、下記一般式(II): In the above general formula (I), X 1 , X 2 and X 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. A is an integer from 1 to 10,
A cyclic low-molecular silazane (I) represented by the following general formula (II):
上記一般式(II)において、X4は、水素原子、置換または非置換の、アルキル基、アリール基、ビニル基または(トリアルコキシシリル)アルキル基であり;X5~X10は、それぞれ独立して、水素原子、置換または非置換の、アルキル基、アリール基、ビニル基または(トリアルコキシシリル)アルキル基である、
で表される鎖状低分子シラザン(II)、もしくは下記一般式(III): In the above general formula (II), X 4 is a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group; X 5 to X 10 are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group,
A linear low molecular weight silazane (II) represented by the following general formula (III):
で表される鎖状低分子シラザン(II)、もしくは下記一般式(III): In the above general formula (II), X 4 is a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group; X 5 to X 10 are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group,
A linear low molecular weight silazane (II) represented by the following general formula (III):
上記一般式(III)において、X11およびX12は、それぞれ独立して、水素原子、置換または非置換の、アルキル基、アリール基、ビニル基または(トリアルコキシシリル)アルキル基であり;X13~X16は、それぞれ独立して、水素原子、置換または非置換の、アルキル基、アリール基、ビニル基または(トリアルコキシシリル)アルキル基である、
で表される鎖状低分子シラザン(III)である、または
低分子シロキサンが、下記一般式(IV): In the general formula (III), X 11 and X 12 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group; X 13 X 16 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group.
Or a low molecular weight siloxane represented by the following general formula (IV):
で表される鎖状低分子シラザン(III)である、または
低分子シロキサンが、下記一般式(IV): In the general formula (III), X 11 and X 12 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group; X 13 X 16 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group.
Or a low molecular weight siloxane represented by the following general formula (IV):
上記一般式(IV)において、Y1およびY2は、それぞれ独立して、水素原子、置換または非置換の、アルキル基、アリール基、ビニル基または(トリアルコキシシリル)アルキル基であり;bは、1~10の整数である、
で表される環状低分子シロキサン(IV)、もしくは下記一般式(V): In the general formula (IV), Y 1 and Y 2 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group; An integer from 1 to 10,
Cyclic low molecular siloxane (IV) represented by the following general formula (V):
で表される環状低分子シロキサン(IV)、もしくは下記一般式(V): In the general formula (IV), Y 1 and Y 2 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group; An integer from 1 to 10,
Cyclic low molecular siloxane (IV) represented by the following general formula (V):
上記一般式(V)において、Y3~Y14は、それぞれ独立して、水素原子、置換または非置換の、アルキル基、アリール基、ビニル基または(トリアルコキシシリル)アルキル基である、
で表される環状低分子シロキサン(V)である。 In the general formula (V), Y 3 to Y 14 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group.
It is cyclic low molecular siloxane (V) represented by these.
で表される環状低分子シロキサン(V)である。 In the general formula (V), Y 3 to Y 14 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group.
It is cyclic low molecular siloxane (V) represented by these.
上記一般式(I)において、X1、X2およびX3は、水素原子、置換または非置換の、アルキル基、アルコキシ基、ハロゲン原子、アリール基、ビニル基または(トリアルコキシシリル)アルキル基である。ここで、X1、X2およびX3は、それぞれ、同じであってもあるいは異なるものであってもよい。また、上記一般式(I)中の置換または非置換の、アルキル基、アリール基、ビニル基または(トリアルコキシシリル)アルキル基は、上記一般式(1)の定義と同様であるため、説明を省略する。アルコキシ基としては、炭素原子数1~8の直鎖または分岐鎖のアルコキシ基が挙げられる。より具体的には、メトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、sec-ブトキシ基、tert-ブトキシ基、n-ペンチルオキシ基、イソペンチルオキシ基、ネオペンチルオキシ基、n-ヘキシルオキシ基、n-ヘプチルオキシ基、n-オクチルオキシ基、2-エチルヘキシルオキシ基などがある。また、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子がある。これらのうち、X1、X2およびX3は、水素原子、炭素数1~4の直鎖または分岐鎖のアルキル基、炭素数1~4の直鎖または分岐鎖のアルコキシ基、またはハロゲン原子であることが好ましく、水素原子、メチル基、メトキシ基であることがより好ましい。また、X1、X2およびX3の組み合わせは、特に制限されないが、X1及びX2がそれぞれメチル基及び水素原子でかつX3がメチル基である;X1及びX2がメチル基でかつX3が水素原子であることが好ましい。
In the general formula (I), X 1 , X 2 and X 3 are a hydrogen atom, a substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group. is there. Here, X 1 , X 2 and X 3 may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (I) is the same as the definition in the general formula (1). Omitted. Examples of the alkoxy group include linear or branched alkoxy groups having 1 to 8 carbon atoms. More specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, There are a neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group and the like. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, X 1 , X 2 and X 3 are a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a halogen atom It is preferable that they are a hydrogen atom, a methyl group, and a methoxy group. The combination of X 1 , X 2 and X 3 is not particularly limited, but X 1 and X 2 are a methyl group and a hydrogen atom, respectively, and X 3 is a methyl group; X 1 and X 2 are a methyl group X 3 is preferably a hydrogen atom.
また、上記一般式(I)中、aは、1~10、好ましくは3~6の整数である。
In the general formula (I), a is an integer of 1 to 10, preferably 3 to 6.
したがって、上記一般式(I)の環状低分子シラザン(I)の好ましい例としては、下記がある。
Therefore, preferred examples of the cyclic low-molecular silazane (I) represented by the general formula (I) include the following.
上記一般式(II)において、X4は、水素原子、置換または非置換の、アルキル基、アルコキシ基、ハロゲン原子、アリール基、ビニル基または(トリアルコキシシリル)アルキル基である。また、X5~X10は、水素原子、置換または非置換の、アルキル基、アリール基、ビニル基または(トリアルコキシシリル)アルキル基である。ここで、X4、X5~X10は、それぞれ、同じであってもあるいは異なるものであってもよい。また、上記一般式(II)中の置換または非置換の、アルキル基、アルコキシ基、ハロゲン原子、アリール基、ビニル基または(トリアルコキシシリル)アルキル基は、上記一般式(1)または(I)の定義と同様であるため、説明を省略する。これらのうち、X4は、水素原子、炭素原子数1~3のアルキル基、ビニル基、アルコキシ基であることが好ましく、水素原子であることがより好ましい。また、X5~X10は、水素原子、炭素原子数1~3のアルキル基、ビニル基、アルコキシ基であることが好ましく、水素原子、メチル基、ビニル基であることがより好ましい。ここで、前記一般式(II)において、X4、またはX5~X10の少なくとも1つが水素原子であることがさらに好ましい。
In the general formula (II), X 4 is a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, an aryl group, a vinyl group, or a (trialkoxysilyl) alkyl group. X 5 to X 10 are a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. Here, X 4 and X 5 to X 10 may be the same or different. Further, the substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (II) is represented by the general formula (1) or (I). Since the definition is the same as that in FIG. Among these, X 4 is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a vinyl group, or an alkoxy group, and more preferably a hydrogen atom. X 5 to X 10 are preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a vinyl group or an alkoxy group, and more preferably a hydrogen atom, a methyl group or a vinyl group. Here, in the general formula (II), it is more preferable that at least one of X 4 or X 5 to X 10 is a hydrogen atom.
したがって、上記一般式(II)の鎖状低分子シラザン(II)の好ましい例としては、下記がある。
Therefore, preferred examples of the chain low-molecular silazane (II) represented by the general formula (II) include the following.
上記一般式(III)において、X11およびX12は、水素原子、置換または非置換の、アルキル基、アルコキシ基、ハロゲン原子、アリール基、ビニル基または(トリアルコキシシリル)アルキル基である。また、X13~X16は、水素原子、置換または非置換の、アルキル基、アルコキシ基、ハロゲン原子、アリール基、ビニル基または(トリアルコキシシリル)アルキル基である。ここで、X11およびX12、X13~X16は、それぞれ、同じであってもあるいは異なるものであってもよい。また、上記一般式(III)中の置換または非置換の、アルキル基、アルコキシ基、ハロゲン原子、アリール基、ビニル基または(トリアルコキシシリル)アルキル基は、上記一般式(1)または(I)の定義と同様であるため、説明を省略する。これらのうち、X11およびX12は、水素原子、炭素原子数1~3のアルキル基、ビニル基、アルコキシ基であることが好ましく、水素原子であることがより好ましい。また、X13~X16は、水素原子、炭素原子数1~5のアルキル基、ビニル基、アルコキシ基であることが好ましく、メチル基、t-ブチル基であることがより好ましい。
In the general formula (III), X 11 and X 12 are a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, an aryl group, a vinyl group, or a (trialkoxysilyl) alkyl group. X 13 to X 16 are a hydrogen atom, a substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group. Here, X 11 and X 12 , and X 13 to X 16 may be the same or different. The substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (III) is represented by the general formula (1) or (I). Since the definition is the same as that in FIG. Of these, X 11 and X 12 represents a hydrogen atom, an alkyl group, a vinyl group having 1 to 3 carbon atoms, preferably an alkoxy group, and more preferably a hydrogen atom. X 13 to X 16 are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a vinyl group or an alkoxy group, and more preferably a methyl group or a t-butyl group.
したがって、上記一般式(III)の鎖状低分子シラザン(III)の好ましい例としては、下記がある。
Therefore, preferred examples of the chain low-molecular silazane (III) represented by the general formula (III) include the following.
上記一般式(IV)において、Y1およびY2は、水素原子、置換または非置換の、アルキル基、アルコキシ基、ハロゲン原子、アリール基、ビニル基または(トリアルコキシシリル)アルキル基である。ここで、Y1およびY2は、それぞれ、同じであってもあるいは異なるものであってもよい。また、上記一般式(IV)中の置換または非置換の、アルキル基、アルコキシ基、ハロゲン原子、アリール基、ビニル基または(トリアルコキシシリル)アルキル基は、上記一般式(1)または(I)の定義と同様であるため、説明を省略する。これらのうち、Y1およびY2の一方は水素原子でありかつ他方は炭素原子数1~3のアルキル基、ビニル基、アルコキシ基であるまたはY1およびY2双方が炭素原子数1~3のアルキル基、ビニル基、アルコキシ基であることが好ましく、Y1およびY2の一方は水素原子でありかつ他方は炭素原子数1~3のアルキル基であるまたはY1およびY2双方が炭素原子数1~3のアルキル基であることがより好ましく、Y1およびY2の一方は水素原子でありかつ他方は炭素原子数1~3のアルキル基であるが特に好ましい。
In the general formula (IV), Y 1 and Y 2 are a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, an aryl group, a vinyl group, or a (trialkoxysilyl) alkyl group. Here, Y 1 and Y 2 may be the same or different. The substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (IV) is represented by the general formula (1) or (I). Since the definition is the same as that in FIG. Of these, one of Y 1 and Y 2 is a hydrogen atom and the other is an alkyl group having 1 to 3 carbon atoms, a vinyl group or an alkoxy group, or both Y 1 and Y 2 have 1 to 3 carbon atoms. In which one of Y 1 and Y 2 is a hydrogen atom and the other is an alkyl group having 1 to 3 carbon atoms, or both Y 1 and Y 2 are carbon. It is more preferably an alkyl group having 1 to 3 atoms, and one of Y 1 and Y 2 is a hydrogen atom and the other is particularly preferably an alkyl group having 1 to 3 carbon atoms.
また、上記一般式(IV)中、bは、1~10、好ましくは3~6の整数である。
In the general formula (IV), b is an integer of 1 to 10, preferably 3 to 6.
したがって、上記一般式(IV)の環状低分子シロキサン(IV)の好ましい例としては、下記がある。
Therefore, preferable examples of the cyclic low-molecular siloxane (IV) represented by the general formula (IV) include the following.
上記一般式(V)において、Y3~Y14は、水素原子、置換または非置換の、アルキル基、アルコキシ基、ハロゲン原子、アリール基、ビニル基または(トリアルコキシシリル)アルキル基である。ここで、Y3~Y14は、それぞれ、同じであってもあるいは異なるものであってもよい。また、上記一般式(V)中の置換または非置換の、アルキル基、アルコキシ基、ハロゲン原子、アリール基、ビニル基または(トリアルコキシシリル)アルキル基は、上記一般式(1)または(I)の定義と同様であるため、説明を省略する。これらのうち、Y3~Y14は、水素原子、炭素原子数1~3のアルキル基、ビニル基、アルコキシド基であることが好ましく、水素原子、炭素原子数1~3のアルキル基であることがより好ましい。
In the general formula (V), Y 3 to Y 14 are a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, an aryl group, a vinyl group, or a (trialkoxysilyl) alkyl group. Here, Y 3 to Y 14 may be the same or different. The substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (V) is represented by the general formula (1) or (I). Since the definition is the same as that in FIG. Among these, Y 3 to Y 14 are preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a vinyl group or an alkoxide group, and preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Is more preferable.
したがって、上記一般式(V)の環状低分子シロキサン(V)の好ましい例としては、下記がある。
Therefore, preferable examples of the cyclic low-molecular siloxane (V) represented by the general formula (V) include the following.
上記低分子シラザンおよび低分子シロキサンのうち、一般式(I)の環状低分子シラザン(I)、一般式(II)の鎖状低分子シラザン(II)、一般式(III)の鎖状低分子シラザン(III)及び一般式(IV)の環状低分子シロキサン(IV)が好ましく、一般式(I)の環状低分子シラザン(I)、一般式(II)の鎖状低分子シラザン(II)がより好ましく、化合物2、3であることが特に好ましい。
Of the above low molecular silazanes and low molecular siloxanes, cyclic low molecular silazanes (I) of general formula (I), linear low molecular silazanes (II) of general formula (II), and linear low molecules of general formula (III) Silazane (III) and cyclic low molecular siloxane (IV) of general formula (IV) are preferred, cyclic low molecular silazane (I) of general formula (I) and chain low molecular silazane (II) of general formula (II) are preferred. More preferably, compounds 2 and 3 are particularly preferable.
(c)金属アルコキシド化合物および金属キレート化合物は、高性能のバリア層を効率的に形成することができる。金属アルコキシド化合物および金属キレート化合物を構成する金属は、特に制限されない。例えば、金属アルコキシドおよび金属キレート化合物は、ベリリウム(Be)、ホウ素(B)、マグネシウム(Mg)、アルミニウム(Al)、ケイ素(Si)、カルシウム(Ca)、スカンジウム(Sc)、チタン(Ti)、バナジウム(V)、クロム(Cr)、マンガン(Mn)、鉄(Fe)、コバルト(Co)、ニッケル(Ni)、銅(Cu)、亜鉛(Zn)、ガリウム(Ga)、ゲルマニウム(Ge)、ストロンチウム(Sr)、イットリウム(Y)、ジルコニウム(Zr)、ニオブ(Nb)、モリブデン(Mo)、テクネチウム(Tc)、ルテニウム(Ru)、ロジウム(Rh)、パラジウム(Pd)、銀(Ag)、カドミウム(Cd)、インジウム(In)、スズ(Sn)、バリウム(Ba)、ランタン(La)、セリウム(Ce)、プラセオジム(Pr)、ネオジム(Nd)、プロメチウム(Pm)、サマリウム(Sm)、ユーロピウム(Eu)、ガドリニウム(Gd)、テルビウム(Tb)、ジスプロジウム(Dy)、ホルミウム(Ho)、エルビウム(Er)、ツリウム(Tm)、イッテルビウム(Yb)、ルテチウム(Lu)、ハフニウム(Hf)、タンタル(Ta)、タングステン(W)、レニウム(Re)、オスミウム(Os)、イリジウム(Ir)、白金(Pt)、金(Au)、水銀(Hg)、タリウム(Tl)、鉛(Pb)、ラジウム(Ra)等の長周期型周期表の第2~14族元素を金属として含む金属アルコキシドおよび金属キレート化合物であることが好ましい。これらの金属は、ポリシラザン中の窒素原子と配位結合を形成しやすい。また、ルイス酸性が高い点で、アルミニウム(Al)、チタン(Ti)、鉄(Fe)、または銅(Cu)を金属として含む金属アルコキシドおよび金属キレート化合物であることがより好ましい。
(C) The metal alkoxide compound and the metal chelate compound can efficiently form a high-performance barrier layer. The metal constituting the metal alkoxide compound and the metal chelate compound is not particularly limited. For example, metal alkoxides and metal chelate compounds are beryllium (Be), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), calcium (Ca), scandium (Sc), titanium (Ti), Vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), Strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), Cadmium (Cd), Indium (In), Tin (Sn), Barium (Ba), Lanthanum (La), Cerium (C ), Praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprodium (Dy), holmium (Ho), erbium ( Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum ( Metal alkoxides and metal chelates containing as a metal Group 2-14 elements of the long-period periodic table such as Pt), gold (Au), mercury (Hg), thallium (Tl), lead (Pb), radium (Ra) A compound is preferred. These metals tend to form coordinate bonds with nitrogen atoms in polysilazane. Further, metal alkoxides and metal chelate compounds containing aluminum (Al), titanium (Ti), iron (Fe), or copper (Cu) as a metal are more preferable in terms of high Lewis acidity.
また、金属アルコキシド化合物は、特に制限されないが、高性能のバリア層をより効率的に形成することができる点で、アルミニウムアルコキシドであることが好ましい。
The metal alkoxide compound is not particularly limited, but aluminum alkoxide is preferable from the viewpoint that a high-performance barrier layer can be formed more efficiently.
金属アルコキシド化合物のより具体的な例としては、例えば、ホウ酸トリメチル、ホウ酸トリエチル、ホウ酸トリn-プロピル、ホウ酸トリイソプロピル、ホウ酸トリn-ブチル、ホウ酸トリtert-ブチル、マグネシウムエトキシド、マグネシウムエトキシエトキシド、マグネシウムメトキシエトキシド、アルミニウムトリメトキシド、アルミニウムトリエトキシド、アルミニウムトリn-プロポキシド、アルミニウムトリイソプロポキシド、アルミニウムトリn-ブトキシド、アルミニウムトリsec-ブトキシド、アルミニウムトリtert-ブトキシド、アセトアルコキシアルミニウムジイソプロピレート、アルミニウムジイソプロピレートモノsec-ブチレート、アルミニウムオキサイドイソプロポキサイドトリマー、アルミニウムオキサイドオクチレートトリマー、カルシウムメトキシド、カルシウムエトキシド、カルシウムイソプロポキシド、チタンテトラメトキシド、チタンテトラエトキシド、チタンテトラノルマルプロポキシド、チタンテトライソプロポキシド、チタンテトラノルマルブトキシド、チタンテトライソブトキシド、チタンジイソプロポキシジノルマルブトキシド、チタンジターシャリーブトキシジイソプロポキシド、チタンテトラtert-ブトキシド、チタンテトライソオクチロキシド、チタンテトラステアリルアルコキシド、バナジウムトリイソブトキシドオキシド、クロムn-プロポキシド、クロムイソプロポキシド、マンガンメトキシド、鉄メトキシド、鉄エトキシド、鉄n-プロポキシド、鉄イソプロポキシド、コバルトイソプロポキシド、銅メトキシド、銅エトキシド、銅イソプロポキシド、亜鉛エトキシド、亜鉛エトキシエトキシド、亜鉛メトキシエトキシド、ガリウムメトキシド、ガリウムエトキシド、ガリウムイソプロポキシド、ゲルマニウムメトキシド、ゲルマニウムエトキシド、ゲルマニウムイソプロポキシド、ゲルマニウムn-ブトキシド、ゲルマニウムtert-ブトキシド、エチルトリエトキシゲルマニウム、ストロンチウムイソプロポキシド、イットリウムn-プロポキシド、イットリウムイソプロポキシド、ジルコニウムエトキシド、ジルコニウムn-プロポキシド、ジルコニウムイソプロポキシド、ジルコニウムブトキシド、ジルコニウムtert-ブトキシド、ニオブエトキシド、ニオブn-ブトキシド、ニオブtert-ブトキシド、モリブデンエトキシド、インジウムイソプロポキシド、インジウムイソプロポキシド、インジウムn-ブトキシド、インジウムメトキシエトキシド、スズn-ブトキシド、スズtert-ブトキシド、バリウムジイソプロポキシド、バリウムtert-ブトキシド、ランタンイソプロポキシド、ランタンメトキシエトキシド、セリウムn-ブトキシド、セリウムtert-ブトキシド、プラセオジムメトキシエトキシド、ネオジムメトキシエトキシド、サマリウムイソプロポキシド、ハフニウムエトキシド、ハフニウムn-ブトキシド、ハフニウムtert-ブトキシド、タンタルメトキシド、タンタルエトキシド、タンタルn-ブトキシド、タンタルブトキシド、タングステンエトキシド、タリウムエトキシド、および下記構造を有する化合物などが挙げられる。
More specific examples of the metal alkoxide compound include, for example, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-tert-butyl borate, magnesium ethoxy Magnesium ethoxy ethoxide, magnesium methoxy ethoxide, aluminum trimethoxide, aluminum triethoxide, aluminum tri n-propoxide, aluminum triisopropoxide, aluminum tri n-butoxide, aluminum tri sec-butoxide, aluminum tri tert -Butoxide, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monosec-butyrate, aluminum oxide isopropoxide trimer, al Nitric oxide octylate trimer, calcium methoxide, calcium ethoxide, calcium isopropoxide, titanium tetramethoxide, titanium tetraethoxide, titanium tetranormal propoxide, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetraisobutoxide , Titanium diisopropoxy dinormal butoxide, titanium ditertiary butoxy diisopropoxide, titanium tetra tert-butoxide, titanium tetraisooctyloxide, titanium tetrastearyl alkoxide, vanadium triisobutoxide oxide, chromium n-propoxide, chromium iso Propoxide, Manganese methoxide, Iron methoxide, Iron ethoxide, Iron n-propoxide, Iron isopropoxide, Cobalt isop Poxide, copper methoxide, copper ethoxide, copper isopropoxide, zinc ethoxide, zinc ethoxy ethoxide, zinc methoxy ethoxide, gallium methoxide, gallium ethoxide, gallium isopropoxide, germanium methoxide, germanium ethoxide, germanium isopropoxide Germanium n-butoxide, germanium tert-butoxide, ethyltriethoxygermanium, strontium isopropoxide, yttrium n-propoxide, yttrium isopropoxide, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium butoxide , Zirconium tert-butoxide, niobium ethoxide, niobium n-butoxide, niobium tert-butoxide, molybdenum Budene ethoxide, indium isopropoxide, indium isopropoxide, indium n-butoxide, indium methoxyethoxide, tin n-butoxide, tin tert-butoxide, barium diisopropoxide, barium tert-butoxide, lanthanum isopropoxide, lanthanum methoxy Ethoxide, cerium n-butoxide, cerium tert-butoxide, praseodymium methoxyethoxide, neodymium methoxyethoxide, samarium isopropoxide, hafnium ethoxide, hafnium n-butoxide, hafnium tert-butoxide, tantalum methoxide, tantalum ethoxide, Tantalum n-butoxide, tantalum butoxide, tungsten ethoxide, thallium ethoxide, and compounds having the following structure Etc., and the like.
また、金属アルコキシド化合物として、シルセスキオキサンも用いることができる。
Silsesquioxane can also be used as the metal alkoxide compound.
シルセスキオキサン(Silsesquioxane)は、主鎖骨格がSi-O結合からなるシロキサン系の化合物であり、Tレジンとも呼ばれるもので、通常のシリカが一般式〔SiO2〕で表されるのに対し、シルセスキオキサン(ポリシルセスキオキサンとも称する)は一般式〔RSiO1.5〕で表される化合物である。通常はテトラエトキシシランに代表されるテトラアルコキシシラン(Si(OR’)4)の1つのアルコキシ基をアルキル基またはアリール基に置き換えた(RSi(OR’)3)化合物の加水分解-重縮合で合成されるポリシロキサンであり、分子配列の形状として、代表的には無定形、ラダー状、かご状(完全縮合ケージ状)がある。
Silsesquioxane is a siloxane-based compound whose main chain skeleton is composed of Si—O bonds, and is also called T-resin, whereas ordinary silica is represented by the general formula [SiO 2 ]. Silsesquioxane (also referred to as polysilsesquioxane) is a compound represented by the general formula [RSiO 1.5 ]. Usually, by hydrolysis-polycondensation of a (RSi (OR ') 3 ) compound in which one alkoxy group of tetraalkoxysilane (Si (OR') 4 ) represented by tetraethoxysilane is replaced with an alkyl group or an aryl group. The polysiloxane to be synthesized, and the molecular arrangement is typically amorphous, ladder-like, or cage-like (fully condensed cage-like).
シルセスキオキサンは、合成されてもあるいは市販品であってもよい。後者の具体例としては、X-40-2308、X-40-9238、X-40-9225、X-40-9227、x-40-9246、KR-500、KR-510(いずれも、信越化学社製)、SR2400、SR2402、SR2405、FOX14(パーヒドロシルセルセスキオキサン)(いずれも、東レ・ダウコーニング社製)、SST-H8H01(パーヒドロシルセルセスキオキサン)(Gelest社製)等が挙げられる。
Silsesquioxane may be synthesized or commercially available. Specific examples of the latter include X-40-2308, X-40-9238, X-40-9225, X-40-9227, x-40-9246, KR-500, KR-510 (all of which are Shin-Etsu Chemical) SR2400, SR2402, SR2405, FOX14 (perhydrosilcelsesquioxane) (all manufactured by Toray Dow Corning), SST-H8H01 (perhydrosilcelsesquioxane) (manufactured by Gelest), etc. Is mentioned.
これら金属アルコキシド化合物の中でも、反応性、溶解性等の観点から分岐状のアルコキシ基を有する化合物が好ましく、2-プロポキシ基、またはsec-ブトキシ基を有する化合物がより好ましい。
Among these metal alkoxide compounds, a compound having a branched alkoxy group is preferable from the viewpoint of reactivity and solubility, and a compound having a 2-propoxy group or a sec-butoxy group is more preferable.
さらに好ましい金属アルコキシド化合物は、具体的には、アルミニウムトリsec-ブトキシド、チタンテトライソプロポキシド、またはアルミニウムジイソプロピレートモノsec-ブチレートである。
More preferred metal alkoxide compounds are specifically aluminum trisec-butoxide, titanium tetraisopropoxide, or aluminum diisopropylate monosec-butyrate.
また、金属キレート化合物は、特に制限されないが、高性能のバリア層をより効率的に形成することができる点で、β-ジケトンを配位子として有する金属キレート化合物であることが好ましい。すなわち、前記金属アルコキシド化合物がアルミニウムアルコキシドである、または前記金属キレート化合物がβ-ジケトンを配位子として有する金属キレート化合物であることが特に好ましい。
The metal chelate compound is not particularly limited, but is preferably a metal chelate compound having a β-diketone as a ligand from the viewpoint that a high-performance barrier layer can be formed more efficiently. That is, it is particularly preferable that the metal alkoxide compound is an aluminum alkoxide, or the metal chelate compound is a metal chelate compound having a β-diketone as a ligand.
β-ジケトンとしては、例えば、アセチルアセトン、アセト酢酸エチル、2,4-ヘキサンジオン、3,5-ヘプタンジオン、2,4-オクタンジオン、2,4-デカンジオン、2,4-トリデカンジオン、5,5-ジメチル-2,4-ヘキサンジオン、2,2-ジメチル-3,5-ノナンジオン、2,2,6,6-テトラメチル-3,5-ヘプタンジオン、1,3-シクロペンタンジオン、1,3-シクロヘキサンジオン、1-シクロヘキシル-1,3-ブタンジオンなどが挙げられる。
Examples of β-diketone include acetylacetone, ethyl acetoacetate, 2,4-hexanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-decanedione, 2,4-tridecanedione, 5 , 5-dimethyl-2,4-hexanedione, 2,2-dimethyl-3,5-nonanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3-cyclopentanedione, Examples include 1,3-cyclohexanedione and 1-cyclohexyl-1,3-butanedione.
β-ジケトンを配位子として有する金属キレート化合物のさらに具体的な例としては、例えば、ベリリウムアセチルアセトネート、マグネシウムアセチルアセトネート、アルミニウムアセチルアセトナート、アルミニウムエチルアセトアセテート・ジイソプロピレート、アルミニウムエチルアセトアセテートジn-ブチレート、アルミニウムジエチルアセトアセテートモノn-ブチレート、アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート、アルミニウムトリスアセチルアセトネート、アルミニウムトリスエチルアセトアセテート、ビス(エチルアセトアセテート)(2,4-ペンタンジオナト)アルミニウム、アルミニウムアルキルアセトアセテートジイソプロピレート、カルシウムアセチルアセトネート、スカンジウムアセチルアセトネート、チタンジイソプロポキシビス(アセチルアセトネート)、チタンテトラアセチルアセトネート、トリス(2,4-ペンタンジオナト)クロム、トリス(2,4-ペンタンジオナト)マンガン、トリス(2,4-ペンタンジオナト)鉄、トリス(2,4-ペンタンジオナト)コバルト、ニッケルアセチルアセトネート、ビス(2,4-ペンタンジオナト)銅、ガリウムアセチルアセトナート、イットリウムアセチルアセトネート、テトラキス(2,4-ペンタンジオナト)ジルコニウム、モリブデンアセチルアセトネート、パラジウムアセチルアセトネート、銀アセチルアセトネート、カドミウムアセチルアセトネート、トリス(2,4-ペンタンジオナト)インジウム、スズアセチルアセトネート、バリウムアセチルアセトネート、ランタンアセチルアセトネート、セリウムアセチルアセトネート、プラセオジムアセチルアセトネート、ネオジムアセチルアセトネート、サマリウムアセチルアセトネート、ユーロピウムアセチルアセトネート、ガドリニウムアセチルアセトネート、テルビウムアセチルアセトネート、ホルミウムアセチルアセトネート、イッテルビウムアセチルアセトネート、ルテチウムアセチルアセトネート、ハフニウムアセチルアセトネート、タンタルテトラメトキシドアセチルアセトネート、イリジウムアセチルアセトネート、イリジウムジカルボニルアセチルアセトネート、タリウムアセチルアセトネート、鉛アセチルアセトネートなどが挙げられる。
Specific examples of metal chelate compounds having β-diketone as a ligand include, for example, beryllium acetylacetonate, magnesium acetylacetonate, aluminum acetylacetonate, aluminum ethylacetoacetate / diisopropylate, aluminum ethylacetate Acetate di n-butyrate, aluminum diethyl acetoacetate mono n-butyrate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum trisacetylacetonate, aluminum trisethylacetoacetate, bis (ethylacetoacetate) (2,4-pentane Diato) aluminum, aluminum alkyl acetoacetate diisopropylate, calcium acetylacetonate, scan Um acetylacetonate, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, tris (2,4-pentanedionato) chromium, tris (2,4-pentanedionato) manganese, tris (2, 4-pentandionato) iron, tris (2,4-pentandionato) cobalt, nickel acetylacetonate, bis (2,4-pentandionato) copper, gallium acetylacetonate, yttrium acetylacetonate, tetrakis (2 , 4-pentanedionato) zirconium, molybdenum acetylacetonate, palladium acetylacetonate, silver acetylacetonate, cadmium acetylacetonate, tris (2,4-pentandionato) indium, tin acetylacetonate, barium acetate Tylacetonate, lanthanum acetylacetonate, cerium acetylacetonate, praseodymium acetylacetonate, neodymium acetylacetonate, samarium acetylacetonate, europium acetylacetonate, gadolinium acetylacetonate, terbium acetylacetonate, holmium acetylacetonate, ytterbium Examples include acetylacetonate, lutetium acetylacetonate, hafnium acetylacetonate, tantalum tetramethoxide acetylacetonate, iridium acetylacetonate, iridium dicarbonylacetylacetonate, thallium acetylacetonate, lead acetylacetonate and the like.
β-ジケトンを配位子として有する金属キレート化合物の中でも、アセチルアセトナート基またはエチルアセトアセテート基を有する金属化合物が好ましい。これらの基は、カルボニル構造によりアルコキシド化合物の中心元素と相互作用を有するため、取り扱い性が容易になり好ましい。さらに好ましくは上記のアルコキシド基、エチルアセトアセテート基またはアセチルアセトナート基を複数種有する化合物が反応性や膜組成の観点からより好ましい。
Among metal chelate compounds having β-diketone as a ligand, metal compounds having an acetylacetonate group or an ethylacetoacetate group are preferable. These groups are preferable because they have an interaction with the central element of the alkoxide compound due to the carbonyl structure, and thus handleability becomes easy. More preferably, a compound having a plurality of alkoxide groups, ethyl acetoacetate groups or acetylacetonate groups is more preferable from the viewpoints of reactivity and film composition.
さらに好ましい金属キレート化合物は、具体的には、アルミニウムエチルアセトアセテート・ジイソプロピレート、アルミニウムエチルアセトアセテートジn-ブチレート、またはアルミニウムジエチルアセトアセテートモノn-ブチレート、アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート、チタンジイソプロポキシビス(アセチルアセトネート)、ビス(2,4-ペンタンジオナト)銅(II)(銅アセチルアセトネート)、トリス(2,4-ペンタンジオナト)鉄(III)(鉄アセチルアセトネート)である。
More preferable metal chelate compounds are, specifically, aluminum ethyl acetoacetate diisopropylate, aluminum ethyl acetoacetate di n-butyrate, or aluminum diethyl acetoacetate mono n-butyrate, aluminum bisethyl acetoacetate monoacetyl acetonate , Titanium diisopropoxybis (acetylacetonate), bis (2,4-pentandionato) copper (II) (copper acetylacetonate), tris (2,4-pentandionato) iron (III) (iron acetyl Acetonate).
金属アルコキシド化合物またはβ-ジケトンを配位子として有するキレート化合物は、市販品を用いてもよいし合成品を用いてもよい。市販品の具体的な例としては、例えば、金属アルコキシド化合物としては、AMD(アルミニウムジイソプロピレートモノsec-ブチレート)、ASBD(アルミニウムセカンダリーブチレート)、プレンアクト(登録商標)AL-M(アセトアルコキシアルミニウムジイソプロピレート、味の素ファインケミカル株式会社製)、オルガチックスシリーズ(マツモトファインケミカル株式会社製)等が挙げられる。市販されているβ-ジケトンを配位子として有する金属キレート化合物としては、ALCH(アルミニウムエチルアセトアセテート・ジイソプロピレート)、ALCH-TR(アルミニウムトリスエチルアセトアセテート)、アルミキレートM(アルミニウムアルキルアセトアセテート・ジイソプロピレート)、アルミキレートD(アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート)、アルミキレートA(W)(アルミニウムトリスアセチルアセトネート)(以上、川研ファインケミカル株式会社製)、オルガチックスシリーズ(マツモトファインケミカル株式会社製)等が挙げられる。
As the chelate compound having a metal alkoxide compound or β-diketone as a ligand, a commercially available product or a synthesized product may be used. Specific examples of commercially available products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), Plenact (registered trademark) AL-M (acetoalkoxyaluminum) as metal alkoxide compounds. Diisopropylate, Ajinomoto Fine Chemical Co., Ltd.), Olga Chix series (Matsumoto Fine Chemical Co., Ltd.) and the like. Commercially available metal chelate compounds having β-diketone as a ligand include ALCH (aluminum ethyl acetoacetate diisopropylate), ALCH-TR (aluminum trisethyl acetoacetate), aluminum chelate M (aluminum alkyl acetoacetate).・ Diisopropylate), aluminum chelate D (aluminum bisethyl acetoacetate monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) (above, manufactured by Kawaken Fine Chemical Co., Ltd.), ORGATIX series ( Matsumoto Fine Chemical Co., Ltd.).
また、上記反応において、(a)原料ポリシラザン、(b)低分子シラザン/シロキサン、および(c)金属アルコキシド/キレート化合物の反応(添加)順序は、特に制限されず、(ア)(a)原料ポリシラザン、(b)低分子シラザン/シロキサン、および(c)金属アルコキシド/キレート化合物を一括して混合して、反応させても;(イ)(a)原料ポリシラザンおよび(c)金属アルコキシド/キレート化合物を予め反応させた後、(b)低分子シラザン/シロキサンを添加して反応させても;(ウ)(a)原料ポリシラザンおよび(b)低分子シラザン/シロキサンを予め反応させた後、(c)金属アルコキシド/キレート化合物を添加して反応させても;または(エ)(b)低分子シラザン/シロキサンおよび(c)金属アルコキシド/キレート化合物を予め反応させた後、(a)原料ポリシラザンを添加して反応させても、いずれでもよい。これらのうち、(イ)、(ウ)、(エ)が好ましく、(イ)がより好ましい。すなわち、変性ポリシラザンは、(a)ケイ素原子、水素原子および窒素原子を含むポリシラザンを、(c)金属アルコキシド化合物および金属キレート化合物の少なくとも一方と反応させた後、(b)低分子シラザンおよび低分子シロキサンの少なくとも一方と反応させることによって得られることが特に好ましい。当該反応によって、ガスバリア性、特に特に過酷な条件(高温高湿条件)下でのガスバリア性を向上できる。詳細には、(b)低分子シラザン/シロキサンおよび(c)金属アルコキシド/キレート化合物は、原料ポリシラザンの-SiH3基のうち末端側から修飾していく。また、(c)金属アルコキシド/キレート化合物による修飾は、(b)低分子シラザンおよび低分子シロキサンによる修飾に比して、外部の酸素の取り込みを促進する(即ち、変性ポリシラザンの活性エネルギー線照射時に酸化反応を促進する)ように作用する。このため、上記(イ)によるように、まず、ポリシラザンの末端の反応点(-SiH3基)を所望の酸化反応促進効果を奏する量の(c)金属アルコキシド/キレート化合物と予め反応させて、原料ポリシラザンの末端-SiH3基を金属アルコキシド/キレート化合物で修飾した後、未反応(残り)の反応点(-SiH3基)を(b)低分子シラザン/シロキサンで修飾して、変性ポリシラザン中の-SiH3基量(数)を適切な範囲に調節することが好ましい。これにより、大気中の水分や酸素との反応を抑制・防止しつつ、ポリシラザンの酸化反応(改質処理)をより効率よく進行することができる。その結果、変性ポリシラザンに活性エネルギー線を照射して改質反応を行うと、外部の酸素の取り込み(変性ポリシラザン中の酸化反応)が促進されて、ガスバリア性、特に特に過酷な条件(高温高湿条件)下でのガスバリア性をより効率的に向上できる。なお、上記(ア)の反応では、(b)低分子シラザン/シロキサンと(c)金属アルコキシド/キレート化合物との反応が、(a)原料ポリシラザンと(b)低分子シラザン/シロキサンまたは(c)金属アルコキシド/キレート化合物との反応に比して、優先して進行してしまう可能性がある。
In the above reaction, the reaction (addition) order of (a) raw material polysilazane, (b) low molecular silazane / siloxane, and (c) metal alkoxide / chelate compound is not particularly limited, and (a) (a) raw material Even if polysilazane, (b) low molecular weight silazane / siloxane, and (c) metal alkoxide / chelate compound are mixed together and reacted; (A) (a) raw material polysilazane and (c) metal alkoxide / chelate compound (B) low molecular silazane / siloxane added and reacted; (c) (a) raw material polysilazane and (b) low molecular silazane / siloxane reacted in advance; ) Metal alkoxide / chelate compound added to react; or (d) (b) low molecular silazane / siloxane and (c) metal alk After reacted in advance Kishido / chelate compounds, also be reacted with the addition of (a) the raw material polysilazane, it may be any. Of these, (A), (C) and (E) are preferable, and (A) is more preferable. That is, the modified polysilazane is obtained by reacting (a) a polysilazane containing a silicon atom, a hydrogen atom and a nitrogen atom with at least one of (c) a metal alkoxide compound and a metal chelate compound, and (b) a low molecular silazane and a low molecular weight compound. It is particularly preferred that it is obtained by reacting with at least one of the siloxanes. By this reaction, gas barrier properties, particularly gas barrier properties under particularly severe conditions (high temperature and high humidity conditions) can be improved. Specifically, (b) the low-molecular silazane / siloxane and (c) the metal alkoxide / chelate compound are modified from the terminal side of the —SiH 3 group of the starting polysilazane. Further, (c) modification with metal alkoxide / chelate compound promotes uptake of external oxygen (that is, when irradiated with active energy rays of modified polysilazane, as compared with modification with (b) low molecular silazane and low molecular siloxane. It promotes the oxidation reaction). Therefore, as described in (a) above, first, the reactive site (-SiH 3 group) at the end of polysilazane is reacted in advance with an amount of (c) a metal alkoxide / chelate compound that exhibits a desired oxidation reaction promoting effect, In the modified polysilazane, after modifying the terminal -SiH 3 group of the raw material polysilazane with a metal alkoxide / chelate compound, the unreacted (remaining) reaction point (-SiH 3 group) is modified with (b) low molecular silazane / siloxane. It is preferable to adjust the amount (number) of —SiH 3 groups in an appropriate range. As a result, the polysilazane oxidation reaction (reforming treatment) can proceed more efficiently while suppressing or preventing reaction with moisture and oxygen in the atmosphere. As a result, when the modified polysilazane is irradiated with active energy rays to carry out the modification reaction, external oxygen uptake (oxidation reaction in the modified polysilazane) is promoted and gas barrier properties, particularly particularly severe conditions (high temperature and high humidity) are promoted. Under the condition), the gas barrier property can be improved more efficiently. In the reaction (a), the reaction between (b) the low molecular silazane / siloxane and (c) the metal alkoxide / chelate compound is performed by (a) the starting polysilazane and (b) the low molecular silazane / siloxane or (c). Compared to the reaction with a metal alkoxide / chelate compound, there is a possibility that the reaction proceeds with priority.
上記反応において、(a)原料ポリシラザンと、(b)低分子シラザン/シロキサンおよび(c)金属アルコキシド/キレート化合物と、の混合比は、(a)原料ポリシラザンの末端-SiH3基が(b)低分子シラザン/シロキサンおよび(c)金属アルコキシド/キレート化合物で十分修飾できる割合であれば、特に制限されない。具体的には、(b)低分子シラザンおよび低分子シロキサンの少なくとも一方、および(c)金属アルコキシド化合物および金属キレート化合物の少なくとも一方の合計仕込み量が、(a)原料ポリシラザン中のケイ素元素数(Si)に対して、5モル%を超えて50モル%以下であることが好ましく、6~30モル%であることがより好ましく、7~20モル%であることがより好ましく、8~15モル%であることが特に好ましい。5モル%を超えれば、高温高湿下でより優れた保存安定性を有するガスバリア性フィルムが得られうる。また、50モル%以下であれば、変性ポリシラザンを用いて形成されるバリア層のガスバリア性が向上しうる。
In the above reaction, the mixing ratio of (a) raw material polysilazane to (b) low molecular weight silazane / siloxane and (c) metal alkoxide / chelate compound is such that (a) terminal polysilazane terminal-SiH 3 group is (b) The ratio is not particularly limited as long as the ratio can be sufficiently modified with low molecular silazane / siloxane and (c) metal alkoxide / chelate compound. Specifically, the total charge amount of at least one of (b) low molecular silazane and low molecular siloxane, and (c) at least one of metal alkoxide compound and metal chelate compound is (a) the number of silicon elements in the raw material polysilazane ( Si) is preferably more than 5 mol% and not more than 50 mol%, more preferably 6 to 30 mol%, more preferably 7 to 20 mol%, and more preferably 8 to 15 mol%. % Is particularly preferred. If it exceeds 5 mol%, a gas barrier film having better storage stability under high temperature and high humidity can be obtained. Moreover, if it is 50 mol% or less, the gas-barrier property of the barrier layer formed using a modified polysilazane can improve.
(b)低分子シラザン/シロキサンおよび(c)金属アルコキシド/キレート化合物の混合比は、特に制限されないが、(b)低分子シラザン/シロキサンおよび(c)金属アルコキシド/キレート化合物の混合比(モル比)が、1:0.1~10であることが好ましく、1:0.5~5であることがより好ましい。このような範囲であれば、変性ポリシラザンを用いて形成されるガスバリア性フィルムは、高温高湿下でより優れた保存安定性を発揮できる。
The mixing ratio of (b) low-molecular silazane / siloxane and (c) metal alkoxide / chelate compound is not particularly limited, but (b) the mixing ratio (molar ratio) of low-molecular silazane / siloxane and (c) metal alkoxide / chelating compound ) Is preferably from 1: 0.1 to 10, more preferably from 1: 0.5 to 5. Within such a range, the gas barrier film formed using the modified polysilazane can exhibit better storage stability under high temperature and high humidity.
また、上記反応は、無溶媒系で行われてもよいが、好ましくは溶剤中に行われることが好ましい。ここで、溶剤としては、(a)原料ポリシラザン、(b)低分子シラザン/シロキサン、および(c)金属アルコキシド/キレート化合物を溶解できるものであれば特に制限されないが、ポリシラザンと容易に反応してしまう水および反応性基(例えば、ヒドロキシル基、あるいはアミン基等)を含まず、ポリシラザンに対して不活性の有機溶剤が好ましく、非プロトン性の有機溶剤がより好ましい。具体的には、溶剤としては、非プロトン性溶剤;例えば、ペンタン、2,2,4-トリメチルペンタン、ヘキサン、シクロヘキサン、トルエン、キシレン、ソルベッソ、ターペン等の、脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素等の炭化水素溶媒;塩化メチレン、トリクロロエタン等のハロゲン炭化水素溶媒;酢酸エチル、酢酸ブチル等のエステル類;アセトン、メチルエチルケトン等のケトン類;ジブチルエーテル、ジオキサン、テトラヒドロフラン、モノ-およびポリアルキレングリコールジアルキルエーテル(ジグライム類)等の脂肪族エーテル、脂環式エーテル等のエーテル類などを挙げることができる。上記溶剤は、単独で使用されてもまたは2種以上の混合物の形態で使用されてもよい。また、上記溶剤は、使用する前にあらかじめ酸素濃度や水分含量を低減させておくことが好ましい。溶剤中の酸素濃度や水分含量を低減する手段は特に限定されず、従来公知の手法が適用されうる。この際、反応溶液中の原料ポリシラザンの濃度は、特に制限されない。例えば、反応後の変性ポリシラザン溶液をガスバリア性フィルムの作製にそのまま使用する場合には、層の膜厚や塗布液のポットライフによっても異なるが、好ましくは1~80質量%、より好ましくは2~50質量%、特に好ましくは10~40質量%である。
The above reaction may be carried out in a solvent-free system, but is preferably carried out in a solvent. Here, the solvent is not particularly limited as long as it can dissolve (a) raw material polysilazane, (b) low molecular silazane / siloxane, and (c) metal alkoxide / chelate compound, but it can easily react with polysilazane. Organic solvents that do not contain water and reactive groups (for example, hydroxyl groups or amine groups) and are inert to polysilazane are preferred, and aprotic organic solvents are more preferred. Specifically, the solvent is an aprotic solvent; for example, pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, solvesso, terpene, aliphatic hydrocarbons, alicyclic carbonization, etc. Hydrocarbon solvents such as hydrogen and aromatic hydrocarbons; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Dibutyl ether, dioxane, tetrahydrofuran, mono- And aliphatic ethers such as polyalkylene glycol dialkyl ethers (diglymes) and ethers such as alicyclic ethers. The said solvent may be used independently or may be used with the form of a 2 or more types of mixture. Moreover, it is preferable to reduce the oxygen concentration and water content of the solvent before use. Means for reducing the oxygen concentration and water content in the solvent are not particularly limited, and conventionally known methods can be applied. At this time, the concentration of the raw material polysilazane in the reaction solution is not particularly limited. For example, when the modified polysilazane solution after reaction is used as it is for the production of a gas barrier film, it varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 1 to 80% by mass, more preferably 2 to 2%. It is 50% by mass, particularly preferably 10 to 40% by mass.
上記反応条件は、(a)原料ポリシラザンの末端-SiH3基が(b)低分子シラザン/シロキサンおよび(c)金属アルコキシド/キレート化合物で十分修飾できる条件であれば、特に制限されない。具体的には、反応温度(反応混合物の温度)が、30℃~100℃、より好ましくは40~90℃、さらにより好ましくは50~80℃であることが好ましい。また、反応時間は、10分~10時間、より好ましくは30分~4時間、さらにより好ましくは1~2時間であることが好ましい。このような条件であれば、(a)原料ポリシラザン同士の架橋反応を抑制しつつ、(a)原料ポリシラザンと、(b)低分子シラザン/シロキサンおよび(c)金属アルコキシド/キレート化合物との反応を十分進行できる。
The reaction conditions are not particularly limited as long as (a) the terminal-SiH 3 group of the starting polysilazane can be sufficiently modified with (b) low molecular silazane / siloxane and (c) metal alkoxide / chelate compound. Specifically, the reaction temperature (temperature of the reaction mixture) is preferably 30 ° C. to 100 ° C., more preferably 40 to 90 ° C., and even more preferably 50 to 80 ° C. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 4 hours, and even more preferably 1 to 2 hours. Under such conditions, the reaction of (a) the raw material polysilazane with (a) the raw material polysilazane and (b) the low molecular silazane / siloxane and (c) the metal alkoxide / chelate compound is suppressed. Can progress sufficiently.
上記反応は、いずれの雰囲気で行われてもよいが、上記したように、水との反応性を考慮すると、不活性な環境下で行われることが好ましく、実質的に酸素や水分を含まない雰囲気下で行われることがより好ましい。ここで、反応系内の酸素濃度は、特に制限されないが、好ましくは0~200体積ppm、より好ましくは0~100ppm、さらにより好ましくは0~30体積ppmである。また、反応系内の水分濃度(水蒸気濃度)は、特に制限されないが、好ましくは0~200体積ppm、より好ましくは0~100ppm、さらにより好ましくは0~30体積ppmである。このような雰囲気中で反応を行うことにより、(a)原料ポリシラザン、(b)低分子シラザン/シロキサンや(c)金属アルコキシド/キレート化合物と水分や酸素との反応を十分抑制できる。
The above reaction may be performed in any atmosphere, but as described above, in consideration of reactivity with water, the reaction is preferably performed in an inert environment and substantially does not contain oxygen or moisture. More preferably, it is performed under an atmosphere. Here, the oxygen concentration in the reaction system is not particularly limited, but is preferably 0 to 200 ppm by volume, more preferably 0 to 100 ppm, and even more preferably 0 to 30 ppm by volume. The water concentration (water vapor concentration) in the reaction system is not particularly limited, but is preferably 0 to 200 ppm by volume, more preferably 0 to 100 ppm, and even more preferably 0 to 30 ppm by volume. By carrying out the reaction in such an atmosphere, the reaction of (a) raw material polysilazane, (b) low molecular silazane / siloxane or (c) metal alkoxide / chelate compound with moisture or oxygen can be sufficiently suppressed.
上記したようにして製造される本発明の変性ポリシラザンは、大気中の水分と反応しやすい末端のSiH3基が少ない。このため、活性エネルギー線を照射による酸化反応を優先的に進行させることが可能である。ゆえに、本発明の変性ポリシラザンは、ガスバリア性、特に過酷な条件(特に高温高湿)下でのガスバリア性に優れるバリア層、ゆえにガスバリア性フィルムの作製に特に有用である。
The modified polysilazane of the present invention produced as described above has a small number of terminal SiH 3 groups that easily react with moisture in the atmosphere. For this reason, it is possible to preferentially advance the oxidation reaction by irradiation with active energy rays. Therefore, the modified polysilazane of the present invention is particularly useful for the production of a barrier layer excellent in gas barrier properties, particularly gas barrier properties under severe conditions (especially high temperature and high humidity), and therefore a gas barrier film.
したがって、本発明は、本発明の変性ポリシラザンを含む塗布液、および基材と、上記塗布液を用いて形成されるバリア層と、を含む、ガスバリア性フィルムをも提供する。
Therefore, the present invention also provides a gas barrier film comprising a coating solution containing the modified polysilazane of the present invention, a substrate, and a barrier layer formed using the coating solution.
<ガスバリア性フィルム>
本発明のガスバリア性フィルムは、基材、および本発明の変性ポリシラザンを含む塗布液で形成されるバリア層と、を含むが、ガスバリア性、特に過酷な条件(特に高温高湿)下でのガスバリア性のさらなる向上効果を考慮すると、基材と上記バリア層との間に、無機化合物を含む無機化合物層をさらに有することが好ましい。すなわち、本発明の好ましい形態によると、ガスバリア性フィルムは、基材と、無機化合物を含む無機化合物層(本明細書中では、「第1のバリア層」とも称する)と、本発明の変性ポリシラザンを含む塗布液で形成されるバリア層(本明細書中では、「第2のバリア層」とも称する)と、をこの順に含む。 <Gas barrier film>
The gas barrier film of the present invention includes a base material and a barrier layer formed of a coating solution containing the modified polysilazane of the present invention, but has a gas barrier property, particularly a gas barrier under severe conditions (especially high temperature and high humidity). In view of the further improvement effect of the property, it is preferable to further include an inorganic compound layer containing an inorganic compound between the base material and the barrier layer. That is, according to a preferred embodiment of the present invention, the gas barrier film comprises a substrate, an inorganic compound layer containing an inorganic compound (also referred to herein as “first barrier layer”), and the modified polysilazane of the present invention. And a barrier layer (also referred to as a “second barrier layer” in this specification) formed of a coating solution containing in this order.
本発明のガスバリア性フィルムは、基材、および本発明の変性ポリシラザンを含む塗布液で形成されるバリア層と、を含むが、ガスバリア性、特に過酷な条件(特に高温高湿)下でのガスバリア性のさらなる向上効果を考慮すると、基材と上記バリア層との間に、無機化合物を含む無機化合物層をさらに有することが好ましい。すなわち、本発明の好ましい形態によると、ガスバリア性フィルムは、基材と、無機化合物を含む無機化合物層(本明細書中では、「第1のバリア層」とも称する)と、本発明の変性ポリシラザンを含む塗布液で形成されるバリア層(本明細書中では、「第2のバリア層」とも称する)と、をこの順に含む。 <Gas barrier film>
The gas barrier film of the present invention includes a base material and a barrier layer formed of a coating solution containing the modified polysilazane of the present invention, but has a gas barrier property, particularly a gas barrier under severe conditions (especially high temperature and high humidity). In view of the further improvement effect of the property, it is preferable to further include an inorganic compound layer containing an inorganic compound between the base material and the barrier layer. That is, according to a preferred embodiment of the present invention, the gas barrier film comprises a substrate, an inorganic compound layer containing an inorganic compound (also referred to herein as “first barrier layer”), and the modified polysilazane of the present invention. And a barrier layer (also referred to as a “second barrier layer” in this specification) formed of a coating solution containing in this order.
以下、上記好ましい形態に係るガスバリア性フィルムについて説明する。なお、本発明は、下記好ましい形態に限定されない。
Hereinafter, the gas barrier film according to the preferred embodiment will be described. In addition, this invention is not limited to the following preferable form.
本発明のガスバリア性フィルムは、基材、第1のバリア層、および第2のバリア層をこの順に有することが好ましい。前記ガスバリア性フィルムは、他の部材をさらに含むものであってもよい。本発明のガスバリア性フィルムは、例えば、基材と第1のバリア層との間、第1のバリア層と第2のバリア層との間、第2のバリア層の上、または第1のバリア層および第2のバリア層が形成されていない基材の他方の面に、他の部材を有していてもよい。ここで、他の部材としては、特に制限されず、従来のガスバリア性フィルムに使用される部材が同様にしてあるいは適宜修飾して使用できる。具体的には、中間層、保護層、平滑層、アンカーコート層、ブリードアウト防止層、水分吸着性を有するデシカント性層や帯電防止層の機能化層などが挙げられる。
The gas barrier film of the present invention preferably has a substrate, a first barrier layer, and a second barrier layer in this order. The gas barrier film may further include other members. The gas barrier film of the present invention is, for example, between the base material and the first barrier layer, between the first barrier layer and the second barrier layer, on the second barrier layer, or on the first barrier. You may have another member in the other surface of the base material in which the layer and the 2nd barrier layer are not formed. Here, the other members are not particularly limited, and members used for conventional gas barrier films can be used similarly or appropriately modified. Specific examples include an intermediate layer, a protective layer, a smooth layer, an anchor coat layer, a bleed-out prevention layer, a desiccant layer having moisture adsorbability, and a functionalized layer of an antistatic layer.
本発明の変性ポリシラザンを用いて形成されるバリア層(第2のバリア層)が第1のバリア層上に配置される場合には、第1のバリア層および第2のバリア層を有するガスバリア性ユニットは、基材の一方の表面上に形成されていてもよく、基材の両方の表面上に形成されていてもよい。また、該ガスバリア性ユニットは、ガスバリア性を必ずしも有しない層を含んでいてもよい。
When the barrier layer (second barrier layer) formed using the modified polysilazane of the present invention is disposed on the first barrier layer, the gas barrier property having the first barrier layer and the second barrier layer The unit may be formed on one surface of the substrate, or may be formed on both surfaces of the substrate. The gas barrier unit may include a layer that does not necessarily have a gas barrier property.
〔基材〕
本発明に係るガスバリア性フィルムは、基材として、プラスチックフィルムまたはプラスチックシートが好ましく用いられ、無色透明な樹脂からなるフィルムまたはシートがより好ましく用いられる。用いられるプラスチックフィルムは、第2のバリア層及び必要であれば第1のバリア層等を保持できるフィルムであれば材質、厚み等に特に制限はなく、使用目的等に応じて適宜選択することができる。前記プラスチックフィルムとしては、具体的には、ポリエチレンテレフタレート(PET)等のポリエステル樹脂、メタクリル樹脂、メタクリル酸-マレイン酸共重合体、ポリスチレン樹脂、透明フッ素樹脂、ポリイミド、フッ素化ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、セルロースアシレート樹脂、ポリウレタン樹脂、ポリエーテルエーテルケトン樹脂、ポリカーボネート樹脂、脂環式ポリオレフィン樹脂、ポリアリレート樹脂、ポリエーテルスルホン樹脂、ポリスルホン樹脂、シクロオレフィルンコポリマー、フルオレン環変性ポリカーボネート樹脂、脂環変性ポリカーボネート樹脂、フルオレン環変性ポリエステル樹脂、アクリロイル化合物などの熱可塑性樹脂が挙げられる。 〔Base material〕
In the gas barrier film according to the present invention, a plastic film or a plastic sheet is preferably used as a substrate, and a film or sheet made of a colorless and transparent resin is more preferably used. The plastic film used is not particularly limited as long as it is a film that can hold the second barrier layer and, if necessary, the first barrier layer, etc., and can be appropriately selected according to the purpose of use. it can. Specific examples of the plastic film include polyester resins such as polyethylene terephthalate (PET), methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, Polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene Examples thereof include thermoplastic resins such as a ring-modified polycarbonate resin, an alicyclic modified polycarbonate resin, a fluorene ring-modified polyester resin, and an acryloyl compound.
本発明に係るガスバリア性フィルムは、基材として、プラスチックフィルムまたはプラスチックシートが好ましく用いられ、無色透明な樹脂からなるフィルムまたはシートがより好ましく用いられる。用いられるプラスチックフィルムは、第2のバリア層及び必要であれば第1のバリア層等を保持できるフィルムであれば材質、厚み等に特に制限はなく、使用目的等に応じて適宜選択することができる。前記プラスチックフィルムとしては、具体的には、ポリエチレンテレフタレート(PET)等のポリエステル樹脂、メタクリル樹脂、メタクリル酸-マレイン酸共重合体、ポリスチレン樹脂、透明フッ素樹脂、ポリイミド、フッ素化ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、セルロースアシレート樹脂、ポリウレタン樹脂、ポリエーテルエーテルケトン樹脂、ポリカーボネート樹脂、脂環式ポリオレフィン樹脂、ポリアリレート樹脂、ポリエーテルスルホン樹脂、ポリスルホン樹脂、シクロオレフィルンコポリマー、フルオレン環変性ポリカーボネート樹脂、脂環変性ポリカーボネート樹脂、フルオレン環変性ポリエステル樹脂、アクリロイル化合物などの熱可塑性樹脂が挙げられる。 〔Base material〕
In the gas barrier film according to the present invention, a plastic film or a plastic sheet is preferably used as a substrate, and a film or sheet made of a colorless and transparent resin is more preferably used. The plastic film used is not particularly limited as long as it is a film that can hold the second barrier layer and, if necessary, the first barrier layer, etc., and can be appropriately selected according to the purpose of use. it can. Specific examples of the plastic film include polyester resins such as polyethylene terephthalate (PET), methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, Polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene Examples thereof include thermoplastic resins such as a ring-modified polycarbonate resin, an alicyclic modified polycarbonate resin, a fluorene ring-modified polyester resin, and an acryloyl compound.
また、本発明において、特開2012-116101号公報の段落「0056」~「0075」や特開2013-226758号公報の段落「0125」~「0131」などに開示されている基材も適宜採用される。
In the present invention, the substrates disclosed in paragraphs “0056” to “0075” of JP2012-116101A, paragraphs “0125” to “0131” of JP2013-226758A, etc. are also appropriately employed. Is done.
本発明に係るガスバリア性フィルムに用いられる基材の厚みは、用途によって適宜選択されるため特に制限がないが、典型的には1~800μmであり、好ましくは10~200μmである。これらのプラスチックフィルムは、透明導電層、プライマー層、クリアハードコート層等の機能層を有していても良い。機能層については、上述したもののほか、特開2006-289627号公報の段落番号「0036」~「0038」に記載されているものを好ましく採用できる。
The thickness of the base material used for the gas barrier film according to the present invention is not particularly limited because it is appropriately selected depending on the application, but is typically 1 to 800 μm, preferably 10 to 200 μm. These plastic films may have functional layers such as a transparent conductive layer, a primer layer, and a clear hard coat layer. As the functional layer, in addition to those described above, those described in paragraph numbers “0036” to “0038” of JP-A-2006-289627 can be preferably used.
基材は、表面の平滑性が高いものが好ましい。表面の平滑性としては、平均表面粗さ(Ra)が2nm以下であるものが好ましい。下限は特にないが、実用上、0.01nm以上である。必要に応じて、基材の両面、少なくともバリア層を設ける側を研摩し、平滑性を向上させておいてもよい。
The substrate preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the barrier layer is provided, may be polished to improve smoothness.
基材の少なくとも本発明に係る第1のバリア層を設ける側には、密着性向上のための公知の種々の処理、例えばコロナ放電処理、火炎処理、酸化処理、またはプラズマ処理や、後述する平滑層の積層等を行ってもよく、必要に応じて上記処理を組み合わせて行うことが好ましい。
On the side of the base material on which the first barrier layer according to the present invention is provided, various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, and smoothing described later. Layer stacking or the like may be performed, and it is preferable to combine the above treatments as necessary.
〔無機化合物層(第1のバリア層)〕
基材の上部に形成される無機化合物層(第1のバリア層)は、無機化合物を含む。ここで、無機化合物としては、特に限定されないが、例えば、金属酸化物、金属窒化物、金属炭化物、金属酸窒化物または金属酸炭化物が挙げられる。中でも、ガスバリア性能の点で、Si、Al、In、Sn、Zn、Ti、Cu、CeおよびTaから選ばれる1種以上の金属を含む、酸化物、窒化物、炭化物、酸窒化物または酸炭化物などを好ましく用いることができ、Si、Al、In、Sn、ZnおよびTiから選ばれる金属の酸化物、窒化物または酸窒化物がより好ましく、特にSiおよびAlの少なくとも1種の、酸化物、窒化物または酸窒化物が好ましい。好適な無機化合物として、具体的には、酸化ケイ素、窒化ケイ素、酸窒化ケイ素、炭化ケイ素、酸炭化ケイ素、酸化アルミニウム、酸化チタン、またはアルミニウムシリケートなどの複合体が挙げられる。副次的な成分として他の元素を含有してもよい。 [Inorganic compound layer (first barrier layer)]
The inorganic compound layer (first barrier layer) formed on the upper part of the substrate contains an inorganic compound. Here, the inorganic compound is not particularly limited, and examples thereof include metal oxides, metal nitrides, metal carbides, metal oxynitrides, and metal oxycarbides. Among these, oxides, nitrides, carbides, oxynitrides or oxycarbides containing one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta in terms of gas barrier performance Are preferably used, and an oxide, nitride or oxynitride of a metal selected from Si, Al, In, Sn, Zn and Ti is more preferable, and in particular, an oxide of at least one of Si and Al, Nitride or oxynitride is preferred. Specific examples of suitable inorganic compounds include composites such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, aluminum oxide, titanium oxide, or aluminum silicate. You may contain another element as a secondary component.
基材の上部に形成される無機化合物層(第1のバリア層)は、無機化合物を含む。ここで、無機化合物としては、特に限定されないが、例えば、金属酸化物、金属窒化物、金属炭化物、金属酸窒化物または金属酸炭化物が挙げられる。中でも、ガスバリア性能の点で、Si、Al、In、Sn、Zn、Ti、Cu、CeおよびTaから選ばれる1種以上の金属を含む、酸化物、窒化物、炭化物、酸窒化物または酸炭化物などを好ましく用いることができ、Si、Al、In、Sn、ZnおよびTiから選ばれる金属の酸化物、窒化物または酸窒化物がより好ましく、特にSiおよびAlの少なくとも1種の、酸化物、窒化物または酸窒化物が好ましい。好適な無機化合物として、具体的には、酸化ケイ素、窒化ケイ素、酸窒化ケイ素、炭化ケイ素、酸炭化ケイ素、酸化アルミニウム、酸化チタン、またはアルミニウムシリケートなどの複合体が挙げられる。副次的な成分として他の元素を含有してもよい。 [Inorganic compound layer (first barrier layer)]
The inorganic compound layer (first barrier layer) formed on the upper part of the substrate contains an inorganic compound. Here, the inorganic compound is not particularly limited, and examples thereof include metal oxides, metal nitrides, metal carbides, metal oxynitrides, and metal oxycarbides. Among these, oxides, nitrides, carbides, oxynitrides or oxycarbides containing one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta in terms of gas barrier performance Are preferably used, and an oxide, nitride or oxynitride of a metal selected from Si, Al, In, Sn, Zn and Ti is more preferable, and in particular, an oxide of at least one of Si and Al, Nitride or oxynitride is preferred. Specific examples of suitable inorganic compounds include composites such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, aluminum oxide, titanium oxide, or aluminum silicate. You may contain another element as a secondary component.
第1のバリア層に含まれる無機化合物の含有量は特に限定されないが、第1のバリア層中、50質量%以上であることが好ましく、80質量%以上であることがより好ましく、95質量%以上であることがさらに好ましく、98質量%以上であることが特に好ましく、100質量%である(すなわち、第1のバリア層は無機化合物からなる)ことが最も好ましい。
The content of the inorganic compound contained in the first barrier layer is not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, and 95% by mass in the first barrier layer. More preferably, it is more preferably 98% by mass or more, and most preferably 100% by mass (that is, the first barrier layer is made of an inorganic compound).
第1のバリア層は無機化合物を含むことで、ガスバリア性を有する。ここで、第1のバリア層のガスバリア性は、基材上に第1のバリア層を形成させた積層体で算出した際、水蒸気透過度(WVTR)が0.1g/(m2・day)以下であることが好ましく、0.01g/(m2・day)以下であることがより好ましい。
The first barrier layer contains an inorganic compound and thus has a gas barrier property. Here, when the gas barrier property of the first barrier layer is calculated using a laminate in which the first barrier layer is formed on the substrate, the water vapor transmission rate (WVTR) is 0.1 g / (m 2 · day). Or less, more preferably 0.01 g / (m 2 · day) or less.
第1のバリア層の形成方法は、特に制限されないが、物理気相成長法(PVD法)、化学気相成長法(CVD法)などの真空成膜法、または無機化合物を含む液、好ましくはケイ素化合物を含有する液を塗布して形成される塗膜を改質処理して形成する方法(以下、単に塗布法とも称する)が好ましく、物理気相成長法または化学気相成長法がより好ましい。
The method for forming the first barrier layer is not particularly limited, but a vacuum film-forming method such as physical vapor deposition (PVD method) or chemical vapor deposition (CVD), or a liquid containing an inorganic compound, preferably A method of modifying and forming a coating film formed by applying a liquid containing a silicon compound (hereinafter also simply referred to as a coating method) is preferred, and a physical vapor deposition method or a chemical vapor deposition method is more preferred. .
以下、真空成膜法および塗布法について説明する。
Hereinafter, the vacuum film forming method and the coating method will be described.
<真空成膜法>
物理気相成長法(Physical Vapor Deposition、PVD法)は、気相中で物質の表面に物理的手法により、目的とする物質、例えば、炭素膜等の薄膜を堆積する方法であり、例えば、スパッタ法(DCスパッタ法、RFスパッタ法、イオンビームスパッタ法、およびマグネトロンスパッタ法等)、真空蒸着法、イオンプレーティング法などが挙げられる。 <Vacuum deposition method>
The physical vapor deposition method (PVD method) is a method of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method. Examples thereof include a DC sputtering method, an RF sputtering method, an ion beam sputtering method, and a magnetron sputtering method, a vacuum deposition method, and an ion plating method.
物理気相成長法(Physical Vapor Deposition、PVD法)は、気相中で物質の表面に物理的手法により、目的とする物質、例えば、炭素膜等の薄膜を堆積する方法であり、例えば、スパッタ法(DCスパッタ法、RFスパッタ法、イオンビームスパッタ法、およびマグネトロンスパッタ法等)、真空蒸着法、イオンプレーティング法などが挙げられる。 <Vacuum deposition method>
The physical vapor deposition method (PVD method) is a method of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method. Examples thereof include a DC sputtering method, an RF sputtering method, an ion beam sputtering method, and a magnetron sputtering method, a vacuum deposition method, and an ion plating method.
スパッタ法は、真空チャンバ内にターゲットを設置し、高電圧をかけてイオン化した希ガス元素(通常はアルゴン)をターゲットに衝突させて、ターゲット表面の原子をはじき出し、基材に付着させる方法である。このとき、チャンバ内に窒素ガスや酸素ガスを流すことにより、アルゴンガスによってターゲットからはじき出された元素と、窒素や酸素とを反応させて無機層を形成する、反応性スパッタ法を用いてもよい。
Sputtering is a method in which a target is placed in a vacuum chamber, a rare gas element (usually argon) ionized by applying a high voltage is collided with the target, and atoms on the target surface are ejected and adhered to the substrate. . At this time, a reactive sputtering method may be used in which an inorganic layer is formed by causing nitrogen and oxygen gas to flow into the chamber to react nitrogen and oxygen with an element ejected from the target by argon gas. .
化学気相成長法(Chemical Vapor Deposition、CVD法)は、基材上に、目的とする薄膜の成分を含む原料ガスを供給し、基材表面または気相での化学反応により膜を堆積する方法である。また、化学反応を活性化する目的で、プラズマなどを発生させる方法などがあり、熱CVD法、触媒化学気相成長法、光CVD法、真空プラズマCVD法、大気圧プラズマCVD法など公知のCVD方式等が挙げられる。特に限定されるものではないが、製膜速度や処理面積の観点から、プラズマCVD法を適用することが好ましい。
The chemical vapor deposition method (Chemical Vapor Deposition, CVD method) is a method of depositing a film by supplying a source gas containing a target thin film component onto a substrate and performing a chemical reaction on the surface of the substrate or in the gas phase. It is. In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like. Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The method etc. are mentioned. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of film forming speed and processing area.
また、本発明に係るCVD法により形成される第1のバリア層の好適な一実施形態として、第1のバリア層は構成元素に炭素、ケイ素、および酸素を含むことが好ましい。より好適な形態は、以下の(i)~(iii)の要件を満たす層である。なお、本明細書において、下記(i)~(iii)の要件を、それぞれ、「要件(i)」、「要件(ii)」および「要件(iii)」とも称する。
As a preferred embodiment of the first barrier layer formed by the CVD method according to the present invention, the first barrier layer preferably contains carbon, silicon, and oxygen as constituent elements. A more preferable form is a layer that satisfies the following requirements (i) to (iii). In the present specification, the following requirements (i) to (iii) are also referred to as “requirement (i)”, “requirement (ii)”, and “requirement (iii)”, respectively.
(i)第1のバリア層の膜厚方向における前記第1のバリア層表面からの距離(L)と、ケイ素原子、酸素原子、および炭素原子の合計量に対するケイ素原子の量の比率(ケイ素の原子比)との関係を示すケイ素分布曲線、前記Lとケイ素原子、酸素原子、および炭素原子の合計量に対する酸素原子の量の比率(酸素の原子比)との関係を示す酸素分布曲線、ならびに前記Lとケイ素原子、酸素原子、および炭素原子の合計量に対する炭素原子の量の比率(炭素の原子比)との関係を示す炭素分布曲線において、前記第1のバリア層の膜厚の90%以上(上限:100%)の領域で、(酸素の原子比)、(ケイ素の原子比)、(炭素の原子比)の順で多い(原子比がO>Si>C);
(ii)前記炭素分布曲線が少なくとも2つの極値を有する;
(iii)前記炭素分布曲線における炭素の原子比の最大値および最小値の差の絶対値(以下、単に「Cmax-Cmin差」とも称する)が3at%以上である。 (I) The distance (L) from the surface of the first barrier layer in the film thickness direction of the first barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon A silicon distribution curve showing a relationship with the atomic ratio), an oxygen distribution curve showing a relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen), and 90% of the film thickness of the first barrier layer in the carbon distribution curve showing the relationship between the L and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon) In the above range (upper limit: 100%), (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) increase in this order (atomic ratio is O>Si>C);
(Ii) the carbon distribution curve has at least two extreme values;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the carbon distribution curve (hereinafter also simply referred to as “C max −C min difference”) is 3 at% or more.
(ii)前記炭素分布曲線が少なくとも2つの極値を有する;
(iii)前記炭素分布曲線における炭素の原子比の最大値および最小値の差の絶対値(以下、単に「Cmax-Cmin差」とも称する)が3at%以上である。 (I) The distance (L) from the surface of the first barrier layer in the film thickness direction of the first barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon A silicon distribution curve showing a relationship with the atomic ratio), an oxygen distribution curve showing a relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen), and 90% of the film thickness of the first barrier layer in the carbon distribution curve showing the relationship between the L and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon) In the above range (upper limit: 100%), (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) increase in this order (atomic ratio is O>Si>C);
(Ii) the carbon distribution curve has at least two extreme values;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the carbon distribution curve (hereinafter also simply referred to as “C max −C min difference”) is 3 at% or more.
以下、(i)~(iii)の要件について説明する。
Hereinafter, the requirements (i) to (iii) will be described.
該第1のバリア層は、(i)前記第1のバリア層の膜厚方向における前記第1のバリア層表面からの距離(L)と、ケイ素原子、酸素原子、および炭素原子の合計量に対するケイ素原子の量の比率(ケイ素の原子比)との関係を示すケイ素分布曲線、前記Lとケイ素原子、酸素原子、および炭素原子の合計量に対する酸素原子の量の比率(酸素の原子比)との関係を示す酸素分布曲線、ならびに前記Lとケイ素原子、酸素原子、および炭素原子の合計量に対する炭素原子の量の比率(炭素の原子比)との関係を示す炭素分布曲線において、前記第1のバリア層の膜厚の90%以上(上限:100%)の領域で、(酸素の原子比)、(ケイ素の原子比)、(炭素の原子比)の順で多い(原子比がO>Si>C)ことが好ましい。前記の条件(i)を満たすと、得られるガスバリア性フィルムのガスバリア性や屈曲性が向上しうる。ここで、上記炭素分布曲線において、上記(酸素の原子比)、(ケイ素の原子比)および(炭素の原子比)の関係は、第1のバリア層の膜厚の、少なくとも90%以上(上限:100%)の領域で満たされることがより好ましく、少なくとも93%以上(上限:100%)の領域で満たされることがより好ましい。ここで、該第1のバリア層の膜厚の少なくとも90%以上とは、第1のバリア層中で連続していなくてもよく、単に90%以上の部分で上記した関係を満たしていればよい。
The first barrier layer is based on (i) the distance (L) from the surface of the first barrier layer in the film thickness direction of the first barrier layer and the total amount of silicon atoms, oxygen atoms, and carbon atoms. Silicon distribution curve showing the relationship with the ratio of the amount of silicon atoms (silicon atomic ratio), the ratio of the amount of oxygen atoms to the total amount of L and silicon atoms, oxygen atoms, and carbon atoms (oxygen atomic ratio) And the carbon distribution curve showing the relationship between the L and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon). In the region of 90% or more (upper limit: 100%) of the film thickness of the barrier layer, (oxygen atomic ratio), (silicon atomic ratio), (carbon atomic ratio) increase in this order (atomic ratio is O> Si> C) is preferred. When the above condition (i) is satisfied, the gas barrier property and flexibility of the obtained gas barrier film can be improved. Here, in the carbon distribution curve, the relationship among the above (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) is at least 90% or more (upper limit) of the film thickness of the first barrier layer. : 100%), and more preferably at least 93% or more (upper limit: 100%). Here, at least 90% or more of the film thickness of the first barrier layer does not have to be continuous in the first barrier layer, and simply satisfies the above-described relationship at 90% or more. Good.
また、該第1のバリア層は、(ii)前記炭素分布曲線が少なくとも2つの極値を有することが好ましい。該第1のバリア層は、前記炭素分布曲線が少なくとも3つの極値を有することがより好ましく、少なくとも4つの極値を有することがさらに好ましいが、5つ以上有していてもよい。前記炭素分布曲線の極値が2つ以上であれば、得られるガスバリア性フィルムを屈曲させた場合におけるガスバリア性が向上しうる。なお、炭素分布曲線の極値の上限は、特に制限されないが、例えば、好ましくは30以下、より好ましくは25以下であるが、極値の数は、第1のバリア層の膜厚にも起因するため、一概に規定することはできない。
The first barrier layer preferably has (ii) the carbon distribution curve has at least two extreme values. The first barrier layer preferably has at least three extreme values in the carbon distribution curve, and more preferably has at least four extreme values, but may have five or more extreme values. When the extreme value of the carbon distribution curve is two or more, the gas barrier property when the obtained gas barrier film is bent can be improved. The upper limit of the extreme value of the carbon distribution curve is not particularly limited. For example, it is preferably 30 or less, more preferably 25 or less, but the number of extreme values is also caused by the film thickness of the first barrier layer. Therefore, it cannot be specified in general.
ここで、少なくとも3つの極値を有する場合においては、前記炭素分布曲線の有する1つの極値および該極値に隣接する極値における前記第1のバリア層の膜厚方向における前記第1のバリア層の表面からの距離(L)の差の絶対値(以下、単に「極値間の距離」とも称する)が、いずれも200nm以下であることが好ましく、100nm以下であることがより好ましく、75nm以下であることが特に好ましい。このような極値間の距離であれば、第1のバリア層中に炭素原子比が多い部位(極大値)が適度な周期で存在するため、第1のバリア層に適度な屈曲性を付与し、ガスバリア性フィルムの屈曲時のクラックの発生をより有効に抑制・防止できる。なお、本明細書において「極値」とは、前記第1のバリア層の膜厚方向における前記第1のバリア層の表面からの距離(L)に対する元素の原子比の極大値または極小値のことをいう。また、本明細書において「極大値」とは、第1のバリア層の表面からの距離を変化させた場合に元素(酸素、ケイ素または炭素)の原子比の値が増加から減少に変わる点であって、かつその点の元素の原子比の値よりも、該点から第1のバリア層の膜厚方向における第1のバリア層の表面からの距離をさらに4~20nmの範囲で変化させた位置の元素の原子比の値が3at%以上減少する点のことをいう。すなわち、4~20nmの範囲で変化させた際に、いずれかの範囲で元素の原子比の値が3at%以上減少していればよい。同様にして、本明細書において「極小値」とは、第1のバリア層の表面からの距離を変化させた場合に元素(酸素、ケイ素または炭素)の原子比の値が減少から増加に変わる点であり、かつその点の元素の原子比の値よりも、該点から第1のバリア層の膜厚方向における第1のバリア層の表面からの距離をさらに4~20nmの範囲で変化させた位置の元素の原子比の値が3at%以上増加する点のことをいう。すなわち、4~20nmの範囲で変化させた際に、いずれかの範囲で元素の原子比の値が3at%以上増加していればよい。ここで、少なくとも3つの極値を有する場合の、極値間の距離の下限は、極値間の距離が小さいほどガスバリア性フィルムの屈曲時のクラック発生抑制/防止の向上効果が高いため、特に制限されないが、第1のバリア層の屈曲性、クラックの抑制/防止効果、熱膨張性などを考慮すると、10nm以上であることが好ましく、30nm以上であることがより好ましい。
Here, in the case of having at least three extreme values, the first barrier in the film thickness direction of the first barrier layer at one extreme value of the carbon distribution curve and an extreme value adjacent to the extreme value. The absolute value of the difference in distance (L) from the surface of the layer (hereinafter also simply referred to as “distance between extreme values”) is preferably 200 nm or less, more preferably 100 nm or less, and 75 nm. It is particularly preferred that With such a distance between extreme values, a portion having a high carbon atom ratio (maximum value) exists in the first barrier layer at an appropriate period, so that appropriate flexibility is imparted to the first barrier layer. In addition, the generation of cracks when the gas barrier film is bent can be more effectively suppressed / prevented. In this specification, “extreme value” means a maximum value or a minimum value of an atomic ratio of an element to a distance (L) from the surface of the first barrier layer in the film thickness direction of the first barrier layer. That means. In this specification, “maximum value” means that the atomic ratio value of an element (oxygen, silicon, or carbon) changes from increasing to decreasing when the distance from the surface of the first barrier layer is changed. In addition, the distance from the surface of the first barrier layer in the film thickness direction of the first barrier layer from the point is further changed within the range of 4 to 20 nm, rather than the atomic ratio value of the element at that point. This is the point where the atomic ratio value of the element at the position decreases by 3 at% or more. That is, it is sufficient that the atomic ratio value of the element is reduced by 3 at% or more in any range when changing in the range of 4 to 20 nm. Similarly, in this specification, the “minimum value” means that the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from a decrease to an increase when the distance from the surface of the first barrier layer is changed. The distance from the surface of the first barrier layer in the film thickness direction of the first barrier layer from the point is further changed within the range of 4 to 20 nm, rather than the value of the atomic ratio of the element at that point. This is the point at which the value of the atomic ratio of the element at the position increases by 3 at% or more. That is, when changing in the range of 4 to 20 nm, the atomic ratio value of the element only needs to increase by 3 at% or more in any range. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is particularly high because the smaller the distance between the extreme values, the higher the effect of suppressing / preventing crack generation when the gas barrier film is bent. Although not limited, in consideration of the flexibility of the first barrier layer, the effect of suppressing / preventing cracks, thermal expansion, and the like, the thickness is preferably 10 nm or more, and more preferably 30 nm or more.
さらに、該第1のバリア層は、(iii)前記炭素分布曲線における炭素の原子比の最大値および最小値の差の絶対値(以下、単に「Cmax-Cmin差」とも称する)が3at%以上であることが好ましい。前記絶対値が3at%以上であれば、得られるガスバリア性フィルムを屈曲させた場合のガスバリア性が向上しうる。Cmax-Cmin差は5at%以上であることがより好ましく、7at%以上であることがさらに好ましく、10at%以上であることが特に好ましい。上記Cmax-Cmin差とすることによって、ガスバリア性をより向上することができる。なお、本明細書において、「最大値」とは、各元素の分布曲線において最大となる各元素の原子比であり、極大値の中で最も高い値である。同様にして、本明細書において、「最小値」とは、各元素の分布曲線において最小となる各元素の原子比であり、極小値の中で最も低い値である。ここで、Cmax-Cmin差の上限は、特に制限されないが、ガスバリア性フィルムの屈曲時のクラック発生抑制/防止の向上効果などを考慮すると、50at%以下であることが好ましく、40at%以下であることがより好ましい。
Further, the first barrier layer has (iii) an absolute value of a difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve (hereinafter, also simply referred to as “C max −C min difference”) of 3 at. % Or more is preferable. When the absolute value is 3 at% or more, the gas barrier property when the obtained gas barrier film is bent can be improved. The C max −C min difference is more preferably 5 at% or more, further preferably 7 at% or more, and particularly preferably 10 at% or more. By setting the C max −C min difference, the gas barrier property can be further improved. In the present specification, the “maximum value” is the atomic ratio of each element that is maximum in the distribution curve of each element, and is the highest value among the maximum values. Similarly, in this specification, the “minimum value” is the atomic ratio of each element that is the minimum in the distribution curve of each element, and is the lowest value among the minimum values. Here, the upper limit of the C max -C min difference is not particularly limited, but it is preferably 50 at% or less in consideration of the effect of suppressing / preventing crack generation during bending of the gas barrier film, and is preferably 40 at% or less. It is more preferable that
本発明において、前記第1のバリア層の前記酸素分布曲線が少なくとも1つの極値を有することが好ましく、少なくとも2つの極値を有することがより好ましく、少なくとも3つの極値を有することがさらに好ましい。前記酸素分布曲線が極値を少なくとも1つ有する場合、得られるガスバリア性フィルムを屈曲させた場合におけるガスバリア性が極値を有さないガスバリア性フィルムと比較してより向上する。なお、酸素分布曲線の極値の上限は、特に制限されないが、例えば、好ましくは20以下、より好ましくは10以下である。酸素分布曲線の極値の数においても、第1のバリア層の膜厚に起因する部分があり一概に規定できない。また、少なくとも3つの極値を有する場合においては、前記酸素分布曲線の有する1つの極値および該極値に隣接する極値における前記第1のバリア層の膜厚方向における第1のバリア層の表面からの距離の差の絶対値がいずれも200nm以下であることが好ましく、100nm以下であることがより好ましい。このような極値間の距離であれば、ガスバリア性フィルムの屈曲時のクラックの発生をより有効に抑制・防止できる。ここで、少なくとも3つの極値を有する場合の、極値間の距離の下限は、特に制限されないが、ガスバリア性フィルムの屈曲時のクラック発生抑制/防止の向上効果、熱膨張性などを考慮すると、10nm以上であることが好ましく、30nm以上であることがより好ましい。
In the present invention, the oxygen distribution curve of the first barrier layer preferably has at least one extreme value, more preferably has at least two extreme values, and further preferably has at least three extreme values. . When the oxygen distribution curve has at least one extreme value, the gas barrier property when the obtained gas barrier film is bent is further improved as compared with a gas barrier film having no extreme value. The upper limit of the extreme value of the oxygen distribution curve is not particularly limited, but is preferably 20 or less, more preferably 10 or less, for example. Even in the number of extreme values of the oxygen distribution curve, there is a portion caused by the film thickness of the first barrier layer, and it cannot be defined unconditionally. In the case of having at least three extreme values, one extreme value of the oxygen distribution curve and the first barrier layer in the thickness direction of the first barrier layer at the extreme value adjacent to the extreme value. The absolute value of the difference in distance from the surface is preferably 200 nm or less, and more preferably 100 nm or less. With such a distance between extreme values, the occurrence of cracks during bending of the gas barrier film can be more effectively suppressed / prevented. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is not particularly limited, but considering the improvement effect of crack generation suppression / prevention when the gas barrier film is bent, the thermal expansion property, etc. The thickness is preferably 10 nm or more, and more preferably 30 nm or more.
前記ケイ素分布曲線、前記酸素分布曲線、前記炭素分布曲線、および前記酸素炭素分布曲線は、X線光電子分光法(XPS:Xray Photoelectron Spectroscopy)の測定とアルゴン等の希ガスイオンスパッタとを併用することにより、試料内部を露出させつつ順次表面組成分析を行う、いわゆるXPSデプスプロファイル測定により作成することができる。このようなXPSデプスプロファイル測定により得られる分布曲線は、例えば、縦軸を各元素の原子比(単位:at%)とし、横軸をエッチング時間(スパッタ時間)として作成することができる。なお、このように横軸をエッチング時間とする元素の分布曲線においては、エッチング時間は膜厚方向における前記第1のバリア層の膜厚方向における前記第1のバリア層の表面からの距離(L)に概ね相関することから、「第1のバリア層の膜厚方向における第1のバリア層の表面からの距離」として、XPSデプスプロファイル測定の際に採用したエッチング速度とエッチング時間との関係から算出される第1のバリア層の表面からの距離を採用することができる。なお、ケイ素分布曲線、酸素分布曲線、炭素分布曲線および酸素炭素分布曲線は、下記測定条件にて作成することができる。
The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination. Thus, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In this way, in the element distribution curve with the horizontal axis as the etching time, the etching time is the distance (L from the surface of the first barrier layer in the film thickness direction of the first barrier layer in the film thickness direction). ) From the relationship between the etching rate and the etching time employed in the XPS depth profile measurement as “the distance from the surface of the first barrier layer in the film thickness direction of the first barrier layer”. The calculated distance from the surface of the first barrier layer can be employed. The silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve can be prepared under the following measurement conditions.
(測定条件)
エッチングイオン種:アルゴン(Ar+)
エッチング速度(SiO2熱酸化膜換算値):0.05nm/sec
エッチング間隔(SiO2換算値):10nm
X線光電子分光装置:Thermo Fisher Scientific社製、機種名"VG Theta Probe"
照射X線:単結晶分光AlKα
X線のスポットおよびそのサイズ:800×400μmの楕円形。 (Measurement condition)
Etching ion species: Argon (Ar + )
Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO 2 equivalent value): 10 nm
X-ray photoelectron spectrometer: Model name "VG Theta Probe", manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 × 400 μm oval.
エッチングイオン種:アルゴン(Ar+)
エッチング速度(SiO2熱酸化膜換算値):0.05nm/sec
エッチング間隔(SiO2換算値):10nm
X線光電子分光装置:Thermo Fisher Scientific社製、機種名"VG Theta Probe"
照射X線:単結晶分光AlKα
X線のスポットおよびそのサイズ:800×400μmの楕円形。 (Measurement condition)
Etching ion species: Argon (Ar + )
Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO 2 equivalent value): 10 nm
X-ray photoelectron spectrometer: Model name "VG Theta Probe", manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 × 400 μm oval.
上記のプラズマCVD法により形成される第1のバリア層の膜厚(乾燥膜厚)は、特に制限されない。例えば、該第1のバリア層の1層当たりの膜厚は、20~3000nmであることが好ましく、50~2500nmであることがより好ましく、100~1000nmであることが特に好ましい。このような膜厚であれば、ガスバリア性フィルムは、優れたガスバリア性および屈曲時のクラック発生抑制/防止効果を発揮できる。なお、上記のプラズマCVD法により形成される第1のバリア層が2層以上から構成される場合には、各第1のバリア層が上記したような膜厚を有することが好ましい。
The film thickness (dry film thickness) of the first barrier layer formed by the plasma CVD method is not particularly limited. For example, the film thickness per layer of the first barrier layer is preferably 20 to 3000 nm, more preferably 50 to 2500 nm, and particularly preferably 100 to 1000 nm. With such a film thickness, the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending. In the case where the first barrier layer formed by the plasma CVD method is composed of two or more layers, it is preferable that each first barrier layer has the film thickness as described above.
本発明において、膜面全体において均一でかつ優れたガスバリア性を有する第1のバリア層を形成するという観点から、前記第1のバリア層が膜面方向(第1のバリア層の表面に平行な方向)において実質的に一様であることが好ましい。ここで、第1のバリア層が膜面方向において実質的に一様とは、XPSデプスプロファイル測定により第1のバリア層の膜面の任意の2箇所の測定箇所について前記酸素分布曲線、前記炭素分布曲線および前記酸素炭素分布曲線を作成した場合に、その任意の2箇所の測定箇所において得られる炭素分布曲線が持つ極値の数が同じであり、それぞれの炭素分布曲線における炭素の原子比の最大値および最小値の差の絶対値が、互いに同じであるかもしくは5at%以内の差であることをいう。
In the present invention, from the viewpoint of forming a first barrier layer having a uniform and excellent gas barrier property over the entire film surface, the first barrier layer is in the film surface direction (parallel to the surface of the first barrier layer). (Direction) is preferably substantially uniform. Here, the fact that the first barrier layer is substantially uniform in the film surface direction means that the oxygen distribution curve and the carbon are measured at any two measurement points on the film surface of the first barrier layer by XPS depth profile measurement. When the distribution curve and the oxygen carbon distribution curve are created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the atomic ratio of carbon in each carbon distribution curve The absolute value of the difference between the maximum value and the minimum value is the same or within 5 at%.
さらに、本発明においては、前記炭素分布曲線は実質的に連続であることが好ましい。ここで、炭素分布曲線が実質的に連続とは、炭素分布曲線における炭素の原子比が不連続に変化する部分を含まないことを意味し、具体的には、エッチング速度とエッチング時間とから算出される前記第1のバリア層のうちの少なくとも1層の膜厚方向における該第1のバリア層の表面からの距離(x、単位:nm)と、炭素の原子比(C、単位:at%)との関係において、下記数式1で表される条件を満たすことをいう。
Furthermore, in the present invention, it is preferable that the carbon distribution curve is substantially continuous. Here, the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, the carbon distribution curve is calculated from the etching rate and the etching time. The distance (x, unit: nm) from the surface of the first barrier layer in the film thickness direction of at least one layer of the first barrier layer and the atomic ratio of carbon (C, unit: at%) ), The condition expressed by the following formula 1 is satisfied.
本発明に係るガスバリア性フィルムにおいて、上記条件(i)~(iii)を全て満たす第1のバリア層は、1層のみを備えていてもよいし2層以上を備えていてもよい。さらに、このような第1のバリア層を2層以上備える場合には、複数の第1のバリア層の材質は、同一であってもよいし異なっていてもよい。
In the gas barrier film according to the present invention, the first barrier layer that satisfies all of the above conditions (i) to (iii) may include only one layer, or may include two or more layers. Further, when two or more such first barrier layers are provided, the materials of the plurality of first barrier layers may be the same or different.
本発明では、第1のバリア層の形成方法は特に制限されず、従来と方法を同様にしてあるいは適宜修飾して適用できる。第1のバリア層は、好ましくは化学気相成長(CVD)法、特に、プラズマ化学気相成長法(プラズマCVD、PECVD(plasma-enhanced chemical vapor deposition)、以下、単に「プラズマCVD法」とも称する)により形成され、基材を一対の成膜ローラー上に配置し、前記一対の成膜ローラー間に放電してプラズマを発生させるプラズマCVD法により形成されることがより好ましい。
In the present invention, the method for forming the first barrier layer is not particularly limited, and the conventional method and the method can be applied in the same manner or appropriately modified. The first barrier layer is preferably a chemical vapor deposition (CVD) method, particularly a plasma chemical vapor deposition method (plasma CVD, PECVD (plasma-enhanced chemical vapor deposition), hereinafter simply referred to as “plasma CVD method”). More preferably, the substrate is disposed on a pair of film forming rollers, and is formed by a plasma CVD method in which plasma is generated by discharging between the pair of film forming rollers.
以下では、基材を一対の成膜ローラー上に配置し、前記一対の成膜ローラー間に放電してプラズマを発生させるプラズマCVD法により、基材上に第1のバリア層を形成する方法を説明する。
Hereinafter, a method of forming a first barrier layer on a base material by a plasma CVD method in which the base material is disposed on a pair of film forming rollers and plasma is generated by discharging between the pair of film forming rollers. explain.
≪プラズマCVD法による第1のバリア層の形成方法≫
本発明に係る第1のバリア層を基材の表面上に形成させる方法としては、ガスバリア性の観点から、プラズマCVD法を採用することが好ましい。なお、前記プラズマCVD法はペニング放電プラズマ方式のプラズマCVD法であってもよい。 << Method for Forming First Barrier Layer by Plasma CVD >>
As a method for forming the first barrier layer according to the present invention on the surface of the base material, it is preferable to employ a plasma CVD method from the viewpoint of gas barrier properties. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.
本発明に係る第1のバリア層を基材の表面上に形成させる方法としては、ガスバリア性の観点から、プラズマCVD法を採用することが好ましい。なお、前記プラズマCVD法はペニング放電プラズマ方式のプラズマCVD法であってもよい。 << Method for Forming First Barrier Layer by Plasma CVD >>
As a method for forming the first barrier layer according to the present invention on the surface of the base material, it is preferable to employ a plasma CVD method from the viewpoint of gas barrier properties. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.
また、プラズマCVD法においてプラズマを発生させる際には、複数の成膜ローラーの間の空間にプラズマ放電を発生させることが好ましく、一対の成膜ローラーを用い、その一対の成膜ローラーのそれぞれに基材を配置して、一対の成膜ローラー間に放電してプラズマを発生させることがより好ましい。このようにして、一対の成膜ローラーを用い、その一対の成膜ローラー上に基材を配置して、かかる一対の成膜ローラー間に放電することにより、成膜時に一方の成膜ローラー上に存在する基材の表面部分を成膜しつつ、もう一方の成膜ローラー上に存在する基材の表面部分も同時に成膜することが可能となって効率よく薄膜を製造できるばかりか、通常のローラーを使用しないプラズマCVD法と比較して成膜レートを倍にでき、なおかつ、略同一である構造の膜を成膜できるので前記炭素分布曲線における極値を少なくとも倍増させることが可能となり、効率よく上記条件(i)~(iii)を全て満たす層を形成することが可能となる。
Further, when plasma is generated in the plasma CVD method, it is preferable to generate plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and each of the pair of film forming rollers is used. More preferably, a substrate is placed and discharged between a pair of film forming rollers to generate plasma. In this way, by using a pair of film forming rollers, placing a base material on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller It is possible not only to produce a thin film efficiently because it is possible to form a film on the surface part of the base material existing in the film while simultaneously forming a film on the surface part of the base material present on the other film forming roller. The film formation rate can be doubled compared to the plasma CVD method without using any roller, and since it is possible to form a film having a structure that is substantially the same, it is possible to at least double the extreme value in the carbon distribution curve, It is possible to efficiently form a layer that satisfies all of the above conditions (i) to (iii).
また、このようにして一対の成膜ローラー間に放電する際には、前記一対の成膜ローラーの極性を交互に反転させることが好ましい。さらに、このようなプラズマCVD法に用いる成膜ガスとしては、有機ケイ素化合物と酸素とを含むものが好ましく、その成膜ガス中の酸素の含有量は、前記成膜ガス中の前記有機ケイ素化合物の全量を完全酸化するのに必要な理論酸素量未満であることが好ましい。また、本発明のガスバリア性フィルムにおいては、前記第1のバリア層が連続的な成膜プロセスにより形成された層であることが好ましい。
Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma CVD method preferably contains an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation. In the gas barrier film of the present invention, the first barrier layer is preferably a layer formed by a continuous film formation process.
また、本発明に係るガスバリア性フィルムは、生産性の観点から、ロールツーロール方式で前記基材の表面上に前記第1のバリア層を形成させることが好ましい。また、このようなプラズマCVD法により第1のバリア層を製造する際に用いることが可能な装置としては、特に制限されないが、少なくとも一対の成膜ローラーと、プラズマ電源とを備え、かつ前記一対の成膜ローラー間において放電することが可能な構成となっている装置であることが好ましく、例えば、図2に示す製造装置を用いた場合には、プラズマCVD法を利用しながらロールツーロール方式で製造することも可能となる。
In addition, the gas barrier film according to the present invention preferably has the first barrier layer formed on the surface of the substrate by a roll-to-roll method from the viewpoint of productivity. Further, an apparatus that can be used when the first barrier layer is manufactured by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source. It is preferable that the apparatus has a configuration capable of discharging between the film forming rollers. For example, in the case where the manufacturing apparatus shown in FIG. 2 is used, a roll-to-roll method using a plasma CVD method is used. Can also be manufactured.
以下、図2を参照しながら、基材を一対の成膜ローラー上に配置し、前記一対の成膜ローラー間に放電してプラズマを発生させるプラズマCVD法による第1のバリア層の形成方法について、より詳細に説明する。なお、図2は、本製造方法より第1のバリア層を製造するために好適に利用することが可能な製造装置の一例を示す模式図である。また、以下の説明および図面中、同一または相当する要素には同一の符号を付し、重複する説明は省略する。
Hereinafter, with reference to FIG. 2, a method for forming a first barrier layer by a plasma CVD method in which a base material is disposed on a pair of film forming rollers and a plasma is generated by discharging between the pair of film forming rollers. This will be described in more detail. FIG. 2 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing the first barrier layer by this manufacturing method. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.
図2に示す製造装置31は、送り出しローラー32と、搬送ローラー33、34、35、36と、成膜ローラー39、40と、ガス供給管41と、プラズマ発生用電源42と、成膜ローラー39および40の内部に設置された磁場発生装置43、44と、巻取りローラー45とを備えている。また、このような製造装置においては、少なくとも成膜ローラー39、40と、ガス供給管41と、プラズマ発生用電源42と、磁場発生装置43、44とが図示を省略した真空チャンバ内に配置されている。さらに、このような製造装置31において前記真空チャンバは図示を省略した真空ポンプに接続されており、かかる真空ポンプにより真空チャンバ内の圧力を適宜調整することが可能となっている。
The manufacturing apparatus 31 shown in FIG. 2 includes a delivery roller 32, transport rollers 33, 34, 35, and 36, film formation rollers 39 and 40, a gas supply pipe 41, a plasma generation power source 42, and a film formation roller 39. And magnetic field generators 43 and 44 installed inside 40 and a winding roller 45. In such a manufacturing apparatus, at least the film forming rollers 39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic field generating apparatuses 43 and 44 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.
このような製造装置においては、一対の成膜ローラー(成膜ローラー39と成膜ローラー40)を一対の対向電極として機能させることが可能となるように、各成膜ローラーがそれぞれプラズマ発生用電源42に接続されている。そのため、このような製造装置31においては、プラズマ発生用電源42により電力を供給することにより、成膜ローラー39と成膜ローラー40との間の空間に放電することが可能であり、これにより成膜ローラー39と成膜ローラー40との間の空間にプラズマを発生させることができる。なお、このように、成膜ローラー39と成膜ローラー40とを電極としても利用する場合には、電極としても利用可能なようにその材質や設計を適宜変更すればよい。また、このような製造装置においては、一対の成膜ローラー(成膜ローラー39および40)は、その中心軸が同一平面上において略平行となるようにして配置することが好ましい。このようにして、一対の成膜ローラー(成膜ローラー39および40)を配置することにより、成膜レートを倍にでき、なおかつ、同じ構造の膜を成膜できるので前記炭素分布曲線における極値を少なくとも倍増させることが可能となる。そして、このような製造装置によれば、CVD法により基材2の表面上に第1のバリア層3を形成することが可能であり、成膜ローラー39上において基材2の表面上に第1のバリア層成分を堆積させつつ、さらに成膜ローラー40上においても基材2の表面上に第1のバリア層成分を堆積させることもできるため、基材2の表面上に第1のバリア層を効率よく形成することができる。
In such a manufacturing apparatus, each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes. 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge into the space between the film forming roller 39 and the film forming roller 40 by supplying electric power from the plasma generating power source 42. Plasma can be generated in the space between the film roller 39 and the film formation roller 40. In this way, when the film forming roller 39 and the film forming roller 40 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming roller (film-forming rollers 39 and 40) so that the central axis may become substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 39 and 40), the film forming rate can be doubled and a film having the same structure can be formed. Can be at least doubled. According to such a manufacturing apparatus, the first barrier layer 3 can be formed on the surface of the substrate 2 by the CVD method, and the first barrier layer 3 is formed on the surface of the substrate 2 on the film formation roller 39. While the first barrier layer component is deposited, the first barrier layer component can be deposited on the surface of the substrate 2 also on the film forming roller 40, so that the first barrier is formed on the surface of the substrate 2. A layer can be formed efficiently.
成膜ローラー39および成膜ローラー40の内部には、成膜ローラーが回転しても回転しないようにして固定された磁場発生装置43および44がそれぞれ設けられている。
In the film forming roller 39 and the film forming roller 40, magnetic field generators 43 and 44 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.
成膜ローラー39および成膜ローラー40にそれぞれ設けられた磁場発生装置43および44は、一方の成膜ローラー39に設けられた磁場発生装置43と他方の成膜ローラー40に設けられた磁場発生装置44との間で磁力線がまたがらず、それぞれの磁場発生装置43、44がほぼ閉じた磁気回路を形成するように磁極を配置することが好ましい。このような磁場発生装置43、44を設けることにより、各成膜ローラー39、40の対向側表面付近に磁力線が膨らんだ磁場の形成を促進することができ、その膨出部にプラズマが収束され易くなるため、成膜効率を向上させることができる点で優れている。
The magnetic field generators 43 and 44 provided on the film forming roller 39 and the film forming roller 40 are respectively a magnetic field generating device 43 provided on one film forming roller 39 and a magnetic field generating device provided on the other film forming roller 40. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between them and the magnetic field generators 43 and 44 form a substantially closed magnetic circuit. By providing such magnetic field generators 43 and 44, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell in the vicinity of the opposing surface of each film forming roller 39 and 40, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.
また、成膜ローラー39および成膜ローラー40にそれぞれ設けられた磁場発生装置43、44は、それぞれローラー軸方向に長いレーストラック状の磁極を備え、一方の磁場発生装置43と他方の磁場発生装置44とは向かい合う磁極が同一極性となるように磁極を配置することが好ましい。このような磁場発生装置43、44を設けることにより、それぞれの磁場発生装置43、44について、磁力線が対向するローラー側の磁場発生装置にまたがることなく、ローラー軸の長さ方向に沿って対向空間(放電領域)に面したローラー表面付近にレーストラック状の磁場を容易に形成することができ、その磁場にプラズマを収束させることができため、ローラー幅方向に沿って巻き掛けられた幅広の基材2を用いて効率的に蒸着膜である第1のバリア層3を形成することができる点で優れている。
The magnetic field generators 43 and 44 provided in the film forming roller 39 and the film forming roller 40 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 43 and the other magnetic field generator. It is preferable to arrange the magnetic poles so that the magnetic poles facing to 44 have the same polarity. By providing such magnetic field generators 43 and 44, the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force of each of the magnetic field generators 43 and 44 are opposed. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained. The material 2 is excellent in that the first barrier layer 3 that is a vapor deposition film can be efficiently formed.
成膜ローラー39および成膜ローラー40としては適宜公知のローラーを用いることができる。このような成膜ローラー39および40としては、より効率よく薄膜を形成せしめるという観点から、直径が同一のものを使うことが好ましい。また、このような成膜ローラー39および40の直径としては、放電条件、チャンバのスペース等の観点から、直径が300~1000mmφの範囲、特に300~700mmφの範囲が好ましい。成膜ローラーの直径が300mmφ以上であれば、プラズマ放電空間が小さくなることがないため生産性の劣化もなく、短時間でプラズマ放電の全熱量が基材2にかかることを回避できることから、基材2へのダメージを軽減でき好ましい。一方、成膜ローラーの直径が1000mmφ以下であれば、プラズマ放電空間の均一性等も含めて装置設計上、実用性を保持することができるため好ましい。
As the film formation roller 39 and the film formation roller 40, known rollers can be used as appropriate. As such film forming rollers 39 and 40, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, the diameter of the film forming rollers 39 and 40 is preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mmφ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated and it is possible to avoid applying the total amount of heat of the plasma discharge to the substrate 2 in a short time. It is preferable because damage to the material 2 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.
このような製造装置31においては、基材2の表面がそれぞれ対向するように、一対の成膜ローラー(成膜ローラー39と成膜ローラー40)上に、基材2が配置されている。このようにして基材2を配置することにより、成膜ローラー39と成膜ローラー40との間の対向空間に放電を行ってプラズマを発生させる際に、一対の成膜ローラー間に存在する基材2のそれぞれの表面を同時に成膜することが可能となる。すなわち、このような製造装置によれば、プラズマCVD法により、成膜ローラー39上にて基材2の表面上に第1のバリア層成分を堆積させ、さらに成膜ローラー40上にて第1のバリア層成分を堆積させることができるため、基材2の表面上に第1のバリア層を効率よく形成することが可能となる。
In such a manufacturing apparatus 31, the base material 2 is disposed on a pair of film forming rollers (the film forming roller 39 and the film forming roller 40) so that the surfaces of the base material 2 face each other. By disposing the base material 2 in this manner, when the plasma is generated by performing discharge in the facing space between the film formation roller 39 and the film formation roller 40, the base existing between the pair of film formation rollers is present. Each surface of the material 2 can be formed simultaneously. That is, according to such a manufacturing apparatus, the first barrier layer component is deposited on the surface of the base material 2 on the film forming roller 39 by the plasma CVD method, and the first film forming roller 40 further performs the first operation. Therefore, it is possible to efficiently form the first barrier layer on the surface of the substrate 2.
このような製造装置に用いる送り出しローラー32および搬送ローラー33、34、35、36としては適宜公知のローラーを用いることができる。また、巻取りローラー45としても、基材2上に第1のバリア層3を形成したガスバリア性フィルム1を巻き取ることが可能なものであればよく、特に制限されず、適宜公知のローラーを用いることができる。
As the feed roller 32 and the transport rollers 33, 34, 35, and 36 used in such a manufacturing apparatus, known rollers can be appropriately used. The winding roller 45 is not particularly limited as long as it can wind the gas barrier film 1 in which the first barrier layer 3 is formed on the substrate 2, and a known roller is appropriately used. Can be used.
また、ガス供給管41および真空ポンプとしては、原料ガス等を所定の速度で供給または排出することが可能なものを適宜用いることができる。
Further, as the gas supply pipe 41 and the vacuum pump, those capable of supplying or discharging the raw material gas at a predetermined speed can be appropriately used.
また、ガス供給手段であるガス供給管41は、成膜ローラー39と成膜ローラー40との間の対向空間(放電領域;成膜ゾーン)の一方に設けることが好ましく、真空排気手段である真空ポンプ(図示せず)は、前記対向空間の他方に設けることが好ましい。このようにガス供給手段であるガス供給管41と、真空排気手段である真空ポンプを配置することにより、成膜ローラー39と成膜ローラー40との間の対向空間に効率良く成膜ガスを供給することができ、成膜効率を向上させることができる点で優れている。
The gas supply pipe 41 as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 39 and the film formation roller 40, and is a vacuum as a vacuum exhaust means. A pump (not shown) is preferably provided on the other side of the facing space. As described above, by providing the gas supply pipe 41 as the gas supply means and the vacuum pump as the vacuum exhaust means, the film formation gas is efficiently supplied to the facing space between the film formation roller 39 and the film formation roller 40. It is excellent in that the film formation efficiency can be improved.
さらに、プラズマ発生用電源42としては、適宜公知のプラズマ発生装置の電源を用いることができる。このようなプラズマ発生用電源42は、これに接続された成膜ローラー39と成膜ローラー40とに電力を供給して、これらを放電のための対向電極として利用することを可能とする。このようなプラズマ発生用電源42としては、より効率よくプラズマCVDを実施することが可能となることから、前記一対の成膜ローラーの極性を交互に反転させることが可能なもの(交流電源など)を利用することが好ましい。また、このようなプラズマ発生用電源42としては、より効率よくプラズマCVDを実施することが可能となることから、印加電力を100W~10kWとすることができ、かつ交流の周波数を50Hz~500kHzとすることが可能なものであることがより好ましい。また、磁場発生装置43、44としては適宜公知の磁場発生装置を用いることができる。さらに、基材2としては、本発明で用いられる基材の他に、第1のバリア層3を予め形成させたものを用いることができる。このように、基材2として第1のバリア層3を予め形成させたものを用いることにより、第1のバリア層3の膜厚を厚くすることも可能である。
Furthermore, as the plasma generating power source 42, a known power source of a plasma generating apparatus can be used as appropriate. Such a plasma generating power supply 42 supplies power to the film forming roller 39 and the film forming roller 40 connected thereto, and makes it possible to use these as counter electrodes for discharge. Such a plasma generating power source 42 can perform plasma CVD more efficiently, and can alternately reverse the polarity of the pair of film forming rollers (AC power source or the like). Is preferably used. In addition, since the plasma generating power source 42 can perform plasma CVD more efficiently, the applied power can be set to 100 W to 10 kW, and the AC frequency can be set to 50 Hz to 500 kHz. More preferably, it is possible to do this. As the magnetic field generators 43 and 44, known magnetic field generators can be used as appropriate. Furthermore, as the base material 2, in addition to the base material used in the present invention, a material in which the first barrier layer 3 is previously formed can be used. As described above, by using the substrate 2 in which the first barrier layer 3 is formed in advance, the thickness of the first barrier layer 3 can be increased.
このような図2に示す製造装置31を用いて、例えば、原料ガスの種類、プラズマ発生装置の電極ドラムの電力、真空チャンバ内の圧力、成膜ローラーの直径、ならびにフィルム(基材)の搬送速度を適宜調整することにより、本発明に係る第1のバリア層を製造することができる。すなわち、図2に示す製造装置31を用いて、成膜ガス(原料ガス等)を真空チャンバ内に供給しつつ、一対の成膜ローラー(成膜ローラー39および40)間に放電を発生させることにより、前記成膜ガス(原料ガス等)がプラズマによって分解され、成膜ローラー39上の基材2の表面上および成膜ローラー40上の基材2の表面上に、第1のバリア層3がプラズマCVD法により形成される。この際、成膜ローラー39、40のローラー軸の長さ方向に沿って対向空間(放電領域)に面したローラー表面付近にレーストラック状の磁場が形成して、磁場にプラズマを収束させる。このため、基材2が、図2中の成膜ローラー39のA地点および成膜ローラー40のB地点を通過する際に、第1のバリア層で炭素分布曲線の極大値が形成される。これに対して、基材2が、図2中の成膜ローラー39のC1およびC2地点、ならびに成膜ローラー40のC3およびC4地点を通過する際に、第1のバリア層で炭素分布曲線の極小値が形成される。このため、2つの成膜ローラーに対して、通常、5つの極値が生成する。また、第1のバリア層の極値間の距離(炭素分布曲線の有する1つの極値および該極値に隣接する極値における第1のバリア層の膜厚方向における第1のバリア層の表面からの距離(L)の差の絶対値)は、成膜ローラー39、40の回転速度(基材の搬送速度)によって調節できる。なお、このような成膜に際しては、基材2が送り出しローラー32や成膜ローラー39等により、それぞれ搬送されることにより、ロールツーロール方式の連続的な成膜プロセスにより基材2の表面上に第1のバリア層3が形成される。
Using such a manufacturing apparatus 31 shown in FIG. 2, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the transport of the film (base material) By appropriately adjusting the speed, the first barrier layer according to the present invention can be produced. That is, using the manufacturing apparatus 31 shown in FIG. 2, a discharge is generated between the pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber. Thus, the film-forming gas (raw material gas or the like) is decomposed by plasma, and the first barrier layer 3 is formed on the surface of the base material 2 on the film-forming roller 39 and on the surface of the base material 2 on the film-forming roller 40. Is formed by plasma CVD. At this time, a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axes of the film forming rollers 39 and 40, and the plasma is converged on the magnetic field. For this reason, when the base material 2 passes the point A of the film forming roller 39 and the point B of the film forming roller 40 in FIG. 2, the maximum value of the carbon distribution curve is formed in the first barrier layer. On the other hand, when the base material 2 passes the points C1 and C2 of the film forming roller 39 and the points C3 and C4 of the film forming roller 40 in FIG. A local minimum is formed. For this reason, five extreme values are usually generated for two film forming rollers. Further, the distance between the extreme values of the first barrier layer (the surface of the first barrier layer in the thickness direction of the first barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value) (The absolute value of the difference in distance (L) from) can be adjusted by the rotation speed of the film forming rollers 39 and 40 (the conveyance speed of the substrate). In such film formation, the substrate 2 is conveyed by the delivery roller 32, the film formation roller 39, and the like, respectively, so that the surface of the substrate 2 is formed by a roll-to-roll continuous film formation process. First barrier layer 3 is formed.
前記ガス供給管41から対向空間に供給される成膜ガス(原料ガス等)としては、原料ガス、反応ガス、キャリアガス、放電ガスが単独または2種以上を混合して用いることができる。第1のバリア層3の形成に用いる前記成膜ガス中の原料ガスとしては、形成する第1のバリア層3の材質に応じて適宜選択して使用することができる。このような原料ガスとしては、例えば、ケイ素を含有する有機ケイ素化合物や炭素を含有する有機化合物ガスを用いることができる。このような有機ケイ素化合物としては、例えば、ヘキサメチルジシロキサン(HMDSO)、ヘキサメチルジシラン(HMDS)、1,1,3,3-テトラメチルジシロキサン、ビニルトリメチルシラン、メチルトリメチルシラン、ヘキサメチルジシラン、メチルシラン、ジメチルシラン、トリメチルシラン、ジエチルシラン、プロピルシラン、フェニルシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、テトラメトキシシラン(TMOS)、テトラエトキシシラン(TEOS)、フェニルトリメトキシシラン、メチルトリエトキシシラン、オクタメチルシクロテトラシロキサンが挙げられる。これらの有機ケイ素化合物の中でも、化合物の取り扱い性および得られる第1のバリア層のガスバリア性等の特性の観点から、ヘキサメチルジシロキサン、1,1,3,3-テトラメチルジシロキサンが好ましい。これらの有機ケイ素化合物は、単独でもまたは2種以上を組み合わせても使用することができる。また、炭素を含有する有機化合物ガスとしては、例えば、メタン、エタン、エチレン、アセチレンを例示することができる。これら有機ケイ素化合物ガスや有機化合物ガスは、第1のバリア層3の種類に応じて適切な原料ガスが選択される。
As the film forming gas (raw material gas or the like) supplied from the gas supply pipe 41 to the facing space, a raw material gas, a reactive gas, a carrier gas, or a discharge gas can be used alone or in combination of two or more. The source gas in the film forming gas used for forming the first barrier layer 3 can be appropriately selected and used according to the material of the first barrier layer 3 to be formed. As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane. , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of the handling properties of the compound and the gas barrier properties of the obtained first barrier layer. These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. As these organosilicon compound gas and organic compound gas, an appropriate source gas is selected according to the type of the first barrier layer 3.
また、前記成膜ガスとしては、前記原料ガスの他に反応ガスを用いてもよい。このような反応ガスとしては、前記原料ガスと反応して酸化物、窒化物等の無機化合物となるガスを適宜選択して使用することができる。酸化物を形成するための反応ガスとしては、例えば、酸素、オゾンを用いることができる。また、窒化物を形成するための反応ガスとしては、例えば、窒素、アンモニアを用いることができる。これらの反応ガスは、単独でもまたは2種以上を組み合わせても使用することができ、例えば酸窒化物を形成する場合には、酸化物を形成するための反応ガスと窒化物を形成するための反応ガスとを組み合わせて使用することができる。
Further, as the film forming gas, a reactive gas may be used in addition to the raw material gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.
前記成膜ガスとしては、前記原料ガスを真空チャンバ内に供給するために、必要に応じて、キャリアガスを用いてもよい。さらに、前記成膜ガスとしては、プラズマ放電を発生させるために、必要に応じて、放電用ガスを用いてもよい。このようなキャリアガスおよび放電用ガスとしては、適宜公知のものを使用することができ、例えば、ヘリウム、アルゴン、ネオン、キセノン等の希ガス;水素を用いることができる。
As the film forming gas, a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon; hydrogen can be used.
このような成膜ガスが原料ガスと反応ガスを含有する場合には、原料ガスと反応ガスの比率としては、原料ガスと反応ガスとを完全に反応させるために理論上必要となる反応ガスの量の比率よりも、反応ガスの比率を過剰にし過ぎないことが好ましい。反応ガスの比率を過剰にし過ぎないことで、形成される第1のバリア層3によって、優れたバリア性や耐屈曲性を得ることができる点で優れている。また、前記成膜ガスが前記有機ケイ素化合物と酸素とを含有するものである場合には、前記成膜ガス中の前記有機ケイ素化合物の全量を完全酸化するのに必要な理論酸素量以下であることが好ましい。
When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary to completely react the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. It is excellent in that excellent barrier properties and flex resistance can be obtained by forming the first barrier layer 3 by not excessively increasing the ratio of the reaction gas. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.
また、真空チャンバ内の圧力(真空度)は、原料ガスの種類等に応じて適宜調整することができるが、0.5Pa~50Paの範囲とすることが好ましい。
Further, the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 Pa to 50 Pa.
また、このようなプラズマCVD法において、成膜ローラー39と成膜ローラー40との間に放電するために、プラズマ発生用電源42に接続された電極ドラム(本実施形態においては、成膜ローラー39および40に設置されている)に印加する電力は、原料ガスの種類や真空チャンバ内の圧力等に応じて適宜調整することができるものであり一概に言えるものでないが、0.1~10kWの範囲とすることが好ましい。このような印加電力が100W以上であれば、パーティクルの発生を十分に抑制することができ、他方、10kW以下であれば、成膜時に発生する熱量を抑えることができ、成膜時の基材表面の温度が上昇するのを抑制できる。そのため基材が熱負けすることなく、成膜時に皺が発生するのを防止できる点で優れている。
In such a plasma CVD method, in order to discharge between the film forming roller 39 and the film forming roller 40, an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used. The power applied to the power source can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, and the like. It is preferable to be in the range. If such an applied power is 100 W or more, the generation of particles can be sufficiently suppressed. On the other hand, if the applied power is 10 kW or less, the amount of heat generated at the time of film formation can be suppressed. An increase in surface temperature can be suppressed. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.
基材2の搬送速度(ライン速度)は、原料ガスの種類や真空チャンバ内の圧力等に応じて適宜調整することができるが、0.25~100m/minの範囲とすることが好ましく、0.5~20m/minの範囲とすることがより好ましい。ライン速度が0.25m/min以上であれば、基材に熱に起因する皺の発生を効果的に抑制することができる。他方、100m/min以下であれば、生産性を損なうことなく、第1のバリア層として十分な膜厚を確保することができる点で優れている。
The conveyance speed (line speed) of the base material 2 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is in the range of 5 to 20 m / min. If the line speed is 0.25 m / min or more, generation of wrinkles due to heat in the substrate can be effectively suppressed. On the other hand, if it is 100 m / min or less, it is excellent at the point which can ensure sufficient film thickness as a 1st barrier layer, without impairing productivity.
上記したように、本実施形態のより好ましい態様としては、本発明に係る第1のバリア層を、図2に示す対向ロール電極を有するプラズマCVD装置(ロールツーロール方式)を用いたプラズマCVD法によって成膜することを特徴とするものである。これは、対向ロール電極を有するプラズマCVD装置(ロールツーロール方式)を用いて量産する場合に、可撓性(屈曲性)に優れ、機械的強度、特にロールツーロールでの搬送時の耐久性と、バリア性能とが両立する第1のバリア層を効率よく製造することができるためである。このような製造装置は、太陽電池や電子部品などに使用される温度変化に対する耐久性が求められるガスバリア性フィルムを、安価でかつ容易に量産することができる点でも優れている。
As described above, as a more preferable aspect of the present embodiment, a plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. 2 as the first barrier layer according to the present invention. The film is formed by the above. This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode. This is because it is possible to efficiently manufacture the first barrier layer in which the barrier performance is compatible. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.
<塗布法>
本発明に係る第1のバリア層は、例えば無機化合物を含有する液、好ましくはケイ素化合物を含有する液を塗布して形成される塗膜を改質処理して形成する方法(塗布法)で形成されてもよい。以下、無機化合物としてケイ素化合物を例に挙げて説明するが、前記無機化合物はケイ素化合物に限定されるものではない。 <Coating method>
The first barrier layer according to the present invention is a method (coating method) formed by modifying a coating film formed by applying a liquid containing an inorganic compound, preferably a liquid containing a silicon compound, for example. It may be formed. Hereinafter, the silicon compound will be described as an example of the inorganic compound, but the inorganic compound is not limited to the silicon compound.
本発明に係る第1のバリア層は、例えば無機化合物を含有する液、好ましくはケイ素化合物を含有する液を塗布して形成される塗膜を改質処理して形成する方法(塗布法)で形成されてもよい。以下、無機化合物としてケイ素化合物を例に挙げて説明するが、前記無機化合物はケイ素化合物に限定されるものではない。 <Coating method>
The first barrier layer according to the present invention is a method (coating method) formed by modifying a coating film formed by applying a liquid containing an inorganic compound, preferably a liquid containing a silicon compound, for example. It may be formed. Hereinafter, the silicon compound will be described as an example of the inorganic compound, but the inorganic compound is not limited to the silicon compound.
(ケイ素化合物)
前記ケイ素化合物としては、ケイ素化合物を含有する塗布液の調製が可能であれば特に限定はされない。 (Silicon compound)
The silicon compound is not particularly limited as long as a coating solution containing a silicon compound can be prepared.
前記ケイ素化合物としては、ケイ素化合物を含有する塗布液の調製が可能であれば特に限定はされない。 (Silicon compound)
The silicon compound is not particularly limited as long as a coating solution containing a silicon compound can be prepared.
具体的には、例えば、パーヒドロポリシラザン、オルガノポリシラザン、シルセスキオキサン、テトラメチルシラン、トリメチルメトキシシラン、ジメチルジメトキシシラン、メチルトリメトキシシラン、トリメチルエトキシシラン、ジメチルジエトキシシラン、メチルトリエトキシシラン、テトラメトキシシラン、テトラメトキシシラン、ヘキサメチルジシロキサン、ヘキサメチルジシラザン、1,1-ジメチル-1-シラシクロブタン、トリメチルビニルシラン、メトキシジメチルビニルシラン、トリメトキシビニルシラン、エチルトリメトキシシラン、ジメチルジビニルシラン、ジメチルエトキシエチニルシラン、ジアセトキシジメチルシラン、ジメトキシメチル-3,3,3-トリフルオロプロピルシラン、3,3,3-トリフルオロプロピルトリメトキシシラン、アリールトリメトキシシラン、エトキシジメチルビニルシラン、アリールアミノトリメトキシシラン、N-メチル-N-トリメチルシリルアセトアミド、3-アミノプロピルトリメトキシシラン、メチルトリビニルシラン、ジアセトキシメチルビニルシラン、メチルトリアセトキシシラン、アリールオキシジメチルビニルシラン、ジエチルビニルシラン、ブチルトリメトキシシラン、3-アミノプロピルジメチルエトキシシラン、テトラビニルシラン、トリアセトキシビニルシラン、テトラアセトキシシラン、3-トリフルオロアセトキシプロピルトリメトキシシラン、ジアリールジメトキシシラン、ブチルジメトキシビニルシラン、トリメチル-3-ビニルチオプロピルシラン、フェニルトリメチルシラン、ジメトキシメチルフェニルシラン、フェニルトリメトキシシラン、3-アクリロキシプロピルジメトキシメチルシラン、3-アクリロキシプロピルトリメトキシシラン、ジメチルイソペンチロキシビニルシラン、2-アリールオキシエチルチオメトキシトリメチルシラン、3-グリシドキシプロピルトリメトキシシラン、3-アリールアミノプロピルトリメトキシシラン、ヘキシルトリメトキシシラン、ヘプタデカフルオロデシルトリメトキシシラン、ジメチルエチキシフェニルシラン、ベンゾイロキシトリメチルシラン、3-メタクリロキシプロピルジメトキシメチルシラン、3-メタクリロキシプロピルトリメトキシシラン、3-イソシアネートプロピルトリエトキシシラン、ジメチルエトキシ-3-グリシドキシプロピルシラン、ジブトキシジメチルシラン、3-ブチルアミノプロピルトリメチルシラン、3-ジメチルアミノプロピルジエトキシメチルシラン、2-(2-アミノエチルチオエチル)トリエトキシシラン、ビス(ブチルアミノ)ジメチルシラン、ジビニルメチルフェニルシラン、ジアセトキシメチルフェニルシラン、ジメチル-p-トリルビニルシラン、p-スチリルトリメトキシシラン、ジエチルメチルフェニルシラン、ベンジルジメチルエトキシシラン、ジエトキシメチルフェニルシラン、デシルメチルジメトキシシラン、ジエトキシ-3-グリシドキシプロピルメチルシラン、オクチロキシトリメチルシラン、フェニルトリビニルシラン、テトラアリールオキシシラン、ドデシルトリメチルシラン、ジアリールメチルフェニルシラン、ジフェニルメチルビニルシラン、ジフェニルエトキシメチルシラン、ジアセトキシジフェニルシラン、ジベンジルジメチルシラン、ジアリールジフェニルシラン、オクタデシルトリメチルシラン、メチルオクタデシルジメチルシラン、ドコシルメチルジメチルシラン、1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン、1,3-ジビニル-1,1,3,3-テトラメチルジシラザン、1,4-ビス(ジメチルビニルシリル)ベンゼン、1,3-ビス(3-アセトキシプロピル)テトラメチルジシロキサン、1,3,5-トリメチル-1,3,5-トリビニルシクロトリシロキサン、1,3,5-トリス(3,3,3-トリフルオロプロピル)-1,3,5-トリメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、1,3,5,7-テトラエトキシ-1,3,5,7-テトラメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン等を挙げることができる。これらケイ素化合物は、単独でもまたは2種以上組み合わせても用いることができる。
Specifically, for example, perhydropolysilazane, organopolysilazane, silsesquioxane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, Tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, dimethyldivinylsilane, dimethyl Ethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,3-trifluoro Ropropyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylaminotrimethoxysilane, N-methyl-N-trimethylsilylacetamide, 3-aminopropyltrimethoxysilane, methyltrivinylsilane, diacetoxymethylvinylsilane, methyltriacetoxy Silane, aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, tetraacetoxysilane, 3-trifluoroacetoxypropyltrimethoxysilane, diaryldimethoxysilane, butyldimethoxy Vinylsilane, trimethyl-3-vinylthiopropylsilane, phenyltrimethylsila , Dimethoxymethylphenylsilane, phenyltrimethoxysilane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3-glycidoxy Propyltrimethoxysilane, 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, dimethylethoxyphenylsilane, benzoyloxytrimethylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3- Methacryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethylethoxy-3-glycidoxypropylsilane, di Butoxydimethylsilane, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, divinylmethylphenylsilane, di Acetoxymethylphenylsilane, dimethyl-p-tolylvinylsilane, p-styryltrimethoxysilane, diethylmethylphenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, decylmethyldimethoxysilane, diethoxy-3-glycidoxypropylmethylsilane , Octyloxytrimethylsilane, phenyltrivinylsilane, tetraaryloxysilane, dodecyltrimethylsilane, diarylmethylphenylsilane, diphenylmethyl Vinylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, octadecyltrimethylsilane, methyloctadecyldimethylsilane, docosylmethyldimethylsilane, 1,3-divinyl-1,1,3,3- Tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylvinylsilyl) benzene, 1,3-bis (3-acetoxypropyl) tetramethyldi Siloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotri Siloxane, octamethylcyclotetrasiloxane, 1,3, , It may be mentioned 7-tetraethoxy-1,3,5,7-tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. These silicon compounds can be used alone or in combination of two or more.
中でも、成膜性、クラック等の欠陥が少ないこと、残留有機物の少なさの点で、パーヒドロポリシラザン、オルガノポリシラザン等のポリシラザン;シルセスキオキサン等のポリシロキサン等が好ましく、ガスバリア性能が高く、屈曲時および高温高湿条件下であってもバリア性能が維持されることから、ポリシラザンがより好ましく、パーヒドロポリシラザンが特に好ましい。なお、ポリシラザンは、上記変性ポリシラザンにおいて説明しものと同様であるため、ここでは説明を省略する。
Among these, polysilazane such as perhydropolysilazane and organopolysilazane; polysiloxane such as silsesquioxane, etc. are preferable in terms of film formation, fewer defects such as cracks, and less residual organic matter, and high gas barrier performance. Polysilazane is more preferable, and perhydropolysilazane is particularly preferable because the barrier performance is maintained even when bent and under high temperature and high humidity conditions. The polysilazane is the same as that described in the modified polysilazane, and the description thereof is omitted here.
ポリシラザンを用いる場合、改質処理前の第1のバリア層中におけるポリシラザンの含有率としては、第1のバリア層の全質量を100質量%としたとき、100質量%でありうる。また、第1のバリア層がポリシラザン以外のものを含む場合には、層中におけるポリシラザンの含有率は、10質量%以上99質量%以下であることが好ましく、40質量%以上95質量%以下であることがより好ましく、特に好ましくは70質量%以上95質量%以下である。
When polysilazane is used, the content of polysilazane in the first barrier layer before the modification treatment may be 100% by mass when the total mass of the first barrier layer is 100% by mass. Moreover, when the first barrier layer contains a material other than polysilazane, the content of polysilazane in the layer is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass or less. More preferably, it is 70 mass% or more and 95 mass% or less.
上記のような第1のバリア層の塗布法による形成方法は、特に制限されず、公知の方法が適用できるが、有機溶剤中にケイ素化合物および必要に応じて触媒を含む第1のバリア層形成用塗布液を公知の湿式塗布方法により塗布し、この溶剤を蒸発させて除去し、次いで、改質処理を行う方法が好ましい。
The method for forming the first barrier layer by the application method as described above is not particularly limited, and a known method can be applied. However, the first barrier layer formation containing a silicon compound and, if necessary, a catalyst in an organic solvent is possible. It is preferable to apply the coating liquid for coating by a known wet coating method, evaporate and remove the solvent, and then perform a modification treatment.
(第1のバリア層形成用塗布液)
第1のバリア層形成用塗布液を調製するための溶剤としては、ケイ素化合物を溶解できるものであれば特に制限されないが、ケイ素化合物と容易に反応してしまう水および反応性基(例えば、ヒドロキシル基、あるいはアミン基等)を含まず、ケイ素化合物に対して不活性の有機溶剤が好ましく、非プロトン性の有機溶剤がより好ましい。具体的には、溶剤としては、非プロトン性溶剤;例えば、ペンタン、2,2,4-トリメチルペンタン、ヘキサン、シクロヘキサン、トルエン、キシレン、ソルベッソ、ターペン等の、脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素等の炭化水素溶媒;塩化メチレン、トリクロロエタン等のハロゲン炭化水素溶媒;酢酸エチル、酢酸ブチル等のエステル類;アセトン、メチルエチルケトン等のケトン類;ジブチルエーテル、ジオキサン、テトラヒドロフラン、モノ-およびポリアルキレングリコールジアルキルエーテル(ジグライム類)等の脂肪族エーテル、脂環式エーテル等のエーテル類などを挙げることができる。上記溶剤は、ケイ素化合物の溶解度や溶剤の蒸発速度等の目的にあわせて選択され、単独で使用されてもまたは2種以上の混合物の形態で使用されてもよい。 (First barrier layer forming coating solution)
The solvent for preparing the first barrier layer forming coating solution is not particularly limited as long as it can dissolve the silicon compound, but water and reactive groups (for example, hydroxyl group) that easily react with the silicon compound. An organic solvent that is inert to the silicon compound and more preferably an aprotic organic solvent. Specifically, the solvent is an aprotic solvent; for example, pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, solvesso, terpene, aliphatic hydrocarbons, alicyclic carbonization, etc. Hydrocarbon solvents such as hydrogen and aromatic hydrocarbons; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Dibutyl ether, dioxane, tetrahydrofuran, mono- And aliphatic ethers such as polyalkylene glycol dialkyl ethers (diglymes) and ethers such as alicyclic ethers. The solvent is selected according to purposes such as the solubility of the silicon compound and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.
第1のバリア層形成用塗布液を調製するための溶剤としては、ケイ素化合物を溶解できるものであれば特に制限されないが、ケイ素化合物と容易に反応してしまう水および反応性基(例えば、ヒドロキシル基、あるいはアミン基等)を含まず、ケイ素化合物に対して不活性の有機溶剤が好ましく、非プロトン性の有機溶剤がより好ましい。具体的には、溶剤としては、非プロトン性溶剤;例えば、ペンタン、2,2,4-トリメチルペンタン、ヘキサン、シクロヘキサン、トルエン、キシレン、ソルベッソ、ターペン等の、脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素等の炭化水素溶媒;塩化メチレン、トリクロロエタン等のハロゲン炭化水素溶媒;酢酸エチル、酢酸ブチル等のエステル類;アセトン、メチルエチルケトン等のケトン類;ジブチルエーテル、ジオキサン、テトラヒドロフラン、モノ-およびポリアルキレングリコールジアルキルエーテル(ジグライム類)等の脂肪族エーテル、脂環式エーテル等のエーテル類などを挙げることができる。上記溶剤は、ケイ素化合物の溶解度や溶剤の蒸発速度等の目的にあわせて選択され、単独で使用されてもまたは2種以上の混合物の形態で使用されてもよい。 (First barrier layer forming coating solution)
The solvent for preparing the first barrier layer forming coating solution is not particularly limited as long as it can dissolve the silicon compound, but water and reactive groups (for example, hydroxyl group) that easily react with the silicon compound. An organic solvent that is inert to the silicon compound and more preferably an aprotic organic solvent. Specifically, the solvent is an aprotic solvent; for example, pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, solvesso, terpene, aliphatic hydrocarbons, alicyclic carbonization, etc. Hydrocarbon solvents such as hydrogen and aromatic hydrocarbons; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Dibutyl ether, dioxane, tetrahydrofuran, mono- And aliphatic ethers such as polyalkylene glycol dialkyl ethers (diglymes) and ethers such as alicyclic ethers. The solvent is selected according to purposes such as the solubility of the silicon compound and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.
第1のバリア層形成用塗布液におけるケイ素化合物の濃度は、特に制限されず、層の膜厚や塗布液のポットライフによっても異なるが、好ましくは1~80質量%、より好ましくは5~50質量%、特に好ましくは10~40質量%である。
The concentration of the silicon compound in the first barrier layer-forming coating solution is not particularly limited and varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 1 to 80% by mass, more preferably 5 to 50. % By mass, particularly preferably 10 to 40% by mass.
第1のバリア層形成用塗布液は、改質を促進するために、触媒を含有することが好ましい。本発明に適用可能な触媒としては、塩基性触媒が好ましく、特に、N,N-ジエチルエタノールアミン、N,N-ジメチルエタノールアミン、トリエタノールアミン、トリエチルアミン、3-モルホリノプロピルアミン、N,N,N’,N’-テトラメチル-1,3-ジアミノプロパン、N,N,N’,N’-テトラメチル-1,6-ジアミノヘキサン等のアミン触媒、Ptアセチルアセトナート等のPt化合物、プロピオン酸Pd等のPd化合物、Rhアセチルアセトナート等のRh化合物等の金属触媒、N-複素環式化合物が挙げられる。これらのうち、アミン触媒を用いることが好ましい。この際添加する触媒の濃度としては、ケイ素化合物を基準としたとき、好ましくは0.1~10質量%、より好ましくは0.5~7質量%の範囲である。触媒添加量をこの範囲とすることで、反応の急激な進行による過剰なシラノール形成、および膜密度の低下、膜欠陥の増大などを避けることができる。
The first barrier layer forming coating solution preferably contains a catalyst in order to promote reforming. As the catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, Amine catalysts such as N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on the silicon compound. By setting the amount of the catalyst to be in this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.
また、特開2005-231039号に記載のように第1のバリア層の形成にゾルゲル法を用いることができる。ゾルゲル法により改質層を形成する際に用いられる塗布液は、ケイ素化合物、ならびにポリビニルアルコール系樹脂およびエチレン・ビニルアルコール共重合体の少なくとも1種を含むことが好ましい。
Further, as described in JP-A-2005-231039, a sol-gel method can be used for forming the first barrier layer. The coating solution used when forming the modified layer by the sol-gel method preferably contains a silicon compound and at least one of a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer.
(第1のバリア層形成用塗布液を塗布する方法)
第1のバリア層形成用塗布液を塗布する方法としては、従来公知の適切な湿式塗布方法が採用され得る。具体例としては、スピンコート法、ロールコート法、フローコート法、インクジェット法、スプレーコート法、プリント法、ディップコート法、流延成膜法、バーコート法、グラビア印刷法等が挙げられる。 (Method for applying first barrier layer forming coating solution)
As a method for applying the first barrier layer forming coating solution, a conventionally known appropriate wet coating method may be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
第1のバリア層形成用塗布液を塗布する方法としては、従来公知の適切な湿式塗布方法が採用され得る。具体例としては、スピンコート法、ロールコート法、フローコート法、インクジェット法、スプレーコート法、プリント法、ディップコート法、流延成膜法、バーコート法、グラビア印刷法等が挙げられる。 (Method for applying first barrier layer forming coating solution)
As a method for applying the first barrier layer forming coating solution, a conventionally known appropriate wet coating method may be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
塗布厚さは、目的に応じて適切に設定され得る。例えば、第1のバリア層1層当たりの塗布厚さは、乾燥後の厚さが10nm~10μm程度であることが好ましく、15nm~1μmであることがより好ましく、20~500nmであることがさらに好ましい。膜厚が10nm以上であれば十分なバリア性を得ることができ、10μm以下であれば、層形成時に安定した塗布性を得ることができ、かつ高い光線透過性を実現できる。
The coating thickness can be appropriately set according to the purpose. For example, the coating thickness per first barrier layer is preferably about 10 nm to 10 μm after drying, more preferably 15 nm to 1 μm, and further preferably 20 to 500 nm. preferable. If the film thickness is 10 nm or more, sufficient barrier properties can be obtained, and if it is 10 μm or less, stable coating properties can be obtained during layer formation, and high light transmittance can be realized.
塗布液を塗布した後は、塗膜を乾燥させることが好ましい。塗膜を乾燥することによって、塗膜中に含有される有機溶媒などの溶剤を除去することができる。この際、塗膜に含有される溶剤は、すべてを乾燥させてもよいが、一部残存させていてもよい。一部の溶剤を残存させる場合であっても、好適な第1のバリア層が得られうる。なお、残存する溶剤は後に除去されうる。
After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, a solvent such as an organic solvent contained in the coating film can be removed. At this time, all of the solvent contained in the coating film may be dried or may be partially left. Even when a part of the solvent is left, a suitable first barrier layer can be obtained. The remaining solvent can be removed later.
塗膜の乾燥温度は、適用する基材によっても異なるが、50~200℃であることが好ましい。例えば、ガラス転位温度(Tg)が70℃のポリエチレンテレフタレート基材を基材として用いる場合には、乾燥温度は、熱による基材の変形等を考慮して150℃以下に設定することが好ましい。上記温度は、ホットプレート、オーブン、ファーネスなどを使用することによって設定されうる。乾燥時間は短時間に設定することが好ましく、例えば、乾燥温度が150℃である場合には30分以内に設定することが好ましい。また、乾燥雰囲気は、大気雰囲気下、窒素雰囲気下、アルゴン雰囲気下、真空雰囲気下、酸素濃度をコントロールした減圧雰囲気下等のいずれの条件であってもよい。
The drying temperature of the coating film varies depending on the substrate to be applied, but is preferably 50 to 200 ° C. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the substrate, the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat. The temperature can be set by using a hot plate, oven, furnace or the like. The drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes. The drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.
<塗布法により形成された第1のバリア層の改質処理>
本発明における塗布法により形成された第1のバリア層の改質処理とは、ケイ素化合物の酸化ケイ素または酸窒化ケイ素等への転化反応を指し、具体的にはガスバリア性フィルムが全体としてガスバリア性(水蒸気透過率が、1×10-3g/m2・day以下)を発現するに貢献できるレベルの無機薄膜を形成する処理をいう。 <Modification treatment of first barrier layer formed by coating method>
The modification treatment of the first barrier layer formed by the coating method in the present invention refers to a conversion reaction of a silicon compound to silicon oxide, silicon oxynitride, or the like. Specifically, the gas barrier film as a whole has gas barrier properties. This refers to a process for forming an inorganic thin film at a level that can contribute to the expression of (water vapor permeability of 1 × 10 −3 g / m 2 · day or less).
本発明における塗布法により形成された第1のバリア層の改質処理とは、ケイ素化合物の酸化ケイ素または酸窒化ケイ素等への転化反応を指し、具体的にはガスバリア性フィルムが全体としてガスバリア性(水蒸気透過率が、1×10-3g/m2・day以下)を発現するに貢献できるレベルの無機薄膜を形成する処理をいう。 <Modification treatment of first barrier layer formed by coating method>
The modification treatment of the first barrier layer formed by the coating method in the present invention refers to a conversion reaction of a silicon compound to silicon oxide, silicon oxynitride, or the like. Specifically, the gas barrier film as a whole has gas barrier properties. This refers to a process for forming an inorganic thin film at a level that can contribute to the expression of (water vapor permeability of 1 × 10 −3 g / m 2 · day or less).
ケイ素化合物の酸化ケイ素または酸窒化ケイ素等への転化反応は、公知の方法を適宜選択して適用することができる。改質処理としては、具体的には、プラズマ処理、紫外線照射処理、加熱処理が挙げられる。
The conversion reaction of the silicon compound to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method. Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment.
(真空紫外線照射処理:エキシマ照射処理)
本発明において、最も好ましい改質処理方法は、真空紫外線照射による処理(エキシマ照射処理)である。真空紫外線照射による処理は、ポリシラザン化合物内の原子間結合力より大きい100~200nmの光エネルギーを用い、好ましくは100~180nmの波長の光エネルギーを用い、原子の結合を光量子プロセスと呼ばれる光子のみの作用により、直接切断しながら活性酸素やオゾンによる酸化反応を進行させることで、比較的低温(約200℃以下)で、酸化ケイ素膜の形成を行う方法である。なお、エキシマ照射処理を行う際は、上述したように熱処理を併用することが好ましく、その際の熱処理条件の詳細は上述したとおりである。 (Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). The treatment by the vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds atoms with only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action. In addition, when performing an excimer irradiation process, it is preferable to use heat processing together as mentioned above, and the detail of the heat processing conditions in that case is as having mentioned above.
本発明において、最も好ましい改質処理方法は、真空紫外線照射による処理(エキシマ照射処理)である。真空紫外線照射による処理は、ポリシラザン化合物内の原子間結合力より大きい100~200nmの光エネルギーを用い、好ましくは100~180nmの波長の光エネルギーを用い、原子の結合を光量子プロセスと呼ばれる光子のみの作用により、直接切断しながら活性酸素やオゾンによる酸化反応を進行させることで、比較的低温(約200℃以下)で、酸化ケイ素膜の形成を行う方法である。なお、エキシマ照射処理を行う際は、上述したように熱処理を併用することが好ましく、その際の熱処理条件の詳細は上述したとおりである。 (Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). The treatment by the vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds atoms with only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action. In addition, when performing an excimer irradiation process, it is preferable to use heat processing together as mentioned above, and the detail of the heat processing conditions in that case is as having mentioned above.
本発明においての放射線源は、100~180nmの波長の光を発生させるものであれば良いが、好適には約172nmに最大放射を有するエキシマラジエータ(例えば、Xeエキシマランプ)、約185nmに輝線を有する低圧水銀蒸気ランプ、並びに230nm以下の波長成分を有する中圧および高圧水銀蒸気ランプ、および約222nmに最大放射を有するエキシマランプである。
The radiation source in the present invention may be any radiation source that emits light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator having a maximum emission at about 172 nm (eg, Xe excimer lamp), and has an emission line at about 185 nm. Low pressure mercury vapor lamps, and medium and high pressure mercury vapor lamps having a wavelength component of 230 nm or less, and excimer lamps having maximum emission at about 222 nm.
このうち、Xeエキシマランプは、波長の短い172nmの紫外線を単一波長で放射することから、発光効率に優れている。この光は、酸素の吸収係数が大きいため、微量な酸素でラジカルな酸素原子種やオゾンを高濃度で発生することができる。
Among these, the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.
また、波長の短い172nmの光のエネルギーは、有機物の結合を解離させる能力が高いことが知られている。この活性酸素やオゾンと紫外線放射が持つ高いエネルギーによって、短時間でポリシラザン塗膜の改質を実現できる。
Also, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.
エキシマランプは光の発生効率が高いため、低い電力の投入で点灯させることが可能である。また、光による温度上昇の要因となる波長の長い光は発せず、紫外線領域で、すなわち短い波長でエネルギーを照射するため、解射対象物の表面温度の上昇が抑えられる特徴を持っている。このため、熱の影響を受けやすいとされるPETなどのフレシキブルフィルム材料に適している。
¡Excimer lamps have high light generation efficiency and can be lit with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.
紫外線照射時の反応には、酸素が必要であるが、真空紫外線は、酸素による吸収があるため紫外線照射工程での効率が低下しやすいことから、真空紫外線の照射は、可能な限り酸素濃度および水蒸気濃度の低い状態で行うことが好ましい。すなわち、真空紫外線照射時の酸素濃度は、10~20,000体積ppmとすることが好ましく、より好ましくは50~10,000体積ppmである。また、転化プロセスの間の水蒸気濃度は、好ましくは1000~4000体積ppmの範囲である。
Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of irradiation with vacuum ultraviolet rays is preferably 10 to 20,000 volume ppm, more preferably 50 to 10,000 volume ppm. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.
真空紫外線照射時に用いられる、照射雰囲気を満たすガスとしては乾燥不活性ガスとすることが好ましく、特にコストの観点から乾燥窒素ガスにすることが好ましい。酸素濃度の調整は照射庫内へ導入する酸素ガス、不活性ガスの流量を計測し、流量比を変えることで調整可能である。
The gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays is preferably a dry inert gas, and particularly preferably dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.
真空紫外線照射工程において、ポリシラザン塗膜が受ける塗膜面での該真空紫外線の照度は1mW/cm2~10W/cm2であると好ましく、30mW/cm2~200mW/cm2であることがより好ましく、50mW/cm2~160mW/cm2であるとさらに好ましい。1mW/cm2以上であれば、十分な改質効率が得られ、10W/cm2以下であれば、塗膜にアブレーションを生じにくく、基材にダメージを与えにくい。
In the vacuum ultraviolet irradiation process, the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane coating is preferably 1 mW / cm 2 to 10 W / cm 2 , more preferably 30 mW / cm 2 to 200 mW / cm 2. preferably, further preferably at 50mW / cm 2 ~ 160mW / cm 2. If it is 1 mW / cm 2 or more, sufficient reforming efficiency is obtained, and if it is 10 W / cm 2 or less, it is difficult to cause ablation in the coating film and damage the substrate.
塗膜面における真空紫外線の照射エネルギー量(積算光量)は、10~10000mJ/cm2であることが好ましく、100~8000mJ/cm2であることがより好ましく、200~6000mJ/cm2であることがさらに好ましい。10mJ/cm2以上であれば、改質が十分に進行しうる。10000mJ/cm2以下であれば、過剰改質によるクラック発生や、基材の熱変形が生じにくい。
Irradiation energy amount of the VUV in the coated surface (integrated quantity of light), it preferably from 10 ~ 10000mJ / cm 2, more preferably 100 ~ 8000mJ / cm 2, a 200 ~ 6000mJ / cm 2 Is more preferable. If it is 10 mJ / cm 2 or more, the modification can proceed sufficiently. If it is 10,000 mJ / cm 2 or less, cracking due to over-reformation and thermal deformation of the substrate are unlikely to occur.
また、改質に用いられる真空紫外光は、CO、CO2およびCH4の少なくとも一種を含むガスで形成されたプラズマにより発生させてもよい。さらに、CO、CO2およびCH4の少なくとも一種を含むガス(以下、炭素含有ガスとも称する)は、炭素含有ガスを単独で使用してもよいが、希ガスまたはH2を主ガスとして、炭素含有ガスを少量添加することが好ましい。プラズマの生成方式としては容量結合プラズマなどが挙げられる。
Further, the vacuum ultraviolet light used for reforming, CO, may be generated by plasma formed in a gas containing at least one of CO 2 and CH 4. Further, as the gas containing at least one of CO, CO 2 and CH 4 (hereinafter also referred to as carbon-containing gas), the carbon-containing gas may be used alone, but carbon containing rare gas or H 2 as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.
〔バリア層(第2のバリア層)〕
本発明の方法によって得られるガスバリア性フィルムは、本発明の変性ポリシラザンを用いて形成されるバリア層(第2のバリア層)を有し、好ましくは第1のバリア層上に本発明の変性ポリシラザンを用いて形成されるバリア層(第2のバリア層)を有する。以下、本発明の変性ポリシラザンを用いて形成されるバリア層(第2のバリア層)が第1のバリア層上に設けられる本発明の好ましい形態について説明するが、本発明は下記形態に限定されるものではない。例えば、第1のバリア層は省略されてもよく、この場合であっても下記形態を適宜修飾して適用できる。 [Barrier layer (second barrier layer)]
The gas barrier film obtained by the method of the present invention has a barrier layer (second barrier layer) formed using the modified polysilazane of the present invention, and preferably the modified polysilazane of the present invention on the first barrier layer. A barrier layer (second barrier layer) formed using Hereinafter, although the preferable form of this invention in which the barrier layer (2nd barrier layer) formed using the modified polysilazane of this invention is provided on the first barrier layer is described, the present invention is limited to the following form. It is not something. For example, the first barrier layer may be omitted, and even in this case, the following form can be appropriately modified and applied.
本発明の方法によって得られるガスバリア性フィルムは、本発明の変性ポリシラザンを用いて形成されるバリア層(第2のバリア層)を有し、好ましくは第1のバリア層上に本発明の変性ポリシラザンを用いて形成されるバリア層(第2のバリア層)を有する。以下、本発明の変性ポリシラザンを用いて形成されるバリア層(第2のバリア層)が第1のバリア層上に設けられる本発明の好ましい形態について説明するが、本発明は下記形態に限定されるものではない。例えば、第1のバリア層は省略されてもよく、この場合であっても下記形態を適宜修飾して適用できる。 [Barrier layer (second barrier layer)]
The gas barrier film obtained by the method of the present invention has a barrier layer (second barrier layer) formed using the modified polysilazane of the present invention, and preferably the modified polysilazane of the present invention on the first barrier layer. A barrier layer (second barrier layer) formed using Hereinafter, although the preferable form of this invention in which the barrier layer (2nd barrier layer) formed using the modified polysilazane of this invention is provided on the first barrier layer is described, the present invention is limited to the following form. It is not something. For example, the first barrier layer may be omitted, and even in this case, the following form can be appropriately modified and applied.
第1のバリア層の上部に設けられる第2のバリア層の組成は、特に制限されないが、少なくともケイ素原子および酸素原子を含有し、かつケイ素原子に対する酸素原子の存在比(O/Si)が1.4~2.2であることが好ましく、ケイ素原子に対する窒素原子の存在比(N/Si)が0~0.4であることがより好ましい。
The composition of the second barrier layer provided on the first barrier layer is not particularly limited, but it contains at least silicon atoms and oxygen atoms, and the abundance ratio of oxygen atoms to silicon atoms (O / Si) is 1. The abundance ratio of nitrogen to silicon atoms (N / Si) is more preferably 0 to 0.4.
本明細書中、「ケイ素原子に対する酸素原子の存在比(O/Si)が1.4~2.2である」とは、後述する装置および方法で測定した第2のバリア層のどの深さの点においても、O/Siが1.4未満、または2.2を超える値を示す部分がないことを意味する。同様に、「ケイ素原子に対する窒素原子の存在比(N/Si)が0~0.4である」とは、後述する装置および方法で測定した第2のバリア層のどの深さの点においても、N/Siが0.4を超える値を示す部分がないことを意味する。
In this specification, “the abundance ratio of oxygen atoms to silicon atoms (O / Si) is 1.4 to 2.2” means that the depth of the second barrier layer measured by the apparatus and method described later. This also means that there is no portion where O / Si shows a value less than 1.4 or more than 2.2. Similarly, “the abundance ratio of nitrogen atoms to silicon atoms (N / Si) is 0 to 0.4” means any depth of the second barrier layer measured by the apparatus and method described later. , N / Si means that there is no portion showing a value exceeding 0.4.
第2のバリア層におけるケイ素原子に対する酸素原子の存在比(O/Si)が1.4以上であれば、高温高湿下において第2のバリア層が水分と反応しバリア性が大きく低下することを防ぐ効果が高い。一方、2.2以下であれば、分子内に存在するシラノール基(Si-OH)の割合が少なくなるため、より高いバリア性が得られうる。該O/Siはより好ましくは1.5~2.1であり、さらに好ましくは1.7~2.0である。
If the abundance ratio of oxygen atoms to silicon atoms (O / Si) in the second barrier layer is 1.4 or more, the second barrier layer reacts with moisture under high temperature and high humidity, and the barrier property is greatly reduced. Highly effective in preventing On the other hand, if the ratio is 2.2 or less, the ratio of silanol groups (Si—OH) present in the molecule decreases, and thus higher barrier properties can be obtained. The O / Si is more preferably 1.5 to 2.1, and still more preferably 1.7 to 2.0.
第2のバリア層におけるケイ素原子に対する窒素原子の存在比(N/Si)が0.4以下であれば、高温高湿下において第2のバリア層が水分と反応しバリア性が低下することを防止する効果が高い。該N/Siはより好ましくは0~0.3であり、さらに好ましくは0~0.2である。
If the abundance ratio of nitrogen atoms to silicon atoms (N / Si) in the second barrier layer is 0.4 or less, the second barrier layer reacts with moisture under high temperature and high humidity, and the barrier property decreases. The effect to prevent is high. The N / Si is more preferably 0 to 0.3, and further preferably 0 to 0.2.
該O/Siおよび該N/Siは、下記の方法で測定することができる。すなわち、第2のバリア層の組成プロファイルは、Arスパッタエッチング装置とX線光電子分光法(XPS)とを組み合わせることで求めることができる。また、深さ方向のプロファイル分布は、FIB(収束イオンビーム)加工装置による膜加工、およびTEM(透過型電子顕微鏡)により実膜厚を求めXPSの結果と対応させることで算出できる。
The O / Si and the N / Si can be measured by the following method. That is, the composition profile of the second barrier layer can be obtained by combining an Ar sputter etching apparatus and X-ray photoelectron spectroscopy (XPS). The profile distribution in the depth direction can be calculated by film processing by a FIB (focused ion beam) processing apparatus and by obtaining the actual film thickness by TEM (transmission electron microscope) and making it correspond to the XPS result.
本発明においては、以下に示す装置および手法を用いた。
In the present invention, the following apparatus and method were used.
(スパッタ条件)
イオン種:Arイオン
加速電圧:1kV
(X線光電子分光測定条件)
装置:VGサイエンティフィックス社製ESCALAB-200R
X線アノード材:Mg
出力:600W(加速電圧15kV、エミッション電流40mA)
尚、測定の分解能は0.5nmでありこれに応じた各サンプリング点において、各元素比をプロットすることで得られる。 (Sputtering conditions)
Ion species: Ar ion Acceleration voltage: 1 kV
(X-ray photoelectron spectroscopy measurement conditions)
Equipment: ESCALAB-200R manufactured by VG Scientific
X-ray anode material: Mg
Output: 600W (acceleration voltage 15kV, emission current 40mA)
The resolution of measurement is 0.5 nm, and can be obtained by plotting each element ratio at each sampling point corresponding to this.
イオン種:Arイオン
加速電圧:1kV
(X線光電子分光測定条件)
装置:VGサイエンティフィックス社製ESCALAB-200R
X線アノード材:Mg
出力:600W(加速電圧15kV、エミッション電流40mA)
尚、測定の分解能は0.5nmでありこれに応じた各サンプリング点において、各元素比をプロットすることで得られる。 (Sputtering conditions)
Ion species: Ar ion Acceleration voltage: 1 kV
(X-ray photoelectron spectroscopy measurement conditions)
Equipment: ESCALAB-200R manufactured by VG Scientific
X-ray anode material: Mg
Output: 600W (acceleration voltage 15kV, emission current 40mA)
The resolution of measurement is 0.5 nm, and can be obtained by plotting each element ratio at each sampling point corresponding to this.
(FIB加工)
装置:SII製SMI2050
加工イオン:(Ga 30kV)
(TEM観察)
装置:日本電子製JEM2000FX(加速電圧:200kV)
電子線照射時間:5秒から60秒。 (FIB processing)
Device: SII SMI2050
Processed ions: (Ga 30 kV)
(TEM observation)
Apparatus: JEOL JEM2000FX (acceleration voltage: 200 kV)
Electron beam irradiation time: 5 to 60 seconds.
装置:SII製SMI2050
加工イオン:(Ga 30kV)
(TEM観察)
装置:日本電子製JEM2000FX(加速電圧:200kV)
電子線照射時間:5秒から60秒。 (FIB processing)
Device: SII SMI2050
Processed ions: (Ga 30 kV)
(TEM observation)
Apparatus: JEOL JEM2000FX (acceleration voltage: 200 kV)
Electron beam irradiation time: 5 to 60 seconds.
(第2のバリア層の表面からの膜厚の深さ方向の元素比)
上述の第2のバリア層表面からのスパッタにより得られた各深さでのXPS測定(Si、O、Nに注目)とTEMによる断層面観察の結果を照合させて、O/SiおよびN/Siの平均値を算出する。 (Element ratio in the depth direction of the film thickness from the surface of the second barrier layer)
The XPS measurement (attention to Si, O, N) at each depth obtained by sputtering from the surface of the second barrier layer described above and the result of tomographic plane observation by TEM are collated, and O / Si and N / The average value of Si is calculated.
上述の第2のバリア層表面からのスパッタにより得られた各深さでのXPS測定(Si、O、Nに注目)とTEMによる断層面観察の結果を照合させて、O/SiおよびN/Siの平均値を算出する。 (Element ratio in the depth direction of the film thickness from the surface of the second barrier layer)
The XPS measurement (attention to Si, O, N) at each depth obtained by sputtering from the surface of the second barrier layer described above and the result of tomographic plane observation by TEM are collated, and O / Si and N / The average value of Si is calculated.
また、第2のバリア層においては、最表面から深さが10nmまでの領域におけるケイ素原子に対する酸素原子の存在比の平均値と、最表面から深さが10nmを超える領域におけるケイ素原子に対する酸素原子の存在比の平均値との差が0.4以下であることが好ましい。かような構成であれば、第2のバリア層の表面部分と内部とで組成変化が少なくなり、高温高湿下における保存安定性がさらに優れたガスバリア性フィルムとなる。この平均値の差はより好ましくは0.3以下であり、さらに好ましくは0.2以下である。
In the second barrier layer, the average value of the abundance ratio of oxygen atoms with respect to silicon atoms in the region from the outermost surface to a depth of 10 nm and the oxygen atoms with respect to silicon atoms in the region where the depth from the outermost surface exceeds 10 nm. The difference from the average value of the abundance ratio is preferably 0.4 or less. With such a configuration, the composition change is small between the surface portion and the inside of the second barrier layer, and the gas barrier film is further excellent in storage stability under high temperature and high humidity. The difference between the average values is more preferably 0.3 or less, and further preferably 0.2 or less.
上記の最表面から深さが10nmまでの領域におけるケイ素原子に対する酸素原子の存在比の平均値、および最表面から深さが10nmを超える領域におけるケイ素原子に対する酸素原子の存在比の平均値は、上記で説明したArスパッタエッチング装置とX線光電子分光法(XPS)とを組み合わせた方法により算出することができる。
The average value of the abundance ratio of oxygen atoms to silicon atoms in the region from the outermost surface to a depth of 10 nm, and the average value of the abundance ratio of oxygen atoms to silicon atoms in a region where the depth from the outermost surface exceeds 10 nm are: It can be calculated by a method combining the Ar sputter etching apparatus described above and X-ray photoelectron spectroscopy (XPS).
<第2のバリア層の形成方法>
第2のバリア層は、本発明の変性ポリシラザンの塗布液を用いて形成されれば、いずれの方法によって形成されてよく、公知の方法が同様にしてまたは適宜修飾して適用できる。例えば、第2のバリア層の形成方法は特に制限されないが、有機溶剤中に、変性ポリシラザン、好ましくは変性ポリシラザンと、必要に応じて触媒や添加化合物とを含む第2のバリア層形成用塗布液を公知の湿式塗布方法により塗布し、この溶剤を蒸発させて除去し、次いで、活性エネルギー線を照射して改質処理を行う方法が好ましい。すなわち、第2のバリア層は、(i)本発明の変性ポリシラザンを含む塗布液(第2のバリア層形成用塗布液)を無機化合物層(第1のバリア層)上に塗布、乾燥することによって、前駆層を形成し;さらに(ii)前記前駆層を活性エネルギー線照射により改質処理することによって形成されることが好ましい。 <Method for Forming Second Barrier Layer>
The second barrier layer may be formed by any method as long as it is formed using the coating solution of the modified polysilazane of the present invention, and a known method can be applied in the same manner or appropriately modified. For example, the method for forming the second barrier layer is not particularly limited, but a second barrier layer forming coating solution containing a modified polysilazane, preferably a modified polysilazane, and, if necessary, a catalyst or an additive compound in an organic solvent. Is preferably applied by a known wet coating method, the solvent is evaporated and removed, and then a modification treatment is performed by irradiation with active energy rays. That is, the second barrier layer is obtained by applying (i) a coating solution containing the modified polysilazane of the present invention (second coating solution for forming a barrier layer) on the inorganic compound layer (first barrier layer) and drying. It is preferable that the precursor layer be formed by further modifying (ii) the precursor layer by irradiation with active energy rays.
第2のバリア層は、本発明の変性ポリシラザンの塗布液を用いて形成されれば、いずれの方法によって形成されてよく、公知の方法が同様にしてまたは適宜修飾して適用できる。例えば、第2のバリア層の形成方法は特に制限されないが、有機溶剤中に、変性ポリシラザン、好ましくは変性ポリシラザンと、必要に応じて触媒や添加化合物とを含む第2のバリア層形成用塗布液を公知の湿式塗布方法により塗布し、この溶剤を蒸発させて除去し、次いで、活性エネルギー線を照射して改質処理を行う方法が好ましい。すなわち、第2のバリア層は、(i)本発明の変性ポリシラザンを含む塗布液(第2のバリア層形成用塗布液)を無機化合物層(第1のバリア層)上に塗布、乾燥することによって、前駆層を形成し;さらに(ii)前記前駆層を活性エネルギー線照射により改質処理することによって形成されることが好ましい。 <Method for Forming Second Barrier Layer>
The second barrier layer may be formed by any method as long as it is formed using the coating solution of the modified polysilazane of the present invention, and a known method can be applied in the same manner or appropriately modified. For example, the method for forming the second barrier layer is not particularly limited, but a second barrier layer forming coating solution containing a modified polysilazane, preferably a modified polysilazane, and, if necessary, a catalyst or an additive compound in an organic solvent. Is preferably applied by a known wet coating method, the solvent is evaporated and removed, and then a modification treatment is performed by irradiation with active energy rays. That is, the second barrier layer is obtained by applying (i) a coating solution containing the modified polysilazane of the present invention (second coating solution for forming a barrier layer) on the inorganic compound layer (first barrier layer) and drying. It is preferable that the precursor layer be formed by further modifying (ii) the precursor layer by irradiation with active energy rays.
(工程(i):前駆層の形成)
本工程では、塗布液(第2のバリア層形成用塗布液)を無機化合物層上に塗布、乾燥することによって、前駆層(塗膜)を形成する。 (Step (i): Formation of precursor layer)
In this step, a precursor layer (coating film) is formed by applying and drying a coating solution (second barrier layer forming coating solution) on the inorganic compound layer.
本工程では、塗布液(第2のバリア層形成用塗布液)を無機化合物層上に塗布、乾燥することによって、前駆層(塗膜)を形成する。 (Step (i): Formation of precursor layer)
In this step, a precursor layer (coating film) is formed by applying and drying a coating solution (second barrier layer forming coating solution) on the inorganic compound layer.
塗布液(第2のバリア層形成用塗布液)は、変性ポリシラザンを溶剤中に溶解して調製される。ここで、変性ポリシラザンの塗布液を構成する溶剤としては、変性ポリシラザンを溶解できるものであれば特に制限されないが、変性ポリシラザンと容易に反応してしまう水および反応性基(例えば、ヒドロキシル基、あるいはアミン基等)を含まず、ポリシラザンに対して不活性の有機溶剤が好ましく、非プロトン性の有機溶剤がより好ましい。具体的には、溶剤としては、非プロトン性溶剤;例えば、ペンタン、2,2,4-トリメチルペンタン、ヘキサン、シクロヘキサン、トルエン、キシレン、ソルベッソ、ターペン等の、脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素等の炭化水素溶媒;塩化メチレン、トリクロロエタン等のハロゲン炭化水素溶媒;酢酸エチル、酢酸ブチル等のエステル類;アセトン、メチルエチルケトン等のケトン類;ジブチルエーテル、ジオキサン、テトラヒドロフラン、モノ-およびポリアルキレングリコールジアルキルエーテル(ジグライム類)等の脂肪族エーテル、脂環式エーテル等のエーテル類などを挙げることができる。上記溶剤は、単独で使用されてもまたは2種以上の混合物の形態で使用されてもよい。また、上記溶剤は、使用する前にあらかじめ酸素濃度や水分含量を低減させておくことが好ましい。溶剤中の酸素濃度や水分含量を低減する手段は特に限定されず、従来公知の手法が適用されうる。また、変性ポリシラザンの塗布液における変性ポリシラザンの濃度は、特に制限されず、層の膜厚や塗布液のポットライフによっても異なるが、好ましくは1~80質量%、より好ましくは2~50質量%、特に好ましくは10~40質量%である。
The coating solution (second barrier layer forming coating solution) is prepared by dissolving modified polysilazane in a solvent. Here, the solvent constituting the coating solution of the modified polysilazane is not particularly limited as long as it can dissolve the modified polysilazane, but water and a reactive group (for example, a hydroxyl group, or easily reacting with the modified polysilazane). An organic solvent that does not contain an amine group and is inert to polysilazane is preferable, and an aprotic organic solvent is more preferable. Specifically, the solvent is an aprotic solvent; for example, pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, solvesso, terpene, aliphatic hydrocarbons, alicyclic carbonization, etc. Hydrocarbon solvents such as hydrogen and aromatic hydrocarbons; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Dibutyl ether, dioxane, tetrahydrofuran, mono- And aliphatic ethers such as polyalkylene glycol dialkyl ethers (diglymes) and ethers such as alicyclic ethers. The said solvent may be used independently or may be used with the form of a 2 or more types of mixture. Moreover, it is preferable to reduce the oxygen concentration and water content of the solvent before use. Means for reducing the oxygen concentration and water content in the solvent are not particularly limited, and conventionally known methods can be applied. Further, the concentration of the modified polysilazane in the coating solution of the modified polysilazane is not particularly limited and varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 1 to 80% by mass, more preferably 2 to 50% by mass. Particularly preferred is 10 to 40% by mass.
なお、本発明の変性ポリシラザンの塗布液は、変性ポリシラザンに加えて、上記したようなポリシラザンを含んでもよいが、好ましくは変性ポリシラザンのみを有効成分として含むことが好ましい。
The modified polysilazane coating solution of the present invention may contain polysilazane as described above in addition to the modified polysilazane, but preferably contains only modified polysilazane as an active ingredient.
また、上述したように、本発明の変性ポリシラザンは、外部の酸素の取り込みを促進する金属アルコキシド/キレート化合物や低分子シラザン/シロキサンで修飾されることが好ましい。また、変性ポリシラザン中の-SiH3基や金属アルコキシド/キレート化合物は、水分との反応性が高い。このため、塗布液の調製工程では、酸素や水蒸気濃度の低い環境で行われることが好ましい。具体的には、酸素濃度が200体積ppm以下、水蒸気濃度が100体積ppm以下の環境下で、変性ポリシラザンを溶剤に溶解して塗布液を調製することが好ましい。変性ポリシラザンは、真空紫外光(~230nm)吸収により反応が進み、緻密なバリア層が形成される。しかしながら、塗布液を調製する段階で、変性ポリシラザンが環境中の酸素や水分と反応すると、真空紫外光を照射する段階ですでに酸化反応が進んでいる状態になるため、真空紫外光が十分に吸収されない。これは、変性ポリシラザンのSi-Nは真空紫外光を吸収するが、変性ポリシラザンのSi-Nが反応しSi-Oになると、エネルギー的に安定化するため、真空紫外光を吸収しなくなるためと考えられる。一方、酸素濃度が200体積ppm以下、水蒸気濃度が100体積ppm以下の環境下で第2のバリア層形成用塗布液を調製すると、調液時におけるポリシラザンと酸素または水分との反応を抑制することができる。その結果、真空紫外光を効果的に吸収することができるため、真空紫外光の照射後にバリア層中に残るSi-Nを低減できる。そのため、高温高湿下での保存安定性に優れるガスバリア性フィルムが得られうる。なお、酸素濃度が200体積ppmを超えると、調液時に環境中の酸素によって塗布液中の変性ポリシラザンの酸化反応が過度に進行する可能性がある。また、水蒸気濃度が100体積ppmを超えると、水分の作用によって塗布液中の変性ポリシラザンの酸化反応が過度に進行する可能性がある。塗布液の調製は、酸素濃度が、より好ましくは0~100体積ppm、さらにより好ましくは0~30体積ppmの環境下で行う。また、水蒸気濃度が、より好ましくは0~50体積ppm、さらにより好ましくは0~30体積ppmの環境下で行う。
Further, as described above, the modified polysilazane of the present invention is preferably modified with a metal alkoxide / chelate compound or a low-molecular silazane / siloxane that promotes external oxygen uptake. Further, the —SiH 3 group and the metal alkoxide / chelate compound in the modified polysilazane are highly reactive with moisture. For this reason, it is preferable to perform in the preparation process of a coating liquid in an environment with low oxygen and water vapor | steam density | concentration. Specifically, it is preferable to prepare a coating solution by dissolving modified polysilazane in a solvent in an environment where the oxygen concentration is 200 ppm by volume or less and the water vapor concentration is 100 ppm by volume or less. The reaction of the modified polysilazane proceeds by absorption of vacuum ultraviolet light (˜230 nm), and a dense barrier layer is formed. However, when the modified polysilazane reacts with oxygen and moisture in the environment at the stage of preparing the coating solution, the oxidation reaction has already progressed at the stage of irradiation with vacuum ultraviolet light, so that the vacuum ultraviolet light is sufficiently absorbed. Not absorbed. This is because Si—N of the modified polysilazane absorbs vacuum ultraviolet light, but when Si—N of the modified polysilazane reacts to become Si—O, it is stabilized in terms of energy, so that it does not absorb vacuum ultraviolet light. Conceivable. On the other hand, when the second barrier layer forming coating solution is prepared in an environment where the oxygen concentration is 200 ppm by volume or less and the water vapor concentration is 100 ppm by volume or less, the reaction between polysilazane and oxygen or moisture during preparation is suppressed. Can do. As a result, vacuum ultraviolet light can be effectively absorbed, so that Si—N remaining in the barrier layer after irradiation with vacuum ultraviolet light can be reduced. Therefore, a gas barrier film having excellent storage stability under high temperature and high humidity can be obtained. In addition, when oxygen concentration exceeds 200 volume ppm, the oxidation reaction of the modified polysilazane in a coating liquid may advance excessively by the oxygen in the environment at the time of liquid preparation. If the water vapor concentration exceeds 100 ppm by volume, the oxidation reaction of the modified polysilazane in the coating solution may proceed excessively due to the action of moisture. The coating solution is prepared in an environment where the oxygen concentration is more preferably 0 to 100 ppm by volume, and even more preferably 0 to 30 ppm by volume. Further, it is carried out in an environment where the water vapor concentration is more preferably 0 to 50 ppm by volume, and still more preferably 0 to 30 ppm by volume.
このような環境は、酸素濃度および水蒸気濃度が管理された、グローブボックス等の調液設備を準備することで実現できる。第2のバリア層形成用塗布液の調製時に用いられる、雰囲気を満たすガスとしては乾燥不活性ガスとすることが好ましい。不活性ガスとしては、窒素、アルゴン、ヘリウム等が例示されるが、特にコストの観点から乾燥窒素ガスにすることが好ましい。酸素濃度の調整はグローブボックス等の調液設備へ導入する酸素ガス、不活性ガスの流量を計測し、流量比を変えることで調整可能である。雰囲気中の水蒸気濃度は、例えば、モレキュラーシーブス等の乾燥剤を用いた乾燥によって低くすることができる。また、雰囲気中の酸素濃度は、例えば、金属銅の触媒等により反応させる、脱酸素剤に吸着させる等の手段によって低くすることができる。
Such an environment can be realized by preparing preparation equipment such as a glove box in which the oxygen concentration and water vapor concentration are controlled. A dry inert gas is preferably used as the gas that satisfies the atmosphere and is used when the second barrier layer forming coating solution is prepared. Examples of the inert gas include nitrogen, argon, helium and the like, but dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rates of oxygen gas and inert gas introduced into the preparation equipment such as a glove box and changing the flow rate ratio. The water vapor concentration in the atmosphere can be lowered by drying using a desiccant such as molecular sieves, for example. Further, the oxygen concentration in the atmosphere can be lowered by means of, for example, reacting with a metal copper catalyst or the like, or adsorbing it to an oxygen scavenger.
このようにして調製された塗布液を、第1のバリア層上に塗布して塗膜を形成し、前記塗膜に真空紫外線を照射して改質処理を行い、ガスバリア性フィルムを製造する。
The coating solution prepared in this manner is applied onto the first barrier layer to form a coating film, and the coating film is irradiated with vacuum ultraviolet rays for modification treatment to produce a gas barrier film.
第2のバリア層形成用塗布液は、改質を促進するために、触媒を含有することが好ましい。本発明に適用可能な触媒としては、塩基性触媒が好ましく、特に、N,N-ジエチルエタノールアミン、N,N-ジメチルエタノールアミン、トリエタノールアミン、トリエチルアミン、3-モルホリノプロピルアミン、N,N,N’,N’-テトラメチル-1,3-ジアミノプロパン、N,N,N’,N’-テトラメチル-1,6-ジアミノヘキサン等のアミン触媒、Ptアセチルアセトナート等のPt化合物、プロピオン酸Pd等のPd化合物、Rhアセチルアセトナート等のRh化合物等の金属触媒、N-複素環式化合物が挙げられる。これらのうち、アミン触媒を用いることが好ましい。この際添加する触媒の濃度としては、変性ポリシラザンを基準としたとき、好ましくは0.1~10質量%、より好ましくは0.5~7質量%の範囲である。触媒添加量をこの範囲とすることで、反応の急激な進行による過剰なシラノール形成、および膜密度の低下、膜欠陥の増大などを避けることができる。なお、これら触媒のうち、アミン触媒は、上記の添加化合物としての役割を担うこともできる。
The second barrier layer forming coating solution preferably contains a catalyst in order to promote reforming. As the catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, Amine catalysts such as N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on the modified polysilazane. By setting the amount of the catalyst to be in this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like. Of these catalysts, the amine catalyst can also serve as the additive compound.
第2のバリア層形成用塗布液には、必要に応じて下記に挙げる添加剤を用いることができる。例えば、セルロースエーテル類、セルロースエステル類;例えば、エチルセルロース、ニトロセルロース、セルロースアセテート、セルロースアセトブチレート等、天然樹脂;例えば、ゴム、ロジン樹脂等、合成樹脂;例えば、重合樹脂等、縮合樹脂;例えば、アミノプラスト、特に尿素樹脂、メラミンホルムアルデヒド樹脂、アルキド樹脂、アクリル樹脂、ポリエステルもしくは変性ポリエステル、エポキシド、ポリイソシアネートもしくはブロック化ポリイソシアネート、ポリシロキサン等である。
In the second barrier layer forming coating solution, the following additives may be used as necessary. For example, cellulose ethers, cellulose esters; for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc., natural resins; for example, rubber, rosin resin, etc., synthetic resins; Aminoplasts, especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.
(第1のバリア層上に塗布液を塗布して塗膜を形成する段階)
次いで、上記で得られた塗布液(第2のバリア層形成用塗布液)を、好ましくは第1のバリア層上に塗布し、塗膜を形成する。 (Step of applying a coating solution on the first barrier layer to form a coating film)
Subsequently, the coating liquid (second barrier layer forming coating liquid) obtained above is preferably applied onto the first barrier layer to form a coating film.
次いで、上記で得られた塗布液(第2のバリア層形成用塗布液)を、好ましくは第1のバリア層上に塗布し、塗膜を形成する。 (Step of applying a coating solution on the first barrier layer to form a coating film)
Subsequently, the coating liquid (second barrier layer forming coating liquid) obtained above is preferably applied onto the first barrier layer to form a coating film.
第2のバリア層形成用塗布液を塗布する方法としては、従来公知の適切な湿式塗布方法が採用され得る。具体例としては、スピンコート法、ロールコート法、フローコート法、インクジェット法、スプレーコート法、プリント法、ディップコート法、流延成膜法、バーコート法、グラビア印刷法等が挙げられる。
As a method for applying the second barrier layer forming coating solution, a conventionally known appropriate wet coating method may be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
塗布厚さは、目的に応じて適切に設定され得る。例えば、第2のバリア層1層当たりの塗布厚さ(乾燥後の厚さ)は、10nm~10μm程度であることが好ましく、15nm~1μmであることがより好ましく、20~500nmであることがさらに好ましい。膜厚が10nm以上であれば十分なバリア性を得ることができ、10μm以下であれば、層形成時に安定した塗布性を得ることができ、かつ高い光線透過性を実現できる。
The coating thickness can be appropriately set according to the purpose. For example, the coating thickness (thickness after drying) per second barrier layer is preferably about 10 nm to 10 μm, more preferably 15 nm to 1 μm, and more preferably 20 to 500 nm. Further preferred. If the film thickness is 10 nm or more, sufficient barrier properties can be obtained, and if it is 10 μm or less, stable coating properties can be obtained during layer formation, and high light transmittance can be realized.
また、塗布液を塗布する雰囲気は、大気雰囲気下、窒素雰囲気下、アルゴン雰囲気下、真空雰囲気下、酸素濃度をコントロールした減圧雰囲気下等等のいずれの条件であってもよいが、好ましくは、塗布液を調製する段階と同様に、酸素濃度が200体積ppm以下、水蒸気濃度が100体積ppm以下に制御された不活性ガス雰囲気下で行うことが好ましい。
Further, the atmosphere for applying the coating solution may be any conditions such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, a reduced pressure atmosphere in which the oxygen concentration is controlled, etc. Similarly to the step of preparing the coating solution, it is preferable to carry out in an inert gas atmosphere in which the oxygen concentration is controlled to 200 volume ppm or less and the water vapor concentration is controlled to 100 volume ppm or less.
塗布液を塗布した後は、塗膜を乾燥させることが好ましい。塗膜を乾燥することによって、塗膜中に含有される有機溶媒などの溶剤を除去することができる。この際、塗膜に含有される溶剤は、すべてを乾燥させてもよいが、一部残存させていてもよい。一部の溶剤を残存させる場合であっても、好適な第2のバリア層が得られうる。なお、残存する溶剤は後に除去されうる。
After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, a solvent such as an organic solvent contained in the coating film can be removed. At this time, all of the solvent contained in the coating film may be dried or may be partially left. Even when a part of the solvent is left, a suitable second barrier layer can be obtained. The remaining solvent can be removed later.
塗膜の乾燥温度は、適用する基材によっても異なるが、50~200℃であることが好ましい。例えば、ガラス転位温度(Tg)が70℃のポリエチレンテレフタレート基材を基材として用いる場合には、乾燥温度は、熱による基材の変形等を考慮して150℃以下に設定することが好ましい。上記温度は、ホットプレート、オーブン、ファーネスなどを使用することによって設定されうる。乾燥時間は短時間に設定することが好ましく、例えば、乾燥温度が150℃である場合には30分以内に設定することが好ましい。また、乾燥雰囲気は、大気雰囲気下、窒素雰囲気下、アルゴン雰囲気下、真空雰囲気下、酸素濃度をコントロールした減圧雰囲気下等のいずれの条件であってもよいが、好ましくは、塗布液を調製する段階と同様に、酸素濃度が200体積ppm以下、水蒸気濃度が100体積ppm以下に制御された不活性ガス雰囲気下で行うことが好ましい。
The drying temperature of the coating film varies depending on the substrate to be applied, but is preferably 50 to 200 ° C. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the substrate, the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat. The temperature can be set by using a hot plate, oven, furnace or the like. The drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes. The drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere in which the oxygen concentration is controlled. Preferably, a coating solution is prepared. As in the step, it is preferable to carry out in an inert gas atmosphere in which the oxygen concentration is controlled to 200 volume ppm or less and the water vapor concentration is controlled to 100 volume ppm or less.
後述のように得られた塗膜に真空紫外線を照射して改質処理を行うが、真空紫外線を照射する直前の塗膜の172nmの光の透過率が、20%以下であることが好ましく、15%以下であることがより好ましく、10%以下であることがさらに好ましい。これは、真空紫外光に対して十分な吸収をもつことによって、真空紫外光による改質が進行し、緻密なバリア層が形成されるためである。真空紫外線を照射する直前の塗膜の172nmの光の透過率の下限値は特に制限されないが、実質的に、0.1%以上である。塗膜の172nmの光の透過率は、実施例に記載の方法で測定した値を採用するものとする。
The coating film obtained as described below is subjected to a modification treatment by irradiating it with vacuum ultraviolet rays, but the transmittance of light at 172 nm of the coating film immediately before irradiation with vacuum ultraviolet rays is preferably 20% or less, It is more preferably 15% or less, and further preferably 10% or less. This is because by having sufficient absorption with respect to vacuum ultraviolet light, modification by vacuum ultraviolet light proceeds and a dense barrier layer is formed. The lower limit of the transmittance of light at 172 nm of the coating film immediately before irradiation with vacuum ultraviolet rays is not particularly limited, but is substantially 0.1% or more. The value measured by the method described in the Examples is adopted as the light transmittance of 172 nm of the coating film.
(工程(ii):活性エネルギー線照射による改質処理)
本工程では、上記工程(i)で得られた前駆層(塗膜)に、紫外線、電子線、X線、α線、β線、γ線、中性子線等の活性エネルギー線を照射して、変性ポリシラザンを改質処理する。 (Process (ii): Modification treatment by active energy ray irradiation)
In this step, the precursor layer (coating film) obtained in the above step (i) is irradiated with active energy rays such as ultraviolet rays, electron beams, X rays, α rays, β rays, γ rays, neutron rays, The modified polysilazane is modified.
本工程では、上記工程(i)で得られた前駆層(塗膜)に、紫外線、電子線、X線、α線、β線、γ線、中性子線等の活性エネルギー線を照射して、変性ポリシラザンを改質処理する。 (Process (ii): Modification treatment by active energy ray irradiation)
In this step, the precursor layer (coating film) obtained in the above step (i) is irradiated with active energy rays such as ultraviolet rays, electron beams, X rays, α rays, β rays, γ rays, neutron rays, The modified polysilazane is modified.
活性エネルギー線照射処理においては、常用されているいずれの活性エネルギー線発生装置を使用することも可能であるが、真空紫外線発生装置が好ましく使用される。例えば、上記「第1のバリア層」の項の(紫外線照射処理)で説明した方法が適用されうる。このため、以下では、特記しない限り、上記「第1のバリア層」の項の(紫外線照射処理)で説明した方法および条件が本工程(ii)においても適用できるため、省略する。
In the active energy ray irradiation treatment, any commonly used active energy ray generator can be used, but a vacuum ultraviolet ray generator is preferably used. For example, the method described in (ultraviolet irradiation process) in the section of the “first barrier layer” can be applied. For this reason, unless otherwise specified, the method and conditions described in the “ultraviolet irradiation treatment” section of the above “first barrier layer” can be applied also in this step (ii), and thus will be omitted.
真空紫外線照射は、特に制限されない。しかし、上述したように、本発明の変性ポリシラザンは、外部の酸素の取り込みを促進する金属アルコキシド/キレート化合物で修飾されている。このため、塗膜の表面からの酸素の供給が重要であり、完全な不活性ガス雰囲気下よりも、酸素が存在する条件下で行うことが好ましい。具体的には、真空紫外線照射が、酸素濃度が200~10,000体積ppmの雰囲気下で行われることが好ましい。すなわち、工程(ii)において、前記改質処理は、酸素濃度が200~10,000体積ppmの雰囲気下で、230nm以下の波長の真空紫外線による照射によって行われることが好ましい。より好ましくは、真空紫外線照射時の酸素濃度は500~5,000体積ppmであり、さらに好ましくは700~2,000体積ppmである。酸素濃度が200体積ppm以上であれば、真空紫外線照射中に酸素が供給され、金属化合物とポリシラザンとの反応が十分に促進され、金属化合物由来の二酸化炭素や、ポリシラザン由来の酸化窒素、アンモニアとして系外に放出される。例えば、第2のバリア層形成用塗布液は金属化合物を含むため、金属化合物に由来する炭素原子がバリア層中に残留する割合が多いとガスバリア性が低下するおそれがあるが、酸素と反応して二酸化炭素として系外に放出されることで得られるバリア層のガスバリア性が向上しうると考えられる。一方、真空紫外線は酸素による吸収があるため、酸素濃度が10,000体積ppm以下の雰囲気下で行うことにより真空紫外線照射工程での効率の低下を抑えることができる。
真空 Vacuum ultraviolet irradiation is not particularly limited. However, as described above, the modified polysilazane of the present invention is modified with a metal alkoxide / chelate compound that promotes external oxygen uptake. For this reason, it is important to supply oxygen from the surface of the coating film, and it is preferable to carry out under conditions where oxygen is present rather than a completely inert gas atmosphere. Specifically, vacuum ultraviolet irradiation is preferably performed in an atmosphere having an oxygen concentration of 200 to 10,000 ppm by volume. That is, in the step (ii), the modification treatment is preferably performed by irradiation with vacuum ultraviolet rays having a wavelength of 230 nm or less in an atmosphere having an oxygen concentration of 200 to 10,000 volume ppm. More preferably, the oxygen concentration at the time of vacuum ultraviolet irradiation is 500 to 5,000 volume ppm, and more preferably 700 to 2,000 volume ppm. If the oxygen concentration is 200 ppm by volume or more, oxygen is supplied during vacuum ultraviolet irradiation, the reaction between the metal compound and polysilazane is sufficiently promoted, and as carbon dioxide derived from the metal compound, nitrogen oxide derived from polysilazane, and ammonia Released outside the system. For example, since the second coating liquid for forming the barrier layer contains a metal compound, if there is a large proportion of carbon atoms derived from the metal compound remaining in the barrier layer, the gas barrier property may decrease, but it reacts with oxygen. Thus, it is considered that the gas barrier property of the barrier layer obtained by being released out of the system as carbon dioxide can be improved. On the other hand, since vacuum ultraviolet rays are absorbed by oxygen, a decrease in efficiency in the vacuum ultraviolet irradiation process can be suppressed by carrying out in an atmosphere having an oxygen concentration of 10,000 ppm by volume or less.
また、真空紫外線の照射は、可能な限り水蒸気濃度の低い状態で行うことが好ましい。真空紫外線照射時の水蒸気濃度は、1000体積ppm以下であることが好ましく、200体積ppm以下であることがより好ましい。
Further, it is preferable that the irradiation with vacuum ultraviolet rays is performed in a state where the water vapor concentration is as low as possible. The water vapor concentration at the time of vacuum ultraviolet irradiation is preferably 1000 ppm by volume or less, and more preferably 200 ppm by volume or less.
真空紫外線照射は、特に制限されないが、塗膜の温度を50~120℃に制御して行うことが好ましい。真空紫外線照射時の塗膜の温度は、より好ましくは60~100℃であり、さらに好ましくは70~90℃である。真空紫外線照射時の塗膜の温度を50℃以上とすることで、金属化合物とポリシラザンとの反応が十分に促進され、ガスバリア性に優れ、高温高湿下での保存安定性に優れたガスバリア性フィルムが得られうる。一方、真空紫外線照射時の塗膜の温度が120℃以下であれば、プラスチックフィルム基材の熱による変形を最小限に抑制することができ好ましい。塗膜の温度を制御する具体的な手段は特に制限されず、従来公知の手法が適宜用いられうる。さらに、真空紫外線照射時の雰囲気の温度も上記の範囲に制御することがより好ましい。雰囲気の温度を制御する手段も特に制限されず、従来公知の手法が適宜用いられうる。
The vacuum ultraviolet irradiation is not particularly limited, but is preferably performed by controlling the temperature of the coating film at 50 to 120 ° C. The temperature of the coating film at the time of irradiation with vacuum ultraviolet rays is more preferably 60 to 100 ° C., further preferably 70 to 90 ° C. By setting the temperature of the coating film to 50 ° C. or higher during irradiation with vacuum ultraviolet rays, the reaction between the metal compound and polysilazane is sufficiently accelerated, the gas barrier property is excellent, and the gas barrier property is excellent in storage stability under high temperature and high humidity. A film can be obtained. On the other hand, if the temperature of the coating film at the time of vacuum ultraviolet irradiation is 120 ° C. or less, it is preferable because deformation of the plastic film substrate due to heat can be minimized. The specific means for controlling the temperature of the coating film is not particularly limited, and a conventionally known method can be appropriately used. Furthermore, it is more preferable to control the temperature of the atmosphere at the time of vacuum ultraviolet irradiation to the above range. A means for controlling the temperature of the atmosphere is not particularly limited, and a conventionally known method can be appropriately used.
なお、真空紫外線照射工程において、第2のバリア層形成用塗布液から形成された塗膜面での該真空紫外線の照度は1mW/cm2~10W/cm2であることが好ましく、30mW/cm2~200mW/cm2であることがより好ましく、50mW/cm2~160mW/cm2であるとさらに好ましい。1mW/cm2以上であれば、十分な改質効率が得られ、10W/cm2以下であれば、塗膜にアブレーションを生じにくく、基材にダメージを与えにくい。
In the vacuum ultraviolet irradiation step, the illuminance of the vacuum ultraviolet light on the surface of the coating film formed from the second barrier layer forming coating solution is preferably 1 mW / cm 2 to 10 W / cm 2 , and 30 mW / cm 2. more preferably 2 ~ 200mW / cm 2, further preferably at 50mW / cm 2 ~ 160mW / cm 2. If it is 1 mW / cm 2 or more, sufficient reforming efficiency is obtained, and if it is 10 W / cm 2 or less, it is difficult to cause ablation in the coating film and damage the substrate.
また、第2のバリア層形成用塗布液から形成された塗膜面における真空紫外線の照射エネルギー量(積算光量)は、10~10000mJ/cm2であることが好ましく、100~8000mJ/cm2であることがより好ましく、200~6000mJ/cm2であることがさらに好ましい。10mJ/cm2以上であれば、改質が十分に進行しうる。10000mJ/cm2以下であれば、過剰改質によるクラック発生や、基材の熱変形が生じにくい。
Further, the amount of irradiation energy (integrated light amount) of vacuum ultraviolet rays on the coating film surface formed from the second barrier layer forming coating solution is preferably 10 to 10000 mJ / cm 2 , and preferably 100 to 8000 mJ / cm 2 . More preferably, it is 200 to 6000 mJ / cm 2 . If it is 10 mJ / cm 2 or more, the modification can proceed sufficiently. If it is 10,000 mJ / cm 2 or less, cracking due to over-reformation and thermal deformation of the substrate are unlikely to occur.
第2のバリア層の膜密度は、目的に応じて適切に設定され得る。例えば、第2のバリア層の膜密度が、1.5~2.6g/cm3の範囲にあることが好ましい。上記範囲であれば、膜の緻密さがより高くなり、バリア性の劣化や、湿度による膜の酸化劣化が起こりにくい。
The film density of the second barrier layer can be appropriately set according to the purpose. For example, the film density of the second barrier layer is preferably in the range of 1.5 to 2.6 g / cm 3 . If it is the said range, the density of a film | membrane will become higher and it will be hard to produce deterioration of barrier property and the oxidation deterioration of the film | membrane by humidity.
該第2のバリア層は、単層でもよいし2層以上の積層構造であってもよい。
The second barrier layer may be a single layer or a laminated structure of two or more layers.
該第2のバリア層が2層以上の積層構造である場合、各第2のバリア層は、同じ組成であっても異なる組成であってもよい。
When the second barrier layer has a laminated structure of two or more layers, each second barrier layer may have the same composition or a different composition.
〔中間層〕
本発明のガスバリア性フィルムは、応力緩和などを目的として、第1のバリア層と第2のバリア層との間に中間層を有していてもよい。該中間層を形成する方法としては、ポリシロキサン改質層を形成する方法を適用することができる。この方法は、ポリシロキサンを含有した塗布液を、湿式塗布法により第1のバリア層上に塗布して乾燥した後、その乾燥して得られた塗膜に真空紫外光を照射することによって、中間層を形成する方法である。ここで、中間層は、特に制限されず、例えば、特開2014-151571号公報、特開2014-046272号公報などに記載される中間層と同様あるいは適宜修飾されて適用できる。 [Middle layer]
The gas barrier film of the present invention may have an intermediate layer between the first barrier layer and the second barrier layer for the purpose of stress relaxation and the like. As a method of forming the intermediate layer, a method of forming a polysiloxane modified layer can be applied. In this method, a coating liquid containing polysiloxane is applied on the first barrier layer by a wet coating method and dried, and then the coating film obtained by drying is irradiated with vacuum ultraviolet light. This is a method of forming an intermediate layer. Here, the intermediate layer is not particularly limited, and can be applied in the same manner or appropriately modified as the intermediate layer described in, for example, Japanese Patent Application Laid-Open Nos. 2014-151571 and 2014-046272.
本発明のガスバリア性フィルムは、応力緩和などを目的として、第1のバリア層と第2のバリア層との間に中間層を有していてもよい。該中間層を形成する方法としては、ポリシロキサン改質層を形成する方法を適用することができる。この方法は、ポリシロキサンを含有した塗布液を、湿式塗布法により第1のバリア層上に塗布して乾燥した後、その乾燥して得られた塗膜に真空紫外光を照射することによって、中間層を形成する方法である。ここで、中間層は、特に制限されず、例えば、特開2014-151571号公報、特開2014-046272号公報などに記載される中間層と同様あるいは適宜修飾されて適用できる。 [Middle layer]
The gas barrier film of the present invention may have an intermediate layer between the first barrier layer and the second barrier layer for the purpose of stress relaxation and the like. As a method of forming the intermediate layer, a method of forming a polysiloxane modified layer can be applied. In this method, a coating liquid containing polysiloxane is applied on the first barrier layer by a wet coating method and dried, and then the coating film obtained by drying is irradiated with vacuum ultraviolet light. This is a method of forming an intermediate layer. Here, the intermediate layer is not particularly limited, and can be applied in the same manner or appropriately modified as the intermediate layer described in, for example, Japanese Patent Application Laid-Open Nos. 2014-151571 and 2014-046272.
中間層を形成するために用いる塗布液は、ポリシロキサンおよび有機溶媒を含有することが好ましい。
The coating solution used for forming the intermediate layer preferably contains polysiloxane and an organic solvent.
中間層の形成に適用可能なポリシロキサンとしては、特に制限はないが、例えば、特開2014-151571号公報、特開2014-046272号公報などに記載されるものなど、従来公知の化合物を使用することができる。
The polysiloxane applicable to the formation of the intermediate layer is not particularly limited, and conventionally known compounds such as those described in JP2014-151571A, JP2014-046272A, and the like are used. can do.
〔保護層〕
本発明に係るガスバリア性フィルムは、第2のバリア層の上部に、有機化合物を含む保護層を設けてもよい。保護層に用いられる有機化合物としては、有機モノマー、オリゴマー、ポリマー等の有機樹脂、有機基を有するシロキサンやシルセスキオキサンのモノマー、オリゴマー、ポリマー等を用いた有機無機複合樹脂層を好ましく用いることができる。ここで、保護層は、特に制限されず、例えば、特開2014-151571号公報、特開2014-046272号公報などに記載される保護層と同様あるいは適宜修飾されて適用できる。 [Protective layer]
In the gas barrier film according to the present invention, a protective layer containing an organic compound may be provided on the second barrier layer. As the organic compound used in the protective layer, an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group is preferably used. Can do. Here, the protective layer is not particularly limited, and can be applied, for example, in the same manner or appropriately modified as the protective layer described in JP2014-151571A, JP2014-046272A, and the like.
本発明に係るガスバリア性フィルムは、第2のバリア層の上部に、有機化合物を含む保護層を設けてもよい。保護層に用いられる有機化合物としては、有機モノマー、オリゴマー、ポリマー等の有機樹脂、有機基を有するシロキサンやシルセスキオキサンのモノマー、オリゴマー、ポリマー等を用いた有機無機複合樹脂層を好ましく用いることができる。ここで、保護層は、特に制限されず、例えば、特開2014-151571号公報、特開2014-046272号公報などに記載される保護層と同様あるいは適宜修飾されて適用できる。 [Protective layer]
In the gas barrier film according to the present invention, a protective layer containing an organic compound may be provided on the second barrier layer. As the organic compound used in the protective layer, an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group is preferably used. Can do. Here, the protective layer is not particularly limited, and can be applied, for example, in the same manner or appropriately modified as the protective layer described in JP2014-151571A, JP2014-046272A, and the like.
〔デシカント性層〕
本発明のガスバリア性フィルムは、デシカント性層(水分吸着層)を有してもよい。デシカント性層として用いられる材料としては、例えば、酸化カルシウムや有機金属酸化物などが挙げられる。酸化カルシウムとしては、バインダー樹脂などに分散されたものが好ましく、市販品としては、例えば、サエスゲッター社のAqvaDryシリーズなどを好ましく用いることができる。また、有機金属酸化物としては、双葉電子工業株式会社製のOleDry(登録商標)シリーズなどを用いることができる。 [Desicant layer]
The gas barrier film of the present invention may have a desiccant layer (moisture adsorption layer). Examples of the material used for the desiccant layer include calcium oxide and organometallic oxide. As calcium oxide, what was disperse | distributed to binder resin etc. is preferable, and, as a commercial item, the AqvaDry series of SAESGETTER, etc. can be used preferably. In addition, as the organic metal oxide, OleDry (registered trademark) series manufactured by Futaba Electronics Co., Ltd. or the like can be used.
本発明のガスバリア性フィルムは、デシカント性層(水分吸着層)を有してもよい。デシカント性層として用いられる材料としては、例えば、酸化カルシウムや有機金属酸化物などが挙げられる。酸化カルシウムとしては、バインダー樹脂などに分散されたものが好ましく、市販品としては、例えば、サエスゲッター社のAqvaDryシリーズなどを好ましく用いることができる。また、有機金属酸化物としては、双葉電子工業株式会社製のOleDry(登録商標)シリーズなどを用いることができる。 [Desicant layer]
The gas barrier film of the present invention may have a desiccant layer (moisture adsorption layer). Examples of the material used for the desiccant layer include calcium oxide and organometallic oxide. As calcium oxide, what was disperse | distributed to binder resin etc. is preferable, and, as a commercial item, the AqvaDry series of SAESGETTER, etc. can be used preferably. In addition, as the organic metal oxide, OleDry (registered trademark) series manufactured by Futaba Electronics Co., Ltd. or the like can be used.
〔平滑層(下地層、プライマー層)〕
本発明のガスバリア性フィルムは、基材のバリア層を有する面、好ましくは基材と第1のバリア層との間に平滑層(下地層、プライマー層)を有していてもよい。平滑層は突起等が存在する基材の粗面を平坦化するために、あるいは、基材に存在する突起により、バリア層に生じた凹凸やピンホールを埋めて平坦化するために設けられる。このような平滑層は、いずれの材料で形成されてもよいが、炭素含有ポリマーを含むことが好ましく、炭素含有ポリマーから構成されることがより好ましい。すなわち、本発明のガスバリア性フィルムは、基材と第1のバリア層との間に、炭素含有ポリマーを含む平滑層をさらに有することが好ましい。 [Smooth layer (underlayer, primer layer)]
The gas barrier film of the present invention may have a smooth layer (underlayer, primer layer) between the surface of the substrate having the barrier layer, preferably between the substrate and the first barrier layer. The smooth layer is provided in order to flatten the rough surface of the substrate on which the protrusions and the like exist, or to fill the unevenness and pinholes generated in the barrier layer with the protrusions on the substrate and to flatten the surface. Such a smooth layer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer. That is, it is preferable that the gas barrier film of the present invention further has a smooth layer containing a carbon-containing polymer between the substrate and the first barrier layer.
本発明のガスバリア性フィルムは、基材のバリア層を有する面、好ましくは基材と第1のバリア層との間に平滑層(下地層、プライマー層)を有していてもよい。平滑層は突起等が存在する基材の粗面を平坦化するために、あるいは、基材に存在する突起により、バリア層に生じた凹凸やピンホールを埋めて平坦化するために設けられる。このような平滑層は、いずれの材料で形成されてもよいが、炭素含有ポリマーを含むことが好ましく、炭素含有ポリマーから構成されることがより好ましい。すなわち、本発明のガスバリア性フィルムは、基材と第1のバリア層との間に、炭素含有ポリマーを含む平滑層をさらに有することが好ましい。 [Smooth layer (underlayer, primer layer)]
The gas barrier film of the present invention may have a smooth layer (underlayer, primer layer) between the surface of the substrate having the barrier layer, preferably between the substrate and the first barrier layer. The smooth layer is provided in order to flatten the rough surface of the substrate on which the protrusions and the like exist, or to fill the unevenness and pinholes generated in the barrier layer with the protrusions on the substrate and to flatten the surface. Such a smooth layer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer. That is, it is preferable that the gas barrier film of the present invention further has a smooth layer containing a carbon-containing polymer between the substrate and the first barrier layer.
また、平滑層は、炭素含有ポリマー、好ましくは硬化性樹脂を含む。前記硬化性樹脂としては特に制限されず、活性エネルギー線硬化性材料等に対して紫外線等の活性エネルギー線を照射し硬化させて得られる活性エネルギー線硬化性樹脂や、熱硬化性材料を加熱することにより硬化して得られる熱硬化性樹脂等が挙げられる。該硬化性樹脂は、単独でもまたは2種以上組み合わせて用いてもよい。
The smooth layer also contains a carbon-containing polymer, preferably a curable resin. The curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material or the like with an active energy ray such as an ultraviolet ray to be cured is heated. And thermosetting resins obtained by curing. These curable resins may be used alone or in combination of two or more.
ここで、平滑層は、特に制限されず、例えば、特開2014-151571号公報、特開2014-046272号公報などに記載される平滑層と同様あるいは適宜修飾されて適用できる。
Here, the smooth layer is not particularly limited, and can be applied, for example, as the smooth layer described in JP-A No. 2014-151571, JP-A No. 2014-046272, or the like as appropriate.
〔アンカーコート層〕
本発明に係る基材の表面には、接着性(密着性)の向上を目的として、アンカーコート層を易接着層として形成してもよい。このアンカーコート層に用いられるアンカーコート剤としては、ポリエステル樹脂、イソシアネート樹脂、ウレタン樹脂、アクリル樹脂、エチレン・ビニルアルコール樹脂、ビニル変性樹脂、エポキシ樹脂、変性スチレン樹脂、変性シリコン樹脂、およびアルキルチタネート等を、1種または2種以上併せて使用することができる。上記アンカーコート剤は、市販品を使用してもよい。具体的には、シロキサン系UV硬化性ポリマー溶液(信越化学工業株式会社製、「X-12-2400」の3%イソプロピルアルコール溶液)を用いることができる。 [Anchor coat layer]
On the surface of the base material according to the present invention, an anchor coat layer may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion). Examples of the anchor coat agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene / vinyl alcohol resin, vinyl-modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. Can be used alone or in combination of two or more. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., “X-12-2400” in 3% isopropyl alcohol) can be used.
本発明に係る基材の表面には、接着性(密着性)の向上を目的として、アンカーコート層を易接着層として形成してもよい。このアンカーコート層に用いられるアンカーコート剤としては、ポリエステル樹脂、イソシアネート樹脂、ウレタン樹脂、アクリル樹脂、エチレン・ビニルアルコール樹脂、ビニル変性樹脂、エポキシ樹脂、変性スチレン樹脂、変性シリコン樹脂、およびアルキルチタネート等を、1種または2種以上併せて使用することができる。上記アンカーコート剤は、市販品を使用してもよい。具体的には、シロキサン系UV硬化性ポリマー溶液(信越化学工業株式会社製、「X-12-2400」の3%イソプロピルアルコール溶液)を用いることができる。 [Anchor coat layer]
On the surface of the base material according to the present invention, an anchor coat layer may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion). Examples of the anchor coat agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene / vinyl alcohol resin, vinyl-modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. Can be used alone or in combination of two or more. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., “X-12-2400” in 3% isopropyl alcohol) can be used.
これらのアンカーコート剤には、従来公知の添加剤を加えることもできる。そして、上記のアンカーコート剤は、ロールコート、グラビアコート、ナイフコート、ディップコート、スプレーコート等の公知の方法により基材上にコーティングし、溶剤、希釈剤等を乾燥除去することによりコーティングすることができる。上記のアンカーコート剤の塗布量としては、0.1~5g/m2(乾燥状態)程度が好ましい。なお、市販の易接着層付き基材を用いてもよい。
Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is coated by drying and removing the solvent, diluent, etc. Can do. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m 2 (dry state). A commercially available base material with an easy-adhesion layer may be used.
または、アンカーコート層は、物理蒸着法または化学蒸着法といった気相法により形成することもできる。例えば、特開2008-142941号公報に記載のように、接着性等を改善する目的で酸化ケイ素を主体とした無機膜を形成することもできる。
Alternatively, the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.
また、アンカーコート層の厚さは、特に制限されないが、0.5~10.0μm程度が好ましい。
The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.
〔ブリードアウト防止層〕
本発明のガスバリア性フィルムは、ブリードアウト防止層をさらに有することができる。ブリードアウト防止層は、平滑層を有するフィルムを加熱した際に、基材中から未反応のオリゴマー等が表面へ移行して、接触する面を汚染する現象を抑制する目的で、平滑層を有する基材の反対面に設けられる。ブリードアウト防止層は、この機能を有していれば、基本的に平滑層と同じ構成をとっても構わない。 [Bleed-out prevention layer]
The gas barrier film of the present invention can further have a bleed-out preventing layer. The bleed-out prevention layer has a smooth layer for the purpose of suppressing the phenomenon of unreacted oligomers moving from the base material to the surface when the film having the smooth layer is heated and contaminating the contact surface. Provided on the opposite surface of the substrate. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.
本発明のガスバリア性フィルムは、ブリードアウト防止層をさらに有することができる。ブリードアウト防止層は、平滑層を有するフィルムを加熱した際に、基材中から未反応のオリゴマー等が表面へ移行して、接触する面を汚染する現象を抑制する目的で、平滑層を有する基材の反対面に設けられる。ブリードアウト防止層は、この機能を有していれば、基本的に平滑層と同じ構成をとっても構わない。 [Bleed-out prevention layer]
The gas barrier film of the present invention can further have a bleed-out preventing layer. The bleed-out prevention layer has a smooth layer for the purpose of suppressing the phenomenon of unreacted oligomers moving from the base material to the surface when the film having the smooth layer is heated and contaminating the contact surface. Provided on the opposite surface of the substrate. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.
ブリードアウト防止層に含ませることが可能な化合物としては、分子中に2個以上の重合性不飽和基を有する多価不飽和有機化合物、あるいは分子中に1個の重合性不飽和基を有する単価不飽和有機化合物等のハードコート剤を挙げることができる。
Compounds that can be included in the bleed-out prevention layer include polyunsaturated organic compounds having two or more polymerizable unsaturated groups in the molecule, or one polymerizable unsaturated group in the molecule. Hard coat agents such as unitary unsaturated organic compounds can be mentioned.
ここで、ブリードアウト防止層は、特に制限されず、例えば、特開2014-151571号公報、特開2014-046272号公報などに記載されるブリードアウト防止層と同様あるいは適宜修飾されて適用できる。
Here, the bleed-out prevention layer is not particularly limited, and can be applied, for example, as the bleed-out prevention layer described in JP-A No. 2014-151571, JP-A No. 2014-046272, or the like or appropriately modified.
《ガスバリア性フィルムの包装形態》
本発明によるガスバリア性フィルムは、連続生産しロール形態に巻き取ることができる(いわゆるロール・トゥ・ロール生産)。その際、バリア層を形成した面に保護シートを貼合して巻き取ることが好ましい。特に、本発明のガスバリア性フィルムを有機薄膜デバイスの封止材として用いる場合、表面に付着したゴミ(例えば、パーティクル)が原因で欠陥となる場合が多く、クリーン度の高い場所で保護シートを貼合してゴミの付着を防止することは非常に有効である。併せて、巻取り時に入るバリア層表面への傷の防止に有効である。 << Packing form of gas barrier film >>
The gas barrier film according to the present invention can be continuously produced and wound into a roll form (so-called roll-to-roll production). In that case, it is preferable to stick and wind up a protective sheet on the surface in which the barrier layer was formed. In particular, when the gas barrier film of the present invention is used as a sealing material for organic thin film devices, it often causes defects due to dust (for example, particles) adhering to the surface, and a protective sheet is applied in a place with a high degree of cleanliness. It is very effective to prevent the adhesion of dust. In addition, it is effective for preventing scratches on the surface of the barrier layer that enters during winding.
本発明によるガスバリア性フィルムは、連続生産しロール形態に巻き取ることができる(いわゆるロール・トゥ・ロール生産)。その際、バリア層を形成した面に保護シートを貼合して巻き取ることが好ましい。特に、本発明のガスバリア性フィルムを有機薄膜デバイスの封止材として用いる場合、表面に付着したゴミ(例えば、パーティクル)が原因で欠陥となる場合が多く、クリーン度の高い場所で保護シートを貼合してゴミの付着を防止することは非常に有効である。併せて、巻取り時に入るバリア層表面への傷の防止に有効である。 << Packing form of gas barrier film >>
The gas barrier film according to the present invention can be continuously produced and wound into a roll form (so-called roll-to-roll production). In that case, it is preferable to stick and wind up a protective sheet on the surface in which the barrier layer was formed. In particular, when the gas barrier film of the present invention is used as a sealing material for organic thin film devices, it often causes defects due to dust (for example, particles) adhering to the surface, and a protective sheet is applied in a place with a high degree of cleanliness. It is very effective to prevent the adhesion of dust. In addition, it is effective for preventing scratches on the surface of the barrier layer that enters during winding.
保護シートとしては、特に限定するものではないが、膜厚100μm程度の樹脂基板に弱粘着性の接着層を付与した構成の一般的な「保護シート」、「剥離シート」を用いることができる。
The protective sheet is not particularly limited, and general “protective sheet” and “release sheet” having a configuration in which a weakly adhesive layer is provided on a resin substrate having a thickness of about 100 μm can be used.
《ガスバリア性フィルムの水蒸気透過率》
本発明の方法によって製造されるガスバリア性フィルムの水蒸気透過率は、低いほど好ましいが、例えば、1×10-3~1×10-5g/m2・dayであることが好ましく、1×10-4~1×10-5g/m2・dayであることがより好ましい。本発明において、水蒸気透過率は後述の実施例に記載の方法によって測定される値を用いるものとする。 << Water vapor permeability of gas barrier film >>
The water vapor permeability of the gas barrier film produced by the method of the present invention is preferably as low as possible. For example, it is preferably 1 × 10 −3 to 1 × 10 −5 g / m 2 · day, and preferably 1 × 10. -4 to 1 × 10 -5 g / m 2 · day is more preferable. In the present invention, the water vapor transmission rate is a value measured by the method described in Examples described later.
本発明の方法によって製造されるガスバリア性フィルムの水蒸気透過率は、低いほど好ましいが、例えば、1×10-3~1×10-5g/m2・dayであることが好ましく、1×10-4~1×10-5g/m2・dayであることがより好ましい。本発明において、水蒸気透過率は後述の実施例に記載の方法によって測定される値を用いるものとする。 << Water vapor permeability of gas barrier film >>
The water vapor permeability of the gas barrier film produced by the method of the present invention is preferably as low as possible. For example, it is preferably 1 × 10 −3 to 1 × 10 −5 g / m 2 · day, and preferably 1 × 10. -4 to 1 × 10 -5 g / m 2 · day is more preferable. In the present invention, the water vapor transmission rate is a value measured by the method described in Examples described later.
〔電子デバイス〕
本発明の方法によって製造されるガスバリア性フィルムは、空気中の化学成分(酸素、水、窒素酸化物、硫黄酸化物、オゾン等)によって性能が劣化するデバイスに好ましく用いることができる。前記デバイスの例としては、例えば、有機EL素子、液晶表示素子(LCD)、薄膜トランジスタ、タッチパネル、電子ペーパー、太陽電池(PV)等の電子デバイスを挙げることができる。本発明の効果がより効率的に得られるという観点から、有機EL素子または太陽電池に好ましく用いられ、有機EL素子に特に好ましく用いられる。すなわち、本発明は、本発明のガスバリア性フィルムを有する、有機EL素子をも提供する。 [Electronic device]
The gas barrier film produced by the method of the present invention can be preferably used for a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. Examples of the device include electronic devices such as an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device. That is, the present invention also provides an organic EL device having the gas barrier film of the present invention.
本発明の方法によって製造されるガスバリア性フィルムは、空気中の化学成分(酸素、水、窒素酸化物、硫黄酸化物、オゾン等)によって性能が劣化するデバイスに好ましく用いることができる。前記デバイスの例としては、例えば、有機EL素子、液晶表示素子(LCD)、薄膜トランジスタ、タッチパネル、電子ペーパー、太陽電池(PV)等の電子デバイスを挙げることができる。本発明の効果がより効率的に得られるという観点から、有機EL素子または太陽電池に好ましく用いられ、有機EL素子に特に好ましく用いられる。すなわち、本発明は、本発明のガスバリア性フィルムを有する、有機EL素子をも提供する。 [Electronic device]
The gas barrier film produced by the method of the present invention can be preferably used for a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. Examples of the device include electronic devices such as an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device. That is, the present invention also provides an organic EL device having the gas barrier film of the present invention.
本発明の方法によって製造されるガスバリア性フィルムは、また、デバイスの膜封止に用いることができる。すなわち、デバイス自体を支持体として、その表面に本発明のガスバリア性フィルムを設ける方法である。ガスバリア性フィルムを設ける前にデバイスを保護層で覆ってもよい。
The gas barrier film produced by the method of the present invention can also be used for device film sealing. That is, it is a method of providing the gas barrier film of the present invention on the surface of the device itself as a support. The device may be covered with a protective layer before providing the gas barrier film.
本発明の方法によって製造されるガスバリア性フィルムは、デバイスの基板や固体封止法による封止のためのフィルムとしても用いることができる。固体封止法とはデバイスの上に保護層を形成した後、接着剤層、ガスバリア性フィルムを重ねて硬化する方法である。接着剤は特に制限はないが、熱硬化性エポキシ樹脂、光硬化性アクリレート樹脂等が例示される。
The gas barrier film produced by the method of the present invention can also be used as a device substrate or a film for sealing by a solid sealing method. The solid sealing method is a method in which after a protective layer is formed on a device, an adhesive layer and a gas barrier film are stacked and cured. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.
<有機EL素子>
ガスバリア性フィルムを用いた有機EL素子の例は、特開2007-30387号公報に詳しく記載されている。 <Organic EL device>
Examples of organic EL elements using a gas barrier film are described in detail in JP-A-2007-30387.
ガスバリア性フィルムを用いた有機EL素子の例は、特開2007-30387号公報に詳しく記載されている。 <Organic EL device>
Examples of organic EL elements using a gas barrier film are described in detail in JP-A-2007-30387.
<液晶表示素子>
反射型液晶表示装置は、下から順に、下基板、反射電極、下配向膜、液晶層、上配向膜、透明電極、上基板、λ/4板、そして偏光膜からなる構成を有する。本発明におけるガスバリア性フィルムは、前記透明電極基板および上基板として使用することができる。カラー表示の場合には、さらにカラーフィルター層を反射電極と下配向膜との間、または上配向膜と透明電極との間に設けることが好ましい。透過型液晶表示装置は、下から順に、バックライト、偏光板、λ/4板、下透明電極、下配向膜、液晶層、上配向膜、上透明電極、上基板、λ/4板および偏光膜からなる構成を有する。カラー表示の場合には、さらにカラーフィルター層を下透明電極と下配向膜との間、または上配向膜と透明電極との間に設けることが好ましい。液晶セルの種類は特に限定されないが、より好ましくはTN型(Twisted Nematic)、STN型(Super Twisted Nematic)またはHAN型(Hybrid Aligned Nematic)、VA型(Vertically Alignment)、ECB型(Electrically Controlled Birefringence)、OCB型(Optically Compensated Bend)、IPS型(In-Plane Switching)、CPA型(Continuous Pinwheel Alignment)であることが好ましい。 <Liquid crystal display element>
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It has a structure consisting of a film. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The type of the liquid crystal cell is not particularly limited, but more preferably a TN type (Twisted Nematic), an STN type (Super Twisted Nematic), a HAN type (Hybrid Aligned Nematic), a VA type (Vertical Alignment), an EC type, a B type. OCB type (Optically Compensated Bend), IPS type (In-Plane Switching), CPA type (Continuous Pinwheel Alignment) are preferable.
反射型液晶表示装置は、下から順に、下基板、反射電極、下配向膜、液晶層、上配向膜、透明電極、上基板、λ/4板、そして偏光膜からなる構成を有する。本発明におけるガスバリア性フィルムは、前記透明電極基板および上基板として使用することができる。カラー表示の場合には、さらにカラーフィルター層を反射電極と下配向膜との間、または上配向膜と透明電極との間に設けることが好ましい。透過型液晶表示装置は、下から順に、バックライト、偏光板、λ/4板、下透明電極、下配向膜、液晶層、上配向膜、上透明電極、上基板、λ/4板および偏光膜からなる構成を有する。カラー表示の場合には、さらにカラーフィルター層を下透明電極と下配向膜との間、または上配向膜と透明電極との間に設けることが好ましい。液晶セルの種類は特に限定されないが、より好ましくはTN型(Twisted Nematic)、STN型(Super Twisted Nematic)またはHAN型(Hybrid Aligned Nematic)、VA型(Vertically Alignment)、ECB型(Electrically Controlled Birefringence)、OCB型(Optically Compensated Bend)、IPS型(In-Plane Switching)、CPA型(Continuous Pinwheel Alignment)であることが好ましい。 <Liquid crystal display element>
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It has a structure consisting of a film. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The type of the liquid crystal cell is not particularly limited, but more preferably a TN type (Twisted Nematic), an STN type (Super Twisted Nematic), a HAN type (Hybrid Aligned Nematic), a VA type (Vertical Alignment), an EC type, a B type. OCB type (Optically Compensated Bend), IPS type (In-Plane Switching), CPA type (Continuous Pinwheel Alignment) are preferable.
<太陽電池>
本発明のガスバリア性フィルムは、太陽電池素子の封止フィルムとしても用いることができる。ここで、本発明のガスバリア性フィルムは、バリア層が太陽電池素子に近い側となるように封止することが好ましい。本発明のガスバリア性フィルムが好ましく用いられる太陽電池素子としては、特に制限はないが、例えば、単結晶シリコン系太陽電池素子、多結晶シリコン系太陽電池素子、シングル接合型、またはタンデム構造型等で構成されるアモルファスシリコン系太陽電池素子、ガリウムヒ素(GaAs)やインジウム燐(InP)等のIII-V族化合物半導体太陽電池素子、カドミウムテルル(CdTe)等のII-VI族化合物半導体太陽電池素子、銅/インジウム/セレン系(いわゆる、CIS系)、銅/インジウム/ガリウム/セレン系(いわゆる、CIGS系)、銅/インジウム/ガリウム/セレン/硫黄系(いわゆる、CIGSS系)等のI-III-VI族化合物半導体太陽電池素子、色素増感型太陽電池素子、有機太陽電池素子等が挙げられる。中でも、本発明においては、上記太陽電池素子が、銅/インジウム/セレン系(いわゆる、CIS系)、銅/インジウム/ガリウム/セレン系(いわゆる、CIGS系)、銅/インジウム/ガリウム/セレン/硫黄系(いわゆる、CIGSS系)等のI-III-VI族化合物半導体太陽電池素子であることが好ましい。 <Solar cell>
The gas barrier film of the present invention can also be used as a sealing film for solar cell elements. Here, the gas barrier film of the present invention is preferably sealed so that the barrier layer is closer to the solar cell element. The solar cell element in which the gas barrier film of the present invention is preferably used is not particularly limited. For example, it is a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, or a tandem structure type. Amorphous silicon-based solar cell elements, III-V group compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI group compound semiconductor solar cell elements such as cadmium tellurium (CdTe), I-III- such as copper / indium / selenium (so-called CIS), copper / indium / gallium / selenium (so-called CIGS), copper / indium / gallium / selenium / sulfur (so-called CIGS), etc. Group VI compound semiconductor solar cell element, dye-sensitized solar cell element, organic solar cell element, etc. And the like. In particular, in the present invention, the solar cell element is a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur. A group I-III-VI compound semiconductor solar cell element such as a system (so-called CIGSS system) is preferable.
本発明のガスバリア性フィルムは、太陽電池素子の封止フィルムとしても用いることができる。ここで、本発明のガスバリア性フィルムは、バリア層が太陽電池素子に近い側となるように封止することが好ましい。本発明のガスバリア性フィルムが好ましく用いられる太陽電池素子としては、特に制限はないが、例えば、単結晶シリコン系太陽電池素子、多結晶シリコン系太陽電池素子、シングル接合型、またはタンデム構造型等で構成されるアモルファスシリコン系太陽電池素子、ガリウムヒ素(GaAs)やインジウム燐(InP)等のIII-V族化合物半導体太陽電池素子、カドミウムテルル(CdTe)等のII-VI族化合物半導体太陽電池素子、銅/インジウム/セレン系(いわゆる、CIS系)、銅/インジウム/ガリウム/セレン系(いわゆる、CIGS系)、銅/インジウム/ガリウム/セレン/硫黄系(いわゆる、CIGSS系)等のI-III-VI族化合物半導体太陽電池素子、色素増感型太陽電池素子、有機太陽電池素子等が挙げられる。中でも、本発明においては、上記太陽電池素子が、銅/インジウム/セレン系(いわゆる、CIS系)、銅/インジウム/ガリウム/セレン系(いわゆる、CIGS系)、銅/インジウム/ガリウム/セレン/硫黄系(いわゆる、CIGSS系)等のI-III-VI族化合物半導体太陽電池素子であることが好ましい。 <Solar cell>
The gas barrier film of the present invention can also be used as a sealing film for solar cell elements. Here, the gas barrier film of the present invention is preferably sealed so that the barrier layer is closer to the solar cell element. The solar cell element in which the gas barrier film of the present invention is preferably used is not particularly limited. For example, it is a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, or a tandem structure type. Amorphous silicon-based solar cell elements, III-V group compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI group compound semiconductor solar cell elements such as cadmium tellurium (CdTe), I-III- such as copper / indium / selenium (so-called CIS), copper / indium / gallium / selenium (so-called CIGS), copper / indium / gallium / selenium / sulfur (so-called CIGS), etc. Group VI compound semiconductor solar cell element, dye-sensitized solar cell element, organic solar cell element, etc. And the like. In particular, in the present invention, the solar cell element is a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur. A group I-III-VI compound semiconductor solar cell element such as a system (so-called CIGSS system) is preferable.
<その他>
その他の適用例としては、特表平10-512104号公報に記載の薄膜トランジスタ、特開平5-127822号公報、特開2002-48913号公報等に記載のタッチパネル、特開2000-98326号公報に記載の電子ペーパー等が挙げられる。 <Others>
As other application examples, the thin film transistor described in JP-T-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., and described in JP-A-2000-98326 Electronic paper and the like.
その他の適用例としては、特表平10-512104号公報に記載の薄膜トランジスタ、特開平5-127822号公報、特開2002-48913号公報等に記載のタッチパネル、特開2000-98326号公報に記載の電子ペーパー等が挙げられる。 <Others>
As other application examples, the thin film transistor described in JP-T-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., and described in JP-A-2000-98326 Electronic paper and the like.
<光学部材>
本発明のガスバリア性フィルムは、光学部材としても用いることができる。光学部材の例としては円偏光板等が挙げられる。 <Optical member>
The gas barrier film of the present invention can also be used as an optical member. Examples of the optical member include a circularly polarizing plate.
本発明のガスバリア性フィルムは、光学部材としても用いることができる。光学部材の例としては円偏光板等が挙げられる。 <Optical member>
The gas barrier film of the present invention can also be used as an optical member. Examples of the optical member include a circularly polarizing plate.
(円偏光板)
本発明におけるガスバリア性フィルムを基板としλ/4板と偏光板とを積層し、円偏光板を作製することができる。この場合、λ/4板の遅相軸と偏光板の吸収軸とのなす角が45°になるように積層する。このような偏光板は、長手方向(MD)に対し45°の方向に延伸されているものを用いることが好ましく、例えば、特開2002-865554号公報に記載のものを好適に用いることができる。 (Circularly polarizing plate)
A circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate using the gas barrier film in the present invention as a substrate. In this case, the lamination is performed so that the angle formed by the slow axis of the λ / 4 plate and the absorption axis of the polarizing plate is 45 °. As such a polarizing plate, one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used. For example, those described in JP-A-2002-865554 can be suitably used. .
本発明におけるガスバリア性フィルムを基板としλ/4板と偏光板とを積層し、円偏光板を作製することができる。この場合、λ/4板の遅相軸と偏光板の吸収軸とのなす角が45°になるように積層する。このような偏光板は、長手方向(MD)に対し45°の方向に延伸されているものを用いることが好ましく、例えば、特開2002-865554号公報に記載のものを好適に用いることができる。 (Circularly polarizing plate)
A circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate using the gas barrier film in the present invention as a substrate. In this case, the lamination is performed so that the angle formed by the slow axis of the λ / 4 plate and the absorption axis of the polarizing plate is 45 °. As such a polarizing plate, one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used. For example, those described in JP-A-2002-865554 can be suitably used. .
本発明の効果を、以下の実施例および比較例を用いて説明する。ただし、本発明の技術的範囲が以下の実施例のみに制限されるわけではない。また、実施例において「部」あるいは「%」の表示を用いるが、特に断りがない限り「質量部」あるいは「質量%」を表す。また、下記操作において、特記しない限り、操作および物性等の測定は室温(20~25℃)/相対湿度40~50%の条件で行う。
The effect of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. Further, in the examples, “part” or “%” is used, but “part by mass” or “% by mass” is expressed unless otherwise specified. In the following operations, unless otherwise specified, the measurement of the operation and physical properties is performed under the conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.
(比較例1:ガスバリア性フィルム101の作製)
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
株式会社きもと製のクリアハードコートを施したPET基材(125μm厚)を、図2に示されるような製造装置31にセットして、搬送させた。次いで、成膜ローラー39と成膜ローラー40との間に磁場を印加すると共に、成膜ローラー39と成膜ローラー40にそれぞれ電力を供給して、成膜ローラー39と成膜ローラー40との間に放電してプラズマを発生させた。次いで、形成された放電領域に、成膜ガス(原料ガスとしてヘキサメチルジシロキサン(HMDSO)と反応ガスとして酸素ガス(放電ガスとしても機能する)との混合ガスを供給し、基材2上に、プラズマCVD法にてガスバリア性の薄膜(無機化合物層、第1のバリア層)を形成した。無機化合物層の厚みは、150nmであった。成膜条件は、以下の通りとした。このようにして形成された無機化合物層は、構成元素として炭素、ケイ素、および酸素を含み、かつ要件(i)~(iii)を満たすことを確認した。 (Comparative Example 1: Production of gas barrier film 101)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
A PET base material (125 μm thick) provided with Kimoto's clear hard coat was set in amanufacturing apparatus 31 as shown in FIG. 2 and conveyed. Next, a magnetic field is applied between the film forming roller 39 and the film forming roller 40, and electric power is supplied to the film forming roller 39 and the film forming roller 40, respectively. Was discharged to generate plasma. Next, a film forming gas (mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (which also functions as a discharge gas) as a source gas) is supplied to the formed discharge region, A gas barrier thin film (inorganic compound layer, first barrier layer) was formed by plasma CVD, and the thickness of the inorganic compound layer was 150 nm. It was confirmed that the inorganic compound layer formed as described above contains carbon, silicon, and oxygen as constituent elements and satisfies the requirements (i) to (iii).
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
株式会社きもと製のクリアハードコートを施したPET基材(125μm厚)を、図2に示されるような製造装置31にセットして、搬送させた。次いで、成膜ローラー39と成膜ローラー40との間に磁場を印加すると共に、成膜ローラー39と成膜ローラー40にそれぞれ電力を供給して、成膜ローラー39と成膜ローラー40との間に放電してプラズマを発生させた。次いで、形成された放電領域に、成膜ガス(原料ガスとしてヘキサメチルジシロキサン(HMDSO)と反応ガスとして酸素ガス(放電ガスとしても機能する)との混合ガスを供給し、基材2上に、プラズマCVD法にてガスバリア性の薄膜(無機化合物層、第1のバリア層)を形成した。無機化合物層の厚みは、150nmであった。成膜条件は、以下の通りとした。このようにして形成された無機化合物層は、構成元素として炭素、ケイ素、および酸素を含み、かつ要件(i)~(iii)を満たすことを確認した。 (Comparative Example 1: Production of gas barrier film 101)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
A PET base material (125 μm thick) provided with Kimoto's clear hard coat was set in a
〔バリア層(第2のバリア層)の形成(塗布法)〕
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
無触媒のパーヒドロポリシラザン(PHPS)を20質量%含むジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NN120-20)と、アミン触媒(N,N,N’,N’-テトラメチル-1,6-ジアミノヘキサン(TMDAH))を5質量%含むパーヒドロポリシラザン20質量%のジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NAX120-20)とを、4:1の割合(質量比)で混合し、さらにジブチルエーテルと2,2,4-トリメチルペンタンとの質量比が65:35となるように混合した溶媒で、塗布液の固形分(パーヒドロポリシラザンの濃度)が2.7質量%になるように調整した(塗布液(1))。
A dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (PHPS) (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20), and an amine catalyst (N, N, N ′, N′— A solution of 20% by mass of perhydropolysilazane containing 5% by mass of tetramethyl-1,6-diaminohexane (TMDAH) (manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20), 4 : 1 in a ratio (mass ratio), and a solvent in which the mass ratio of dibutyl ether and 2,2,4-trimethylpentane is 65:35, and the solid content of the coating solution (perhydropolysilazane) The concentration was adjusted to 2.7% by mass (coating liquid (1)).
上記で作製された塗布液(1)中のパーヒドロポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、下記方法に従って測定し、その結果を表1に示す。
The ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the perhydropolysilazane coating solution (1) prepared by the above the [(SiH 3) :( SiH + SiH 2)], the following The measurement was performed according to the method, and the results are shown in Table 1.
(29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]の測定方法)
ポリシラザン含有塗布液について、以下のようにして29Si-NMR測定を行う。具体的には、29Si-NMR測定結果において、-50ppm付近に観測されるSiH3に帰属されるピークの面積を1としたときの、-35ppm近傍に観測されるSiH及びSiH2に帰属されるピークの面積の比をSiH3比とする。測定は、日本電子社製の500MHzNMR装置に、29Si測定用のNMRチューブ管を用い、溶媒として重ベンゼンを用いて測定を行う。 (Measurement method of ratio [(SiH 3 ) :( SiH + SiH 2 )] of SiH 3 measured by 29 Si-NMR and the sum of SiH and SiH 2 )
With respect to the polysilazane-containing coating solution, 29 Si-NMR measurement is performed as follows. Specifically, in the 29 Si-NMR measurement result, it is attributed to SiH and SiH 2 observed in the vicinity of −35 ppm when the area of the peak attributed to SiH 3 observed in the vicinity of −50 ppm is 1. The ratio of the peak areas is the SiH 3 ratio. The measurement is performed using a 500 MHz NMR apparatus manufactured by JEOL Ltd. using an NMR tube tube for 29 Si measurement and using heavy benzene as a solvent.
ポリシラザン含有塗布液について、以下のようにして29Si-NMR測定を行う。具体的には、29Si-NMR測定結果において、-50ppm付近に観測されるSiH3に帰属されるピークの面積を1としたときの、-35ppm近傍に観測されるSiH及びSiH2に帰属されるピークの面積の比をSiH3比とする。測定は、日本電子社製の500MHzNMR装置に、29Si測定用のNMRチューブ管を用い、溶媒として重ベンゼンを用いて測定を行う。 (Measurement method of ratio [(SiH 3 ) :( SiH + SiH 2 )] of SiH 3 measured by 29 Si-NMR and the sum of SiH and SiH 2 )
With respect to the polysilazane-containing coating solution, 29 Si-NMR measurement is performed as follows. Specifically, in the 29 Si-NMR measurement result, it is attributed to SiH and SiH 2 observed in the vicinity of −35 ppm when the area of the peak attributed to SiH 3 observed in the vicinity of −50 ppm is 1. The ratio of the peak areas is the SiH 3 ratio. The measurement is performed using a 500 MHz NMR apparatus manufactured by JEOL Ltd. using an NMR tube tube for 29 Si measurement and using heavy benzene as a solvent.
上記で得られた塗布液を、スピンコーターにて、上記の無機化合物層上に、厚さ(乾燥膜厚)が80nmになるよう成膜し、2分間放置した後、80℃のホットプレートで1分間追加加熱処理を行い、ポリシラザン塗膜(前駆層)を形成した。
The coating solution obtained above is formed on the inorganic compound layer with a spin coater so that the thickness (dry film thickness) is 80 nm, left for 2 minutes, and then heated on an 80 ° C. hot plate. Additional heat treatment was performed for 1 minute to form a polysilazane coating film (precursor layer).
ポリシラザン塗膜を形成した後、下記の方法に従って、172nmの真空紫外線を6000mJ/cm2になるように真空紫外線照射処理を施して、バリア層(第2のバリア層)を無機化合物層(第1のバリア層)上に形成した。このようにして、ガスバリア性フィルム101を作製した。ここで、得られたバリア層(第2のバリア層)について、上記と同様にして、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(1)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。
After forming the polysilazane coating film, a vacuum ultraviolet ray irradiation treatment is performed so that a vacuum ultraviolet ray of 172 nm becomes 6000 mJ / cm 2 according to the following method. On the barrier layer). Thus, the gas barrier film 101 was produced. Here, when the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured in the same manner as described above, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (1) is read as SiH 3 ratio of the barrier layer (second barrier layer).
〈真空紫外線照射条件・照射エネルギーの測定〉
真空紫外線照射は、図3に模式図で示した装置を用いて行った。 <Measurement of vacuum ultraviolet irradiation conditions and irradiation energy>
The vacuum ultraviolet irradiation was performed using the apparatus schematically shown in FIG.
真空紫外線照射は、図3に模式図で示した装置を用いて行った。 <Measurement of vacuum ultraviolet irradiation conditions and irradiation energy>
The vacuum ultraviolet irradiation was performed using the apparatus schematically shown in FIG.
図3において、21は装置チャンバであり、図示しないガス供給口から内部に窒素と酸素とを適量供給し、図示しないガス排出口から排気することで、チャンバ内部から実質的に水蒸気を除去し、酸素濃度を所定の濃度に維持することができる。ここでは酸素濃度を1,000体積ppmに調節して真空紫外線照射を行った。なお、チャンバ内の酸素濃度は、酸素濃度計(東レエンジニアリング社製ジルコニア型酸素濃度計LC-450A)を用いて測定した。22は172nmの真空紫外線を照射する二重管構造を有するXeエキシマランプ、23は外部電極を兼ねるエキシマランプのホルダーである。24は試料ステージである。試料ステージ24は、図示しない移動手段により装置チャンバ21内を水平に所定の速度で往復移動することができる。また、試料ステージ24は図示しない加熱手段により、所定の温度に維持することができる。ここでは100℃に設定した。25はポリシラザン塗膜が形成された試料である。試料ステージが水平移動する際、試料の塗布層表面と、エキシマランプ管面との最短距離が6mmとなるように試料ステージの高さが調整されている。26は遮光板であり、Xeエキシマランプ22のエージング中に試料の塗布層に真空紫外光が照射されないようにしている。
In FIG. 3, reference numeral 21 denotes an apparatus chamber, which supplies appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) to the inside and exhausts gas from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber. The oxygen concentration can be maintained at a predetermined concentration. Here, vacuum ultraviolet irradiation was performed with the oxygen concentration adjusted to 1,000 ppm by volume. The oxygen concentration in the chamber was measured using an oxygen concentration meter (zirconia oxygen concentration meter LC-450A manufactured by Toray Engineering Co., Ltd.). Reference numeral 22 denotes an Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, and reference numeral 23 denotes an excimer lamp holder that also serves as an external electrode. Reference numeral 24 denotes a sample stage. The sample stage 24 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 21 by a moving means (not shown). The sample stage 24 can be maintained at a predetermined temperature by a heating means (not shown). Here, it was set to 100 ° C. Reference numeral 25 denotes a sample on which a polysilazane coating film is formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the surface of the sample coating layer and the excimer lamp tube surface is 6 mm. Reference numeral 26 denotes a light shielding plate, which prevents the application layer of the sample from being irradiated with vacuum ultraviolet light during aging of the Xe excimer lamp 22.
真空紫外線照射工程で塗膜表面に照射されるエネルギーは、浜松ホトニクス株式会社製の紫外線積算光量計:C8026/H8025 UV POWER METERを用い、172nmのセンサヘッドを用いて測定した。測定に際しては、Xeエキシマランプ管面とセンサヘッドの測定面との最短距離が、6mmとなるようにセンサヘッドを試料ステージ24中央に設置し、かつ、装置チャンバ21内の雰囲気が、真空紫外線照射工程と同一の酸素濃度となるように窒素と酸素とを供給し、試料ステージ24を0.5m/minの速度(図3のV)で移動させて測定を行った。測定に先立ち、Xeエキシマランプ12の照度を安定させるため、Xeエキシマランプ点灯後に10分間のエージング時間を設け、その後試料ステージを移動させて測定を開始した。
The energy irradiated to the coating film surface in the vacuum ultraviolet irradiation process was measured using a 172 nm sensor head using a UV integrating light meter: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics Co., Ltd. In the measurement, the sensor head is placed in the center of the sample stage 24 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 6 mm, and the atmosphere in the apparatus chamber 21 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as in the process, and the measurement was performed by moving the sample stage 24 at a speed of 0.5 m / min (V in FIG. 3). Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp 12, an aging time of 10 minutes was provided after the Xe excimer lamp was turned on, and then the sample stage was moved to start the measurement.
この測定で得られた照射エネルギーを元に、試料ステージの移動速度を調整することで6000mJ/cm2の照射エネルギーとなるように調整した。尚、真空紫外線照射に際しては、照射エネルギー測定時と同様に、10分間のエージング後に行った。
Based on the irradiation energy obtained by this measurement, the irradiation speed was adjusted to 6000 mJ / cm 2 by adjusting the moving speed of the sample stage. The vacuum ultraviolet irradiation was performed after aging for 10 minutes as in the case of irradiation energy measurement.
(比較例2:ガスバリア性フィルム102の作製)
比較例1において、塗布液(1)の代わりに、ALCH(川研ファインケミカル株式会社製、アルミニウムエチルアセトアセテート・ジイソプロピレート)をパーヒドロポリシラザンのSi元素数に対して1mol%となる量で塗布液(1)にさらに加え、80℃で1時間撹拌反応させた後冷却することによって調製した塗布液(2)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム102を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。ここで、反応系内の酸素濃度は、酸素濃度計(東レエンジニアリング社製ジルコニア型酸素濃度計LC-450A)を用いて測定した。また、反応系内の水蒸気濃度は、露点計(ヴァイサラ社製、DMT型露点計)を用いて露点を測定し、測定した露点から水蒸気濃度を求めた。 (Comparative Example 2: Production of gas barrier film 102)
In Comparative Example 1, instead of the coating solution (1), ALCH (Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate) was applied in an amount of 1 mol% with respect to the number of Si elements in perhydropolysilazane. In addition to the liquid (1), agas barrier film 102 was produced in the same manner as in Comparative Example 1 except that the coating liquid (2) prepared by stirring and reacting at 80 ° C. for 1 hour and then cooling was used. . In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. Here, the oxygen concentration in the reaction system was measured using an oxygen concentration meter (zirconia type oxygen concentration meter LC-450A manufactured by Toray Engineering Co., Ltd.). In addition, the water vapor concentration in the reaction system was determined by measuring the dew point using a dew point meter (manufactured by Vaisala, DMT type dew point meter), and obtaining the water vapor concentration from the measured dew point.
比較例1において、塗布液(1)の代わりに、ALCH(川研ファインケミカル株式会社製、アルミニウムエチルアセトアセテート・ジイソプロピレート)をパーヒドロポリシラザンのSi元素数に対して1mol%となる量で塗布液(1)にさらに加え、80℃で1時間撹拌反応させた後冷却することによって調製した塗布液(2)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム102を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。ここで、反応系内の酸素濃度は、酸素濃度計(東レエンジニアリング社製ジルコニア型酸素濃度計LC-450A)を用いて測定した。また、反応系内の水蒸気濃度は、露点計(ヴァイサラ社製、DMT型露点計)を用いて露点を測定し、測定した露点から水蒸気濃度を求めた。 (Comparative Example 2: Production of gas barrier film 102)
In Comparative Example 1, instead of the coating solution (1), ALCH (Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate) was applied in an amount of 1 mol% with respect to the number of Si elements in perhydropolysilazane. In addition to the liquid (1), a
また、上記で作製された塗布液(2)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(2)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。
The ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane of the coating liquid (2) in which is prepared as described above for [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1. When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (2) is read as SiH 3 ratio of the barrier layer (second barrier layer).
(比較例3:ガスバリア性フィルム103の作製)
比較例1において、塗布液(1)の代わりに、ALCH(川研ファインケミカル株式会社製、アルミニウムエチルアセトアセテート・ジイソプロピレート)をパーヒドロポリシラザンのSi元素数に対して5mol%となる量で塗布液(1)にさらに加え、80℃で1時間撹拌反応させた後冷却することによって調製した塗布液(3)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム103を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、上記で作製された塗布液(3)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(3)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Comparative Example 3: Production of gas barrier film 103)
In Comparative Example 1, instead of the coating solution (1), ALCH (aluminum ethyl acetoacetate diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.) was applied in an amount of 5 mol% with respect to the number of Si elements in perhydropolysilazane. In addition to the liquid (1), agas barrier film 103 was produced in the same manner as in Comparative Example 1 except that the coating liquid (3) prepared by stirring and reacting at 80 ° C. for 1 hour and then cooling was used. . In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. The ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane of the coating liquid (3) in which is prepared as described above for [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1. When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (3) is read as SiH 3 ratio of the barrier layer (second barrier layer).
比較例1において、塗布液(1)の代わりに、ALCH(川研ファインケミカル株式会社製、アルミニウムエチルアセトアセテート・ジイソプロピレート)をパーヒドロポリシラザンのSi元素数に対して5mol%となる量で塗布液(1)にさらに加え、80℃で1時間撹拌反応させた後冷却することによって調製した塗布液(3)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム103を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、上記で作製された塗布液(3)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(3)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Comparative Example 3: Production of gas barrier film 103)
In Comparative Example 1, instead of the coating solution (1), ALCH (aluminum ethyl acetoacetate diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.) was applied in an amount of 5 mol% with respect to the number of Si elements in perhydropolysilazane. In addition to the liquid (1), a
(実施例1:ガスバリア性フィルム104の作製)
比較例1において、塗布液(1)の代わりに、ALCH(川研ファインケミカル株式会社製、アルミニウムエチルアセトアセテート・ジイソプロピレート)をパーヒドロポリシラザンのSi元素数に対して10mol%となる量で塗布液(1)にさらに加え、80℃で1時間撹拌反応させた後冷却することによって調製した塗布液(4)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム104を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、上記で作製された塗布液(4)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(4)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Example 1: Production of gas barrier film 104)
In Comparative Example 1, instead of the coating solution (1), ALCH (Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate) was applied in an amount of 10 mol% with respect to the number of Si elements in perhydropolysilazane. A gas barrier film 104 was produced in the same manner as in Comparative Example 1 except that the coating liquid (4) prepared by further stirring and reacting at 80 ° C. for 1 hour and then cooling was used in addition to the liquid (1). . In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. The ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane of the coating liquid (4) in which is produced above the [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1. When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (4) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
比較例1において、塗布液(1)の代わりに、ALCH(川研ファインケミカル株式会社製、アルミニウムエチルアセトアセテート・ジイソプロピレート)をパーヒドロポリシラザンのSi元素数に対して10mol%となる量で塗布液(1)にさらに加え、80℃で1時間撹拌反応させた後冷却することによって調製した塗布液(4)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム104を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、上記で作製された塗布液(4)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(4)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Example 1: Production of gas barrier film 104)
In Comparative Example 1, instead of the coating solution (1), ALCH (Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate) was applied in an amount of 10 mol% with respect to the number of Si elements in perhydropolysilazane. A gas barrier film 104 was produced in the same manner as in Comparative Example 1 except that the coating liquid (4) prepared by further stirring and reacting at 80 ° C. for 1 hour and then cooling was used in addition to the liquid (1). . In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. The ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane of the coating liquid (4) in which is produced above the [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1. When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (4) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
(実施例2:ガスバリア性フィルム105の作製)
比較例1において、塗布液(1)の代わりに、AMD(川研ファインケミカル株式会社製、アルミニウムジイソプロピレートモノセカンダリーブチレート)をパーヒドロポリシラザンのSi元素数に対して10mol%となる量で塗布液(1)にさらに加え、80℃で1時間撹拌反応させた後冷却することによって調製した塗布液(5)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム105を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、上記で作製された塗布液(5)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(5)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Example 2: Production of gas barrier film 105)
In Comparative Example 1, in place of the coating liquid (1), AMD (Kawaken Fine Chemical Co., Ltd., aluminum diisopropylate monosecondary butyrate) was applied in an amount of 10 mol% with respect to the number of Si elements of perhydropolysilazane. In addition to the liquid (1), agas barrier film 105 was produced in the same manner as in Comparative Example 1 except that the coating liquid (5) prepared by stirring and reacting at 80 ° C. for 1 hour and then cooling was used. . In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. The ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane of the coating solution (5) in which is prepared as described above for [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1. When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (5) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
比較例1において、塗布液(1)の代わりに、AMD(川研ファインケミカル株式会社製、アルミニウムジイソプロピレートモノセカンダリーブチレート)をパーヒドロポリシラザンのSi元素数に対して10mol%となる量で塗布液(1)にさらに加え、80℃で1時間撹拌反応させた後冷却することによって調製した塗布液(5)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム105を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、上記で作製された塗布液(5)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(5)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Example 2: Production of gas barrier film 105)
In Comparative Example 1, in place of the coating liquid (1), AMD (Kawaken Fine Chemical Co., Ltd., aluminum diisopropylate monosecondary butyrate) was applied in an amount of 10 mol% with respect to the number of Si elements of perhydropolysilazane. In addition to the liquid (1), a
(実施例3:ガスバリア性フィルム106の作製)
比較例1において、塗布液(1)の代わりに、アルミキレートD(川研ファインケミカル株式会社製、アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート)をパーヒドロポリシラザンのSi元素数に対して10mol%となる量で塗布液(1)にさらに加え、80℃で1時間撹拌反応させた後冷却することによって調製した塗布液(6)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム106を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、上記で作製された塗布液(6)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(6)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Example 3: Production of gas barrier film 106)
In Comparative Example 1, instead of the coating solution (1), aluminum chelate D (produced by Kawaken Fine Chemical Co., Ltd., aluminum bisethyl acetoacetate / monoacetylacetonate) was 10 mol% with respect to the number of Si elements in perhydropolysilazane. Gas barrier film in the same manner as in Comparative Example 1, except that the coating solution (6) prepared by further stirring and reacting at 80 ° C. for 1 hour and then cooling was used. 106 was produced. In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. The ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane coating liquid (6) in which is prepared as described above for [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1. When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (6) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
比較例1において、塗布液(1)の代わりに、アルミキレートD(川研ファインケミカル株式会社製、アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート)をパーヒドロポリシラザンのSi元素数に対して10mol%となる量で塗布液(1)にさらに加え、80℃で1時間撹拌反応させた後冷却することによって調製した塗布液(6)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム106を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、上記で作製された塗布液(6)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(6)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Example 3: Production of gas barrier film 106)
In Comparative Example 1, instead of the coating solution (1), aluminum chelate D (produced by Kawaken Fine Chemical Co., Ltd., aluminum bisethyl acetoacetate / monoacetylacetonate) was 10 mol% with respect to the number of Si elements in perhydropolysilazane. Gas barrier film in the same manner as in Comparative Example 1, except that the coating solution (6) prepared by further stirring and reacting at 80 ° C. for 1 hour and then cooling was used. 106 was produced. In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. The ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane coating liquid (6) in which is prepared as described above for [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1. When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (6) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
(実施例4:ガスバリア性フィルム107の作製)
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
比較例1と同様にして、プラズマCVD法によって、厚みが150nmであるガスバリア性の薄膜(無機化合物層、第1のバリア層)を基材上に形成した。 (Example 4: Production of gas barrier film 107)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
比較例1と同様にして、プラズマCVD法によって、厚みが150nmであるガスバリア性の薄膜(無機化合物層、第1のバリア層)を基材上に形成した。 (Example 4: Production of gas barrier film 107)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
〔バリア層(第2のバリア層)の形成(塗布法)〕
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
無触媒のパーヒドロポリシラザンを20質量%含むジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NN120-20)と、アミン触媒(N,N,N’,N’-テトラメチル-1,6-ジアミノヘキサン(TMDAH))を5質量%含むパーヒドロポリシラザン20質量%のジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NAX120-20)とを、4:1の割合(質量比)で混合し、さらにジブチルエーテルと2,2,4-トリメチルペンタンとの質量比が65:35となるように混合した溶媒で、塗布液の固形分(パーヒドロポリシラザンの濃度)が2.7質量%になるように、塗布液(7-1)を調製した。このようにして調製された塗布液(7-1)に、ALCH(川研ファインケミカル株式会社製、アルミニウムエチルアセトアセテート・ジイソプロピレート)をパーヒドロポリシラザンのSi元素数に対して5mol%となる量でさらに添加した後、80℃で1時間撹拌反応させた後冷却して、塗布液(7-2)を調製した。次に、この塗布液(7-2)に、下記構造を有する化合物1をパーヒドロポリシラザンのSi元素数に対して5mol%となる量でさらに添加した後、80℃で1時間撹拌反応させた後冷却して、塗布液(7-3)を調製した。なお、上記で作製された塗布液(7-3)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20) and amine catalyst (N, N, N ′, N′-tetramethyl-) 20% by weight of a perhydropolysilazane containing 5% by mass of 1,6-diaminohexane (TMDAH) (manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20) Mixing at a ratio (mass ratio) and further mixing so that the mass ratio of dibutyl ether and 2,2,4-trimethylpentane is 65:35, solid content of coating solution (concentration of perhydropolysilazane) The coating solution (7-1) was prepared so that the ratio was 2.7% by mass. In the coating solution (7-1) thus prepared, ALCH (Aluminum ethyl acetoacetate diisopropylate, manufactured by Kawaken Fine Chemical Co., Ltd.) is used in an amount of 5 mol% based on the number of Si elements in perhydropolysilazane. After that, the mixture was further reacted with stirring at 80 ° C. for 1 hour and then cooled to prepare a coating solution (7-2). Next, Compound 1 having the following structure was further added to this coating solution (7-2) in an amount of 5 mol% with respect to the number of Si elements of perhydropolysilazane, and then stirred at 80 ° C. for 1 hour. After cooling, a coating solution (7-3) was prepared. The ratio of SiH 3 and the total of SiH and SiH 2 measured by 29 Si-NMR of the modified polysilazane in the coating solution (7-3) prepared above [(SiH 3 ) :( SiH + SiH 2 )] Was measured in the same manner as in Comparative Example 1, and the results are shown in Table 1.
比較例1において、塗布液(1)の代わりに、上記したようにして調製された塗布液(7-3)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム107を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(7)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。
In Comparative Example 1, a gas barrier film 107 was produced in the same manner as in Comparative Example 1, except that the coating liquid (7-3) prepared as described above was used instead of the coating liquid (1). . In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. Further, the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (7) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
(実施例5~11:ガスバリア性フィルム108~114の作製)
実施例4において、化合物1の代わりに、下記構造を有する化合物2~8を、それぞれ、使用した以外は、実施例4と同様にして、ガスバリア性フィルム108~114を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、本実施例で作製された各塗布液中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、各ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される各塗布液のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Examples 5 to 11: Production ofgas barrier films 108 to 114)
In Example 4,gas barrier films 108 to 114 were produced in the same manner as in Example 4, except that compounds 2 to 8 having the following structures were used instead of compound 1, respectively. In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. Further, the ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane in each coating solution was prepared in this example [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1. Incidentally, the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of each polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solutions shown in Table 1 is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
実施例4において、化合物1の代わりに、下記構造を有する化合物2~8を、それぞれ、使用した以外は、実施例4と同様にして、ガスバリア性フィルム108~114を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、本実施例で作製された各塗布液中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、各ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される各塗布液のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Examples 5 to 11: Production of
In Example 4,
(実施例12:ガスバリア性フィルム115の作製)
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
比較例1と同様にして、プラズマCVD法によって、厚みが150nmであるガスバリア性の薄膜(無機化合物層、第1のバリア層)を基材上に形成した。 (Example 12: Production of gas barrier film 115)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
比較例1と同様にして、プラズマCVD法によって、厚みが150nmであるガスバリア性の薄膜(無機化合物層、第1のバリア層)を基材上に形成した。 (Example 12: Production of gas barrier film 115)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
〔バリア層(第2のバリア層)の形成(塗布法)〕
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
無触媒のパーヒドロポリシラザンを20質量%含むジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NN120-20)と、アミン触媒(N,N,N’,N’-テトラメチル-1,6-ジアミノヘキサン(TMDAH))を5質量%含むパーヒドロポリシラザン20質量%のジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NAX120-20)とを、4:1の割合(質量比)で混合し、さらにジブチルエーテルと2,2,4-トリメチルペンタンとの質量比が65:35となるように混合した溶媒で、塗布液の固形分(パーヒドロポリシラザンの濃度)が2.7質量%になるように、塗布液(8-1)を調製した。このようにして調製された塗布液(8-1)に、AMD(川研ファインケミカル株式会社製、アルミニウムジイソプロピレートモノセカンダリーブチレート)をパーヒドロポリシラザンのSi元素数に対して5mol%となる量でさらに添加した後、80℃で1時間撹拌反応させた後冷却して、塗布液(8-2)を調製した。次に、この塗布液(8-2)に、上記化合物1をパーヒドロポリシラザンのSi元素数に対して5mol%となる量でさらに添加した後、80℃で1時間撹拌反応させた後冷却して、塗布液(8-3)を調製した。なお、上記で作製された塗布液(8-3)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20) and amine catalyst (N, N, N ′, N′-tetramethyl-) A solution of 20% by mass of perhydropolysilazane containing 5% by mass of 1,6-diaminohexane (TMDAH) (manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20) Mixing at a ratio (mass ratio) and further mixing so that the mass ratio of dibutyl ether and 2,2,4-trimethylpentane is 65:35, solid content of coating solution (concentration of perhydropolysilazane) A coating solution (8-1) was prepared so that the ratio was 2.7% by mass. In the coating solution (8-1) thus prepared, AMD (aluminum diisopropylate monosecondary butyrate manufactured by Kawaken Fine Chemical Co., Ltd.) is used in an amount of 5 mol% with respect to the number of Si elements in perhydropolysilazane. After further addition, the mixture was allowed to react with stirring at 80 ° C. for 1 hour and then cooled to prepare a coating solution (8-2). Next, the compound 1 is further added to the coating solution (8-2) in an amount of 5 mol% with respect to the number of Si elements of perhydropolysilazane, and then stirred at 80 ° C. for 1 hour and then cooled. Thus, a coating solution (8-3) was prepared. The ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane of the coating liquid (8-3) in which is prepared as described above [(SiH 3) :( SiH + SiH 2)] Was measured in the same manner as in Comparative Example 1, and the results are shown in Table 1.
比較例1において、塗布液(1)の代わりに、上記したようにして調製された塗布液(8-3)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム115を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(8-3)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。
In Comparative Example 1, a gas barrier film 115 was produced in the same manner as in Comparative Example 1, except that the coating liquid (8-3) prepared as described above was used instead of the coating liquid (1). . In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. Further, the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (8-3) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
(実施例13~14:ガスバリア性フィルム116~117の作製)
実施例12において、化合物1の代わりに、上記化合物3及び5を、それぞれ、使用した以外は、実施例12と同様にして、ガスバリア性フィルム116~117を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、本実施例で作製された各塗布液中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される各塗布液のSiH3比は対応するバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Examples 13 to 14: Production of gas barrier films 116 to 117)
In Example 12, gas barrier films 116 to 117 were produced in the same manner as in Example 12 except that thecompounds 3 and 5 were used instead of the compound 1, respectively. In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. Further, the ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane in each coating solution was prepared in this example [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1. When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solutions shown in Table 1 is replaced with SiH 3 ratio of the corresponding barrier layer (second barrier layer).
実施例12において、化合物1の代わりに、上記化合物3及び5を、それぞれ、使用した以外は、実施例12と同様にして、ガスバリア性フィルム116~117を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、本実施例で作製された各塗布液中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される各塗布液のSiH3比は対応するバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Examples 13 to 14: Production of gas barrier films 116 to 117)
In Example 12, gas barrier films 116 to 117 were produced in the same manner as in Example 12 except that the
(実施例15:ガスバリア性フィルム118の作製)
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
比較例1と同様にして、プラズマCVD法によって、厚みが150nmであるガスバリア性の薄膜(無機化合物層、第1のバリア層)を基材上に形成した。 (Example 15: Production of gas barrier film 118)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
比較例1と同様にして、プラズマCVD法によって、厚みが150nmであるガスバリア性の薄膜(無機化合物層、第1のバリア層)を基材上に形成した。 (Example 15: Production of gas barrier film 118)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
〔バリア層(第2のバリア層)の形成(塗布法)〕
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
無触媒のパーヒドロポリシラザンを20質量%含むジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NN120-20)と、アミン触媒(N,N,N’,N’-テトラメチル-1,6-ジアミノヘキサン(TMDAH))を5質量%含むパーヒドロポリシラザン20質量%のジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NAX120-20)とを、4:1の割合(質量比)で混合し、さらにジブチルエーテルと2,2,4-トリメチルペンタンとの質量比が65:35となるように混合した溶媒で、塗布液の固形分(パーヒドロポリシラザンの濃度)が2.7質量%になるように、塗布液(9-1)を調製した。このようにして調製された塗布液(9-1)に、アルミキレートD(川研ファインケミカル株式会社製、アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート)をパーヒドロポリシラザンのSi元素数に対して5mol%となる量でさらに添加した後、80℃で1時間撹拌反応させた後冷却して、塗布液(9-2)を調製した。次に、この塗布液(9-2)に、上記化合物1をパーヒドロポリシラザンのSi元素数に対して5mol%となる量でさらに添加した後、80℃で1時間撹拌反応させた後冷却して、塗布液(9-3)を調製した。なお、上記で作製された塗布液(9-3)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20) and amine catalyst (N, N, N ′, N′-tetramethyl-) A solution of 20% by mass of perhydropolysilazane containing 5% by mass of 1,6-diaminohexane (TMDAH) (manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20) Mixing at a ratio (mass ratio) and further mixing so that the mass ratio of dibutyl ether and 2,2,4-trimethylpentane is 65:35, solid content of coating solution (concentration of perhydropolysilazane) The coating solution (9-1) was prepared so that the ratio was 2.7% by mass. In the coating solution (9-1) thus prepared, aluminum chelate D (produced by Kawaken Fine Chemical Co., Ltd., aluminum bisethylacetoacetate / monoacetylacetonate) was added in an amount of 5 mol with respect to the number of Si elements in perhydropolysilazane. % Was added, followed by stirring and reaction at 80 ° C. for 1 hour, followed by cooling to prepare a coating solution (9-2). Next, the compound 1 is further added to the coating solution (9-2) in an amount of 5 mol% with respect to the number of Si elements of perhydropolysilazane, followed by stirring at 80 ° C. for 1 hour and cooling. Thus, a coating solution (9-3) was prepared. The ratio of SiH 3 and the total of SiH and SiH 2 measured by 29 Si-NMR of the modified polysilazane in the coating solution (9-3) produced above [(SiH 3 ) :( SiH + SiH 2 )] Was measured in the same manner as in Comparative Example 1, and the results are shown in Table 1.
比較例1において、塗布液(1)の代わりに、上記したようにして調製された塗布液(9-3)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム118を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(9-3)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。
In Comparative Example 1, a gas barrier film 118 was produced in the same manner as in Comparative Example 1 except that the coating liquid (9-3) prepared as described above was used instead of the coating liquid (1). . In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. Further, the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (9-3) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
(実施例16~17:ガスバリア性フィルム119~120の作製)
実施例15において、化合物1の代わりに、上記化合物3及び5を、それぞれ、使用した以外は、実施例15と同様にして、ガスバリア性フィルム119~120を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、本実施例で作製された各塗布液中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される各塗布液のSiH3比は対応するバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Examples 16 to 17: Production of gas barrier films 119 to 120)
In Example 15, gas barrier films 119 to 120 were produced in the same manner as in Example 15 except that thecompounds 3 and 5 were used instead of the compound 1, respectively. In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. Further, the ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane in each coating solution was prepared in this example [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1. When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solutions shown in Table 1 is replaced with SiH 3 ratio of the corresponding barrier layer (second barrier layer).
実施例15において、化合物1の代わりに、上記化合物3及び5を、それぞれ、使用した以外は、実施例15と同様にして、ガスバリア性フィルム119~120を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、本実施例で作製された各塗布液中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される各塗布液のSiH3比は対応するバリア層(第2のバリア層)のSiH3比と読み替えられる。 (Examples 16 to 17: Production of gas barrier films 119 to 120)
In Example 15, gas barrier films 119 to 120 were produced in the same manner as in Example 15 except that the
(実施例18:ガスバリア性フィルム121の作製)
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
比較例1と同様にして、プラズマCVD法によって、厚みが150nmであるガスバリア性の薄膜(無機化合物層、第1のバリア層)を基材上に形成した。 (Example 18: Production of gas barrier film 121)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
比較例1と同様にして、プラズマCVD法によって、厚みが150nmであるガスバリア性の薄膜(無機化合物層、第1のバリア層)を基材上に形成した。 (Example 18: Production of gas barrier film 121)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
〔バリア層(第2のバリア層)の形成(塗布法)〕
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
無触媒のパーヒドロポリシラザンを20質量%含むジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NN120-20)と、アミン触媒(N,N,N’,N’-テトラメチル-1,6-ジアミノヘキサン(TMDAH))を5質量%含むパーヒドロポリシラザン20質量%のジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NAX120-20)とを、4:1の割合(質量比)で混合し、さらにジブチルエーテルと2,2,4-トリメチルペンタンとの質量比が65:35となるように混合した溶媒で、塗布液の固形分(パーヒドロポリシラザンの濃度)が2.7質量%になるように、塗布液(10-1)を調製した。このようにして調製された塗布液(10-1)に、上記化合物3をパーヒドロポリシラザンのSi元素数に対して5mol%となる量でさらに添加した後、80℃で1時間撹拌反応させた後冷却して、塗布液(10-2)を調製した。次に、この塗布液(10-2)に、ALCH(川研ファインケミカル株式会社製、アルミニウムエチルアセトアセテート・ジイソプロピレート)をパーヒドロポリシラザンのSi元素数に対して5mol%となる量でさらに添加した後、80℃で1時間撹拌反応させた後冷却して、塗布液(10-3)を調製した。なお、上記で作製された塗布液(10-3)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20) and amine catalyst (N, N, N ′, N′-tetramethyl-) 20% by weight of a perhydropolysilazane containing 5% by mass of 1,6-diaminohexane (TMDAH) (manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20) Mixing at a ratio (mass ratio) and further mixing so that the mass ratio of dibutyl ether and 2,2,4-trimethylpentane is 65:35, solid content of coating solution (concentration of perhydropolysilazane) The coating solution (10-1) was prepared so that the ratio was 2.7 mass%. To the coating solution (10-1) thus prepared, the above compound 3 was further added in an amount of 5 mol% with respect to the number of Si elements of perhydropolysilazane, and then stirred at 80 ° C. for 1 hour. After cooling, a coating solution (10-2) was prepared. Next, ALCH (produced by Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate) was further added to this coating solution (10-2) in an amount of 5 mol% with respect to the number of Si elements in perhydropolysilazane. Then, the mixture was allowed to react with stirring at 80 ° C. for 1 hour and then cooled to prepare a coating solution (10-3). The ratio of SiH 3 and the total of SiH and SiH 2 measured by 29 Si-NMR of the modified polysilazane in the coating solution (10-3) produced above [(SiH 3 ) :( SiH + SiH 2 )] Was measured in the same manner as in Comparative Example 1, and the results are shown in Table 1.
比較例1において、塗布液(1)の代わりに、上記したようにして調製された塗布液(10-3)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム121を作製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(10-3)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。
In Comparative Example 1, a gas barrier film 121 was produced in the same manner as in Comparative Example 1, except that the coating liquid (10-3) prepared as described above was used instead of the coating liquid (1). . In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. Further, the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (10-3) is read as SiH 3 ratio of the barrier layer (second barrier layer).
(実施例19:ガスバリア性フィルム122の作製)
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
比較例1と同様にして、プラズマCVD法によって、厚みが150nmであるガスバリア性の薄膜(無機化合物層、第1のバリア層)を基材上に形成した。 (Example 19: Production of gas barrier film 122)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
比較例1と同様にして、プラズマCVD法によって、厚みが150nmであるガスバリア性の薄膜(無機化合物層、第1のバリア層)を基材上に形成した。 (Example 19: Production of gas barrier film 122)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
〔バリア層(第2のバリア層)の形成(塗布法)〕
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
上記化合物3およびALCH(川研ファインケミカル株式会社製、アルミニウムエチルアセトアセテート・ジイソプロピレート)を1:1(モル比)の割合で混合した。この混合物を80℃で1時間撹拌反応させた後冷却して、塗布液(11-1)を調製した。
Compound 3 and ALCH (produced by Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate / diisopropylate) were mixed at a ratio of 1: 1 (molar ratio). The mixture was stirred and reacted at 80 ° C. for 1 hour and then cooled to prepare a coating solution (11-1).
別途、無触媒のパーヒドロポリシラザンを20質量%含むジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NN120-20)と、アミン触媒(N,N,N’,N’-テトラメチル-1,6-ジアミノヘキサン(TMDAH))を5質量%含むパーヒドロポリシラザン20質量%のジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NAX120-20)とを、4:1の割合(質量比)で混合し、さらにジブチルエーテルと2,2,4-トリメチルペンタンとの質量比が65:35となるように混合した溶媒で、塗布液の固形分(パーヒドロポリシラザンの濃度)が2.7質量%になるように、塗布液(11-2)を調製した。
Separately, a dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NN120-20) and an amine catalyst (N, N, N ′, N′-tetra) 20% by mass of a perhydropolysilazane containing 5% by mass of methyl-1,6-diaminohexane (TMDAH) (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NAX120-20) In a solvent mixed at a ratio (mass ratio) of 1 and further so that the mass ratio of dibutyl ether and 2,2,4-trimethylpentane is 65:35, the solid content of the coating solution (perhydropolysilazane The coating solution (11-2) was prepared so that the concentration was 2.7% by mass.
このようにして調製された塗布液(11-2)に、上記塗布液を、上記化合物3及びALCHをそれぞれをパーヒドロポリシラザンのSi元素数に対して5mol%となる量でさらに添加した後、80℃で1時間撹拌反応させた後冷却して、塗布液(11-3)を調製した。なお、上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。また、上記で作製された塗布液(11-3)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。
To the coating solution (11-2) thus prepared, the above-described coating solution was further added with each of the compound 3 and ALCH in an amount of 5 mol% based on the number of Si elements in perhydropolysilazane. After stirring and reacting at 80 ° C. for 1 hour, the mixture was cooled to prepare a coating solution (11-3). In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. Further, the ratio of SiH 3 and the total of SiH and SiH 2 measured by 29 Si-NMR of the modified polysilazane in the coating liquid (11-3) produced above [(SiH 3 ) :( SiH + SiH 2 )] Was measured in the same manner as in Comparative Example 1, and the results are shown in Table 1.
比較例1において、塗布液(1)の代わりに、上記したようにして調製された塗布液(11-3)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム122を作製した。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(11-3)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。
In Comparative Example 1, a gas barrier film 122 was produced in the same manner as in Comparative Example 1 except that the coating liquid (11-3) prepared as described above was used instead of the coating liquid (1). . When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (11-3) is read as SiH 3 ratio of the barrier layer (second barrier layer).
(実施例20:ガスバリア性フィルム123の作製)
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
比較例1と同様にして、プラズマCVD法によって、厚みが150nmであるガスバリア性の薄膜(無機化合物層、第1のバリア層)を基材上に形成した。 (Example 20: Production of gas barrier film 123)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
〔無機化合物層(第1のバリア層)の形成(プラズマCVD法)〕
比較例1と同様にして、プラズマCVD法によって、厚みが150nmであるガスバリア性の薄膜(無機化合物層、第1のバリア層)を基材上に形成した。 (Example 20: Production of gas barrier film 123)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
〔バリア層(第2のバリア層)の形成(塗布法)〕
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
(ポリシラザン含有塗布液の調製および成膜)
ポリシラザン含有塗布液の調製および成膜は、通常大気環境下(具体的には、25℃60%RHの環境下)で行った。 [Formation of barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
Preparation and film formation of the polysilazane-containing coating solution were usually performed in an atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).
無触媒のパーヒドロポリシラザンを20質量%含むジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NN120-20)と、アミン触媒(N,N,N’,N’-テトラメチル-1,6-ジアミノヘキサン(TMDAH))を5質量%含むパーヒドロポリシラザン20質量%のジブチルエーテル溶液(AZエレクトロニックマテリアルズ株式会社製、アクアミカ(登録商標)NAX120-20)とを、4:1の割合(質量比)で混合し、さらにジブチルエーテルと2,2,4-トリメチルペンタンとの質量比が65:35となるように混合した溶媒で、塗布液の固形分(パーヒドロポリシラザンの濃度)が2.7質量%になるように、塗布液(12-1)を調製した。このようにして調製された塗布液(12-1)に、ALCH(川研ファインケミカル株式会社製、アルミニウムエチルアセトアセテート・ジイソプロピレート)及び上記化合物3をそれぞれをパーヒドロポリシラザンのSi元素数に対して5mol%となる量でさらに添加した後、80℃で1時間撹拌反応させた後冷却して、塗布液(12-2)を調製した。なお、上記で作製された塗布液(12-2)中の変性ポリシラザンの29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]を、比較例1と同様にして測定し、その結果を表1に示す。
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20) and amine catalyst (N, N, N ′, N′-tetramethyl-) 20% by weight of a perhydropolysilazane containing 5% by mass of 1,6-diaminohexane (TMDAH) (manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20) Mixing at a ratio (mass ratio) and further mixing so that the mass ratio of dibutyl ether and 2,2,4-trimethylpentane is 65:35, solid content of coating solution (concentration of perhydropolysilazane) The coating solution (12-1) was prepared so that the content of 2.7 was 2.7% by mass. The coating liquid (12-1) thus prepared was mixed with ALCH (aluminum ethyl acetoacetate diisopropylate) manufactured by Kawaken Fine Chemical Co., Ltd. and the above compound 3 with respect to the number of Si elements in perhydropolysilazane. After further adding in an amount of 5 mol%, the mixture was reacted with stirring at 80 ° C. for 1 hour and then cooled to prepare a coating solution (12-2). The ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane of the coating solution (12-2) in which is prepared as described above [(SiH 3) :( SiH + SiH 2)] Was measured in the same manner as in Comparative Example 1, and the results are shown in Table 1.
比較例1において、塗布液(1)の代わりに、上記したようにして調製された塗布液(12-2)を使用した以外は、比較例1と同様にして、ガスバリア性フィルム123を作製した。上記反応は、水蒸気濃度及び酸素濃度がそれぞれ10体積ppm以下の雰囲気中で行った。なお、得られたバリア層(第2のバリア層)について、SiH3比を測定したところ、ポリシラザン含有塗布液のSiH3比と同様の値を示した。このため、下記表1に示される塗布液(12-2)のSiH3比はバリア層(第2のバリア層)のSiH3比と読み替えられる。
In Comparative Example 1, a gas barrier film 123 was produced in the same manner as in Comparative Example 1, except that the coating liquid (12-2) prepared as described above was used instead of the coating liquid (1). . The above reaction was performed in an atmosphere having a water vapor concentration and an oxygen concentration of 10 ppm by volume or less. When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (12-2) is read as SiH 3 ratio of the barrier layer (second barrier layer).
上記比較例及び実施例で作製したガスバリア性フィルムについて、下記方法に従って水蒸気バリア性の評価を行った。
The water vapor barrier properties of the gas barrier films produced in the comparative examples and examples were evaluated according to the following methods.
《水蒸気バリア性(水蒸気透過率WVTR)の評価》
上記で作製されたたガスバリア性フィルムについて、85℃、85%RHの高温高湿下に500hr曝したサンプル(劣化試験後サンプル)を各々準備し、下記の水蒸気バリア性について、劣化試験前後の評価を行い、保持率を求めた。保持率の指標としては70%以上あれば許容とし、70%未満は不適合と判断した。劣化試験前後の保持率(%)ついて結果を表1に示した。 << Evaluation of water vapor barrier property (water vapor transmission rate WVTR) >>
About the gas barrier film produced above, each sample (sample after deterioration test) exposed to high temperature and high humidity of 85 ° C. and 85% RH for 500 hours was prepared, and the following water vapor barrier properties were evaluated before and after the deterioration test. And the retention rate was determined. As an index of retention rate, 70% or more was considered acceptable, and less than 70% was judged as nonconforming. The results of the retention rate (%) before and after the deterioration test are shown in Table 1.
上記で作製されたたガスバリア性フィルムについて、85℃、85%RHの高温高湿下に500hr曝したサンプル(劣化試験後サンプル)を各々準備し、下記の水蒸気バリア性について、劣化試験前後の評価を行い、保持率を求めた。保持率の指標としては70%以上あれば許容とし、70%未満は不適合と判断した。劣化試験前後の保持率(%)ついて結果を表1に示した。 << Evaluation of water vapor barrier property (water vapor transmission rate WVTR) >>
About the gas barrier film produced above, each sample (sample after deterioration test) exposed to high temperature and high humidity of 85 ° C. and 85% RH for 500 hours was prepared, and the following water vapor barrier properties were evaluated before and after the deterioration test. And the retention rate was determined. As an index of retention rate, 70% or more was considered acceptable, and less than 70% was judged as nonconforming. The results of the retention rate (%) before and after the deterioration test are shown in Table 1.
(金属カルシウム製膜装置)
蒸着装置:日本電子株式会社製、真空蒸着装置JEE-400
恒温恒湿度オーブン:Yamato Humidic ChamberIG47M
(原材料)
水分と反応して腐食する金属:カルシウム(粒状)
水蒸気不透過性の金属:アルミニウム(φ3~5mm、粒状)
(水蒸気バリア性評価試料の作製)
真空蒸着装置(日本電子製真空蒸着装置 JEE-400)を用い、作製したガスバリアフィルムの第2のバリア層表面に、マスクを通して12mm×12mmのサイズで金属カルシウムを蒸着させた。この際、蒸着膜厚は80nmとなるようにした。 (Metal calcium film forming equipment)
Vapor deposition device: JEOL Ltd., vacuum vapor deposition device JEE-400
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation sample)
Using a vacuum vapor deposition device (vacuum vapor deposition device JEE-400 manufactured by JEOL Ltd.), calcium metal was deposited on the surface of the second barrier layer of the produced gas barrier film in a size of 12 mm × 12 mm through a mask. At this time, the deposited film thickness was set to 80 nm.
蒸着装置:日本電子株式会社製、真空蒸着装置JEE-400
恒温恒湿度オーブン:Yamato Humidic ChamberIG47M
(原材料)
水分と反応して腐食する金属:カルシウム(粒状)
水蒸気不透過性の金属:アルミニウム(φ3~5mm、粒状)
(水蒸気バリア性評価試料の作製)
真空蒸着装置(日本電子製真空蒸着装置 JEE-400)を用い、作製したガスバリアフィルムの第2のバリア層表面に、マスクを通して12mm×12mmのサイズで金属カルシウムを蒸着させた。この際、蒸着膜厚は80nmとなるようにした。 (Metal calcium film forming equipment)
Vapor deposition device: JEOL Ltd., vacuum vapor deposition device JEE-400
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation sample)
Using a vacuum vapor deposition device (vacuum vapor deposition device JEE-400 manufactured by JEOL Ltd.), calcium metal was deposited on the surface of the second barrier layer of the produced gas barrier film in a size of 12 mm × 12 mm through a mask. At this time, the deposited film thickness was set to 80 nm.
その後、真空状態のままマスクを取り去り、シート片側全面にアルミニウムを蒸着させて仮封止をした。次いで、真空状態を解除し、速やかに乾燥窒素ガス雰囲気下に移して、アルミニウム蒸着面に封止用紫外線硬化樹脂(ナガセケムテックス株式会社製)を介して厚さ0.2mmの石英ガラスを張り合わせ、紫外線を照射して樹脂を硬化接着させて本封止することで、水蒸気バリア性評価試料を作製した。
Thereafter, the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet and temporarily sealed. Next, the vacuum state is released, and it is immediately transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum vapor-deposited surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX Corporation). The water vapor barrier property evaluation sample was produced by irradiating ultraviolet rays to cure and adhere the resin to perform main sealing.
得られた試料を85℃、85%RHの高温高湿下で保存し、保存時間に対して金属カルシウムが腐食して行く様子を観察した。観察は12mm×12mmの金属カルシウム蒸着面積に対する金属カルシウムが腐食した面積が50%になる時間を観察結果から直線で内挿して求め、劣化したカルシウムの量から水蒸気透過率WVTR(g/m2/day)を求めた。
The obtained sample was stored at a high temperature and high humidity of 85 ° C. and 85% RH, and the state in which the metal calcium was corroded with respect to the storage time was observed. Observation was obtained by linearly interpolating the time when the area where metal calcium was corroded with respect to the metal calcium deposition area of 12 mm × 12 mm to 50% from the observation results, and the water vapor transmission rate WVTR (g / m 2 / g from the amount of deteriorated calcium. day).
上記表1から明らかなように、本発明の実施例により作製したガスバリア性フィルムは、高温高湿下に長時間さらされた後であっても組成変化に伴うガスバリア性の低下がほとんど起きないことが分かる。
As is apparent from Table 1 above, the gas barrier film produced according to the examples of the present invention hardly deteriorates in gas barrier property due to composition change even after being exposed to high temperature and high humidity for a long time. I understand.
《有機薄膜電子デバイスの作製》
上記比較例及び実施例で作製されたたガスバリア性フィルムを封止フィルムとして用いて、有機薄膜電子デバイスである有機EL素子を作製した。 << Production of organic thin film electronic devices >>
Using the gas barrier films produced in the comparative examples and examples as sealing films, organic EL elements that are organic thin film electronic devices were produced.
上記比較例及び実施例で作製されたたガスバリア性フィルムを封止フィルムとして用いて、有機薄膜電子デバイスである有機EL素子を作製した。 << Production of organic thin film electronic devices >>
Using the gas barrier films produced in the comparative examples and examples as sealing films, organic EL elements that are organic thin film electronic devices were produced.
〔有機EL素子の作製〕
(第1電極層の形成)
無アルカリガラス上にスパッタ法により製膜した厚さ150nmのITO(インジウムチンオキシド)を、フォトリソグラフィー法によりパターニングを行い、第1電極層を形成した。なお、パターンは発光面積が50mm平方になるようなパターンとした。 [Production of organic EL elements]
(Formation of first electrode layer)
A 150-nm-thick ITO (indium tin oxide) film formed by sputtering on an alkali-free glass was patterned by photolithography to form a first electrode layer. The pattern was such that the light emission area was 50 mm square.
(第1電極層の形成)
無アルカリガラス上にスパッタ法により製膜した厚さ150nmのITO(インジウムチンオキシド)を、フォトリソグラフィー法によりパターニングを行い、第1電極層を形成した。なお、パターンは発光面積が50mm平方になるようなパターンとした。 [Production of organic EL elements]
(Formation of first electrode layer)
A 150-nm-thick ITO (indium tin oxide) film formed by sputtering on an alkali-free glass was patterned by photolithography to form a first electrode layer. The pattern was such that the light emission area was 50 mm square.
(正孔輸送層の形成)
第1電極層が形成された各ガスバリア性フィルムの第1電極層の上に、以下に示す正孔輸送層形成用塗布液を、25℃、相対湿度50%RHの環境下で、押出し塗布機で塗布した後、下記の条件で乾燥および加熱処理を行い、正孔輸送層を形成した。正孔輸送層形成用塗布液は乾燥後の厚みが50nmになるように塗布した。 (Formation of hole transport layer)
On the first electrode layer of each gas barrier film on which the first electrode layer is formed, a coating liquid for forming a hole transport layer shown below is extrusion-coated in an environment of 25 ° C. and a relative humidity of 50% RH. After coating, the substrate was dried and heated under the following conditions to form a hole transport layer. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.
第1電極層が形成された各ガスバリア性フィルムの第1電極層の上に、以下に示す正孔輸送層形成用塗布液を、25℃、相対湿度50%RHの環境下で、押出し塗布機で塗布した後、下記の条件で乾燥および加熱処理を行い、正孔輸送層を形成した。正孔輸送層形成用塗布液は乾燥後の厚みが50nmになるように塗布した。 (Formation of hole transport layer)
On the first electrode layer of each gas barrier film on which the first electrode layer is formed, a coating liquid for forming a hole transport layer shown below is extrusion-coated in an environment of 25 ° C. and a relative humidity of 50% RH. After coating, the substrate was dried and heated under the following conditions to form a hole transport layer. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.
正孔輸送層形成用塗布液を塗布する前に、ガスバリア性フィルムの洗浄表面改質処理を、波長184.9nmの低圧水銀ランプを使用し、照射強度15mW/cm2、距離10mmで実施した。帯電除去処理は、微弱X線による除電器を使用し行った。
Before applying the coating solution for forming the hole transport layer, the gas barrier film was subjected to cleaning surface modification using a low-pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm 2 and a distance of 10 mm. The charge removal treatment was performed using a static eliminator with weak X-rays.
〈正孔輸送層形成用塗布液の準備〉
ポリエチレンジオキシチオフェン・ポリスチレンスルホネート(PEDOT/PSS、Bayer社製 Bytron P AI 4083)を純水で65%、メタノール5%で希釈した溶液を正孔輸送層形成用塗布液として準備した。 <Preparation of hole transport layer forming coating solution>
A solution prepared by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) with pure water at 65% and methanol at 5% was prepared as a coating solution for forming a hole transport layer.
ポリエチレンジオキシチオフェン・ポリスチレンスルホネート(PEDOT/PSS、Bayer社製 Bytron P AI 4083)を純水で65%、メタノール5%で希釈した溶液を正孔輸送層形成用塗布液として準備した。 <Preparation of hole transport layer forming coating solution>
A solution prepared by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) with pure water at 65% and methanol at 5% was prepared as a coating solution for forming a hole transport layer.
〈乾燥および加熱処理条件〉
正孔輸送層形成用塗布液を塗布した後、成膜面に向け高さ100mm、吐出風速1m/s、幅手の風速分布5%、温度100℃で溶媒を除去した後、引き続き、加熱処理装置を用い温度150℃で裏面伝熱方式の熱処理を行い、正孔輸送層を形成した。 <Drying and heat treatment conditions>
After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment. The back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.
正孔輸送層形成用塗布液を塗布した後、成膜面に向け高さ100mm、吐出風速1m/s、幅手の風速分布5%、温度100℃で溶媒を除去した後、引き続き、加熱処理装置を用い温度150℃で裏面伝熱方式の熱処理を行い、正孔輸送層を形成した。 <Drying and heat treatment conditions>
After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment. The back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.
(発光層の形成)
上記で形成した正孔輸送層上に、以下に示す白色発光層形成用塗布液を、下記の条件により押出し塗布機で塗布した後、下記の条件で乾燥および加熱処理を行い、発光層を形成した。白色発光層形成用塗布液は乾燥後の厚みが40nmになるように塗布した。 (Formation of light emitting layer)
On the hole transport layer formed above, the following coating solution for forming a white light emitting layer is applied by an extrusion coater under the following conditions, followed by drying and heat treatment under the following conditions to form a light emitting layer. did. The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.
上記で形成した正孔輸送層上に、以下に示す白色発光層形成用塗布液を、下記の条件により押出し塗布機で塗布した後、下記の条件で乾燥および加熱処理を行い、発光層を形成した。白色発光層形成用塗布液は乾燥後の厚みが40nmになるように塗布した。 (Formation of light emitting layer)
On the hole transport layer formed above, the following coating solution for forming a white light emitting layer is applied by an extrusion coater under the following conditions, followed by drying and heat treatment under the following conditions to form a light emitting layer. did. The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.
〈白色発光層形成用塗布液〉
ホスト材として下記化学式H-Aで表される化合物1.0gと、ドーパント材として下記化学式D-Aで表される化合物を100mg、ドーパント材として下記化学式D-Bで表される化合物を0.2mg、ドーパント材として下記化学式D-Cで表される化合物を0.2mg、100gのトルエンに溶解し白色発光層形成用塗布液として準備した。 <White luminescent layer forming coating solution>
As a host material, 1.0 g of a compound represented by the following chemical formula HA, 100 mg of a compound represented by the following chemical formula DA as a dopant material, and 0.1 mg of a compound represented by the following chemical formula DB as a dopant material. 2 mg of a compound represented by the following chemical formula DC as a dopant material was dissolved in 0.2 mg and 100 g of toluene to prepare a white light emitting layer forming coating solution.
ホスト材として下記化学式H-Aで表される化合物1.0gと、ドーパント材として下記化学式D-Aで表される化合物を100mg、ドーパント材として下記化学式D-Bで表される化合物を0.2mg、ドーパント材として下記化学式D-Cで表される化合物を0.2mg、100gのトルエンに溶解し白色発光層形成用塗布液として準備した。 <White luminescent layer forming coating solution>
As a host material, 1.0 g of a compound represented by the following chemical formula HA, 100 mg of a compound represented by the following chemical formula DA as a dopant material, and 0.1 mg of a compound represented by the following chemical formula DB as a dopant material. 2 mg of a compound represented by the following chemical formula DC as a dopant material was dissolved in 0.2 mg and 100 g of toluene to prepare a white light emitting layer forming coating solution.
〈塗布条件〉
塗布工程を窒素ガス濃度99%以上の雰囲気で、塗布温度を25℃とし、塗布速度1m
/minで行った。 <Application conditions>
The coating process is performed in an atmosphere with a nitrogen gas concentration of 99% or more, the coating temperature is 25 ° C., and the coating speed is 1 m.
/ Min.
塗布工程を窒素ガス濃度99%以上の雰囲気で、塗布温度を25℃とし、塗布速度1m
/minで行った。 <Application conditions>
The coating process is performed in an atmosphere with a nitrogen gas concentration of 99% or more, the coating temperature is 25 ° C., and the coating speed is 1 m.
/ Min.
〈乾燥および加熱処理条件〉
白色発光層形成用塗布液を塗布した後、成膜面に向け高さ100mm、吐出風速1m/s、幅手の風速分布5%、温度60℃で溶媒を除去した後、引き続き、温度130℃で加熱処理を行い、発光層を形成した。 <Drying and heat treatment conditions>
After applying the white light emitting layer forming coating solution, the solvent was removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., and then a temperature of 130 ° C. A heat treatment was performed to form a light emitting layer.
白色発光層形成用塗布液を塗布した後、成膜面に向け高さ100mm、吐出風速1m/s、幅手の風速分布5%、温度60℃で溶媒を除去した後、引き続き、温度130℃で加熱処理を行い、発光層を形成した。 <Drying and heat treatment conditions>
After applying the white light emitting layer forming coating solution, the solvent was removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., and then a temperature of 130 ° C. A heat treatment was performed to form a light emitting layer.
(電子輸送層の形成)
上記で形成した発光層の上に、以下に示す電子輸送層形成用塗布液を下記の条件により押出し塗布機で塗布した後、下記の条件で乾燥および加熱処理し、電子輸送層を形成した。電子輸送層形成用塗布液は、乾燥後の厚みが30nmになるように塗布した。 (Formation of electron transport layer)
On the light emitting layer formed above, the following electron transport layer forming coating solution was applied by an extrusion coater under the following conditions, and then dried and heat-treated under the following conditions to form an electron transport layer. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.
上記で形成した発光層の上に、以下に示す電子輸送層形成用塗布液を下記の条件により押出し塗布機で塗布した後、下記の条件で乾燥および加熱処理し、電子輸送層を形成した。電子輸送層形成用塗布液は、乾燥後の厚みが30nmになるように塗布した。 (Formation of electron transport layer)
On the light emitting layer formed above, the following electron transport layer forming coating solution was applied by an extrusion coater under the following conditions, and then dried and heat-treated under the following conditions to form an electron transport layer. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.
〈塗布条件〉
塗布工程は窒素ガス濃度99%以上の雰囲気で、電子輸送層形成用塗布液の塗布温度を25℃とし、塗布速度1m/minで行った。 <Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.
塗布工程は窒素ガス濃度99%以上の雰囲気で、電子輸送層形成用塗布液の塗布温度を25℃とし、塗布速度1m/minで行った。 <Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.
〈電子輸送層形成用塗布液〉
電子輸送層は下記化学式E-Aで表される化合物を2,2,3,3-テトラフルオロ-1-プロパノール中に溶解し0.5質量%溶液とし電子輸送層形成用塗布液とした。 <Coating liquid for electron transport layer formation>
The electron transport layer was prepared by dissolving a compound represented by the following chemical formula EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating solution for forming an electron transport layer.
電子輸送層は下記化学式E-Aで表される化合物を2,2,3,3-テトラフルオロ-1-プロパノール中に溶解し0.5質量%溶液とし電子輸送層形成用塗布液とした。 <Coating liquid for electron transport layer formation>
The electron transport layer was prepared by dissolving a compound represented by the following chemical formula EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating solution for forming an electron transport layer.
〈乾燥および加熱処理条件〉
電子輸送層形成用塗布液を塗布した後、成膜面に向け高さ100mm、吐出風速1m/s、幅手の風速分布5%、温度60℃で溶媒を除去した後、引き続き、加熱処理部で、温度200℃で加熱処理を行い、電子輸送層を形成した。 <Drying and heat treatment conditions>
After applying the electron transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C. Then, heat treatment was performed at a temperature of 200 ° C. to form an electron transport layer.
電子輸送層形成用塗布液を塗布した後、成膜面に向け高さ100mm、吐出風速1m/s、幅手の風速分布5%、温度60℃で溶媒を除去した後、引き続き、加熱処理部で、温度200℃で加熱処理を行い、電子輸送層を形成した。 <Drying and heat treatment conditions>
After applying the electron transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C. Then, heat treatment was performed at a temperature of 200 ° C. to form an electron transport layer.
(電子注入層の形成)
上記で形成した電子輸送層上に、電子注入層を形成した。まず、基板を減圧チャンバに投入し、5×10-4Paまで減圧した。あらかじめ、真空チャンバにタンタル製蒸着ボートに用意しておいたフッ化セシウムを加熱し、厚さ3nmの電子注入層を形成した。 (Formation of electron injection layer)
An electron injection layer was formed on the electron transport layer formed above. First, the substrate was put into a decompression chamber and decompressed to 5 × 10 −4 Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.
上記で形成した電子輸送層上に、電子注入層を形成した。まず、基板を減圧チャンバに投入し、5×10-4Paまで減圧した。あらかじめ、真空チャンバにタンタル製蒸着ボートに用意しておいたフッ化セシウムを加熱し、厚さ3nmの電子注入層を形成した。 (Formation of electron injection layer)
An electron injection layer was formed on the electron transport layer formed above. First, the substrate was put into a decompression chamber and decompressed to 5 × 10 −4 Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.
(第2電極の形成)
上記で形成した電子注入層の上であって、第1電極22の取り出し電極になる部分を除く部分に、5×10-4Paの真空下で、第2電極形成材料としてアルミニウムを使用し、取り出し電極を有するように蒸着法にて、発光面積が50mm平方になるようにマスクパターン成膜し、厚さ100nmの第2電極を積層した。 (Formation of second electrode)
Aluminum is used as the second electrode forming material on the electron injection layer formed as described above, except for the portion that becomes the extraction electrode of thefirst electrode 22 under a vacuum of 5 × 10 −4 Pa, A mask pattern was formed by vapor deposition so as to have an extraction electrode so that the light emission area was 50 mm square, and a second electrode having a thickness of 100 nm was laminated.
上記で形成した電子注入層の上であって、第1電極22の取り出し電極になる部分を除く部分に、5×10-4Paの真空下で、第2電極形成材料としてアルミニウムを使用し、取り出し電極を有するように蒸着法にて、発光面積が50mm平方になるようにマスクパターン成膜し、厚さ100nmの第2電極を積層した。 (Formation of second electrode)
Aluminum is used as the second electrode forming material on the electron injection layer formed as described above, except for the portion that becomes the extraction electrode of the
(封止)
準備したガスバリア性フィルムを所定のサイズにトリミングし、バリア層面側に熱硬化性接着剤を、ディスペンサを使用して厚み20μmで均一に塗布し、接着剤層を形成した。このとき、熱硬化性接着剤としては、ビスフェノールAジグリシジルエーテル(DGEBA)、ジシアンジアミド(DICY)及びエポキシアダクト系硬化促進剤を含むエポキシ系接着剤を使用した。 (Sealing)
The prepared gas barrier film was trimmed to a predetermined size, and a thermosetting adhesive was uniformly applied to the barrier layer surface side with a thickness of 20 μm using a dispenser to form an adhesive layer. At this time, an epoxy adhesive containing bisphenol A diglycidyl ether (DGEBA), dicyandiamide (DICY) and an epoxy adduct curing accelerator was used as the thermosetting adhesive.
準備したガスバリア性フィルムを所定のサイズにトリミングし、バリア層面側に熱硬化性接着剤を、ディスペンサを使用して厚み20μmで均一に塗布し、接着剤層を形成した。このとき、熱硬化性接着剤としては、ビスフェノールAジグリシジルエーテル(DGEBA)、ジシアンジアミド(DICY)及びエポキシアダクト系硬化促進剤を含むエポキシ系接着剤を使用した。 (Sealing)
The prepared gas barrier film was trimmed to a predetermined size, and a thermosetting adhesive was uniformly applied to the barrier layer surface side with a thickness of 20 μm using a dispenser to form an adhesive layer. At this time, an epoxy adhesive containing bisphenol A diglycidyl ether (DGEBA), dicyandiamide (DICY) and an epoxy adduct curing accelerator was used as the thermosetting adhesive.
第1の電極上にパターニングされた取り出し電極(ここでは第1の電極、および第2の電極の取出し電極を含む)が露出する様に、上記ガスバリア性フィルムを密着・配置して、真空ラミネーターを用い密着封止した。封止した後、110℃で15分間後硬化処理を行い、有機EL素子を作製した。
The gas barrier film is closely attached and arranged so that the extraction electrode (including the extraction electrodes of the first electrode and the second electrode) patterned on the first electrode is exposed, and the vacuum laminator is Used tightly sealed. After sealing, post-curing treatment was performed at 110 ° C. for 15 minutes to produce an organic EL element.
《有機EL素子の評価》
上記作製した有機EL素子について、下記の方法に従って、耐久性の評価を行った。 << Evaluation of organic EL elements >>
About the produced organic EL element, durability was evaluated in accordance with the following method.
上記作製した有機EL素子について、下記の方法に従って、耐久性の評価を行った。 << Evaluation of organic EL elements >>
About the produced organic EL element, durability was evaluated in accordance with the following method.
〔耐久性の評価〕
(加速劣化処理)
上記作製した各有機EL素子を、85℃、85%RHの環境下で500時間の加速劣化処理を施した後、下記のダークスポットに関する評価を行った。 [Evaluation of durability]
(Accelerated deterioration processing)
Each of the produced organic EL devices was subjected to an accelerated deterioration treatment for 500 hours in an environment of 85 ° C. and 85% RH, and then the following dark spots were evaluated.
(加速劣化処理)
上記作製した各有機EL素子を、85℃、85%RHの環境下で500時間の加速劣化処理を施した後、下記のダークスポットに関する評価を行った。 [Evaluation of durability]
(Accelerated deterioration processing)
Each of the produced organic EL devices was subjected to an accelerated deterioration treatment for 500 hours in an environment of 85 ° C. and 85% RH, and then the following dark spots were evaluated.
(ダークスポット(DS、黒点)の評価)
加速劣化処理を施した有機EL素子に対し、1mA/cm2の電流を印加し、100倍のマイクロスコープ(株式会社モリテックス製MS-804、レンズMP-ZE25-200)でパネルの一部分を拡大し、撮影を行った。撮影画像を20mm四方スケール相当に切り抜き、ダークスポットの発生面積比率を求め、下記の基準に従って耐久性を評価した。評価ランクが、△であれば実用的な特性、○であればより実用的な特性、◎であれば全く問題のない好ましい特性であると判定した。 (Evaluation of dark spots (DS, black spots))
A current of 1 mA / cm 2 is applied to the organic EL element that has been subjected to accelerated deterioration treatment, and a part of the panel is enlarged with a 100 × microscope (MORITEX MS-804, lens MP-ZE25-200). , Took a picture. The photographed image was cut out in a 20 mm square scale, the dark spot generation area ratio was determined, and the durability was evaluated according to the following criteria. When the evaluation rank was Δ, it was judged as a practical characteristic, when it was ○, a more practical characteristic, and when it was ◎, it was judged as a preferable characteristic having no problem at all.
加速劣化処理を施した有機EL素子に対し、1mA/cm2の電流を印加し、100倍のマイクロスコープ(株式会社モリテックス製MS-804、レンズMP-ZE25-200)でパネルの一部分を拡大し、撮影を行った。撮影画像を20mm四方スケール相当に切り抜き、ダークスポットの発生面積比率を求め、下記の基準に従って耐久性を評価した。評価ランクが、△であれば実用的な特性、○であればより実用的な特性、◎であれば全く問題のない好ましい特性であると判定した。 (Evaluation of dark spots (DS, black spots))
A current of 1 mA / cm 2 is applied to the organic EL element that has been subjected to accelerated deterioration treatment, and a part of the panel is enlarged with a 100 × microscope (MORITEX MS-804, lens MP-ZE25-200). , Took a picture. The photographed image was cut out in a 20 mm square scale, the dark spot generation area ratio was determined, and the durability was evaluated according to the following criteria. When the evaluation rank was Δ, it was judged as a practical characteristic, when it was ○, a more practical characteristic, and when it was ◎, it was judged as a preferable characteristic having no problem at all.
ダークスポットの評価結果を、上記表1に示す。
The evaluation results of dark spots are shown in Table 1 above.
上記表1から明らかなように、本発明の実施例により作製したガスバリア性フィルムは、有機EL素子の封止フィルムとして用いることでダークスポットの発生を低減させる効果があり、非常に高いガスバリア性を有していることが分かる。
As apparent from Table 1 above, the gas barrier film produced according to the example of the present invention has the effect of reducing the occurrence of dark spots by using it as a sealing film for organic EL elements, and has a very high gas barrier property. You can see that
さらに、本出願は、2014年2月7日に出願された日本特許出願番号2014-022790号に基づいており、その開示内容は、参照され、全体として、組み入れられている。
Furthermore, this application is based on Japanese Patent Application No. 2014-022790 filed on February 7, 2014, the disclosure content of which is incorporated by reference as a whole.
Claims (14)
- 29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]が1:10~30である変性ポリシラザン。 29 the ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by Si-NMR [(SiH 3) :( SiH + SiH 2)] is 1: 10 to 30 in which the modified polysilazane.
- 前記29Si-NMRで測定されるSiH3とSiH及びSiH2の合計との比[(SiH3):(SiH+SiH2)]が1:12~28である、請求項1に記載の変性ポリシラザン。 The modified polysilazane according to claim 1, wherein the ratio [(SiH 3 ) :( SiH + SiH 2 )] of SiH 3 measured by 29 Si-NMR and the sum of SiH and SiH 2 is from 1:12 to 28.
- 前記変性ポリシラザンは、(a)ケイ素原子、水素原子および窒素原子を含むポリシラザンを、(b)低分子シラザンおよび低分子シロキサンの少なくとも一方、ならびに(c)金属アルコキシド化合物および金属キレート化合物の少なくとも一方と反応させることによって得られる、請求項1または2に記載の変性ポリシラザン。 The modified polysilazane comprises (a) a polysilazane containing a silicon atom, a hydrogen atom and a nitrogen atom, (b) at least one of a low molecular silazane and a low molecular siloxane, and (c) at least one of a metal alkoxide compound and a metal chelate compound. The modified polysilazane according to claim 1 or 2 obtained by reacting.
- 前記変性ポリシラザンは、(a)ケイ素原子、水素原子および窒素原子を含むポリシラザンを、(c)金属アルコキシド化合物および金属キレート化合物の少なくとも一方と反応させた後、(b)低分子シラザンおよび低分子シロキサンの少なくとも一方と反応させることによって得られる、請求項3に記載の変性ポリシラザン。 The modified polysilazane is obtained by reacting (a) a polysilazane containing a silicon atom, a hydrogen atom and a nitrogen atom with at least one of (c) a metal alkoxide compound and a metal chelate compound, and (b) a low molecular silazane and a low molecular siloxane. The modified polysilazane according to claim 3, which is obtained by reacting with at least one of the following.
- 前記金属アルコキシド化合物がアルミニウムアルコキシドである、または前記金属キレート化合物がβ-ジケトンを配位子として有する金属キレート化合物である、請求項3または4に記載の変性ポリシラザン。 The modified polysilazane according to claim 3 or 4, wherein the metal alkoxide compound is an aluminum alkoxide, or the metal chelate compound is a metal chelate compound having a β-diketone as a ligand.
- (b)前記低分子シラザンおよび低分子シロキサンの少なくとも一方、ならびに(c)前記金属アルコキシド化合物および金属キレート化合物の少なくとも一方の合計仕込み量が、(a)前記ポリシラザン中のケイ素元素数(Si)に対して、5モル%を超えて50モル%以下である、請求項3~5のいずれか1項に記載の変性ポリシラザン。 (B) The total charge of at least one of the low molecular silazane and low molecular siloxane, and (c) at least one of the metal alkoxide compound and metal chelate compound is (a) the number of silicon elements (Si) in the polysilazane. The modified polysilazane according to any one of claims 3 to 5, which is more than 5 mol% and not more than 50 mol%.
- 前記低分子シラザンが、下記一般式(I):
で表される環状低分子シラザン(I)、下記一般式(II):
で表される鎖状低分子シラザン(II)、もしくは下記一般式(III):
で表される鎖状低分子シラザン(III)である、または
前記低分子シロキサンが、下記一般式(IV):
で表される環状低分子シロキサン(IV)、もしくは下記一般式(V):
で表される環状低分子シロキサン(V)である、請求項3~6のいずれか1項に記載の変性ポリシラザン。 The low-molecular silazane is represented by the following general formula (I):
A cyclic low-molecular silazane (I) represented by the following general formula (II):
A linear low molecular weight silazane (II) represented by the following general formula (III):
Or a low molecular weight siloxane represented by the following general formula (IV):
Cyclic low molecular siloxane (IV) represented by the following general formula (V):
The modified polysilazane according to any one of claims 3 to 6, which is a cyclic low-molecular siloxane (V) represented by: - 請求項1~7のいずれか1項に記載の変性ポリシラザンを含む塗布液。 A coating solution containing the modified polysilazane according to any one of claims 1 to 7.
- ガスバリア層用の塗布液である、請求項8に記載の塗布液。 The coating solution according to claim 8, which is a coating solution for a gas barrier layer.
- 基材と、請求項8または9に記載の塗布液を用いて形成されるバリア層と、を含む、ガスバリア性フィルム。 A gas barrier film comprising a substrate and a barrier layer formed using the coating liquid according to claim 8 or 9.
- 前記基材および前記バリア層の間に、無機化合物を含む無機化合物層をさらに有する、請求項10に記載のガスバリア性フィルム。 The gas barrier film according to claim 10, further comprising an inorganic compound layer containing an inorganic compound between the substrate and the barrier layer.
- 前記バリア層は、
(i)請求項7に記載の塗布液を前記無機化合物層上に塗布、乾燥することによって、前駆層を形成し;さらに
(ii)前記前駆層を活性エネルギー線照射により改質処理する、
ことによって形成される、請求項11に記載のガスバリア性フィルム。 The barrier layer is
(I) A precursor layer is formed by applying and drying the coating solution according to claim 7 on the inorganic compound layer; and (ii) modifying the precursor layer by active energy ray irradiation.
The gas-barrier film of Claim 11 formed by this. - 前記工程(ii)において、前記改質処理は、酸素濃度が200~10,000体積ppmの雰囲気下で、230nm以下の波長の真空紫外線による照射によって行われる、請求項12に記載のガスバリア性フィルム。 The gas barrier film according to claim 12, wherein in the step (ii), the reforming treatment is performed by irradiation with vacuum ultraviolet rays having a wavelength of 230 nm or less in an atmosphere having an oxygen concentration of 200 to 10,000 ppm by volume. .
- 請求項10~13のいずれか1項に記載のガスバリア性フィルムを有する、有機EL素子。 An organic EL device having the gas barrier film according to any one of claims 10 to 13.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201580006849.2A CN105939959A (en) | 2014-02-07 | 2015-02-06 | Modified polysilazane, coating solution containing said modified polysilazane, and gas barrier film produced using said coating solution |
JP2015561067A JPWO2015119260A1 (en) | 2014-02-07 | 2015-02-06 | Modified polysilazane, coating solution containing the modified polysilazane, and gas barrier film produced using the coating solution |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-022790 | 2014-02-07 | ||
JP2014022790 | 2014-02-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015119260A1 true WO2015119260A1 (en) | 2015-08-13 |
Family
ID=53778057
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/053435 WO2015119260A1 (en) | 2014-02-07 | 2015-02-06 | Modified polysilazane, coating solution containing said modified polysilazane, and gas barrier film produced using said coating solution |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPWO2015119260A1 (en) |
CN (1) | CN105939959A (en) |
WO (1) | WO2015119260A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020513435A (en) * | 2016-11-24 | 2020-05-14 | リッジフィールド・アクウィジション | Siloxazane compound, composition containing the same, and method for forming siliceous film using the same |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI756475B (en) * | 2017-10-06 | 2022-03-01 | 日商東京威力科創股份有限公司 | Particle generation preventing method and vacuum apparatus |
CN112480817B (en) * | 2020-11-26 | 2021-11-30 | 徐玲 | Heat-curable, moisture-curable or UV-curable corrosion-inhibiting composition |
CN113105663A (en) * | 2021-04-13 | 2021-07-13 | 中山大学 | High-barrier biodegradable film with transparent silicon oxide coating and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011007543A1 (en) * | 2009-07-17 | 2011-01-20 | 三井化学株式会社 | Laminate and process for production thereof |
WO2011043264A1 (en) * | 2009-10-05 | 2011-04-14 | 株式会社Adeka | Coating liquid for forming insulation film, insulation film using the same, and method for producing compound used in the same |
WO2012014653A1 (en) * | 2010-07-27 | 2012-02-02 | コニカミノルタホールディングス株式会社 | Gas barrier film, process for production of gas barrier film, and electronic device |
JP2012131194A (en) * | 2010-12-24 | 2012-07-12 | Konica Minolta Holdings Inc | Gas barrier film |
JP2012148416A (en) * | 2011-01-17 | 2012-08-09 | Mitsui Chemicals Inc | Laminate and method for producing the same |
JP2013001721A (en) * | 2011-06-13 | 2013-01-07 | Adeka Corp | Inorganic polysilazane, silica film-forming coating liquid containing the same, and method for forming silica film |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4933160A (en) * | 1987-08-13 | 1990-06-12 | Petroleum Energy Center | Reformed, inorganic polysilazane |
CN102302318B (en) * | 2011-09-20 | 2013-11-20 | 孙荣华 | Crystal transparent coat and hat rack |
CN105885654A (en) * | 2016-04-27 | 2016-08-24 | 安徽荣程玻璃制品有限公司 | Nano-indium modified transparent heat-insulating nano glass coating and preparation method thereof |
-
2015
- 2015-02-06 CN CN201580006849.2A patent/CN105939959A/en active Pending
- 2015-02-06 JP JP2015561067A patent/JPWO2015119260A1/en active Pending
- 2015-02-06 WO PCT/JP2015/053435 patent/WO2015119260A1/en active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011007543A1 (en) * | 2009-07-17 | 2011-01-20 | 三井化学株式会社 | Laminate and process for production thereof |
WO2011043264A1 (en) * | 2009-10-05 | 2011-04-14 | 株式会社Adeka | Coating liquid for forming insulation film, insulation film using the same, and method for producing compound used in the same |
WO2012014653A1 (en) * | 2010-07-27 | 2012-02-02 | コニカミノルタホールディングス株式会社 | Gas barrier film, process for production of gas barrier film, and electronic device |
JP2012131194A (en) * | 2010-12-24 | 2012-07-12 | Konica Minolta Holdings Inc | Gas barrier film |
JP2012148416A (en) * | 2011-01-17 | 2012-08-09 | Mitsui Chemicals Inc | Laminate and method for producing the same |
JP2013001721A (en) * | 2011-06-13 | 2013-01-07 | Adeka Corp | Inorganic polysilazane, silica film-forming coating liquid containing the same, and method for forming silica film |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020513435A (en) * | 2016-11-24 | 2020-05-14 | リッジフィールド・アクウィジション | Siloxazane compound, composition containing the same, and method for forming siliceous film using the same |
Also Published As
Publication number | Publication date |
---|---|
CN105939959A (en) | 2016-09-14 |
JPWO2015119260A1 (en) | 2017-03-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2014119750A1 (en) | Gas barrier film | |
JP6504284B2 (en) | Gas barrier film, method for producing the same, and electronic device using the same | |
JP6274213B2 (en) | Gas barrier film | |
JP6252493B2 (en) | Gas barrier film | |
WO2015002156A1 (en) | Gas-barrier film and method for producing same, and electronic device using same | |
JP6319316B2 (en) | Method for producing gas barrier film | |
KR101881244B1 (en) | Gas barrier film and electronic device using same | |
JP6060848B2 (en) | Gas barrier film | |
WO2015119260A1 (en) | Modified polysilazane, coating solution containing said modified polysilazane, and gas barrier film produced using said coating solution | |
JP6354756B2 (en) | Gas barrier film and electronic device | |
WO2014119754A1 (en) | Gas barrier film, method for producing same, and electronic device using same | |
WO2015147221A1 (en) | Gas barrier film and manufacturing method for gas barrier film | |
WO2015146886A1 (en) | Gas barrier film, method for manufacturing same, and electronic device using same | |
JP6295864B2 (en) | Gas barrier film, method for producing the same, and electronic device using the same | |
WO2015053055A1 (en) | Functional film | |
JPWO2015146886A6 (en) | Gas barrier film, method for producing the same, and electronic device using the same | |
JPWO2015029732A1 (en) | Gas barrier film and method for producing gas barrier film | |
WO2015029795A1 (en) | Method for producing gas barrier film | |
JP6295865B2 (en) | Gas barrier film | |
WO2014188981A1 (en) | Gas barrier film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15746719 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015561067 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15746719 Country of ref document: EP Kind code of ref document: A1 |