CN107249873B - Gas barrier film - Google Patents
Gas barrier film Download PDFInfo
- Publication number
- CN107249873B CN107249873B CN201680011616.6A CN201680011616A CN107249873B CN 107249873 B CN107249873 B CN 107249873B CN 201680011616 A CN201680011616 A CN 201680011616A CN 107249873 B CN107249873 B CN 107249873B
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- Prior art keywords
- layer
- gas barrier
- silicon
- barrier film
- atom
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- 229910052689 Holmium Inorganic materials 0.000 description 1
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- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
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- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
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- 229910004481 Ta2O3 Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
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- KFDXCXLJBAVJMR-UHFFFAOYSA-N dibutylsilane Chemical compound CCCC[SiH2]CCCC KFDXCXLJBAVJMR-UHFFFAOYSA-N 0.000 description 1
- RWCLZNAGACFNEX-UHFFFAOYSA-N dihexylsilane Chemical compound CCCCCC[SiH2]CCCCCC RWCLZNAGACFNEX-UHFFFAOYSA-N 0.000 description 1
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- SCTSYHSKWVXLNV-UHFFFAOYSA-N methyl(pentyl)silane Chemical compound CCCCC[SiH2]C SCTSYHSKWVXLNV-UHFFFAOYSA-N 0.000 description 1
- ONUDQGKJYPMMMB-UHFFFAOYSA-N methyl(propyl)silicon Chemical compound CCC[Si]C ONUDQGKJYPMMMB-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical class CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
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- 239000005011 phenolic resin Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- TZPUFQUQYUYVQC-UHFFFAOYSA-N phenylsilylmethanamine Chemical compound NC[SiH2]C1=CC=CC=C1 TZPUFQUQYUYVQC-UHFFFAOYSA-N 0.000 description 1
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- 239000002952 polymeric resin Substances 0.000 description 1
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- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 description 1
- 125000002206 pyridazin-3-yl group Chemical group [H]C1=C([H])C([H])=C(*)N=N1 0.000 description 1
- 125000004940 pyridazin-4-yl group Chemical group N1=NC=C(C=C1)* 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003252 quinoxalines Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- 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
Abstract
The present invention provides a kind of gas barrier film of excellent in te pins of durability under hot and humid environment.A kind of gas barrier film includes layer (A) on resin base material, is formed containing transistion metal compound, also, by gas phase membrane formation process;Silicon-containing layer (B), it connects with the layer (A) and obtains by the following method, the method includes the coating fluid containing silicon-containing compound is coated and is dried, wherein, in the atom composition distribution map obtained when carrying out XPS composition analysis along the thickness direction of the gas barrier film, with SiMxNyWhen indicating composition, there is the region (a) for meeting following formula (1) and formula (2), SiMxNy0.2≤x≤3.0 (1), 0≤y≤0.6 (2).
Description
Technical field
The present invention relates to a kind of gas barrier films.
Background technique
In flexible electrical equipment, particularly flexible organic el device, it can be used gas barrier film as substrate film or sealing
Film.To the gas barrier film for these equipment, it is desirable that compared with high barrier.
In general, gas barrier film is by utilizing gas phases membrane formation process shapes on base material film such as vapour deposition method, sputtering method, CVD method
It is manufactured at inorganic barrier layer.In recent years, it begins one's study and energy is applied to the precursor layer for being coated with solution on substrate and being formed, from
And form the manufacturing method of gas barrier layer.The research for using polysilazane compounds as precursor is especially carried out extensively, as simultaneous
The technology of high productivity and barrier property of the tool based on coating is being studied.Especially with the standard point that wavelength is 172nm
The modification of the polysilazane layer of sub-light is concerned.
Here, (being equivalent to U.S. Patent Application Publication No. 2014/374665 at International Publication No. 2011/122547
Specification) in disclose a kind of formed body, have in the layer containing polysilazane compounds inject hydrocarbon compound from
Layer obtained from son.In addition, (being equivalent to U.S. Patent Application Publication No. 2010/ in Japanese Unexamined Patent Application Publication 2009-503157 bulletin
No. 166977 specifications) in disclose that there are as below methods: by the solution coating containing polysilazane and catalyst on substrate, then
It removes solvent and forms polysilazane layer, then, in the atmosphere containing vapor, with the wavelength components contained lower than 230nm
VUV radioactive ray and the UV radioactive ray of the wavelength components containing 230~300nm above-mentioned polysilazane layer is irradiated, by
This, forms gas barrier layer on substrate.Also, a kind of flexible gas barrier film is disclosed in Japanese Unexamined Patent Publication 2009-255040 bulletin
Manufacturing method comprising: polysilazane is applied on resin base material and forms the first step of film thickness 250nm polymer film below
Suddenly;To the second step for being formed by polymer film irradiation vacuum-ultraviolet light;Weight on the film formed in above-mentioned second step
The third step answering above-mentioned first step and above-mentioned second step and overlapped film and being formed.
Summary of the invention
But (U.S. Patent Application Publication No. just is equivalent to International Publication No. 2011/122547 with quasi-molecule light
No. 2014/374665 specification), Japanese Unexamined Patent Application Publication 2009-503157 bulletin (be equivalent to U.S. Patent Application Publication No. 2010/
No. 166977 specifications) and Japanese Unexamined Patent Publication 2009-255040 bulletin documented by polysilazane be modified and the resistance that is formed
For gas-bearing formation, although gas barrier property is good in a low temperature of 40 DEG C or so, 80 DEG C of 85%RH high temperature and humidity very
Under harsh environment, it is known that gas barrier property timely reduces.
As described above, seeking to inhibit the gas barrier layer as obtained from being modified polysilazane under the condition of high temperature and high humidity
Performance deterioration, so as to be used as electronic equipment gas barrier film.
Therefore, the object of the present invention is to provide a kind of gas barrier films of excellent in te pins of durability under hot and humid environment.
The present inventor in order to solve the above technical problems, has made intensive studies.The result found that passing through a kind of choke
Property film, solve above-mentioned technical problem, the gas barrier film includes layer (A) on resin base material, contain transition metal compound
Object, and formed by gas phase membrane formation process;Silicon-containing layer (B) connects with the layer (A) and obtains by the following method, described
Method includes being coated with the coating fluid containing silicon-containing compound and being dried, and through-thickness obtain when XPS composition analysis
Atom composition distribution map in, comprising having the region that specifically forms, thus complete the present invention.
That is, the present invention is a kind of gas barrier film, included on resin base material
Layer (A), forms containing transistion metal compound, also, by gas phase membrane formation process;
Silicon-containing layer (B) connects with the layer (A) and obtains by the following method, and the method includes coatings to contain
The coating fluid of silicon compound is simultaneously dried, wherein
Along the gas barrier film thickness direction carry out XPS composition analysis when obtain atom composition distribution map in, with
SiMxNyWhen indicating composition, there is the region (a) for meeting following formula (1) and formula (2),
[mathematical expression 1]
SiMxNy
0.2≤x≤3.0 (1)
0≤y≤0.6 (2)
M: transition metal
X: transition metal and silicon atom there are atomic ratios
Y: nitrogen-atoms and silicon atom there are atomic ratios.
Detailed description of the invention
Fig. 1 is the diagrammatic cross-section for indicating the gas barrier film of an embodiment of the invention, and 10 be gas barrier film, and 11 are
Substrate, 12 be layer (B), and 13 be layer (A).
Fig. 2 is the diagrammatic cross-section for indicating the gas barrier film of other embodiments of the present invention, and 10 be gas barrier film, and 11 are
Substrate, 12 be layer (B), and 13 be layer (A).
Fig. 3 is the diagrammatic cross-section of vacuum ultraviolet beam irradiating apparatus used in embodiment, and 1 is device room, and 2 is with photographs
The Xe Excimer lamp of the double-sleeve structure of the vacuum ultraviolet of 172nm is penetrated, 3 be the frame for having both the Excimer lamp of external electrode, and 4 are
Sample table, 5 be the sample for being formed with polysilazane compounds coating layer, and 6 be barn door.
Specific embodiment
The present invention is a kind of gas barrier film, and layer (A) (hereinafter, also referred to as layer (A)) is included on resin base material,
It is formed containing transistion metal compound also, by gas phase membrane formation process;Silicon-containing layer (B) (hereinafter, also referred to as layer (B)), with
The layer (A) connects and obtains by the following method, and the method includes coating fluid of the coating containing silicon-containing compound and progress
It is dry, in the atom composition distribution map obtained when carrying out XPS composition analysis along the thickness direction of the gas barrier film, with
SiMxNyWhen indicating composition, there is the region (a) for meeting following formula (1) and formula (2) (hereinafter, also referred to as region (a)).Have
The gas barrier film of the invention of this composition excellent in te pins of durability under hot and humid environment.
[mathematical expression 2]
SiMxNy
0.2≤x≤3.0 (1)
0≤y≤0.6 (2)
M: transition metal
X: transition metal and silicon atom there are atomic ratios
Y: nitrogen-atoms and silicon atom there are atomic ratios
Using gas barrier film of the invention why said effect can be obtained, details is not yet clear, but is contemplated that such as
The lower mechanism.It should be noted that following mechanism is to speculate, the present invention is not by following mechanism any restrictions.
Including coating fluid of the coating containing silicon-containing compound and silicon-containing layer (B) obtained from being dried is by with specific
Composition and show gas barrier property.In addition, from by gas phase membrane formation process formation the case where it is different, layer (B) form a film when almost without
The foreign matters such as particle are mixed into, and can form the considerably less gas barrier layer of defect.But the layer (B) is not complete stability relative to oxidation,
Sometimes it is slowly oxidized under hot and humid environment, gas barrier property reduces.
In contrast, in gas barrier film of the invention, the layer (A) for being adjacent to layer (B) contains transistion metal compound, along resistance
The thickness direction of gas film carries out in the atom obtained when XPS composition analysis composition distribution map, with SiMxNyWhen indicating composition,
With the region (a) for meeting above-mentioned formula (1) and formula (2).Layer (A) is oxidized easily compared with layer (B), result, it is believed that layer (A) is first
It is first oxidized, thus can inhibit the oxidation of layer (B), thus the excellent in te pins of durability under hot and humid environment.And think, due to tool
There is region (a), the durability under hot and humid environment further increases.
Hereinafter, the preferred embodiment of the present invention will be described.It should be noted that the present invention is not limited to
The following embodiments and the accompanying drawings.In addition, for convenience of description, the dimensional ratios of attached drawing are exaggerated, it is sometimes different from actual ratio.
In addition, in the description of the drawings, adding identical symbol to identical element, the repetitive description thereof will be omitted.
In the present specification, unless otherwise specified, the measurement such as transitivity is operated in room temperature (20~25 DEG C)/relatively wet
It is measured under conditions of 40~50%RH of degree.
Fig. 1 is the diagrammatic cross-section for indicating the gas barrier film of an embodiment of the invention.The gas barrier film 10 of Fig. 1 according to
It is secondary to be configured with substrate 11, layer (B) 12 and layer (A) 13.In addition, Fig. 2 is the gas barrier film for indicating other embodiments of the present invention
Diagrammatic cross-section.The gas barrier film 10 of Fig. 2 is configured in order substrate 11, layer (A) 13 and layer (B) 12.As long as that is, layer (A) and
Layer (B) is adjacent and configures, then can be the sequence of layer (A), layer (B) from substrate side, or the sequence of layer (B), layer (A).
In addition, not only in the form of a face forming layer (A) of substrate, layer (B), but also can be in the two sides forming layer (A) and layer of substrate
(B).And it is possible to configure other layers between substrate and each layer or on each layer.
It is configured at from due to layer (A) on the layer of substrate apparent surface (B), layer (A) is easier to be oxidized, and sends out more significantly
From the aspect of waving based on layer (A) to the protection of layer (B), preferably it is arranged in order with substrate, layer (B), layer (A).
[layer of (A) containing transistion metal compound]
Gas barrier film of the invention has the layer (A) containing transistion metal compound formed by gas phase membrane formation process.Layer
(A) it is oxidized easily compared with layer (B) in electrochemistry, thus the oxidation of inhibition layer (B).
As transistion metal compound contained in layer (A), it is not particularly limited, it can be mentioned, for example: the oxygen of transition metal
Compound, nitride, carbide, nitrogen oxides or oxycarbide.Wherein, go out from the viewpoint of the oxidation of more effectively inhibition layer (B)
Hair, transistion metal compound is preferably transition metal oxide.Transistion metal compound can be used alone, can also group
It closes and uses two or more.
Transition metal atoms refer to from the 3rd race's element to the 12nd race's element, as transition metal, can enumerate: Sc, Ti, V,
Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Tc、Ru、Pd、Ag、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、
Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt and Au etc..
Wherein, the preferably low metal of oxidation-reduction potential compared with silicon of the transition metal in transistion metal compound.It is logical
The layer for being adjusted to the compound containing the low transition metal of the oxidation-reduction potential compared with silicon is crossed, more good barrier can be obtained
Property.The concrete example of the metal low as the oxidation-reduction potential compared with silicon, it can be mentioned, for example: niobium, tantalum, vanadium, zirconium, titanium, hafnium, yttrium,
Lanthanum, cerium etc..These metals can be used alone or two or more mixes and uses.Wherein, especially as the 5th race's element
Niobium, tantalum, vanadium can be it is preferable to use since the effect of the oxidation of its inhibition layer (B) is high.That is, of the invention preferred one
Embodiment is a kind of gas barrier film, wherein transition metal is at least one kind of metal in vanadium, niobium and tantalum.Also, from light
From the perspective of learning characteristic, the good compound of the transparency is particularly preferably can be obtained in the transition metal in transistion metal compound
Niobium, tantalum.
The standard oxidationreduction potential of main metal is shown in following tables.
[chemical formula 1]
Metal | Standard oxidationreduction potential (V) | The oxide of stoichiometry | Maximum valence mumber |
Si | -0.91 | SiO2 | 4 |
Nb | -1.10 | NbO2.5 | 5 |
Ta | -1.12 | TaO2.5 | 5 |
V | -1.19 | VO2.5 | 5 |
Zr | -1.53 | ZrO2 | 4 |
Ti | -1.63 | TiO2 | 4 |
Hf | -1.70 | HfO2 | 4 |
Y | -2.37 | YO1.5 | 3 |
La | -2.37 | LaO1.5 | 3 |
Ce | -2.50 | CeO2 | 4 |
For the content of the transistion metal compound in layer (A), as long as generating effect of the invention, do not limit especially
Fixed, the content of transistion metal compound is preferably 50 mass % or more relative to the gross mass of layer (A), more preferably 80 mass %
More than, further preferably 95 mass % or more, particularly preferably 98 mass % or more, most preferably 100 mass % (i.e. layers
(A) it is made of transistion metal compound).
From the viewpoint of being easily adjusted the ratio of components of metallic element and oxygen, the forming method of layer (A) is gas phase membrane formation process.
As gas phase membrane formation process, it is not particularly limited, it can be mentioned, for example: the growth of the physical vapors such as sputtering method, vapour deposition method, ion plating method
Method (PVD) method, plasma CVD (chemical vapor deposition (chemical vapor deposition)) method, ALD (atomic layer deposition
Product (Atomic Layer Deposition)) etc. chemical vapor depositions method.Wherein, it damages from can not be generated to lower layer
Film is formed from the aspect of having high productivity preferably by sputtering method.
Using sputtering method film forming can by 2 pole sputterings, magnetron sputtering, use have centre frequency field dual magnetic
Keyholed back plate (DMS) sputtering, ion beam sputtering, ECR sputtering etc. are used alone or two or more combines and uses.In addition, the application of target
Mode is suitably selected according to target type, and any sputtering of DC (direct current) sputtering and RF (high frequency) sputtering can be used.In addition,
The reactive sputtering method that the transition mode of metal mode and the centre as oxide mode is utilized can be used.Pass through control
Sputtering phenomenon to become transitional region, object film forming can be oxidized metal with high film forming speed, therefore preferably.Carrying out DC
When sputtering or DMS are sputtered, transition metal is used in its target, and oxygen is imported in process gas, it is possible thereby to form transition
The film of metal oxide.In addition, transition metal oxide can be used in the case where being formed a film with RF (high frequency) sputtering
Target.As the non-active gas for process gas, He, Ne, Ar, Kr, Xe etc. can be used, it is preferable to use Ar.Also,
By importing oxygen, nitrogen, carbon dioxide, carbon monoxide in process gas, can make the oxide of transition metal, nitride,
The transistion metal compounds film such as oxynitride, oxycarbide.As the membrance casting condition in sputtering method, application electric work can be enumerated
Rate, discharge current, discharge voltage, time etc., but these conditions can be fitted according to the material of sputtering equipment or film, film thickness etc.
Work as selection.
Wherein, higher from rate of film build, there is higher productivity from the aspect of, preferably the oxide of transition metal is used
Make the sputtering method of target.
Layer (A) can be single layer, or 2 layers or more of laminated construction.The laminated construction for being 2 layers or more at layer (A)
When, transistion metal compound contained in layer (A) may be the same or different.
Layer (A) is considered to have the function of the oxidation of inhibition layer (B) and the layer of gas barrier property is maintained therefore not necessarily to need
Want gas barrier property.Therefore, for layer (A), even if for effect can also be played than relatively thin layer.Specifically, in substrate-layer
(B) in the case that the layer of-layer (A) is constituted, from the viewpoint of the inner evenness of gas barrier property, the thickness of layer (A) (is being 2 layers
It is its overall thickness in the case where above laminated construction) it is preferably 1~200nm, more preferably 2~100nm, further preferably
For 3~50nm.Especially if it is 50nm hereinafter, then the productivity of layer (A) film forming further increases.In addition, in substrate-layer
(A) in the case that the layer of-layer (B) is constituted, from the viewpoint of the inner evenness of gas barrier property, the thickness of layer (A) (is being 2 layers
It is its overall thickness in the case where above laminated construction) it is preferably 1~200nm, more preferably 2~150nm, further preferably
For 10~150nm.
[(B) siliceous layer]
Layer (B) is layer siliceous obtained from including coating fluid of the coating containing silicon-containing compound and being dried.
It as the above-mentioned silicon-containing compound that can be used in the present invention, can enumerate for example: polysiloxanes, poly- sesquialter
Siloxanes, polysilazane, polysilazane, polysilane, Polycarbosilane etc..
Wherein, preferably have at least one kind of in silicon-nitrogen key, silicon-hydrogen bond and silicon-silicon bond.
As the preferred concrete example of silicon-containing compound, it is preferable to use the poly- silicon with silicon-nitrogen key and silicon-hydrogen bond
Azane, with silicon-nitrogen key polysilazane, the polysiloxanes with silicon-hydrogen bond, the polysilsesquioxane with silicon-hydrogen bond, tool
There is the polysilane of silicon-silicon bond.
There is at least one kind of silicon-containing compound in silicon-nitrogen key, silicon-hydrogen bond and silicon-silicon bond by using being originated from
Silicon-containing layer (B), with SiMxNyOzWhen indicating the atom composition of region (a), the region of (4+ax)-easy to form (3y+2z) > 0
(b).Here, M is transition metal, a is the valence mumber (maximum valence mumber) of the stoichiometry of transition metal M.
Silicon-containing layer (B) of the invention includes to be coated with the coating fluid containing silicon-containing compound and be dried to obtain.Layer (B)
Show gas barrier property, in addition, it is different from the case where formation with gas phase membrane formation process, there is no the foreign matters such as particle to be mixed into film forming, therefore,
The gas barrier layer few as defect.Layer (B) can be single layer, or 2 layers or more of laminated construction.
About the concrete example of polysiloxanes, polysilsesquioxane and polysilazane, Japanese Unexamined Patent Publication 2012- can be enumerated
The compound recorded in paragraph " 0093 "~" 0121 " of No. 116101 bulletins.As polysiloxanes, preferably hydrogenation (hydrogen) poly- silicon
Oxygen alkane.
The form of polysilane is not particularly limited, and can be non-annularity polysilane (the poly- silicon of straight-chain polysilane, branched
Alkane, mesh-shape polysilane etc.) or homopolymers such as cyclic polysilanes, or random copolymer, block copolymer, alternately altogether
The copolymers such as polymers, comb type copolymer.
In the case where polysilane is non-annularity polysilane, the terminal groups (terminal substituent) of polysilane can be former for hydrogen
Son, or halogen atom (chlorine atom etc.), alkyl, hydroxyl, alkoxy, silicyl etc..
Polysilane is used as concrete example, can enumerate: polydimethylsiloxane, poly- (methyl-propyl silane), poly- (methyl butyl silicon
Alkane), poly- (methyl amyl silane), poly- (dibutyl silane), the poly-diakyls silane, poly- (diphenyl silicon such as poly- (dihexyl silane)
Alkane) etc. the homopolymers such as poly- diaryl silane, poly- (aminomethyl phenyl silane) etc. poly- (alkyl aryl silanes);Dimethylsilane-methyl
The copolymer of the dialkyl silanes such as hexyl silane copolymer and other dialkyl silanes, phenyl silane-aminomethyl phenyl silane copolymerization
The aryl-silanes such as object-alkyl aryl silanes copolymer, dimethylsilane-aminomethyl phenyl silane copolymer, dimethylsilane-phenyl
Hexyl silane copolymer, dimethylsilane-methyl naphthalene base silane copolymer, methyl-propyl silane-aminomethyl phenyl silane copolymer
Copolymers such as equal dialkyl silanes-alkyl aryl silanes copolymer etc..
Polycarbosilane is the high-molecular compound with (- Si-C-) key on main chain in the molecule.Wherein, as being used for
Polycarbosilane of the invention preferably comprises the repetitive unit indicated with following formula (d).
[chemical formula 2]
In formula, Rw, Rv separately indicate the heterocycle of hydrogen atom, hydroxyl, alkyl, aryl, alkenyl or 1 valence.It is multiple
Rw, Rv can be identical respectively, can also be different.
The heterocycle of heterocycle as 1 valence, as long as former containing at least one oxygen atom, nitrogen-atoms, sulphur except carbon atom
Heteroatomic 3~10 yuan of the cyclic compound such as son, is not particularly limited.
The heterocycle of 1 valence is used as concrete example, can enumerate: 2- pyridyl group, 3- pyridyl group, 4- pyridyl group, 2- thienyl, 3-
Thienyl, 2- furyl, 3- furyl, 3- pyrazolyl, 4- pyrazolyl, 2- imidazole radicals, 4- imidazole radicals, 1,2,4- triazine -3- base,
1,2,4- triazine -5- base, 2- pyrimidine radicals, 4- pyrimidine radicals, 5- pyrimidine radicals, 3- pyridazinyl, 4- pyridazinyl, 2- pyrazinyl, 2- (1,3,
5- triazine) base, 3- (1,2,4- triazine) base, 6- (1,2,4- triazine) base, 2- thiazolyl, 5- thiazolyl, 3- isothiazolyl, 5- be different
Thiazolyl, 2- (1,3,4- thiadiazoles) base, 3- (1,2,4- thiadiazoles) base, 2- oxazolyl, 4- oxazolyl, 3- isoxazolyl, 5-
Isoxazolyl, 2- (1,3,4- oxadiazoles) base, 3- (1,2,4- oxadiazoles) base, 5- (1,2,3- oxadiazoles) base etc..
These groups can have the substituent groups such as alkyl, aryl, alkoxy, aryloxy group on arbitrary position.
In formula, R indicates the heterocycle of alkylidene, arlydene or divalent.
As the alkylidene of R, can enumerate: methylene, ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene,
The alkylidene of the carbon numbers 1~10 such as hexa-methylene, eight methylene.
It as arlydene, can enumerate: to the arlydene of the carbon numbers 6~20 such as phenylene, Isosorbide-5-Nitrae-naphthylene, 2,5- naphthylene.
As the heterocycle of divalent, as long as carbon atom is also containing in the hetero atoms such as oxygen atom, nitrogen-atoms, sulphur atom
Divalent group derived from 3~10 yuan of the heterocyclic compound institute of at least one, is just not particularly limited.
The concrete example of heterocycle as divalent can be enumerated: the thiophene diyl base such as 2,5- thiophene diyls;2,5- furans diyl
The furans diyl base such as base;The selenophens diyl base such as 2,5- selenophen diyl;Pyrroles' diyl base such as 2,5- pyrroles's diyl base;2,5- pyridine two
The pyridines diyl bases such as Ji Ji, 2,6- pyridine diyl base;2,5- thieno [3,2-b] thiophene diyl base, 2,5- thieno [2,3-b]
The thienothiophenes diyl base such as thiophene diyl base;The quinoline diyl base such as 2,6- quinoline diyl;1,4- isoquinolin diyl base, 1,5- are different
The isoquinolin diyl base such as quinoline diyl base;The quinoxalines diyl bases such as 5,8- quinoxaline diyl base;4,7- benzo [1,2,5] thiadiazoles
The benzos such as diyl base [1,2,5] thiadiazoles diyl base;The benzothiazoles diyl bases such as 4,7- benzothiazole diyl base;2,7- carbazole two
The carbazoles diyl bases such as Ji Ji, 3,6- carbazole diyl base;The phenol oxazines diyl bases such as 3,7- phenol oxazines diyl base;3,7- phenothiazine diyl
The phenothiazines diyl base such as base;2,7- dibenzo thiophene coughs up the dibenzo thiophene such as diyl and coughs up diyl;2,6- benzo [1,2-b:4,5-b '] two
Thiophene diyl, 2,6- benzo [1,2-b:5,4-b '] Dithiophene diyl, 2,6- benzo [2,1-b:3,4-b '] Dithiophene diyl, 2,
Benzene thiophenes diyls such as 6- benzo [1,2-b:3,4-b '] Dithiophene diyl etc..
It should be noted that the heterocycle of the alkylidene of R, arlydene, divalent can have on arbitrary position alkyl,
The substituent groups such as aryl, alkoxy, halogen atom.
Wherein, in formula (d), Rw, Rv are separately hydrogen atom, alkyl or aryl, further preferably R be alkylidene or
The repetitive unit of arlydene, Rw, Rv are separately hydrogen atom or alkyl, and further preferably R is the repetition of alkylidene
Unit.
The weight average molecular weight of the Polycarbosilane of repetitive unit with formula (d) expression is usually 400~12,000.
As the forming material of layer (B), more preferable polysilazane.
Polysilazane is with silicon-nitrogen key polymer, for the SiO with keys such as Si-N, Si-H, N-H2、Si3N4And two
The intermediate solid solution SiO of personxNyEqual ceramic precursors inorganic polymer.
Specifically, polysilazane preferably has following structures.
[chemical formula 3]
Logical formula (I):
-[Si(R1)(R2)-N(R3)]n-
In above-mentioned logical formula (I), R1、R2And R3It is separately hydrogen atom, substituted or non-substituted alkyl, substitution or non-
Substituted aryl, substituted or non-substituted vinyl or (trialkoxysilyl) alkyl.At this point, R1、R2And R3It respectively can be with
It is identical or can be different.
In addition, n is integer in above-mentioned logical formula (I), preferably it is determined, so as to be indicated with above-mentioned logical formula (I)
The polysilazane of structure there is 150~150,000g/ moles of number-average molecular weight.
In the compound of the structure indicated with above-mentioned logical formula (I), one of preferred mode is R1、R2And R3Whole
For the Perhydropolysilazane of hydrogen atom.
Alternatively, as polysilazane, the structure with the following general formula (II) expression.
[chemical formula 4]
Logical formula (II)
-[Si(R1’)(R2’)-N(R3’)]n’-[Si(R4’)(R5’)-N(R6’)]p-
In above-mentioned logical formula (II), R1’、R2’、R3’、R4’、R5’And R6’It is separately hydrogen atom, substituted or non-substituted
Alkyl, substituted or non-substituted aryl, substituted or non-substituted vinyl or (trialkoxysilyl) alkyl.At this point, R1’、
R2’、R3’、R4’、R5’And R6’It respectively can be identical or can be different.In addition, n ' and p are integer, preferably in above-mentioned logical formula (II)
It is determined, so that having 150~150,000g/ moles of number with the polysilazane of the structure indicated with logical formula (II)
Average molecular weight.It should be noted that n ' and p can be identical or can be different.
In the polysilazane of above-mentioned logical formula (II), preferably R1’、R3’And R6’Respectively indicate hydrogen atom, R2’、R4’And R5’Respectively
Indicate the compound of methyl;R1’、R3’And R6’Respectively indicate hydrogen atom, R2’、R4’Respectively indicate methyl, R5’Indicate the change of vinyl
Close object;R1’、R3’、R4’And R6’Respectively indicate hydrogen atom, R2’And R5’Respectively indicate the compound of methyl.
Alternatively, as polysilazane, the structure with the following general formula (III) expression.
[chemical formula 5]
Logical formula (III):
-[Si(R1”)(R2”)-N(R3”)]n”-[Si(R4”)(R5”)-N(R6”)]p”-[Si(R7”)(R8”)-N(R9”)]q-
In above-mentioned logical formula (III), R1”、R2”、R3”、R4”、R5”、R6”、R7”、R8”And R9”It is separately hydrogen atom, replaces
Or non-substituted alkyl, substituted or non-substituted aryl, substituted or non-substituted vinyl or (trialkoxysilyl) alkane
Base.At this point, R1”、R2”、R3”、R4”、R5”、R6”、R7”、R8”And R9”It respectively can be identical or can be different.
In addition, n ", p " and q are integer in above-mentioned logical formula (III), preferably it is determined, so as to have logical formula (III)
The number-average molecular weight that the polysilazane of the structure of expression is 150~150,000g/ moles.It should be noted that n ", p " and q can
With identical or can be different.
In the polysilazane of above-mentioned logical formula (III), preferably R1”、R3”And R6”Respectively indicate hydrogen atom, R2”、R4”、R5”And R8”
Respectively indicate methyl, R9”Indicate (triethoxysilyl) propyl, R7”Indicate the compound of alkyl or hydrogen atom.
On the other hand, it has the advantages that and is replaced and obtained by alkyl etc. with a part of the Si hydrogen moiety being bonded
The organopolysilazane arrived improves the cementability with the substrate as substrate and with alkyl such as methyl, and can make hard
And the ceramic membrane that crisp polysilazane is formed has toughness, in the case where further thickening (average) film thickness, can also press down
The generation in crack processed.Therefore, these Perhydropolysilazanes and organopolysilazane can be suitably selected depending on the application, it can also be into
Row is mixed and is used.
Perhydropolysilazane is estimated as that there are the structures of linear chain structure and the ring structure centered on 6 member rings and 8 member rings.Its
Molecular weight is calculated as about 600~2000 or so (in terms of polystyrene) by number-average molecular weight (Mn), there is the substance of liquid or solid, shape
State is different because of molecular weight difference.
Polysilazane is commercially available with the solution state progress for being dissolved in organic solvent, can be by commercially available product directly as layer (B)
Formation coating fluid and use.As the commercially available product of polysilazane solution, can enumerate: AZ Electronic Materials is public
Take charge of manufacture NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20,
NL150A, NP110, NP140, SP140 etc..These polysilazane solution can be used alone, or two or more can also be combined and
It uses.
As the other examples for the polysilazane that can be used in the present invention, be not restricted to hereinafter, it can be mentioned, for example:
Silicon alkoxide addition polysilazane (Japanese Unexamined Patent Publication 5-238827 public affairs obtained from reacting silicon alkoxide with above-mentioned polysilazane
Report), make glycidol react obtained from glycidol addition polysilazane (Japanese Unexamined Patent Publication 6-122852 bulletin), make alcohol
Alcohol addition polysilazane obtained from reaction (Japanese Unexamined Patent Publication 6-240208 bulletin) makes obtained from carboxylate metal reactant salt
Metal carboxylate addition polysilazane (Japanese Unexamined Patent Publication 6-299118 bulletin) keeps the acetylacetonate complex containing metal anti-
Acetylacetonate complex addition polysilazane obtained from answering (Japanese Unexamined Patent Publication 6-306329 bulletin), addition metal particle and
Obtained metal particle addition polysilazane (Japanese Unexamined Patent Publication 7-196986 bulletin) etc. carries out the poly- of ceramic at low temperature
Silazane.
In the case where using polysilazane, the containing ratio of the polysilazane in layer (B) before being irradiated as vacuum ultraviolet,
It can be 100 mass % when the gross mass of layer (B) is set as 100 mass %.In addition, the layer (B) before vacuum ultraviolet irradiation
In the case where containing the substance other than polysilazane, the containing ratio of the polysilazane in layer is preferably 10 mass % or more, 99 matter
% is measured hereinafter, more preferably 40 mass % or more, 95 mass % is hereinafter, particularly preferably 70 mass % or more, 95 mass % or less.
(layer (B), which is formed, uses coating fluid)
As the solvent for being used to prepare layer (B) formation coating fluid, as long as silicon-containing compound can be dissolved, without spy
It does not limit, does not contain the water and reactive group (such as hydroxyl or amido etc.) easily reacted with silicon-containing compound preferably,
It and relative to silicon-containing compound is inactive organic solvent, the more preferably organic solvent of aprotic.Specifically, conduct
Solvent can enumerate non-protonic solvent;Such as (aromatic naphtha is molten for pentane, hexane, hexamethylene, toluene, dimethylbenzene, Sol dimension rope
Agent, Solvesso), the hydrocarbon solvents such as aliphatic hydrocarbons, ester ring type hydrocarbon, the aromatic hydrocarbon such as turpentine oil;The halogen such as methylene chloride, trichloroethanes
Hydrocarbon solvent;The esters such as ethyl acetate, butyl acetate;The ketones such as acetone, methyl ethyl ketone;Dibutyl ethers, dioxanes, tetrahydrofuran
The ethers such as equal fatty ethers, ester ring type ether: such as tetrahydrofuran, dibutyl ethers, mono- and polyalkyleneglycol dialkylether (two
Glyme class) etc..The purpose of above-mentioned solvent is with the solubility of polysilazane or the evaporation rate of solvent is consistent and selects, can
To be used alone, or can also be used in the form of mixture of more than two kinds.
Layer (B) formation is not particularly limited with the concentration of the silicon-containing compound in coating fluid, film thickness or coating due to layer
Working life of liquid is different and different, preferably 1~80 mass %, more preferably 5~50 mass %, further preferably 10~40
Quality %.
In the case where carrying out the modification of layer (B), in order to promote to be modified, layer (B) formation preferably comprises catalysis with coating fluid
Agent.It as catalyst of the invention, preferably basic catalyst is applicable to, especially enumerates: N, N- diethyl ethylene diamine, N, N- bis-
Methylethanolamine, triethanolamine, triethylamine, 3- morphoinopropyl amine, N, N, N ', N '-tetramethyl -1,3- diaminopropanes,
N, N, N ', the Pd chemical combination such as Pt compound, the propionic acid Pd such as amine catalysts, the Pt acetylacetone,2,4-pentanedione such as N '-tetramethyl -1,6- diamino hexane
The metallic catalysts such as the Rh compounds such as object, Rh acetylacetone,2,4-pentanedione, N- hetero ring type compound.Wherein, it is preferable to use amine catalyst.As
The concentration of the catalyst added at this time, when using silicon compound as benchmark, preferably 0.1~10 mass %, more preferably 0.5~
The range of 7 mass %.It is excessive caused by can sharp being carried out to avoid reaction by the way that catalyst loading is set as the range
Silanol formed and reduction, the increase of film defect of film density etc..
It is formed at layer (B) in coating fluid, be can according to need using following additives enumerated.For example, cellulose ether
Class, cellulose esters;Such as the natural resins such as ethyl cellulose, NC Nitroncellulose, cellulose acetate, cellulose acetate-butyrate;
Such as rubber, rosin resin etc., synthetic resin;For example, polymer resin etc., condensation resin;Such as aminoplast, particularly urea
Resin, melamine resin, alkyd resin, acrylic resin, polyester resin or modified polyester resin, epoxy resin,
Polyisocyanate or blocked polyisocyanate, polysiloxanes etc..
(coating layer (B) forms the method for using coating fluid)
As the method being coated to layer (B) formation with coating fluid, conventionally known wet coating appropriate can be used
Method.As concrete example, can enumerate: spin-coating method, rolling method, flowing coating process, ink-jet method, spray coating method, print process, dip coating,
Casting filming therapy, stick coating method, dispensing coating process, gravure printing method etc..
Coating thickness can suitably be set according to preferred thickness or purpose.
After applied coating solution, film is dried.By the way that film is dried, can remove contained in film
Organic solvent.At this point, organic solvent contained in film can all be dried, a part of can also remain.Even if
In the case where remaining a part of organic solvent, preferred layer (B) also can be obtained.It should be noted that remaining solvent can be rear
Face is removed.
The drying temperature of film is since used substrate is different and different, and preferably 50~200 DEG C.For example, by glass
In the case that the polyethylene terephthalate substrate that glass transition temperature (Tg) is 70 DEG C is used as substrate, drying temperature is preferred
Consider deformation of substrate caused by heat etc. and is set as 150 DEG C or less.Above-mentioned temperature can be by using electric hot plate, baking oven, stove
Deng and be set.Drying time is preferably set to the short time, such as in the case where drying temperature is 150 DEG C, is preferably set to
Within 30 minutes.In addition, dry atmosphere can under air atmosphere, under nitrogen atmosphere, under argon atmospher, under vacuum atmosphere, control
The inferior any condition of the reduced atmosphere of oxygen concentration.
Film obtained from being coated to layer (B) formation with coating fluid may include before the irradiation of vacuum ultraviolet or
Dewatered process in the irradiation of vacuum ultraviolet.It is carried out as dewatered method, preferably maintenance low-humidity environment
The mode of dehumidifying.Since the humidity under low-humidity environment changes according to temperature, the relationship of temperature and humidity is in dew point temperature
The specified middle preferred mode of expression of degree.Preferred dew-point temperature is 4 DEG C or less (25 DEG C/humidity 25% of temperature), more preferably
Dew-point temperature be -5 DEG C or less (25 DEG C/humidity 10% of temperature), the maintained time is preferably appropriate according to the film thickness of layer (B)
Setting.Specifically, it is preferable that dew-point temperature is -5 DEG C hereinafter, the maintained time is 1 minute or more.It should be noted that dew
The lower limit of point temperature is not particularly limited, usually -50 DEG C or more, preferably -40 DEG C or more.From by before modification,
Or from the perspective of removing dehydration of the moisture to promote the layer (B) for being converted into silanol in modification, for preferred side
Formula.
< vacuum ultraviolet irradiates >
The film containing silicon-containing compound formed as described above can be directly set as layer (B), but can also passed through
Vacuum ultraviolet is irradiated to obtained film, carries out the conversion reaction and forming layer (B) to silicon oxynitride etc..From substrate side according to
In the secondary mode with layer (B) and layer (A), by carrying out vacuum ultraviolet irradiation, with after forming layer (B) to forming layer (A)
, be not easily susceptible to through when Conservation environment influence caused by gas barrier property deteriorate the advantages of.Successively have from substrate side layer (A) and
In the mode of layer (B), by carrying out vacuum ultraviolet irradiation, gas barrier property is improved, it is therefore preferable that carrying out vacuum ultraviolet irradiation.
Vacuum ultraviolet irradiation both may be adapted to batch process, also may be adapted to continuous processing, can be according to the tree used
The shape of aliphatic radical material and it is suitably selected.For example, the ultraviolet light for having ultraviolet light generating source can be used in the case where batch process
Firing furnace is handled.The manufacture of EYE GRAPHICS Co., Ltd. can be used for example in commonly known ultraviolet light firing furnace itself
Ultraviolet light firing furnace.In addition, can have by existing while being conveyed to it in the case where object is that strip is membranaceous
The arid region of standby ultraviolet light generating source as described above continuously irradiates ultraviolet light and carries out ceramic.Needed for ultraviolet light irradiation
The time wanted depends on composition, the concentration of substrate or layer (B) used, but generally 0.1 second~10 minutes, preferably 0.5
Second~3 minutes.
Be modified as following method caused by vacuum ultraviolet irradiation: use is than silicon-containing compound (especially polysilazane
Close object) in the big 100~200nm of interatomic bond resultant force light energy, it is preferable to use the wavelength of 100~180nm light energy,
By the bonding of atom only by being referred to as the effect of the photon of light quantum technique, directly cut off on one side, on one side progress active oxygen or
Oxidation reaction caused by ozone carries out the formation of the film containing silicon oxynitride as a result, under relatively low temperature (about 200 DEG C or less).
It should be noted that heat treatment is preferably used in combination when carrying out quasi-molecule treatment with irradiation.
As long as the vacuum ultraviolet line source in the present invention generates the light of the wavelength of 100~180nm, preferably about
172nm with the maximum excimer radiation device (such as Xe Excimer lamp) radiated, in about 185nm there is the low-pressure mercury of bright line to steam
Gas lamp and middle pressure with 230nm wavelength components below and high pressure mercury vapor lamp, Ji Yue 222nm are put with maximum
The Excimer lamp penetrated.
Wherein, ultraviolet light of the Xe Excimer lamp due to radiating the shorter 172nm of wavelength with single wavelength, shine effect
Rate is excellent.The light since the absorption coefficient of oxygen is big, micro oxygen, the oxygen atom generated free radicals with high concentration can be used
Kind or ozone.
Additionally, it is known that the energy of the light of the shorter 172nm of wavelength keeps the ability of the bonding dissociation of organic matter high.Pass through the work
Property oxygen or ozone and ultra violet radiation energy with higher, can realize the modification of film in a short time.
Excimer lamp since the generation efficiency of light is high, can apply low electric power makes its illumination.In addition, not issuing
As light cause temperature rise will because long wavelength light, in ultraviolet range, i.e., with short wavelength illumination energy, therefore,
With the feature for inhibiting irradiation object object surface temperature to rise.Therefore, suitable for flexibility such as the PET that thinks to be easy to be affected by the heat
Membrane material.
Oxygen is needed in reaction in vacuum ultraviolet irradiation, but vacuum ultraviolet caused by oxygen there are absorbing, it is therefore, purple
Efficiency in outside line irradiation process is easily reduced, and therefore, the irradiation of vacuum ultraviolet is preferably as far as possible in oxygen concentration and vapor
It is carried out in the state that concentration is low.That is, oxygen concentration when vacuum ultraviolet irradiates is preferably set to 10~20,000 volume ppm (0.001
~2 volume %), more preferably it is set as 50~10,000 volume ppm (0.005~1 volume %).In addition, the water between conversion procedure
Vapor concentration is preferably the range of 1,000~4,000 volume ppm (0.1~0.4 volume %).
As the gas full of irradiation atmosphere used when vacuum ultraviolet irradiates, it is preferably set to dry nonactive gas
Body is preferably set to drying nitrogen especially from the viewpoint of cost.The adjustment of oxygen concentration can be irradiated in library by opposite direction to be led
The flow of the oxygen, non-active gas that enter is measured, and is changed flow-rate ratio and be adjusted.
In vacuum ultraviolet irradiation process, the illumination for the vacuum ultraviolet in film coated surface that film is subject to is preferably
1mW/cm2~10W/cm2, more preferably 30mW/cm2~200mW/cm2, further preferably 50mW/cm2~160mW/cm2.Such as
Fruit its be 1mW/cm2More than, then modification efficiency improves, if it is 10W/cm2Hereinafter, can then reduce can produce in film
Abrasion or the damage to substrate.
Successively have for the irradiation energy (exposure) of vacuum ultraviolet from substrate side in film coated surface when modification
In the mode of layer (B) and layer (A), preferably 0.1~10J/cm2, more preferably 0.1~7J/cm2, further preferably 0.1~
3J/cm2.In the mode successively from substrate side with layer (A) and layer (B), preferably 1~10J/cm2, more preferably 3~7J/
cm2.If it is the range, the excessive modified caused generation in crack or the thermal deformation of resin base material can be inhibited, in addition, raw
Yield improves.
The vacuum ultraviolet used can contain CO, CO by utilizing2And CH4At least one of gas formed plasma
Body generates.Also, contain CO, CO2And CH4At least one of gas (hereinafter referred to as carbonaceous gas) can be used alone and contain
Carbon gas, preferably with rare gas or H2For predominant gas, carbonaceous gas is added on a small quantity.As the generating mode of plasma,
Capacitance coupling plasma etc. can be enumerated.
[resin base material]
As resin base material of the invention, specifically, can enumerate comprising polyester resin, methacrylic resin, methyl
Acid-co-maleic acid, polystyrene resin, transparent fluororesin, polyimides, fluorinated polyimide resin, polyamide
Resin, polyamide-imide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether-ether-ketone tree
Rouge, polycarbonate resin, ester ring type polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cyclic olefine copolymer,
The heat such as fluorenes ring modified polycarbonate resin, alicyclic modified polycarbonate resin, fluorenes ring modified polyester resin, acryl compound
The substrate of plastic resin.The resin base material can be used alone, or combines two or more and use.
Resin base material is preferably formed by the material with heat resistance.Specifically, using linear expansion coefficient be 15ppm/K with
Upper 100ppm/K or less and glass transition temperature (Tg) are 100 DEG C or more 300 DEG C of resin base materials below.The substrate meets
As condition required for electronic component purposes, display stack membrane.That is, gas barrier film of the invention is used for these purposes
In the case where, process that gas barrier film is exposed to 150 DEG C or more sometimes.In this case, the line expansion of the substrate in gas barrier film
When coefficient is more than 100ppm/K, when gas barrier film to be moved to the process of temperature as described above, it is easy to produce substrate size
It is unstable, to thermal expansion and shrink the inconvenience for intercepting performance and deteriorating, or do not tolerate the bad of thermal process
Situation.If it is lower than 15ppm/K, the flexibility that film cracks as glass sometimes is deteriorated.
The Tg or linear expansion coefficient of substrate can be adjusted according to additive etc..As the thermoplastic resin that can be used as substrate
The preferred concrete example of rouge, it can be mentioned, for example: polyethylene terephthalate (PET:70 DEG C), poly- naphthalenedicarboxylic acid ethylene glycol
Ester (PEN:120 DEG C), polycarbonate (PC:140 DEG C), ester ring type polyolefin (such as Zeon Co., Ltd., Japan manufacture, ZEONOR
1600:160 DEG C of (registered trademark)), polyarylate (PAr:210 DEG C), polyether sulfone (PES:220 DEG C), polysulfones (PSF:190 DEG C), ring
Olefin copolymer (COC: compound documented by Japanese Unexamined Patent Publication 2001-150584 bulletin: 162 DEG C), polyimides (such as three
Water chestnut gas Chemical Co., Ltd. manufacture, Neopulim (registered trademark): 260 DEG C), fluorenes ring modified polycarbonate (BCF-PC: Japan
Compound documented by special open 2000-227603 bulletin: 225 DEG C), alicyclic modified polycarbonate (IP-PC: Japanese Unexamined Patent Publication
Compound documented by 2000-227603 bulletin: 205 DEG C), acryl compound (Japanese Unexamined Patent Publication 2002-80616 public affairs
Compound documented by reporting: 300 DEG C or more) etc. (bracket in indicate Tg).
Since gas barrier film of the invention is utilized as electronic equipments such as organic EL elements, resin base material is preferred
It is transparent.That is, light transmittance is usually 80% or more, preferably 85% or more, further preferably 90% or more.Light is saturating
The rate of penetrating can be by using the method recorded in JIS K7105:1981, i.e. integrating sphere type spectral transmission measurement device measurement is complete
Light transmittance and amount of scattered light are subtracted diffused transmission rate by full light transmittance and are calculated.
But it even if is not provided in the case that gas barrier film of the invention is used for display applications in observation side
Situation etc. not necessarily requires the transparency.Therefore, in this case, opaque material also can be used as plastic foil.Make
For opaque material, it can be mentioned, for example: polyimides, polyacrylonitrile, well known liquid crystal polymer etc..
In addition, the above-mentioned resin base material enumerated can be unstretching film, or stretched film.The resin base material can lead to
Conventionally known general method is crossed to manufacture.About the manufacturing method of these substrates, International Publication No. may be appropriately used
The item recorded in No. 2013/002026 paragraph " 0051 "~" 0055 ".
The surface of resin base material can be carried out for improving various processing well known to adaptation, such as at corona discharge
Reason, flame treatment, oxidation processes or corona treatment etc. also can according to need the above-mentioned processing of combination and carry out.
The resin base material can be single layer, or 2 layers or more of laminated construction.The resin base material is 2 layers or more
In the case where laminated construction, each resin base material can be identical type, or different types.
The thickness (being its overall thickness in the case where its laminated construction for 2 layers or more) of resin base material of the invention is preferably
It is 10~200 μm, more preferably 20~150 μm.
[the layer sequence of layer (A), layer (B)]
Layer (A), layer (B) layer sequence can be resin base material/layer (B)/layer (A) sequence, or resin base material/
The sequence of layer (A)/layer (B).
< resin base material/layer (B)/layer (A) mode >
In the case where the mode of resin base material/layer (B)/layer (A) sequence, it is preferably formed as layer (B), is subsequently formed layer (A).
That is, the preferred manufacturing method of the gas barrier film of the method includes: including being coated on resin base material containing silicon-containing compound
The process of coating fluid and the formation silicon-containing layer (B) being dried;Contained on the silicon-containing layer (B) by the formation of gas phase membrane formation process
The process of the layer (A) of transistion metal compound.As long as this is because forming region (a), the vacuum that can carry out layer (B) is purple
It is modified caused by outside line irradiation, it can also be without.As long as forming region (a), good gas barrier property can be obtained, it can high speed
Film forming, and high productivity can be obtained.But from the viewpoint of more effectively forming region (a), it is purple that layer (B) is based on vacuum
Irradiation energy is preferably adjusted to lower than 3J/cm by the modification that outside line irradiation carries out2, more preferably it is adjusted to lower than 1J/cm2, can also be with
Preferably select 0J/cm2, i.e., without the mode for the modification irradiated based on vacuum ultraviolet.
At forming layer (B), in the case where irradiating without vacuum ultraviolet, preferably coating contains silicon-containing compound
Coating fluid and film obtained from being dried save 1 at 5~40 DEG C, under conditions of 0~60%RH of relative humidity~
1000 hours, thereafter, forming layer (A).That is, layer (B) is that coating contains for a preferred embodiment of the invention
The coating fluid of silicon compound and film obtained from being dried at 5~40 DEG C, under conditions of 0~60%RH of relative humidity
Obtained from saving 1~1000 hour.By this preservation process, can inhibit after dry from the coating of layer (B) to formation
During layer (A), undesirable variation is generated in the surface composition of layer (B), it is therefore contemplated that the gas barrier property under the conditions of high temperature and humidity
It can improve.Undesirable variation is following variation: when being enumerated in case where to use polysilazane as silicon-containing compound,
Moisture and polysilazane in atmosphere are reacted, and the nitrogen content on the surface layer (B) reduces, and oxygen content increases.
From the viewpoint of gas barrier properties, 1 tunic of the layer (B) in the mode of resin base material/layer (B)/layer (A) sequence
Thick (being its overall thickness in the case where its laminated construction for 2 layers or more) is preferably 10~1000nm, more preferably 50~
600nm, further preferably 50~300nm.If it is the range, the balance of gas barrier property and durability becomes well, therefore excellent
Choosing.
< resin base material/layer (A)/layer (B) mode >
In the case where the mode of resin base material/layer (A)/layer (B) sequence, from the viewpoint of gas barrier property, it is preferably formed as
After layer (A), it is coated with the coating fluid containing silicon-containing compound and is dried and forms film, even more preferably pass through vacuum
UV treatment is modified and forming layer (B).That is, the preferred manufacturing method of the gas barrier film of the method includes: in resin
The process that the layer (A) containing transistion metal compound is formed by gas phase membrane formation process on substrate;It is included in described containing transition gold
Belong to the coating fluid containing silicon-containing compound is coated on the layer (A) of compound and be dried and the process that forms silicon-containing layer (B).
In the case where the mode of the resin base material/layer (A)/layer (B) sequence, close to layer (A) layer (B) region into
When having gone modified, the oxidizing and depressing effect based on layer (A) layer (B) generated is improved, it is therefore preferable that the side layer (A) in layer (B)
Lower surface be modified.Therefore, from upper surface irradiation 172nm vacuum ultraviolet layer (B) is modified in the case where, be
Make the 172nm light to the lower surface for reaching layer (B), preferably the thickness of layer (B) is than relatively thin.Specifically, 1 tunic of layer (B) is thick
(being its overall thickness in the case that it is 2 layers or more laminated construction) be preferably 300nm hereinafter, more preferably 200nm hereinafter,
Further preferably 150nm is hereinafter, particularly preferably 100nm or less.On the other hand, even if layer (B) is excessively thin, gas barrier property is also bad
Change, accordingly, it is considered to when gas barrier property, preferably 5nm or more, more preferably 10nm or more, further preferably 20nm or more, especially
Preferably 40nm or more.That is, for a preferred embodiment of the invention, layer (B) with a thickness of 5nm or more, 300nm
Below.
As the method in the region (a) formed in the method, it can be mentioned, for example after forming layer (A), at 5~40 DEG C
Under, save 1~1000 hour under conditions of 0~60%RH of relative humidity, the method for being subsequently formed layer (B).
[atom composition figure]
In the atom composition distribution map that gas barrier film of the invention is obtained when thickness direction carries out XPS composition analysis,
Use SiMxNyWhen indicating composition, there is the region (a) for meeting following formula (1) and formula (2) (hereinafter, also referred to as region (a)).Tool
There are the gas barrier film of the invention of this composition, the excellent in te pins of durability under hot and humid environment.
[mathematical expression 3]
SiMxNy
0.2≤x≤3.0
0≤y≤0.6
M: transition metal
X: transition metal and silicon atom there are atomic ratios
Y: nitrogen-atoms and silicon atom there are atomic ratios
The preferably described silicon-containing compound contains polysilazane, and the y meets the mode of following formula (3).
[mathematical expression 4]
0.05≤y≤0.6
X is transition metal and silicon atom there are atomic ratio, y be nitrogen and silicon atom there are atomic ratios, but region (a) needs
To meet formula (1) and formula (2) simultaneously.That is, the condition that discovery shows high gas barrier property is: at least silicon atom and transition metal atoms
Simultaneous region, and transition metal atoms/silicon atom ratio is 0.2 or more 3.0 or less.The mechanism that gas barrier property shows is not
It is clear, but presumption is: and silicon atom and transition metal atoms exist simultaneously, by forming silicon atom and transition metal atoms direct key
The high-density region of synthesis and show gas barrier property.Even if being believed that transition metal atoms/silicon atom ratio is lower than 0.2, separately
Outside, even more than 3.0, also due to the bonding of silicon atom and transition metal atoms is reduced, therefore gas barrier property is reduced.
In the present invention, use polysilazane as in the case where the mode of silicon-containing compound, particularly significant height can be obtained
Gas barrier property.In this approach, it finds: forming silicon atom, transition metal atoms and the simultaneous region of nitrogen-atoms, transition gold
Belonging to atom/silicon atom ratio is 0.2 or more 3.0 hereinafter, and nitrogen-atoms/silicon atom ratio is 0.05 or more 0.6 hereinafter, being
Show the condition of significantly high gas barrier property.The methods of think silicon-nitrogen key (Si-N bonding) of polysilazane and use gas phase membrane formation process
When the transition metal atoms of formation connect, or apply the energy such as vacuum ultraviolet in the state of connecting with transition metal atoms,
Thus it is easy to form be the bonding of silicon-transition metal, presumption are as follows: with use without other silicon-nitrogen key silicon-containing compound
Situation is compared, and significantly high gas barrier property can be obtained.It is believed that nitrogen-atoms/silicon atom ratio is suitable the case where being lower than 0.05
The low situation of the containing ratio of the polysilazane contained in layer (B) or polysilazane be modified and the case where silicon-nitrogen key is reduced
Deng so that gas barrier property reduces.Furthermore it is possible to think, in the case that nitrogen-atoms/silicon atom ratio is more than 0.6, nitrogen-atoms increases
Add, correspondingly in contrast silicon atom and transition metal atoms are reduced, and the bonding of silicon-transition metal is also reduced, therefore, similarly
Gas barrier property reduces.
It should be noted that the thickness in region (a) is in the XPS analysis shown in following, with SiO2Meter obtains depth direction
It is the thickness of the integral multiple of 2.5nm therefore using 2.5nm as the depth map of scale.
In addition, being calculated in the case that region (a) has a variety of M by the summation that the content to each metal is weighted
x。
The control of the composition or thickness of this region (a) can be carried out by the methods of following, that is, form institute as above
After the layer (A) (or layer (B)) stated, until during forming layer (B) (or layer (A)), it is right under conditions of lower temperature and humidity
Film is saved, and is saved under dry nitrogen atmosphere.
From the viewpoint of can be obtained higher gas barrier property, with SiMxNyOzIt is excellent when indicating the atom composition of region (a)
It is selected in the region (b) further indicated with following formula (4) in the region (a).
[mathematical expression 5]
SiMxNyOz
(4+ax)-(3y+2z) > 0 (4)
M: transition metal
A: the valence mumber of the stoichiometry of transition metal M
X: transition metal and silicon atom there are atomic ratios
Y: nitrogen-atoms and silicon atom there are atomic ratios
Z: oxygen atom and silicon atom there are atomic ratios
Above-mentioned formula (4) means that the total bond number of the total bond number ratio Si and M of O and N is few.It is presumption, it is believed that
In the case that (4+ax)-(3y+2z) of above-mentioned formula (4) is more than 0, the direct bonding of Si and M is formed, it is believed that (4+
Ax)-(3y+2z) value is bigger, and the ratio of the Direct Bonding of Si and M is more, and the density of the composition in region (a) more increases, choke
Property more further increases.
The maximum value of (4+ax)-(3y+2z) in region (b) is more preferably 1 or more, further preferably 2 or more, spy
It You Xuanwei 3 or more.
The control of the value of (4+ax)-(3y+2z) can carry out as follows: for example, to carry out containing transition metal by sputtering
When enumerating in case where the formation of the layer of M, use the metal oxide of oxygen defect in metal or stoichiometry as target,
The amount for the oxygen that appropriate adjustment is imported in sputtering.
The position of forming region (b) is not particularly limited, preferably near the interface of layer (A) and layer (B).Mean: if
It is formed about region (b) at interface, then forms the compound oxynitride layer of Si and M on the interface of layer (A) and layer (B), this recognizes
To be because the cooxidation nitride layer of the Si and M show higher damp and hot patience.
It should be noted that being calculated in the case that region (b) has a variety of M by the summation of the weighting of the content of each metal
x。
The composition in region (a) and region (b) can be measured by the following method.
The measurement of the composition in region (a)
By XPS analysis, the composition distribution map of thickness direction is nearby measured to the interface of layer (A) and layer (B), is used
SiMxNyOzIndicate composition.At this point, being determined whether by the relationship of x and y with region (a).In addition, having the case where region (a)
Under, the value of (4+ax)-(3y+2z) is found out, whether further determine has region (b).
" XPS analysis condition "
Device: the QUANTERASXM of ULVAC-PHI manufacture
X-ray source: monochromatization Al-K α
Plasma sputter: Ar (2keV)
Depth map: with SiO2After meter is equivalent to the sputtering of 2.5nm, replication obtains SiO2It is every to count depth direction
The depth map of 2.5nm
It is quantitative: to find out background with Shirley method, determined by obtained peak area using relative sensitivity coefficient method
Amount.The MultiPak that data processing is manufactured using ULVAC-PHI Co., Ltd..
[layer with various functions]
In gas barrier film of the invention, the layer with various functions can be set.
(anchor coat)
On the surface for the resin base material for forming layer (A) and the side layer (B) of the invention, with improve resin base material and layer (A) or
For the purpose of the adaptation of layer (B), anchor coat can be formed.
It, can be by polyester resin, isocyanate resin, polyurethane resin, third as the anchoring paint for anchor coat
Olefin(e) acid resinoid, ethylene vinyl alcohol, vinyl modified resin, epoxy resin, modified styrene resin, modified polyorganosiloxane
Resin and Alkyl titanate etc. are used alone or two or more combines and uses.
In these anchoring paints, conventionally known additive can be added.Moreover, above-mentioned anchoring paint can pass through
It is coated on supporting mass using method well known to roller coating, intaglio plate coating, cutter painting, dip-coating, spraying etc., and to solvent, diluent etc.
Removing is dried and carries out anchoring coating.As the coating weight of above-mentioned anchoring paint, preferably 0.1~5.0g/m2It is (dry
State) left and right.
In addition, anchor coat can use vapor phase method as physical vapor deposition or chemical vapor deposition and be formed.For example, such as
Documented by Japanese Unexamined Patent Publication 2008-142941 bulletin like that, can be to improve cementability the purpose of, is formed based on silica
The inoranic membrane of body.Alternatively, being utilized on it by forming anchor coat documented by Japanese Unexamined Patent Publication 2004-314626 bulletin
When vapor phase method forms inorganic thin film, the gas generated from substrate side can be intercepted, in a way to control the group of inorganic thin film
At purpose formed anchor coat.
In addition, the thickness of anchor coat is not particularly limited, preferably 0.5~10 μm or so.
(stick coating)
It can have stick coating on the surface (surface or two surfaces) of resin base material.As contained in stick coating
The example of material, it can be mentioned, for example heat-curing resin or active energy ray-curable resins, but from forming be easy from the aspect of,
It is preferred that active energy ray-curable resin.This curable resin can be used alone or two or more combines and uses.
Active energy ray-curable resin refers to: being irradiated, is passed through by active energy ray as ultraviolet light or electron beam
Cross-linking reaction etc. and carry out cured resin.As active energy ray-curable resin, it is preferable to use containing having olefinic insatiable hunger
With the ingredient of the monomer of double bond, its solidification is made by active energy ray as irradiation ultraviolet light or electron beam, formation contains
The layer of the solidfied material of active energy ray-curable resin, i.e. stick coating.As active energy ray-curable resin, as representative
Resin enumerates uv curing resin or electronic beam curing resin etc., but is preferably carried out by ultraviolet light irradiation cured
Uv curing resin.The commercially available resin base material for being pre-formed stick coating can be used.
(smooth layer)
In gas barrier film of the invention, smooth layer can have between resin base material and layer (A) or layer (B).This hair
Smooth layer used in bright is in order to planarize the asperities of resin base material existing for protrusion etc., or landfill is due to being present in
It the protrusion of resin base material and the bumps or pin hole that are generated on transparent inorganic compound layer and thereby is planarized and is arranged.This
Kind smooth layer substantially makes photosensitive material or thermoset materials solidify and make.
As the photosensitive material of smooth layer, it can be mentioned, for example: containing with free-radical reactive unsaturated compound
The resin combination of acrylate compounds, the resin group containing acrylate compounds and sulfhydryl compound with mercapto
Close object;Make epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyalkylene glycol propylene
Resin combination made of the dissolution of the polyfunctional acrylate monomers such as acid esters, glyceral methacrylate etc..Specifically, can be with
Material OPSTAR (registered trademark) series is applied using the UV curing type hybrid stick of JSR Corp..Furthermore it is possible to
Using any mixture of resin combination as described above, as long as there is 1 or more optical polymerism not containing intramolecular
The photoresist of the reactive monomeric of saturated bond, is not particularly limited.
As thermoset materials, specifically, can enumerate: the Tutto prom series of Clariant company manufacture (has
Machine polysilazane), CERAMIC COAT Co., Ltd. manufacture SP COAT heat-resisting transparent coating, Asahi Denka Co., Ltd. manufacture
UNIDIC (registered trademark) V-8000 series, the EPICLON (registrar that nano hybridization polysiloxanes, Dainippon Ink Chemicals manufacture
Mark) EXA-4710 (superelevation heat-resistance epoxy resin), the various polyorganosiloxane resins of Shin-Etsu Chemial Co., Ltd's manufacture, day
Dong Fang Co., Ltd. manufacture inorganic-organic nanocomposite synthetic material SSG coating, by the pure and mild isocyanate prepolymer of acrylic acid multielement
The Thermocurable polyurethane resin of formation, urea melamine, epoxy resin, unsaturated polyester resin, gathers phenolic resin
Silicone resin etc..Wherein, particularly preferably there is the material of the epoxy resin substrate of heat resistance.
The forming method of smooth layer is not particularly limited, preferably by spin-coating method, spray-on process, scraper plate coating process, infusion process
It waits the dry types such as wet coating methods or vapour deposition method coating process and is formed.
In the formation of smooth layer, antioxidant, ultraviolet light can be added as needed in above-mentioned photoresist
The additives such as absorbent, plasticizer.In addition, the lamination station with smooth layer is unrelated, even if in any smooth layer, it can be in order to
Film forming improves and prevents film from generating pin hole etc. and using resin appropriate or additive.
As the thickness of smooth layer, from the heat resistance of raising film, and it is easily adjusted the viewpoint of the balance of the optical characteristics of film
It sets out, preferably 1~10 μm of range is further preferably set as 2 μm~7 μm of range.
The flatness of smooth layer is the value shown with the surface roughness specified in JIS B 0601:2001, and 10 points average
Roughness Rz is preferably 10nm or more, 30nm or less.If it is the range, even if with the feelings of coated form coating gas barrier layer
Under condition, though with bar, contact apparatus for coating with smooth layer surface without coating methods such as bars in the case where, the damage of coating
Evil is also less, in addition, being also easy to make the concave-convex smoothing after coating.
[electronic equipment]
Gas barrier film of the invention can be preferably applied to due to chemical component (oxygen, water, nitrogen oxides, the sulphur in air
Oxide, ozone etc.) and cause performance deteriorate equipment.That is, the present invention provides a kind of electronic equipment, it includes resistances of the invention
Gas film and electronic equipment ontology.
It as the example of the electronic equipment ontology for electronic equipment of the invention, can enumerate for example: organic electroluminescence hair
Optical element (organic EL element), liquid crystal display element (LCD), thin film transistor (TFT), touch panel, Electronic Paper, solar battery
(PV) etc..From the viewpoint of more effectively obtaining effect of the invention, the electronic equipment ontology be preferably organic EL element or
Solar battery, more preferably organic EL element.
Embodiment
Illustrate effect of the invention using following Examples and Comparative Examples.But the range of technology of the invention is not
It is only limitted to embodiment below.
(comparative example 1: the production of gas barrier film 1)
[resin base material]
With two sides carried out easy Nian Jie processing with a thickness of 100 μm of polyethylene terephthalate film (the beautiful strain in east
The manufacture of formula commercial firm, Lumirror (registered trademark) (U48)) forming layer (B) the opposite surface face in surface on, being formed has thickness
The transparent rods coating for the anti-caking function that degree is 0.5 μm.That is, coating UV gel-type resin (AICA Industrial Co., Ltd system, product
Number: Z731L) and make 0.5 μm of dry film thickness, then, be dried at 80 DEG C, thereafter, under air, use high pressure water
Silver-colored lamp is in irradiation energy 0.5J/cm2Under conditions of solidified.
Then, on the surface of the side layer (B) for forming resin base material, the following transparent rods coating for forming 2 μm of thickness.It applies
UV gel-type resin OPSTAR (registered trademark) Z7527 of cloth JSR Corp. manufacture, makes 2 μm of dry film thickness, then,
It is dried at 80 DEG C, thereafter, under air, uses high-pressure mercury-vapor lamp irradiation energy 0.5J/cm2Under conditions of solidified.
In this way, obtaining the resin base material with stick coating.Below, in Examples and Comparative Examples, for convenience, by the tree with stick coating
Aliphatic radical material is referred to as resin base material.
[formation of layer (B)]
Fox-14 (Dong Li DOW CORNING Co., Ltd. as silicon-containing compound, used as hydrogen silesquioxane polymer
Manufacture, 14 mass %MIBK solution).As catalyst, the acetylacetone,2,4-pentanedione platinum of 0.5 mass % is added relative to solid component, into
One step is diluted with methyl iso-butyl ketone (MIBK) (MIBK), makes the coating fluid of 8 mass % of solid component.
Coating fluid is coated on above-mentioned resin base material using spin-coating method, and making it dry film thickness is 100nm, at 80 DEG C
It is 2 minutes dry.It is set to gas barrier film 1.
(embodiment 1: the production of gas barrier film 2)
Above-mentioned gas barrier film 1 is saved 24 hours in the environment of 20 DEG C, relative humidity 50%RH.Thereafter, using magnetic control
Tube sputtering device, using target and membrance casting condition shown in following, the forming layer (A) on layer (B).
[formation of layer (A)]
Use oxygen defect type Nb2O5Target is as target, by using Ar and O2As process gas DC sputtering carry out at
Film.It advances with glass substrate to form a film, the exploration of composition condition is carried out by adjusting partial pressure of oxygen, find since surface layer
Depth 10nm near composition become Nb2O3Condition.Using the condition, formed a film with thickness 15nm.It is set to choke
Property film 2.The membrance casting condition is set as " membrance casting condition a ".Film forming condition below is visited also by same pre research is carried out
Rope condition.
(comparative example 2: the production of gas barrier film 3)
It on above-mentioned resin base material, operates similarly with example 1, direct forming layer (A).It is set to gas barrier film 3.
The measurement of the composition in region (a)
To gas barrier film 2, XPS measurement is carried out under the conditions of aftermentioned.Show the result in following table 1.Such as following table 1 institute
Show, confirms forming region (a).
The Ca method of < gas barrier film evaluates >
According to the water vapo(u)r transmission of measuring method below evaluation gas barrier film 1~3.
By the Ca method made as described below evaluation sample (type evaluated using penetrating concentration) in 40 DEG C of 90%RH
It is saved under environment, the rate of corrosion of every 5 hours to 100 hours observation Ca measures penetrating concentration (any 4 points be averaged).Comparative example
The penetrating concentration that is measured at the time of 5 hours of gas barrier film 1 and 3 be lower than the 50% of penetrating concentration initial value, in contrast, this
The penetrating concentration that the gas barrier film 2 of invention measures at the time of 100 hours is 50% or more of penetrating concentration initial value, has height
Gas barrier property.
(embodiment 2: the production of gas barrier film 4)
[formation of layer (B)]
For layer (B), by the coating fluid containing polysilazane shown in following be coated on above-mentioned resin base material and into
Row drying and form film, carry out as needed based on vacuum ultraviolet irradiate carry out modification and formed.
By containing 20 mass % Perhydropolysilazanes dibutyl ethers solution (AZ Electronics Materials Co., Ltd manufacture,
NN120-20) and contain amine catalyst (N, N, N', N'- tetramethyl -1,6- diamino hexane (TMDAH)) Perhydropolysilazane
The dibutyl ethers solution (AZ Electronics Materials Co., Ltd manufacture, NAX120-20) of 20 mass % with the ratio of 4:1 (mass ratio) into
Row mixing, and in order to adjust dry film thickness, it is suitably diluted with dibutyl ethers, prepares coating fluid.
Coating fluid is coated on above-mentioned resin base material using spin-coating method, makes dry film thickness 150nm, it is dry at 80 DEG C
2 minutes.Then, to dry film, dress is irradiated using the vacuum ultraviolet of Fig. 3 of the Xe Excimer lamp with wavelength 172nm
It sets, vacuum ultraviolet treatment with irradiation is carried out under the conditions of the irradiation energy shown in following table 2-1.At this point, irradiation atmosphere is set with nitrogen
It changes, oxygen concentration is adjusted to 0.1 volume %.In addition, the load sample platform temperature that sample is arranged is adjusted to 80 DEG C.
In Fig. 3,1 is device room, nitrogen and oxygen is supplied in right amount from gas supply port (not shown) to inside, from (not shown)
Gas discharge outlet is exhausted, thus, it is possible to substantially remove vapor from chamber interior, oxygen concentration is maintained specified dense
Degree.2 be Xe Excimer lamp (the Excimer lamp luminous intensity: 130mW/ of the double-sleeve structure of the vacuum ultraviolet with irradiation 172nm
cm2), 3 be the frame for having both the Excimer lamp of external electrode.4 be sample table.Sample table 4 can use mobile device (not shown)
Make to move back and forth in device room 1 in level with specified speed.In addition, sample table 4 can use heating device (not shown)
Maintain specified temperature.5 be the sample for being formed with polysilazane compounds coating layer.When sample table is horizontally moved, adjust
The height of whole sample table, so that the shortest distance in the painting layer surface of sample and quasi-molecule fluorescent tube face is 3mm.6 be barn door,
In the aging of Xe Excimer lamp 2, vacuum ultraviolet is not irradiated to the coating layer of sample.
The energy that sample coating layer surface is irradiated in vacuum ultraviolet irradiation process uses Hamamatsu
The ultraviolet light accumulated light meter of Photonics Co., Ltd. manufacture: C8026/H8025UV POWER METER uses 172nm's
Sensor head is measured.In measurement, sensor head is set to 4 center of sample table and makes the quasi-molecule fluorescent tube face Xe and sensing
The shortest distance of the aspect of measure of device head is 3mm, and supplies nitrogen and oxygen, becomes the atmosphere in device room 1 and shines with vacuum ultraviolet
The identical oxygen concentration of process is penetrated, keeps sample table 4 mobile with the speed of 0.5m/min and is measured.Before measurement, in order to make
The illumination of Xe Excimer lamp 2 is stablized, and 10 minutes ageing times are arranged after the illumination of Xe Excimer lamp, makes sample table mobile thereafter
And start to measure.
The movement speed that sample table is adjusted based on the irradiation energy obtained in the measurement, is thus adjusted, so that
As irradiation energy shown in table 2-1.In addition, being carried out after aging in 10 minutes in vacuum ultraviolet irradiation.
[formation of layer (A)]
Before forming layer (A), layer (B) is formed into completed film and is protected in the environment of 20 DEG C, relative humidity 50%RH
It deposits 24 hours.Thereafter, using magnetic controlled tube sputtering apparatus, using target and membrance casting condition shown in following, the forming layer on layer (B)
(A)。
Use oxygen defect type Nb2O5Target is as target, by using Ar and O2As process gas DC sputtering carry out at
Film, film thickness are set as 15nm.Partial pressure of oxygen is adjusted, film composition is made to become Nb2O3(membrance casting condition a).In this way, production gas barrier film 4.
(embodiment 3: the production of gas barrier film 5)
The irradiation energy of vacuum ultraviolet when by forming layer (B) is changed to 0.2J/cm2, in addition to this, with embodiment 2
It operates in the same way, makes gas barrier film 5.
(embodiment 4: the production of gas barrier film 6)
It at forming layer (B), without the irradiation of vacuum ultraviolet, in addition to this, operates, makes similarly to Example 2
Make gas barrier film 6.
(embodiment 5: the production of gas barrier film 7)
Using target and membrance casting condition shown in following, the forming layer (A) on layer (B) is in addition to this, same with embodiment 4
It operates to sample, makes gas barrier film 7.
Use oxygen defect type Nb2O5Target is as target, by using Ar and O2As process gas DC sputtering carry out at
Film, film thickness are set as 30nm.Partial pressure of oxygen is adjusted, film group is made to become Nb2O3.The membrance casting condition is set as " membrance casting condition b ".
(embodiment 6: the production of gas barrier film 8)
Using target and membrance casting condition shown in following, the forming layer (A) on layer (B) is in addition to this, same with embodiment 2
It operates to sample, makes gas barrier film 8.
Use oxygen defect type Nb2O5Target is as target, by using Ar and O2As process gas DC sputtering carry out at
Film, film thickness are set as 15nm.Partial pressure of oxygen is adjusted, film group is made to become Nb2O4.The membrance casting condition is set as " membrance casting condition c ".
(embodiment 7: the production of gas barrier film 9)
Using target and membrance casting condition shown in following, the forming layer (A) on layer (B) is in addition to this, same with embodiment 2
It operates to sample, makes gas barrier film 9.
Use Ta2O5Target is as target, by using Ar and O2RF sputtering as process gas forms a film, film thickness
It is set as 15nm.Partial pressure of oxygen is adjusted, film group is made to become Ta2O3.The membrance casting condition is set as " membrance casting condition d ".
(embodiment 8: the production of gas barrier film 10)
Using target and membrance casting condition shown in following, the forming layer (A) on layer (B) is in addition to this, same with embodiment 2
It operates to sample, makes gas barrier film 10.
Use Ce target as target, by using Ar and O2RF sputtering as process gas forms a film, and film thickness is set
For 15nm.Partial pressure of oxygen is adjusted, film group is made to become CeO1.9.The membrance casting condition is set as " membrance casting condition e ".
(comparative example 3: the production of gas barrier film 11)
It in addition to not formed layer (A), operates similarly to Example 2, makes gas barrier film 11.
(comparative example 4: the production of gas barrier film 12)
Using target and membrance casting condition shown in following, the layer containing Si is formed on layer (B), in addition to this, with implementation
Example 2 operates in the same way, and makes gas barrier film 12.
Use polycrystal Si target as target, by using Ar and O2DC sputtering as process gas forms a film,
Film thickness is set as 15nm.Partial pressure of oxygen is adjusted, film group is made to become SiO2.The membrance casting condition is set as " membrance casting condition f ".
(comparative example 5: the production of gas barrier film 13)
Using target and membrance casting condition shown in following, the layer containing Al is formed on layer (B), in addition to this, with implementation
Example 2 operates in the same way, and makes gas barrier film 13.
Use Al target as target, by using Ar and O2DC sputtering as process gas forms a film, and film thickness is set
For 15nm.Partial pressure of oxygen is adjusted, film group is made to become Al2O3.The membrance casting condition is set as " membrance casting condition g ".
(embodiment 9: the production of gas barrier film 14)
Layer is sequentially formed with layer (A)-layer (B) on resin base material, in addition to this, is operated similarly to Example 2, is made
Make gas barrier film 14.It should be noted that after forming layer (A), before forming layer (B), by the film of forming layer (A) 20
DEG C, save 24 hours in the environment of relative humidity 50%RH.
(embodiment 10: the production of gas barrier film 15)
The dry film thickness of layer (A) is set as 40nm, in addition to this, is operated similarly to Example 9, gas barrier property 15 is made.
(embodiment 11: the production of gas barrier film 16)
The dry film thickness of layer (A) is set as 100nm, in addition to this, is operated similarly to Example 9, gas barrier property 16 is made.
(embodiment 12: the production of gas barrier film 17)
The dry film thickness of layer (A) is set as 250nm, in addition to this, is operated similarly to Example 9, gas barrier property 17 is made.
(embodiment 13: the production of gas barrier film 18)
Layer is sequentially formed on resin base material, with layer (A)-layer (B), in addition to this, is operated similarly to Example 6,
Make gas barrier film 18.
(comparative example 6: the production of gas barrier film 19)
It in addition to not formed layer (A), operates similarly to Example 12, makes gas barrier film 19.
(comparative example 7: the production of gas barrier film 20)
Layer is sequentially formed with layer (A)-layer (B) on resin base material, in addition to this, is operated in the same way with comparative example 4, is made
Make gas barrier film 20.
(comparative example 8: the production of gas barrier film 21)
Layer is sequentially formed with layer (A)-layer (B) on resin base material, in addition to this, is operated in the same way with comparative example 5, is made
Make gas barrier film 21.
(evaluation method)
The measurement of the composition in region (a)
By XPS analysis, near the interface of layer (A) and layer (B), the composition distribution map of thickness direction is measured, is used
SiMxNyOzIndicate composition.At this point, being determined whether by the relationship of x and y with region (a).In addition, having the case where region (a)
Under, the value of (4+ax)-(3y+2z) is found out, whether further determine has region (b).
" XPS analysis condition "
Device: the QUANTERASXM of ULVAC-PHI manufacture
X-ray source: monochromatization Al-K α
Plasma sputter: Ar (2keV)
Depth map: with SiO2After meter is equivalent to the sputtering of 2.5nm, replication is obtained with SiO2Count depth direction with
2.5nm is the depth map of scale.
It is quantitative: to find out background with Shirley method, determined by obtained peak area using relative sensitivity coefficient method
Amount.The MultiPak that data processing is manufactured using ULVAC-PHI company.
The Ca method of < gas barrier film evaluates >
The water vapo(u)r transmission (gas barrier property) of each gas barrier film is evaluated according to measuring method below.
By the Ca method made as described below evaluation sample (type evaluated using penetrating concentration) at 85 DEG C 85%
It is saved under RH environment, at interval of the rate of corrosion of certain time observation Ca.1 hour, 5 hours, 10 hours, 20 hours, it is later every
It is observed within 20 hours, is measured penetrating concentration (any 4 points be averaged), the penetrating concentration of measurement is become lower than at the beginning of penetrating concentration
Time value 50% at the time of observing time be set as the index of gas barrier property.The penetrating concentration measured under preservation in 500 hours is
50% or more situation of penetrating concentration initial value is set as 500 hours or more.
After the choke layer surface of gas barrier film is carried out UV cleaning, in choke level using 20 μm of thickness fittings as
The sheet bonding agent (epoxylite) of the thermohardening type of sealing resin layer.It is punched into after the size of 50mm × 50mm,
It is put into glove box, be dried within 24 hours.
UV cleaning is carried out to a surface of the alkali-free glass plate (thickness 0.7mm) of 50mm × 50mm size.It uses
The vacuum deposition apparatus of ALSTechnology Co., Ltd. manufacture, in the center of glass plate across mask with 20mm × 20mm's
Ca is deposited in size.The thickness of Ca is set as 80nm.The glass plate for having carried out Ca vapor deposition in glove box is taken out, is configured so that being pasted
The Ca vapor deposition face for closing the sealing resin level and glass plate that have the gas barrier film of sealing resin layer connects, and is carried out by vacuum lamination
Bonding.At this point, carrying out 110 DEG C of heating.Also, the sample of bonding is made into glass plate on the electric hot plate for being set as 110 DEG C
It places down, solidifies it 30 minutes, make evaluation slot.
The manufacturing condition of the gas barrier film of each Examples and Comparative Examples and atom composition are shown in table 2 and table 3, will be commented
Valence result is shown in table 4 and table 5.
From the above results: for gas barrier film 4~10 and 14~18, the durability under hot and humid environment is excellent
It is different.Known to: by the way that compared with the gas barrier film 11~13 and 19~21 for not having region (a), this effect passes through region
(a) exist and realize.
It is further known that: the maximum value of (4+ax)-(3y+2z) is 3 or more gas barrier films 5~7 and 16~17, and high temperature is high
Durability under wet environment is more excellent.
It should be noted that the application is based on 2 25th, 2015 applied Japanese patent application 2015-35040
Number, the disclosure of which by referring to being cited as a whole.
Claims (10)
1. a kind of gas barrier film, includes on resin base material
Layer (A), forms containing transistion metal compound, and by gas phase membrane formation process;
Silicon-containing layer (B) connects with the layer (A) and obtains by the following method, and the method includes coatings to contain silicide-comprising
It closes the coating fluid of object and is dried, wherein
In the atom composition distribution map obtained when carrying out XPS composition analysis along the thickness direction of the gas barrier film, with SiMxNy
When indicating composition, there is the region (a) for meeting following formula (1) and formula (2),
[mathematical expression 1]
SiMxNy
0.2≤x≤3.0 (1)
0≤y≤0.6 (2)
M: transition metal
X: transition metal and silicon atom there are atomic ratios
Y: nitrogen-atoms and silicon atom there are atomic ratios.
2. gas barrier film as described in claim 1, wherein
The silicon-containing compound has at least one kind of in silicon-nitrogen key, silicon-hydrogen bond and silicon-silicon bond.
3. gas barrier film as claimed in claim 1 or 2, wherein
The silicon-containing compound contains polysilazane, and the y meets following formula (3),
[mathematical expression 2]
0.05≤y≤0.6 (3)。
4. gas barrier film as claimed in claim 1 or 2, wherein
Transition metal in the transistion metal compound is the oxidation-reduction potential metal lower than silicon.
5. gas barrier film as claimed in claim 1 or 2, wherein
The transition metal is at least one kind of metal in vanadium, niobium and tantalum.
6. gas barrier film as claimed in claim 1 or 2, wherein
Along the gas barrier film thickness direction carry out XPS composition analysis when obtain atom composition distribution map in, with
SiMxNyOzWhen indicating the atom composition of the region (a), further having in the region (a) is indicated with following formula (4)
Region (b),
[mathematical expression 3]
SiMxNyOz
(4+ax)-(3y+2z) > 0 (4)
M: transition metal
A: the valence mumber of the stoichiometry of transition metal M
X: transition metal and silicon atom there are atomic ratios
Y: nitrogen-atoms and silicon atom there are atomic ratios
Z: oxygen atom and silicon atom there are atomic ratios.
7. gas barrier film as claimed in claim 6, wherein
The maximum value of (4+ax)-(3y+2z) in the region (b) is 3 or more.
8. a kind of electronic equipment comprising:
Gas barrier film according to any one of claims 1 to 7, and
Electronic device body.
9. a kind of manufacturing method of gas barrier film is the manufacturer of gas barrier film according to any one of claims 1 to 7
Method,
The manufacturing method includes:
The process that the layer (A) containing transistion metal compound is formed by gas phase membrane formation process on resin base material;
The process for forming silicon-containing layer (B) comprising coating contains silicon-containing compound on the layer (A) containing transition metal
Coating fluid is simultaneously dried,
In the atom composition distribution map obtained when carrying out XPS composition analysis along the thickness direction of gas barrier film, with SiMxNyIt indicates
When composition, there is the region (a) for meeting following formula (1) and formula (2),
[mathematical expression 4]
SiMxNy
0.2≤x≤3.0 (1)
0≤y≤0.6 (2)
M: transition metal
X: transition metal and silicon atom there are atomic ratios
Y: nitrogen-atoms and silicon atom there are atomic ratios.
10. a kind of manufacturing method of gas barrier film is the manufacturer of gas barrier film according to any one of claims 1 to 7
Method,
The described method includes:
The process for forming silicon-containing layer (B) comprising be coated with the coating fluid containing silicon-containing compound on resin base material and done
It is dry;
The process for forming the layer (A) containing transistion metal compound on the silicon-containing layer (B) by gas phase membrane formation process,
In the atom composition distribution map obtained when carrying out XPS composition analysis along the thickness direction of gas barrier film, with SiMxNyIt indicates
When composition, there is the region (a) for meeting following formula (1) and formula (2),
[mathematical expression 5]
SiMxNy
0.2≤x≤3.0 (1)
0≤y≤0.6 (2)
M: transition metal
X: transition metal and silicon atom there are atomic ratios
Y: nitrogen-atoms and silicon atom there are atomic ratios.
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WO2018021021A1 (en) * | 2016-07-28 | 2018-02-01 | コニカミノルタ株式会社 | Gas barrier membrane, gas barrier film using same, electronic device using said gas barrier membrane or said gas barrier film, and production method for gas barrier membrane |
TW201823501A (en) * | 2016-11-16 | 2018-07-01 | 美商陶氏全球科技有限責任公司 | Process for producing thin coatings on film |
JP2019177645A (en) * | 2018-03-30 | 2019-10-17 | 東洋製罐グループホールディングス株式会社 | Barrier film for electronic device |
KR102294031B1 (en) * | 2018-10-26 | 2021-08-27 | 주식회사 엘지화학 | A barrier film |
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