CN109477202A - Gas barrier film, using it barrier properties for gases membrane material and using they electronic equipment and gas barrier film manufacturing method - Google Patents

Gas barrier film, using it barrier properties for gases membrane material and using they electronic equipment and gas barrier film manufacturing method Download PDF

Info

Publication number
CN109477202A
CN109477202A CN201780046487.9A CN201780046487A CN109477202A CN 109477202 A CN109477202 A CN 109477202A CN 201780046487 A CN201780046487 A CN 201780046487A CN 109477202 A CN109477202 A CN 109477202A
Authority
CN
China
Prior art keywords
film
metal
layer
transition metal
region
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201780046487.9A
Other languages
Chinese (zh)
Inventor
森孝博
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Konica Minolta Opto Inc
Original Assignee
Konica Minolta Opto Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Opto Inc filed Critical Konica Minolta Opto Inc
Publication of CN109477202A publication Critical patent/CN109477202A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/42—Silicides

Abstract

The present invention provides the means for the high water vapor barrier property that gas barrier film can be made to get both under excellent bendability and hot and humid environment.The present invention relates to a kind of gas barrier film, in the atom component distribution curve obtained when thickness direction carries out XPS composition analysis, by M1M2xNyWhen indicating composition, there is the region (a) for meeting following formula (1) and following formula (2).M1M2xNy, 0.2≤x≤3.0 (1), 0.6≤y≤1.4 (2), x: transition metal M 2 and nontransition metal M1 atom there are atomic ratio, y: nitrogen-atoms and nontransition metal M1 atom there are atomic ratios.

Description

Gas barrier film, using it barrier properties for gases membrane material and use their electronics The manufacturing method of equipment and gas barrier film
Technical field
The present invention relates to gas barrier film, using it barrier properties for gases membrane material and using they electronic equipment, with And the manufacturing method of gas barrier film.
Background technique
Using gas barrier film is used to encapsulate in flexible electronic devices, particularly flexible organic EL element, specifically, Use the barrier properties for gases membrane material with gas barrier film as substrate membrane material, encapsulation membrane material.As such with institute on the way The gas barrier film used, it is desirable that moisture-vapor transmission (WVTR) is 10-6g/(m2The high water vapor barrier of grade for 24 hours) Property.As gas barrier film, monofilm, stacked film are known, in order to realize high barrier property, as the generation studied now The gas barrier film of table, for example, the alternate multiple stacked film of silicon oxide film and silicon nitride film, silicon nitride film can be enumerated and had Alternate multiple stacked film of machine film etc..
Formation side as each film that these gas barrier films, the gas barrier film with stepped construction are included Method, it is known to the gas phases membrane formation process such as vapour deposition method, sputtering method, CVD method.In addition, in recent years, being investigated molten to being coated on substrate Liquid and the precursor layer that is formed applies energy to form the manufacturing method of gas barrier film.In these, as realization 10-6g/ (m2The method of the water vapor barrier property of grade for 24 hours), the general inoranic membrane using by 1 μm of thickness of CVD method formation or more Method.However, due to leading to the problem of crack when 1 μm of thickness or more of inoranic membrane appears in bending, thus be dfficult to apply to as The upper flexible apparatus.In addition, alternate multiple stacked film is easy the trend being further enlarged there are thickness because of its composition.By This, it is desirable that film thickness is reduced while maintaining high water vapor barrier property.
Herein, it is believed that alternate multiple stacked film delays vapor transmission because of the labyrinth effect that stepped construction is formed significantly The time of barrier properties for gases layer, so surface, which seems, realizes low moisture-vapor transmission, i.e. high water vapor barrier property.Cause This, for using organic EL element of the alternate multiple stacked film as encapsulation purposes, in the early stage without true in luminescent inspection Recognize blackening etc. shine it is bad, but hot and humid environment after accelerated test at present sometimes blackening delay generate.As a result, in order to Shining for inhibiting not confirm in luminescent inspection in the early stage be bad, durability that is improving element, it is desirable that is not that surface seems Height, but the gas barrier film with real high water vapor barrier property.
In the presence of such requirement, it is constantly used to form the inoranic membrane with real high water vapor barrier property Technological development.Such as in Japanese Unexamined Patent Publication 2012-149278 bulletin, a kind of manufacturing method of silicon-containing film is disclosed, including under State process: using dry method make at least containing silicon atom, nitrogen-atoms dry type deposition film after deposited on substrates, to film surface into The a length of 150nm of traveling wave light irradiation below.According to the document, it is known that in the silicon-containing film manufactured with this method, i.e. barrier properties for gases In film, become Si3N4The fine and close Si-N-Si key on the basis of structure forms more in modification area, shows that high water vapor hinders Every property, humidity resistance.
Summary of the invention
However, in the technology disclosed in Japanese Unexamined Patent Publication 2012-149278 bulletin, there are following problems: applied to soft It is shown under the thickness of excellent bendability when property equipment, cannot achieve the vapor water barriers of grade required by organic EL element etc. Property.
Therefore, the purpose of the present invention is to provide the bendability that gas barrier film can be made to get both excellent and high temperature and humidity The means of high water vapor barrier property under environment.
The above subject of the invention can be solved by means below.
The 1st aspect of the present invention is related to a kind of gas barrier film, obtains when thickness direction carries out XPS composition analysis Atom component distribution curve in, by M1M2xNyWhen indicating composition, there is the region for meeting following formula (1) and following formula (2) (a)。
M1M2xNy
0.2≤x≤3.0(1)
0.6 y≤1.4 < (2)
X: transition metal M 2 and nontransition metal M1 atom there are atomic ratio,
Y: nitrogen-atoms and nontransition metal M1 atom there are atomic ratios
The 2nd aspect of the present invention is related to a kind of manufacturing method of gas barrier film, including will contain nontransition metal M1 Layer and layer containing transition metal M 2 the step of being formed in such a way that the two connects,
Above-mentioned gas barrier film has in thickness direction contains nontransition metal M1 as the principal component of metallic element Region (A) and region (B) containing transition metal M 2 as the principal component of metallic element,
Above-mentioned zone (A) connects with above-mentioned zone (B),
The atom component distribution curve obtained when the thickness direction of above-mentioned gas barrier film carries out XPS composition analysis In, by M1M2xNyWhen indicating composition, there is the region (a) for meeting following formula (1) and following formula (2).
M1M2xNy
0.2≤x≤3.0 (1)
0.6 y≤1.4 < (2)
X: transition metal M 2 and nontransition metal M1 atom there are atomic ratio,
Y: nitrogen-atoms and nontransition metal M1 atom there are atomic ratios
Detailed description of the invention
Fig. 1 be illustrate gas barrier film that one embodiment of the present invention is related to, non-transition gold analyzed by XPS method Belong to the schematic chart for forming elemental profiles and Mixed Zone when being distributed of M1 and transition metal M 2.
Fig. 2 is the stacking for indicating to be formed in the manufacturing method for the gas barrier film that one embodiment of the present invention is related to The schematic cross-section of structure.
Fig. 3 is the layer for indicating to be formed in the manufacturing method for the gas barrier film that another embodiment of the present invention is related to The schematic cross-section of stack structure.
Fig. 4 is vacuum plasma used in the formation for the gas barrier film for indicating that one embodiment of the present invention is related to The schematic diagram of one example of body CVD device.
Fig. 5 is the schematic cross-section of ultraviolet lamp used in embodiment.
Specific embodiment
Hereinafter, being illustrated to the preferred embodiment of the present invention.It should be noted that the present invention is not limited to embodiment party below Formula.In this specification, indicate that " X~Y " of range refers to " X or more Y or less ".In addition, in this specification, as long as no special theory It is bright, then it operates and is carried out under conditions of room temperature (20~25 DEG C)/40~50%RH of relative humidity with the measurement of physical property etc..
In addition, for convenience of explanation, the dimensional ratios of attached drawing are exaggerated sometimes, it is different from actual ratio.In addition, attached Identical symbol is marked to identical element in figure explanation, the repetitive description thereof will be omitted.
<gas barrier film>
The gas barrier film that the 1st aspect of the present invention is related to is obtained when thickness direction carries out XPS composition analysis In atom component distribution curve, by M1M2xNyWhen indicating composition, there is the region (a) for meeting following formula (1) and following formula (2).
M1M2xNy
0.2≤x≤3.0 (1)
0.6≤y≤1.4 (2)
X: transition metal M 2 and nontransition metal M1 atom there are atomic ratio,
Y: nitrogen-atoms and nontransition metal M1 atom there are atomic ratios
It should be noted that in this specification, " by M1M2xNyExpression " refers to is concerned only with nontransition metal M1 in there are atom Atom, 2 atom of transition metal M and nitrogen-atoms (N) and indicate composition, region (a) can also be containing atom in addition to them.
First method according to the present invention is capable of providing the bendability for making gas barrier film get both excellent and high temperature and humidity The method of high water vapor barrier property under environment.It should be noted that the water vapor barrier property under hot and humid environment mentioned herein It is also illustrated in the transmission for inhibiting vapor when carrying out accelerated test with high grade, that is, gas barrier film shows significantly high Water vapor barrier property.In addition, bendability mentioned herein indicates the Gao Shui under can also maintaining hot and humid environment in bending Vapor barrier properties.
The present inventor infers that the mechanism for solving project by above-mentioned composition is as follows.Firstly, the 1st aspect of the present invention is related to Gas barrier film in Mixed Zone include M1M2xNyRegion (a) with specific composition.By making comprising such area The Mixed Zone in domain exists, so that composition continuously or periodically changes in the thickness direction of gas barrier film.Cause This, Mixed Zone is able to suppress stress concentration, realizes the excellent bendability of gas barrier film.In addition, hot and humid environment Under the performance mechanism of high water vapor barrier property be still not clear, thus it is speculated that in region (a), the compound from nontransition metal M1 It is mutually chemically bonded with the compound from transition metal M 2, or carries out secondary or physical bond by intermolecular interaction etc. It closes, to form high-density region.And, thus it is speculated that high water vapor barrier property is presented in high-density region, as a result, it is high to become high temperature Water vapor barrier property under hot and humid environment of the wet environment through accelerated test at present improves.It should be noted that above-mentioned mechanism is Speculate, correctness does not influence technical scope of the invention.
Hereinafter, to constitute gas barrier film each region be illustrated, first to the definition of the technical terms used into Row explanation.
In present specification, " region " refers to the face substantially vertical in the thickness direction relative to gas barrier film (i.e. the face parallel with the most surface of the gas barrier film) divides the gas barrier film with certain or arbitrary thickness When opposed two face that is formed between three-dimensional range in (region), the composition of the constituent in the region can in thickness direction Be it is constant, be also possible to slowly varying.
" constituent " referred in present specification refers to the compound for constituting the specific region of gas barrier film Or metal or nonmetallic simple substance.In addition, " principal component " that refers in the present invention refers to that containing ratio is most in terms of atomic composition ratio Big constituent.For example, refer in the metallic element contained by constituent for " principal component of metallic element ", with The maximum metallic element of atomic composition ratio meter containing ratio.
The barrier properties for gases for the gas barrier film that a mode of the invention is related to is when in film forming object (such as substrate Deng) on be formed with the laminated body of the gas barrier film and calculate when, the oxygen that is measured by method based on JIS K 7126-1987 Transmitance is preferably 1 × 10-3ml/(m2Atm for 24 hours) hereinafter, more preferably less than 1 × 10-5ml/(m2Atm for 24 hours), into One step is preferably 1 × 10-6ml/(m2Atm for 24 hours) (lower limit 0ml/ (m below2·24h·atm)).In addition, by being based on The moisture-vapor transmission (25 ± 0.5 DEG C, relative humidity (90 ± 2) %RH) of the method measurement of JIS K 7129-1992 is preferably 1 ×10-3g/(m2High water vapor barrier property below for 24 hours), more preferably less than 1 × 10-5g/(m2For 24 hours), further preferably 1×10-6g/(m2(lower limit 0g/m below for 24 hours)2·24h)。
(atom constituent curve)
The gas barrier film that a mode of the invention is related to must contain nontransition metal M1, transition metal M 2 and nitrogen. It should be noted that it is preferred that the gas barrier film that a mode of the invention is related to only contains nontransition metal M1 and transition metal M 2 is made For metallic element.It can be by gas barrier film containing nontransition metal M1, transition metal M 2 and nitrogen in gas barrier film XPS (the X-ray Photoelectron Spectroscopy) composition analysis that is discussed below confirms.
(XPS analysis condition)
For Mixed Zone, region (a), region (A) and the region of the gas barrier film that a mode of the invention is related to The presence or absence of (B) composition distribution and the thickness in each region and in these regions etc., can be by being penetrated using X described below Photoelectron Spectroscopy (X-ray Photoelectron Spectroscopy, referred to as: XPS) measurement is to find out.
Hereinafter, being illustrated to the measuring method in each region based on XPS analysis method.
The concentration of element distribution curve of the thickness direction for the gas barrier film that a mode of the invention is related to is (hereinafter referred to as " depth profiling ") it can specifically be made by following manner: it is directed to the element of nontransition metal M1 (such as silicon (Si) etc.) Concentration, concentration of element, oxygen (O), nitrogen (N), the concentration of element of carbon (C) of transition metal M 2 (such as niobium (Nb), tantalum (Ta) etc.) etc., And sputtered with noble gas ions such as the measurement of X-ray photoelectron spectroscopy and argons, make internal from the surface of gas barrier film Expose and successively carries out surface composition analysis.
The longitudinal axis can be for example set as the atom of each element by the distribution curve that XPS depth profiling in this way measures It is set as etching period (sputtering time) than (unit: atm%), by horizontal axis and makes.It should be noted that in this way horizontal axis being set as losing Carve the time element distribution curve in, etching period with from the surface of above-mentioned gas barrier film start thickness direction away from It is related from substantially, therefore as " distance for the thickness direction started from the surface of gas barrier film ", it can be using by XPS What the surface for the slave gas barrier film that the relationship of the etching speed used and etching period calculates when depth profiling measures was started The distance of thickness direction.In addition, as the sputtering method used in the measurement of such XPS depth profiling, it is preferred to use use argon (Ar+) noble gas ion sputtering method as etch ion kind, making its etching speed (etch-rate) is 0.05nm/sec (SiO2Heat oxide film scaled value).
The tool of the XPS analysis of the composition analysis for the gas barrier film that a mode for use in the present invention described below is related to One example of concrete conditions in the establishment of a specific crime.
Device: ULVAC-PHI corporation QUANTERASXM
X-ray source: monochromatization Al-K α
Plasma sputter: Ar (2keV)
Depth profiling: with SiO2Conversion sputtering thickness gauge, is repeatedly measured with defined thickness interval, obtains depth direction Depth profiling
It is quantitative: to find out background value with Shirley method, determined using relative sensitivity coefficient method by obtained peak area Amount.Data processing uses the MultiPak of ULVAC-PHI corporation.It should be noted that the element to be analyzed is non-transition metal M 1 (such as silicon (Si) etc.), transition metal M 2 (such as niobium (Nb), tantalum (Ta) etc.), oxygen (O), nitrogen (N), carbon (C).It should be noted that In this measurement, other elements, such as other metallic elements can also be analyzed as needed.
The measurement resolution ratio (defined thickness interval) of depth profiling can be 3nm hereinafter, can be 2nm hereinafter, can also Think 1nm or less.It should be noted that in the later-described embodiments, the measurement resolution ratio of depth profiling is 1nm.
Next, each region is described in detail.
(Mixed Zone)
The atom that the gas barrier film that a mode of the invention is related to is obtained when thickness direction carries out XPS composition analysis In component distribution curve, with transition metal M 2 and nontransition metal M1 atom there are the values of atomic ratio to meet 0.02~49 model The region of element composition in enclosing, i.e. Mixed Zone.
Fig. 1 be illustrate gas barrier film that one embodiment of the present invention is related to, utilize XPS method to analyze non-transition gold Belong to the schematic chart for forming elemental profiles and Mixed Zone when being distributed of M1 and transition metal M 2.It should be noted that in this figure In, the gas barrier film with aftermentioned region (A) and region (B) is illustrated, as long as but gas barrier film tool There is the Mixed Zone of inclusion region (a), the present invention is not limited to this.
Fig. 1 be since the surface (left part of figure) of gas barrier film depth direction carry out nontransition metal M1, The elemental analysis of transition metal M 2, oxygen (O), nitrogen (N), carbon (C), horizontal axis indicate the depth (thickness: nm) of sputtering, and the longitudinal axis indicates non- The chart of the containing ratio (atm%) of transition metal M 1 and transition metal M 2.In addition, dotted line indicates containing for nontransition metal M1 Rate, solid line indicate the containing ratio of transition metal M 2.In being shown on the right side as metal with nontransition metal M1 (such as silicon for figure (Si) etc.) it is region region (A) that the element of principal component forms, it is mutually grounded with it and shows as metal on the left of figure with mistake Cross the region (B) that the element that metal M2 (such as niobium (Nb), tantalum (Ta) etc.) is principal component forms.It is hindered moreover, showing in gas Every in property film have Mixed Zone.It should be noted that gas barrier film has aftermentioned region (A) and region as this figure (B) when, region of the Mixed Zone as a part of region (A) and a part of Chong Die display of region (B).
The type of preferred nontransition metal M1 in Mixed Zone and the preferred non-transition gold in aftermentioned region (A) The type for belonging to M1 is identical, the type and the preferred mistake in aftermentioned region (B) of the preferred transition metal M 2 in Mixed Zone The type for crossing metal M2 is identical.
The thickness of Mixed Zone is not particularly limited, preferably more than thickness direction continued presence 5nm.The reason is to pass through Make it more than thickness direction continued presence 5nm, bendability improvement effect becomes much larger, and aftermentioned region is in addition more readily formed (a).From the same viewpoint, the thickness of Mixed Zone is preferably continuously 8nm or more in thickness direction, more preferably 10nm with On, further preferably 20nm or more.The upper limit of the thickness of Mixed Zone is not particularly limited, and examines from the viewpoint of optical characteristics Consider, preferably 100nm hereinafter, more preferably 50nm hereinafter, further preferably 30nm or less.
Herein, since Mixed Zone can have nitrogen-atoms, so its composition can also be expressed as M1M2xNy(0.02≤x ≤ 49, y >=0).
Mixed Zone can (nontransition metal M1 simple substance contains non-mistake containing the compound from nontransition metal M1 Cross the compound of metal M1 simple substance) (2 simple substance of transition metal M contains transition metal with the compound from transition metal M 2 The compound of M2) mixture as constituent, or can also be containing from nontransition metal M1 and transition metal M 2 Compound is as constituent.Alternatively, it is also possible to contain above-mentioned both sides as constituent.
Herein, in this specification, compound from nontransition metal M1 in Mixed Zone with come from transition metal M 2 Compound mixture refer to compound from nontransition metal M1 and the compound from transition metal M 2 mutually not into Substance of the row chemical bond combined into admixture.As mixture, for example, niobium oxide and silica can be enumerated mutually without changing Key is learned combined into the substance etc. of admixture.
Mixing in Mixed Zone containing the compound from nontransition metal M1 and the compound from transition metal M 2 When object, the preferred compound from nontransition metal M1 in the mixture and preferably coming from aftermentioned region (A) The compound of nontransition metal M1 is identical.In addition, the preferred compound from transition metal M 2 in the mixture with it is aftermentioned Region (A) in the preferred compound from transition metal M 2 it is identical.
In addition, being indicated from nontransition metal M1 and the compound of transition metal M 2 from non-transition gold in this specification The compound and the compound from transition metal M 2 for belonging to M1 be mutually chemically bonded and the compound that is formed or by point Interaction etc. carries out physical bond and the compound that is formed between son.In this specification, as from nontransition metal M1 and mistake The compound of metal M2 is crossed, for example, can enumerate with niobium atom and silicon atom directly or via oxygen atom formation chemical bond The compound etc. of structure.
Mixed Zone is usually in the thickness direction of gas barrier film, and composition is continuously or phasic Chang.Therefore, it mixes Conjunction region is able to suppress stress and concentrates the excellent bendability, it can be achieved that gas barrier film.It should be noted that from the sight of bendability Point considers that the composition of preferably Mixed Zone continuously changes.
It should be noted that in gas barrier film of the present invention, since Mixed Zone includes aftermentioned region (a), So by the member there are the maximum value of the value of atomic ratio greater than 0.6 of nitrogen-atoms and nontransition metal M1 atom in Mixed Zone Element composition indicates.The position of Mixed Zone as the maximum value is preferably included in aftermentioned region (a).
It should be noted that be preferably formed in region (A) that gas barrier film has and the interface of region (B) attached for Mixed Zone Closely.At this point, by forming continuously or the bendability improvement effect of gas barrier film brought by phasic Chang is bigger. That is, the gas barrier film that a preferred mode of the invention is related to has region (A) and region (B) in thickness direction, on It states region (A) and contains principal component of the nontransition metal M1 as metallic element, above-mentioned zone (B) is containing transition metal M 2 as gold Belong to the principal component of element, above-mentioned zone (A) connects with above-mentioned zone (B).
(region (a))
Region (a) indicates the M1M2 in above-mentioned Mixed ZonexNyWith the region specifically formed.With such structure At the high water vapor barrier property that can get both under excellent bendability and hot and humid environment of gas barrier film of the invention. The gas barrier film that one embodiment of the present invention is related to, the atom composition obtained when thickness direction carries out XPS composition analysis In distribution curve, by M1M2xNyWhen indicating composition, have the region (a) for meeting following formula (1) and following formula (2) (also simple below Referred to as region (a)).
M1M2xNy
0.2≤x≤3.0 (1)
0.6 y≤1.4 < (2)
X: transition metal M 2 and nontransition metal M1 atom there are atomic ratio,
Y: nitrogen-atoms and nontransition metal M1 atom there are atomic ratios.
X is transition metal M 2 and nontransition metal M1 there are atomic ratio, y be nitrogen and nontransition metal M1 there are atoms Than region (a) must simultaneously meet formula (1) and formula (2).That is, the inventors discovered that at least nontransition metal M1 is former Son and the simultaneous region of 2 atom of transition metal M and transition metal M 2 and nontransition metal M1 atom there are atomic ratios It is that high water vapor resistance is showed under hot and humid environment that (2 atoms of transition metal M/nontransition metal M1 atom), which are 0.2~3.0, Every the condition of property.Herein, it is believed that transition metal M 2 and nontransition metal M1 atom there are atomic ratio (2 atom of transition metal M/ Nontransition metal M1 atom) less than 0.2 or when being greater than 3.0, nontransition metal M1 atom is bonded with 2 atom of transition metal M It reduces, so the water vapor barrier property under hot and humid environment reduces.In addition, forming nontransition metal M1 atom, transition metal M2 atom and the simultaneous region of nitrogen-atoms and transition metal M 2 and nontransition metal M1 atom there are atomic ratio (transition Metal M2 atom/nontransition metal M1 atom) be 0.2~3.0 and nitrogen-atoms and nontransition metal M1 atom there are atoms It is greater than 0.6 than (nitrogen-atoms/nontransition metal M1 atom) and is to show high water under hot and humid environment for 1.4 or less The condition of vapor barrier properties.
The high water vapor barrier property under hot and humid environment can be assigned to gas barrier film due to region (a), so gas Body barrier film is able to maintain that the water vapor barrier property under the hot and humid environment of the grade of the requirements such as organic EL element, and energy Enough filmings, have excellent bendability.
When region (a) has a variety of nontransition metal M1 or a variety of transition metal Ms 2, by the content of each metal is weighted Obtained by summation calculate x.
Silicon is used to be remarkably improved the water vapor barrier property under hot and humid environment as the mode of nontransition metal M1, Thus particularly preferably.
Herein, the nitrogen-atoms in region (a) and nontransition metal M1 atom there are the maximum value of atomic ratio (y maximum values) Expression is formed by the element in the range of above-mentioned y, therefore is greater than 0.6 and for 1.4 hereinafter, from obtaining under hot and humid environment more From the viewpoint of high water vapor barrier property, preferably 0.65 or more.In addition, from the higher water obtained under hot and humid environment From the viewpoint of vapor barrier properties, nitrogen-atoms and nontransition metal M1 atom there are the maximum value of atomic ratio (y maximum value) is excellent 1 is selected as hereinafter, more preferably 0.9 or less.
By M1M2xNyWhen indicating composition, region (a) is the region for meeting above-mentioned formula (1) and above-mentioned formula (2).Herein, from into From the viewpoint of one step improves the water vapor barrier property under hot and humid environment, region (a) is preferably continuously deposited in thickness direction In 1nm or more, it is more preferably the presence of 2nm or more, still more preferably there is 3nm or more, particularly preferably there is 4nm or more.Moreover, When the aftermentioned layer containing nontransition metal M1 and the layer containing transition metal M 2 being passed through gas phase forming a film to be formed, from more stable From the viewpoint of ground obtains the high water vapor barrier property under high bendability and hot and humid environment, region (a) is optimal It is selected in thickness direction continued presence 5nm or more.As a result, a preferred mode of the invention be region (a) with a thickness of 5nm with On the gas barrier film that is related to of a mode of the invention.In addition, region (a) is not particularly limited, it is more good from obtaining From the viewpoint of light transmittance, preferably in thickness direction continued presence 30nm hereinafter, being more preferably the presence of 15nm hereinafter, further preferably There are 10nm hereinafter, particularly preferably there are 8nm or less.
The control of the composition, thickness of such region (a) can pass through the manufacturing method in aftermentioned gas barrier film In properly select the layer containing nontransition metal M1 and the layer containing transition metal M 2 forming method, formation sequence, in shape At the layer (layer either containing transition metal M 2) containing nontransition metal M1 afterwards arrive formed containing transition metal M 2 layer (or Layer containing nontransition metal M1) during keeping method etc. and carry out.
(region (A))
The gas barrier film that one embodiment of the present invention is related to preferably comprises region (A), which contains non-transition Principal component (in this specification, also referred to as " region (A) ") of the metal M1 as metallic element.
Exist in the thickness direction of gas barrier film and contains area of the nontransition metal M1 as the principal component of metallic element Domain can be confirmed by the composition analysis using above-mentioned XPS analysis method.
It should be noted that maximum metallic element is in terms of atomic composition ratio sometimes in the thickness direction of gas barrier film Both nontransition metal M1 and transition metal M 2, that is, the atomic composition ratio of the nontransition metal M1 in metallic element and transition The atomic composition ratio of metal M2 is maximum and identical.In the present invention, such region (or point) is used as and is comprised in region (A) region in is handled.
Herein, from from the viewpoint of further increasing the water vapor barrier property under hot and humid environment, region (A) is interior , the amount of nontransition metal M1 atom relative to nontransition metal M1, transition metal M 2, oxygen (O), nitrogen (N) and carbon (C) atom Total amount ratio (unit: atm%) (hereinafter also referred to [M1]) thickness direction average value be preferably 20atm% with On, more preferably 22atm% or more, further preferably 24atm% or more.In addition, from the sight of more good light transmittance is obtained Point considers, the average value of the thickness direction of (M1) in region (A) be preferably 40atm% hereinafter, more preferably 38atm% with Under, further preferably 36atm% or less.
In addition, as described above, in the presence of the amount of [M1] and nontransition metal M2 atom relative to nontransition metal M1, transition gold It is identical for belonging to the ratio (unit: atm%) (hereinafter also referred to [M2]) of the total amount of the atom of M2, oxygen (O), nitrogen (N) and carbon (C) Value region (or point) in the case where, examined from the viewpoint for further increasing the water vapor barrier property under hot and humid environment Consider, which is preferably 10atm%~25atm%, more preferably 12atm%~20atm%.
It should be noted that region (A) can be containing unless transition metal M 1, transition metal M 2, oxygen (O), nitrogen (N) and carbon (C) Atom in addition, such as hydrogen.Herein, the ratio (unit: atm%) of the atomic weight of the hydrogen in region (A) can pass through rutherford Backscattering analysis (Rutherford Backscattering Spectroscpy:RBS), HFS analyze (Hydrogen Forward Scattering Spectrometry) it measures.Wherein, from the water further increased under hot and humid environment From the viewpoint of vapor barrier properties, nontransition metal M1 present in region (A), transition metal M 2, oxygen (O), nitrogen (N) and carbon (C) total amount of atom is excellent relative to the average value of the thickness direction of the ratio (unit: atm%) of the total amount of whole atoms It is selected as 90atm% or more, more preferably 95atm% or more, further preferably 99atm% or more (upper limit 100atm%).
It as nontransition metal M1, is not particularly limited, from the viewpoint of water vapor barrier property, preferably from selected from long week The metal of nontransition metal M1 selection in the 12nd race~the 14th race metal of the phase type periodic table of elements.In these, more preferably Containing Si, Al, Zn, In perhaps Sn further preferably Si, Sn or Zn, particularly preferably contain Si.It is of the invention as a result, A preferred mode is the gas barrier film that non-transition metal M 1 is Si.Nontransition metal M1 can be used alone, Two or more kinds may be used.
Region (A) if the nontransition metal M1 as constituent form be the chemical combination from nontransition metal M1 Object (nontransition metal M1 simple substance or the compound containing nontransition metal M1), is just not particularly limited.Nontransition metal M1 Such as it can enumerate and be contained with the state of the oxide of nontransition metal M1, nitride, carbide, nitrogen oxides or oxycarbide Have.Wherein, nontransition metal M1 is preferably contained with the state of the compound containing nontransition metal M1, more preferably to contain non-mistake The state for crossing metal M1 and nitrogen compound contains.It should be noted that the form of nontransition metal M1 contained by region (A) can be single 1 kind is solely used, also two or more kinds may be used.
Region (A) can be single layer, or 2 layers or more of stepped construction.The stacking knot that region (A) is 2 layers or more When structure, nontransition metal compound contained by region (A) be may be the same or different.
From the viewpoint of water vapor barrier property, the thickness (the stepped construction Shi Zhiqi total thickness for 2 layers or more) of region (A) Preferably 5nm or more, more preferably 10nm or more.In addition, the upper limit of the thickness of region (A) is not particularly limited, from formation area The deduction mechanism in domain (A) considers, can be 100nm hereinafter, can be 50nm or less, or 30nm or less.
(region (B))
The gas barrier film that one embodiment of the present invention is related to preferably comprises region (B), which contains transition gold Belong to principal component (in this specification, also referred to as " region (B) ") of the M2 as metallic element.
There is the region containing transition metal M 2 as the principal component of metallic element in the thickness direction of gas barrier film It can be confirmed by the composition analysis using above-mentioned XPS analysis method etc..
Herein, from the water vapor barrier property further increased under hot and humid environment from the viewpoint of, in region (B) The average value of thickness direction of (M2) be preferably 16atm% or more, more preferably 18atm% or more, further preferably 20atm% or more.In addition, the thickness direction of (M2) in region (B) is put down from the viewpoint of obtaining more good light transmittance Mean value is preferably 40atm% hereinafter, more preferably 38atm% is hereinafter, further preferably 36atm% or less.
It should be noted that region (B) can be containing unless transition metal M 1, transition metal M 2, oxygen (O), nitrogen (N) and carbon (C) Atom in addition, such as hydrogen.Herein, the measuring method of the ratio (unit: atm%) of the atomic weight of the hydrogen in region (B) and area The ratio of the atomic weight of hydrogen in domain (A) is same.Wherein, from the water vapor barrier property further increased under hot and humid environment From the viewpoint of, nontransition metal M1 present in region (B), transition metal M 2, oxygen (O), nitrogen (N) and carbon (C) atom Total amount is preferably 90atm% relative to the average value of the thickness direction of the ratio (unit: atm%) of the total amount of whole atoms More than, more preferably 95atm% or more, further preferably 99atm% or more (upper limit 100atm%).
It as transition metal (M2), is not particularly limited, can be used alone or be applied in combination arbitrary transition metal.This Place, transition metal refer to long period type periodic table from the 3rd race's element to the 11st race's element, as transition metal, can enumerate Sc, Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Y、Zr、Nb、Mo、Tc、Ru、Pd、Ag、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、 Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt and Au etc..
Wherein, as the transition metal (M2) of good water vapor barrier property is obtained, can enumerate Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce etc..In these, according to various results of study, from the nontransition metal for being easy to produce with containing in gas barrier film (M1) Nb, Ta, V from the viewpoint of bonding, particularly preferably used as the 5th race's element.As a result, of the invention preferred one The transition metal M 2 for the gas barrier film that a mode is related to is at least one kind of metal in Nb, Ta and V.
Especially if the non-mistake that transition metal (M2) is the 5th race's element (especially Nb), detailed content is described below Crossing metal (M1) is Si, then can obtain the improvement effect of significant water vapor barrier property, be particularly preferred combination.Think this It is to be particularly easy to generate with the 5th being bonded for race's element (especially Nb) due to Si.Also, from the viewpoint of optical characteristics, mistake It crosses metal (M2) and is particularly preferably Nb, Ta that the good compound of the transparency can be obtained, most preferably Nb.
As region (B) if constituent transition metal M 2 form be the compound from transition metal M 2 (2 simple substance of transition metal M or the compound containing transition metal M 2), is just not particularly limited.Transition metal M 2 can for example lift Contained out with the state of the oxide of transition metal M 2, nitride, carbide, nitrogen oxides or oxycarbide.Wherein, mistake It crosses metal M2 preferably to contain with the state of the compound containing transition metal M 2, more preferably be contained with the state of transition metal oxide Have.It should be noted that the form of transition metal M 2 contained by region (B) can be used alone or two or more kinds may be used.
Region (B) can be single layer, or 2 layers or more of stepped construction.The stacking knot that region (B) is 2 layers or more When structure, 2 compound of transition metal M contained by region (B) be may be the same or different.
Think that region (B) is formed and with region (A) adjoining, so that forming region (a), assigns under hot and humid environment High water vapor barrier property, so water vapor barrier property is not necessarily required in region (B) in itself.Therefore, region (B) is even if be relatively thin Layer can also play effect.Specifically, to realize that the thickness of the higher water vapor barrier property under hot and humid environment is formed From the viewpoint of region (a), the thickness of region (B) is preferably 2nm or more, more preferably 4nm or more, further preferably 5nm More than, particularly preferably 6nm or more.In addition, the thickness of region (B) is preferred from the viewpoint of obtaining more good light transmittance For 50nm hereinafter, more preferably 30nm is hereinafter, be still more preferably 25nm hereinafter, particularly preferably 15nm is hereinafter, extremely excellent It is selected as 12nm or less.
(lamination order of region (A) and region (B))
In the gas barrier film that one embodiment of the present invention is related to, region (A) and the lamination order of region (B) do not have Especially limitation can press region (A)/region (B) from film forming object side in film forming object (such as resin base material etc.) It is arranged in order, it can also be on film forming object from film forming object side being arranged in order by region (B)/region (A).However, From the viewpoint of the higher water vapor barrier property and superior bendability obtained under hot and humid environment, preferably forming a film From film forming object side being arranged in order by region (A)/region (B) on object.In addition, obtaining the gas of excellent bendability In the range of the thickness of body barrier film, gas barrier film can have will be by the stepped construction institute in region (A)/region (B) Structure that is multiple and being formed, example is laminated by the unit that the stepped construction in region (B)/region (A) is constituted in the unit of composition Such as alternatively layered structure.
<manufacturing method of gas barrier film>
The manufacturing method for the gas barrier film that one embodiment of the present invention is related to is not particularly limited, and preferably includes to contain There is the step of layer of nontransition metal M1 and the layer containing transition metal M 2 are formed in such a way that the two connects.
That is, the 2nd aspect of the present invention is related to a kind of manufacturing method of gas barrier film, including non-transition gold will be contained The step of layer of category M1 and the layer containing transition metal M 2 are formed in a manner of connecting, the above-mentioned layer containing nontransition metal M1 contains There is principal component of the nontransition metal M1 as metallic element, the above-mentioned layer containing transition metal M 2 contains transition metal M 2 as gold Belong to the principal component of element,
The atom component distribution curve obtained when the thickness direction of above-mentioned gas barrier film carries out XPS composition analysis In, by M1M2xNyWhen indicating composition, there is the region (a) for meeting following formula (1) and following formula (2).
M1M2xNy
0.2≤x≤3.0 (1)
0.6 y≤1.4 < (2)
X: transition metal M 2 and nontransition metal M1 atom there are atomic ratio,
Y: nitrogen-atoms and nontransition metal M1 atom there are atomic ratios
Second method according to the present invention, being also capable of providing can make gas barrier film get both excellent bendability and high temperature The means of high water vapor barrier property under high humidity environment.In addition, the gas barrier film that second method according to the present invention is related to Manufacturing method, the barrier properties for gases membrane material that the above explained 1st aspect of the present invention is related to can be manufactured.
Fig. 2 is the stacking for indicating to be formed in the manufacturing method for the gas barrier film that one embodiment of the present invention is related to The schematic cross-section of structure, Fig. 3 are the manufacturing methods for indicating the gas barrier film being related in another embodiment of the present invention The schematic cross-section of the stepped construction of middle formation.Herein, the gas barrier film formed on film forming object that Fig. 2 is related to Stepped construction 10 is to form the layer 12 containing nontransition metal M1 on film forming object 11, is subsequently formed containing transition metal M 2 Layer 13 obtained from.In addition, the stepped construction 10 ' for the gas barrier film formed on film forming object that Fig. 3 is related to is The layer 13 containing transition metal M 2 is formed on film forming object 11, the layer 12 containing nontransition metal M1 is subsequently formed and obtains 's.In figure 2 and figure 3, the layer 12 containing nontransition metal M1 is with the layer 13 containing transition metal M 2 in such a way that the two connects It is formed.In addition, film forming object 11 is not particularly limited as long as being the object that can form gas barrier film.For example, When manufacturing barrier properties for gases membrane material, film forming object 11 can be the resin for being formed with the layer with various functions as needed Substrate.Think region (A), region (B) and inclusion region (a) Mixed Zone be as formed containing nontransition metal M1 12 (layer 13 either containing transition metal M 2) of layer afterwards, form the layer 13 containing transition metal M 2 and (or contain nontransition metal The layer 12 of M1) when, the substance containing transition metal M 2 enters the layer 12 containing nontransition metal M1 or contains nontransition metal The substance of M1 enters the result of the layer 13 containing transition metal M 2 and is formed.Additionally, it is believed that region (A), region (B) and comprising The Mixed Zone in region (a) be as after forming the layer containing nontransition metal M1 and the layer containing transition metal M 2, These interlayers occur the result of substance spontaneously spread and are formed.
Herein, controlling for the composition, thickness in region (a) can be by the layer containing nontransition metal M1 and containing transition gold Belong to the forming method of the layer of M2, formation sequence, (or contain transition metal M 2 forming the layer containing nontransition metal M1 Layer) arrive keeping method etc. during layer (or layer containing nontransition metal M1) of the formation containing transition metal M 2 afterwards and into Row.
In the manufacturing method for the gas barrier film that a mode of the invention is related to, the layer containing nontransition metal M1 and Layer containing transition metal M 2 formation sequence be not particularly limited, can film forming object (such as resin base material etc.) on from Film forming object side is sequentially formed by the layer containing nontransition metal M1/layer containing transition metal M 2, can also formed a film It is sequentially formed on object from film forming object side by the layer containing transition metal M 2/layer containing nontransition metal M1.So And from the viewpoint of the higher water vapor barrier property and superior bendability obtained under hot and humid environment, preferably exist The layer containing nontransition metal M1/layer containing transition metal M 2 sequence shape is pressed from film forming object side on film forming object At.The reason is that the formation in region (a) is easier, and the thickness in region (a) can be made bigger.In addition, obtain it is excellent In the range of the thickness of the gas barrier film of bendability, the manufacturing method of gas barrier film, which can be, to be concatenated to form by containing The layer of nontransition metal M1/unit that layer containing transition metal M 2 is constituted or by the layer containing transition metal M 2/is containing non- Unit that the layer of transition metal M 1 is constituted and the method that stepped construction is made, such as the method that alternatively layered structure is made.
It should be noted that gas manufactured by the manufacturing method for the gas barrier film being related to using one embodiment of the present invention Barrier film is same as the gas barrier film that above-mentioned one embodiment of the present invention is related to.
(formation of the layer containing nontransition metal M1)
It as the method for forming the layer containing nontransition metal M1, is not particularly limited, for example, gas phase film forming can be enumerated Method, rubbing method.Wherein, from can be continuously formed the layer containing nontransition metal M1 while carrying film forming object and contain There is the layer of transition metal M 2, from the viewpoint of productivity is excellent, preferred gas phase membrane formation process.Herein, film forming pair is carried as one side As the method that object on one side forms a film each layer, for example, roll-to-roll method can be enumerated.That is, what a preferred mode of the invention was related to Manufacturing method is the manufacturing method for including the steps that being formed the layer containing nontransition metal M1 with gas phase membrane formation process.
In one embodiment of the present invention, as long as the raw material for being used to form the layer containing nontransition metal M1 is from non-mistake The compound (nontransition metal M1 simple substance or the compound containing nontransition metal M1) for crossing metal M1, does not just limit especially System.In addition, can further contain the object from other metals as the raw material for being used to form the layer containing nontransition metal M1 Matter (metal simple-substance, the compound containing metal).At this point, in the raw material of the layer containing nontransition metal M1, it can be further Containing the raw material that can form the layer containing transition metal M 2, i.e., (2 simple substance of transition metal M contains the substance from transition metal M 2 The compound of transition metal M 2).In this case, it such as makes decision the classification of layer.Firstly, only by the layer containing nontransition metal M1 It is in addition formed a film on film forming object under the same conditions in the manufacture with gas barrier film.Next, with above-mentioned gas The atom constituent curve of barrier film similarly, the atom group of metallic element contained by constituent is measured with XPS analysis method At the atomic composition ratio (atm%) than (atm%) and nontransition metal M1.Then, contained by the constituent in the layer of production Metallic element in, by the maximum layer of the content of the nontransition metal M1 using in terms of atomic composition ratio as containing nontransition metal M1's The formation processing of layer.
(gas phase membrane formation process)
It as gas phase membrane formation process, is not particularly limited, for example, the physics gas such as sputtering method, vapour deposition method, ion plating method can be enumerated Mutually deposition (PVD) method, chemical vapor deposition (chemical vapor deposition, CVD) method, ALD (Atomic Layer The chemical vapour deposition techniques such as Deposition).Wherein, from can not to film forming object cause damage in the case where form a film, Angle with high productivity is set out, preferably physical vaporous deposition, more preferable sputtering method or CVD method, further preferably Sputtering method.
From the viewpoint of water vapor barrier property, the film forming when layer containing nontransition metal M1 is formed with gas phase membrane formation process Setting thickness (the stepped construction Shi Zhiqi total thickness for 2 layers or more) is preferably 10nm or more, more preferably 30nm or more.In addition, From the viewpoint of bendability, film forming setting thickness when forming the layer containing nontransition metal M1 with gas phase membrane formation process is preferably 500nm is hereinafter, more preferably 300nm or less.
Layer containing nontransition metal M1 by carrying out XPS composition analysis when the obtained result of atom component distribution curve Calculating, nitrogen-atoms and nontransition metal M1 atom is preferably 0.10 there are the average value of the thickness direction of atomic ratio (N/M1) More than, particularly preferably 0.50 or more, extremely preferred is 0.90 or more.If the presence of nitrogen-atoms and nontransition metal M1 atom The average value of the thickness direction of atomic ratio (N/M1) is 0.90 or more, then region (a) is more readily formed in Mixed Zone.Separately Outside, in the formation of the layer containing transition metal M 2, for example, by using the nitride of transition metal M 2, nitrogen oxides conduct Raw material, and nitrogen etc. is imported in film forming, so that the layer containing transition metal M 2 is formed as nitrogenous layer, at this point, in mixed zone Region (a) is more readily formed in domain.At this point, when forming nitrogenous layer as layer containing transition metal M 2, nitrogen-atoms and non-transition Metal M1 atom is preferably 0.50 or more there are the average value of the thickness direction of atomic ratio (N/M1).The reason is if it is upper State range, then it being capable of forming region (a) better.From the same viewpoint, it forms nitrogenous layer and is used as and contain transition metal When the layer of M2, nitrogen-atoms and nontransition metal M1 atom there are the average values of the thickness direction of atomic ratio (N/M1) to be more preferably 0.60 or more, further preferably 0.80 or more, particularly preferably 0.85 or more, extremely preferred is 0.90 or more.In addition, nitrogen is former Son and nontransition metal M1 atom are preferably 1.4 or less there are the average value of the thickness direction of atomic ratio (N/M1).It should say Bright, XPS measurement analysis mentioned herein and atom component distribution curve are used and are described in the explanation of above-mentioned atom constituent curve The same content of content.
When forming the layer containing nontransition metal M1 using gas phase membrane formation process, for example, can be former selected from film forming by adjusting When the ratio of non-active gas and reactant gas when the ratio of above-mentioned nontransition metal M1 and oxygen in material, film forming, film forming Gas supply amount, film forming when vacuum degree, film forming when magnetic force and electric power when film forming in a kind or it is of more than two kinds Condition comes the composition and thickness of control area (a).
《CVD》
Chemical vapor deposition (Chemical Vapor Deposition, CVD) method is in film forming object (such as resin Substrate etc.) the layer to be formed containing nontransition metal M1 material on, supply the ingredient containing aimed thin film unstrpped gas, The method of surface in the material of the layer to be formed containing nontransition metal M1 or the chemical reaction deposit film by gas phase.Separately Outside, for the purpose of activation chemical reaction, there is the method etc. for generating plasma etc., thermal cvd, catalytic chemical vapor can be enumerated CVD method well known to sedimentation, optical cvd method, vacuum plasma CVD method, atmospheric pressure plasma CVD method etc. etc..These methods It is not particularly limited, from the viewpoint of film forming speed, processing area, it is preferred to use plasma CVD method.If being steamed using chemistry Plating method forms the layer containing nontransition metal M1, then advantageous in terms of the water vapor barrier property under hot and humid environment.In addition, If being formed using the plasma CVD method under the pressure near vacuum plasma CVD method, atmospheric pressure or atmospheric pressure and containing non-mistake Cross the layer of metal M1, then by be selected as raw material (also referred to as raw material) metallic compound, decompose gas, decomposition temperature, The conditions such as input power are capable of forming the layer containing nontransition metal M1 for being made of and constituting target, thus preferably.
Herein, as plasma CVD, it is preferable to use CCP (Capacitively Coupled Plasma, capacitive coupling Plasma)-CVD, ICP (Inductively Coupled Plasma, inductively coupled plasma body)-CVD, microwave CVD, The various plasma CVDs such as ECR (Electron Cyclotron Resonance)-CVD, atmospheric pressure barrier discharge CVD.
It as device used in plasma CVD method, is not particularly limited, well known device can be used, for example, can To use commercially available vacuum C CP (Capacitively Coupled Plasma, capacitance coupling plasma)-CVD device.
Unstrpped gas used in plasma CVD method is not particularly limited, can be appropriate when nontransition metal M1 is silicon Ground selection uses silane gas, disilane gas, TEOS (tetraethoxysilane), HMDSO (hexamethyldisiloxane), HMDSN Well known to (hexamethyldisilazane), TMS (tetramethylsilane), hydrazine gas, ammonia, nitrogen, hydrogen, argon gas, neon, helium etc. The unstrpped gas used in the film forming using the silicon-containing film of plasma CVD method.A preferred example as unstrpped gas Son can enumerate the combination of silane gas, ammonia and hydrogen.Herein, from the vapor resistance further increased under hot and humid environment From the viewpoint of property, preferred raw material gas contains nitrogen.As a preferred example for unstrpped gas, silane can be enumerated The combination of gas, ammonia, hydrogen and nitrogen.
Herein, the flow of unstrpped gas is preferably 10~1000sccm, more preferably 100~800sccm, further preferably For 200~700sccm.In addition, the flow of nitrogen is preferably 0~70% relative to the ratio of the flow of unstrpped gas, more preferably It is 30~60%.
In addition, membrance casting condition also substantially can suitably be set according to thickness of the layer of the unstrpped gas, film forming that use etc. It is fixed.In the film forming, can by suitably controlling the supply amount of reaction gas, the balance between supply and demand of each reaction gas, at membrane pressure Power, plasma exciatiaon power, plasma excitation frequency, bias etc. supply electric power, the object that forms a film (such as substrate etc.) is warm Pressure, film forming object are reached before degree, film forming at a distance from plasma generating area etc., to control containing nontransition metal M1 Layer, control the composition of gas barrier film.For example, interelectrode distance is preferably 10~40mm.For example, the film pressure of chamber Preferably 1~100Pa.Moreover, for example, plasma exciatiaon power is preferably 100~2000W.
Hereinafter, the vacuum plasma CVD method as the preferred embodiment in CVD method is specifically described referring to Fig. 4. Fig. 4 is an example for indicating the vacuum plasma CVD device used in the formation of the layer containing nontransition metal M1 Schematic diagram.
In Fig. 4, vacuum plasma CVD device 101 has vacuum tank 102, the bottom surface side in the inside of vacuum tank 102 Configured with pedestal 105.In addition, being configured with cathode in the position opposed with pedestal 105 in the ceiling side of the inside of vacuum tank 102 Electrode 103.There are heat medium circulation system 106, vacuum pumping system 107, gas delivery system in the exterior arrangement of vacuum tank 102 108 and high frequency electric source 109.Thermal medium is configured in heat medium circulation system 106.It is provided in heat medium circulation system 106 Heating-cooling device 160, have the pump for keeping thermal medium mobile, by the heating device of thermal medium heating, carry out cooling cooling The storage device of the set temperature of device, the temperature sensor of the temperature of measurement thermal medium, storage thermal medium.
Thermal medium is heated or cooled to the set temperature of storage to measure the temperature of thermal medium by heating-cooling device 160, And it is constituted to the mode that pedestal 105 supplies.The thermal medium being supplied to heats pedestal 105 or cold in the internal flow of pedestal 105 But heating-cooling device 160 is returned to afterwards.At this point, the temperature of thermal medium is more high or low than set temperature, heating-cooling device 160 will Thermal medium is heated or cooled to set temperature, and supplies to pedestal 105.Such cooling medium is in pedestal and heating-cooling device It is recycled between 160, the thermal medium for the set temperature that pedestal 105 is supplied to is heated or cooled.
Vacuum tank 102 is connect with vacuum pumping system 107, starts to carry out using the vacuum plasma CVD device 101 Before film process, the inside of vacuum tank 102 is vacuum-evacuated in advance, and by thermal medium heating from room temperature to setting Determine temperature, the thermal medium of set temperature is supplied to pedestal 105.Pedestal 105 is room temperature when using starting, if supply setting temperature The thermal medium of degree, then pedestal 105 heats up.
Make set temperature thermal medium recycle after a certain period of time, while maintaining the vacuum atmosphere in vacuum tank 102 to Film forming object (such as resin substrate etc.) 110 is moved in vacuum tank 102, is configured on pedestal 105.
Multiple nozzles (hole) is formed in the face opposed with pedestal 105 of cathode electrode 103.Cathode electrode 103 and gas Import system 108 connects, if importing CVD gas from gas delivery system 108 to cathode electrode 103, CVD gas is electric from cathode The nozzle of pole 103 is sprayed into the vacuum tank 102 of vacuum atmosphere.Cathode electrode 103 is connect with high frequency electric source 109,105 He of pedestal Vacuum tank 102 is connect with earthing potential.
It, will be certain from heating-cooling device 160 if supplying CVD gas into vacuum tank 102 from gas delivery system 108 The thermal medium of temperature is supplied to pedestal 105, while starting high frequency electric source 109, applies high frequency voltage to cathode electrode 103, then shape At the plasma of imported CVD gas.The film forming object on CVD gas to motor seat 105 being activated in plasma The surface of object 110 is deposited as the film of the layer containing nontransition metal M1 on the surface of film forming object 110.Suitably set Pedestal 105 at this time is at a distance from cathode electrode 103.
Additionally, it is contemplated that unstrpped gas and decomposition gaseous species etc. suitably set unstrpped gas and decompose the flow of gas. As an embodiment, the flow of unstrpped gas is 30~300sccm, and the flow for decomposing gas is 100~1000sccm.
In film deposition, the thermal medium of certain temperature is supplied from heating-cooling device 160 to pedestal 105, pedestal 105 It is heated or cooled by thermal medium, forms film to maintain the state of certain temperature.In general, depositing temperature when forming film Lower limit temperature is determined that ceiling temperature is permitted by the damage in the film formed on object 110 that forms a film by the film quality of film Perhaps range determines.Lower limit temperature, ceiling temperature according to the material of the film of formation, material of the film formed etc. without Together, the film quality high in order to ensure water vapor barrier property, preferred lower limit temperature are 50 DEG C or more, ceiling temperature preferably film forming pair As object heat resisting temperature below.
In advance find out with vacuum plasma CVD method formed the film quality of film and the correlativity of film-forming temperature and The correlativity of damage and film-forming temperature that film forming object 110 is subject to and determine lower limit temperature ceiling temperature.For example, vacuum The temperature of film forming object 110 in plasma CVD process is preferably 50~250 DEG C.
In addition, measured in advance to cathode electrode 103 apply 13.56MHz or more high frequency voltage formed plasma when The relationship of the temperature of the temperature and film forming object 110 of the thermal medium supplied to pedestal 105, in order in vacuum plasma CVD The temperature for the object 110 that forms a film is maintained into lower limit temperature~ceiling temperature in technique, finds out the thermal medium supplied to pedestal 105 Temperature.For example, being set to storage lower limit temperature (preferably 50 DEG C), temperature being controlled to the heat of the temperature more than lower limit temperature The mode that medium is supplied to pedestal 105.The thermal medium to flow back from pedestal 105 is heated or cooled, and (preferably 50 DEG C of set temperature More than) thermal medium be fed into pedestal 105.Herein, for example, the mixed gas conduct of supply silane gas, ammonia and nitrogen Film forming object 110 is maintained lower limit temperature~ceiling temperature temperature condition, is consequently formed as silicon-containing layer by CVD gas Silicon nitride (SiN) film.
After vacuum plasma CVD device 101 just starting, pedestal 105 is room temperature, from pedestal 105 to the cooling dress of heating The temperature for setting the thermal medium of 160 reflux is lower than set temperature.Therefore, after rigid starting, heating-cooling device 160 is by the warm of reflux Medium heating is allowed to warm to set temperature, supplies to pedestal 105.At this point, pedestal 105 and film forming object 110 are by thermal medium It heats and heats up, film forming object 110 is maintained at lower limit temperature~ceiling temperature range.
If being formed continuously film to multi-disc film forming object 110, utilize from the hot by pedestal 105 of plasma inflow Heating.At this point, the thermal medium to flow back from pedestal 105 to heating-cooling device 160 is higher than lower limit temperature (preferably 50 DEG C), therefore Heating-cooling device 160 is cooling by thermal medium, and the thermal medium of set temperature is supplied to pedestal 105.As a result, in the object that will form a film Object 110 forms film while being maintained at lower limit temperature~ceiling temperature range.In this way, heating-cooling device 160 is flowing back Thermal medium temperature it is lower than set temperature when thermal medium is heated, when higher than set temperature that thermal medium is cooling, any feelings The thermal medium of set temperature is all supplied to pedestal under condition, as a result, film forming object 110 is maintained lower limit temperature~upper limit The temperature range of temperature.After the film for forming regulation film thickness to, the object 110 that forms a film is moved to the outside of vacuum tank 102, it will not The film forming object 110 of film forming is moved in vacuum tank 102, as described above. while supplying the thermal medium of set temperature Form film.
" sputtering "
Have rate of film build higher using the film forming of sputtering method, has the advantages that higher productivity.In addition, will contain non- The layer of transition metal M 1 and layer containing transition metal M 2 are formed by sputtering method, are especially used when carrying and forming a film object When sputtering method is formed continuously each layer, existing has the advantages that high productivity.
Diode sputtering of more than two kinds, magnetron sputtering can be used alone or in combination, in using the film forming of sputtering method Between double magnetic controls (DMS) sputtering of frequency field, ion beam sputtering, ECR sputtering etc..In addition, the applying mode of target is according to target kind And properly select, any one of DC (direct current) sputtering and RF (high frequency) sputtering can be used.It is utilized alternatively, it is also possible to use The reactive sputtering method of the transition mode of centre as metal mode and oxide mode.Reactive sputtering method by at Sputtering phenomenon is controlled for the mode of transitional region, metal oxide can be formed a film with high rate of film build, thus preferably.Into When row DC sputtering, DMS sputtering, target uses the target containing nontransition metal M1, and oxygen is imported in process gas, thus, it is possible to Enough form the film of the oxide of nontransition metal M1.In addition, the oxygen of nontransition metal M1 can be used when with RF spatter film forming The target of compound.As non-active gas used in process gas, He, Ne, Ar, Kr, Xe etc. can be used, it is preferable to use Ar. In addition, being capable of forming the oxidation of nontransition metal M1 by importing oxygen, nitrogen, carbon dioxide, carbon monoxide in process gas The films such as object, nitride, nitrogen oxides, oxycarbide.As the membrance casting condition of sputtering method, it can enumerate and apply power, electric discharge electricity Stream, discharge voltage, time etc., these can be properly selected according to sputtering equipment, the material of film, film thickness etc..For example, at membrane pressure Power is preferably 0.1~5Pa.In addition, for example, shielding power supply power is preferably 2~10W/cm2。
The type of nontransition metal M1 contained by target, the type of preferred nontransition metal M1 with it is described for region (A) Bright nontransition metal M1 is same.In addition, also can be used as the target for containing above-mentioned nontransition metal M1 and be directed to region (A) the same substance of the compound from nontransition metal M1 illustrated by.Herein, as containing above-mentioned nontransition metal M1 A particularly preferred example for target, can enumerate commercially available silicon target.In addition, as the target for containing above-mentioned nontransition metal M1, example Such as, Japanese Unexamined Patent Publication 2000-026961 bulletin, Japanese Unexamined Patent Publication 2009-215651 bulletin, Japanese Unexamined Patent Publication 2003- can be used The target containing multiple elements recorded in No. 160862 bulletins, Japanese Unexamined Patent Publication 2012-007218 bulletin etc..
(rubbing method)
Layer containing nontransition metal M1 can use rubbing method and be formed.Layer containing nontransition metal M1 can pass through painting Cloth has the coating fluid of the compound containing nontransition metal M1 and drying and obtains.It is formed with rubbing method golden containing non-transition Belong to the layer of M1 because the foreign matters such as particle will not be mixed into film forming, so becoming the few layer of defect.Layer containing nontransition metal M1 It can be single layer, or 2 layers or more of stepped construction.
The atom obtained when the layer containing nontransition metal M1 formed using rubbing method is by carrying out XPS composition analysis forms The result of distribution curve calculates, nitrogen-atoms and nontransition metal M1 atom there are atomic ratios (N/M1) away from containing non-transition The thickness in region within surface layer side (surface side of the side to connect with the layer containing transition metal M 2) 30nm of the layer of metal M1 The maximum value for spending direction is preferably 0.50 or more, and extremely preferred is 0.90 or more.If away from the region within the 30nm of surface layer side Nitrogen-atoms and nontransition metal M1 atom there are the maximum value of the thickness direction of atomic ratio (N/M1) be 0.90 or more, then exist Region (a) is more readily formed in Mixed Zone.In addition, in the formation of the layer containing transition metal M 2, such as by using mistake Cross the nitride of metal M2, nitrogen oxides imports nitrogen etc. as raw material and in film forming, so that transition metal M 2 will be contained When layer is formed as nitrogenous layer, in Mixed Zone, it is easier to forming region (a).It is used as at this point, forming nitrogenous layer containing transition gold When belonging to the layer of M2, in the region within the surface layer side 30nm away from the layer containing nontransition metal M1, nitrogen-atoms and non-transition gold Belong to M1 atom is preferably 0.50 or more there are the maximum value of the thickness direction of atomic ratio (N/M1).The reason is if it is above-mentioned Range, then being capable of forming region (a) better.From the same viewpoint, it is used as in formation nitrogenous layer and contains transition metal When the layer of M2, in the region within the surface layer side 30nm away from the layer containing nontransition metal M1, nitrogen-atoms and nontransition metal M1 atom is more preferably 0.60 or more there are the maximum value of the thickness direction of atomic ratio (N/M1), it is extremely preferred be 0.90 with On.In addition, in region within the surface layer side 30nm away from the layer containing nontransition metal M1, nitrogen-atoms and nontransition metal M1 Atom is preferably 1.4 or less there are the maximum value of the thickness direction of atomic ratio (N/M1).Herein, it is specified that away from non-transition gold is contained The reasons why belonging to the optimum condition of the maximum value in the region within the surface layer side 30nm of the layer of M1 is that rubbing method is formed in thickness direction Distribution it is big, so the maximum value has a great impact to the formation in region (a).It should be noted that XPS measurement point mentioned herein Analysis and atom component distribution curve use content same as the content described in the explanation of above-mentioned atom constituent curve.
Hereinafter, being illustrated in case where nontransition metal M1 is silicon (Si), but the present invention is not limited to this.
" silicon-containing compound "
Layer (silicon-containing layer is also referred to as in this specification) containing Si can be by being coated with the coating fluid containing silicon-containing compound And drying obtains.As silicon-containing compound, for example, polysiloxanes, polysilsesquioxane, polysilazane, poly- silicon oxygen can be enumerated Azane, polysilane, Polycarbosilane etc..It should be noted that as polysiloxanes, polysilsesquioxane, polysilazane, poly- silicon oxygen nitrogen Well known compound can be used in alkane, polysilane, Polycarbosilane.In these, preferably have selected from silicon-nitrogen key, silicon-hydrogen bond and It is at least one kind of in silicon-silicon bond conjunction.As the preferred concrete example of silicon-containing compound, preferably using have silicon-nitrogen key and The polysilazane of silicon-hydrogen bond, with silicon-nitrogen key silicones azane, the polysiloxanes with silicon-hydrogen bond, with silicon-hydrogen bond Polysilsesquioxane, the polysilane with silicon-silicon bond.Silicon-containing compound can be used alone or combine two or more use.
As silicon-containing compound, more preferable polysilazane.Polysilazane refers to silicon-nitrogen key polymer, is to have The SiO of the keys such as Si-N, Si-H, N-H2、Si3N4With the intermediate solid solution SiO of the twozNyEqual ceramic precursors inorganic polymer.Poly- silicon Azane is not particularly limited, and well known substance can be used, further preferably with the structure of following logical formula (I)s.
Logical formula (I)
-[Si(R1)(R2)-N(R3)]n-
In logical formula (I), R1、R2And R3It is each independently preferably hydrogen atom, substituted or non-substituted alkyl, aryl, second Alkenyl or (trialkoxysilyl) alkyl.At this point, R1、R2And R3It can be respectively same or different.In addition, n is whole Number, preferably with the side of number-average molecular weight of the polysilazane with 150~150000g/ moles of the structure indicated with logical formula (I) Formula determines.It should be noted that the structure that logical formula (I) indicates can form ring structure.
In these, in the compound for the structure that there is logical formula (I) to indicate, particularly preferred R1、R2And R3All hydrogen atoms Perhydropolysilazane.Infer that Perhydropolysilazane is the knot there are linear chain structure and the ring structure centered on 6 and 8 member rings Structure.Its molecular weight is about 600~2000 or so (polystyrene conversions) in terms of number-average molecular weight (Mn), has liquid or solid Substance, state is different according to molecular weight.
It as other examples of polysilazane workable in the present invention, is not limited by the following, for example, Japanese spy can be enumerated Open flat 5-238827 bulletin, Japanese Unexamined Patent Publication 6-122852 bulletin, Japanese Unexamined Patent Publication 6-240208 bulletin, Japanese Unexamined Patent Publication It is recorded in flat 6-299118 bulletin, Japanese Unexamined Patent Publication 6-306329 bulletin, Japanese Unexamined Patent Publication 7-196986 bulletin etc. Example.
Commercially available product can be used in polysilazane.Commercially available product is generally dissolved in the solution state in organic solvent, this feelings Under condition, commercially available product can be directly used as to layer (B) formation and use coating fluid.As the commercially available product of polysilazane solution, can enumerate silent NN120-10, NN120-20 of gram Co. Ltd. system, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140 etc..
These polysilazanes or polysilazane solution can be used alone or combine two or more use.
As the containing ratio of the polysilazane in the silicon-containing layer before aftermentioned modification, by before modification containing non- It can be 100 mass % when the gross mass of the layer of transition metal M 1 is set as 100 mass %.In addition, the silicon-containing layer before modification When containing substance in addition to polysilazane, the containing ratio of the polysilazane in layer is preferably the 10 mass % of mass %~99.9, The more preferably 10 mass % of mass %~99.5, the further preferably 10 mass % of mass %~99, are still more preferably 40 The mass % of quality %~98, particularly preferably 70 mass of mass %~97 %, extremely preferred is the 90 mass % of mass %~97, most Preferably 93 mass of mass %~97 %.
" silicon-containing layer, which is formed, uses coating fluid "
Silicon-containing layer formation is with coating fluid must be containing the liquid of silicon-containing compound.Silicon-containing layer formation coating fluid can be into One step contains solvent.As solvent, it is not particularly limited as long as being the solvent that can dissolve silicon-containing compound, preferably without appearance The water and reactive group (such as hydroxyl or amido etc.) that easily react with silicon-containing compound for silicon-containing compound are non-live The organic solvent of property, the organic solvent of more preferable aprotic.Specifically, as solvent non-protonic solvent can be enumerated: example Such as pentane, hexane, hexamethylene, toluene, dimethylbenzene, SOLVESSO, TARPEN aliphatic hydrocarbon, ester ring type hydrocarbon, aromatic hydrocarbon etc. Hydrocarbon solvent；The halogenated hydrocarbon solvents such as methylene chloride, trichloroethanes；The esters such as ethyl acetate, butyl acetate；The ketone such as acetone, methyl ethyl ketone Class；Butyl oxide, twoThe ethers such as the fatty ethers such as alkane, tetrahydrofuran, ester ring type ether: such as tetrahydrofuran, butyl oxide, Dan He Ployalkylene glycol dialkyl ether (diethylene glycol dimethyl ether class) etc..Above-mentioned solvent can be according to the solubility of polysilazane, solvent The purpose of evaporation rate, selects, and can be used alone or is used in the form of mixture of more than two kinds.
Silicon-containing layer formation is not particularly limited with the concentration of the silicon-containing compound in coating fluid, according to the film thickness of layer, coating Validity period of liquid and different, preferably 0.5~80 mass %, more preferably 1~50 mass %, further preferred 2~40 matter Measure %.
When carrying out the modification of silicon-containing layer, in order to promote to be modified, silicon-containing layer formation preferably comprises catalyst with coating fluid.As Catalyst, preferably basic catalyst, can especially enumerate N, N- diethyl ethylene diamine, N, N- dimethylethanolamine, triethanolamine, Triethylamine, morpholinyl propylamine, N, N, N ', N '-tetramethyl -1,3- diaminopropanes, N, N, N ', N '-tetramethyl -1,6- diamino The amine catalysts such as base hexane, rhodium compounds such as the palladium compounds such as the platinum compounds such as acetylacetone,2,4-pentanedione platinum, palladium propionate, acetylacetone,2,4-pentanedione rhodium etc. Metallic catalyst, N- hetero ring type compound., it is preferable to use amine catalyst in these.As the concentration of the catalyst added at this time, When using silicon compound as benchmark, preferably 0.1~10 mass %, the more preferably range of 0.5~7 mass %.By making to be catalyzed Agent additive amount is the range, can be avoided reaction it is violent carry out caused by excessive silanol formed and the reduction of film density, The increase etc. of film defect.
In addition, silicon-containing layer formation coating fluid can be further containing other additives.As other additives, do not have There is special limitation, well known additive can be used, for example, cellulose ethers, cellulose esters, natural resin, conjunction can be enumerated At resin, condensation resin etc..
" coating method "
As the method for coating silicon-containing layer formation coating fluid, well known wet coating side appropriate all the time can be used Method.As concrete example, spin-coating method, rolling method, flow coat method, ink-jet method, spray coating method, print process, Dipcoat method, curtain coating can be enumerated Membrane formation process, stick coating method, die coating method, gravure printing method etc..
Coating thickness can suitably be set according to preferred thickness, purpose.
After being coated with coating fluid, make dried coating film.By by dried coating film, can remove contain in film it is organic molten Agent.At this point, the organic solvent contained in film can be dried all, a part can also be remained.Remain the organic molten of a part When agent, layer appropriate (B) also can be obtained.It should be noted that remaining solvent can be removed later.
The drying temperature of film is preferably 50~200 DEG C.For example, using gas obstructs in the form of barrier properties for gases membrane material Property film when, and when the use of glass transition temperature (Tg) being 70 DEG C of polyethylene terephthalate substrate, it is contemplated that heat is drawn The deformation etc. of the resin base material risen, drying temperature are preferably set to 150 DEG C or less.Above-mentioned temperature can be by using hot plate, baking Case, furnace etc. and set.Drying time is preferably set to the short time, for example, drying time is excellent when drying temperature is 50~150 DEG C Choosing was set within 30 minutes.At this point, the lower limit of drying time does not limit especially as long as the drying regime that can be realized target System, such as preferably 30 seconds or more.In addition, dry atmosphere can under air atmosphere, under nitrogen atmosphere, under argon atmospher, vacuum gas Under atmosphere, control oxygen concentration reduced atmosphere it is inferior in either condition.
For film obtained from coating silicon-containing layer formation coating fluid, before the irradiation of vacuum ultraviolet or vacuum is purple It may include dewatered process in the irradiation of outside line.Humidity under low-humidity environment changes according to temperature, therefore temperature Preferred mode is shown by the regulation of dew-point temperature with the relationship of humidity.Dew-point temperature is preferably 4 DEG C or less (temperature 25 DEG C/relative humidity 25%RH), the time of maintenance is preferably 1 minute or more.It should be noted that the lower limit of dew-point temperature is not special Limitation, usually -50 DEG C or more.
" modified (conversion) "
Film (silicon-containing layer forms coating fluid) containing silicon-containing compound can be directly prepared into silicon-containing layer, it can also be right Obtained film is modified processing, carries out the conversion reaction to silicon oxynitride etc. and forms silicon-containing layer.As method of modifying, do not have There is special limitation, well known method can be used, preferably carry out the method for vacuum ultraviolet irradiation.Vacuum ultraviolet irradiation has The advantages of further increasing the water vapor barrier property under hot and humid environment.In addition, vacuum ultraviolet irradiation is with following excellent Point: further suppress during the formation of silicon-containing layer and the formation of the layer containing transition metal M 2 by through when the environment that saves influence The deterioration of caused water vapor barrier property.
Vacuum ultraviolet irradiation uses batch processing or continuous processing, can suitably select.For example, batch processing In the case where, it can be handled with the ultraviolet light baking furnace for having ultraviolet light generating source.Ultraviolet light baking furnace itself is usually Known, it is, for example, possible to use the ultraviolet light baking furnaces of Eyegraphics Co. Ltd. system.In addition, object is that strip is membranaceous When, it can be to make its ceramics in the arid region Continuous irradiation ultraviolet light for having ultraviolet light generating source as described above when carrying it Change.The time that ultraviolet light irradiation needs is according to the composition of silicon-containing layer, concentration and forms a film the type of object and different, generally 0.1 second~10 minutes, preferably 0.5 second~3 minutes.
Refer to following methods using the modification that vacuum ultraviolet irradiates: use is than silicon-containing compound (especially polysilazane Compound) in the big 100~200nm of interatomic bond resultant force luminous energy, it is preferable to use 100~180nm wavelength luminous energy, utilize The referred to as effect of the only photon of light quantum technique, directly cuts off the bonding of atom, while being aoxidized using active oxygen, ozone Reaction, thus under lower temperature (about 200 DEG C or less), carries out the formation of the film containing silicon oxynitride.It should be noted that carrying out quasi- When molecule treatment with irradiation, heat treatment is preferably used in combination.
Vacuum ultraviolet line source preferably about 172nm have greatest irradiation excimer radiation device (such as Xe Excimer lamp), In low pressure mercury vapor lamp of the about 185nm with bright line and the medium and high pressure mercury vapour with 230nm wavelength components below Lamp and about 222nm have greatest irradiation Excimer lamp.
Wherein, since Xe Excimer lamp is with the ultraviolet light of the 172nm of single wavelength radiated wave length, so luminous efficiency is excellent It is different.Since the absorption coefficient of the oxygen of the light is big, so the free radical oxygen atom kind, smelly of high concentration can be generated with micro oxygen Oxygen.
Additionally, it is known that the ability that the energy of the light of the short 172nm of wavelength dissociates the key of organic matter is high.Utilize the activity Oxygen, ozone, high-energy possessed by ultraviolet radiation, can realize the modification of film in a short time.
Since the light generation efficiency of Excimer lamp is high, so can be lighted with low electric power investment.In addition, having as follows Feature: not issuing the light of the long wavelength for an important factor for rising as photogenic temperature, in ultraviolet range i.e. with short wavelength Irradiation energy, so being able to suppress the rising of the surface temperature of irradiation object object.Therefore, it is suitble to be easy the PET of heated influence Etc. flexible film materials.
Vacuum ultraviolet can use by containing CO, CO2And CH4At least one of gas formed plasma and It generates.
Oxygen concentration when vacuum ultraviolet irradiates is preferably 10~20000 volume ppm (0.001~2 volume %), more preferably For 50~10000 volume ppm (0.005~1 volume %).In addition, the water vapor concentration during conversion process be preferably 1000~ The range of 4000 volume ppm.
The gas of the satisfaction irradiation atmosphere used when as vacuum ultraviolet irradiation, preferably dry non-active gas are special It is not the more preferably drying nitrogen from the viewpoint of cost.The adjustment of oxygen concentration can be imported by measurement into irradiation library Oxygen, non-active gas flow, change flow-rate ratio and adjust.
In vacuum ultraviolet irradiation process, the illumination of the vacuum ultraviolet suffered by film in coated surface is preferably 1mW/cm2~10W/cm2, more preferably 30mW/cm2~200mW/cm2, further preferably 50mW/cm2~160mW/cm2.Such as Fruit is 1mW/cm2More than, then modification efficiency improves, if it is 10W/cm2Hereinafter, can then reduce the ablation, right for resulting from film The damage of film forming object.
The irradiation energy (exposure) of the vacuum ultraviolet on the surface of film is preferably 0.1~10J/cm2, more preferably 0.1~7J/cm2.If it is the range, the generation in crack caused by being able to suppress because of excess modification, the object that forms a film heat Deformation, and productivity improves.
Using the silicon-containing layer formed by above explained rubbing method as representative, contain nontransition metal M1 with what rubbing method was formed The thickness of layer be preferably 10~500nm, more preferably 30~300nm.
When forming the layer containing nontransition metal M1 using rubbing method, for example, can be by adjusting selected from containing above-mentioned non- The film forming raw material type (polysilazane type etc.) of transition metal (M1), catalyst content, coating film thickness, is done catalyst type Dry temperature-time, method of modifying, the one kind or two or more condition in modified condition, come the composition and thickness of control area (a) Degree.
(forming method of the layer containing transition metal M 2)
It as the method for forming the layer containing transition metal M 2, is not particularly limited, gas phase membrane formation process, coating can be enumerated Method.Wherein, from film forming object can be carried with side, while being formed continuously the layer containing nontransition metal M1 and containing transition metal M 2 Layer, from the viewpoint of productivity is excellent, preferred gas phase membrane formation process.Herein, as while carry form a film object while by each layer at The method of film, for example, roll-to-roll method can be enumerated.That is, the manufacturing method that a preferred mode of the invention is related to is to include using Gas phase membrane formation process forms the manufacturing method of the step of layer containing transition metal M 2.
In one embodiment of the present invention, as long as the raw material for being used to form the layer containing transition metal M 2 is from transition gold The compound (2 simple substance of transition metal M or the compound containing transition metal M 2) for belonging to M2, is just not particularly limited.In addition, making For the raw material for being used to form the layer containing transition metal M 2, can further containing from other metals substance (metal simple-substance, Compound containing metal).At this point, in the raw material of the layer containing transition metal M 2, can further containing can be formed containing The raw material of the layer of nontransition metal M1, i.e., (nontransition metal M1 simple substance contains non-transition gold to the substance from nontransition metal M1 Belong to the compound of M1).In this case, it such as makes decision the classification of layer.Firstly, only by the layer containing transition metal M 2 with gas The manufacture of barrier film under the same conditions, in addition forms a film on film forming object.Next, with above-mentioned gas barrier film Atom constituent curve similarly, with XPS analysis method measurement constituent contained by metallic element atomic composition ratio (atm%) and the atomic composition ratio of nontransition metal M2 (atm%).Then, the gold contained by the constituent in the layer of production Belong in element, by the maximum layer of the content of the transition metal M 2 using in terms of atomic composition ratio as the formation of the layer containing transition metal M 2 It is handled.
(gas phase membrane formation process)
It as gas phase membrane formation process, is not particularly limited, for example, the physics gas such as sputtering method, vapour deposition method, ion plating method can be enumerated Mutually deposition (PVD) method, chemical vapor deposition (chemical vapor deposition, CVD) method, ALD (Atomic Layer The chemical vapour deposition techniques such as Deposition).Wherein, from can not to film forming object cause damage in the case where form a film, Angle with high productivity is set out, preferably physical vaporous deposition, more preferable sputtering method or CVD method, further preferably Sputtering method.
Have the advantages that rate of film build is higher, has higher productivity using the film forming of sputtering method.In addition, will contain non- The layer of transition metal M 1 and layer containing transition metal M 2 are formed by sputtering method, are especially used when carrying and forming a film object Sputtering method be formed continuously each layer exist have the advantages that high productivity.
Diode sputtering of more than two kinds, magnetron sputtering can be used alone or in combination, in utilization using the film forming of sputtering method Between double magnetic controls (DMS) sputtering of frequency field, ion beam sputtering, ECR sputtering etc..The detailed content of sputtering method removes following special theory It is same as the content illustrated in above-mentioned (formation of the layer containing nontransition metal M1) item other than bright content, therefore save herein Slightly illustrate.
The type of the type of transition metal M 2, preferred transition metal M 2 contained by target used in sputtering method be directed to area The transition metal M 2 that domain (B) illustrates is same.In addition, can be used as the target for containing above-mentioned transition metal M 2 and be directed to region (B) illustrate from the same substance of the compound of transition metal M 2.Herein, as the target containing transition metal M 2, from film forming Rate is higher, from the viewpoint of having higher productivity, the target of the oxide of transition metal M 2 is preferably comprised, from further mentioning From the viewpoint of water vapor barrier property of the height under hot and humid environment, the oxide of the transition metal M 2 of more preferable oxygen-starved. Herein, the preference as the target containing transition metal M 2 can enumerate commercially available oxygen-starved niobium oxide target, commercially available included a tantalum target etc..
Herein, the oxidation film of transition metal M 2 is formed as when the layer containing transition metal M 2 using sputtering method, for example, The mixed gas of non-active gas and oxygen can be used as process gas, at this point, partial pressure of oxygen is excellent relative to the ratio of stagnation pressure It is selected as 0~40%, more preferably 5~30%.
When forming the layer containing transition metal M 2 using gas phase membrane formation process, for example, film forming raw material can be selected from by adjusting In above-mentioned transition metal (M2) and oxygen ratio, film forming when non-active gas and reactant gas ratio, film forming when The one kind or two or more item in electric power when magnetic force and film forming when vacuum degree when the supply amount of gas, film forming, film forming Part comes the composition and thickness of control area (a).Herein, the method as the thickness for controlling Mixed Zone and region (a), especially It is preferred that the method for the film formation time of layer of the control containing transition metal M 2.
When forming the layer containing transition metal M 2 using gas phase membrane formation process, preferably form a film under nitrogenous environment.This When, the layer containing transition metal M 2 can become the nitrogenous films such as nitride film, oxynitride film.Moreover, by making containing transition The layer of metal M2 contains nitrogen, to occur using at the interface of the layer containing nontransition metal M1 and the layer containing transition metal M 2 The spontaneous diffusion of substance, when forming the layer containing transition metal M 2, substance enters the layer containing nontransition metal M1, thus holds Easily nitrogen is imported in interface near zone.Moreover, as a result, nitrogen-atoms is deposited with nontransition metal M1 atom in Mixed Zone Value in the range of atomic ratio (y) is easier to be controlled as meeting above-mentioned formula (2).Therefore, a preferred side of the invention The manufacturing method for the gas barrier film that formula is related to is that the atmosphere of above-mentioned gas phase membrane formation process is the manufacturing method of the atmosphere containing nitrogen. It as the introduction method of nitrogen, is not particularly limited, for example, using sputtering method to form the nitride film of transition metal M 2 as containing When the layer of transition metal M 2, it is, for example, possible to use the mixed gas of non-active gas and nitrogen as process gas.At this point, nitrogen Dividing relative to the ratio of stagnation pressure is preferably 10~90%, and more preferably 20~80%.
From the region (a) for forming adequate thickness, the viewpoint of the higher water vapor barrier property under hot and humid environment is obtained Consider, film forming setting thickness when forming the layer containing transition metal M 2 is preferably 3nm or more, more preferably 5nm or more.Separately Outside, even if increasing to the thickness more than it, the thickness in region (a) also reaches saturation, therefore obtains high temperature from thinner film thickness The viewpoint of high water vapor barrier property under high humidity environment and from the viewpoint of obtaining superior bendability, preferably 30nm Hereinafter, more preferably 20nm is hereinafter, further preferably 15nm or less.
(forming Mixed Zone using vapour deposition method altogether)
As described above, the layer containing nontransition metal M1, the layer containing transition metal M 2 can be respectively further to contain Transition metal M 2 and the form of nontransition metal M1 are formed.As it can be seen that containing nontransition metal M1's using the formation of gas phase membrane formation process When layer or layer containing transition metal M 2, by using well known vapour deposition method altogether, Mixed Zone can be directly formed.As this The total vapour deposition method of sample, preferably enumerates cosputtering method.Cosputtering method for example can be to be use by containing nontransition metal M1 and transition The composition target of the alloy composition of both metal M2 is answered by what the composite oxides of nontransition metal M1 and transition metal M 2 were constituted Single source that target is closed as sputtering target sputters.Cosputtering method for example may be to use the simple substance containing nontransition metal M1 or its oxygen The multi-source of multiple sputtering targets of the simple substance or its oxide of compound and transition metal M 2 sputters simultaneously.About these sputtering targets of production Method, the method for film that is made of using the production of these sputtering targets composite oxides, for example, can be suitably special referring to Japan It opens in 2000-160331 bulletin, Japanese Unexamined Patent Publication 2004-068109 bulletin, Japanese Unexamined Patent Publication 2013-047361 bulletin etc. It records.In addition, using when vapour deposition method forms Mixed Zone altogether, it, can direct forming region (a) by being properly directed into nitrogen.
Wherein, in manufacturing method of the present invention, it is respectively formed the nontransition metal only containing nontransition metal M1 M1 layers can preferably obtain effect of the invention with only 2 layers of the transition metal M containing transition metal M 2, thus preferably.At this point, The details for the reasons why preferably playing effect of the invention is still not clear, but be presumably due to Mixed Zone (a) composition, Non-transition element M1, transition elements M2 and the existence of nitrogen-atoms in Mixed Zone (a) etc., which easily become, is more suitable for this hair The state of bright effect.
<manufacturing method of the gentle body barrier property membrane material of barrier properties for gases membrane material>
Another way of the invention is related to the barrier properties for gases being related on resin base material with the 1st aspect of the present invention The barrier properties for gases membrane material of film.Such barrier properties for gases membrane material for example can by the object that will form a film as resin base material, Manufacturing method for the gas barrier film being related to using the 2nd aspect of the present invention etc. is manufactured.
In the barrier properties for gases membrane material that one embodiment of the present invention is related to, the resin base material face of gas barrier film is formed It is not particularly limited, can be single side, or two sides.In addition, gas barrier film is with region (A) and region (B) Situation and two sides formed gas barrier film in the case where, constitute the region (A) of gas barrier film and the layer of region (B) Folded number and lamination order may be the same or different in the one side and another side of resin base material.
(resin base material)
Resin base material used in the barrier properties for gases membrane material being related to as one embodiment of the present invention, can enumerate by resin The membrane material of the composition membrane material that perhaps sheet material is preferably made of colorless and transparent resin or sheet material.As such resin base material Used in resin, for example, it is poly- to enumerate polyethylene terephthalate (PET), polyethylene naphthalate (PEN) etc. It is the polyolefin-based resins such as ester system resin, polyethylene (PE), polypropylene (PP), cyclopolyolefin, polyamide resin, polycarbonate-based Saponified, the polyacrylonitrile tree of resin, polystyrene resin, polyvinyl alcohol resin, vinyl-vinyl acetate copolymer Rouge, acetal system resin, polyimides system resins, cellulose esters system resin.
In these resins, preferably from polyester based resin, polyimides system resins, cyclopolyolefin system resin and polycarbonate It is the resin selected in resin, more preferable polyester based resin, further preferred polyethylene terephthalate (PET), poly- naphthalene Naphthalate (PEN), particularly preferred polyethylene terephthalate (PET).In addition, these resins can individually make With a kind or combine two or more use.
Resin base material can be single layer, or 2 layers or more of stepped construction.The layer that the resin base material is 2 layers or more When stack structure, each layer can be the resin of identical type, or different types of resin.
The thickness of resin base material considers stability when manufacturing barrier properties for gases membrane material of the invention and suitably sets.From From the viewpoint of can also membrane material be carried in a vacuum, the thickness of resin base material is (to refer to that it is total when 2 layers or more of stepped construction It is thick) it is preferably 5~500 μm of range.
In addition, using plasma CVD method formed one embodiment of the present invention be related to gas barrier film when, due to Film is formed while electric discharge by resin base material, so the thickness of resin base material is (to refer to that it is total when 2 layers or more of stepped construction It is thick) it is more preferably 50~200 μm of range, particularly preferably 50~100 μm of range.
In addition, being preferably used for from from the viewpoint of the adaptation of aftermentioned gas barrier film to resin base material implementation Clean the surface-active-treatment on the surface of resin base material.As such surface-active-treatment, for example, easy abutting edge can be enumerated Reason, sided corona treatment, corona treatment, flame treatment.In these, preferably easy bonding processing.
(layer with various functions)
In the barrier properties for gases membrane material that one embodiment of the present invention is related to, the layer with various functions can be set.
" anchor coat "
For the purpose for the adaptation for improving resin base material and gas barrier film, a side of the invention can formed The surface of the resin base material of the side for the gas barrier film that formula is related to forms anchor coat.
As paint is anchored used in anchor coat, polyester resin, isocyanate resin, polyurethane tree can be used Rouge, acrylic resin, ethylene vinyl alcohol, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon tree It a kind in rouge and alkyl titanate etc. or is used in combination of two or more.
Well known additive all the time can also be added in these anchoring paints.Furthermore, it is possible to utilize roller coating, intaglio plate Above-mentioned anchoring paint is coated on supporting mass by method well known to coating, blade coating, dip-coating, spraying etc., and is dried and removed Thus solvent, diluent etc. carry out anchoring coating.As the coating weight of above-mentioned anchoring paint, preferably 0.1~5.0g/m2 (drying regime) left and right.
In addition, the vapor phase method that anchor coat also can use physical vapor deposition or chemical vapor deposition etc is formed.For example, It can be formed with silica in order to improve cementability etc. as documented by Japanese Unexamined Patent Publication 2008-142941 bulletin and be The inoranic membrane of main body.Or the anchor coat as recorded in Japanese Unexamined Patent Publication 2004-314626 bulletin can also be formed, from And when being formed on inorganic thin film using vapor phase method, it is controlled for obstructed to a certain degree from the gas that resin base material side generates The purpose of the composition of inorganic thin film processed etc forms anchor coat.
In addition, the thickness of anchor coat is not particularly limited, preferably 0.5~10 μm or so.
" hard conating "
It can have hard conating on the surface (on one side or two sides) of resin base material.Example as material contained by hard conating Son for example, heat-curing resin, active energy ray-curable resin can be enumerated, but from easy angle is formed, is preferably lived Property energy line curable resin.Such curable resin can be used alone or combine two or more use.
Active energy ray-curable resin refers to through irradiation ultraviolet light, active energy ray as electron beam via being crosslinked Reaction etc. carries out cured resin.As active energy ray-curable resin, it is preferable to use containing having ethylenic bond unsaturated bond Monomer ingredient, its solidification is made by irradiation ultraviolet light, active energy ray as electron beam, formation contains active energy ray The layer of the solidfied material of curable resin, i.e. hard conating.As active energy ray-curable resin, ultra-violet solidified tree can be enumerated Rouge, electronic beam curing resin etc. are preferably carried out by ultraviolet light irradiation cured ultra-violet solidified as the resin represented Resin.As uv curing resin, for example, the resin combination containing (methyl) acrylate compounds can be enumerated, contain There is the resin combination of (methyl) acrylate compounds and the mercaptan compound containing mercapto, contains epoxy (methyl) acrylic acid Ester, carbamate (methyl) acrylate, polyester (methyl) acrylate, melamine (methyl) acrylate, polyethers (first Base) the multifunctional (methyl) acrylates list such as acrylate, polyethylene glycol (methyl) acrylate, (methyl) glycerol acrylate The resin combination of body, the resin combination etc. containing amorphous fluoropolymer.Herein, (methyl) acrylate indicates acrylic acid Ester or methacrylate.In addition, commercially available product can be used as uv curing resin, as commercially available product, for example, Love chemical industry Co. Ltd. system Z731L, JSR Corp. OPSTAR (registered trademark) Z7527 etc. can be enumerated.Furthermore it is possible to Use the commercially available resin base material for being pre-formed with hard conating.
The forming method of hard conating is not particularly limited, wet preferably by spin-coating method, spray-on process, knife coating, infusion process etc. The dry types cladding process such as formula cladding process (rubbing method) or vapour deposition method is formed.
The drying temperature of film when forming hard conating is not particularly limited, and preferably 40~120 DEG C.
The active energy ray used when as by hard coat layer, preferably ultraviolet light.
It as ultraviolet lamp, is not particularly limited, for example, high-pressure sodium lamp etc. can be enumerated.Ultraviolet light irradiation condition It is not particularly limited, is carried out under air for example, can enumerate.Ultraviolet light irradiation energy is not particularly limited, preferably 0.3~ 5J/cm2。
In addition, the thickness of hard conating is not particularly limited, preferably 0.5~10 μm or so.
As hard conating, it is not particularly limited, it is preferable to use transparent hard-coating layer.It should be noted that it is preferred that above-mentioned anchoring applies The others layer such as layer, aftermentioned smooth layer has both the function of hard conating.
" smooth layer "
In the barrier properties for gases membrane material that one embodiment of the present invention is related to, between resin base material and gas barrier film It can have smooth layer.Smooth layer used in a mode of the invention is that there are the asperities of the resin base material of protrusion etc. in order to make Planarization or landfill make it in the bumps of transparent inorganic compound layer generation, pin hole due to being present in the protrusion of resin base material Planarization and be arranged.Such smooth layer is substantially to solidify photosensitive material or thermoset materials and make.
It is more preferably ultraviolet as the photosensitive material of smooth layer, preferably active energy line curing resin composition Line hardening resin composition.As ultra-violet solidified resin composition, for example, can enumerate containing (methyl) acroleic acid esterification The resin combination of object is closed, the resin combination of (methyl) acrylate compounds and mercaptan compound with mercapto is contained Object contains epoxy (methyl) acrylate, carbamate (methyl) acrylate, polyester (methyl) acrylate, polyethers (first Base) polyfunctional acrylate monomers such as acrylate, polyethylene glycol (methyl) acrylate, (methyl) glycerol acrylate tree Oil/fat composition, the resin combination etc. containing amorphous fluoropolymer.Herein, (methyl) acrylate indicate acrylate or Methacrylate.As uv curing resin, commercially available product can be used, as commercially available product, it is, for example, possible to use JSR The UV curing type organic/inorganic mixing of Co. Ltd. system is hard to apply material OPSTAR (registered trademark) series.As JSR Corp. OPSTAR (registered trademark) series of system, for example, OPSTAR (registered trademark) Z7527 etc. can be enumerated.Alternatively, it is also possible to use as The arbitrary mixture of the upper resin combination, as long as containing in the molecule with 1 or more optical polymerism insatiable hunger It is just not particularly limited with the photosensitive material of the reactive monomer of key.
As thermoset materials, specifically, the Tuttoprom series that can enumerate Clariant corporation is (organic poly- Silazane), the SP COAT heat-resisting transparent coating of CERAMICCOAT Co. Ltd. system, ADEKA Corp. Nano Hybrid Silicone, UNIDIC (registered trademark) V-8000 series of Dainippon Ink Chemicals, EPICLON (registered trademark) The meeting of strain formula is spun in EXA-4710 (superelevation heat-resistance epoxy resin), the various silicone resin of Shin-Etsu Chemial Co., Ltd, day east Inorganic organic nano composite material SSG COAT of society, the thermosetting being made of the pure and mild isocyanate prepolymer of acrylic acid multielement The property changed polyurethane resin, phenolic resin, urea melamine, epoxy resin, unsaturated polyester resin, silicone resin etc..Its In, particularly preferably there is the material of the epoxy matrix material of heat resistance.
The forming method of smooth layer is not particularly limited, wet preferably by spin-coating method, spray-on process, knife coating, infusion process etc. The dry types cladding process such as formula cladding process (rubbing method) or vapour deposition method is formed.
The condition of light irradiation when the drying condition of smooth layer and the material for forming smooth layer are photosensitive material can be with Using condition same as the condition of above-mentioned hard conating.
When forming smooth layer, antioxidant can be added as needed in above-mentioned photoresist, ultraviolet light is inhaled Receive the additives such as agent, plasticizer.In addition, the stratification position with smooth layer is not related, in order to improve film forming and prevent film Pin hole generation etc., can use resin appropriate, additive in arbitrary smooth layer.
The sight of the balance of the optical characteristics of membrane material is easily adjusted from the heat resistance for improving membrane material as the thickness of smooth layer Point consideration, preferably 1~10 μm of range, more preferably 2~7 μm of range.
The flatness of smooth layer is the value that the surface roughness as specified in JIS B 0601:2001 indicates, 10 points average Roughness Rz is preferably 10nm~30nm.If it is the range, either with the feelings of coated form coating gas barrier film Under condition, still with wire rod, in the case where contacting coating mechanism with smooth layer surface without coating methods such as bars, coating damage Mistake is all less, in addition, being also easy to make the concave-convex smoothing after coating.
<manufacturing method of electronic equipment and electronic equipment>
The gas barrier film that gas barrier film that one embodiment of the present invention is related to, one embodiment of the present invention are related to The equipment that the chemical component (oxygen, water, nitrogen oxides, oxysulfide, ozone etc.) that material is applicable in air causes performance to deteriorate. Another way of the invention is the gas barrier film being related to comprising one embodiment of the present invention or of the invention one as a result, The electronic equipment for the barrier properties for gases membrane material that mode is related to.
In addition, another mode of the invention is related to the manufacturing method of a kind of electronic equipment, comprising: using comprising of the invention The package parts for the barrier properties for gases membrane material that the gas barrier film or one embodiment of the present invention that one mode is related to are related to, The step of functional plane of electronic equipment is packaged.
Can be gas barrier film monomer as the package parts comprising gas barrier film, at this point it is possible to by The functional plane of electronic equipment directly forms gas barrier film and carries out the encapsulation of the functional plane of electronic equipment.In addition, making For the package parts containing barrier properties for gases membrane material, barrier properties for gases membrane material and potting resin layer are pasted for example, can enumerate Laminated body made of conjunction.It as potting resin layer, is not particularly limited, for example, the sheet bonding agent (ring of thermohardening type can be enumerated Oxygen system resin) etc..Herein, as used the package parts comprising gas barrier film or barrier properties for gases membrane material, it is electric One example of the packaging method of the functional plane of sub- equipment, can enumerate following method.Firstly, will include gas barrier film Or the functional plane of the bonding agent forming face of the package parts of barrier properties for gases membrane material and electronic equipment carry out it is continuously be overlapped.It connects Get off, by the configuration of the laminated body of package parts and electronic equipment in decompressor, under the conditions of high-temperature pressure-reduction, to the base of overlapping Material and package parts, which apply, to be squeezed and keeps.Then, so that sample is returned to atmospheric pressure environment, further heat one under high temperature environment Fixing time solidifies bonding agent.
As electronic equipment, for example, organic electroluminescent device (organic EL element), liquid crystal display element can be enumerated (LCD), thin film transistor (TFT), touch panel, Electronic Paper, solar battery (PV) etc..From more efficiently obtaining effect of the invention From the viewpoint of, the preferably electronic device body is organic EL element or solar battery, more preferably organic EL element, into One step is preferably organic EL illuminating element.
Embodiment
Effect of the invention is illustrated using embodiment below and comparative example.But technical scope of the invention It is not limited only to embodiment below.
<manufacture of the barrier properties for gases membrane material with gas barrier film>
(comparative example 1: the manufacture of barrier properties for gases membrane material 1)
(resin base material)
As resin base material, 50 μm of thickness of the polyethylene terephthalate that easily bonding processing is implemented on two sides is used Ester membrane material (TORAY Co. Ltd. system, Lumirror (registered trademark) U48).The resin base material with form barrier properties for gases 0.5 μm of thickness of the transparent hard-coating layer with the function that prevents adhesion is formed on the opposite face in the face of film.That is, by ultra-violet solidified tree Rouge (love chemical industry Co. Ltd. system, product number: Z731L) is coated on resin base material in such a way that dry film thickness becomes 0.5 μm It is dry at 80 DEG C after upper, thereafter, under air, using high-pressure sodium lamp in irradiation energy 0.5J/cm2Under conditions of consolidated Change.
Next, forming 2 μm of thickness transparent as follows on the face of the side of the formation gas barrier film of resin base material Hard conating is as smooth layer.By JSR Corp. uv curing resin OPSTAR (registered trademark) Z7527 with desciccator diaphragm After thickness is coated on resin base material as 2 μm of mode, it is dried at 80 DEG C, thereafter, under air, is being shone using high-pressure sodium lamp Penetrate energy 0.5J/cm2Under conditions of solidified.In this way, obtaining the resin base material with transparent hard-coating layer.Hereinafter, in this implementation In example and comparative example, for convenience, which is referred to as resin base material.
(the forming method A1 of the layer containing nontransition metal M1)
The resin base material of above-mentioned preparation is set to vacuum plasma CVD device 101 shown in Fig. 4, carries out vacuum row After gas, on the surface (that is, surface of 2 μm of thickness of transparent hard-coating layer) of the side of the formation gas barrier film of resin base material The silicon nitride film of thickness 50nm is formed as the layer containing nontransition metal Si.The high frequency electric source used at this time is 27.12MHz's High frequency electric source, interelectrode distance 20mm.In addition, making silane gas flow 7.5sccm as unstrpped gas, making ammonia flow Amount is 50sccm, and making hydrogen flowing quantity 200sccm, (sccm is the cm at 133.322Pa3/ min), it imports in vacuum chamber. Also, make 100 DEG C of resin base material temperature when forming a film and starting.So obtain barrier properties for gases membrane material 1.
(comparative example 2: the manufacture of barrier properties for gases membrane material 2)
The forming method A1 of layer containing nontransition metal M1 is changed to following forming method A2, in addition to this, equally Ground carries out, and gets similarly barrier properties for gases membrane material 2 with comparative example 1.
(the forming method A2 of the layer containing nontransition metal M1)
Use commercially available vacuum C CP (Capacitively Coupled Plasma；Capacitance coupling plasma)-CVD dress It sets.As unstrpped gas, silane gas (SiH is used4), ammonia (NH3), nitrogen (N2) and hydrogen (H2).In addition, as power supply, The high frequency electric source of frequency of use 13.56MHz.
The indoor substrate holder of the vacuum chamber that resin base material is set to CVD device closes vacuum chamber.Next, right It is exhausted in vacuum chamber, at the time of pressure becomes 0.1Pa, imports unstrpped gas.It should be noted that the flow of silane gas For 80sccm, the flow of ammonia is 60sccm, and the flow of nitrogen is 350sccm, and the flow of hydrogen is 80sccm.
It is after 50Pa stablizes, from high frequency electric source to the plasma exciatiaon of electrode supply 600W in the indoor pressure of vacuum chamber Power forms the silicon nitride film of thickness 50nm as containing nontransition metal Si's on the surface of the transparent hard-coating layer of resin base material Layer.
(comparative example 3: the manufacture of barrier properties for gases membrane material 3)
The forming method A2 of layer containing nontransition metal M1 is changed to following forming method A3, in addition to this, with than It is carried out similarly compared with example 2, obtains barrier properties for gases membrane material 3.
(the forming method A3 of the layer containing nontransition metal M1)
In the forming method A2 of the layer containing nontransition metal M1, makes the flow 80sccm of silane gas, make ammonia Flow be 150sccm, make the flow 200sccm of nitrogen, make the flow 170sccm of hydrogen, make plasma exciatiaon function Rate is 1200W, in addition to this, is carried out similarly, and forms the silicon nitride film of thickness 50nm as the layer containing nontransition metal Si.
(comparative example 4: the manufacture of barrier properties for gases membrane material 4)
The forming method A2 of layer containing nontransition metal M1 is changed to following forming method A4, in addition to this, with than It is carried out similarly compared with example 2, obtains barrier properties for gases membrane material 4.
(the forming method A4 of the layer containing nontransition metal M1)
It in the forming method A2 of the layer containing nontransition metal M1, is formed in such a way that thickness becomes 100nm, except this it Outside, it is carried out similarly, forms silicon nitride film.
(comparative example 5: the manufacture of barrier properties for gases membrane material 5)
The forming method A2 of layer containing nontransition metal M1 is changed to following forming method A5, in addition to this, with than It is carried out similarly compared with example 2, obtains barrier properties for gases membrane material 5.
(the forming method A5 of the layer containing nontransition metal M1)
It in the forming method A2 of the layer containing nontransition metal M1, is formed in such a way that thickness becomes 300nm, except this it Outside, it is carried out similarly, forms silicon nitride film.
(comparative example 6: the manufacture of barrier properties for gases membrane material 6)
The forming method A2 of layer containing nontransition metal M1 is changed to following forming method A6, in addition to this, with than It is carried out similarly compared with example 2, obtains barrier properties for gases membrane material 6.
(the forming method A6 of the layer containing nontransition metal M1)
Nitridation in the forming method A2 of the layer containing nontransition metal M1, using following device and condition to obtaining Silicon fiml further progress is handled with the wavelength 150nm plasma irradiating below for shining (105nm, 107nm, 121nm), is removed It except this, is carried out similarly, forms the silicon nitride film of thickness 50nm as the layer containing nontransition metal Si.
" plasma irradiating processing "
Plasma processing apparatus: low-voltage capacitance coupled plasma processing unit (U-Tech Co. Ltd. system),
(comparative example 7: the manufacture of barrier properties for gases membrane material 7)
The forming method A5 of layer containing nontransition metal M1 is changed to following forming method A7, in addition to this, with than It is carried out similarly compared with example 5, obtains barrier properties for gases membrane material 7.
(the forming method A7 of the layer containing nontransition metal M1)
In the forming method A5 of the layer containing nontransition metal M1, with the shape with the above-mentioned layer containing nontransition metal M1 Same method is handled to obtained silicon nitride film further progress plasma irradiating at the plasma irradiating in method A6 Processing, in addition to this, is carried out similarly, and forms the silicon nitride film of thickness 300nm.
(comparative example 8: the manufacture of barrier properties for gases membrane material 8)
The forming method A1 of layer containing nontransition metal M1 is changed to following forming method A8, in addition to this, with than It is carried out similarly compared with example 1, obtains barrier properties for gases membrane material 8.
(the forming method A8 of the layer containing nontransition metal M1)
Using magnetic control sputtering device (Canon Anelva Co. Ltd. system: model EB1100), in the formation of resin base material The surface of the side of gas barrier film forms the silicon nitride film of thickness 50nm as the layer containing nontransition metal Si.At this point, As target, using commercially available silicon target, process gas uses Ar and N2, make ratio 50% of the nitrogen partial pressure relative to stagnation pressure, pass through DC sputtering forms a film.In addition, making shielding power supply power 5.0W/cm2, make film pressure 0.4Pa.Moreover, thickness passes through As under type adjusts: taking data of the Thickness Variation relative to film formation time in the range of 100~300nm, calculate per unit time After the thickness of film forming, film formation time is set in a manner of becoming setting thickness.
(comparative example 9: the manufacture of barrier properties for gases membrane material 9)
The forming method A8 of layer containing nontransition metal M1 is changed to following forming method A9, in addition to this, with than It is carried out similarly compared with example 8, obtains barrier properties for gases membrane material 9.
(the forming method A9 of the layer containing nontransition metal M1)
In the forming method A8 of the layer containing nontransition metal M1, with the shape with the above-mentioned layer containing nontransition metal M1 Same method is handled at the plasma irradiating in method A6, plasma irradiating processing is carried out to obtained silicon nitride film, remove It except this, is carried out similarly, forms the silicon nitride film of thickness 50nm as the layer containing nontransition metal Si.
(comparative example 10: the manufacture of barrier properties for gases membrane material 10)
After the forming method A1 of the layer containing nontransition metal M1, layer and resin containing nontransition metal M1 are carried The laminated body of substrate carries out oxygen on the surface of obtained silicon nitride film with the forming method B1 of following layers containing transition metal M 2 Change the formation of niobium film.In addition to this, it is carried out similarly with comparative example 1, obtains barrier properties for gases membrane material 10.
(the forming method B1 of the layer containing transition metal M 2)
Using magnetic control sputtering device (Canon Anelva Co. Ltd. system: model EB1100), by containing non-transition The niobium oxide film that the surface for the silicon nitride film that the forming method A1 of the layer of metal M1 is obtained forms thickness 6nm is used as containing transition gold Belong to the layer of M2.At this point, using commercially available oxygen-starved niobium oxide target, (group becomes Nb as target12O29), process gas using Ar and O2, make ratio 12% of the partial pressure of oxygen relative to stagnation pressure, formed a film by DC sputtering.In addition, making shielding power supply power 5.0W/cm2, make film pressure 0.4Pa.Moreover, thickness adjusts in the following way: taking thickness in the range of 100~300nm The data for changing opposite film formation time after calculating the thickness to form a film per unit time, are set in a manner of becoming setting thickness The film time.
(comparative example 11: the manufacture of barrier properties for gases membrane material 11)
The forming method B1 of layer containing transition metal M 2 is changed to following forming method B2, in addition to this, compared with Example 10 is carried out similarly, and obtains barrier properties for gases membrane material 11.
(the forming method B2 of the layer containing transition metal M 2)
In the forming method B1 of the layer containing transition metal M 2, formed in such a way that thickness becomes 10nm, in addition to this, It is carried out similarly, forms niobium oxide film.
(embodiment 1: the manufacture of barrier properties for gases membrane material 12)
After the forming method A2 of the layer containing nontransition metal M1, layer and resin containing nontransition metal M1 are carried The laminated body of substrate, it is further on the surface of obtained silicon nitride film with the forming method B1 of the above-mentioned layer containing transition metal M 2 Carry out the formation of niobium oxide film.In addition to this, it is carried out similarly with comparative example 2, obtains barrier properties for gases membrane material 12.
(embodiment 2: the manufacture of barrier properties for gases membrane material 13)
After the forming method A3 of the layer containing nontransition metal M1, layer and resin containing nontransition metal M1 are carried The laminated body of substrate, it is further on the surface of obtained silicon nitride film with the forming method B1 of the above-mentioned layer containing transition metal M 2 Carry out the formation of niobium oxide film.In addition to this, it is carried out similarly with comparative example 3, obtains barrier properties for gases membrane material 13.
(embodiment 3: the manufacture of barrier properties for gases membrane material 14)
After the forming method A3 of the layer containing nontransition metal M1, layer and resin containing nontransition metal M1 are carried The laminated body of substrate, it is further on the surface of obtained silicon nitride film with the forming method B2 of the above-mentioned layer containing transition metal M 2 Carry out the formation of niobium oxide film.In addition to this, it is carried out similarly with comparative example 3, obtains barrier properties for gases membrane material 14.
(embodiment 4: the manufacture of barrier properties for gases membrane material 15)
After the forming method A8 of the layer containing nontransition metal M1, layer and resin containing nontransition metal M1 are carried The laminated body of substrate, it is further on the surface of obtained silicon nitride film with the forming method B1 of the above-mentioned layer containing transition metal M 2 Carry out the formation of the layer containing transition metal Nb.In addition to this, it is carried out similarly with comparative example 8, obtains having by containing The surface of the layer of nontransition metal Si forms the barrier properties for gases of gas barrier film obtained from the layer containing transition metal Nb Membrane material 15.
(embodiment 5: the manufacture of barrier properties for gases membrane material 16)
The forming method B1 of layer containing transition metal M 2 is changed to the forming method of following forming method layer B3, removes this Except, it is performed in the same manner as in Example 2, obtains barrier properties for gases membrane material 16.
(the forming method B3 of the layer containing transition metal M 2)
In the forming method B1 of the layer containing transition metal M 2, make partial pressure of oxygen using commercially available included a tantalum target (Ta) as target Ratio relative to stagnation pressure is 18%, in addition to this, is carried out similarly, and the tantalum-oxide film of thickness 6nm is formed.
(embodiment 6: the manufacture of barrier properties for gases membrane material 17)
The forming method B1 of layer containing transition metal M 2 is changed to following forming method B4, in addition to this, compared with Example 10 is carried out similarly, and obtains barrier properties for gases membrane material 17.
(the forming method B4 of the layer containing transition metal M 2)
In the forming method B1 of the layer containing transition metal M 2, nitrogen is imported in process gas, process gas uses Ar and N2, it is carried out similarly nitrogen partial pressure in addition to this relative to the ratio 50% of stagnation pressure, forms the nitridation oxygen of thickness 6nm Change niobium (nitrogen oxidation niobium) film as the layer containing transition metal M 2.
(comparative example 12: the manufacture of barrier properties for gases membrane material 18)
The forming method B1 of layer containing transition metal M 2 is changed to following forming method B5, in addition to this, with implementation Example 2 is carried out similarly, and obtains barrier properties for gases membrane material 18.
(the layer B5 containing transition metal M 2)
In the forming method B1 of the layer containing transition metal M 2, formed in such a way that thickness becomes 2nm, in addition to this, It is carried out similarly, forms nitrogen oxidation niobium film.
(comparative example 13: the manufacture of barrier properties for gases membrane material 19)
The forming method A1 of layer containing nontransition metal M1 is changed to following forming method A10, in addition to this, with than It is carried out similarly compared with example 1, obtains barrier properties for gases membrane material 19.
(the forming method A10 of the layer containing nontransition metal M1)
By containing 20 mass % Perhydropolysilazanes butyl oxide solution (Merck Co. Ltd. system, NN120-20) with relative to 100 mass parts of Perhydropolysilazane contain 5 mass parts amine catalysts (N, N, N ', N '-tetramethyl -1,6- diamino hexane (TMDAH)) the butyl oxide solution (Merck Co. Ltd. system, NAX120-20) containing 20 mass % Perhydropolysilazanes is with 4:1 The ratio of (mass ratio) mixes, and is further diluted in such a way that concentration becomes 3 mass % with butyl oxide, and preparation contains non-transition gold Belong to the coating fluid of Si.The preparation of coating fluid carries out in glove box.
Coating fluid is coated on to the formation gas of above-mentioned resin base material by spin-coating method in such a way that dry film thickness becomes 100nm The surface of the side of body barrier film, it is 2 minutes dry at 80 DEG C.Next, using the Xe Excimer lamp with wavelength 172nm Fig. 5 vacuum ultraviolet beam irradiating apparatus, irradiation energy become 6.0J/cm2Under conditions of vacuum is carried out to dry film Ultraviolet treatment with irradiation.At this point, irradiation atmosphere is replaced with nitrogen, oxygen concentration is made to become 0.1 volume %.In addition, changing setting sample ( Property processing before barrier properties for gases membrane material) microscope carrier temperature be 80 DEG C.
In Fig. 5,1 is device chamber, by internally supplying nitrogen and oxygen in right amount from gas supply port (not shown), never The gas discharge outlet of diagram is vented, and thus substantially removes vapor from chamber interior, oxygen concentration can be maintained defined Concentration.2 for irradiation 172nm vacuum ultraviolet with cannula structure Xe Excimer lamp (Excimer lamp luminous intensity: 130mW/cm2), 3 be as the bracket of the Excimer lamp of external electrode, and 4 be sample stage.Sample stage 4, which can use, not to be schemed The mobile mechanism shown moves back and forth in device chamber 1 with defined speed (V of Fig. 5) is horizontal.In addition, sample stage 4 can be with Defined temperature is maintained using heating mechanism (not shown).5 be the sample for being formed with polysilazane compounds coating layer.Sample When microscope carrier moves horizontally, examination is adjusted in such a way that the shortest distance in the painting layer surface of sample and quasi-molecule fluorescent tube face becomes 3mm The height of sample microscope carrier.6 be barn door, in order to not irradiate vacuum ultraviolet to the coating layer of sample in the aging of Xe Excimer lamp 2 Line.
Herein, Hamamatsu is used to the energy of sample coating layer surface irradiation in vacuum ultraviolet treatment with irradiation The ultraviolet light accumulated light meter (C8026/H8025UV POWER METER) of Photonics Co. Ltd. system, utilizes 172nm's Sensor senses head measurement.When measurement, become with 2 pipe face of Xe Excimer lamp and the shortest distance of the aspect of measure of sensor sensing head Sensor sensing head is set to 4 center of sample stage by the mode of 3mm, and is become and vacuum purple with the atmosphere in device chamber 1 The mode of the identical oxygen concentration of outside line irradiation process supplies nitrogen and oxygen, make sample stage 4 with the speed of 0.5m/min it is mobile and into Row measurement.Before measurement, in order to stablize the illumination of Xe Excimer lamp 2, it is arranged after lighting Xe Excimer lamp 10 minutes Ageing time makes thereafter sample stage mobile and starts to measure.Based on irradiation energy obtained in the measurement, by adjusting sample The movement speed of microscope carrier adjusts irradiation energy.It should be noted that when irradiating vacuum ultraviolet, it is laggard in agings in 10 minutes Row.
As a result, resin base material formation gas barrier film side surface formed thickness 100nm contain nitrogen oxygen The polysilazane Modified Membrane of SiClx film is as the layer containing nontransition metal Si.It should be noted that being carried out by aftermentioned XPS analysis The measurement of the composition distribution of the thickness direction of this layer, as a result the N/Si of this layer with the average value of the thickness direction of layer entirety than being calculated as 0.1, the part thickness about 30nm of the surface layer side of the side opposite with resin base material side of polysilazane Modified Membrane is original gathers Remaining silicon oxynitride (silicon oxynitride) film occurs for the nitrogen (N) that silazane contains, and the maximum value of the N/Si ratio of the part is 0.6.
(embodiment 7: the manufacture of barrier properties for gases membrane material 20)
Using the forming method B4 of the above-mentioned layer containing transition metal M 2 in the shape by the layer containing nontransition metal M1 At the formation of the surface further progress nitrogen oxidation niobium film of the obtained polysilazane Modified Membrane of method A10.In addition to this, compared with Example 13 is carried out similarly, and obtains barrier properties for gases membrane material 20.
The manufacturing condition of gas barrier film in barrier properties for gases membrane material 1~20 is shown in following table 1.
<evaluation of barrier properties for gases membrane material>
(measurement of the composition distribution of the thickness direction of gas barrier film)
The component distribution curve of the thickness direction of gas barrier film is measured by XPS analysis.XPS analysis condition is such as Under.
(XPS analysis condition)
Device: ULVAC-PHI corporation QUANTERASXM
X-ray source: monochromatization Al-K α
Plasma sputter: Ar (2keV)
Depth profiling: with SiO2Conversion sputtering thickness, is repeatedly measured with defined thickness interval, obtains depth direction Depth profiling.1nm (obtaining the data of every 1nm in depth direction) is divided between the thickness
It is quantitative: to find out background value with Shirley method, determined using relative sensitivity coefficient method by obtained peak area Amount.Data processing uses the MultiPak of ULVAC-PHI corporation.It should be noted that the element of analysis is nontransition metal M1 (silicon (Si)), transition metal M 2 (niobium (Nb), tantalum (Ta)), oxygen (O), nitrogen (N), carbon (C).
According to measurement result, determine whether contain nontransition metal M1 as the region (A) of the principal component of metallic element and Region (B), Mixed Zone and region (a) containing transition metal M 2 as the principal component of metallic element.In addition, according to survey It is fixed as a result, find out the N/Si ratio (average value of thickness direction) of the layer containing nontransition metal M1, whether there is or not Mixed Zone, by M1M2xNyThe presence of nitrogen-atoms and nontransition metal M1 atom when the composition of (0.02≤x≤49, y >=0) expression Mixed Zone The thickness of maximum value (the y maximum value) and region (a) of atomic ratio.
Herein, about whether there is or not the judgement of Mixed Zone, meet transition gold when the thickness direction in gas barrier film has When belonging to the region that there are the value of atomic ratio for element 0.02~49 range in forms of the M2 with nontransition metal M1 atom, show With Mixed Zone.
In addition, about whether there is or not the judgements in region (a), by M1M2xNyIndicate composition when, when have meet following formula (1) and under When stating the region of formula (2), show with region (a).
M1M2xNy
0.2≤x≤3.0 (1)
0.6 y≤1.4 < (2)
X: 2 atom of transition metal M and nontransition metal M1 atom there are atomic ratio,
Y: nitrogen-atoms and nontransition metal M1 atom there are atomic ratios
It should be noted that containing nontransition metal M1's about barrier properties for gases membrane material 10~18 and 20 in this evaluation The N/Si ratio (average value of thickness direction) of layer makes in addition to not forming M2 layers of nontransition metal, of same as these membrane materials Method formed on resin base material only with the layer containing nontransition metal M1 measurement sample, use its measured value.
These results are shown in following table 2.It should be noted that by M1M2xNyWhen indicating the composition of Mixed Zone, gas barrier The y maximum value for the gas barrier film that property membrane material 10~18 and 20 (Examples 1 to 7) is related to is present in the model of 0.2≤x≤3.0 In enclosing.
(water vapo(u)r transmission (water vapor barrier property) of gas barrier film evaluates (Ca method))
(production that unit is used in water vapo(u)r transmission evaluation)
According to measuring method below, by the water vapo(u)r transmission of each barrier properties for gases membrane material with gas barrier film It is evaluated under the conditions of 3 kinds.Herein, in order to make a kind of water vapo(u)r transmission evaluation unit, 2 barrier properties for gases are needed Membrane material, therefore in order to be evaluated under the conditions of 3 kinds, each barrier properties for gases membrane material respectively prepares 6.
Unit is used in following production water vapo(u)r transmission evaluation.Firstly, to the gas barrier film of 1 barrier properties for gases membrane material After surface carries out UV cleaning, in the sheet bonding agent (asphalt mixtures modified by epoxy resin of 20 μm of thermohardening type of barrier properties for gases film surface coating thickness Rouge) it is used as potting resin layer.Next, the laminated body of obtained barrier properties for gases membrane material and potting resin layer is punched into 50mm It after the size of × 50mm, is put into glove box, be dried within 24 hours.In addition, being rushed by another 1 barrier properties for gases membrane material After being cut into the size of 50mm × 50mm, UV cleaning is carried out to the surface of gas barrier film possessed by barrier properties for gases membrane material. Next, using the vacuum deposition apparatus of ALS Technology Co. Ltd. system, the gas possessed by barrier properties for gases membrane material Ca is deposited according to the size of 20mm × 20mm via mask in the central location on body barrier film surface.Herein, Ca with a thickness of 80nm.Then, the barrier properties for gases membrane material for being vapor-deposited with Ca is fetched into above-mentioned glove box, with the above-mentioned gas by punching The Ca of barrier properties for gases membrane material of the potting resin level of the laminated body of barrier property membrane material and potting resin layer with being vapor-deposited with Ca steams The mode that surfacing connects configures, and is bonded by vacuum lamination.Herein, vacuum lamination is in the laminated body that will be bonded (laminated body of barrier properties for gases membrane material of the laminated body of barrier properties for gases membrane material and potting resin layer with being vapor-deposited with Ca) is in 110 DEG C It is carried out in the state of heating.Thereafter, the laminated body being bonded using vacuum lamination is fitted with encapsulation tree with the laminated body The barrier properties for gases membrane material side mode directed downwardly of rouge layer is placed on the hot plate for being set in 110 DEG C, is solidified 30 minutes, thus Unit is used in production water vapo(u)r transmission evaluation.
In order to be evaluated under the conditions of 3 kinds, after making 3 kinds of water vapo(u)r transmission evaluation units by the above method, carry out Pre-treatment needed for the evaluation of each condition.
" condition 1: standard "
Directly using water vapo(u)r transmission evaluation unit, pre-treatment was not carried out.
" condition 2: bending process 1 "
Bending process is carried out with unit to water vapo(u)r transmission evaluation.Firstly, preparing the gold of diameter 10mm, length 100mm The pipe of category.Next, being fitted with potting resin layer with cylinder part and water vapo(u)r transmission evaluation unit Water vapo(u)r transmission evaluation unit central portion is wound in circle with 180 ° by the mode of the membrane material face contact of barrier properties for gases membrane material Cartridge unit.Then, the gas for being vapor-deposited with Ca in the face as opposite side of unit is used using cylinder part and water vapo(u)r transmission evaluation Water vapo(u)r transmission evaluation unit central portion is wound in cylinder with 180 ° by the mode of the membrane material face contact of body barrier property membrane material Component.1 bending will be set as with operating winding of the 2 membrane material faces of water vapo(u)r transmission evaluation unit on the cylinder part Processing repeats bending process 100 times.
" condition 3: bending process 2 "
On the surface of the barrier properties for gases membrane material for being fitted with potting resin layer of water vapo(u)r transmission evaluation unit, use Commercially available transparent sheet adhesive (20 μm of thickness), after being bonded 125 μm of thickness of PET film material of the size for being punched into 50mm × 50mm, Carry out bending process same as bending process 1.Bending process 2 is carrying out bending process by being bonded PET film material in side When, each gas barrier film of 2 barrier properties for gases membrane materials there are positions substantially to deviate from flexural center.Therefore, knee Reason 2 is the bigger processing of the damage to gas barrier film compared with bending process 1.
(being handled under hot and humid environment)
After the preceding processing needed for the evaluation for carrying out each condition, high temperature height is carried out with unit to water vapo(u)r transmission evaluation Under wet environment through when handle, evaluate the water vapo(u)r transmission of gas barrier film possessed by each barrier properties for gases membrane material.Herein, The water vapo(u)r transmission evaluation unit of bending process 2 by above-mentioned condition 3 is after having removed transparent sheet adhesive and PET film material Carry out hot and humid environment under through when handle.Specifically, water vapo(u)r transmission is evaluated as follows: being commented according to by water vapo(u)r transmission It is when valence is maintained under 85 DEG C of 85%RH environment with unit, relative to for the holding time compared with the penetrating concentration at initial stage penetrate The degree of concentration decline carries out grade evaluation based on following indexs.Penetrating concentration measurement uses Konica Minolta Opto Inc. The black and white penetrating concentration meter TM-5 of system calculates its average value in any 4 points of measurements of unit.Herein, concentration declines 100% table Show the penetrating concentration in the case where not carrying out Ca vapor deposition and making Ca evaluation unit.It should be noted that the pole indicated above of grade 8 Its excellent characteristic,
10: it is dropped by less than 2% by 200 hour concentrations,
9: 2% is fallen to more than and less than 5% by 200 hour concentrations,
8: 5% is fallen to more than and less than 10% by 200 hour concentrations,
7: 10% is fallen to more than and less than 20% by 200 hour concentrations,
6: 20% is fallen to more than and less than 50% by 200 hour concentrations,
5: 50% is fallen to more than and less than 80% by 200 hour concentrations,
4: it is dropped by less than 80% by 100 hour concentrations, falls to 80% or more by 200 hour concentrations,
3: it is dropped by less than 80% by 50 hour concentrations, falls to 80% or more by 100 hour concentrations,
2: it is dropped by less than 80% by 20 hour concentrations, falls to 80% or more by 50 hour concentrations,
1: 80% or more is fallen to by 20 hour concentrations,
The result that water vapo(u)r transmission is evaluated is shown in following Table 3.
[table 1]
[table 2]
[table 3]
(evaluation of 3 water vapor barrier property of table)
According to the above results, it is thus identified that the barrier properties for gases of the embodiment with gas barrier film of the present invention Membrane material gets both compared with the barrier properties for gases membrane material of the comparative example of the gas barrier film with the composition outside the scope of the invention Significantly high water vapor barrier property under extremely excellent bendability and hot and humid environment.
In the manufacturing method of the barrier properties for gases membrane material of above-mentioned production, by the layer containing nontransition metal M1 and containing non- The manufacturer for the barrier properties for gases membrane material 12~17 (Examples 1 to 6) that the layer of transition metal M 2 continuously uses gas phase membrane formation process to form a film The productivity of method is excellent.In addition, layer containing nontransition metal M1 and the layer containing nontransition metal M2 are continuously used in these The barrier properties for gases membrane material 15 (embodiment 4) of sputtering film-forming, which does not need change film formation device, continuously to form a film, therefore raw Yield is especially excellent.
<durability evaluation of organic EL illuminating element>
Using the organic EL illuminating element made as follows, under hot and humid environment through when after carry out blackening evaluation.
(manufacture for comparing package parts barrier properties for gases membrane material)
(manufacture for comparing package parts barrier properties for gases membrane material 21)
In the manufacture of barrier properties for gases membrane material 3, will mixing following substances obtained from organic film formation coating fluid with Thickness after drying is coated on as the mode of 1000nm to be obtained using the forming method A3 of the above-mentioned layer containing nontransition metal M1 The surface of the silicon nitride film of the thickness 50nm arrived is dried at 80 DEG C and obtains coating film.Next, using high pressure under atmosphere Mercury lamp is with irradiation energy 0.5J/cm2Irradiation ultraviolet light solidifies coating film, forms organic film.Then, according to above-mentioned containing non- The same condition of forming method A3 of the layer of transition metal M 1 forms the silicon nitride film of thickness 50nm.So obtaining has successively Form the barrier properties for gases membrane material 21 of gas barrier film obtained from silicon nitride film/organic film/silicon nitride film.Then, with its Its barrier properties for gases membrane material similarly carries out the group ingredient of the thickness direction of gas barrier film to barrier properties for gases membrane material 21 The measurement of cloth.
" organic film, which is formed, uses coating fluid "
In the manufacture of barrier properties for gases membrane material 21, pass through the forming method of forming method and silicon nitride film with organic film The organic film of thickness 1000nm and the silicon nitride film of thickness 50nm is further laminated in same method.So obtaining has successively Form the barrier properties for gases of gas barrier film obtained from silicon nitride film/organic film/silicon nitride film/organic film/silicon nitride film Membrane material 22.Then, gas barrier film is carried out to barrier properties for gases membrane material 22 in the same manner as other barrier properties for gases membrane materials The measurement of the composition distribution of thickness direction.
(production of organic EL illuminating element)
Use alkali-free glass plate (thickness 0.7mm) as substrate, using the barrier properties for gases membrane material 3 of above-mentioned production, 13, 14,18,21 and 22 package parts are used as, with method as follows, in such a way that the area of light emitting region becomes 5cm × 5cm, Make the organic EL illuminating element 101~106 of bottom emitting type.
(formation of substrate layer, the 1st electrode)
The alkali-free glass plate sufficiently cleaned is fixed on to the substrate holder of commercially available vacuum deposition apparatus, by following chemical combination Object 118 is put into the resistance-heated boat of tungsten, these substrate holders and resistance-heated boat are installed to vacuum deposition apparatus In 1st vacuum tank.In addition, silver-colored (Ag) is put into the resistance-heated boat of tungsten, and it is installed on the 2nd vacuum of vacuum deposition apparatus In slot.
Next, the 1st vacuum tank of vacuum deposition apparatus is decompressed to 4 × 10-4After Pa, add to equipped with compound 118 Hot boat energization is heated, with the substrate layer of the 1st electrode of evaporation rate 0.1nm/ seconds~0.2nm/ seconds setting thickness 10nm.
Then, it will be formed to the substrate of substrate layer and moved on in the 2nd vacuum tank in the state of vacuum, the 2nd vacuum tank is subtracted It is depressed into 4 × 10-4After Pa, the heated boat energization equipped with silver is heated.As a result, with 0.1nm/ seconds~0.2nm/ of evaporation rate Second forms the 1st electrode of thickness 8nm being made of silver.
(organic function layer~the 2nd electrode)
Next, being decompressed to vacuum degree 1 × 10 using commercially available vacuum deposition apparatus-4After Pa, in moving substrate with 0.1nm/ seconds vapor deposition compound HT-1 of evaporation rate, are arranged the hole transporting layer (HTL) of 20nm.
Next, by following compound A-3 (blue-light-emitting dopant) and following compound H-1 (host compound) Total vapor deposition is carried out in the following manner and forms luminescent layer, and the mode is relative to film thickness with compound A-3 linearly from 35 matter The mode that amount % becomes 5 mass % becomes 95 mass %'s from 65 mass % with compound H-1 according to position change evaporation rate Mode makes the thickness of luminescent layer become 70nm according to position change evaporation rate.
Thereafter, by following compound ET-1 evaporation film-forming thickness 30nm, electron supplying layer is formed, further with thickness 2nm It is formed potassium fluoride (KF).Further AM aluminum metallization 110nm and form the 2nd electrode.
(solid encapsulation)
Next, preparing to be fitted with 20 μm of thickness in the barrier properties for gases film surface of the barrier properties for gases membrane material of above-mentioned production Thermohardening type package parts of the sheet bonding agent (epoxy system resin) as potting resin layer.Use the package parts, weight It is laminated on the sample for being fabricated into the 2nd electrode.At this point, being exposed to external side with the end of the 1st electrode and the extraction electrode of the 2nd electrode Formula is continuously overlapped the bonding agent forming face of package parts and the organic functions level of element.
Next, by sample configuration in decompressor, under 90 DEG C, the reduced pressure of 0.1MPa, to the substrate of overlapping Apply with package parts and squeezes and kept for 5 minutes.Then, so that sample is returned to atmospheric pressure environment, further heat 30 at 120 DEG C Minute solidifies bonding agent.
Above-mentioned packaging process under atmospheric pressure, under moisture content 1ppm nitrogen atmosphere below, be based on JIS B 9920:2002, The cleannes of measurement are grade 100, dew-point temperature is -80 DEG C or less, oxygen concentration is to carry out under 0.8ppm atmospheric pressure below. It should be noted that omitting the record of the formation about the wiring drawn from anode, cathode etc..
The area of so production light emitting region is the organic EL illuminating element of 5cm × 5cm size.
It should be noted that each barrier properties for gases membrane material used in the production of the package parts of each organic EL illuminating element is as follows It states shown in table 4.
(blackening (DS) evaluation)
(evaluation of initial stage blackening)
So that organic EL illuminating element is shone, shoot luminance, 1 pixel of production is equivalent to 10 μm of high-resolution number Image.Non-luminescent points more than 4 pixels is denoted as blackening, position (center) is generated with the position record of pixel.
(deterioration blackening and delay is forced to generate the evaluation of blackening)
In the early stage after the evaluation of blackening, organic EL illuminating element is saved 300 hours in the environment of 85 DEG C of 85%RH.Its Afterwards, so that organic EL illuminating element is shone, find out the number for the blackening that circle conversion diameter is 200 μm or more, it is bad as forcing Change blackening, carries out grade evaluation based on following indexs.In addition, having 200 μm generated in the position of no record initial stage blackening When the above blackening, delay has been evaluated as it and has generated blackening.It should be noted that blackening number is class 5 and does not prolong in blackening evaluation The case where generating blackening late indicates extremely excellent characteristic,
5:0~9,
4:10~19,
3:20~29,
2:30~49,
1:50 or more,
These results are shown in following table 4.
[table 4]
According to the above results, it is thus identified that the barrier properties for gases of the embodiment with gas barrier film of the present invention Membrane material can be realized the high water vapor barrier property of grade required by organic EL element etc., is able to suppress blackening delay and generates.Separately On the one hand, it is thus identified that the barrier properties for gases membrane material of the comparative example of the gas barrier film with the composition outside the scope of the invention is in height Water vapor barrier property under warm high humidity environment is poorer than the barrier properties for gases membrane material of embodiment, or blackening delay can not be inhibited to produce It is raw.
The application is based on Japanese patent application No. Patent 2016-148796 filed on July 28th, 2016, with reference Form is generally introduced the disclosure of which.
Symbol description
1 device chamber,
The Xe Excimer lamp with cannula structure of the vacuum ultraviolet of 2 irradiation 172nm,
3 as external electrode Excimer lamp bracket,
4 sample stages,
5 be formed with polysilazane compounds coating layer sample,
6 barn doors,
The movement speed of V sample stage,
10, the stepped construction of the 10 ' gas barrier films formed on film forming object
11,110 film forming objects,
12 layers containing nontransition metal M1
13 layers containing transition metal M 2,
101 vacuum plasma CVD devices,
102 vacuum tanks,
103 cathode electrodes,
105 pedestals,
106 heat medium circulation systems,
107 vacuum pumping systems,
108 gas delivery systems,
109 high frequency electric sources,
160 heating-cooling devices.

Claims (11)

1. a kind of gas barrier film, in the atom component distribution curve that is obtained when thickness direction carries out XPS composition analysis, by M1M2xNyWhen indicating composition, there is the region a for meeting following formula (1) and following formula (2),
M1M2xNy
0.2≤x≤3.0 (1)
0.6 y≤1.4 < (2)
X: transition metal M 2 and nontransition metal M1 atom there are atomic ratio,
Y: nitrogen-atoms and nontransition metal M1 atom there are atomic ratios.
2. gas barrier film according to claim 1, wherein there is region A and region B, the area in thickness direction Domain A connects with the region B, and the region A contains principal component of the nontransition metal M1 as metallic element, and the region B contains There is principal component of the transition metal M 2 as metallic element.
3. gas barrier film according to claim 1 or 2, wherein the nontransition metal M1 is Si.
4. gas barrier film described in any one of claim 1 to 3, wherein the transition metal M 2 be selected from Nb, At least one kind of metal in Ta and V.
5. gas barrier film according to any one of claims 1 to 4, wherein the region a with a thickness of 5nm with On.
6. a kind of barrier properties for gases membrane material has barrier properties for gases according to any one of claims 1 to 5 on resin base material Film.
7. a kind of electronic equipment, including gas barrier film according to any one of claims 1 to 5 or claim 6 institute The barrier properties for gases membrane material stated.
8. a kind of manufacturing method of gas barrier film, including the layer containing nontransition metal M1 and transition metal M 2 will be contained The step of layer is formed in a manner of connecting, the layer for containing nontransition metal M1 contains nontransition metal M1 as metallic element Principal component, principal component of the layer containing transition metal M 2 containing transition metal M 2 as metallic element,
In the atom component distribution curve obtained when the thickness direction of the gas barrier film carries out XPS composition analysis, by M1M2xNyWhen indicating composition, there is the region a for meeting following formula (1) and following formula (2),
M1M2xNy
0.2≤x≤3.0 (1)
0.6 y≤1.4 < (2)
X: transition metal M 2 and nontransition metal M1 atom there are atomic ratio,
Y: nitrogen-atoms and nontransition metal M1 atom there are atomic ratios.
9. the manufacturing method of gas barrier film according to claim 8, wherein the layer benefit containing transition metal M 2 It is formed with gas phase membrane formation process.
10. the manufacturing method of gas barrier film according to claim 9, wherein the atmosphere of the gas phase membrane formation process is Atmosphere containing nitrogen.
11. the manufacturing method of gas barrier film according to any one of claims 8 to 10, wherein described containing non- The layer of transition metal M 1 is formed using gas phase membrane formation process.
CN201780046487.9A 2016-07-28 2017-07-11 Gas barrier film, using it barrier properties for gases membrane material and using they electronic equipment and gas barrier film manufacturing method Pending CN109477202A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2016148796 2016-07-28
JP2016-148796 2016-07-28
PCT/JP2017/025316 WO2018021021A1 (en) 2016-07-28 2017-07-11 Gas barrier membrane, gas barrier film using same, electronic device using said gas barrier membrane or said gas barrier film, and production method for gas barrier membrane

Publications (1)

Publication Number Publication Date
CN109477202A true CN109477202A (en) 2019-03-15

Family

ID=61015890

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780046487.9A Pending CN109477202A (en) 2016-07-28 2017-07-11 Gas barrier film, using it barrier properties for gases membrane material and using they electronic equipment and gas barrier film manufacturing method

Country Status (3)

Country Link
JP (1) JPWO2018021021A1 (en)
CN (1) CN109477202A (en)
WO (1) WO2018021021A1 (en)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005035128A (en) * 2003-07-18 2005-02-10 Sumitomo Bakelite Co Ltd Transparent gas barrier film and display device using it
CN102387920A (en) * 2009-04-09 2012-03-21 住友化学株式会社 Gas-barrier multilayer film
JP2012509203A (en) * 2008-11-17 2012-04-19 スリーエム イノベイティブ プロパティズ カンパニー Gradient composition barrier
CN103154052A (en) * 2010-10-06 2013-06-12 株式会社日本触媒 Diene-based carboxylate anion and salt thereof, and polymerizable or curable composition thereof
CN103796827A (en) * 2011-06-27 2014-05-14 柯尼卡美能达株式会社 Gas barrier film, manufacturing process for gas barrier film, and electronic device
CN104553115A (en) * 2014-12-26 2015-04-29 常州二维碳素科技有限公司 Composite gas barrier film and preparation method thereof
US20150158981A1 (en) * 2013-12-06 2015-06-11 Shin-Etsu Chemical Co., Ltd. Curable composition and an optical semiconductor device
CN105026141A (en) * 2013-03-11 2015-11-04 柯尼卡美能达株式会社 Gas barrier film, method for producing gas barrier film, and organic electroluminescent element
WO2015178069A1 (en) * 2014-05-20 2015-11-26 コニカミノルタ株式会社 Gas barrier film
WO2016039060A1 (en) * 2014-09-10 2016-03-17 コニカミノルタ株式会社 Gas barrier film and organic electroluminescent element
CN105593013A (en) * 2013-10-10 2016-05-18 柯尼卡美能达株式会社 Method for manufacturing gas barrier film
JP2016095893A (en) * 2014-11-11 2016-05-26 シーゲイト テクノロジー エルエルシーＳｅａｇａｔｅ Ｔｅｃｈｎｏｌｏｇｙ ＬＬＣ Devices including amorphous gas barrier layer, and method of forming the same
CN105658424A (en) * 2013-10-24 2016-06-08 柯尼卡美能达株式会社 Gas barrier film

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2016136842A1 (en) * 2015-02-25 2017-12-14 コニカミノルタ株式会社 Gas barrier film
JP6720964B2 (en) * 2015-03-18 2020-07-08 コニカミノルタ株式会社 Gas barrier film

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005035128A (en) * 2003-07-18 2005-02-10 Sumitomo Bakelite Co Ltd Transparent gas barrier film and display device using it
JP2012509203A (en) * 2008-11-17 2012-04-19 スリーエム イノベイティブ プロパティズ カンパニー Gradient composition barrier
CN102387920A (en) * 2009-04-09 2012-03-21 住友化学株式会社 Gas-barrier multilayer film
CN103154052A (en) * 2010-10-06 2013-06-12 株式会社日本触媒 Diene-based carboxylate anion and salt thereof, and polymerizable or curable composition thereof
CN103796827A (en) * 2011-06-27 2014-05-14 柯尼卡美能达株式会社 Gas barrier film, manufacturing process for gas barrier film, and electronic device
CN105026141A (en) * 2013-03-11 2015-11-04 柯尼卡美能达株式会社 Gas barrier film, method for producing gas barrier film, and organic electroluminescent element
CN105593013A (en) * 2013-10-10 2016-05-18 柯尼卡美能达株式会社 Method for manufacturing gas barrier film
CN105658424A (en) * 2013-10-24 2016-06-08 柯尼卡美能达株式会社 Gas barrier film
US20150158981A1 (en) * 2013-12-06 2015-06-11 Shin-Etsu Chemical Co., Ltd. Curable composition and an optical semiconductor device
WO2015178069A1 (en) * 2014-05-20 2015-11-26 コニカミノルタ株式会社 Gas barrier film
WO2016039060A1 (en) * 2014-09-10 2016-03-17 コニカミノルタ株式会社 Gas barrier film and organic electroluminescent element
JP2016095893A (en) * 2014-11-11 2016-05-26 シーゲイト テクノロジー エルエルシーＳｅａｇａｔｅ Ｔｅｃｈｎｏｌｏｇｙ ＬＬＣ Devices including amorphous gas barrier layer, and method of forming the same
CN104553115A (en) * 2014-12-26 2015-04-29 常州二维碳素科技有限公司 Composite gas barrier film and preparation method thereof

Also Published As

Publication number Publication date
JPWO2018021021A1 (en) 2019-05-09
WO2018021021A1 (en) 2018-02-01

Similar Documents

Publication Publication Date Title
JP5929775B2 (en) Gas barrier film, method for producing the same, and electronic device including the gas barrier film
JP6504284B2 (en) Gas barrier film, method for producing the same, and electronic device using the same
CN104736335B (en) Gas barrier film and the manufacture method of gas barrier film
JP5803937B2 (en) GAS BARRIER FILM, METHOD FOR PRODUCING GAS BARRIER FILM, AND ELECTRONIC DEVICE
CN100594259C (en) Interface engineering to improve adhesion between low k stacks
WO2013172359A1 (en) Gas barrier film, manufacturing method for gas barrier film, and electronic device
JP2019050196A (en) Electronic device and manufacturing method thereof
JP2015003464A (en) Gas barrier film, method for producing the same, and electronic device using the same
WO2014073438A1 (en) Electronic device and gas barrier film fabrication method
WO2015053405A1 (en) Method for manufacturing gas barrier film
JPWO2016136842A1 (en) Gas barrier film
JP5884531B2 (en) Water vapor barrier film manufacturing method, water vapor barrier film and electronic device
JPWO2016136842A6 (en) Gas barrier film
CN106414063B (en) Gas barrier film and use its electronic device
JP2014201032A (en) Gas barrier film and method for producing the same
JP2014240051A (en) Gas barrier film, manufacturing method of gas barrier film, and manufacturing apparatus of gas barrier film
WO2016194559A1 (en) Gas barrier film
JP2017095758A (en) Method for producing gas barrier film
CN109477202A (en) Gas barrier film, using it barrier properties for gases membrane material and using they electronic equipment and gas barrier film manufacturing method
JP2013226732A (en) Method for manufacturing gas barrier film
JPWO2016163215A1 (en) Organic electroluminescence device
JPWO2015029795A1 (en) Method for producing gas barrier film
JP2018012234A (en) Gas barrier film and electronic device
TWI627063B (en) Gas barrier film and method of manufacturing same
JP2016089083A (en) Method for producing gas barrier film, gas barrier film and electronic device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20190315