CN105829093A

CN105829093A - Gas barrier film

Info

Publication number: CN105829093A
Application number: CN201580003271.5A
Authority: CN
Inventors: 森健太郎
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2014-01-29
Filing date: 2015-01-23
Publication date: 2016-08-03
Anticipated expiration: 2035-01-23
Also published as: WO2015115314A1; JPWO2015115314A1; KR102355268B1; TW201534481A; CN105829093B; JP6578943B2; KR20160114038A; TWI668120B

Abstract

The purpose of the present invention is to provide a gas barrier film which exhibits high gas barrier performance, while having excellent bending resistance. A gas barrier film according to the present invention sequentially comprises, on at least one surface of a polymer base, an inorganic layer (A) and a silicon compound layer (B) in this order from the polymer base side. The silicon compound layer (B) contains at least silicon compounds having structures represented by SiNxHy, SiOpNq and SiOa(OH)4-2a (wherein x + y = 4, p + q =4, a < 2 and x, y, p, q > 0); and the inorganic layer (A) and the silicon compound layer (B) are in contact with each other.

Description

Gas barrier film

Technical field

The present invention relates to for needing the food of high-gas resistance, pharmaceutical packing purposes, solaode, Electronic Paper, having The gas barrier film of the electronic device purposes such as organic electro luminescent (EL) display.

Background technology

There is the surface at polymer base material, utilize the physical vapor growth methods such as vacuum vapour deposition, sputtering method, ion plating method The chemistry gas such as (PVD method) and plasma enhanced chemical vapor growth method, thermal chemical vapor growth method, photochemical vapor growth method Phase growth methods (CVD) etc., form the film of the inorganic matters (comprising inorganic oxide) such as aluminium oxide, silicon oxide, magnesium oxide Gas barrier film, this film is used as to need the packing timber of the blocking-up food of the various gas such as steam, oxygen, medicine etc. and slim electricity Device component depending on, solaode etc..

Develop skill as gas barrier property, disclose such as, use the gas of the steam containing organo-silicon compound and oxygen, By plasma CVD method, using Si oxide as main body on base material, make at least one containing carbon, hydrogen, silicon and oxygen Compound, thus while maintaining the transparency, improve the method (patent documentation 1) of gas barrier property.Additionally, as utilizing plasma Gas barrier property beyond the film build methods such as CVD develops skill, and has following technology: utilizing to decrease becomes the pin making gas barrier property reduce Hole, the projection of producing cause of crackle, the technology of concavo-convex smooth substrates；Use and to be provided with using surface smoothing as purpose The technology (patent documentation 2,3 and 4) of the base material of priming coat.The most known polysilazanes film conversion making to be formed by wet coating method For silicon oxide film, the method (patent documentation 5 and 6) of silicon oxynitride film.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 8-142252 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2002-113826 publication

Patent documentation 3: International Publication the 2012/137662nd

Patent documentation 4: International Publication the 2013/061726th

Patent documentation 5: International Publication the 2011/007543rd

Patent documentation 6: International Publication the 2011/004698th

Summary of the invention

Invent problem to be solved

But, as described in Patent Document 1, formed Si oxide as main constituent by plasma CVD method In the method for gas barrier layer, according to the kind of base material, the film quality of the gas barrier layer formed is different, can not get stable gas barrier property.For Making gas barrier property stable, need to thicken, its result has resistance to bend(ing) to reduce, manufacturing cost increases such problem.Additionally, As described in Patent Document 2, the base material forming gas barrier layer uses the method for smooth substrates, use to be provided with and turn to the smooth of surface The method of the base material of the priming coat of purpose is by preventing the generation of pin hole, crackle, although gas barrier property improves, but the raising of performance is not Fully.On the other hand, in patent documentation 3,4, the film quality of the gas barrier layer owing to being formed is enhanced, although observe performance Improve, but have the stably such problem of performance high-gas resistance difficulty.Additionally, disclosed in patent documentation 5 and 6 by poly-silicon nitrogen Alkane layer is formed in the method for gas barrier layer, it is easy to affected by condition during cambium layer, has sufficiently resistance to stably obtain The gas barrier film of gas, needs multiple polysilazane layers are carried out lamination.Its result is to have resistance to bend(ing) reduction, manufacturing cost to increase Add such problem.

The present invention in view of the background of such prior art, even if its problem be provide do not thicken, the most multilayer laminated also There is the gas barrier property of height, resistance to bend(ing), the gas barrier film of excellent adhesion.

For the method solving problem

The present invention is to solve such problem, use following methods.That is,

(1) a kind of gas barrier film, is to have successively from above-mentioned polymer base material side at least side of polymer base material Inorganic layer [A] and the gas barrier film of silicon compound layer [B], silicon compound layer [B] is including at least having SiN_xH_y、SiO_pN_qAnd SiO_a (OH)_4-2aThe silicon compound of the structure shown in (x+y=4, p+q=4, a≤2x, y, p, q ＞ 0), and inorganic layer [A] and silication Compound layer [B] connects.

Additionally, as the optimal way of the present invention, have following such method.

(2) according to the gas barrier film described in (1), above-mentioned inorganic layer [A] comprises zinc compound and Si oxide.

(3) according to the gas barrier film described in (1) or (2), at above-mentioned silicon compound layer [B]²⁹Si CP/MAS NMR spectra In, when the peak area summation of-30～-120ppm is set to 100, the peak area summation of-30～-50ppm is more than 10 ,-50 ～the peak area summation of-90ppm is more than 10, and the peak area summation of-90～-120ppm is less than 80.

(4) according to the gas barrier film described in any one of (1)～(3), above-mentioned inorganic layer [A] is selected from following inorganic layer Any one in [A1]～[A3].

Inorganic layer [A1]: comprise the inorganic layer of the coexisting phase of (i)～(iii)

(i) zinc oxide

(ii) silicon dioxide

(iii) aluminium oxide

Inorganic layer [A2]: comprise the inorganic layer of the coexisting phase of zinc sulfide and silicon dioxide

Inorganic layer [A3]: using oxygen atom relative to silicon atom atomic number than be 1.5～2.0 Si oxide as main one-tenth The inorganic layer divided

(5) according to the gas barrier film described in (4), above-mentioned inorganic layer [A] is above-mentioned inorganic layer [A1], and this inorganic layer [A1] is By the zinc atom concentration recorded by ICP emission spectrometry method be 20～40atom%, atom concentration be 5～ 20atom%, aluminum atomic concentration are 0.5～5atom%, concentration of oxygen atoms is constituted by the composition of 35～70atom%.

(6) according to the gas barrier film described in (4), above-mentioned inorganic layer [A] is above-mentioned inorganic layer [A2], and this inorganic layer [A2] is Formed by zinc sulfide constituted relative to what the mole fraction of zinc sulfide and the total of silicon dioxide was 0.7～0.9.

(7) according to the gas barrier film described in any one of (1)～(6), at above-mentioned polymer base material and above-mentioned inorganic layer [A] Between there is priming coat [C], described priming coat [C] comprise by there is aromatic ring structure urethanes [C1] crosslinking and The structure obtained.

(8) according to the gas barrier film described in (7), above-mentioned priming coat [C] includes organic silicon compound and/or inorganic silicon chemical combination Thing.

Additionally, the present invention also provides for employing the following electronic device of gas barrier film.

(9) a kind of electronic device, it uses the gas barrier film described in any one of (1)～(8).

The effect of invention

According to the present invention it is possible to provide the gas barrier property relative to steam with height, resistance to bend(ing), excellent adhesion Gas barrier film.

Accompanying drawing explanation

Fig. 1 is the sectional view of an example of the gas barrier film of the display present invention.

Fig. 2 is the skeleton diagram of the takeup type sputter equipment schematically showing the gas barrier film for manufacturing the present invention.

Fig. 3 is the skeleton diagram of the takeup type CVD device schematically showing the gas barrier film for manufacturing the present invention.

Fig. 4 is the gas barrier film of the present invention that display is obtained by embodiment 1, silicon compound layer [B]²⁹Si CP/MAS The figure of NMR spectra.

Fig. 5 is the skeleton diagram of resistance to bend(ing) test.

Fig. 6 is the sectional view of an example of the gas barrier film of the display present invention.

Detailed description of the invention

Inventors etc. have the gas barrier property of height to obtain relative to steam etc., resistance to bend(ing), adaptation also excellence Further investigation is repeated for the purpose of gas barrier film, has found by least side at polymer base material, by inorganic layer [A] With comprising, there is SiN_xH_y、SiO_pN_qAnd SiO_a(OH)_4-2a3 of structure shown in (x+y=4, p+q=4, a≤2x, y, p, q ＞ 0) The silicon compound layer [B] of individual silicon compound carries out lamination in the way of connecting successively, and result solves above-mentioned problem.

It addition, the implication of above-mentioned 3 structures is as follows.

SiN_xH_y: combine nitrogen and hydrogen on the silicon atom in the presence of compound, from silicon to the binding number of each element be x and y。

SiO_pN_q: combine oxygen and nitrogen on the silicon atom in the presence of compound, from silicon to the binding number of each element be p and q。

SiO_a(OH)_4-2a: the structure of compound when silicon atom is set to 1.

Fig. 1 is the sectional view of an example of the gas barrier film of the display present invention.About the gas barrier film of the present invention, such as Fig. 1 institute Show that in the side of polymer base material (symbol 1), inorganic layer [A] (symbol 2) has with comprising from polymer base material side like that SiN_xH_y、SiO_pN_qAnd SiO_a(OH)_4-2aThe silicon compound layer [B] of 3 silicon compounds of the structure shown in (x+y=4, a≤2) (symbol 3) lamination successively.It addition, the minimal composition of the gas barrier film of the example display present invention of Fig. 1, only inorganic layer [A] and silicon compound layer [B] are configured at the side of polymer base material, but can join between polymer base material and inorganic layer [A] Put other layer, furthermore, it is possible to configure other layer in the opposition side with the side of lamination inorganic layer [A] of polymer base material 1.

In the present invention, it is thus achieved that significantly the reason of effect estimates as follows.That is, by by inorganic layer [A] and silicon compound Layer [B] connect such that it is able to inorganic layer [A] formation silicon compound layer [B] side near surface existing for pin hole, The defects such as crackle fill the composition constituting silicon compound layer [B], show high barrier.Additionally, above-mentioned 3 kinds of silicon compounds easily with The composition constituting inorganic layer [A] forms chemical bond, and therefore inorganic layer [A] is not say with the adaptation raising of silicon compound layer [B] And explain, the adaptation of excellence can also be obtained in the case of silicon compound layer [B] superimposed layer has other layer.Further, bag The flexibility of the silicon compound layer [B] containing said structure is the most excellent, therefore can also obtain the resistance to bend(ing) of excellence.

[polymer base material]

Polymer base material used in the present invention, from the viewpoint of guaranteeing flexibility, preferably has film form.As film Composition, can for monofilm or more than 2 layers such as by film obtained by coetrusion masking.As the kind of film, permissible Use the film etc. stretched along single shaft direction or biaxially oriented.

The raw material of polymer base material used in the present invention is not particularly limited, and is preferably organic polymer as master Want the raw material of constituent.As the present invention can be suitable for the organic polymer that uses, can enumerate such as, polyethylene, poly- The crystalline polyolefins such as propylene, there is the noncrystalline cyclic polyolefin of circulus, polyethylene terephthalate, poly-naphthalene two Polyester, polyamide, Merlon, polystyrene, polyvinyl alcohol, the soaps of ethylene vinyl acetate copolymer such as formic acid glycol ester The various polymer etc. such as compound, polyacrylonitrile, polyacetals.Wherein, the transparency, versatility, mechanical property are preferably comprised excellent Noncrystalline cyclic polyolefin or polyethylene terephthalate.Additionally, above-mentioned organic polymer can be homopolymer, copolymer Any one, as organic polymer, can only use a kind, it is also possible to be used in mixed way multiple.

Surface to the side of the formation inorganic layer [A] of polymer base material, in order to make adaptation, flatness good, permissible Implement sided corona treatment, Cement Composite Treated by Plasma, UV treatment, ion bom bardment process, solvent process, by Organic substance or inorganic matter or The pre-treatments such as the formation process of the priming coat that their mixture is constituted.Additionally, side contrary forming inorganic layer [A] Side, rises to purpose with the sliding during winding of film, can have Organic substance, inorganic matter or the coating of their mixture with lamination Layer.

The thickness of polymer base material used in the present invention is not particularly limited, from the viewpoint of guaranteeing flexibility, excellent Elect below 500 μm as, from the viewpoint of guaranteeing relative to the intensity stretching, impacting, more than preferably 5 μm.Further from film Processing, the easiness of operation set out, the thickness of polymer base material is more than 10 μm, below more preferably 200 μm.

[inorganic layer [A]]

Inorganic layer [A] in the present invention can illustrate zinc (Zn), silicon (Si), aluminum (Al), titanium (Ti), zirconium (Zr), stannum (Sn), The oxide of element, nitride, sulfide or their mixture such as indium (In), niobium (Nb), molybdenum (Mo), tantalum (Ta).If bag Containing such inorganic matter, being not particularly limited, inorganic layer [A] preferably comprises Si oxide, even more preferably comprises zinc impregnation Compound and Si oxide.Additionally, as the inorganic layer [A] of acquisition high-gas resistance, be suitable for using the inorganic layer [A1] selected from following ～any one in [A3].

(i) zinc oxide

(ii) silicon dioxide

(iii) aluminium oxide

Inorganic layer [A1]～[A3] each detailed content carries out aftermentioned.

About the thickness of the inorganic layer [A] in the present invention, as the thickness of the layer of performance gas barrier property, preferably more than 10nm Below 1,000nm.If the thickness of layer is little, then produce the place that can not guarantee gas barrier property fully, sometimes at polymer base material Gas barrier property dispersion in face.If additionally, the thickness of layer is excessive, in layer, the stress of residual becomes big the most sometimes, therefore owing to bending, coming From outside impact, inorganic layer [A] is prone to crack, and along with use, gas barrier property reduces.Therefore, the thickness of inorganic layer [A] Degree is more than 10nm, is more than 100nm further, is on the other hand 1, below 000nm, below 500nm.The thickness of inorganic layer [A] Degree is usually measured by the cross-section utilizing transmission electron microscope (TEM) to carry out.

The median plane mean roughness SRa of inorganic layer used in the present invention [A] is preferably below 10nm.If SRa is big In 10nm, then the concaveconvex shape on inorganic layer [A] surface becomes big, forms gap between the sputtering particle of lamination, and therefore film quality is difficult to Become fine and close, even if form thickness be sometimes not easy to obtain the raising effect of gas barrier property thickly.If additionally, SRa is more than 10nm, Then on inorganic layer [A], the film quality of the silicon compound layer [B] of institute's lamination will not become uniform, and gas barrier property reduces the most sometimes.Therefore, The SRa of inorganic layer [A] is preferably below 10nm, more preferably below 7nm.

The SRa of the inorganic layer [A] in the present invention can use three-dimensional surface roughness measuring machine to be measured.

In the present invention, the method forming inorganic layer [A] is not particularly limited, for example, it is possible to by vacuum vapour deposition, spatter Penetrate method, ion plating method, CVD etc. to be formed.In these methods, due to can be easy and densely be formed inorganic layer [A], Therefore sputtering method or CVD it are preferably.

[inorganic layer [A1]]

For applicable that use, as comprising (i) zinc oxide, (ii) silicon dioxide as inorganic layer [A] in the present invention (iii) coexisting phase of aluminium oxide is (following, sometimes by the coexisting phase of (i) zinc oxide, (ii) silicon dioxide and (iii) aluminium oxide Be expressed as " zinc oxide-silicon dioxide-aluminium oxide coexisting phase ") the inorganic layer [A1] of layer, details is described.It addition, dioxy SiClx (SiO₂) according to condition when generating, sometimes generate from the silicon of above-mentioned composition formula and the group of the some deviations of the composition ratio of oxygen An accepted way of doing sth (SiO～SiO₂), but it is expressed as silicon dioxide or SiO here₂.About the deviation with the chemical formula of such ratio of components, right Also it is same process in zinc oxide, aluminium oxide, each unrelated with the deviation of the ratio of components of the condition depended on when generating, respectively It is expressed as zinc oxide or ZnO, aluminium oxide or Al₂O₃。

The gas barrier film of the present invention is made by application inorganic layer [A1] gas barrier property become good reason and speculate be Because the crystalline composition that zinc oxide is comprised coexists with the noncrystalline composition of silicon dioxide, thus suppression easily generates crystallite The crystalline growth of zinc oxide, particle diameter diminishes, therefore layer densification, passing through of suppression steam.

Furthermore, it is possible to think by making aluminium oxide coexist, thus with make zinc oxide compared with the situation that silicon dioxide coexists, Crystalline growth can be suppressed further, therefore can realize the densification of further layer, accompany with this, for being split by when using Gas barrier property caused by the generation of stricture of vagina reduces and can also suppress.

The composition of inorganic layer [A1] as described later, can be measured by ICP emission spectrometry method.Preferably pass through The zinc atom concentration that ICP emission spectrometry method measures is 20～40atom%, and atom concentration is 5～20atom%, and aluminum is former Sub-concentration is 0.5～5atom%, and O atom concentration is 35～70atom%.If zinc atom concentration is more than 40atom%, or silicon Atomic concentration is less than 5atom%, then silicon dioxide and/or the aluminium oxide of the crystalline growth of inhibited oxidation zinc are not enough, the most sometimes Gap, defect part increase, and can not get high-gas resistance.If zinc atom concentration is less than 20atom%, or atom concentration More than 20atom%, the noncrystalline composition of the silicon dioxide within layer increases and the reduction of the flexibility of layer the most sometimes.If additionally, Aluminum atomic concentration is more than 5atom%, then zinc oxide exceedingly uprises with the affinity of silicon dioxide, and therefore film is hardening, has phase For heat, it is prone to crack from outside stress.If aluminum atomic concentration is less than 0.5atom%, then zinc oxide and two The affinity of silicon oxide becomes insufficient, and cambial interparticle adhesion can not improve, and flexibility reduces the most sometimes.This Outward, if concentration of oxygen atoms is more than 70atom%, then the defect level in inorganic layer [A1] increases, and the most sometimes can not get desired Gas barrier property.If concentration of oxygen atoms is less than 35atom%, then zinc, silicon, the state of oxidation of aluminum become insufficient, it is impossible to suppression knot Crystals growth, particle diameter becomes big, and gas barrier property reduces the most sometimes.Consider from the tendency brought by the content of each atom illustrated above, More preferably zinc atom concentration is 25～35atom%, and atom concentration is 10～15atom%, aluminum atomic concentration be 1～ 3atom%, concentration of oxygen atoms is 50～64atom%.

Forming by being formed forming as the mixed sintering material used when being formed of layer of inorganic layer [A1], because of This is by using the mixed sintering material of the composition consistent with the composition of the layer of target such that it is able to adjust the group of inorganic layer [A1] Become.

The composition of inorganic layer [A1] by ICP emission spectrometry method, quantitative zinc, silicon, each element of aluminum, with zinc oxide with The mode of the ratio of components of silicon dioxide, aluminium oxide and contained inorganic oxide calculates.It addition, oxygen atom assumes that zinc is former Son, silicon atom, aluminum atom are each with zinc oxide (ZnO), silicon dioxide (SiO₂), aluminium oxide (Al₂O₃) mode exist to calculate Go out.ICP emission spectrographic analysis is can be by produced luminous light when sample imports together with argon plasma source portion Spectrum, carries out the analysis method measured while multielement, can apply to composition analysis.At the upper further lamination of inorganic layer [A1] In the case of inorganic layer, resin bed, can process shielding layer as desired by ion(ic) etching, medicinal liquid, then carry out ICP Emission spectrographic analysis.

[inorganic layer [A2]]

It follows that for applicable that use, as comprising zinc sulfide and silicon dioxide as inorganic layer [A] in the present invention Coexisting phase (following, sometimes the coexisting phase of zinc sulfide Yu silicon dioxide is expressed as " zinc sulfide-silicon dioxide coexisting phase ") The inorganic layer [A2] of layer, illustrates details.It addition, here, silicon dioxide (SiO₂) condition when generating according to it, sometimes give birth to Become from the silicon of above-mentioned composition formula and composition formula (SiO～SiO of the some deviations of the composition ratio of oxygen₂), be expressed as silicon dioxide or SiO₂.About the deviation with the chemical formula of such ratio of components, be also same process for zinc sulfide, with depend on generate time The deviation of ratio of components of condition unrelated, be expressed as zinc sulfide or ZnS.

In the gas barrier film of the present invention by application inorganic layer [A2] gas barrier property become good reason and speculate be because of For, the crystalline composition that zinc sulfide is comprised coexists with the noncrystalline composition of silicon dioxide, thus suppression easily generates crystallite The crystalline growth of zinc sulfide, particle diameter diminishes, therefore layer densification, passing through of suppression steam.

Additionally, comprise the zinc sulfide-silicon dioxide coexisting phase of the zinc sulfide inhibiting crystalline growth and only by inorganic oxide The layer that thing or metal-oxide are formed is compared flexibility and is become higher, becomes relative to heat, is not likely to produce from outside stress The layer of crackle, it can be considered that by applying such inorganic layer [A2], hence for by the generation institute of crackle when using The gas barrier property caused reduces and can also suppress.

The preferred zinc sulfide that forms of inorganic layer [A2] is 0.7 relative to the mole fraction of zinc sulfide and the total of silicon dioxide ～0.9.If zinc sulfide is more than 0.9 relative to the mole fraction of zinc sulfide and the total of silicon dioxide, then suppress zinc sulfide The silicon dioxide of crystalline growth is not enough, and gap, defect part increase the most sometimes, can not get the gas barrier property of regulation.Additionally, If zinc sulfide is less than 0.7 relative to the mole fraction of zinc sulfide and the total of silicon dioxide, then the two of inorganic layer [A2] inside The noncrystalline composition of silicon oxide increases and the flexibility of layer reduces, and gas barrier film is relative to mechanical bent flexibility the most sometimes Reduce.About zinc sulfide relative to zinc sulfide and the further preferred range of the mole fraction of the total of silicon dioxide, from Shown on the tendency brought of the content of each compound consider, be 0.75～0.85.

The composition of inorganic layer [A2] is by being formed, therefore forming as the mixed sintering material used when being formed of layer By using the mixed sintering material of the composition consistent with purpose, it is possible to adjust the composition of inorganic layer [A2].

First the composition analysis of inorganic layer [A2] can obtain the ratio of components of zinc and silicon by ICP emission spectrographic analysis, Use rd's backscatter method based on this value, each element is carried out quantitative analysis, know zinc sulfide and silicon dioxide and contained The ratio of components of other inorganic oxide having.ICP emission spectrographic analysis is can be by sample imports together with argon plasma Produced luminescent spectrum during body light source portion, carries out the analysis method measured while multielement, can apply to composition analysis. Additionally, the charged particle accelerated with high voltage can be irradiated in sample by rd's backscatter method, rebounded by from it The number of charged particle, energy carry out the specific, quantitative of element, know the ratio of components of each element.It addition, inorganic layer [A2] is Sulfide and the composite bed of oxide, therefore pass through to carry out sulfur real with rd's backscatter method that the ratio of components of oxygen is analyzed Execute analysis.In the case of inorganic layer [A2] upper further lamination inorganic layer, resin bed, can lose as desired by ion Carve, medicinal liquid processes shielding layer, then utilizes ICP emission spectrographic analysis and rd's backscatter method to be analyzed.

[inorganic layer [A3]]

It follows that for that be suitable for using as inorganic layer [A] in the present invention, by former relative to silicon atom of oxygen atom Subnumber than be 1.5～2.0 Si oxide as the inorganic layer [A3] of main constituent, details is described.Here, so-called main one-tenth Point, refer to more than 60 mass % that inorganic layer [A3] is overall, if more than 80 mass % the most preferred.It addition, above-mentioned main constituent Silicon dioxide (SiO₂) condition when generating according to it, sometimes generate from the silicon of above-mentioned composition formula and the composition ratio of oxygen some partially From composition formula (SiO～SiO₂), but it is expressed as silicon dioxide or SiO₂。

The forming method of inorganic layer [A3] preferably can form the CVD of the film of densification.In CVD, can by after The silane stated or the gas of organo-silicon compound are set to monomer, are activated by the plasma of high intensity, utilize polymerization anti- The film of densification should be formed.Here so-called organo-silicon compound, can enumerate such as, methyl-monosilane, dimethylsilane, trimethyl silicane Alkane, tetramethylsilane, ethylsilane, diethylsilane, triethyl silicane, tetraethyl silane, npropoxysilane, dipropoxy silicon Alkane, tripropoxy silane, tetrapropoxysilane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, dimethyl two Siloxanes, tetramethyl disiloxane, hexamethyl disiloxane, hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethyl Pentamethylene. siloxanes, ten monomethyl ring six siloxanes, dimethyl disilazane, trimethyldisilazane, tetramethyl-disilazane, Hexamethyldisiloxane, pregnancy basic ring three silazane, octamethylcyclotetrasilazane, decamethyl ring five silazane, ten monomethyl rings Six silazane etc..Wherein, from operating aspect, preferably hexamethyl disiloxane, tetraethoxysilane.

The composition of inorganic layer [A3] can pass through x-ray photoelectron optical spectroscopy (XPS method) as described later and be measured.Logical The oxygen atom crossing XPS method mensuration compares the scope of preferably 1.5～2.0 relative to the atomic number of silicon atom, is even more preferably The scope of 1.4～1.8.If silicon atom relative to the atomic number ratio of oxygen atom more than 2.0, then the oxygen atom quantitative change comprised Many, gap, defect part increase the most sometimes, can not get the gas barrier property of regulation.If additionally, silicon atom is former relative to oxygen The atomic number ratio of son is less than 1.5, and oxygen atom reduces the most sometimes, becomes fine and close film, but flexibility reduces.

[silicon compound layer [B]]

It follows that for silicon compound layer [B], details is described.Silicon compound layer [B] in the present invention is for comprising tool There is SiN_xH_y、SiO_pN_qAnd SiO_a(OH)_4-2aThe silicon compound of the structure shown in (x+y=4, p+q=4, a≤2x, y, p, q ＞ 0) Layer.Using the control of refractive index, hardness, adaptation etc. as purpose, can comprise alkoxy silane, organopolysiloxane etc. its Its silicon compound.It addition, the composition of each compound of silicon compound layer [B] can pass through²⁹Si CP/MAS NMR method is surveyed Fixed.

By applying silicon compound layer [B] in the gas barrier film of the present invention, thus gas barrier property becomes good reason such as Following (i) and (ii) estimates like that.

I () first, as the contribution of layer, presumption layer is by comprising SiO_pN_qShown silicon-oxygen nitride, thus with only by SiO₂The layer formed compares passing through of the layer becoming fine and close, suppression oxygen and steam, therefore becomes the layer that gas barrier property is high, additionally, With only by Si₃N₄It is high that the layer formed compares flexibility, and when therefore using, the stress relative to heat, from outside is not likely to produce crackle, Become and can suppress to be generated by crackle the layer that the gas barrier property caused reduces.

(ii) it follows that as by inorganic layer [A] and silicon compound layer [B] lamination and the tribute that brings in the way of connecting Offer, estimate as follows.

Constitute the composition of silicon compound layer [B] be filled in the defects such as pin hole, crackle that inorganic layer [A] had and can table Existing high barrier.

Silicon compound layer [B] is by connecting with inorganic layer [A], and the composition such as zinc that above-mentioned inorganic layer [A] is comprised is as urging Agent works and the film quality of silicon compound layer [B] becomes prone to modification, and gas barrier property improves further.

By comprising 3 kinds of silicon compounds, and only by SiO_pN_qThe layer formed as main constituent is compared, with composition inorganic layer It is easy that the composition of [A] forms chemical bond, and therefore inorganic layer [A] carries with the adaptation of the interface zone of silicon compound layer [B] High, it is possible to obtain excellent resistance to bend(ing) during use.

The thickness of silicon compound layer used in the present invention [B] is preferably more than 50nm 2, below 000nm, more preferably More than 50nm 1,000nm.If the thickness of silicon compound layer [B] diminishes, stable water-vapor barrier the most sometimes can not be obtained Energy.If the thickness of silicon compound layer [B] becomes excessive, then sometimes due to the stress remained in silicon compound layer [B] becomes big And polymer base material warpage, silicon compound layer [B] and/or inorganic layer [A] crack and gas barrier property reduction.

The thickness of silicon compound layer [B] can enter from the cross-section image obtained by transmission electron microscope (TEM) Row measures.

The median plane mean roughness SRa of silicon compound layer used in the present invention [B] is preferably below 10nm.If made SRa is below 10nm, then the reproducibility of gas barrier property improves, the most preferably.If the SRa on the surface of silicon compound layer [B] More than 10nm, then concentrated the crackle caused to be prone to produce in concavo-convex many parts by stress, the most sometimes become the weight of gas barrier property The reason that multiple repeatability reduces.Therefore, in the present invention, it is preferred to the SRa making silicon compound layer [B] is below 10nm, more preferably For below 7nm.

The SRa of the silicon compound layer [B] in the present invention can use three-dimensional surface roughness measuring machine to be measured.

By the silicon compound layer [B] of the present invention²⁹Si CP/MAS NMR spectra is shown in Figure 4.It is-30 in chemical shift ～the region of region ,-50～the-90ppm of-50ppm and-90～-120ppm observes the absorption of silicon, it is meant that from the left side of figure Rise and be respectively present SiN_xH_y、SiO_pN_qAnd SiO_a(OH)_4-2a(x+y=4, p+q=4, a≤2x, y, p, q ＞ 0) (list of references: P.Diehl, E.Fluck, R.Kosfeld etc. write " NMR Basic Principles and Progress " Springer- Verlag Berlin Heidelberg issue, 1981 152-163 page).If by-30～-120ppm face, peak When long-pending summation is set to 100, the peak area summation of-30～-50ppm be more than 10 ,-50～the peak area summation of-90ppm be 10 with On, and the peak area summation of-90～-120ppm is less than 80, then become the gas barrier property with height, and resistance to bend(ing), The layer of excellent adhesion, the most preferably.Further, more preferably when the peak area summation of-30～-120ppm is set to 100 ,- The peak area summation of 30～-50ppm is 10～40, and the peak area summation of-50～-90ppm is 10～40, and-90～- The peak area summation of 120ppm is 30～80.In the case of being unsatisfactory for above-mentioned scope, silicon compound layer [B] becomes and exceedingly causes Close film and flexibility is not enough, be prone to crack due to heat, from outside stress, sometimes make gas barrier property reduce.Additionally, The compactness of silicon compound layer [B] is not enough on the contrary, sometimes can not get sufficient gas barrier property.From such a viewpoint, more excellent Choosing and stating the peak area summation of-30～-50ppm is 13～30, and the peak area summation of-50～-90ppm is 13～35, and And the peak area summation of-90～-120ppm is 40～75.From the viewpoint of moisture-vapor transmission, silicon compound layer [B] is preferred 3 kinds of silicon compounds 0.1～100 mass % of the present invention is comprised with summation meter.

As the raw material of silicon compound layer used in the present invention [B], the silication with polysilazane skeleton is preferably used Compound.As the silicon compound with polysilazane skeleton, it may be preferred to use and such as there is the portion shown in following chemical formula (1) The compound of separation structure.Specifically, it is possible to use in Perhydropolysilazane, organopolysilazane and their derivant At least one.In the present invention, from the viewpoint of gas barrier property improves, R following chemical formula (1) shown in is preferably used₁、R₂、 R₃The Perhydropolysilazane of all hydrogen but it also may part or all using hydrogen be instead of by organic groups such as alkyl Organopolysilazane.Furthermore, it is possible to use with single composition, it is also possible to by use mixed above for binary.It addition, n table Show the integer of more than 1.

It follows that the forming method of the silicon compound layer [B] of the explanation present invention.First on inorganic layer [A], will bag Coating containing above-claimed cpd (1) adjusts solid component concentration in the way of dried thickness becomes desired thickness, logical Cross reverse rubbing method, gravure coating process, bar rubbing method, stick coating method, die coating method, spraying process, method of spin coating etc. to be coated.This Outward, in the present invention, from the viewpoint of coating adaptability, it is also preferred that use organic solvent will comprise above-mentioned chemical formula (1) Coating is diluted.Specifically, it is possible to use the hydrocarbon system solvents such as dimethylbenzene, toluene, Oleum Terebinthinae, Solvesso, dibutyl ethers, The ether series solvents etc. such as ethyl-butyl ether, oxolane.And preferably solid component concentration is diluted to below 10 mass % and makes With.These solvents can be used alone or two or more are used in mixed way.

In comprising the coating of raw material of silicon compound layer [B], in the scope of the effect not damaging silicon compound layer [B] In, various additive can be coordinated as required.It is, for example possible to use catalyst, antioxidant, light stabilizer, ultraviolet are inhaled Receive stabilizer, surfactant, levelling agent, the antistatic additive etc. such as agent.

Then, the film after preferably making coating is dried and removes retarder thinner.Here, as being dried the heat used Source, is not particularly limited, it is possible to use the arbitrary thermal source such as steam heater, electric heater, infrared heater.It addition, be Raising gas barrier property, heating-up temperature preferably carries out at 50～150 DEG C.Additionally, heating treatment time preferably carries out several seconds～1 little Time.Further, in heat treated, temperature can be certain, it is possible to so that temperature changes lentamente.Additionally, in dried, Can be while humidity be adjusted while carrying out heat treated with relative humidity in the range of 20～90%RH.Above-mentioned heating Process can be carried out when enclosing in air or in non-active gas.

It follows that can be by dried film is implemented Cement Composite Treated by Plasma, ultraviolet treatment with irradiation, flash lamp arteries and veins Punching processes isoreactivity energy-ray treatment with irradiation and makes the composition modification of above-mentioned film, it is thus achieved that the present invention closes containing 3 kinds of silication The silicon compound layer [B] of thing.As active energy beam treatment with irradiation, from easy and productivity excellence, and it is readily available all The composition of even silicon compound layer [B] sets out, and UV treatment is preferably used.As UV treatment, under atmospheric pressure or decompression Under any one can, but from the viewpoint of versatility, production efficiency, the most under atmospheric pressure carry out UV treatment. About oxygen concentration when carrying out above-mentioned UV treatment, from the viewpoint of the composition control of silicon compound layer [B], oxygen partial pressure It is preferably less than 1.0%, more preferably less than 0.5%.Can set the wettest in the way of becoming desired ratio of components Degree.Additionally, more preferably when above-mentioned UV treatment, use nitrogen to reduce oxygen concentration.

As ultraviolet occurring source, it is possible to use high-pressure mercury-vapor lamp metal halide lamp, microwave mode electrodeless lamp, low pressure The known ultraviolet occurring source such as finsen lamp, xenon lamp, from the viewpoint of production efficiency, in the present invention, it is preferred to use xenon lamp.

The accumulative light quantity that ultraviolet irradiates is preferably 0.5～10J/cm², more preferably 0.8～7J/cm².If it is above-mentioned tired Photometric amount is 0.5J/cm²Above, then desired silicon compound layer [B] composition can be obtained, the most preferably.If on additionally, Stating accumulative light quantity is 10J/cm²Hereinafter, then can reduce polymer base material, the destruction of inorganic layer [B], the most preferably.

Additionally, in the present invention, during UV treatment, in order to improve production efficiency, more preferably by dried painting Film carries out heating while carrying out UV treatment.As heating-up temperature, preferably 50～150 DEG C, more preferably 80～130 DEG C. If heating-up temperature is more than 50 DEG C, then can obtain high efficiency, the most preferably, if additionally, heating-up temperature is 150 DEG C Hereinafter, then it is difficult to cause the deformation of other materials such as polymer base material, go bad, the most preferably.

[priming coat [C]]

For the gas barrier film of the present invention, in order to improve gas barrier property, improve resistance to bend(ing), preferably at above-mentioned polymer base material And priming coat [C] is set between above-mentioned inorganic layer [A].In the case of polymer base material exists the defect such as projection, little scratch, Sometimes using drawbacks described above as starting point for the inorganic layer [A] being stacked on polymer base material also produce pin hole, crackle and damage Gas barrier property, resistance to bend(ing), be therefore preferably provided with the priming coat [C] of the present invention.Additionally, at polymer base material and inorganic layer [A] In the case of the difference of thermal dimensional stability is big, gas barrier property, resistance to bend(ing) also reduce sometimes, are therefore preferably provided with priming coat [C].This Outward, about priming coat used in the present invention [C], from the viewpoint of thermal dimensional stability, resistance to bend(ing), preferably comprise and will have The urethanes [C1] having aromatic ring structure cross-link obtained by structure, further, more preferably contain selected from olefinic In unsaturated compound [C2], Photoepolymerizationinitiater initiater [C3] and organo-silicon compound [C4] and inorganic silicon compound [C5] 1 Plant above silicon compound.

[there is the urethanes [C1] of aromatic ring structure]

The urethanes [C1] with aromatic ring structure that can use in the present invention has at main chain or side chain Aromatic ring and amino-formate bond, for example, it is possible to make intramolecular have epoxy (methyl) acrylic acid of hydroxyl and aromatic ring Ester (c1), diol compound (c2), diisocyanate cpd (c3) carry out being polymerized to obtain.

There is as intramolecular epoxy (methyl) acrylate (c1) of hydroxyl and aromatic ring, bisphenol A-type, hydrogen can be made Change di-epoxy compounds and (methyl) of the aromatic diols such as bisphenol A-type, bisphenol-f type, A Hydrogenated Bisphenol A F type, resorcinol, hydroquinone Acrylic acid derivative carries out reacting obtaining.

As diol compound (c2), it is possible to use such as, ethylene glycol, diethylene glycol, Polyethylene Glycol, propylene glycol, 1,3-third Glycol, 1,3 butylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-HD, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonyl Glycol, 1,10-decanediol, 2,4-dimethyl-2-ethyl hexane-1,3-glycol, neopentyl glycol, 2-ethyl-2-butyl-1,3-third Glycol, 3-methyl isophthalic acid, 5-pentanediol, 1,2-cyclohexanedimethanol, 1,4 cyclohexane dimethanol, 2,2,4,4-tetramethyl-1,3- Cyclobutanediol, 4,4 '-sulfur for xenol, bisphenol-A, 4,4 '-methylene-di-phenol, 4,4 '-(2-Asia norborny) xenols, 4, 4 '-dihydroxybiphenyl phenol, o-dihydroxy benzenes, m-dihydroxy benzenes, p-dihydroxy benzenes, 4,4 '-isopropylidene phenol, 4,4 '-different Propylidene xenol (4,4 '-イソプロピリデ Application PVC Application ジオ Le), Pentamethylene .-1,2-glycol, hexamethylene-1,2-two Alcohol, hexamethylene-1,4-glycol, bisphenol-A etc..They can be used alone with a kind, or be two kinds or more use.

As diisocyanate cpd (c3), can enumerate such as, 1,3-phenylene diisocyanate, Isosorbide-5-Nitrae-penylene two isocyanide Acid esters, 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI), 2,4-methyl diphenylene diisocyanate, 4,4-hexichol Fragrance family diisocyanate, ethylidene diisocyanate, hexamethylene diisocyanate, the 2,2,4-such as dicyclohexylmethane diisocyanate Trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, lysinediisocyanate, bad ammonia Fat family diisocyanate cpd, isophorone diisocyanate, the dicyclohexyl methyl hydride-4,4-two such as acid triisocyanate Alicyclic ring family isocyanate compound, xylene diisocyanate, the tetramethyls such as isocyanates, methylcyclohexylidene diisocyanate The aromatic-aliphatic system isocyanate compounds etc. such as base XDI.They can be used alone with a kind, or will Two or more and with use.

Above-mentioned (c1), (c2), (c3) as long as component ratio become the scope of desired weight average molecular weight, just there is no spy Do not limit.The weight average molecular weight (Mw) of the urethanes [C1] with aromatic ring structure of the present invention is preferably 5,000 ～100,000.If weight average molecular weight (Mw) is 5,000～100,000, then the cured film of gained thermal dimensional stability, Resistance to bend(ing) is excellent, the most preferably.It addition, the weight average molecular weight (Mw) in the present invention is to use gel permeation chromatography to survey Value that is fixed, that obtain with polystyrene standard conversion.

[alefinically unsaturated compounds [C2]]

As can enumerating such as, Isosorbide-5-Nitrae-fourth two as the alefinically unsaturated compounds [C2] of the raw material of priming coat [C] Two (methyl) acrylate, the tetramethylolmethane three (first such as alcohol two (methyl) acrylate, 1,6-HD two (methyl) acrylate Base) acrylate, tetramethylolmethane four (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five Multifunctional (methyl) acrylate, the bisphenol type epoxies two such as (methyl) acrylate, dipentaerythritol six (methyl) acrylate The epoxies such as (methyl) acrylate, bisphenol F type epoxy two (methyl) acrylate, bisphenol S type epoxy two (methyl) acrylate Acrylate etc..Wherein, preferably thermal dimensional stability, multifunctional (methyl) acrylate that surface protection performance is excellent.This Outward, they can use with single composition, it is also possible to by use mixed above for binary.

The content of alefinically unsaturated compounds [C2] is not particularly limited, from thermal dimensional stability, surface protection performance Viewpoint is set out, with in total amount 100 mass % of the urethanes [C1] with aromatic ring structure, preferably 5～ The scope of 90 mass %, the scope of more preferably 10～80 mass %.

[Photoepolymerizationinitiater initiater [C3]]

As can be as the Photoepolymerizationinitiater initiater [C3] of the raw material of priming coat [C], if the resistance of the present invention can be kept The gas barrier property of gas film and resistance to bend(ing), can cause photopolymerization, be not particularly limited.As the present invention being suitable for make Photoepolymerizationinitiater initiater, following compound can be illustrated.

2,2-dimethoxy-1,2-diphenylethane-1-ketone, 1-hydroxy-cyciohexyl phenyl ketone, 2-hydroxy-2-methyl- 1-phenyl-propan-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxyl- 1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl] phenyl }-2-methyl-propan-1-ketone, phenylglyoxylic acid methyl ester, 2-first Base-1-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-fourth The alkylbenzenes such as ketone-1,2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone Ketone system Photoepolymerizationinitiater initiater.

2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, double (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide etc. Acylphosphine oxide system Photoepolymerizationinitiater initiater.

The titanocenes such as double (η 5-2,4-cyclopentadiene-1-bases)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles's-1-base)-phenyl) titanium It it is Photoepolymerizationinitiater initiater.

1,2-octanedione, 1-[4-(thiophenyl)-, 2-(0-benzoyl oxime)] etc. has the photopolymerization of oxime ester structure to be caused Agent etc..

Wherein, from the viewpoint of curable, surface protection performance, be preferably selected from 1-hydroxy-cyciohexyl phenyl ketone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, double Photoepolymerizationinitiater initiater in (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide.Additionally, they can make with single composition With, it is also possible to by use mixed above for binary.

The content of Photoepolymerizationinitiater initiater [C3] is not particularly limited, from the viewpoint of curable, surface protection performance, and phase For total amount 100 mass % of polymerizable component, the scope of preferably 0.01～10 mass %, more preferably 0.1～5 matter The scope of amount %.

[organo-silicon compound [C4]]

As can enumerating such as, vinyl trimethoxy as the organo-silicon compound [C4] of the raw material of priming coat [C] Base silane, VTES, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl group Methyl dimethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl diethoxy silicon Alkane, 3-glycidoxypropyl group triethoxysilane, 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methyl-prop Alkene acryloxypropylethoxysilane trimethoxy silane, 3-methacryloyloxypropyl methyl diethoxy silane, 3-methacryloxypropyl Base propyl-triethoxysilicane, 3-acryloxypropyl trimethoxy silane, N-2-(amino-ethyl)-3-amino propyl methyl Dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330,3-TSL 8330,3- Aminopropyltriethoxywerene werene, 3-isocyanates propyl-triethoxysilicane etc..

Wherein, from the viewpoint of the polymerization activity when curable, active energy beam irradiate, preferably comprise selected from 3- Methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl, vinyl trimethoxy The organo-silicon compound of at least one in base silane and VTES.Additionally, they can be with single composition Use, it is also possible to by use mixed above for binary.

The content of organo-silicon compound [C4] is not particularly limited, from the viewpoint of curable, surface protection performance, In total amount 100 mass % of polymerizable component, the scope of preferably 0.01～10 mass %, more preferably 0.1～5 mass % Scope.

[inorganic silicon compound [C5]]

As can be as the inorganic silicon compound [C5] of the raw material of priming coat [C], from surface protection performance, the transparency Viewpoint is set out, preferably silicon dioxide granule, and further, the primary particle size of silicon dioxide granule is preferably the model of 1～300nm Enclose, more preferably 5～the scope of 80nm.It addition, so-called primary particle size here, refer to utilize gas adsorption method and the ratio obtained The particle diameter d that surface area s obtains for following formula (2).

D=6/ ρ s (2)

Here ρ is the density of particle.

[thickness of priming coat [C]]

The thickness of priming coat [C] is preferably more than 200nm 4, below 000nm, more preferably more than 300nm 3,000nm with Under, more preferably more than 500nm 2, below 000nm.If the thickness of priming coat [C] is too small, the most sometimes can not suppress by The harmful effect of the defect that projection existing on polymer base material, little scratch etc. are caused.If the thickness mistake of priming coat [C] Greatly, the flatness of priming coat [C] reduces and the concave-convex on inorganic layer [A] surface that is stacked on above-mentioned priming coat [C] the most sometimes Shape also becomes big, forms gap between the sputtering particle of institute's lamination, and therefore film quality is difficult to become fine and close, is difficult to obtain carrying of gas barrier property High effect.

The median plane mean roughness SRa of priming coat [C] is preferably below 10nm.If making SRa is below 10nm, the most easily In at the upper inorganic layer [A] obtaining homogenizing of priming coat [C], the reproducibility of gas barrier property improves, the most preferably.If priming coat The SRa on the surface of [C] is excessive, and the concaveconvex shape on inorganic layer [A] surface on priming coat [C] also becomes big, at lamination the most sometimes Forming gap between sputtering particle, therefore film quality is difficult to become fine and close, is difficult to obtain the raising effect of gas barrier property.Additionally, concavo-convex The crackle that many parts are caused by stress collection is prone to produce, and the most sometimes becomes the reason that the reproducibility of gas barrier property reduces. Therefore, in the present invention, it is preferred to the SRa making priming coat [C] is below 10nm, more preferably below 7nm.

The SRa of the priming coat [C] in the present invention can use three-dimensional surface roughness measuring machine to be measured.

[other layer]

On the most surface of the gas barrier film of the present invention, can be formed with scratch resistance in the range of gas barrier property not reducing Property the hard conating rising to purpose, can be by comprise organic high molecular compound film lamination lamination constitute.Separately Outward, so-called most surface, refers on polymer base material here, inorganic layer [A] and silicon compound layer [B] in the way of connecting successively The surface of the silicon compound layer [B] of side after being stacked, that do not connect with inorganic layer [A].

[electronic device]

The gas barrier film of the present invention has high-gas resistance, therefore may be used for various electronic device.For example, it is possible to be suitable for using In electronic device as the tergite, flexible circuit board of solaode.Employ the electronics device of the gas barrier film of the present invention Part has the gas barrier property of excellence, and the performance of the device brought by steam etc. therefore can be suppressed to reduce.

[other purposes]

The gas barrier film of the present invention has high-gas resistance, therefore in addition to electronic device, it is also possible to be suitable as food, The film for packaging etc. of electronic unit.

Embodiment

Hereinafter, the present invention is specifically described based on embodiment.But, the present invention is not limited to following embodiment.

[evaluation methodology]

First, the evaluation methodology in each embodiment and comparative example is described.As long as no recording especially, then it is every for evaluating n number Individual level is 5 corpse or other object for laboratory examination and chemical testing, using the meansigma methods of the measured value of 5 corpse or other object for laboratory examination and chemical testing of gained as measurement result.

(1) thickness of layer

Use micro-sampler ((strain) Hitachi FB-2000A), by focused ion bundle (Focused Ion Beam:FIB) method makes cross-section sample.By transmission electron microscope ((strain) Hitachi H- 9000UHRII), making accelerating potential is 300kV, observes the cross section of observation sample, measures inorganic layer [A], silicon compound layer [B], the thickness of priming coat [C].

(2) median plane mean roughness SRa

Use three-dimensional surface roughness measuring machine (little Ban institute society system), under the following conditions each layer surface is entered Row measures.

System: three-dimensional surface roughness resolution system " i-Face model TDA31 "

X-axis measured length/spacing: 500 μm/1.0 μm

Y-axis measured length/spacing: 400 μm/5.0 μm

Finding speed: 0.1mm/s

Measure environment: temperature 23 DEG C, relative humidity 65%RH, in air.

(3) moisture-vapor transmission (g/ (m²·d))

By vacuum evaporation, silicon compound layer [B] face of gas barrier film forms the calcium layer of thickness 100nm, then, same Sample passes through vacuum evaporation, in above-mentioned calcium layer, forms the aluminium lamination of thickness 3000nm in the way of covering the whole region of calcium layer.Enter one Step, after aluminium lamination is formed, across the glass of thermosetting epoxy resin coating thickness 1mm on above-mentioned aluminium lamination face, 100 DEG C of process 1 hour, it is thus achieved that evaluate sample.The sample of gained is processed 800 hours at temperature 40 DEG C, relative humidity 90%RH, above-mentioned place After reason, measured the transit dose of steam by the amount calculating the calcium corroded due to steam.Moisture-vapor transmission sample Number be each level be 2 corpse or other object for laboratory examination and chemical testing, measure number of times for carry out 5 times for each corpse or other object for laboratory examination and chemical testing, the meansigma methods of the 10 of gained is set to water steaming Vapor permeability (g/ (m²·d))。

(4) composition of inorganic layer [A1]

The composition analysis of [A1] by ICP emission spectrographic analysis (エスアイアイ Na ノテ Network ノロジ society system, SPS4000) carry out.The stage of inorganic layer [A1] will be formed with (by silicon compound layer [B] on polymer base material or priming coat Before carrying out lamination) the sample nitric acid that sampled and sulphuric acid carries out heat resolve, and carry out heating dissolving with dust technology and filter Separate.After insoluble composition heating ashing, utilize sodium carbonate to melt, utilize dust technology to dissolve, with previous filtrate Merge and carry out constant volume.For this solution, measure zinc atom, silicon atom, the content of aluminum atom, be converted into atomic number ratio.It addition, oxygen Atom is for supposing that zinc atom, silicon atom, aluminum atom are respectively with zinc oxide (ZnO), silicon dioxide (SiO₂), aluminium oxide (Al₂O₃) The value of calculation that mode exists and obtains.

(5) composition of inorganic layer [A2]

The composition analysis of inorganic layer [A2] passes through ICP emission spectrographic analysis (エスアイアイ Na ノテ Network ノロジ Society's system, SPS4000) carry out.Silication (is closed by the stage that will be formed with inorganic layer [A2] on polymer base material or priming coat Before nitride layer [B] carries out lamination) the sample nitric acid that sampled and sulphuric acid carries out heat resolve, carries out, with dust technology, dissolving of heating And filter separation.After insoluble composition heating ashing, utilize sodium carbonate to melt, utilize dust technology to dissolve, with previously Filtrate merge carry out constant volume.For this solution, measure zinc atom, the content of silicon atom.It follows that make further based on this value With rd's backscatter method (day new Ha イボ Le テジ (strain) AN-2500 processed), by zinc atom, silicon atom, sulphur atom, oxygen Atom carries out quantitative analysis, obtains the ratio of components of zinc sulfide and silicon dioxide.

(6) composition of inorganic layer [A3]

The composition analysis of inorganic layer [A3] by use x-ray photoelectron optical spectroscopy (XPS method), calculate oxygen atom relative to The atomic number ratio of silicon atom.Condition determination is as described below.

Device: Quantera SXM (PHI society system)

X ray excited: monochromatic AlK α 1,2

X-ray footpath: 100 μm

Photoelectron abjection angle: 10 °.

(7) composition of silicon compound layer [B],

The powdered sample having reamed silicon compound layer [B] with single-blade is filled in the coupon of 7.5mm φ, uses²⁹Si CP/MAS NMR method carries out composition analysis, obtains spectrum as show example in Fig. 4.Calculate by above-mentioned spectrum- The peak area of peak area summation ,-50～the-90ppm of-30～-50ppm when the peak area summation of 30～-120ppm is set to 100 The peak area summation of summation ,-90～-120ppm.Condition determination is as described below.

Device: Chemagnetics society CMX-300

Mensuration core frequency: 59.636511MHz (²⁹Si core)

Spectral width: 30.03kHz

Pulse width: 4.5sec (90 ° of pulses), 2.2sec (45 ° of pulses)

Pulse-recurrence time: ACQTM；0.0682sec, PD；5.0sec

Time of contact: 2.0sec

Observation station: 2048 data points；8192

Primary standard substance: hexamethyl cyclotrisiloxane (outside reference；-9.66ppm)

Temperature: room temperature (about 22 DEG C)

Sample rotation rate: 5.0kHz

Calculating of peak area: integration method.

(8) resistance to bend(ing)

Each for gas barrier film level 2 corpse or other object for laboratory examination and chemical testing is sampled into 100mm × 140mm.As shown in Figure 5, for gas barrier film, Solid at the central part with face opposing face (symbol 21) side of the inorganic layer [A] and silicon compound layer [B] being formed with (symbol 19) Determine the metal cylinder (symbol 20) of diameter 5mm, along this cylinder, from the angle of embrace 0 ° (sample is the state of plane) of cylinder to right The angle of embrace of cylinder becomes in the range of 180 ° (states turned back around cylinder), carries out 100 bending actions, then with (3) Suo Shi Method carry out moisture-vapor transmission evaluation.The meansigma methods of the 10 of gained, for carry out 5 times for each corpse or other object for laboratory examination and chemical testing, is set by mensuration number of times Moisture-vapor transmission after testing for resistance to bend(ing).

(9) adaptation

According to JIS K5600-5-6:1999, at the grid pattern 25 at the right angle of the upper incision 1 × 1mm of silicon compound layer [B] The otch of block, evaluates adaptation.By evaluation result from adaptation well be categorized as 6 grades of classification 0～classification 5 successively.

[forming method of the inorganic layer [A] in embodiment 1～11]

(formation of inorganic layer [A1])

Use the coiled sputter equipment (symbol 6a) of the structure shown in Fig. 2, in the one side of polymer base material (symbol 5) Use the sputtering target as the mixed sintering material formed by zinc oxide, silicon dioxide and aluminium oxide to implement sputtering, arrange inorganic Layer [A1].

Concrete operation is as described below.First, sputtering electrode (symbol 13) is provided with zinc oxide/silicon dioxide/oxygen Change in the coiling chamber (symbol 7) of takeup type sputter equipment that composition mass ratio is the sputtering target that 77/20/3 sintering obtains of aluminum, On let off roll (symbol 8) by arrange the face of the side of inorganic layer [A1] opposed with sputtering electrode in the way of place polymer base material, Unreel, via unreeling side deflector roll (symbol 9,10,11), by drum cooler (symbol 12).So that degree of decompression becomes 2 × 10^- ¹The mode of Pa imports argon and oxygen as oxygen partial pressure 10%, applies to put into electric power 4,000W by DC source, thus Make argon, oxygen gas plasma produce, form inorganic layer [A1] on the surface of polymer base material by sputtering at.Thickness passes through film Transporting velocity is adjusted.Then, it is wound in take-up roll (symbol 18) via winding side deflector roll (symbol 15,16,17).

(formation of inorganic layer [A2])

Use the coiled sputter equipment (symbol 6a) of the structure shown in Fig. 2, at the one of polymer base material (symbol 5) Face, uses the sputtering target as the mixed sintering material formed by zinc sulfide and silicon dioxide to implement sputtering, arranges inorganic layer [A2]。

Concrete operation is as described below.First, sputtering electrode (symbol 13) is provided with rubbing of zinc sulfide/silicon dioxide That ratio is in the coiling chamber (symbol 7) of takeup type sputter equipment of the sputtering target that 80/20 sintering obtains, at let off roll (symbol 8) Upper placement polymer base material, unreels, via unreeling side deflector roll (symbol 9,10,11), by drum cooler (symbol 12).So that Degree of decompression becomes 2 × 10^-1The mode of Pa imports argon, applies to put into electric power 500W by high frequency electric source, so that argon etc. Gas ions produces, and forms inorganic layer [A2] by sputtering on the surface of polymer base material.Thickness is carried out by film transporting velocity Adjust.Then, it is wound in take-up roll (symbol 18) via winding side deflector roll (symbol 15,16,17).

(formation of inorganic layer [A3])

Use the coiled CVD device (symbol 6b) of the structure shown in Fig. 3, in the one side of polymer base material (5), implement Using hexamethyl disiloxane as the chemical vapor coating of raw material, inorganic layer [A3] is set.

Concrete operation is as described below.First, in the coiling chamber (symbol 7) of takeup type CVD device, at let off roll (symbol Numbers 8) place polymer base material on, unreel, via unreeling side deflector roll (symbol 9,10,11), by drum cooler (symbol 12). So that degree of decompression becomes 2 × 10^-1The mode of Pa imports oxygen 0.5L/ minute and hexamethyl disiloxane 70cc/ minute, by high frequency CVD electrode is applied to put into electric power 3,000W by power supply, so that plasma produces, by CVD at above-mentioned polymer base material Inorganic layer [A3] is formed on surface.Thickness is adjusted by film transporting velocity.Then, via winding side deflector roll (symbol 15, 16,17) it is wound in take-up roll.

[there is the synthesis example of the urethanes [C1] of aromatic ring structure]

In 4 mouthfuls of flasks of 5 liters, addition bisphenol-A diglycidyl ether acrylic acid adduct (chemistry society of common prosperity society system, Trade name: epoxy-ester 3000A) 300 mass parts, ethyl acetate 710 mass parts, carry out heating so that interior temperature becomes 60 DEG C.Add Tin dilaurate di-n-butyl stannum 0.2 mass parts, as synthetic catalyst, stirs and dripped dicyclohexyl first through 1 hour Alkane 4,4 '-diisocyanate (Tokyo chemical conversion industry society system) 200 mass parts.Reaction in 2 hours is proceeded, then after completion of dropwise addition Diethylene glycol (Wako Pure Chemical Industries, Ltd.'s system) 25 mass parts are dripped through 1 hour.Reaction in 5 hours is proceeded, it is thus achieved that weight after dropping The urethanes with aromatic ring structure of average molecular weight 20,000.

(embodiment 1)

As polymer base material, use polyethylene terephthalate film (east レ Co., Ltd. system " Le of thickness 50 μm ミラ " (registered trade mark) U48), the one side at this polymer base material arranges inorganic layer [A1] so that thickness becomes 180nm.Inorganic Layer [A1] composition be Zn atomic concentration be 27.5atom%, Si atomic concentration be that 13.1atom%, Al atomic concentration is 2.3atom%, O atom concentration is 57.1atom%.Vertical 100mm, the examination of horizontal 100mm is cut out from the film being formed with inorganic layer [A1] Test sheet, implement the evaluation of the median plane mean roughness SRa of inorganic layer [A1].Show the result in table 1.

Then, the masking liquid formed as silicon compound layer [B], modulate using Perhydropolysilazane as main constituent Smears (AZ エレ Network トロニッ Network マテリア Le ズ society's system " NN120-20 ", solid component concentration 20 mass %) 100 mass The masking liquid 1 that part dibutyl ethers 300 mass parts is diluted.Inorganic layer [A1] utilizes microgravure coating machine (intaglio plate Wire size 200UR, intaglio plate speed ratio 100%) coating masking liquid 1, it is dried 1 minute at 120 DEG C, after drying, implements under the following conditions UV treatment, arranges the silicon compound layer [B] of thickness 120nm, it is thus achieved that gas barrier film.

Apparatus for ultraviolet light treamtent: MEIRH-M-1-152-H (エ system ディエキシマ society system)

Import gas: N₂

Oxygen concentration: 300～800ppm

Accumulative light quantity: 3,000mJ/cm²

Sample homoiothermic: 100 DEG C.

Gas barrier film for gained uses²⁹Si CP/MAS NMR method carries out composition analysis, calculates in the spectrum that will obtain -30～-120ppm peak area summation when being set to 100-30～-50ppm the peak of peak area summation ,-50～-90ppm The peak area summation of area summation ,-90～-120ppm.Show the result in table 1.

Additionally, cut out vertical 100mm, the test film of horizontal 140mm from the gas barrier film of gained, implement commenting of moisture-vapor transmission Valency.Show the result in table 1.

(embodiment 2)

As polymer base material, use polyethylene terephthalate film (east レ Co., Ltd. system " Le of thickness 50 μm ミラ " (registered trade mark) U48).

The masking liquid formed as priming coat [C], by above-mentioned urethanes 150 mass parts, dipentaerythritol 6 third Olefin(e) acid ester (chemistry society of common prosperity society system, trade name: ライトア Network リレト DPE-6A) 20 mass parts, 1-hydroxy-cyciohexyl benzene Base-one (BASF ジャパ Application society system, trade name: " IRGACURE " (registered trade mark) 184) 5 mass parts, 3-methacryloxypropyl Base hydroxypropyl methyl diethoxy silane (SHIN-ETSU HANTOTAI シリコン society system, trade name: KBM-503) 3 mass parts, ethyl acetate 170 matter Amount part, toluene 350 mass parts and Ketohexamethylene 170 mass parts carry out cooperation to adjust masking liquid 2.Then, profit on polymer base material It is coated with masking liquid 2 with microgravure coating machine (intaglio plate wire size 150UR, intaglio plate speed ratio 100%), is dried 1 minute at 100 DEG C, dry After dry, implement UV treatment under the following conditions, thickness 1 is set, the priming coat [C] of 000nm.

Apparatus for ultraviolet light treamtent: LH10-10Q-G (Off ュジョ Application UV システ system ズジャパ Application society system)

Import gas: N₂(nitrogen inertia BOX)

Ultraviolet occurring source: microwave mode electrodeless lamp

Accumulative light quantity: 400mJ/cm²

Sample homoiothermic: room temperature.

Then, inorganic layer [A1] and silicon compound layer [B] are arranged by priming coat [C] similarly to Example 1 into Row evaluation similarly to Example 1.Show the result in table 1.

(embodiment 3)

As polymer base material, use noncrystalline cyclic polyolefin film (Japan ゼオ Application society system " the ゼオ of thickness 100 μm ノア Off ィ Le system " ZF14) (" ゼオノア " is registered trade mark), in addition, operate similarly to Example 1, it is thus achieved that resistance Gas film.

(embodiment 4)

As polymer base material, use noncrystalline cyclic polyolefin film (Japan ゼオ Application society system " the ゼオ of thickness 100 μm ノア Off ィ Le system " ZF14), in addition, operate similarly to Example 2, it is thus achieved that gas barrier film.

(embodiment 5)

Inorganic layer [A1] is set so that thickness becomes 950nm, in addition, operates similarly to Example 2, it is thus achieved that resistance Gas film.

(embodiment 6)

Replace inorganic layer [A1] that inorganic layer [A2] is set so that thickness becomes 150nm, in addition, same with embodiment 2 Sample ground operation, it is thus achieved that gas barrier film.

(embodiment 7)

Replace inorganic layer [A1] that inorganic layer [A3] is set so that thickness becomes 150nm, in addition, same with embodiment 2 Sample ground operation, it is thus achieved that gas barrier film.

(embodiment 8)

Silicon compound layer [B] is set so that thickness becomes 50nm, in addition, operates similarly to Example 2, it is thus achieved that Gas barrier film.

(embodiment 9)

Silicon compound layer [B] is set so that thickness becomes 1,000nm, in addition, operates similarly to Example 2, obtain Obtained gas barrier film.

(embodiment 10)

When silicon compound layer [B] is formed, ultraviolet is irradiated accumulative light quantity and is changed to 1,500mJ/cm², in addition, with Embodiment 2 similarly operates, it is thus achieved that gas barrier film.

(embodiment 11)

When silicon compound layer [B] is formed, ultraviolet is irradiated accumulative light quantity and is changed to 1,000mJ/cm², in addition, with Embodiment 2 similarly operates, it is thus achieved that gas barrier film.

(comparative example 1)

Polymer base material is not formed inorganic layer [A], and silicon compound layer is directly set on the surface of polymer base material [B], so that thickness becomes 120nm, in addition, operates, it is thus achieved that gas barrier film similarly to Example 1.

(comparative example 2)

Inorganic layer [A] is not provided with silicon compound layer [B], in addition, operates similarly to Example 1, it is thus achieved that Gas barrier film.

(comparative example 3)

In embodiment 1, the order forming inorganic layer [A] with silicon compound layer [B] is changed, it is thus achieved that with embodiment 1 layer Constitute different gas barrier films.

(comparative example 4)

Inorganic layer [A] is not provided with silicon compound layer [B], in addition, operates similarly to Example 7, it is thus achieved that Gas barrier film.

(comparative example 5)

By CVD, inorganic layer [A] arranges inorganic layer [A3], in addition, operates similarly to Example 2, obtain Obtained gas barrier film.

(comparative example 6)

In example 2, silicon compound layer [B] is replaced to be formed without SiN_xH_yAnd SiO_a(OH)_4-2aOnly by SiO_pN_q The layer formed, in addition, operates, it is thus achieved that gas barrier film similarly to Example 2.

It addition, only by SiO_pN_qThe forming method of the layer formed is to use the coiled sputtering dress of the structure shown in Fig. 2 Put, for the one side of polymer base material, use the sputtering target formed by silicon nitride to implement sputtering, arrange only by SiO_pN_qFormed Layer.Concrete operation is, first, is provided with the takeup type sputter equipment of the sputtering target formed by silicon nitride on sputtering electrode Coiling chamber in, to arrange SiO on let off roll_pN_qThe mode that the face of the side of layer is opposed with sputtering electrode is placed polymer-based Material, unreels polymer base material, via deflector roll, passes through drum cooler.So that degree of decompression becomes 2 × 10^-1The mode of Pa is as oxygen Dividing potential drop 10% imports argon and oxygen to sputtering chamber.Apply to put into electric power 1,000W by high frequency electric source further, so that argon Gas, oxygen gas plasma produce, by sputtering at formation SiO on the surface of polymer base material_pN_qLayer.Thickness is by film conveying speed Degree is adjusted.Then, it is wound in take-up roll via deflector roll.

[table 1]

Industry utilizability

The gas barrier film of the present invention is excellent due to the gas barrier property relative to oxygen, steam etc., therefore for example, it is possible to conduct Packing timber and the electronic device component such as slim TV, solaode of food, medicine etc. usefully use.

The explanation of symbol

1 polymer base material

2 inorganic layers [A]

3 silicon compound layers [B]

4 priming coats [C]

5 polymer base materials

6a takeup type sputter equipment

6b takeup type CVD device

7 coiling chambers

8 let off roll

9,10,11 side deflector roll is unreeled

12 drum coolers

13 sputtering electrodes

14 CVD electrodes

15,16,17 winding side deflector roll

18 take-up rolls

19 gas barrier films

20 metal cylinders

The opposing face in 21 faces being formed with inorganic layer [A] and silicon compound layer [B].

Claims

1. a gas barrier film, is to have inorganic layer at least side of polymer base material successively from described polymer base material side [A] and the gas barrier film of silicon compound layer [B], silicon compound layer [B] is including at least having SiN_xH_y、SiO_pN_qAnd SiO_a (OH)_4-2aThe silicon compound of shown structure, and inorganic layer [A] connects with silicon compound layer [B],

At SiN_xH_y、SiO_pN_qAnd SiO_a(OH)_4-2aIn, x+y=4, p+q=4, a≤2, x, y, p, q ＞ 0.

Gas barrier film the most according to claim 1, described inorganic layer [A] comprises zinc compound and Si oxide.

Gas barrier film the most according to claim 1 and 2, at described silicon compound layer [B]²⁹Si CP/MAS NMR spectra In, when the peak area summation of-30～-120ppm is set to 100, the peak area summation of-30～-50ppm is more than 10 ,-50 ～the peak area summation of-90ppm is more than 10, and the peak area summation of-90～-120ppm is less than 80.

4., according to the gas barrier film described in any one of claims 1 to 3, described inorganic layer [A] is selected from following inorganic layer Any one in [A1]～[A3],

(i) zinc oxide

(ii) silicon dioxide

(iii) aluminium oxide

Inorganic layer [A3]: using oxygen atom relative to silicon atom atomic number than be 1.5～2.0 Si oxide as main constituent Inorganic layer.

Gas barrier film the most according to claim 4, described inorganic layer [A] is described inorganic layer [A1], this inorganic layer [A1] Be by the zinc atom concentration recorded by ICP emission spectrometry method be 20～40atom%, atom concentration be 5～ 20atom%, aluminum atomic concentration are 0.5～5atom%, concentration of oxygen atoms is constituted by the composition of 35～70atom%.

Gas barrier film the most according to claim 4, described inorganic layer [A] is described inorganic layer [A2], this inorganic layer [A2] Formed by zinc sulfide constituted relative to what the mole fraction of zinc sulfide and the total of silicon dioxide was 0.7～0.9.

7. according to the gas barrier film described in any one of claim 1～6, at described polymer base material and described inorganic layer [A] Between there is priming coat [C], described priming coat [C] comprise by there is aromatic ring structure urethanes [C1] crosslinking and The structure obtained.

Gas barrier film the most according to claim 7, described priming coat [C] includes organic silicon compound and/or inorganic silication Compound.

9. an electronic device, it uses the gas barrier film described in any one of claim 1～8.