CN105829093B - Gas barrier film - Google Patents

Abstract

The purpose of the present invention is to provide the gas barrier property with height, and the gas barrier film that resistance to bend(ing) is excellent.The gas barrier film of the present invention is that the gas barrier film with inorganic layer [A] and silicon compound layer [B], silicon compound layer [B] are included at least with SiN successively from above-mentioned polymer base material side in at least side of polymer base material_xH_y、SiO_pN_q、SiO_a(OH)_4‑2aThe silicon compound of structure shown in (x+y=4, p+q=4, a ＜ 2x, y, p, q ＞ 0), and inorganic layer [A] connects with silicon compound layer [B].

Description

Gas barrier film

Technical field

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

Background technology

Have on the surface of polymer base material, utilizes the physical vapors growth method 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 method (CVD method) etc. is formed made of the film of the inorganic matters such as aluminium oxide, silica, magnesia (including inorganic oxide) Gas barrier film, the film are used as the packing timber for needing to block food, the drugs of various gases such as vapor, oxygen etc. and slim electricity Depending on the device component of, solar cell etc..

Develop skill as gas barrier property, disclose for example, using the steam containing organo-silicon compound and oxygen gas, By plasma CVD method, using Si oxide as main body on base material, it is made containing at least one kind of of carbon, hydrogen, silicon and oxygen Compound improves the method (patent document 1) of gas barrier property while to maintain the transparency.In addition, as plasma is utilized Gas barrier property other than the film build methods such as CVD method develops skill, and has following technologies：Make the needle of gas barrier property reduction using reducing Hole, crackle producing cause protrusion, the technology of concave-convex smooth substrates；Using being provided with surface smoothing as a purpose The technology (patent document 2,3 and 4) of the base material of priming coat.In addition the known polysilazanes film conversion for making to be formed by wet coating For the method (patent document 5 and 6) of silicon oxide film, silicon oxynitride film.

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 8-142252 bulletins

Patent document 2：Japanese Unexamined Patent Publication 2002-113826 bulletins

Patent document 3：International Publication No. 2012/137662

Patent document 4：International Publication No. 2013/061726

Patent document 5：International Publication No. 2011/007543

Patent document 6：International Publication No. 2011/004698

Invention content

Problems to be solved by the invention

However, as described in Patent Document 1, being formed using Si oxide as principal component by plasma CVD method In the method for gas barrier layer, according to the type of base material, the film quality for being formed by gas barrier layer is different, the gas barrier property that cannot stablize.For So that gas barrier property is stablized, thickened, result has that resistance to bend(ing) reduces, manufacturing cost increases this problem.In addition, As described in Patent Document 2, the base material of gas barrier layer is formed to turn to the smooth of surface using the method for smooth substrates, using being provided with 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, the raising of performance is not Fully.On the other hand, in patent document 3,4, the film quality due to being formed by gas barrier layer is enhanced, although observing performance It improves, but has steadily performance high-gas resistance difficulty this problem.In addition, disclosed in patent document 5 and 6 by poly- silicon nitrogen Alkane layer is formed in the method for gas barrier layer, and condition when being susceptible to forming layer influences, and has adequately resistance to steadily obtain The gas barrier film of gas needs multiple polysilazane layers carrying out lamination.As a result, thering is resistance to bend(ing) to reduce, manufacturing cost increases Add this problem.

The present invention in view of such prior art background, project be to provide even if do not thicken, it is not multilayer laminated Gas barrier property with height, resistance to bend(ing), excellent adhesion gas barrier film.

The method used for solving the problem

The present invention is in order to solve such project, using following methods.That is,

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

In addition, the preferred embodiment as the present invention, there is following such method.

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

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

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

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

(i) zinc oxide

(ii) silica

(iii) aluminium oxide

Inorganic layer [A2]：Include the inorganic layer of the coexisting phase of zinc sulphide and silica

Inorganic layer [A3]：Using oxygen atom relative to silicon atom atomicity than the Si oxide for 1.5~2.0 as it is main at 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], which is By a concentration of 20~40atom% of the zinc atom measured by ICP emission spectrometry methods, atom concentration be 5~ 20atom%, aluminium atom a concentration of 0.5~5atom%, concentration of oxygen atoms are made of forming for 35~70atom%.

(6) according to the gas barrier film described in (4), above-mentioned inorganic layer [A] is above-mentioned inorganic layer [A2], which is It is formed and is constituted by 0.7~0.9 relative to total mole fraction of zinc sulphide and silica by zinc sulphide.

(7) according to any one of them gas barrier film of (1)~(6), in above-mentioned polymer base material and above-mentioned inorganic layer [A] Between have priming coat [C], the priming coat [C] include will with 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 organo-silicon compound and/or inorganic silicon chemical combination Object.

In addition, the present invention also provides the electronic devices below for having used gas barrier film.

(9) a kind of electronic device, it uses any one of them gas barrier films of (1)~(8).

The effect of invention

According to the present invention it is possible to the gas barrier property for having height relative to vapor is provided, resistance to bend(ing), excellent adhesion Gas barrier film.

Description of the drawings

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 for the takeup type sputter equipment for schematically showing gas barrier film for manufacturing the present invention.

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

Fig. 4 is to show the gas barrier film of the invention 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) experiment.

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

Specific implementation mode

For inventors etc. to obtain the gas barrier property for having height relative to vapor etc., resistance to bend(ing), adaptation are also excellent It has been repeated further investigation for the purpose of gas barrier film, has found by at least side of polymer base material, by inorganic layer [A] With comprising with SiN_xH_y、SiO_pN_qAnd SiO_a(OH)_4-2aThe 3 of structure shown in (x+y=4, p+q=4, a≤2x, y, p, q ＞ 0) The silicon compound layer [B] of a silicon compound carries out lamination in a manner of connecting successively, as a result solves the above subject.

In addition, the meaning difference of above-mentioned 3 structures is as follows.

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

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

SiO_a(OH)_4-2a：The structure of compound when silicon atom is set as 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 institutes Show like that, in the side of polymer base material (symbol 1), from polymer base material side inorganic layer [A] (symbol 2) with comprising with SiN_xH_y、SiO_pN_qAnd SiO_a(OH)_4-2aThe silicon compound layer [B] of 3 silicon compounds of structure shown in (x+y=4, a≤2) (symbol 3) lamination successively.In addition, the minimal composition of the gas barrier film of the example display present invention of Fig. 1, only inorganic layer [A] is configured at the side of polymer base material with silicon compound layer [B], but can match between polymer base material and inorganic layer [A] Other layers are set, furthermore, it is possible in the other layers of opposite side configuration with the side of lamination inorganic layer [A] of polymer base material 1.

In the present invention, the reasons why obtaining significant effect estimates as follows.That is, by by inorganic layer [A] and silicon compound Layer [B] connects, so as to present in the surface of the side of the formation silicon compound layer [B] of inorganic layer [A] near pin hole, The filling of the defects of crackle constitutes the ingredient of silicon compound layer [B], shows high barrier.In addition, above-mentioned 3 kinds of silicon compounds be easy with The ingredient for constituting inorganic layer [A] forms chemical bond, therefore inorganic layer [A] and the adaptation raising of silicon compound layer [B] are not say And explain, it can also obtain excellent adaptation in the case where silicon compound layer [B] superimposed layer has other layers.Further, it wraps The flexibility of silicon compound layer [B] containing above structure is also excellent, therefore can also obtain excellent resistance to bend(ing).

[polymer base material]

Polymer base material used in the present invention preferably has film form from the viewpoint of ensuring flexibility.As film Composition, can be film obtained by being for example film-made by coetrusion of monofilm or 2 layers or more.It, can be with as the type of film Use the film etc. stretched along uniaxial direction or biaxially oriented.

The raw material of polymer base material used in the present invention are not particularly limited, preferably using organic polymer as master Want the raw material of constituent.As the organic polymer that can be suitble to use in the present invention, can enumerate for example, polyethylene, poly- The crystalline polyolefins such as propylene, the noncrystalline cyclic polyolefin with cyclic structure, polyethylene terephthalate, poly- naphthalene two The soap of the polyester such as formic acid glycol ester, polyamide, makrolon, polystyrene, polyvinyl alcohol, ethylene vinyl acetate copolymer Various polymer such as compound, polyacrylonitrile, polyacetals etc..Wherein, it is excellent that the transparency, versatility, mechanical property are preferably comprised Noncrystalline cyclic polyolefin or polyethylene terephthalate.In addition, above-mentioned organic polymer can be homopolymer, copolymer It is any, as organic polymer, a kind can be used only, can also be used in mixed way a variety of.

It, can be in order to keep adaptation, flatness good to the surface of the side of the formation inorganic layer [A] of polymer base material Implement sided corona treatment, corona treatment, UV treatment, ion bombardment processing, solvent processing, by organic matter or inorganic matter or The pre-treatments such as the formation processing for the priming coat that their mixture is constituted.In addition, forming the opposite of the side of inorganic layer [A] Side can have the coating of organic matter, inorganic matter or their mixture for the purpose of the sliding when winding of film improves with lamination Layer.

The thickness of polymer base material used in the present invention is not particularly limited, excellent from the viewpoint of ensuring flexibility Be selected as 500 μm hereinafter, from the viewpoint of ensure relative to stretch, impact intensity, preferably 5 μm or more.Further from film Processing, operation easiness set out, the thickness of polymer base material is 10 μm or more, more preferably 200 μm or less.

[inorganic layer [A]]

Inorganic layer [A] in the present invention may be exemplified zinc (Zn), silicon (Si), aluminium (Al), titanium (Ti), zirconium (Zr), tin (Sn), Oxide, nitride, sulfide or their mixture of the elements such as indium (In), niobium (Nb), molybdenum (Mo), tantalum (Ta).If packet It containing such inorganic matter, is not particularly limited, inorganic layer [A] preferably comprises Si oxide, even more preferably includes zinc impregnation Close object and Si oxide.In addition, as the inorganic layer [A] for obtaining high-gas resistance, it is suitble to using inorganic layer selected from the following [A1] Any one of~[A3].

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

(i) zinc oxide

(ii) silica

(iii) aluminium oxide

Inorganic layer [A2]：Include the inorganic layer of the coexisting phase of zinc sulphide and silica

Inorganic layer [A3]：Using oxygen atom relative to silicon atom atomicity than the Si oxide for 1.5~2.0 as it is main at The inorganic layer divided

Respectively detailed content progress is aftermentioned by inorganic layer [A1]~[A3].

About the thickness of the inorganic layer [A] in the present invention, the thickness of the layer as performance gas barrier property, preferably 10nm or more 1,000nm or less.If the thickness of layer is small, the place that cannot fully ensure gas barrier property is generated, sometimes in polymer base material Gas barrier property is disperseed in face.In addition, if the thickness of layer is excessive, then remaining stress becomes larger in layer sometimes, therefore due to being bent, From external impact, inorganic layer [A] is easy to crack, along with using and gas barrier property reduces.Therefore, the thickness of inorganic layer [A] Degree is 10nm or more, is further 100nm or more, is on the other hand 1,000nm hereinafter, 500nm or less.The thickness of inorganic layer [A] Degree usually can be measured by using the cross-section that transmission electron microscope (TEM) carries out.

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

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

In the present invention, formed inorganic layer [A] method be not particularly limited, for example, can by vacuum vapour deposition, splash Method, ion plating method, CVD method etc. are penetrated to be formed.In these methods, due to can be easy and inorganic layer [A] denselying be formed, Therefore preferably sputtering method or CVD method.

[inorganic layer [A1]]

For in the present invention as inorganic layer [A] be suitble to it is using, as comprising (i) zinc oxide, (ii) silica The coexisting phase of (iii) aluminium oxide is (hereinafter, sometimes by the coexisting phase of (i) zinc oxide, (ii) silica and (iii) aluminium oxide Be expressed as " zinc oxide-silicon dioxide-aluminium oxide coexisting phase ") layer inorganic layer [A1], illustrate details.In addition, dioxy SiClx (SiO₂) according to condition when generating, the group from the silicon of above-mentioned composition formula and several deviations of the composition ratio of oxygen is generated sometimes An accepted way of doing sth (SiO~SiO₂), but it is expressed as silica or SiO here₂.It is right about the deviation of the chemical formula with such ratio of components In zinc oxide, aluminium oxide be also same processing, respectively with depending on generating when the deviation of ratio of components of condition it is unrelated, respectively It is expressed as zinc oxide or ZnO, aluminium oxide or Al₂O₃。

So that gas barrier property is become good reason supposition by application inorganic layer [A1] in the gas barrier film of the present invention is Because the noncrystalline component of crystalline ingredient and silica that zinc oxide is included coexists, to inhibit to easily generate crystallite Zinc oxide crystalline growth, grain size becomes smaller, therefore layer is densified, and inhibits the transmission of vapor.

Furthermore, it is possible to think by making aluminium oxide coexist, to make zinc oxide compared with the case where silica coexists, Crystalline growth can be further suppressed, therefore the densification of further layer may be implemented, along with this, splitting when for by using Gas barrier property reduction caused by the generation of line can also inhibit.

The composition of inorganic layer [A1] is as described later, can be measured by ICP emission spectrometry methods.It is preferred that passing through A concentration of 20~40atom% of zinc atom that ICP emission spectrometry methods measure, atom concentration are 5~20atom%, and aluminium is former Son a concentration of 0.5~5atom%, a concentration of 35~70atom% of O atom.If zinc atom concentration is more than 40atom% or silicon Atomic concentration is less than 5atom%, then inhibits the silica of the crystalline growth of zinc oxide and/or aluminium oxide insufficient, therefore sometimes Gap section, defect part increase, and cannot get high-gas resistance.If zinc atom concentration is less than 20atom% or atom concentration More than 20atom%, then the noncrystalline component of the silica inside layer increases sometimes and the flexibility of layer reduces.In addition, if Aluminium atom concentration is more than 5atom%, then the compatibility of zinc oxide and silica is exceedingly got higher, therefore film is hardened, and has phase It is easy to crack for heat, from external stress.If aluminium atom concentration is less than 0.5atom%, zinc oxide and two The compatibility of silica becomes inadequate, and cambial interparticle binding force cannot improve, therefore flexibility reduces sometimes.This Outside, if concentration of oxygen atoms is more than 70atom%, the defects of inorganic layer [A1] amount increases, therefore cannot get sometimes desired Gas barrier property.If concentration of oxygen atoms be less than 35atom%, zinc, silicon, aluminium the state of oxidation become inadequate, cannot inhibit to tie Crystals growth, grain size become larger, therefore gas barrier property reduces sometimes.The tendency consideration brought from the content by each atom illustrated above, More preferable a concentration of 25~35atom% of zinc atom, atom concentration are 10~15atom%, aluminium atom a concentration of 1~ 3atom%, concentration of oxygen atoms are 50~64atom%.

Used mixed sintering material, which similarly forms, when the composition of inorganic layer [A1] is by formation with layer is formed, because This by using the layer with target composition consistent composition mixed sintering material, so as to adjust the group of inorganic layer [A1] At.

The composition of inorganic layer [A1] by ICP emission spectrometry methods, quantitative zinc, silicon, aluminium each element, with zinc oxide with The mode of the ratio of components of silica, aluminium oxide and contained inorganic oxide calculates.In addition, oxygen atom assumes that zinc original Son, silicon atom, aluminium atom are respectively with zinc oxide (ZnO), silica (SiO₂), aluminium oxide (Al₂O₃) mode exist and calculate Go out.ICP emission spectrographic analyses are generated luminous light when can be by sample to be imported to plasma source portion together with argon gas Spectrum carries out the analysis method of measurement while multielement, can be applied to composition analysis.The further lamination on inorganic layer [A1] In the case of inorganic layer, resin layer, shielding layer can be carried out as desired by ion(ic) etching, liquid processing, then carry out ICP Emission spectrographic analysis.

[inorganic layer [A2]]

Next, in the present invention as inorganic layer [A] be suitble to it is using, as comprising zinc sulphide and silica Coexisting phase (hereinafter, being sometimes expressed as the coexisting phase of zinc sulphide and silica " zinc sulphide-silica coexisting phase ") The inorganic layer [A2] of layer, illustrates details.In addition, here, silica (SiO₂) condition when being generated according to it, it gives birth to sometimes At composition formula (SiO~SiO from the silicon of above-mentioned composition formula and several deviations of the composition ratio of oxygen₂), be expressed as silica or SiO₂.Also it is same processing for zinc sulphide, when with depending on generating about the deviation of the chemical formula with such ratio of components Condition ratio of components deviation it is unrelated, be expressed as zinc sulphide or ZnS.

In the gas barrier film of the present invention by application inorganic layer [A2] gas barrier property become good reason supposition be because For the noncrystalline component of crystalline ingredient and silica that zinc sulphide is included coexists, to inhibit to easily generate crystallite The crystalline growth of zinc sulphide, grain size become smaller, therefore layer is densified, and inhibits the transmission of vapor.

In addition, the zinc sulphide comprising the zinc sulphide for inhibiting crystalline growth-silica coexisting phase with only by inorganic oxide The layer that object or metal oxide are formed becomes higher compared to flexibility, becomes and is not likely to produce relative to heat, from external stress The layer of crackle, it can be considered that by the such inorganic layer of application [A2], the generation institute of crackle when hence for by using Caused gas barrier property reduction can also inhibit.

The preferred zinc sulphide of composition of inorganic layer [A2] is 0.7 relative to total mole fraction of zinc sulphide and silica ~0.9.If zinc sulphide is more than 0.9 relative to total mole fraction of zinc sulphide and silica, inhibit zinc sulphide The silica of crystalline growth is insufficient, therefore gap section, defect part increase sometimes, cannot get defined gas barrier property.In addition, If zinc sulphide is less than 0.7, the two of inorganic layer [A2] inside relative to total mole fraction of zinc sulphide and silica The noncrystalline component of silica increases and the flexibility of layer reduces, thus sometimes gas barrier film relative to mechanical bent flexibility It reduces.Further preferred range about zinc sulphide relative to zinc sulphide and total mole fraction of silica, from Shown on the tendency brought of content of each compound consider, be 0.75~0.85.

Same group of used mixed sintering material is shaped as when the composition of inorganic layer [A2] is by with the formation of layer, therefore By using the mixed sintering material of the composition consistent with purpose, the composition of inorganic layer [A2] can be adjusted.

The composition analysis of inorganic layer [A2] can find out the ratio of components of zinc and silicon first by ICP emission spectrographic analyses, Rutherford's backscattering method is used based on the value, each element is subjected to quantitative analysis, knows zinc sulphide and silica and contained The ratio of components for the other inorganic oxides having.ICP emission spectrographic analyses are can be by importing plasma by sample together with argon gas Generated luminescent spectrum when body light source portion carries out the analysis method of measurement while multielement, can be applied to composition analysis. In addition, the charged particle accelerated with high voltage can be irradiated in sample by rutherford's backscattering method, by rebounding from it The number of charged particle, energy into the specific, quantitative of row element, know the ratio of components of each element.In addition, inorganic layer [A2] is The composite layer of sulfide and oxide, thus it is real by the way that rutherford's backscattering method that the ratio of components of sulphur and oxygen is analyzed can be carried out Apply analysis.In the case of further lamination inorganic layer, resin layer on inorganic layer [A2], it can be lost as desired by ion Quarter, liquid processing carry out shielding layer, are then analyzed using ICP emission spectrographic analyses and rutherford's backscattering method.

[inorganic layer [A3]]

Next, for being suitble to original use, by oxygen atom relative to silicon atom as inorganic layer [A] in the present invention Inorganic layer [A3] of the subnumber than the Si oxide for 1.5~2.0 as principal component, illustrates details.Here, it is so-called it is main at Point, refer to the 60 mass % or more of inorganic layer [A3] entirety, it is then preferred if it is 80 mass % or more.In addition, above-mentioned principal component Silica (SiO₂) condition when being generated according to it, it generates sometimes several partially from the silicon of above-mentioned composition formula and the composition ratio of oxygen From composition formula (SiO~SiO₂), but it is expressed as silica or SiO₂。

The forming method of inorganic layer [A3] is preferably that can form the CVD method of fine and close film.In CVD method, can will after The gas of the silane or organo-silicon compound stated is set as monomer, is activated by the plasma of high intensity, anti-using polymerization Fine and close film should be formed.Here so-called organo-silicon compound can be enumerated for example, methyl-monosilane, dimethylsilane, trimethyl silicane Alkane, tetramethylsilane, ethylsilane, diethylsilane, triethylsilane, tetraethyl silane, npropoxysilane, dipropoxy silicon Alkane, tripropoxy silane, tetrapropoxysilane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, dimethyl two Siloxanes, tetramethyl disiloxane, hexamethyldisiloxane, hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethyl Pentamethylene siloxanes, ten monomethyl rings, six siloxanes, dimethyl disilazane, trimethyldisilazane, tetramethyl-disilazane, Hexamethyldisilazane, hexamethyl cyclotrisilazane, octamethylcyclotetrasilazane, five silazane of decamethyl ring, ten monomethyl rings Six silazane etc..Wherein, from operating aspect, preferably hexamethyldisiloxane, tetraethoxysilane.

The composition of inorganic layer [A3] can be measured by x-ray photoelectron optical spectroscopy (XPS methods) as described later.It is logical Cross XPS methods measurement oxygen atom relative to silicon atom atomicity than be preferably 1.5~2.0 range, even more preferably for 1.4~1.8 range.If silicon atom relative to oxygen atom atomicity ratio be more than 2.0, including oxygen atom quantitative change It is more, therefore gap section, defect part increase sometimes, cannot get defined gas barrier property.In addition, if silicon atom is relative to oxygen original The atomicity ratio of son is less than 1.5, then oxygen atom is reduced sometimes, becomes fine and close film, but flexibility reduces.

[silicon compound layer [B]]

Next, for silicon compound layer [B], illustrate details.Silicon compound layer [B] in the present invention is to include tool There is SiN_xH_y、SiO_pN_qAnd SiO_a(OH)_4-2aThe silicon compound of structure shown in (x+y=4, p+q=4, a≤2x, y, p, q ＞ 0) Layer.As a purpose by the control of refractive index, hardness, adaptation etc., can include alkoxy silane, organopolysiloxane etc. its Its silicon compound.In addition, the composition of each compound of silicon compound layer [B] can pass through²⁹Si CP/MAS NMR methods are surveyed It is fixed.

By applying silicon compound layer [B] in the gas barrier film of the present invention, to which gas barrier property becomes good reason such as (i) below and (ii) is estimated like that.

(i) first, as the contribution of layer, presumption layer is by including SiO_pN_qShown in silicon-oxygen nitride, to only by SiO₂The layer of formation is compared as fine and close layer, inhibits the transmission of oxygen and vapor, therefore as the high layer of gas barrier property, in addition, With only by Si₃N₄The layer of formation is high compared to flexibility, therefore is not likely to produce crackle relative to heat, from external stress when use, As can inhibit by crackle generate caused by gas barrier property reduce layer.

(ii) next, as lamination and the tribute that brings in a manner of connecting by inorganic layer [A] and silicon compound layer [B] It offers, presumption is as follows.

Constitute ingredient the defects of being filled in pin hole, crackle possessed by inorganic layer [A] of silicon compound layer [B] and being capable of table Existing high barrier.

By connecting with inorganic layer [A], the ingredients such as zinc that above-mentioned inorganic layer [A] is included are used as and urge silicon compound layer [B] Agent works and the film quality of silicon compound layer [B] becomes prone to be modified, and gas barrier property further increases.

By comprising 3 kinds of silicon compounds, and only by SiO_pN_qThe layer formed as principal component is compared, with composition inorganic layer It is easy that the ingredient of [A], which forms chemical bond, therefore inorganic layer [A] and the adaptation of the interface zone of silicon compound layer [B] carry Height can obtain excellent resistance to bend(ing) when use.

The thickness of silicon compound layer [B] used in the present invention is preferably 50nm or more 2, and 000nm is hereinafter, more preferably 50nm or more 1,000nm.If the thickness of silicon compound layer [B] becomes smaller, stable water-vapor barrier cannot be obtained sometimes Energy.If the thickness of silicon compound layer [B] becomes too much, sometimes due to the remaining stress of institute becomes larger in silicon compound layer [B] 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 from the cross-section image obtained by transmission electron microscope (TEM) into Row measures.

The median plane mean roughness SRa of silicon compound layer [B] used in the present invention is preferably 10nm or less.If made SRa be 10nm hereinafter, then gas barrier property reproducibility improve, therefore preferably.If the SRa on the surface of silicon compound layer [B] More than 10nm, then in the part more than bumps, the crackle caused by stress concentration is easy to generate, therefore becomes the weight of gas barrier property sometimes The reason of multiple reproducibility reduces.Therefore, in the present invention, it is preferred to make the SRa of silicon compound layer [B] for 10nm hereinafter, more preferably For 7nm or less.

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

By the silicon compound layer [B] of the present invention²⁹Si CP/MAS NMR spectras are shown in Figure 4.It is -30 in chemical shift The region of~-50ppm, the region of -50~-90ppm and -90~-120ppm observe the absorption of silicon, it is meant that from the left side of figure It rises and has been 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) (bibliography： P.Diehl, E.Fluck, R.Kosfeld etc. write " NMR Basic Principles and Progress " Springer- Verlag Berlin Heidelberg distribution, 1981 152-163 pages).If by the peak face of -30~-120ppm For product summation when being set as 100, the peak area summation of -30~-50ppm is 10 or more, the peak area summation of -50~-90ppm be 10 with On, and the peak area summation of -90~-120ppm be 80 hereinafter, then become with height gas barrier property, and resistance to bend(ing), The layer of excellent adhesion, therefore preferably.Further, more preferably when the peak area summation of -30~-120ppm is set as 100, - The peak area summation of 30~-50ppm is 10~40, the peak area summation of -50~-90ppm is 10~40, and -90~- The peak area summation of 120ppm is 30~80.In the case where being unsatisfactory for above range, silicon compound layer [B], which becomes, exceedingly to be caused Close film and flexibility is insufficient, be easy to crack due to heat, from external stress, so that gas barrier property is reduced sometimes.In addition, The compactness of silicon compound layer [B] is insufficient on the contrary, cannot get sufficient gas barrier property sometimes.From such a viewpoint, more excellent It is 13~30 to choose and state the peak area summation of -30~-50ppm, 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 Include 3 kinds of silicon compounds, 0.1~100 mass % of the present invention with summation meter.

Raw material as silicon compound layer used in the present invention [B] is, it is preferable to use the silication with polysilazane skeleton Close object.As the silicon compound with polysilazane skeleton, it is preferable to use for example with shown in following chemical formula (1) The compound of separation structure.Specifically, can use in Perhydropolysilazane, organopolysilazane and their derivative At least one.In the present invention, it is preferable to use R shown in following chemical formula (1) from the viewpoint of gas barrier property raising₁、R₂、 R₃All hydrogen Perhydropolysilazane, but can also use hydrogen part or all by the organic groups such as alkyl instead of Organopolysilazane.Furthermore, it is possible to form use with single, more than binary can also will be used in mixed way.In addition, n tables Show 1 or more integer.

Next, illustrating the forming method of the silicon compound layer [B] of the present invention.It is preferred that will be wrapped on inorganic layer [A] first Coating containing above compound (1) adjusts solid component concentration in such a way that the thickness after drying becomes desired thickness, leads to Reversed rubbing method, gravure coating process, bar rubbing method, stick coating method, die coating method, spray coating method, method of spin coating etc. is crossed to be coated.This Outside, in the present invention, from the viewpoint of coating adaptability, it is also preferred that the use of organic solvent will include above-mentioned chemical formula (1) Coating is diluted.Specifically, can use the hydrocarbon system solvents such as dimethylbenzene, toluene, turpentine oil, Solvesso, dibutyl ethers, Ether series solvents such as ethyl-butyl ether, tetrahydrofuran etc..And solid component concentration is preferably diluted to 10 mass % or less to make With.These solvents can be used alone or be used in mixed way two or more.

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

Then, the film after coating is preferably made to be dried to remove retarder thinner.Here, as hot used in drying Source is not particularly limited, and can use the arbitrary heat sources such as steam heater, electric heater, infrared heater.In addition, being Raising gas barrier property, heating temperature are preferably carried out at 50~150 DEG C.In addition, preferably to carry out several seconds~1 small for heating treatment time When.Further, in heat treatment, temperature can be certain, temperature can also be made slowly to change.In addition, in drying process, It can heat while being adjusted humidity in the range of 20~90%RH with relative humidity.Above-mentioned heating Processing carries out in the state of can be in enclosed air or in non-active gas.

Next, can be by implementing corona treatment, ultraviolet treatment with irradiation, flash lamp arteries and veins to the film after drying Punching handles isoreactivity energy-ray treatment with irradiation to make the composition of above-mentioned film be modified, and obtains being closed containing 3 kinds of silication for the present invention The silicon compound layer [B] of object.It is excellent from easy and productivity as active energy beam treatment with irradiation, and be easy to get The composition of even silicon compound layer [B] sets out, it is preferable to use UV treatment.As UV treatment, under atmospheric pressure or depressurize Under any one can, but from the viewpoint of versatility, production efficiency, preferably carry out UV treatment under atmospheric pressure. Oxygen concentration when about the above-mentioned UV treatment of progress, from the viewpoint of the composition control of silicon compound layer [B], oxygen partial pressure Preferably 1.0% hereinafter, more preferably 0.5% or less.It can be set in a manner of as desired ratio of components relatively wet Degree.In addition, more preferably in above-mentioned UV treatment, oxygen concentration is reduced using nitrogen.

As ultraviolet light occurring source, high-pressure mercury-vapor lamp metal halide lamp, microwave mode electrodeless lamp, low pressure can be used Ultraviolet light occurring source known to mercury vapor lamp, xenon lamp etc., from the viewpoint of production efficiency, in the present invention, it is preferred to use xenon lamp.

The accumulative light quantity of ultraviolet light irradiation is preferably 0.5~10J/cm², more preferably 0.8~7J/cm².If above-mentioned tired Photometric amount is 0.5J/cm²More than, then desired silicon compound layer [B] composition can be obtained, therefore preferably.On in addition, if It is 10J/cm to state accumulative light quantity²Hereinafter, the destruction to polymer base material, inorganic layer [B] can be then reduced, therefore preferably.

In addition, in the present invention, when UV treatment, in order to improve production efficiency, more preferably on one side by the painting after drying Film is heated carries out UV treatment on one side.As heating temperature, preferably 50~150 DEG C, more preferably 80~130 DEG C. If heating temperature is 50 DEG C or more, high efficiency can be obtained, therefore preferably, in addition, if heating temperature is 150 DEG C Hereinafter, be then not easy to cause deforming, going bad for the other materials such as polymer base material, therefore 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 in above-mentioned polymer base material Priming coat [C] is set between above-mentioned inorganic layer [A].On polymer base material there are in the case of the defects of protrusion, small scratch, Sometimes using drawbacks described above as starting point for the inorganic layer [A] being stacked on polymer base material also generate pin hole, crackle and damage Gas barrier property, resistance to bend(ing), therefore it is preferably provided with the priming coat [C] of the present invention.In addition, in polymer base material and inorganic layer [A] In the case that the difference of thermal dimensional stability is big, gas barrier property, resistance to bend(ing) also reduce sometimes, therefore are preferably provided with priming coat [C].This Outside, about priming coat used in the present invention [C], from the viewpoint of thermal dimensional stability, resistance to bend(ing), preferably comprising will have Structure obtained by having the urethanes [C1] of aromatic ring structure to be crosslinked further further preferably is selected from olefinic 1 in unsaturated compound [C2], Photoepolymerizationinitiater initiater [C3] and organo-silicon compound [C4] and inorganic silicon compound [C5] Kind or more silicon compound.

[urethanes [C1] with aromatic ring structure]

The urethanes [C1] with aromatic ring structure that can be used in the present invention have in main chain or side chain Aromatic ring and urethane bond, for example, epoxy (methyl) acrylic acid of intramolecular with hydroxyl and aromatic ring can be made Ester (c1), diol compound (c2), diisocyanate cpd (c3) are polymerize to obtain.

Epoxy (methyl) acrylate (c1) as intramolecular with hydroxyl and aromatic ring, can make bisphenol A-type, hydrogen Change the di-epoxy compounds of aromatic diols such as bisphenol A-type, bisphenol-f type, A Hydrogenated Bisphenol A F types, resorcinol, quinhydrones and (methyl) Acrylic acid derivative is reacted to obtain.

As diol compound (c2), can use for example, ethylene glycol, diethylene glycol (DEG), polyethylene glycol, propylene glycol, 1,3- third Glycol, 1,3 butylene glycol, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonyls Glycol, 1,10- decanediols, 2,4- dimethyl -2- ethyl hexane -1,3- glycol, neopentyl glycol, 2- ethyl -2- butyl -1,3- third Glycol, 3- methyl-1s, 5- pentanediols, 1,2- cyclohexanedimethanols, 1,4 cyclohexane dimethanol, 2,2,4,4- tetramethyls -1,3- Cyclobutanediol, 4,4 '-thio xenols, bisphenol-A, 4,4 '-methylene-di-phenols, 4,4 '-(Asias 2- norborny) xenols, 4, It is 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 ビ Application ジ オ ー 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 for example, 1,3- phenylene diisocyanate, two isocyanide of Isosorbide-5-Nitrae-penylene Acid esters, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, 2,4- methyl diphenylene diisocyanates, 4,4- hexichol The aromatic systems such as dicyclohexylmethane diisocyanate diisocyanate, ethylidene diisocyanate, hexamethylene diisocyanate, 2,2,4- Trimethyl hexamethylene diisocyanate, lysine diisocyanate, relies ammonia at 2,4,4- trimethyl hexamethylene diisocyanates The fatty families such as sour triisocyanate diisocyanate cpd, isophorone diisocyanate, dicyclohexyl methyl hydride -4,4- two Alicyclic ring families isocyanate compound, xylene diisocyanate, the tetramethyls such as isocyanates, methylcyclohexylidene diisocyanate The aromatic-aliphatics such as base benzene dimethylene diisocyanate system isocyanate compound etc..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 range of desired weight average molecular weight, without special It does 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) be 5,000~100,000, then gained cured film thermal dimensional stability, Resistance to bend(ing) is excellent, therefore preferably.In addition, the weight average molecular weight (Mw) in the present invention is surveyed using gel permeation chromatography It is fixed, the value to be converted with standard polystyren.

[olefinic unsaturated compound [C2]]

As the olefinic unsaturated compound [C2] for the raw material that can be used as priming coat [C], can enumerate for example, Isosorbide-5-Nitrae-fourth two Two (methyl) acrylate such as alcohol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, three (first of pentaerythrite Base) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five The multifunctional (methyl) acrylates such as (methyl) acrylate, dipentaerythritol six (methyl) acrylate, bisphenol type epoxy two The epoxies such as (methyl) acrylate, bisphenol F type epoxy two (methyl) acrylate, bisphenol S type epoxy two (methyl) acrylate Acrylate etc..Wherein, the preferably excellent multifunctional (methyl) acrylate of thermal dimensional stability, surface protection performance.This Outside, they can form use with single, more than binary can also will be used in mixed way.

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

[Photoepolymerizationinitiater initiater [C3]]

As the Photoepolymerizationinitiater initiater [C3] for the raw material that can be used as priming coat [C], if the resistance of the present invention can be kept The gas barrier property and resistance to bend(ing) of gas film, can cause photopolymerization, be not particularly limited.As can be suitble to make in the present invention Photoepolymerizationinitiater initiater may be exemplified compound below.

2,2- dimethoxy -1,2- diphenylethane -1- ketone, 1- hydroxy-cyciohexyls phenyl ketone, 2- hydroxy-2-methyls - 1- phenyl-propan -1- ketone, 1- [4- (2- hydroxyl-oxethyls)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone, 2- hydroxyls - 1- { 4- [4- (2- hydroxy-2-methyls-propionyl)-benzyl] phenyl } -2- methyl-propan -1- ketone, phenylglyoxylic acid methyl ester, 2- first Base -1- (4- methyl mercaptos phenyl) -2- morpholino propane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls)-fourth The alkylbenzenes such as ketone -1,2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] -1- butanone Ketone system Photoepolymerizationinitiater initiater.

2,4,6- trimethylbenzoyl-diphenyls-phosphine oxide, bis- (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides etc. Acylphosphine oxide system Photoepolymerizationinitiater initiater.

The titanocenes such as bis- (η 5-2,4- cyclopentadiene -1- bases)-bis- (bis- fluoro- 3- of 2,6- (1H- pyrroles -1- bases)-phenyl) titaniums It is Photoepolymerizationinitiater initiater.

There is the photopolymerization of oxime ester structure to cause by 1,2- octanediones, 1- [4- (thiophenyl)-, 2- (0- benzoyls oxime)] etc. Agent etc..

Wherein, from the viewpoint of curability, surface protection performance, be preferably selected from 1- hydroxy-cyciohexyls phenyl ketone, It is 2- methyl-1s-(4- methyl mercaptos phenyl) -2- morpholino propane -1- ketone, 2,4,6- trimethylbenzoyl-diphenyls-phosphine oxide, double Photoepolymerizationinitiater initiater in (2,4,6- trimethylbenzoyls)-phenyl phosphine oxide.In addition, they can be made with single forming With more than binary can also being used in mixed way.

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

[organo-silicon compound [C4]]

As the organo-silicon compound [C4] for the raw material that can be used as priming coat [C], can enumerate for example, vinyl trimethoxy Base silane, vinyltriethoxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- glycidoxypropyl groups Methyl dimethoxysilane, 3- glycidoxypropyltrime,hoxysilanes, 3- glycidoxypropyl diethoxy silicon Alkane, 3- glycidoxypropyl groups triethoxysilane, 3- methacryloxypropylmethyl dimethoxysilanes, 3- methyl-props Alkene acryloxypropylethoxysilane trimethoxy silane, 3- methacryloxypropyl methyl diethoxysilanes, 3- methacryloxypropyls Base propyl-triethoxysilicane, 3- acryloyloxypropyltrimethoxysilanes, N-2- (amino-ethyl) -3- amino propyl methyls Dimethoxysilane, N-2- (amino-ethyl) -3- TSL 8330s, 3- TSL 8330s, 3- Aminopropyltriethoxywerene werene, 3- isocyanate propyl triethoxysilanes etc..

Wherein, preferably include to be selected from 3- from the viewpoint of polymerization activity when curability, active energy beam irradiate Methacryloxypropyl trimethoxy silane, 3- methacryloxypropyls, vinyl trimethoxy At least one kind of organo-silicon compound in base silane and vinyltriethoxysilane.In addition, they can be formed with single It uses, more than binary can also will be used in mixed way.

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

[inorganic silicon compound [C5]]

As the inorganic silicon compound [C5] for the raw material that can be used as 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 It encloses, more preferably the range of 5~80nm.In addition, so-called primary particle size here, refers to the ratio that will be found out using gas adsorption method The particle diameter d that surface area s is found out 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 200nm or more 4,000nm hereinafter, more preferably 300nm or more 3,000nm with Under, further preferably 500nm or more 2,000nm or less.If the thickness of priming coat [C] is too small, cannot inhibit sometimes by The harmful effect of defect on polymer base material caused by existing protrusion, small scratch etc..If the thickness mistake of priming coat [C] Greatly, then the flatness of priming coat [C] reduces and is stacked on the concave-convex on surface inorganic layer [A] on above-mentioned priming coat [C] sometimes Shape also becomes larger, and gap is formed between the sputtering particle of institute's lamination, therefore film quality is not easy to become fine and close, is not easy to obtain carrying for gas barrier property High effect.

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

The median plane mean roughness SRa of priming coat [C] is preferably 10nm or less.If make SRa be 10nm hereinafter, if easily It is improved in the reproducibility of the inorganic layer [A] for obtaining homogeneous on priming coat [C], gas barrier property, therefore preferably.If priming coat The SRa on the surface of [C] is excessive, then the concaveconvex shape on surface inorganic layer [A] on priming coat [C] also becomes larger sometimes, in lamination Gap is formed between sputtering particle, therefore film quality is not easy to become fine and close, is not easy to obtain the improvement effect of gas barrier property.In addition, in bumps The reason of more parts crackle caused by stress collection is easy to generate, therefore the reproducibility for becoming gas barrier property sometimes reduces. Therefore, in the present invention, it is preferred to make priming coat [C] SRa be 10nm hereinafter, further preferably 7nm or less.

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

[other layers]

On the most surface of the gas barrier film of the present invention, it can be formed with scratch resistance in the range of not reducing gas barrier property Property raising for the purpose of hard conating, can be will include organic high molecular compound film layer pressure made of lamination constitute.Separately Outside, so-called most surface here, refer on polymer base material, inorganic layer [A] and silicon compound layer [B] in a manner of connecting successively The surface of the silicon compound layer [B] of side after being stacked, not connecting with inorganic layer [A].

[electronic device]

The gas barrier film of the present invention has high-gas resistance, therefore can be used for various electronic devices.For example, can be suitble to use The electronic device as the tergite, flexible circuit board of solar cell.The electronics device of the gas barrier film of the present invention is used Part has excellent gas barrier property, therefore can inhibit the reduced performance of the device brought by vapor etc..

[other purposes]

The gas barrier film of the present invention has high-gas resistance, therefore other than electronic device, can also be suitable as food, The film for packaging etc. of electronic unit.

Embodiment

Hereinafter, specifically describing the present invention based on embodiment.However, the present invention is not limited to the following examples.

[evaluation method]

First, illustrate the evaluation method in each embodiment and comparative example.It is recorded as long as no special, then it is every to evaluate n numbers A level is 5 specimen, using the average value of the measured value of 5 specimen of gained as measurement result.

(1) thickness of layer

Using micro- sampling system ((strain) Hitachi FB-2000A), pass through focused ion beam (Focused Ion Beam：FIB) method makes cross-section sample.Pass through transmission electron microscope ((strain) Hitachi H- 9000UHRII), it is 300kV to make accelerating potential, observes the section of observation sample product, measures inorganic layer [A], silicon compound layer The thickness of [B], priming coat [C].

(2) median plane mean roughness SRa

Using three-dimensional surface roughness measuring machine (society of little Ban research institutes system), under the following conditions for each layer surface into Row measures.

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

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

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

Finding speed：0.1mm/s

Determination of the environment：23 DEG C, relative humidity 65%RH of temperature, in air.

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

By vacuum evaporation, the calcium layer of thickness 100nm is formed on face silicon compound layer [B] of gas barrier film, then, together Sample is by vacuum evaporation, and in above-mentioned calcium layer, the aluminium layer of thickness 3000nm is formed in a manner of covering calcium layer whole region.Into one Step, across the glass of thermosetting epoxy resin coating thickness 1mm on above-mentioned aluminium layer face, is handled after aluminium layer is formed at 100 DEG C 1 hour, obtain evaluation sample.The sample of gained is handled 800 hours in 40 DEG C of temperature, relative humidity 90%RH, above-mentioned place After reason, the transit dose of vapor is measured by calculating the amount of the calcium corroded due to vapor.Moisture-vapor transmission sample Number is that each level is 2 specimen, and it is that each specimen is carried out 5 times to measure number, and 10 points of average value of gained is set as water steaming Vapor permeability (g/ (m²·d))。

(4) composition of inorganic layer [A1]

The composition analysis of [A1] by ICP emission spectrographic analyses (エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ ー societies system, SPS4000 it) carries out.The stage of inorganic layer [A1] will be formed on polymer base material or priming coat (by silicon compound layer [B] Before carrying out lamination) the sample nitric acid that has sampled and sulfuric acid carries out heat resolve, and it carries out heating dissolving with dust technology and filter Separation.After insoluble ingredient heating ashing, is melted using sodium carbonate, dissolved using dust technology, with previous filtrate Merge and carries out constant volume.For the solution, the content of zinc atom, silicon atom, aluminium atom is measured, atomicity ratio is converted into.In addition, oxygen Atom is to assume zinc atom, silicon atom, aluminium atom respectively with zinc oxide (ZnO), silica (SiO₂), aluminium oxide (Al₂O₃) Mode exists and the calculated value that finds out.

(5) composition of inorganic layer [A2]

The composition analysis of inorganic layer [A2] passes through ICP emission spectrographic analyses (エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ ー societies system, SPS4000) it carries out.The stage that inorganic layer [A2] is formed on polymer base material or priming coat (is closed silication Before nitride layer [B] carries out lamination) the sample nitric acid that has sampled and sulfuric acid carries out heat resolve, carry out heating dissolving with dust technology And it is separated by filtration.After insoluble ingredient heating ashing, is melted using sodium carbonate, dissolved using dust technology, and it is previous Filtrate merge carry out constant volume.For the solution, the content of zinc atom, silicon atom is measured.Next, further being made based on the value With rutherford's backscattering method (day new Ha イ ボ ル テ ー ジ (strain) AN-2500 processed), by zinc atom, silicon atom, sulphur atom, oxygen Atom carries out quantitative analysis, finds out the ratio of components of zinc sulphide and silica.

(6) composition of inorganic layer [A3]

The composition analysis of inorganic layer [A3] by using x-ray photoelectron optical spectroscopy (XPS methods), calculate oxygen atom relative to The atomicity ratio of silicon atom.Determination condition is as described below.

Device：Quantera SXM (PHI societies system)

It is X ray excited：monochromatic AlKα1,2

X-ray diameter：100μm

Photoelectron deviates from angle：10°.

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

The powdered sample for having reamed silicon compound layer [B] with single-blade is filled in the coupon of 7.5mm φ, is used²⁹Si CP/MAS NMR methods carry out composition analysis, find out spectrum as show example in Fig. 4.Calculate by above-mentioned spectrum- The peak area summation of -30~-50ppm when the peak area summation of 30~-120ppm is set as 100, the peak area of -50~-90ppm Summation, the peak area summation of -90~-120ppm.Determination condition is as described below.

Device：Chemagnetics societies CMX-300

Measure nuclear frequency：59.636511MHz(²⁹Si cores)

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 point：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

The calculating of peak area：Integration method.

(8) resistance to bend(ing)

By each 2 specimen of the level sampling of gas barrier film at 100mm × 140mm.As shown in Figure 5, for gas barrier film, Central portion in face opposing face (symbol 21) side with the inorganic layer [A] and silicon compound layer [B] that are formed with (symbol 19) is solid The metal cylinder (symbol 20) for determining diameter 5mm, along the cylinder, 0 ° of the angle of embrace (sample is the state of plane) from cylinder to pair In the range of the angle of embrace of cylinder becomes 180 ° (states turned back around cylinder), 100 bending actions are carried out, then with shown in (3) Method carry out moisture-vapor transmission evaluation.It is that each specimen is carried out 5 times to measure number, and 10 points of average value of gained is set Moisture-vapor transmission after being tested for resistance to bend(ing).

(9) adaptation

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

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

(formation of inorganic layer [A1])

Using the coiled sputter equipment (symbol 6a) of structure shown in Fig. 2, in the one side of polymer base material (symbol 5) Implement to sputter used as the sputtering target of the mixed sintering material formed by zinc oxide, silica and aluminium oxide, setting is inorganic Layer [A1].

Specific operation is as described below.First, zinc oxide/silica/oxygen is provided on sputtering electrode (symbol 13) In the coiling chamber (symbol 7) for changing the takeup type sputter equipment that the composition mass ratio of aluminium is sintered obtained sputtering target for 77/20/3, On let off roll (symbol 8) by be arranged the face of side of inorganic layer [A1] it is opposed with sputtering electrode in a manner of place polymer base material, It is unreeled, via side deflector roll (symbol 9,10,11) is unreeled, passes through cooling drum (symbol 12).So that degree of decompression becomes 2 × 10^{- 1}The mode of Pa imports argon gas and oxygen as oxygen partial pressure 10%, applies input electric power 4,000W by DC power supply, to So that argon gas, oxygen gas plasma is generated, forms inorganic layer [A1] on the surface by sputtering at polymer base material.Thickness passes through film Conveying speed 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])

Using the coiled sputter equipment (symbol 6a) of structure shown in Fig. 2, the one of polymer base material (symbol 5) Face implements to sputter used as the sputtering target of the mixed sintering material formed by zinc sulphide and silica, and inorganic layer is arranged [A2]。

Specific operation is as described below.First, it is provided with rubbing for zinc sulphide/silica on sputtering electrode (symbol 13) In your coiling chamber (symbol 7) than the takeup type sputter equipment of the sputtering target obtained for 80/20 sintering, at let off roll (symbol 8) Upper placement polymer base material, is unreeled, and via side deflector roll (symbol 9,10,11) is unreeled, passes through cooling drum (symbol 12).So that Degree of decompression becomes 2 × 10^-1The mode of Pa imports argon gas, applies input electric power 500W by high frequency electric source, to make argon gas etc. Gas ions generate, and inorganic layer [A2] is formed on the surface by sputtering at polymer base material.Thickness is carried out by film conveying speed Adjustment.Then, it is wound in take-up roll (symbol 18) via winding side deflector roll (symbol 15,16,17).

(formation of inorganic layer [A3])

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

Specific operation is as described below.First, in the coiling chamber (symbol 7) of takeup type CVD device, in let off roll (symbol Number 8) polymer base material is placed on, is unreeled, via side deflector roll (symbol 9,10,11) is unreeled, passes through cooling drum (symbol 12). So that degree of decompression becomes 2 × 10^-1The mode of Pa imports oxygen 0.5L/ minutes and hexamethyldisiloxane 70cc/ minutes, by high frequency Power supply applies input electric power 3,000W to CVD electrodes, to make plasma generate, by CVD in above-mentioned polymer base material Inorganic layer [A3] is formed on surface.Thickness is adjusted by film conveying speed.Then, via winding side deflector roll (symbol 15, 16,17) it is wound in take-up roll.

[synthesis examples of the urethanes [C1] with aromatic ring structure]

In 5 liters of 4 mouthfuls of flasks, addition bisphenol-A diglycidyl ether acrylic acid adduct (chemistry society of common prosperity society system, Trade name：Epoxy-ester 3000A) 300 mass parts, 710 mass parts of ethyl acetate, heated so that interior temperature become 60 DEG C.Addition 0.2 mass parts of tin dilaurate di-n-butyl tin pass through 1 hour while stirring and dicyclohexyl first are added dropwise as synthetic catalyst Alkane 4,4 '-diisocyanate (Tokyo chemical conversion industry society system) 200 mass parts.Continue to react for 2 hours after completion of dropwise addition, then Diethylene glycol (DEG) (Wako Pure Chemical Industries, Ltd.'s system) 25 mass parts were added dropwise through 1 hour.Continue to react for 5 hours after dropwise addition, obtains weight The urethanes with aromatic ring structure of average molecular weight 20,000.

(embodiment 1)

As polymer base material, 50 μm of polyethylene terephthalate film (eastern レ Co. Ltd. systems " Le of thickness is used ミ ラ ー " (registered trademark) U48), inorganic layer [A1] is set so that thickness becomes 180nm in the one side of the polymer base material.It is inorganic The composition of layer [A1] is that Zn atomic concentrations are 27.5atom%, and Si atomic concentrations are 13.1atom%, and Al atomic concentrations are 2.3atom%, a concentration of 57.1atom% of O atom.The examination of vertical 100mm, horizontal 100mm are cut out from the film for forming inorganic layer [A1] Piece is tested, the evaluation of the median plane mean roughness SRa of inorganic layer [A1] is implemented.It shows the result in table 1.

Then, the masking liquid as silicon compound layer [B] formation, modulating will be using Perhydropolysilazane as principal component Smears (AZ エ レ Network ト ロ ニ ッ Network マ テ リ ア Le ズ society's systems " NN120-20 ", 20 mass % of solid component concentration) 100 mass Part has carried out diluted masking liquid 1 with 300 mass parts of dibutyl ethers.Microgravure coating machine (intaglio plate is utilized on inorganic layer [A1] Wire size 200UR, intaglio plate speed ratio 100%) coating masking liquid 1, it is 1 minute dry at 120 DEG C, after dry, implement under the following conditions UV treatment, the silicon compound layer [B] of setting thickness 120nm, obtains gas barrier film.

Apparatus for ultraviolet light treamtent：MEIRH-M-1-152-H (エ system デ ィ エ キ シ マ societies system)

Import gas：N₂

Oxygen concentration：300~800ppm

Accumulative light quantity：3,000mJ/cm²

Sample temperature adjustment：100℃.

The gas barrier film of gained is used²⁹Si CP/MAS NMR methods carry out composition analysis, calculate in the spectrum that will be found out The peak area summation of -30~-50ppm when being set as 100 of the peak area summation of -30~-120ppm, -50~-90ppm peak Area summation, the peak area summation of -90~-120ppm.It shows the result in table 1.

In addition, cutting out the test film of vertical 100mm, horizontal 140mm from the gas barrier film of gained, implement commenting for moisture-vapor transmission Valence.It shows the result in table 1.

(embodiment 2)

As polymer base material, 50 μm of polyethylene terephthalate film (eastern レ Co. Ltd. systems " Le of thickness is used ミ ラ ー " (registered trademark) U48).

As the masking liquid of priming coat [C] formation, by 150 mass parts of above-mentioned urethanes, dipentaerythritol 6 third Olefin(e) acid ester (chemistry society of common prosperity society system, trade name：ラ イ ト ア Network リ レ ー ト DPE-6A) 20 mass parts, 1- hydroxy-cyciohexyl benzene Base -one (BASF ジ ャ パ Application society system, trade name：" IRGACURE " (registered trademark) 184) 5 mass parts, 3- methacryloxypropyls Base hydroxypropyl methyl diethoxy silane (シ リ コ ー Application society of SHIN-ETSU HANTOTAI system, trade name：KBM-503) 3 mass parts, 170 matter of ethyl acetate Amount part, 350 mass parts of toluene and 170 mass parts of cyclohexanone are coordinated to adjust masking liquid 2.Then, sharp 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%), it is 1 minute dry at 100 DEG C, it does After dry, implement UV treatment under the following conditions, thickness 1, the priming coat [C] of 000nm are set.

Apparatus for ultraviolet light treamtent：LH10-10Q-G (フ ュ ー ジ ョ Application UV シ ス テ system ズ ジ ャ パ Application society system)

Import gas：N₂(nitrogen inertia BOX)

Ultraviolet light occurring source：Microwave mode electrodeless lamp

Accumulative light quantity：400mJ/cm²

Sample temperature adjustment：Room temperature.

Then, on priming coat [C] by inorganic layer [A1] and silicon compound layer [B] be arranged similarly to Example 1 with into The evaluation of row similarly to Example 1.It shows the result in table 1.

(embodiment 3)

As polymer base material, 100 μm of noncrystalline cyclic polyolefin film (Japanese ゼ オ Application society system " ゼ オ of thickness are used ノ ア Off ィ Le system " ZF14) (" ゼ オ ノ ア " is registered trademark), it in addition to this, operates similarly with example 1, is hindered Gas film.

(embodiment 4)

As polymer base material, 100 μm of noncrystalline cyclic polyolefin film (Japanese ゼ オ Application society system " ゼ オ of thickness are used ノ ア Off ィ Le system " ZF14), it in addition to this, operates similarly to Example 2, obtains gas barrier film.

(embodiment 5)

Inorganic layer [A1] is set so that thickness operates similarly to Example 2 in addition to this as 950nm, is hindered Gas film.

(embodiment 6)

Inorganic layer [A2] is set instead of inorganic layer [A1] so that thickness becomes 150nm, in addition to this, together with embodiment 2 It operates to sample, obtains gas barrier film.

(embodiment 7)

Inorganic layer [A3] is set instead of inorganic layer [A1] so that thickness becomes 150nm, in addition to this, together with embodiment 2 It operates to sample, obtains gas barrier film.

(embodiment 8)

Silicon compound layer [B] is set so that thickness operates similarly to Example 2 in addition to this as 50nm, is obtained Gas barrier film.

(embodiment 9)

Silicon compound layer [B] is set so that thickness in addition to this, is operated, obtained as 1,000nm similarly to Example 2 Obtained gas barrier film.

(embodiment 10)

When silicon compound layer [B] formation, ultraviolet light is irradiated into accumulative light quantity and is changed to 1,500mJ/cm², in addition to this, with Embodiment 2 similarly operates, and obtains gas barrier film.

(embodiment 11)

When silicon compound layer [B] formation, ultraviolet light is irradiated into accumulative light quantity and is changed to 1,000mJ/cm², in addition to this, with Embodiment 2 similarly operates, and obtains gas barrier film.

(comparative example 1)

It does not form inorganic layer [A] on polymer base material, and silicon compound layer is directly set on the surface of polymer base material [B] obtains gas barrier film so that thickness operates similarly with example 1 in addition to this as 120nm.

(comparative example 2)

Silicon compound layer [B] is not arranged on inorganic layer [A] to operate similarly with example 1 in addition to this, obtains Gas barrier film.

(comparative example 3)

In embodiment 1, it changes and forms the sequence of inorganic layer [A] and silicon compound layer [B], obtain and 1 layer of embodiment Constitute different gas barrier films.

(comparative example 4)

Silicon compound layer [B] is not arranged on inorganic layer [A] to operate similarly to Example 7 in addition to this, obtains Gas barrier film.

(comparative example 5)

By CVD method, setting inorganic layer [A3] operates similarly to Example 2 in addition to this on inorganic layer [A], obtains Obtained gas barrier film.

(comparative example 6)

In example 2, it is formed instead of silicon compound layer [B] and is free of SiN_xH_yAnd SiO_a(OH)_4-2aOnly by SiO_pN_q The layer of formation operates similarly to Example 2 in addition to this, obtains gas barrier film.

In addition, only by SiO_pN_qThe forming method of the layer of formation is to be filled using the coiled sputtering of structure shown in Fig. 2 It sets, for the one side of polymer base material, implements to sputter using the sputtering target formed by silicon nitride, be arranged only by SiO_pN_qIt is formed Layer.Specific operation is first, the takeup type sputter equipment of the sputtering target formed by silicon nitride to be provided on sputtering electrode Coiling chamber in, SiO is arranged on let off roll_pN_qThe face mode opposed with sputtering electrode of the side of layer is placed polymer-based Material unreels polymer base material, via deflector roll, is roused by cooling.So that degree of decompression becomes 2 × 10^-1The mode of Pa is as oxygen Partial pressure 10% imports argon gas and oxygen to sputtering chamber.Input electric power 1,000W is further applied by high frequency electric source, to make argon Gas, oxygen gas plasma generate, and SiO is formed on the surface by sputtering at polymer base material_pN_qLayer.Thickness conveys speed by film 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 since the gas barrier property relative to oxygen, vapor etc. is excellent, for example, can conduct The electronic devices such as the packing timber and slim TV of food, drug etc., solar cell are usefully used with component.

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 equipments

6b takeup type CVD devices

7 coiling chambers

8 let off roll

9,10,11 side deflector roll is unreeled

12 cooling drums

13 sputtering electrodes

14 CVD electrodes

15,16,17 winding side deflector roll

18 take-up rolls

19 gas barrier films

20 metal cylinders

21 form the opposing face in the face of inorganic layer [A] and silicon compound layer [B].

Claims (12)

1. a kind of gas barrier film is that have inorganic layer successively from the polymer base material side in at least side of polymer base material The gas barrier film of [A] and silicon compound layer [B], silicon compound layer [B] include to have SiN_xH_y、SiO_pN_qAnd SiO_a(OH)_4-2aInstitute The silicon compound for the structure shown, and inorganic layer [A] connects with silicon compound layer [B],

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

2. gas barrier film according to claim 1, the inorganic layer [A] includes zinc compound and Si oxide.

3. gas barrier film according to claim 1, in the silicon compound layer [B]²⁹In Si CP/MAS NMR spectras, When the peak area summation of -30~-120ppm is set as 100, the peak area summation of -30~-50ppm is 10 or more, -50~- The peak area summation of 90ppm is 10 or more, and the peak area summation of -90~-120ppm is 80 or less.

4. gas barrier film according to claim 2, in the silicon compound layer [B]²⁹In Si CP/MAS NMR spectras, When the peak area summation of -30~-120ppm is set as 100, the peak area summation of -30~-50ppm is 10 or more, -50~- The peak area summation of 90ppm is 10 or more, and the peak area summation of -90~-120ppm is 80 or less.

5. according to any one of them gas barrier film of Claims 1 to 4, the inorganic layer [A] is inorganic layer selected from the following Any one of A1~A3,

Inorganic layer A1：Include the inorganic layer of the coexisting phase of (i)~(iii)

(i) zinc oxide

(ii) silica

(iii) aluminium oxide

Inorganic layer A2：Include the inorganic layer of the coexisting phase of zinc sulphide and silica

Inorganic layer A3：Using oxygen atom relative to silicon atom atomicity than the Si oxide for 1.5~2.0 as the nothing of principal component Machine layer.

6. gas barrier film according to claim 5, the inorganic layer [A] is the inorganic layer A1, inorganic layer A1 be by A concentration of 20~40atom% of zinc atom for being measured by ICP emission spectrometry methods, atom concentration be 5~20atom%, Aluminium atom a concentration of 0.5~5atom%, concentration of oxygen atoms are made of forming for 35~70atom%.

7. gas barrier film according to claim 5, the inorganic layer [A] is the inorganic layer A2, inorganic layer A2 be by Zinc sulphide is formed and is constituted by 0.7~0.9 relative to total mole fraction of zinc sulphide and silica.

8. according to Claims 1 to 4,6,7 any one of them gas barrier film, in the polymer base material and the inorganic layer It includes to hand over the urethanes [C1] with aromatic ring structure to have priming coat [C], the priming coat [C] between [A] Structure obtained by connection.

9. gas barrier film according to claim 5 has primary coat between the polymer base material and the inorganic layer [A] Layer [C], the priming coat [C] include structure obtained by having urethanes [C1] crosslinking of aromatic ring structure.

10. gas barrier film according to claim 8, the priming coat [C] includes organo-silicon compound and/or inorganic silication Close object.

11. gas barrier film according to claim 9, the priming coat [C] includes organo-silicon compound and/or inorganic silication Close object.

12. a kind of electronic device, it uses any one of them gas barrier films of claim 1~11.