CN108349210B - Gas barrier film - Google Patents
Gas barrier film Download PDFInfo
- Publication number
- CN108349210B CN108349210B CN201680066364.7A CN201680066364A CN108349210B CN 108349210 B CN108349210 B CN 108349210B CN 201680066364 A CN201680066364 A CN 201680066364A CN 108349210 B CN108349210 B CN 108349210B
- Authority
- CN
- China
- Prior art keywords
- gas barrier
- ratio
- film
- layer thickness
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 230000004888 barrier function Effects 0.000 title claims abstract description 229
- 239000007789 gas Substances 0.000 claims abstract description 295
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 69
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 55
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 20
- 238000004458 analytical method Methods 0.000 claims abstract description 16
- 238000001228 spectrum Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 75
- 239000000463 material Substances 0.000 claims description 30
- 238000005520 cutting process Methods 0.000 abstract description 11
- 238000004804 winding Methods 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 208
- 239000010408 film Substances 0.000 description 187
- 230000015572 biosynthetic process Effects 0.000 description 47
- 238000000151 deposition Methods 0.000 description 34
- 230000008021 deposition Effects 0.000 description 34
- 208000028659 discharge Diseases 0.000 description 31
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 25
- 238000000034 method Methods 0.000 description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 23
- 238000009826 distribution Methods 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 22
- 239000002994 raw material Substances 0.000 description 21
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 12
- 238000005229 chemical vapour deposition Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000009467 reduction Effects 0.000 description 9
- 230000035699 permeability Effects 0.000 description 8
- -1 acryl compounds Chemical class 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 239000002985 plastic film Substances 0.000 description 7
- 229920006255 plastic film Polymers 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 6
- 125000005647 linker group Chemical group 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000005401 electroluminescence Methods 0.000 description 5
- 230000001747 exhibiting effect Effects 0.000 description 5
- 238000009499 grossing Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 150000003961 organosilicon compounds Chemical class 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 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
- 238000012935 Averaging Methods 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 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
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 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
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001883 metal evaporation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 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 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 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
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 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
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/42—Silicides
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
本发明的课题是提供气体阻隔性良好、辊卷取时的表背面接触引起的气体阻隔性的降低小、并且裁切时的裂纹的产生得到了抑制的气体阻隔膜。该气体阻隔膜的特征在于，在通过X射线光电子分光法得到的光谱中，将气体阻隔层的层厚方向的由来自硅原子、氧原子和碳原子的峰强度的比率所换算的组成比的合计量设为100％时，基于与碳原子有关的C1s的波形解析的由来自于C‑C、C＝C和C‑H键的峰强度的比率所换算的组成比的比例X(％)满足：将上述气体阻隔层的最表面的层厚设为0％、将与上述基材的界面的层厚设为100％时层厚5～30％区域中的上述比例X的最大值(％)为5～41(％)的范围内。
An object of the present invention is to provide a gas barrier film having good gas barrier properties, a small decrease in gas barrier properties due to contact between the front and back surfaces during roll winding, and suppressed occurrence of cracks during cutting. The gas barrier film is characterized in that, in a spectrum obtained by X-ray photoelectron spectroscopy, a composition ratio converted from the ratio of peak intensities derived from silicon atoms, oxygen atoms, and carbon atoms in the layer thickness direction of the gas barrier layer Ratio X (%) of the composition ratio converted from the ratio of the peak intensities derived from C-C, C=C and C-H bonds based on the waveform analysis of C1s related to carbon atoms when the total amount is 100% Satisfies: the maximum value (% ) is in the range of 5 to 41 (%).
Description
Technical Field
The present invention relates to a gas barrier film. More specifically, the present invention relates to a gas barrier film having good gas barrier properties, having little reduction in gas barrier properties due to contact between the front and back surfaces when wound on a roll, and having suppressed occurrence of cracks in a cut surface when cut.
Background
Conventionally, a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on a surface of a plastic substrate or a film has been used for packaging articles in the fields of foods, medical supplies, and the like. By using the gas barrier film, the deterioration of the article due to the gas such as water vapor or oxygen can be prevented.
In recent years, development of such gas barrier films for preventing permeation of water vapor, oxygen, and the like into electronic devices such as organic Electroluminescence (EL) devices and Liquid Crystal Display (LCD) devices has been desired, and many studies have been made. In these electronic devices, high gas barrier properties, for example, gas barrier properties comparable to those of glass substrates, are required.
As a method for producing a gas barrier film having more flexibility than a glass substrate, for example, a CVD method (chemical vapor Deposition method ) is used.
For example, patent document 1 discloses that a silicon carbide oxide (SiOC) film formed by a plasma chemical vapor deposition method is improved in gas barrier property, flexibility, and impact resistance.
However, the gas barrier film described in patent document 1 has a problem that the gas barrier property is not sufficient. In addition, when cutting the electronic device into a desired width and shape, particularly when sealing the electronic device, a crack propagates through the entire film due to external force such as bending, starting from the occurrence of a fine crack in the cut surface, and a significant reduction in gas barrier property is likely to occur, which causes a problem that the effective area having the gas barrier property is reduced due to the occurrence of the crack.
However, such a gas barrier film has the following problems because the density and strength in the layer thickness direction are relatively uniform: sufficient strength is not obtained with respect to stress applied from the surface and the side surface at the time of roll winding and cutting.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-73430
Patent document 2: japanese patent laid-open No. 2014-00782
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above problems and situations, and an object of the present invention is to provide a gas barrier film which has good gas barrier properties, is reduced in the decrease in gas barrier properties due to the contact between the front and back surfaces when wound on a roll, and is suppressed in the occurrence of cracks in a cut surface when cut.
Means for solving the problems
In order to solve the above problems, the present inventors have made studies on the causes of the above problems and the like, and have found that a gas barrier film having a gas barrier layer containing at least silicon atoms, oxygen atoms and carbon atoms on a substrate has a gas barrier film excellent in gas barrier properties, has a small decrease in gas barrier properties due to surface-back surface contact at the time of roll winding, and is capable of suppressing the occurrence of cracks in a cut surface at the time of cutting by setting the ratio of carbon atoms derived from C-C, C ═ C and C-H bonds in a predetermined region in the vicinity of the outermost surface of the gas barrier layer to be within a predetermined range, and have completed the present invention.
That is, the above problem according to the present invention is solved by the following means.
1. A gas barrier film characterized by having a gas barrier layer containing at least silicon atoms (Si), oxygen atoms (O) and carbon atoms (C) on a substrate, wherein, when the total amount of composition ratios in the thickness direction of the gas barrier layer, which are converted from the ratios of peak intensities derived from the silicon atoms (Si), the oxygen atoms (O) and the carbon atoms (C), is 100% in a spectrum obtained by X-ray photoelectron spectroscopy, the ratio X (%) of the composition ratio, which is converted from the ratio of the peak intensities derived from C-C, C ═ C and C-H bonds, analyzed based on the waveform of C1s related to the carbon atoms, satisfies the following (1).
(1): in the layer thickness direction of the gas barrier layer, when the layer thickness of the outermost surface of the gas barrier layer is 0% and the layer thickness of the interface with the substrate is 100%, the maximum value (%) of the ratio X in the region of the layer thickness of 5 to 30% is in the range of 5 to 41 (%).
2. The gas barrier film according to claim 1, wherein an average value (%) of the ratio X in the region of 5 to 30% of the layer thickness is in a range of 2 to 20%.
3. The gas barrier film according to claim 1 or 2, wherein the minimum value (%) of the ratio X in the region of 5 to 30% of the layer thickness is in the range of 1 to 10%.
4. The gas barrier film according to any one of items 1 to 3, wherein a maximum value (%) of the ratio X in a region of 5 to 30% of the layer thickness is larger than a maximum value (%) of the ratio X in a region of 30 to 95% of the layer thickness.
5. The gas barrier film according to any one of items 1 to 4, wherein an average value (%) of the ratio X in a region of 5 to 30% of the layer thickness is larger than an average value (%) of the ratio X in a region of 30 to 95% of the layer thickness.
6. The gas barrier film according to any one of items 1 to 5, wherein a minimum value (%) of the ratio X in a region of 5 to 30% of the layer thickness is larger than a minimum value (%) of the ratio X in a region of 30 to 95% of the layer thickness.
ADVANTAGEOUS EFFECTS OF INVENTION
The above means of the present invention can provide a gas barrier film having good gas barrier properties, having little reduction in gas barrier properties due to contact between the front and back surfaces when wound on a roll, and having suppressed occurrence of cracks in the cut surface when cut.
The mechanism of development and action of the effect of the present invention are not clear, but are presumed as follows.
In the gas barrier film of the present invention, carbon atoms derived from C-C, C ═ C and C-H bonds are present at a predetermined ratio in the region near the outermost surface of the gas barrier film layer, and the amount of the carbon atoms present is increased as compared with the conventional gas barrier film. Accordingly, the region in the vicinity of the outermost surface of the gas barrier layer of the present invention can be made dense and has appropriate flexibility, and therefore, the gas barrier layer is considered to have good gas barrier properties and can suppress damage due to contact between the front and back surfaces during roll winding. Further, since the region in the vicinity of the outermost surface of the gas barrier layer can be made to be a region with few fine voids, it is considered that when cutting is performed from the vicinity of the outermost surface, the occurrence of cracks in the cut surface is suppressed, and cracks due to the shear force at the time of cutting are less likely to occur.
Drawings
Fig. 1 is a cross-sectional view showing an example of the gas barrier film of the present invention.
Fig. 2 is a graph showing an example of the distribution of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier layer according to the present invention.
Fig. 3 is a schematic view showing an example of a manufacturing apparatus used for forming a gas barrier layer according to the present invention.
Fig. 4 is a graph showing an example of the distribution of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier layer according to the comparative example.
Detailed Description
The gas barrier film of the present invention is characterized by having a gas barrier layer containing at least silicon atoms (Si), oxygen atoms (O), and carbon atoms (C) on a substrate, and satisfying the following (1) with a ratio X (%) of a composition ratio, which is calculated from a ratio of peak intensities derived from C-C, C ═ C and C-H bonds analyzed based on a waveform of C1s related to carbon atoms, assuming that the total amount of composition ratios, which are calculated from ratios of peak intensities derived from silicon atoms (Si), oxygen atoms (O), and carbon atoms (C), in the thickness direction of the gas barrier layer in a spectrum obtained by X-ray photoelectron spectroscopy is 100%. This feature is a feature common to the inventions recited in the respective claims.
(1): the maximum value (%) of the ratio X in the region of 5 to 30% of the layer thickness is in the range of 5 to 41 (%) with respect to the layer thickness direction of the gas barrier layer, where 0% is the layer thickness of the outermost surface of the gas barrier layer and 100% is the layer thickness of the interface with the substrate.
In the embodiment of the present invention, it is preferable that the average (%) of the ratio X in the region of 5 to 30% of the layer thickness is in the range of 2 to 20% from the viewpoint of more effectively exhibiting the effects of the present invention.
In the embodiment of the present invention, from the viewpoint of more effectively exhibiting the effects of the present invention, the minimum value (%) of the ratio X in the region of 5 to 30% of the layer thickness is preferably in the range of 1 to 10%.
In the embodiment of the present invention, from the viewpoint of more effectively exhibiting the effects of the present invention, it is preferable that the maximum value (%) of the ratio X in the region of 5 to 30% of the layer thickness is larger than the maximum value (%) of the ratio X in the region of 30 to 95% of the layer thickness.
In the embodiment of the present invention, from the viewpoint of more effectively exhibiting the effects of the present invention, it is preferable that the average (%) of the ratio X in the region of 5 to 30% of the layer thickness is larger than the average (%) of the ratio X in the region of 30 to 95% of the layer thickness.
In the embodiment of the present invention, from the viewpoint of more effectively exhibiting the effects of the present invention, it is preferable that the minimum value (%) of the ratio X in the region of 5 to 30% of the layer thickness is larger than the minimum value (%) of the ratio X in the region of 30 to 95% of the layer thickness.
The present invention and its constituent elements, and modes and forms for carrying out the present invention will be described in detail below. In the present application, "to" indicating a numerical range is used in a meaning including numerical values described before and after the range as a lower limit value and an upper limit value.
[ gas Barrier film ]
As shown in fig. 1, the gas barrier film 1 of the present invention is configured by laminating a gas barrier layer 3 on a substrate 2.
The gas barrier layer 3 contains silicon carbide oxide (SiOC) while its composition and bonding state vary in the layer thickness direction.
Gas Barrier layer
The gas barrier layer according to the present invention contains at least silicon atoms (Si), oxygen atoms (O), and carbon atoms (C), and is characterized in that the ratio X (%) of the composition ratio, which is obtained by analyzing the waveform of C1s related to carbon atoms and is converted from the ratio of peak intensities derived from C-C, C ═ C and C-H bonds, satisfies the following (1) when the total amount of the composition ratios, which are converted from the ratio of peak intensities derived from silicon atoms (Si), oxygen atoms (O), and carbon atoms (C), in the thickness direction of the gas barrier layer in the spectrum obtained by X-ray photoelectron spectroscopy is taken as 100%. (1): the maximum value (%) of the ratio X in the region of 5 to 30% of the layer thickness is in the range of 5 to 41 (%) with respect to the layer thickness direction of the gas barrier layer, where 0% is the layer thickness of the outermost surface of the gas barrier layer and 100% is the layer thickness of the interface with the substrate.
This makes it possible to provide a gas barrier layer having high denseness, appropriate flexibility, and few fine voids, and therefore, the following effects can be obtained: the gas barrier property is good, the reduction of the gas barrier property due to the contact of the front and back surfaces when the roll is wound is small, and the generation of cracks in the cut surface when cutting is suppressed.
In the present invention, the "interface with the substrate" refers to "a position of a depth from the outermost surface side in the layer thickness direction of the gas barrier layer when the composition ratio of oxygen atoms (O) which are a part of the composition constituting the gas barrier layer is 30% or less". The composition ratio of the oxygen atoms (O) can be calculated by X-ray photoelectron spectroscopy, which will be described later.
In the gas barrier film of the present invention, the average value (%) of the ratio X is preferably within a range of 2 to 20% in a region having a layer thickness of 5 to 30%, and the minimum value (%) of the ratio X is preferably within a range of 1 to 10%. This can improve the durability of the inside of the gas barrier layer due to the distribution of a certain amount or more of carbon bonds between C-C, C ═ C and C-H in a region of 5 to 30% of the thickness of the gas barrier layer, and can more effectively exhibit the effects of the present invention.
In the gas barrier film of the present invention, it is preferable that the maximum value (%), the average value (%), and the minimum value (%) of the ratio X in the region of 5 to 30% of the layer thickness are larger than the maximum value (%), the average value (%), and the minimum value (%) of the ratio X in the region of 30 to 95% of the layer thickness, respectively. Thus, the amount of carbon bonds derived from C-C, C ═ C and C-H can be distributed more in absolute terms in the vicinity of the outermost surface of the gas barrier layer where stress is concentrated at the time of slitting or roll winding of the gas barrier film, that is, in the region of 5 to 30% of the layer thickness, and the effects of the present invention can be more effectively exhibited.
< X-ray photoelectron spectroscopy >
A carbon distribution curve (a curve showing the relationship between the distance (L) from the outermost surface of the gas barrier layer in the layer thickness direction of the gas barrier layer and the ratio of the number of carbon atoms to the total number of carbon atoms (100 at%) of carbon atoms, silicon atoms, and oxygen atoms (carbon atom ratio)) can be prepared by XPS depth profile measurement, which is a technique in which XPS measurement by X-ray Photoelectron Spectroscopy (XPS) and sputtering of rare gas ions such as argon are used together to expose the inside of a sample and surface composition analysis is sequentially performed, a silicon distribution curve (a curve showing the relationship between the distance L and the ratio of the number of silicon atoms (silicon atom ratio) with respect to the total number of carbon atoms, silicon atoms, and oxygen atoms (100 at%)) and an oxygen distribution curve (a curve showing the relationship between the distance L and the ratio of the number of oxygen atoms (oxygen atom ratio) with respect to the total number of carbon atoms, silicon atoms, and oxygen atoms (100 at%)).
(measurement of element distribution Curve)
The XPS depth profile can be measured under the following conditions, for example, to obtain a carbon profile, a silicon profile, and an oxygen profile with respect to the distance from the surface of the thin film layer in the layer thickness direction.
Etching ion species: argon (Ar)+)
Etch Rate (SiO)2Thermal oxide film conversion value): 0.05nm/sec
Etch Spacer (SiO)2Conversion value): 2nm
X-ray photoelectron spectroscopy apparatus: model name "VG ThetaProbe" manufactured by Thermo Fisher Scientific Inc "
Irradiation with X-ray Single Crystal spectroscopic AlK α
Spot (スポット) of X-rays and its size: oval shape of 800 μm × 400 μm
The profile obtained by such XPS depth profile measurement can be created, for example, by setting the vertical axis as the atomic ratio (at%) of each element and the horizontal axis as the etching time (sputtering time).
The atomic ratio (at%) in each region is a value obtained by averaging values etched in the depth direction by XPS depth profile measurement, for example, measured at 2nm intervals.
By performing the wide-scan spectroscopic analysis for measuring the entire region of the gas barrier layer as described above, a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve can be obtained.
< analysis of bonding State of carbon atom >
With respect to carbon atoms, the bonding state of carbon was analyzed by high-resolution spectroscopy (narrow scan analysis) of C1 s. Specifically, in the present invention, for example, the carbon bond (C) is divided into 5 bonding groups such as (1) C-C, C ═ C and C-H, (2) C-SiO, (3) C-O, (4) C ═ O, and (5) O-C-O by waveform analysis based on C1s, and the ratio of carbon atoms derived from (1) to (5) is calculated from the intensity ratio of each peak. Then, the ratio (%) of carbon atoms from each of the bonding groups (1) to (5) to the total amount (100%) of the composition ratios converted from the ratios of the peak intensities of the respective spectra of silicon atoms, oxygen atoms and carbon atoms was calculated. The analysis of the peak intensity can be performed using, for example, data analysis software PeakFit (manufactured by SYSTAT software inc.).
Fig. 2 shows the analysis results of the gas barrier film of the present invention. In the graph of fig. 2, the horizontal axis represents the depth of the gas barrier layer in the layer thickness direction (the depth (%) when the outermost surface is 0% and the interface with the base material is 100%), and the vertical axis represents the proportion (%) of each atom when the total amount of the composition ratios converted from the ratios of the peak intensities derived from silicon atoms, oxygen atoms, and carbon atoms, which are obtained by the X-ray photoelectron spectroscopy, is 100%. The carbon atoms are represented by the ratio of the above-mentioned 5 bonding groups. In fig. 2, (1) to (5) correspond to carbon atoms derived from (1) C-C, C ═ C and C-H, (2) C-SiO, (3) C-O, (4) C ═ O, (5) O-C-O, (6) corresponds to an oxygen atom, and (7) corresponds to a silicon atom, respectively.
In the above description, for carbon atoms, the peak related to all carbon bonds in the waveform analysis of C1s was analyzed for 5 bonding groups by waveform analysis based on C1s, for example, (1) C-C, C ═ C and C-H, (2) C-SiO, (3) C-O, (4) C ═ O, and (5) O-C-O, and the respective ratios were calculated from the composition of the gas barrier layer.
< method for measuring layer thickness of gas barrier layer >
The thickness of the gas barrier layer can be determined by measuring the depth from the outermost surface to the interface with the substrate in the stacking direction of the gas barrier layers by cross-sectional observation using a Transmission Electron Microscope (TEM). In the cross-sectional observation with a transmission electron microscope, the layer thickness was arbitrarily measured at 10 sites, and the average value was taken as the layer thickness of the gas barrier layer.
(TEM image of a cross section in the layer thickness direction)
For TEM observation of the cross section, a thin slice was prepared using the following Focused Ion Beam (FIB) processing apparatus for an observation sample, and then TEM observation was performed. Here, if the sample is continuously irradiated with the electron beam, a contrast difference occurs between a portion damaged by the electron beam and a portion not damaged, and therefore the thickness of the gas barrier layer can be measured by the contrast difference.
(FIB working)
The device comprises the following steps: SMI2050 manufactured by SII
Processing ions: ga (30kV)
Thickness of the sample: 100 to 200nm
(TEM observation)
The device comprises the following steps: JEM2000FX manufactured by Japan Electron System (acceleration Voltage: 200kV)
< layer thickness of gas Barrier layer >
The layer thickness of the gas barrier layer according to the present invention is preferably within a range of 10 to 500nm, and more preferably within a range of 20 to 300nm, from the viewpoint of achieving both the reduction in thickness and the gas barrier property.
< water vapor transmission through gas Barrier layer >
The gas barrier layer preferably has gas barrier properties. Here, the term "having a gas barrier property" means that the water vapor transmission rate (38 ℃ C., relative humidity 90% RH) measured by an MOCON water vapor transmission rate measuring apparatus Aquatran manufactured by MOCON corporation in which only gas barrier layers are laminated on a substrate is less than 0.1 g/(m)2Day), preferably less than 0.01 g/(m)2Day).
Substrate
As the base material of the gas barrier film of the present invention, a plastic film is used. The plastic film to be used is not particularly limited in material, thickness, and the like as long as it can hold the gas barrier layer, and can be appropriately selected according to the purpose of use and the like.
Specific examples of the plastic film include thermoplastic resins such as polyester resins, methacrylic-maleic acid copolymers, polystyrene resins, transparent fluororesins, polyimides, fluorinated polyimide resins, polyamide resins, polyamideimide resins, polyetherimide resins, cellulose acylate resins, polyurethane resins, polyether ether ketone resins, polycarbonate resins, alicyclic polyolefin resins, polyarylate resins, polyether sulfone resins, polysulfone resins, cycloolefin copolymers, fluorene ring-modified polycarbonate resins, alicyclic modified polycarbonate resins, fluorene ring-modified polyester resins, and acryl compounds.
When the gas barrier film is used as a substrate of an electronic device such as an organic EL element, the base material is preferably made of a material having heat resistance. Specifically, a linear expansion coefficient of 15 × 10 is used-6～100×10-6(K) and a glass transition temperature Tg of 100 to 300 ℃. The substrate satisfies the requirements for use as an electronic component and a laminated film for a display.
That is, when the gas barrier film is used in these applications, the step of exposing the gas barrier film to 150 ℃. In this case, the linear expansion coefficient of the substrate passing through the gas barrier film was 15 × 10-6～100×10-6The heat resistance is high and the flexibility is good within the range of (/ K). The linear expansion coefficient and Tg of the base material can be adjusted by additives and the like.
More preferred specific examples of the thermoplastic resin that can be used as the base material include polyethylene terephthalate (PET: 70 ℃ C.), polyethylene naphthalate (PEN: 120 ℃ C.), polycarbonate (PC: 140 ℃ C.), alicyclic polyolefin (e.g., compound described in Japanese Rayleigh corporation, ZEONOR (registered trademark) 1600: 160 ℃ C.), polyarylate (PAr: 210 ℃ C.), polyethersulfone (PES: 220 ℃ C.), polysulfone (PSF: 190 ℃ C.), cycloolefin copolymer (COC: 2001:. sup.150584 ℃ C.), polyimide (e.g., compound described in Mitsubishi gas chemical corporation, ネオプリム (registered trademark): 260 ℃ C.), fluorene ring-modified polycarbonate (BCF-PC: 225 ℃ C.), and alicyclic 7676PC (IP-P: 2000. sup.227603 ℃ C.), 205 ℃ C.), and the like, An acryloyl compound (a compound described in Japanese patent application laid-open No. 2002-80616: 300 ℃ C. or higher), etc. (note that the numerical value in parentheses represents Tg). Particularly when transparency is required, alicyclic polyolefins and the like are preferably used.
The gas barrier film is preferably transparent in a plastic film for use as an electronic device such as an organic EL device. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.
As for the light transmittance, JIS K7105: 1981, the total light transmittance and the amount of scattered light were measured using an integrating sphere type light transmittance measuring device, and the diffusion transmittance was subtracted from the total light transmittance to calculate the total light transmittance.
However, even in the case where the gas barrier film is used for display applications, transparency is not necessarily required in the case where the gas barrier film is not provided on the viewing side or the like. Therefore, in such a case, an opaque material can also be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and a known liquid crystal polymer.
The thickness of the plastic film used in the gas barrier film is not particularly limited and is suitably selected according to the application, and is typically in the range of 1 to 800 μm, preferably in the range of 10 to 200 μm. These plastic films may have functional layers such as a known transparent conductive layer and a smoothing layer, which have been used in conventional gas barrier films. In addition to the above-described functional layers, the functional layers described in paragraphs 0036 to 0038 of jp 2006-289627 a can be preferably used.
The substrate using the above-listed resins and the like may be an unstretched film or a stretched film.
The substrate can be manufactured by a conventional method known in the art. For example, an unstretched substrate that is substantially amorphous and has no orientation can be produced by melting a resin to be a material using an extruder, extruding the material using an annular die or a T-die, and quenching the material. Further, a stretched substrate can be produced by stretching an unstretched substrate in the direction of flow (vertical axis) of the substrate or in the direction perpendicular to the direction of flow (horizontal axis) of the substrate by a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, or tubular simultaneous biaxial stretching. The stretch ratio in this case can be appropriately selected depending on the resin to be used as a raw material of the base material, and is preferably in the range of 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.
The both surfaces of the base material, at least the side provided with the gas barrier layer, may be subjected to various known treatments for improving adhesiveness, corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, lamination of a smoothing layer, and the like in combination as necessary.
Anchor coating
An anchor coat layer may be formed as an easy-adhesion layer on the surface of the base material according to the present invention in order to improve adhesion (adhesiveness). As the material and method of forming the anchor coat layer, those disclosed in paragraphs 0229 to 0232 of Japanese patent application laid-open No. 2013 and 52561 are suitably used.
Smooth layer
The gas barrier film of the present invention may have a smooth layer on the side of the substrate having the gas barrier layer. The smoothing layer is provided to flatten a rough surface of the substrate where the projections or the like are present, or to fill and flatten irregularities or pinholes generated in the gas barrier layer due to the projections present on the resin substrate. As the material and method for forming the smoothing layer, the surface roughness, the layer thickness, and the like, those disclosed in paragraphs 0233 to 0248 of Japanese patent application laid-open No. 2013-52561 are suitably used.
(seepage-proofing layer)
The gas barrier film of the present invention can further have a bleed-out prevention layer. The anti-bleeding layer is provided on the opposite surface of the substrate having the smooth layer in order to suppress the following phenomenon: when the film having the smooth layer is heated, unreacted oligomers and the like migrate from the resin base material to the surface, and the surface in contact therewith is contaminated. The anti-bleeding layer may have substantially the same structure as the smoothing layer as long as it has this function. The materials, methods, and layer thicknesses of the anti-bleeding layer are suitably those disclosed in paragraphs 0249 to 0262 of Japanese patent application laid-open No. 2013-52561.
Electronic device
The gas barrier film of the present invention has excellent gas barrier properties, transparency, and flexibility. Therefore, the gas barrier film of the present invention can be used in various applications such as a package of an electronic device or the like, a gas barrier film used in an electronic device such as a photoelectric conversion element (solar cell element), an organic EL element, and a liquid crystal display element, and an electronic device using the same.
[ method for producing gas Barrier film ]
The gas barrier layer according to the present invention can be formed by a plasma chemical vapor deposition method (plasma CVD, PECVD (plasma-enhanced chemical vapor deposition), hereinafter also referred to simply as "plasma CVD method").
The plasma CVD method is not particularly limited, and examples thereof include a plasma CVD method at or near atmospheric pressure described in japanese laid-open patent publication No. 2006/033233, and a plasma CVD method using a plasma CVD apparatus having a counter roller electrode. The plasma CVD method may be a plasma CVD method of penning discharge plasma system.
Among them, it is preferable to use a raw material gas containing an organosilicon compound and oxygen gas, and to form the organic layer by a discharge plasma chemical vapor deposition method (roll-to-roll method) having a discharge space between rolls to which a magnetic field is applied. By using the discharge plasma chemical vapor deposition method as described above, a gas barrier layer having an extremum and in which the atomic ratio of carbon in each region is controlled within a certain range can be easily produced, and a gas barrier film having an appropriate stress balance in the layer can be produced. Further, by using the discharge plasma chemical vapor deposition method, the gas barrier layer is densified, and the gas barrier property can be improved.
The method of forming the gas barrier layer according to the present invention by a discharge plasma chemical vapor deposition method in which a discharge space is provided between rollers to which a magnetic field is applied, using a raw material gas containing an organic silicon compound and oxygen, will be described below.
When plasma is generated in the plasma CVD method, it is preferable to generate plasma discharge in a space between the plurality of deposition rollers, and it is more preferable to use a pair of deposition rollers, in which a substrate (the substrate referred to herein also includes a substrate treated) is disposed, and plasma is generated by discharge between the pair of deposition rollers.
By using the pair of deposition rollers, disposing the substrate on the pair of deposition rollers, and performing electric discharge between the pair of deposition rollers, it is possible to form a film on the surface portion of the substrate existing on one deposition roller at the time of film formation, and simultaneously form a film on the surface portion of the substrate existing on the other deposition roller, and thus a thin film can be efficiently produced. Further, the film formation rate can be doubled as compared with a general plasma CVD method not using a roll.
In addition, when the electric discharge is performed between the pair of deposition rollers, it is preferable that the polarities of the pair of deposition rollers are alternately reversed. Further, the film-forming gas used in such a plasma CVD method preferably contains an organosilicon compound and oxygen, and the content of oxygen in the film-forming gas is preferably adjusted in accordance with the theoretical amount of oxygen required for completely oxidizing the entire amount of the organosilicon compound in the film-forming gas.
The method for forming the gas barrier layer according to the present invention will be described in more detail below with reference to fig. 3. Fig. 3 is a schematic view showing an example of a manufacturing apparatus that can be preferably used for manufacturing the gas barrier layer according to the present invention. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description thereof is omitted.
The manufacturing apparatus 10 shown in fig. 3 includes a delivery roller 12, transport rollers 13 to 18, film formation rollers 19 and 20, a gas supply pipe 21, a power supply 22 for plasma generation, magnetic field generation devices 23 and 24 provided inside the film formation rollers 19 and 20, respectively, and a take-up roller 25. In the manufacturing apparatus 10, at least the deposition rollers 19 and 20, the gas supply pipe 21, the plasma generation power source 22, and the magnetic field generation devices 23 and 24 are disposed in the deposition (vacuum) chamber 28. In the manufacturing apparatus 10, the film forming chamber 28 is connected to a vacuum pump, not shown, and the pressure in the vacuum chamber 28 can be appropriately adjusted by the vacuum pump.
The delivery roller 12 and the transport roller 13 are disposed in the transport chamber 27, and the take-up roller 25 and the transport roller 18 are disposed in the transport chamber 29. The conveyance chambers 27 and 29 and the film forming chamber 28 are connected via connecting portions 30 and 31, respectively. For example, vacuum gate valves may be provided at the connection portions 30 and 31 to physically isolate the film forming chamber 28 from the conveyance system chambers 27 and 29. By using a vacuum gate valve, for example, only the film forming chamber 28 can be made vacuum system, and the transfer system chambers 27 and 29 can be made atmospheric. In addition, by physically isolating the film forming chamber 28 from the conveyance- system chambers 27 and 29, contamination of the conveyance- system chambers 27 and 29 with particles generated in the film forming chamber 28 can be suppressed.
In such a manufacturing apparatus, the respective film formation rollers 19 and 20 are connected to a plasma generation power source 22 so that the pair of film formation rollers (film formation rollers 19 and 20) can function as a pair of opposed electrodes. Therefore, in the manufacturing apparatus 10, by supplying power from the power supply 22 for generating plasma, discharge can be performed in the space between the film formation roller 19 and the film formation roller 20, and plasma can be generated in the space between the film formation roller 19 and the film formation roller 20. When the film-forming roll 19 and the film-forming roll 20 are also used as electrodes in this way, the material and design thereof may be appropriately changed so that they can also be used as electrodes.
In the manufacturing apparatus 10, it is preferable that the pair of deposition rollers (deposition rollers 19 and 20) are disposed so that their central axes are substantially parallel to each other on the same plane. By arranging the pair of deposition rollers (deposition rollers 19 and 20) in this way, the deposition rate can be doubled as compared with a normal plasma CVD method that does not use rollers.
According to the manufacturing apparatus 10, the gas barrier layer 3 can be formed on the surface of the substrate 2 (the substrate referred to herein also includes a substrate treated) by the CVD method, and the gas barrier layer component can be deposited on the surface of the substrate 2 on the film formation roll 19 and also deposited on the surface of the substrate 2 on the film formation roll 20 at the same time, so that the gas barrier layer can be efficiently formed on the surface of the substrate 2.
Inside the film forming rollers 19 and 20, magnetic field generating devices 23 and 24 are provided, respectively, which are fixed so as not to rotate even if the film forming rollers 19 and 20 rotate.
In the magnetic field generating devices 23 and 24 provided in the film forming rollers 19 and 20, respectively, it is preferable that the magnetic poles are arranged so that magnetic lines of force do not cross between the magnetic field generating device 23 provided in one film forming roller 19 and the magnetic field generating device 24 provided in the other film forming roller 20, and the magnetic field generating devices 23 and 24 form a substantially closed magnetic circuit, respectively. By providing such magnetic field generating devices 23 and 24, formation of a magnetic field in which magnetic lines of force swell in the vicinity of the facing side surfaces of the respective film forming rollers 19 and 20 can be promoted, and plasma can be easily converged on the swollen portions, so that film forming efficiency can be improved, which is excellent in this point.
Further, the magnetic field generators 23 and 24 provided in the film forming rollers 19 and 20 respectively have magnetic poles in a race track shape elongated in the roller axis direction, and it is preferable that the magnetic poles of one magnetic field generator 23 and the magnetic field generator 24 are arranged so that the magnetic poles facing each other have the same polarity. By providing such magnetic field generating devices 23 and 24, magnetic lines of force do not cross over the magnetic field generating devices on the opposing roll sides with respect to the magnetic field generating devices 23 and 24, a racetrack-shaped magnetic field can be easily formed in the vicinity of the roll surface facing the opposing space (discharge region) in the longitudinal direction of the roll shaft, and plasma can be converged in the magnetic field, so that the gas barrier layer 3 as a vapor deposited film can be efficiently formed using the wide base material 2 wound in the roll width direction, which is excellent in this point.
The tension of each of the film forming rollers 19 and 20 with respect to the substrate 2 may be the same, or the tension of only the film forming roller 19 or the film forming roller 20 may be high to form a film. By increasing the tension to the base material 2 in the film forming rollers 19 and 20, the following advantages are obtained: the adhesion between the substrate 2 and the film forming rollers 19 and 20 is improved, heat exchange is efficiently performed, the film uniformity is improved, and thermal wrinkles are suppressed.
As the film forming rollers 19 and 20, known rollers can be suitably used. As such film formation rollers 19 and 20, rollers having the same diameter are preferably used from the viewpoint of more efficiently forming a thin film. The diameters of the deposition rollers 19 and 20 are preferably in the range of 300 to 1000mm phi, and particularly preferably in the range of 300 to 700mm phi, from the viewpoints of discharge conditions, chamber space, and the like. If the diameter of the deposition roller is 300mm Φ or more, the plasma discharge space is not reduced, and therefore, there is no deterioration in productivity, and it is possible to avoid applying the entire heat of the plasma discharge to the substrate 2 in a short time, and therefore, it is possible to reduce damage to the substrate 2, which is preferable. On the other hand, if the diameter of the deposition roller is 1000mm φ or less, uniformity of the plasma discharge space is also included, and the device design can be maintained practically, so that it is preferable. Each of the film forming rolls 19 and 20 may have a nip roll, and by having a nip roll, the adhesion of the substrate 2 to the film forming rolls 19 and 20 is improved. This has the following advantages: heat exchange is efficiently performed between the substrate 2 and the film forming rollers 19 and 20, film uniformity is improved, and thermal wrinkle is suppressed.
In such a manufacturing apparatus 10, the substrate 2 is disposed on a pair of film formation rollers (film formation rollers 19 and 20) such that surfaces of the substrate 2 face each other. By disposing the substrate 2 in this manner, when the plasma is generated by discharging in the space between the film formation rollers 19 and 20, the surface of each of the substrates 2 existing between the pair of film formation rollers (film formation rollers 19 and 20) can be simultaneously formed. That is, according to the manufacturing apparatus 10, since the gas barrier layer component can be deposited on the surface of the substrate 2 on the deposition roller 19 and further the gas barrier layer component can be deposited on the deposition roller 20 by the plasma CVD method, the gas barrier layer can be efficiently formed on the surface of the substrate 2.
As the delivery rollers 12 and the transport rollers 13 to 18 used in the manufacturing apparatus 10, known rollers can be suitably used. The winding roll 25 is not particularly limited as long as the gas barrier film 1 having the gas barrier layer 3 formed on the substrate 2 can be wound, and a known roll can be suitably used. The delivery roller 12 and the take-up roller 25 may be of a turntable type. The turntable may have a multi-axis structure with 2 or more axes, or may have a structure in which only some of the axes are open to the atmosphere.
As the gas supply pipe 21 and the vacuum pump, a gas supply pipe and a vacuum pump capable of supplying or discharging a raw material gas or the like at a predetermined speed can be suitably used.
Further, the gas supply pipe 21 as a gas supply means is preferably provided in one of the opposing spaces (discharge region, film formation region) between the film formation roll 19 and the film formation roll 20, and the vacuum pump (not shown) as a vacuum exhaust means is preferably provided in the other of the opposing spaces. By disposing the gas supply pipe 21 as the gas supply means and the vacuum pump as the vacuum exhaust means in this manner, the film forming gas can be efficiently supplied to the space between the film forming roll 19 and the film forming roll 20, the film forming efficiency can be improved, and this is excellent in this point.
In fig. 3, the gas supply pipe 21 is provided on the center line between the deposition roller 19 and the deposition roller 20, but is not limited thereto, and may be shifted to any side from the center line between the deposition roller 19 and the deposition roller 20 (may be shifted from the center line in the left-right direction), for example. Since the gas supply pipe 21 is shifted from the center line between the film formation rollers 19 and 20 so as to be close to one film formation roller and be away from the other film formation roller, the composition of the film formed on the film formation roller 19 by the supply of the source gas and the composition of the film formed on the film formation roller 20 become different, and the position of the gas supply pipe 21 can be shifted as appropriate when the film quality is to be changed. The gas supply pipe 21 may be spaced apart from or close to the deposition roller on the center line as appropriate (the arrangement position may be moved on the center line in the vertical direction). The gas supply tube 21 is separated from the discharge space by being spaced apart from the center axis of the deposition roller, whereby there is an advantage that the adhesion of particles to the gas supply tube 21 can be suppressed, and the gas supply tube 21 is brought closer to the discharge space on the center axis of the deposition roller, whereby there is an advantage that the deposition rate can be increased.
In fig. 3, one gas supply pipe 21 is provided, but a plurality of gas supply pipes 21 may be provided, and different supply gases may be discharged from the respective nozzles.
Further, as the power source 22 for plasma generation, a power source of a known plasma generation device can be suitably used. The plasma generation power source 22 supplies power to the film formation roller 19 and the film formation roller 20 connected thereto, and can be used as a counter electrode for discharge. As such a power supply 22 for generating plasma, a power supply (an ac power supply or the like) capable of alternately reversing the polarity of the pair of deposition rollers is preferably used, because plasma CVD can be performed more efficiently.
In addition, as such a power source 22 for generating plasma, it is preferable that the applied power is in the range of 100W to 20kW, more preferably 100W to 10kW, and the frequency of the alternating current is in the range of 50Hz to 13.56MHz, more preferably 50Hz to 500kHz, in order to enable plasma CVD to be performed more efficiently.
In addition, from the viewpoint of stabilization of the plasma process, a high-frequency power supply in which both a high-frequency current wave and a voltage wave are sinusoidal waves can be used.
In fig. 3, both the film forming rollers 19 and 20 are energized by one plasma generating power source 22 (both film forming rollers are energized), but the present invention is not limited to this configuration, and one film forming roller may be energized (one film forming roller is energized) and the other film forming roller may be grounded.
Further, as a method of feeding the film forming roller, the roller may be fed from only one of the roller ends, or may be fed from both the roller ends. In the case of supplying a high frequency band, both ends of the roller may be supplied with electricity, in order to make uniform supply possible.
Further, as the feeding method, double frequency feeding in which different frequencies are applied may be performed, and a mode in which different double frequencies are applied to one film forming roller may be employed, or a mode in which different frequencies are applied to one film forming roller and the other film forming roller may be employed. By such double-frequency power supply, the plasma density is increased, and the film formation rate can be increased.
Although not shown in fig. 3, a feedback circuit may be provided to monitor the plasma emission intensity in the discharge space from the outside and adjust the distance between the magnetic fields (the distance between the opposed rollers), the magnetic field intensity, the power applied by the power supply, the power supply frequency, the amount of supplied gas, and the like so that the plasma emission intensity becomes a desired plasma emission intensity when the plasma emission intensity is not a desired one. By having such a feedback circuit, film formation/production can be stabilized.
In addition, as the magnetic field generating devices 23 and 24, known magnetic field generating devices can be suitably used. Further, as the substrate 2, in addition to the substrate used in the present invention, a substrate on which the gas barrier layer 3 is formed in advance can be used. By using a substrate on which the gas barrier layer 3 is formed in advance as the substrate 2 in this way, the thickness of the gas barrier layer 3 can be increased.
Using such a manufacturing apparatus 10 shown in fig. 3, for example, a gas barrier layer containing carbon atoms, silicon atoms, and oxygen atoms can be formed. In this case, the method of controlling the atomic ratio of the content of carbon atoms in the gas barrier layer is not particularly limited, and the atomic ratio of the content of carbon atoms can be controlled by controlling the ratio of the raw materials used, the power, the pressure, and the like.
The pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted depending on the type of the raw material gas, and is preferably about 0.5 to 50Pa, and more preferably in the range of 0.5 to 10 Pa.
In the plasma CVD method, the power applied to the electrode drums (provided to the deposition rollers 19 and 20 in the present embodiment) connected to the plasma generation power source 22 for causing electric discharge between the deposition roller 19 and the deposition roller 20 can be appropriately adjusted depending on the type of the raw material gas, the pressure in the vacuum chamber, and the like, but is preferably set to be in the range of 0.1 to 10kW although this cannot be said in any way. If the applied power is 0.1kW (100W) or more, the generation of particles can be sufficiently suppressed, while if it is 10kW or less, the amount of heat generated at the time of film formation can be suppressed, and the temperature rise of the substrate surface at the time of film formation can be suppressed. Therefore, the substrate is excellent in that it does not resist heat and can prevent wrinkles from occurring during film formation.
The transport speed (linear velocity) of the substrate 2 can be appropriately adjusted depending on the type of the raw material gas, the pressure in the vacuum chamber, and the like, and is preferably set to a range of 0.25 to 100m/min, and more preferably set to a range of 0.5 to 100 m/min.
The composition ratio of each of the silicon atoms, oxygen atoms and carbon atoms, and the ratio of the types of carbon bonds in the gas barrier layer can be controlled within the scope of the present invention by using the following methods (1) to (4), for example.
(1) Control of source gas for CVD using plasma
The ratio of carbon, hydrogen, oxygen and silicon in the molecule can be controlled by appropriately using the raw material for plasma CVD.
Specifically, as the raw material for plasma CVD, an organosilicon compound having a low proportion of intramolecular Si — C bonds is preferably used. The number of Si — C bonds in 1 molecule in these organosilicon compounds is preferably 1, 2 or less, and more preferably 1 or 0, per 1 Si atom in 1 molecule.
Specifically, as compared with disiloxanes such as hexamethyldisiloxane and tetramethyldisiloxane, alkoxysilanes such as cyclic siloxanes such as octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane and alkoxysilanes containing 1 Si in 1 molecule, such as tetramethoxysilane and methyltrimethoxysilane, are preferably used. These compounds can be used alone in 1 or more than 2 kinds in combination.
(2) Control of the amount of oxygen supplied using as a reactant gas
The amount of oxygen gas, which is a reactive gas supplied during CVD film formation, can be controlled by increasing or decreasing the amount.
Specifically, when the above-described preferred raw materials are oxidized to form a gas barrier film containing silicon atoms, oxygen atoms, and carbon atoms as main components, the amount of oxygen to be supplied is controlled to such an extent that the oxygen is not completely oxidized, and conversely, a certain amount of oxygen is supplied to such an extent that excess carbon does not remain in the gas barrier layer.
(3) Control of the amount of inert gas added
During the film formation, an inert gas such as nitrogen, argon, or helium is supplied, and the amount of the inert gas supplied is adjusted to stabilize plasma during the formation of the gas barrier layer, and the oxidation reaction is adjusted to control the plasma.
(4) Control of inter-electrode distance in plasma discharge
The distance between the electrodes for generating the plasma discharge can be controlled by continuously changing the distance.
In the case of using the apparatus in which the pair of electrodes face each other, the plasma space generated on the surface of the substrate in contact with the electrodes changes continuously, and therefore the composition in the gas barrier layer can be changed continuously by the change in the film formation conditions caused by the continuous change in the distance between the electrodes.
Next, a film forming gas for forming a gas barrier layer will be described.
As the film forming gas, a reactive gas other than the source gas can be used. As such a reaction gas, a gas that reacts with the raw material gas to form an inorganic compound such as an oxide can be appropriately selected and used. Since the gas barrier layer 3 of the present embodiment contains oxygen, oxygen or ozone can be used as the reaction gas, and oxygen is preferably used from the viewpoint of simplicity. In addition, a reaction gas for forming a nitride may be used, and for example, nitrogen or ammonia may be used. These reaction gases can be used alone or in combination of 2 or more, and for example, in the case of forming an oxynitride, a reaction gas for forming an oxide and a reaction gas for forming a nitride can be used in combination.
As the film forming gas, a carrier gas may be used as necessary to supply the source gas into the film forming chamber 28. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such a carrier gas and a discharge gas, known gases can be suitably used, and for example, a rare gas such as helium, argon, neon, or xenon, hydrogen, and nitrogen can be used.
In the case where the film forming gas contains the raw material gas and the reactive gas, the ratio of the raw material gas to the reactive gas is preferably adjusted to 50% or more and 300% or more, with respect to 100% of the theoretically required amount of the reactive gas for completely oxidizing the raw material gas and the reactive gas. By adjusting the ratio of the reactive gas within this range, the carbon atoms in the gas barrier layer to be formed can be adjusted to a preferable composition distribution, and excellent gas barrier properties and bending resistance can be obtained.
When the ratio is lower than the above ratio, the ratio of carbon atoms in the gas barrier layer increases, and it becomes difficult to maintain sufficient gas barrier properties, whereas when the ratio is higher than the above ratio, it becomes difficult to form the carbon-related bond of the present invention in the gas barrier layer due to active participation.
By using the manufacturing apparatus 10 shown in fig. 3, a film forming gas (a raw material gas or the like) is supplied into the film forming chamber 28, and electric discharge is generated between a pair of film forming rollers (the film forming rollers 19 and 20), whereby the film forming gas (the raw material gas or the like) is decomposed by plasma, and a 1 st film forming layer is formed on the surface of the substrate 2 on the film forming roller 19 and the surface of the substrate 2 on the film forming roller 20 by a plasma CVD method. At this time, a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the opposing space (discharge region) along the longitudinal direction of the roller shafts of the film formation rollers 19 and 20, and the plasma is converged in the magnetic field. By repeating this process for the 2 nd and 3 rd film formation layers in which one or more of the above conditions are changed, the composition of each constituent atom continuously changes in the layer thickness direction.
Specifically, in the carbon distribution curve, the silicon distribution curve, and the oxygen distribution curve, when the substrate 2 passes through the point a of the film formation roller 19 and the point B of the film formation roller 20, the maximum value of the carbon distribution curve and the minimum value of the oxygen distribution curve are formed. And the substrate 2 passes through the C1 and C2 points of the film forming roller 19 and the C3 and C4 points of the film forming roller 20, the minimum value of the carbon distribution curve and the maximum value of the oxygen distribution curve are formed.
The existence of such an extremum indicates that the existence ratio of carbon atoms and oxygen atoms in the film is not uniform, and the existence of a portion having low density where carbon atoms are locally few makes the entire layer flexible and improves the durability against bending.
As described above, a more preferable embodiment of the present embodiment is characterized in that the gas barrier layer according to the present invention is formed into a film by a plasma CVD method using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode shown in fig. 3. This is because, in the case of mass production using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode, a gas barrier layer having excellent flexibility (bendability), high gas barrier property under high temperature and high humidity, and less defects such as reduction in mechanical strength, particularly durability and gas barrier property during roll-to-roll conveyance can be efficiently produced. Such a manufacturing apparatus is also excellent in that it is possible to easily mass-produce a gas barrier film used for solar cells, electronic components, and the like, which requires durability against temperature changes at low cost.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Production of gas Barrier films 1 to 12
(preparation of resin base Material)
As the resin substrate in a sheet roll form, a 100 μm thick polyethylene terephthalate film (manufactured by Toyo Boseki K.K., コスモシャイン A4300) having both surfaces easily subjected to adhesive processing was used as a thermoplastic resin support.
(formation of anchor coat layer)
On one side of the easy adhesion surface of the resin substrate, a UV-curable organic/inorganic hybrid hard coat material OPSTAR (registered trademark) Z7501 manufactured by JSR corporation was applied with a wire bar so that the layer thickness after drying became 3 μm, and then the resultant was driedDrying was carried out at 80 ℃ for 3 minutes. Next, a high-pressure mercury lamp was used under an air atmosphere, under curing conditions: 1.0J/cm2Then, the curing is carried out to form the anchoring coating.
(formation of bleed-out preventive layer)
On the other easy adhesion surface side of the resin substrate, a UV curable organic/inorganic hybrid hard coat material OPSTAR (registered trademark) Z7535 manufactured by JSR corporation was coated with a wire bar so that the layer thickness after drying became 3 μm, and then dried at 80 ℃ for 3 minutes, and then a high pressure mercury lamp was used under an air atmosphere under curing conditions: 1.0J/cm2Then, the solidification is carried out to form the anti-seepage layer. After the formation of the barrier layer, the resin substrate was stored under a reduced pressure of 5Pa and at a temperature of 35 ℃ for 96 hours to adjust the humidity.
(formation of gas Barrier layer: roll CVD method)
The surface of the resin base material on which the barrier layer was formed was brought into contact with the film-forming roll by using an inter-roll discharge plasma CVD apparatus (hereinafter, this method is referred to as a roll CVD method) to which a magnetic field was applied as shown in fig. 3, the resin base material was mounted on the apparatus, the raw material gas, oxygen gas, the degree of vacuum in the vacuum chamber, and the applied power from the power source for plasma generation were varied within the ranges described below under the film-forming conditions (plasma CVD conditions) so as to vary the atomic ratio of carbon, and the resultant film was formed on the anchor coat layer by combining a plurality of times so that the final layer thickness became 140nm according to the method for measuring the layer thickness of the gas barrier layer described below, and this was used as a gas barrier layer.
In the gas barrier layer of the present invention, the adjustment is mainly performed by increasing the supply amount of the raw material gas or decreasing the supply amount of the oxygen gas in the entire supply gas in order to increase the atomic ratio of carbon, and the degree of vacuum in the vacuum chamber is increased or decreased in order to adjust the layer thickness. The supply amounts of the raw material gas and the oxygen gas were adjusted to values shown in table 1 and supplied.
In Table 1, TMCTS and MTMS are abbreviations for tetramethylcyclotetrasiloxane and methyltrimethoxysilane, respectively.
Plasma CVD conditions
Supply amount of raw material gas (described in table 1): 50 or 100sccm (Standard Cubic Centimeter Minute)
Oxygen (O)2) Supply amount of (2): 50 to 1000sccm
Degree of vacuum in vacuum chamber: 1.0 to 3.5Pa
Applied power from the power supply for plasma generation: 1.0-3.0 kW
Frequency of power supply for plasma generation: 70kHz
Conveying speed of resin base material: 3 to 6m/min
The gas barrier films 1 to 9 were formed by 1 time at a transport speed of 3 m/min. The gas barrier films 10 to 12 were formed at 2 times at a transport speed of 6m/min, and the oxygen gas supply amounts at the 1 st time (lower layer side) and the 2 nd time (upper layer side) were formed at the supply amounts (sccm) shown in table 1.
< method for measuring layer thickness of gas barrier layer >
The depth from the outermost surface to the interface with the substrate in the stacking direction of the gas barrier layers was measured by cross-sectional observation using a Transmission Electron Microscope (TEM) for the layer thickness of the gas barrier layers. In the present invention, the layer thickness was arbitrarily measured at 10 positions, and the average value was defined as the layer thickness of the gas barrier layer.
(TEM image of a cross section in the layer thickness direction)
For TEM observation of the cross section, a thin slice was prepared using the following Focused Ion Beam (FIB) processing apparatus for an observation sample, and then TEM observation was performed. Here, when the sample was continuously irradiated with the electron beam, a difference in contrast occurred between a portion damaged by the electron beam and a portion not damaged, and therefore the layer thickness of the gas barrier layer was measured by the difference in contrast.
(FIB working)
The device comprises the following steps: SMI2050 manufactured by SII
Processing ions: ga (30kV)
Thickness of the sample: 100 to 200nm
(TEM observation)
The device comprises the following steps: JEM2000FX manufactured by Japan Electron System (acceleration Voltage: 200kV)
Analysis of gas Barrier layer
(measurement of element distribution Curve)
The gas barrier layer formed as described above was subjected to XPS depth profile measurement under the following conditions, and a carbon profile, a silicon profile, and an oxygen profile were obtained with respect to the distance from the surface of the thin film layer in the layer thickness direction.
Etching ion species: argon (Ar)+)
Etch Rate (SiO)2Thermal oxide film conversion value): 0.05nm/sec
Etch Spacer (SiO)2Conversion value): 2nm
X-ray photoelectron spectroscopy apparatus: model name "VG ThetaProbe" manufactured by Thermo Fisher Scientific Inc "
Irradiation with X-ray Single Crystal spectroscopic AlK α
Spot and size of X-ray: oval shape of 800 μm × 400 μm
By performing the wide scan spectral analysis for measuring the entire layer area of the gas barrier layer as described above, a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve were obtained. Wherein the depth from the outermost surface side in the layer thickness direction of the gas barrier layer when the composition ratio of oxygen atoms (O), which is a part of the total composition forming the gas barrier layer, is 30% or less is calculated and is taken as the position of the interface. In the thickness direction of the gas barrier layer, the analysis of the silicon atoms, oxygen atoms, and carbon atoms in the gas barrier layer was performed as follows, with the outermost surface of the gas barrier layer being 0% and the interface with the substrate being 100%.
(analysis of silicon atom, oxygen atom and carbon atom of gas Barrier layer)
The depth of the gas barrier layer in the layer thickness direction was calculated as the ratio (%) of each atom when the total amount of the composition ratios converted from the ratios of the peak intensities derived from silicon atoms, oxygen atoms and carbon atoms, which were obtained by the X-ray photoelectron spectroscopy, was taken as 100%. Further, with respect to carbon atoms, the bonding state of carbon was analyzed by high-resolution spectroscopy (narrow scan analysis) of C1 s. Specifically, the carbon atoms were divided into 5 bonding groups of (1) C-C, C ═ C and C-H, (2) C-SiO, (3) C-O, (4) C ═ O, and (5) O-C-O, and the ratio of carbon atoms from each group was calculated from the composition ratio converted from the ratio of peak intensities of each spectrum.
Here, the proportion of the composition ratio converted from the ratio of peak intensities derived from C-C, C ═ C and C-H bonds (the above (1)) analyzed based on the waveform of C1s concerning carbon atoms is given as a proportion X (%) assuming that the total amount of the composition ratios converted from the ratios of peak intensities derived from silicon atoms, oxygen atoms and carbon atoms in the layer thickness direction of the gas barrier layer is 100%.
Table 1 shows the maximum value (%), the average value (%), and the minimum value (%) of the ratio X in the region of 5 to 30% of the layer thickness and the region of 30 to 95% of the layer thickness, where 0% is the outermost surface of the gas barrier layer and 100% is the interface with the substrate, with respect to the layer thickness direction of the gas barrier layer.
Fig. 2 shows a graph of the analysis results of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier film 5 of the present invention. In addition, as a reference example, a graph of the analysis results of silicon atoms, oxygen atoms, and carbon atoms in the gas barrier film 1 of the comparative example is shown in fig. 4.
The coordinate diagrams in fig. 2 and 4 show the horizontal axis as the depth of the gas barrier layer in the layer thickness direction (the depth (%) when the outermost surface is 0% and the interface with the substrate is 100%), and the vertical axis as the proportion (%) of each atom when the total amount of the composition ratios converted from the ratios of the peak intensities of silicon atoms, oxygen atoms, and carbon atoms obtained by X-ray photoelectron spectroscopy is 100%. Here, the ratio of the carbon atoms divided into the above-mentioned 5 bonding groups is shown. In fig. 2 and 4, (1) to (5) correspond to carbon atoms derived from (1) C-C, C ═ C and C-H, (2) C-SiO, (3) C-O, (4) C ═ O, (5) O-C-O, (6) corresponds to an oxygen atom, and (7) corresponds to a silicon atom, respectively.
Evaluation of gas Barrier film
< evaluation of gas Barrier Property >
(1) Determination of Water Vapor Transmission Rate (WVTR)
For each gas barrier film produced, the water vapor permeability [ g/(m) at 38 ℃ and 90% RH was measured using an MOCON water vapor permeability measuring apparatus Aquatran manufactured by MOCON2Sky)]The gas barrier properties were evaluated according to the following evaluation grades.
The evaluation results are shown in table 1. In the present invention, the water vapor permeability is less than 0.100 g/(m)2Day) was determined to be acceptable (class 3 to 5).
5: the water vapor permeability is less than 0.005 g/(m)2Sky)
4: the water vapor permeability is 0.005 g/(m)2Day) or more and less than 0.010 g/(m)2Sky)
3: the water vapor permeability is 0.010 g/(m)2Day) or more and less than 0.100 g/(m)2Sky)
2: the water vapor permeability is 0.100 g/(m)2Day) or more and less than 0.500 g/(m)2Sky)
1: the water vapor permeability is 0.500 g/(m)2Day) above
< evaluation of reduction in gas barrier property due to contact between the front and back surfaces during winding of roll: evaluation of flaw resistance
The gas barrier films produced were wound in a roll shape with a length of 10m of each gas barrier film having a radius of 3.8cm and a tension of 20N/m, and the number of corroded portions obtained by the calcium test was compared with the number of corroded portions of the gas barrier films which were not wound in a roll shape, and the increase rate of the corroded portions was evaluated.
The calcium test is described below. On the surface (outermost surface) of the gas barrier layer, metallic calcium was deposited by masking the portions other than the portions (1 side of a square 5cm square) of the barrier film sample where gas is to be deposited, using a vacuum deposition apparatus (JEE-400, manufactured by japan electronics corporation). Then, the mask was removed while maintaining a vacuum state, and aluminum was evaporated on the calcium evaporation surface from another metal evaporation source. After sealing with aluminum, the vacuum state was released, and quartz glass having a thickness of 0.2mm was rapidly allowed to face the aluminum sealing side through an ultraviolet-curable resin for sealing (manufactured by ナガセケムテックス) in a dry nitrogen atmosphere, and irradiated with ultraviolet rays, thereby producing a cell for evaluation.
The obtained samples (evaluation cells) sealed on both sides were stored at 60 ℃ under high temperature and high humidity at 90% RH for 360 hours, and then the corrosion sites of the Ca vapor deposition layer newly grown from the initial state were observed with an optical microscope, and evaluated according to the following evaluation scale. In the present invention, the case where the increase rate of the number of corroded sites is less than 50% (class 3 to 5) is defined as a pass. The evaluation results are shown in table 1.
In order to confirm that there was no permeation of water vapor from other than the gas barrier film surface, the comparative sample was prepared by storing a sample in which a 0.2mm thick quartz glass plate was used and metal calcium was deposited in place of the gas barrier film sample at the same high temperature and high humidity of 60 ℃ and 90% RH, and it was confirmed that no corrosion spot having a diameter exceeding 100 μm was generated even after 1000 hours had elapsed.
5: no change in the number of corroded sites was observed
4: the increase rate of the number of corroded sites was less than 10%
3: the increase rate of the number of corroded sites is 10% or more but less than 50%
2: the increase rate of the number of corroded sites is 50% or more but less than 100%
1: the increase rate of the number of corroded sites exceeds 100%
< evaluation of the number of cracks generated in the cut surface at the time of cutting: evaluation of crack resistance >
Each gas barrier film was cut into a 10cm square size from the outermost surface side of the gas barrier layer toward the thickness direction of the gas barrier layer using DISK CUTTER DC-230(CADL corporation), and then each cut end portion was observed with a magnifying glass to confirm the total number of cracks generated on the four sides, and suitability for cutting was evaluated according to the following criteria. In the present invention, the case where the number of cracks generated is 5 or less (class 3 to 5) is defined as a pass. The evaluation results are shown in table 1.
5: no crack generation was found at all
4: the number of cracks generated is 1 to 2
3: the number of cracks generated is 3 to 5
2: the number of cracks generated is 6 to 10
1: the number of cracks generated is 11 or more
From the above results, it is understood that the gas barrier film of the present invention is a gas barrier film having good gas barrier properties, little reduction in gas barrier properties due to the contact of the front and back surfaces at the time of roll winding, and suppressed generation of cracks in the cut surface at the time of cutting. Whereas the gas barrier film of the comparative example was inferior in any item.
Industrial applicability
The gas barrier film of the present invention has good gas barrier properties, and is reduced in the reduction of gas barrier properties due to the contact between the front and back surfaces during roll winding, and the occurrence of cracks during cutting is suppressed. Such a gas barrier film can be suitably used for electronic devices requiring a high gas barrier property, such as organic electroluminescent devices and liquid crystal display devices.
Description of reference numerals
1 gas barrier film
2 base material
3 gas barrier layer
10 manufacturing device
12 delivery roller
13 to 18 conveying roller
19. 20 film-forming roller
21 gas supply pipe
22 power supply for plasma generation
23. 24 magnetic field generating device
25 take-up roll
27. 29 transfer system chamber
28 film forming chamber
30. 31 connecting part
Claims (6)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015225266 | 2015-11-18 | ||
| JP2015-225266 | 2015-11-18 | ||
| PCT/JP2016/082653 WO2017086170A1 (en) | 2015-11-18 | 2016-11-02 | Gas barrier film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108349210A CN108349210A (en) | 2018-07-31 |
| CN108349210B true CN108349210B (en) | 2020-05-12 |
Family
ID=58718703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680066364.7A Expired - Fee Related CN108349210B (en) | 2015-11-18 | 2016-11-02 | Gas barrier film |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6897567B2 (en) |
| CN (1) | CN108349210B (en) |
| WO (1) | WO2017086170A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1795289A (en) * | 2003-03-28 | 2006-06-28 | 东洋制罐株式会社 | Chemical vapor deposition film formed by plasma cvd process and method for forming same |
| JP2009154449A (en) * | 2007-12-27 | 2009-07-16 | Toppan Printing Co Ltd | Barrier film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4424033B2 (en) * | 2003-08-08 | 2010-03-03 | 東洋製罐株式会社 | Deposition film by plasma CVD method |
| WO2012046767A1 (en) * | 2010-10-08 | 2012-04-12 | 住友化学株式会社 | Layered film |
-
2016
- 2016-11-02 CN CN201680066364.7A patent/CN108349210B/en not_active Expired - Fee Related
- 2016-11-02 WO PCT/JP2016/082653 patent/WO2017086170A1/en active Application Filing
- 2016-11-02 JP JP2017551812A patent/JP6897567B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1795289A (en) * | 2003-03-28 | 2006-06-28 | 东洋制罐株式会社 | Chemical vapor deposition film formed by plasma cvd process and method for forming same |
| JP2009154449A (en) * | 2007-12-27 | 2009-07-16 | Toppan Printing Co Ltd | Barrier film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6897567B2 (en) | 2021-06-30 |
| JPWO2017086170A1 (en) | 2018-08-30 |
| CN108349210A (en) | 2018-07-31 |
| WO2017086170A1 (en) | 2017-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104220249B (en) | Stacked film, Organnic electroluminescent device, photoelectric conversion device and liquid crystal display | |
| US8846187B2 (en) | Transparent gas barrier film and method for producing transparent gas barrier film | |
| TWI647110B (en) | Method for manufacturing laminate | |
| WO2014123201A1 (en) | Gas barrier film and method for manufacturing same | |
| CN105848880B (en) | Laminated films and flexible electronics | |
| WO2015098671A1 (en) | Laminate film and flexible electronic device | |
| CN100559513C (en) | transparent conductive film | |
| JP2012517530A (en) | Two-layer barrier on polymer substrate | |
| JP2004160836A (en) | Method for manufacturing gas barrier film | |
| CN105848881B (en) | Laminated film, organic electroluminescent device, photoelectric conversion device, and liquid crystal display | |
| WO2015115510A1 (en) | Gas-barrier film and method for manufacturing same | |
| CN108290376B (en) | Gas barrier film | |
| CN108349210B (en) | Gas barrier film | |
| CN111032338B (en) | Laminated film | |
| JP2015214049A (en) | Gas barrier film | |
| TWI772498B (en) | Laminated film | |
| JP5895855B2 (en) | Method for producing gas barrier film | |
| WO2015163358A1 (en) | Gas barrier film and manufacturing method thereof | |
| JPWO2016132901A1 (en) | Gas barrier film and method for producing the same | |
| CN108349211B (en) | Gas barrier film, lighting device and display device | |
| WO2017104357A1 (en) | Electrode for plasma cvd film formation apparatus, method for producing electrode, plasma cvd film formation apparatus, and method for producing functional film | |
| CN109415805B (en) | Method for producing gas barrier film | |
| WO2016159206A1 (en) | Gas barrier film and method for manufacturing same | |
| CN109778149B (en) | Gas barrier film, organic electroluminescent element, electronic paper, and method for producing gas barrier film | |
| JP6579098B2 (en) | Method for producing gas barrier film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200512 Termination date: 20211102 |