WO2017090602A1 - Film doté de propriétés de barrière contre les gaz et dispositif électronique mettant en oeuvre ce film - Google Patents

Film doté de propriétés de barrière contre les gaz et dispositif électronique mettant en oeuvre ce film Download PDF

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WO2017090602A1
WO2017090602A1 PCT/JP2016/084587 JP2016084587W WO2017090602A1 WO 2017090602 A1 WO2017090602 A1 WO 2017090602A1 JP 2016084587 W JP2016084587 W JP 2016084587W WO 2017090602 A1 WO2017090602 A1 WO 2017090602A1
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gas barrier
transition metal
region
film
layer
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PCT/JP2016/084587
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Japanese (ja)
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西尾　昌二
森　孝博
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コニカミノルタ株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots

Definitions

  • the present invention relates to a gas barrier film and an electronic device including the same, and more particularly to a gas barrier film having high gas barrier properties and excellent productivity, and an electronic device including the same.
  • organic electroluminescence (organic EL) elements such as organic electroluminescence (organic EL) elements, solar cells, touch panels, electronic papers, etc.
  • High moisture barrier properties are required for plastic substrates such as plastic substrates or films for sealing circuit boards.
  • the inorganic gas barrier layer has a higher gas barrier property than an organic film formed of a so-called gas barrier resin or the like, but due to the nature of the film, structural defects such as pinholes and cracks, There is a bond defect (M-OH bond) that becomes a gas passage in the MOM network (M is a metal element), and as a result, this alone is required in the field of organic EL devices. Therefore, the high gas barrier property that has been achieved cannot be satisfied, and further improvement of the gas barrier property is demanded.
  • M-OH bond bond defect
  • a gas barrier layer having low flexibility i.e., low flexibility
  • the product life was shortened.
  • flexibility is improved by thinning the gas barrier film, there is a problem that flatness deteriorates.
  • the present invention has been made in view of the above problems and situations, and a solution to the problem is to provide a gas barrier film having high gas barrier properties and excellent productivity, and an electronic device including the same. It is to be.
  • the gas barrier layer has a mixed region containing a specific material at least in the thickness direction, It has been found that the provision of the curl balance adjusting layer on the opposite side of the gas barrier layer can provide a gas barrier film and an electronic device having high gas barrier properties and excellent productivity. Invented.
  • a gas barrier film having a gas barrier layer on a substrate has a mixed region containing at least a group 5 transition metal (M2) and a group 12-14 non-transition metal (M1) in the thickness direction;
  • the gas barrier layer includes a region containing the transition metal (M2) or a compound thereof as a main component a (hereinafter referred to as “A region”) and the non-transition metal (M1) or a compound thereof as a main component b. And a region (hereinafter referred to as “B region”) contained as The mixed region is interposed between the A region and the B region, and the mixed region contains a compound derived from the main component a and the main component b.
  • the gas barrier film according to 1.
  • An electronic device comprising the gas barrier film according to item 1 or 2.
  • the gas barrier film of the present invention is not only remarkably improved in gas barrier properties such as moisture barrier properties, but also excellent in productivity, and thus is useful as a substrate and a sealing layer for various electronic devices. Practical application to organic EL elements can be expected.
  • a gas barrier layer is formed by using an oxygen-deficient composition film containing a compound (for example, an oxide) of a non-transition metal (M1) alone, or a transition metal (M2)
  • a gas barrier layer is formed by using an oxygen-deficient composition film of a compound (for example, an oxide) alone, a tendency to improve the gas barrier property as the degree of oxygen deficiency increases is observed, but a remarkable gas barrier is observed. It did not lead to improvement of sex.
  • a mixed region containing the non-transition metal (M1) and the transition metal (M2) is interposed between the A region and the B region, and the mixed region has an oxygen deficient composition. It has been found that the gas barrier property is remarkably improved as the degree of oxygen deficiency increases.
  • Sectional drawing which shows schematic structure as an example of the gas barrier film of this invention Graph showing the ratio of the number of atoms to the depth in the thickness direction of the gas barrier layer
  • Sectional drawing which shows schematic structure as an example of the organic EL element which comprised the gas barrier film of this invention
  • the gas barrier layer has a mixed region containing at least the group 5 transition metal (M2) and the group 12-14 non-transition metal (M1) in the thickness direction.
  • a curl balance adjusting layer is provided on the side of the substrate opposite to the gas barrier layer.
  • the gas barrier layer comprises a region A containing a transition metal (M2) or a compound thereof as a main component a and a non-transition metal (M1) or a compound thereof.
  • B region contained as the main component b the mixed region is interposed between the A region and the B region, and the compound derived from the main component a and the main component b is contained in the mixed region
  • the gas barrier film of the present invention can be suitably provided for an electronic device. Moreover, it is preferable that the said electronic device has a quantum dot containing resin layer.
  • the electronic device preferably includes an organic electroluminescence element.
  • ⁇ representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
  • FIG. 1 the schematic sectional drawing of the gas barrier film 1 of this invention is shown as an example.
  • the gas barrier film 1 has a gas barrier layer 3 on a substrate 2, and a curl balance adjusting layer 4 is disposed so as to face the gas barrier layer 3 with the substrate 2 interposed therebetween.
  • the gas barrier layer 3 has a mixed region containing at least a group 5 transition metal (M2) and a group 12-14 non-transition metal (M1) in at least the thickness direction.
  • the “region” is an opposing surface formed when the gas barrier layer is divided at a constant or arbitrary thickness on a plane perpendicular to the thickness direction (stacking direction) of the gas barrier layer.
  • the three-dimensional space (region) between the two surfaces is defined, and the composition of the components in the region may be constant in the thickness direction or may gradually change.
  • the gas barrier layer 3 is provided on only one surface of the base material 2 is shown.
  • the gas barrier layer 3 may be provided on both surfaces of the base material 2, or one of the base materials 2 may be provided.
  • a gas barrier layer 3 composed of a plurality of layers may be provided on the surface.
  • the gas barrier layer 3 includes a region containing the transition metal (M2) or a compound thereof as the main component a (hereinafter referred to as “A region”), a non-transition metal (M1) of group 12 to 14 or a compound thereof. Is contained as a main component b (hereinafter referred to as “B region”), and a mixed region is preferably interposed between the A region and the B region. At this time, the compound derived from the main component a and the main component b is contained in the mixed region.
  • the gas barrier layer 3 may be composed only of the mixed region without having the A region and the B region.
  • the “compound derived from the main component a and the main component b” refers to the composite compound formed by the reaction between the main component a and the main component b themselves and the main component a and the main component b.
  • a “composite oxide” will be described as a specific example of the composite compound.
  • the “composite oxide” is a compound (oxide) formed by chemically bonding the constituent components of the A region and the B region to each other. Say. For example, a compound having a chemical structure in which a niobium atom and a silicon atom form a chemical bond directly or through an oxygen atom.
  • composite compound includes a complex formed by the structural components of the A region and the B region being physically bonded to each other by an intermolecular interaction or the like.
  • main component refers to a component having the maximum content as an atomic composition ratio.
  • metal main component refers to a metal component having the maximum content as an atomic ratio among the metal components in the constituent components.
  • consistuent component refers to a compound constituting a specific region of the gas barrier layer or a simple substance of metal or nonmetal.
  • a resin base material is preferable because flexibility and light transmittance can be obtained, and a resin film is more preferable.
  • the resin film applicable to the present invention is not particularly limited in material, thickness and the like as long as it can hold a gas barrier layer, a curl balance adjusting layer, and the like, and can be appropriately selected according to the purpose of use.
  • Specific examples of the resin film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide resin.
  • Cellulose acylate resin Polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic modification
  • the film include thermoplastic resins such as polycarbonate resin, fluorene ring-modified polyester resin, and acryloyl compound.
  • the thickness of the substrate is preferably in the range of 5 to 500 ⁇ m, more preferably in the range of 15 to 250 ⁇ m.
  • base material manufacturing methods for example, techniques disclosed in paragraphs 0125 to 0136 of JP2013-226758A can be appropriately employed.
  • the gas barrier layer according to the present invention has a mixed region containing a group 5 transition metal (M2) and a group 12-14 non-transition metal (M1) at least in the thickness direction. ing.
  • the mixed region is between the A region containing the transition metal (M2) or a compound thereof as the main component a and the B region containing the non-transition metal (M1) or a compound thereof as the main component b. It may be interposed.
  • the gas barrier layer has a ratio of the ratio of the number of atoms of the transition metal (M2) to the non-transition metal (M1) (number of atoms of the transition metal (M2) / number of atoms of the non-transition metal (M1). Is preferably 5 nm or more continuously in the thickness direction in the range of 0.02 to 49.
  • thickness or “layer thickness” means a depth in the thickness direction of the gas barrier layer as described later, and XPS analysis is performed. The sputter depth is expressed in terms of SiO 2 .
  • the “layer thickness” of the gas barrier layer is from the outermost surface side of the gas barrier layer to the interface with the substrate, and the “interface with the substrate” is the gas barrier layer (in the present invention, in the composition analysis by XPS).
  • B region is the position that is the intersection of the main component distribution curve and the main component distribution curve of the substrate.
  • oxygen is preferably contained in addition to the transition metal (M2) and the non-transition metal (M1).
  • the mixed region includes at least a mixture of an oxide of a transition metal (M2) and an oxide of a non-transition metal (M1) or a composite oxide of a transition metal (M2) and a non-transition metal (M1). It is a preferable form that one of them is contained, and a more preferred form is that a composite oxide of a transition metal (M2) and a non-transition metal (M1) is contained.
  • the “mixture” refers to a product in a state where the constituent components of the A region and the B region are mixed without chemically bonding to each other. For example, a state in which niobium oxide and silicon oxide are mixed without being chemically bonded to each other.
  • the oxygen permeability measured by a method according to JIS K 7126-1987 when the gas barrier layer was formed on the substrate and calculated as a laminate was 1 ⁇ 10 ⁇ 3.
  • measured water vapor permeability by the method based on JIS K 7129-1992 (25 ⁇ 0.5 °C , 90 ⁇ 2% RH) is 1 ⁇ 10 -3 g
  • the gas barrier property is not more than / (m 2 ⁇ 24 h).
  • the A region according to the present invention is a region containing the transition metal (M2) of the Group 5 element of the long-period periodic table or a compound thereof as the main component a.
  • the compound that is, “a compound of transition metal (M2)” refers to a compound containing a transition metal (M2), and examples thereof include transition metal oxides.
  • transition metal (M2) of the Group 5 element in the long-period periodic table examples include Nb, Ta, and V.
  • the transition metal (M2) is a Group 5 element (especially Nb)
  • the non-transition metal (M1) described later is Si
  • a significant gas barrier property improvement effect can be obtained. This is presumably because the bond between Si and the Group 5 element (particularly Nb) is particularly likely to occur.
  • the transition metal (M2) is particularly preferably Nb or Ta from which a compound with good transparency can be obtained.
  • the thickness of the A region is preferably in the range of 2 to 50 nm, more preferably in the range of 4 to 25 nm, more preferably in the range of 5 to 15 nm from the viewpoint of achieving both gas barrier properties and optical characteristics. More preferably within the range.
  • the region B according to the present invention is a region containing the non-transition metal (M1) of the group 12-14 element of the long-period periodic table or a compound thereof as the main component b.
  • the compound that is, “a compound of a non-transition metal (M1)” refers to a compound containing a non-transition metal (M1), for example, a non-transition metal (M1) oxide.
  • the non-transition metal (M1) is not particularly limited, and any metal of Group 12 to 14 can be used alone or in combination. Examples thereof include Si, Al, Zn, In, and Sn. . Among these, as the non-transition metal (M1), Si, Sn or Zn is preferably contained, Si is more preferably contained, and Si alone is particularly preferred.
  • the thickness of the region B is preferably in the range of 10 to 1000 nm, more preferably in the range of 20 to 500 nm, and more preferably in the range of 50 to 300 nm from the viewpoint of achieving both gas barrier properties and productivity. More preferably within the range.
  • the mixed region according to the present invention is (1)
  • the gas barrier layer is composed of a plurality of regions having chemical compositions different from each other at least in the thickness direction, and one region (A region) includes transition metal (M2) or a compound thereof (for example, Transition metal oxides (niobium oxide, etc.) are contained, and non-transition metal (M1) or a compound thereof is contained in the other region (B region) directly or indirectly facing the one region.
  • transition metal (M2) or a compound thereof for example, Transition metal oxides (niobium oxide, etc.
  • the mixed region is continuously present in a thickness of a predetermined value or more (specifically, 5 nm or more) in the thickness direction of the gas barrier layer. If the mixed region has a thickness of at least about 5 nm, high gas barrier performance can be exhibited. Therefore, even when a very thin gas barrier film is used, high gas barrier performance can be obtained. That is, the gas barrier film of the present invention can be made to be a gas barrier film having excellent bending resistance because the gas barrier layer can be made very thin while gas barrier performance is high.
  • the region other than the mixed region of the gas barrier layer may be a region such as a non-transition metal (M1) oxide, nitride, oxynitride, or oxycarbide, or a transition metal (M2) oxide or nitridation. It may be a region such as a product, an oxynitride, an oxycarbide.
  • M1 non-transition metal
  • M2 transition metal
  • the oxygen deficient composition is a condition that when the composition of the mixed region is represented by the following chemical composition formula (1), at least a part of the composition of the mixed region is defined by the following relational expression (2). It is defined as satisfying.
  • the oxygen deficiency index indicating the degree of oxygen deficiency in the mixed region, the minimum value obtained by calculating (2y + 3z) / (a + bx) in the mixed region described later is used.
  • composition represented by the chemical composition formula (1) is simply referred to as the composition of the composite region.
  • the composition of the composite region of the transition metal (M2) and the non-transition metal (M1) according to the present invention is represented by the chemical composition formula (1).
  • the composition of the composite region may partially include a nitride structure, and is preferably a composition including a nitride structure from the viewpoint of gas barrier properties.
  • the maximum valence of the non-transition metal (M1) is a
  • the maximum valence of the transition metal (M2) is b
  • the valence of O is 2
  • the valence of N is 3.
  • composition of the composite region (including a part of the nitride) is a stoichiometric composition
  • (2y + 3z) / (a + bx) 1.0.
  • This formula means that the total number of bonds of non-transition metal (M1) and transition metal (M2) is equal to the total number of bonds of O and N.
  • non-transition metal (M1) And the transition metal (M2) are bonded to either O or N.
  • the maximum valence of each element is set to The composite valence calculated by performing the weighted average according to the existence ratio is adopted as the values of a and b of each “maximum valence”.
  • the remaining bonds of the non-transition metal (M1) and the transition metal (M2) have the possibility of bonding to each other, and the metals of the non-transition metal (M1) and the transition metal (M2) When they are directly bonded, it is considered that a denser and higher-density structure is formed than when bonded between metals via O or N, and as a result, gas barrier properties are improved.
  • the mixed region is a region where the value of x satisfies 0.02 ⁇ x ⁇ 49 (0 ⁇ y, 0 ⁇ z). This is because the value of the ratio of the number ratio of the transition metal (M2) to the non-transition metal (M1) (number of transition metal (M2) atoms / number of non-transition metal (M1) atoms) is 0. This is the same definition as defined as a region having a thickness in the range of .02 to 49 and a thickness of 5 nm or more.
  • the mixed region is a region satisfying 0.1 ⁇ x ⁇ 10.
  • a thickness of 5 nm or more more preferably include a region satisfying 0.2 ⁇ x ⁇ 5 at a thickness of 5 nm or more, and a region satisfying 0.3 ⁇ x ⁇ 4 to a thickness of 5 nm or more. It is further preferable to contain.
  • the effect of improving the gas barrier property is exhibited.
  • at least a part of the composition of the mixed region preferably satisfies (2y + 3z) / (a + bx) ⁇ 0.9, and satisfies (2y + 3z) / (a + bx) ⁇ 0.85. More preferably, it is more preferable to satisfy (2y + 3z) / (a + bx) ⁇ 0.8.
  • the thickness of the mixed region where good gas barrier properties can be obtained is 5 nm or more as the sputtering thickness in terms of SiO 2 in the XPS analysis method described later, and this thickness is 8 nm or more. Is preferably 10 nm or more, more preferably 20 nm or more.
  • the thickness of the mixed region is not particularly limited from the viewpoint of gas barrier properties, but is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less from the viewpoint of optical characteristics. preferable.
  • a gas barrier layer having a mixed region having a specific structure as described above exhibits a very high gas barrier property that can be used as a gas barrier layer for an electronic device such as an organic EL element.
  • composition analysis by XPS and measurement of the thickness of the mixed region The composition distribution in the gas barrier layer according to the present invention, the composition distribution in the A region and the B region, the thickness of each region, and the like are measured by X-ray photoelectron spectroscopy (XPS) described in detail below. Can be obtained.
  • XPS X-ray photoelectron spectroscopy
  • the element concentration distribution curve (hereinafter referred to as “depth profile”) in the thickness direction of the gas barrier layer according to the present invention specifically includes the element concentration of the non-transition metal (M1) (for example, silicon), the transition metal. (M2) Element concentration of (for example, niobium), oxygen (O), nitrogen (N), carbon (C) element concentration, etc. are used in combination with X-ray photoelectron spectroscopy measurement and rare gas ion sputtering such as argon. Accordingly, the surface composition analysis can be performed sequentially while exposing the inside from the surface of the gas barrier layer.
  • M1 for example, silicon
  • M2 transition metal
  • Element concentration of (for example, niobium), oxygen (O), nitrogen (N), carbon (C) element concentration, etc. are used in combination with X-ray photoelectron spectroscopy measurement and rare gas ion sputtering such as argon. Accordingly, the surface composition analysis can be performed sequentially while exposing the inside from the surface of
  • a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).
  • the etching time is roughly correlated with the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer in the layer thickness direction.
  • the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time used in the XPS depth profile measurement is adopted. can do.
  • etching rate is 0.05 nm / It is preferable to set to sec (SiO 2 thermal oxide film conversion value).
  • ⁇ Analyzer QUANTERA SXM manufactured by ULVAC-PHI ⁇
  • X-ray source Monochromatic Al-K ⁇ ⁇ Sputtering ion: Ar (2 keV)
  • Depth profile Measurement is repeated at a predetermined thickness interval with a SiO 2 equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).
  • Quantification The background is obtained by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area.
  • Data processing uses MultiPak manufactured by ULVAC-PHI.
  • the analyzed elements are non-transition metal (M1) (for example, silicon (Si)), transition metal (M2) (for example, niobium (Nb)), oxygen (O), nitrogen (N), and carbon (C). It is. From the obtained data, the composition ratio is calculated, the ratio of the atomic ratio of the transition metal (M2) and the non-transition metal (M1), and the non-transition metal (M1) and the transition metal (M2) coexist.
  • the range in which the value of (the atomic ratio of transition metal (M2) / the atomic ratio of non-transition metal (M1)) is 0.02 to 49 is determined, this is defined as a mixed region, and the thickness is determined .
  • the thickness of the mixed region represents the sputter depth in XPS analysis in terms of SiO 2 .
  • FIG. 2 is a graph for explaining an element profile and a mixed region when the composition distribution of the non-transition metal (M1) and the transition metal (M2) in the thickness direction of the gas barrier layer is analyzed by the XPS method.
  • elemental analysis of non-transition metal (M1), transition metal (M2), O, N, and C is performed in the depth direction from the surface of the gas barrier layer (surface opposite to the base material). sputtering the axial depth: the (nm SiO 2 equivalent), the content of the vertical axis with non-transition metals (M1) and transition metal (M2) (at%) is a graph showing a.
  • a B region which is an elemental composition mainly composed of a non-transition metal (M1) (for example, Si) as a metal is shown, and a transition metal (as a metal toward the gas barrier layer surface side in contact with this) M2)
  • a region which is an elemental composition mainly composed of niobium (for example, niobium) is shown.
  • the value of the ratio of the number of atoms of the transition metal (M2) and the non-transition metal (M1) is 0.
  • a method for forming the A region containing the transition metal (M2) is not particularly limited, and for example, a conventionally known vapor deposition method using an existing thin film deposition technique can be used to efficiently form the mixed region. It is preferable from the viewpoint of formation.
  • the vapor deposition method is not particularly limited.
  • a physical vapor deposition (PVD) method such as a sputtering method, a vapor deposition method, an ion plating method, or an ion assisted vapor deposition method, a plasma CVD (Chemical Vapor).
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • ALD Atomic Layer Deposition
  • bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more.
  • the target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used.
  • a reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can be used.
  • a metal oxide film can be formed at a high film formation speed, which is preferable.
  • the inert gas used for the process gas He, Ne, Ar, Kr, Xe or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, thin films of non-transition metal (M1) and transition metal (M2) composite oxides, oxynitrides, oxycarbides, etc. are formed. can do. Examples of film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, and these can be appropriately selected depending on the sputtering apparatus, the material of the film, the thickness, and the like.
  • the sputtering method may be a multi-source simultaneous sputtering method using a plurality of sputtering targets including a transition metal (M2) alone or its oxide.
  • M2 transition metal
  • a method for producing these sputtering targets and a method for producing a thin film made of a composite oxide using these sputtering targets for example, JP 2000-160331 A, JP 2004-068109 A, JP
  • JP The methods and conditions described in JP 2013-047361 A can be referred to as appropriate.
  • the film forming conditions for carrying out the co-evaporation method include the ratio of the transition metal (M2) and oxygen in the film forming raw material, the ratio of the inert gas to the reactive gas during the film forming, and the gas concentration during the film forming. Examples include one or more conditions selected from the group consisting of supply amount, degree of vacuum during film formation, and power during film formation.
  • These film formation conditions preferably oxygen partial pressure
  • a mixed region made of a complex oxide having an oxygen deficient composition can be formed. That is, by forming the gas barrier layer using the co-evaporation method as described above, almost all regions in the thickness direction of the formed gas barrier layer can be mixed regions.
  • a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixed region.
  • what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method, for example, in order to control the thickness of a mixing area
  • a vapor-phase film-forming method can be used by a well-known method.
  • the vapor deposition method is not particularly limited.
  • chemical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assisted vapor deposition, chemistry such as plasma CVD, ALD, and the like.
  • a vapor deposition (CVD) method may be mentioned.
  • PVD physical vapor deposition
  • M1) can be used as a target.
  • a method of forming by a wet coating method using a polysilazane-containing coating solution containing Si as a non-transition metal (M1) is one of the preferable methods.
  • polysilazane applicable to the formation of the B region is a polymer having a silicon-nitrogen bond in the structure, and includes SiO 2 , Si 3 made of Si—N, Si—H, NH, or the like.
  • N is 4 and both of the intermediate solid solution SiO x N preceramic inorganic polymers, such as y.
  • the relatively Polysilazanes that can be modified to silicon oxide, silicon nitride or silicon oxynitride at low temperatures are preferred.
  • Examples of such polysilazane include compounds having a structure represented by the following general formula (1).
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.
  • PHPS perhydropolysilazane
  • organopolysilazanes in which hydrogen atoms bonded to Si are partially substituted with alkyl groups or the like have an alkyl group such as a methyl group, so that the adhesion to an adjacent substrate is improved, and it may be hard.
  • a ceramic film made of polysilazane can be tough, and even when the B region is made thicker, it is preferable in that the generation of cracks is suppressed.
  • perhydropolysilazane and organopolysilazane can be appropriately selected and used, or they can be used in combination.
  • Perhydropolysilazane is presumed to have a structure in which a linear structure and a ring structure centered on a 6- or 8-membered ring coexist.
  • the molecular weight of polysilazane is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn) and varies depending on the molecular weight of a liquid or solid substance.
  • Mn number average molecular weight
  • These polysilazane compounds are commercially available in a solution state dissolved in an organic solvent, and a commercially available product can be used as a polysilazane compound-containing coating solution as it is.
  • polysilazanes that are ceramicized at a low temperature include silicon alkoxide-added polysilazanes obtained by reacting the above polysilazanes with silicon alkoxides (Japanese Patent Laid-Open No. 5-238827), and glycidol-added polysilazanes obtained by reacting glycidol (specially No. 6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (Japanese Patent Laid-Open No. 6-240208), and a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (Japanese Patent Laid-Open No. 6-299118). No.
  • acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (JP-A-7- 1969 6 No.), and the like.
  • polysilazane examples include, for example, paragraphs 0024 to 0040 of JP2013-255910A, paragraphs 0037 to 0043 of JP2013-188942, and paragraphs 0014 to 0021 of JP2013-151123A.
  • paragraphs 0033 to 0045 of JP 2013-052569 A paragraphs 0062 to 0075 of JP 2013-129557 A, paragraphs 0037 to 0064 of JP 2013-226758 A, and the like. Can be applied.
  • organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane.
  • Suitable organic solvents include, for example, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, or ethers such as aliphatic ethers and alicyclic ethers. Can be used.
  • organic solvents such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran.
  • organic solvents may be selected according to the purpose such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of organic solvents may be mixed.
  • the concentration of polysilazane in the coating liquid containing polysilazane varies depending on the thickness of the target gas barrier layer and the pot life of the coating liquid, but is preferably about 0.2 to 35% by mass.
  • an amine or a metal catalyst may be added to the coating liquid containing polysilazane in order to promote modification to silicon oxide, silicon nitride, or silicon oxynitride.
  • a polysilazane solution containing a catalyst such as NAX120-20, NN120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, SP140 manufactured by AZ Electronic Materials Co., Ltd. as a commercial product is used. be able to.
  • these commercial items may be used independently and may be used in mixture of 2 or more types.
  • the addition amount of the catalyst is adjusted to 2% by mass or less with respect to polysilazane in order to avoid excessive silanol formation by the catalyst, decrease in film density, increase in film defects, and the like. It is preferable to do.
  • the coating liquid containing polysilazane can contain an inorganic precursor compound in addition to polysilazane.
  • the inorganic precursor compound other than polysilazane is not particularly limited as long as a coating liquid can be prepared.
  • compounds other than polysilazane described in paragraphs 0110 to 0114 of JP2011-143577A can be appropriately employed.
  • An organometallic compound of a metal element other than Si can be added to the coating liquid containing polysilazane.
  • an organometallic compound of a metal element other than Si By adding an organometallic compound of a metal element other than Si, the replacement of N atom and O atom of polysilazane is promoted in the coating and drying process, and the coating composition can be changed to a stable composition close to SiO 2 after drying. it can.
  • metal elements other than Si include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), chromium (Cr), iron (Fe), Magnesium (Mg), tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), germanium (Ge), copper (Cu), sodium (Na), Examples include potassium (K), calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), and the like.
  • Al, B, Ti and Zr are preferable, and among them, an organometallic compound containing Al is preferable.
  • Examples of the aluminum compound applicable to the present invention include aluminum isopoloxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, aluminum tri-n- Examples include butyrate, aluminum tri-sec-butylate, aluminum ethyl acetoacetate / diisopropylate, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monoaluminum-t-butylate, aluminum trisethylacetoacetate, aluminum oxide isopropoxide trimer, etc. be able to.
  • Specific commercial products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate / diisopropylate), ALCH-TR (aluminum trisethyl acetoate).
  • Acetate aluminum chelate M (aluminum alkyl acetoacetate / diisopropylate), aluminum chelate D (aluminum bisethylacetoacetate / monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) Ken Fine Chemical Co., Ltd.), Preneact (registered trademark) AL-M (acetoalkoxyaluminum diisopropylate, Ajinomoto Fine Chemical Co., Ltd.) It is possible.
  • the temperature is preferably raised to 30 to 100 ° C. and maintained for 1 minute to 24 hours with stirring.
  • the content of the additive metal element in the polysilazane-containing layer constituting the gas barrier layer according to the present invention is preferably in the range of 0.05 to 10 mol% with respect to the silicon (Si) content of 100 mol%, More preferably, it is in the range of 0.5 to 5 mol%.
  • Modification process In the formation of the B region using polysilazane, it is preferable to perform a modification treatment after forming the polysilazane-containing layer.
  • the modification treatment is treatment for imparting energy to polysilazane and converting part or all of it into silicon oxide or silicon oxynitride.
  • a known method based on the conversion reaction of polysilazane can be selected, and examples thereof include known plasma treatment, plasma ion implantation treatment, ultraviolet irradiation treatment, vacuum ultraviolet irradiation treatment and the like.
  • a conversion reaction using plasma, ozone or ultraviolet light that can be converted at a low temperature is preferable.
  • a conventionally known method can be used as the conversion reaction by plasma or ozone.
  • a gas barrier layer is applied by applying a vacuum ultraviolet ray irradiation treatment in which a coating film of a polysilazane-containing coating solution of a coating method is provided on a substrate, and a modification treatment is performed by irradiating a vacuum ultraviolet ray (VUV) having a wavelength of 200 nm or less.
  • VUV vacuum ultraviolet ray
  • a rare gas excimer lamp is preferably used.
  • an excimer lamp (single wavelength of 172 nm, 222 nm, 308 nm, for example, manufactured by USHIO INC., Manufactured by M.D. Can be mentioned.
  • the treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in polysilazane, and the bonding of atoms is an action of only a photon called a photon process.
  • a silicon oxide film is formed at a relatively low temperature (about 200 ° C. or less) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly.
  • Method for forming mixed region there is a method of forming the mixed region between the A region and the B region by appropriately adjusting the respective formation conditions when forming the A region and the B region as described above. preferable.
  • a mixed region is formed by adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation. can do.
  • a film forming raw material type polysilazane type or the like
  • M1 non-transition metal
  • the mixed region can be formed by adjusting one or more conditions selected from the group consisting of time, reforming method and reforming conditions.
  • the ratio of the transition metal (M2) and oxygen in the deposition material for example, the ratio of the transition metal (M2) and oxygen in the deposition material, the ratio of the inert gas and the reactive gas during the deposition, and the deposition
  • the mixed region is formed by adjusting one or more conditions selected from the group consisting of the amount of gas supplied, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation. be able to.
  • the formation conditions of the method of forming the A region and the B region can be adjusted as appropriate.
  • a desired thickness can be obtained by controlling the deposition time.
  • a method of directly forming a mixed region of the non-transition metal (M1) and the transition metal (M2) is also preferable.
  • a co-sputtering method is preferable.
  • the co-sputtering method employed in the present invention is, for example, a composite target made of an alloy containing both a non-transition metal (M1) and a transition metal (M2), or a composite of a non-transition metal (M1) and a transition metal (M2).
  • M1 non-transition metal
  • M2 transition metal
  • M2 non-transition metal
  • M2 a composite of a non-transition metal
  • M2 transition metal
  • M2 a composite of a non-transition metal
  • M2 transition metal
  • the co-sputtering method in the present invention is multi-source simultaneous sputtering using a plurality of sputtering targets including a single non-transition metal (M1) or its oxide and a single transition metal (M2) or its oxide. May be.
  • M1 non-transition metal
  • M2 single transition metal
  • the film forming conditions for performing the co-evaporation method include the ratio of transition metal (M2) and oxygen in the film forming raw material, the ratio of inert gas to reactive gas during film formation, Examples include one or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, and the power during film formation.
  • These film formation conditions preferably oxygen partial pressure
  • what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method, for example, in order to control the thickness of a mixing area
  • the curl balance adjustment layer has a positive gas barrier direction (perpendicular to the gas barrier layer surface) when the rise of the end face is measured after conditioning a sample of 5 mm x 50 mm for 24 hours at 25 ° C and 20% RH. In terms of value, this is a layer for adjusting the amount of warpage of the gas barrier film to be within ⁇ 5 mm.
  • Such a curl balance adjusting layer is formed, for example, by curing a photosensitive resin.
  • the photosensitive resin used for forming the curl balance adjusting layer include a resin composition containing an acrylate compound having a radical reactive unsaturated bond, and a resin composition containing a mercapto compound having an acrylate compound and a thiol group.
  • Resin compositions in which polyfunctional acrylate monomers such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate are dissolved.
  • any mixture of the above resin compositions can be used, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used.
  • a reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.
  • the photosensitive resin composition contains a photopolymerization initiator.
  • limiting in particular as a photoinitiator A well-known photoinitiator can be used by 1 type or in combination of 2 or more types.
  • additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary.
  • an appropriate resin or additive may be used for improving the film forming property on the formed curl balance adjusting layer, preventing the generation of pinholes, or the like.
  • One preferred embodiment as an additive to be added when forming the curl balance adjusting layer is a reactive silica particle in which a photosensitive group having photopolymerization reactivity is introduced into the photosensitive resin (hereinafter simply referred to as “also referred to as “reactive silica particles”).
  • the photosensitive group having photopolymerization reactivity include polymerizable unsaturated groups represented by (meth) acryloyloxy groups.
  • the photosensitive resin also contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be a thing.
  • what adjusted solid content by mixing a general purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.
  • the average particle diameter of the reactive silica particles is preferably in the range of 0.001 to 0.1 ⁇ m.
  • the average particle size is preferably in the range of 0.001 to 0.1 ⁇ m.
  • the curl balance adjusting layer preferably contains a matting agent composed of inorganic particles as described above within a range of 20 to 60% by mass.
  • a matting agent composed of inorganic particles as described above within a range of 20 to 60% by mass.
  • the matting agent is 20% by mass or more, the adhesion to the substrate is improved.
  • the matting agent is 60% by mass or less, the film can be prevented from curving and cracking can be prevented when heat treatment is performed, and optical properties such as transparency and refractive index of the gas barrier film can be prevented. Does not affect physical properties.
  • the polymerizable unsaturated group-modified hydrolyzable silane seems to be chemically bonded to the silica particles by generating a silyloxy group by the hydrolysis reaction of the hydrolyzable silyl group.
  • the hydrolyzable silyl group include a carboxylylated silyl group such as an alkoxysilyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oximesilyl group, and a hydridosilyl group.
  • Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.
  • the method for forming the curl balance adjusting layer on the surface of the substrate is not particularly limited, but examples thereof include a spin coating method, a spray method, a blade coating method, a wet coating method such as a dip method, or a vapor deposition method. It is preferable to apply a dry coating method.
  • Solvents used when forming the curl balance adjusting layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol Terpenes such as ⁇ - or ⁇ -terpineol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, toluene, xylene, tetramethylbenzene, etc.
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol Terpenes such as ⁇ - or ⁇ -terpineol
  • ketones such as acetone, methyl ethyl ketone, cyclo
  • the smoothness of the curl balance adjusting layer is a value expressed by the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably in the range of 10 to 30 nm. If Rt (p) is 10 nm or more, it is stable when the coating means comes into contact with the surface of the curl balance adjustment layer by a coating method such as a wire bar or a wireless bar at the stage of applying the subsequent polysilazane-containing coating solution. Application property is obtained. Moreover, if Rt (p) is 30 nm or less, the unevenness
  • the thickness of the curl balance adjusting layer is preferably in the range of 1 to 10 ⁇ m, more preferably in the range of 2 to 7 ⁇ m.
  • the thickness 1 ⁇ m or more it becomes easy to make the smoothness as a gas barrier film sufficiently, and by making it 10 ⁇ m or less, it becomes easy to adjust the balance of optical properties of the gas barrier film, and gas The amount of warping of the barrier film can be easily suppressed.
  • An anchor coat layer may be disposed on the surface of the base material on the side where the gas barrier layer according to the present invention is formed for the purpose of improving the adhesion between the base material and the gas barrier layer.
  • polyester resin isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicone resin, alkyl titanate, etc. are used alone. Or it can use in combination of 2 or more types.
  • the above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to.
  • the application amount of the anchor coating agent is preferably about 0.1 to 5.0 g / m 2 (dry state).
  • the anchor coat layer can also be formed by a vapor deposition method such as physical vapor deposition or chemical vapor deposition.
  • a vapor deposition method such as physical vapor deposition or chemical vapor deposition.
  • an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.
  • an anchor coat layer as described in Japanese Patent Application Laid-Open No. 2004-314626, when an inorganic thin film is formed thereon by a vapor deposition method, a gas generated from the substrate side is reduced.
  • An anchor coat layer can also be formed for the purpose of blocking to some extent and controlling the composition of the inorganic thin film.
  • the thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10 ⁇ m.
  • a clear hard coat layer may be disposed on the surface (one side or both sides) of the substrate.
  • the material contained in the clear hard coat layer include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because of easy molding.
  • Such curable resins can be used singly or in combination of two or more.
  • the active energy ray-curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams.
  • active energy ray curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam to cure the active energy ray.
  • a layer containing a cured product of the conductive resin, that is, a clear hard coat layer is formed.
  • Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin that is cured by irradiation with ultraviolet rays is preferable.
  • a commercially available base material on which a clear hard coat layer is formed in advance may be used.
  • the thickness of the clear hard coat layer is preferably in the range of 0.1 to 15 ⁇ m and more preferably in the range of 1 to 5 ⁇ m from the viewpoint of smoothness and bending resistance.
  • Examples of the active energy ray-curable resin applicable to the material for forming the clear hard coat layer include, for example, a resin composition containing an acrylate compound having a radical-reactive unsaturated compound, an acrylate compound and a mercapto compound having a thiol group And a resin composition in which a polyfunctional acrylate monomer such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, glycerol methacrylate or the like is dissolved.
  • a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.
  • thermosetting materials include Tutprom Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, and Unidic manufactured by DIC. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistance epoxy resin), various silicone resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG manufactured by Nittobo Co., Ltd.
  • thermosetting urethane resin composed of a coat, an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicone resin.
  • a heat-resistant epoxy resin-based material is particularly preferable.
  • the formation method of the clear hard coat layer is not particularly limited, but it is preferably formed by a spin coating method, a spray method, a blade coating method, a wet coating method such as a dip method, or a dry coating method such as a vapor deposition method.
  • additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above active energy ray-curable resin as necessary.
  • an appropriate resin or additive may be used in any clear hard coat layer in order to improve the film formability and prevent the generation of pinholes in the film.
  • the thickness of the clear hard coat layer is preferably in the range of 1 to 10 ⁇ m, more preferably in the range of 2 to 7 ⁇ m from the viewpoint of improving the heat resistance of the film and facilitating the balance adjustment of the optical properties of the film. It is preferable to be inside.
  • the gas barrier film of the present invention can be preferably applied to an electronic device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air.
  • Examples of the electronic device body used in the electronic device provided with the gas barrier film of the present invention include, for example, a QD film having a quantum dot (QD) -containing resin layer, an organic electroluminescence element (organic EL element), and a liquid crystal display.
  • An element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like can be given.
  • the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.
  • the gas barrier film of the present invention can be applied to a QD film containing quantum dots.
  • QD quantum dots
  • Quantum dot In general, semiconductor nanoparticles exhibiting a quantum confinement effect with a nanometer-sized semiconductor material are also referred to as “quantum dots”. Such a quantum dot is a small lump within about 10 and several nanometers in which several hundred to several thousand semiconductor atoms are gathered, but when absorbing energy from an excitation source and reaching an energy excited state, the energy of the quantum dot Releases energy corresponding to the band gap.
  • quantum dots have unique optical characteristics due to the quantum size effect. Specifically, (1) By controlling the size of the particles, various wavelengths and colors can be emitted. (2) The absorption band is wide and fine particles of various sizes can be obtained with a single wavelength of excitation light. It has the characteristics that it can emit light, (3) it has a symmetrical fluorescence spectrum, and (4) it has excellent durability and fading resistance compared to organic dyes.
  • the quantum dot contained in the QD-containing resin layer may be a known one, and can be generated using any known method.
  • suitable quantum dots and methods for forming them include US Pat. No. 6,225,198, US Patent Application Publication No. 2002/0066401, US Pat. No. 6,207,229, US Pat. No. 6,322,901, And those described in US Pat. No. 6,949,206, US Pat. No. 7,572,393, US Pat. No. 7,267,865, US Pat. No. 7,374,807, US Patent Application No. 11/299299, and US Pat. No. 6,861,155. .
  • Quantum dots are generated from any suitable material, preferably an inorganic material, more preferably an inorganic conductor or semiconductor material.
  • suitable semiconductor materials include any type of semiconductor, including II-VI, III-V, IV-VI and IV semiconductors.
  • Suitable semiconductor materials include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb. , InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe , BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si 3 N 4 , Ge 3 N 4 , Al 2 O 3 , (Al,
  • the following core / shell type quantum dots for example, CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, CdTe / ZnS, and the like can be preferably used.
  • Resin can be used for a QD containing resin layer as a binder holding a quantum dot.
  • a QD containing resin layer for example, polycarbonate, polyarylate, polysulfone (including polyethersulfone), polyester such as polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate Cellulose esters such as pionate and cellulose acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, norbornene, polymethylpentene, polyether ketone, polyether ketone imide And acrylic resins such as polyamide resins, fluororesins, nylon resins, and polymethyl methacrylate.
  • the QD-containing resin layer preferably has a thickness in the range of 50 to 200 ⁇ m.
  • the optimum amount of quantum dots in the QD-containing resin layer varies depending on the compound used, but is generally preferably in the range of 15 to 60% by volume.
  • Organic EL element A typical example of an electronic device to which the gas barrier film of the present invention is applied is an organic EL element as shown in FIG.
  • the organic EL element 10 covers a support 11 with a pair of electrodes 12 and 14, an organic functional layer 13 positioned between the pair of electrodes 12 and 14, and the organic functional layer 13. Sealing material 15 to be provided.
  • the gas barrier film 1 of the present invention can be applied as the support 11.
  • the curl balance adjusting layer 4 is peeled off from the base material 2 from the viewpoint of making the film thinner, and the electrode 12 is formed on the base material 2. It may be formed.
  • the organic functional layer 13 includes at least a light emitting layer, and includes a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and the like as necessary.
  • the light-emitting layer contains a light-emitting organic compound, an organometallic complex, or the like, and is directly injected from one electrode (anode) or from the anode through a hole transport layer, and the other. Electrons directly injected from the electrode (cathode) or electrons injected through the electron transport layer or the like emit light by recombination.
  • the organic functional layer 13 and the electrodes 12 and 14 are liable to deteriorate due to the intrusion of gas such as oxygen and water in the atmosphere.
  • the organic EL element 10 includes the above-described gas barrier film 1 as the support 11 in order to suppress a decrease in light emission performance due to such deterioration of the organic functional layer 13 and the like, but a gas barrier as the sealing material 15.
  • the film 1 can also be provided.
  • a UV curable resin manufactured by Aika Industry Co., Ltd., product number: Z731L
  • Z731L the dry layer thickness
  • the formed coating film is dried at 80 ° C., and then cured in air using a high-pressure mercury lamp under the condition of an irradiation energy amount of 0.5 J / cm 2 to clear the back side.
  • Hard coat layer 1 was formed.
  • UV curable resin “OPSTAR (registered trademark) Z7527” manufactured by JSR Corporation on the surface side of the PET film (surface on which the gas barrier layer is formed), wet coating so that the dry layer thickness is 2 ⁇ m. After coating by the method, it is dried at 80 ° C., and then cured under a condition of irradiation energy of 0.5 J / cm 2 using a high-pressure mercury lamp in the air, and a clear hard coat layer having a thickness of 2 ⁇ m on the surface side. 2 was formed.
  • a film containing a non-transition metal (M1) was formed on the surface of the base material on which the clear hard coat layer 2 was formed by a vapor phase method / sputtering (a magnetron sputtering apparatus manufactured by Canon Anelva, model EB1100).
  • the sputtering apparatus used is capable of two-way simultaneous sputtering.
  • a polycrystalline Si target was used as a target, a mixed gas of Ar and O 2 was used as a process gas, and a film was formed to a thickness of 92 nm by DC sputtering.
  • the sputtering power source power was 5.0 W / cm 2 and the film forming pressure was 0.4 Pa.
  • Film formation was performed by adjusting the oxygen partial pressure so that the composition was SiO 2 .
  • film formation using a glass substrate is performed in advance, and the condition of the composition is determined by adjusting the oxygen partial pressure. The condition where the composition near the depth of 10 nm from the surface layer becomes SiO 2 is found, and the condition is applied. did.
  • the thickness data on the change in thickness with respect to the film formation time is obtained within a range of 100 to 300 nm, the film formation per unit time is calculated, and then the film is formed to have a set thickness. Set the time.
  • the composition is a region that is a non-transition metal oxides SiO 2, was formed in a thickness of 92 nm.
  • a film containing a transition metal (M2) was formed on the formed film containing a non-transition metal (M1) by a vapor phase method / sputtering (a magnetron sputtering apparatus manufactured by Canon Anelva, model EB1100).
  • a commercially available metal Nb target was used, and a mixed gas of Ar and O 2 was used as a process gas, and the film was formed to a thickness of 15 nm by DC sputtering.
  • the sputtering power source power was 5.0 W / cm 2 and the film forming pressure was 0.4 Pa. Further, the oxygen partial pressure was 12% under the film forming conditions. It should be noted that, after film formation using a glass substrate material in advance, the thickness change data with respect to the film formation time is taken under the film formation conditions, the thickness to be formed per unit time is calculated, The film formation time was set so that
  • composition distribution profile in the thickness direction was measured from the surface side of the gas barrier layer by XPS analysis.
  • the XPS analysis conditions are as follows.
  • the sample used for the analysis was a sample stored in an environment of 20 ° C. and 50% RH after sample preparation.
  • XPS analysis conditions ⁇ Device: QUANTERA SXM manufactured by ULVAC-PHI ⁇
  • X-ray source Monochromatic Al-K ⁇ ⁇ Sputtering ion: Ar (2 keV)
  • Depth profile Measurement was repeated at a predetermined thickness interval with a SiO 2 equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).
  • Quantification The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area.
  • MultiPak manufactured by ULVAC-PHI was used.
  • the analyzed elements are non-transition metal (Si), transition metal (Nb), O, N, and C.
  • the gas barrier film 102 was produced in the same manner except that the target for forming the film containing the transition metal was changed to a metal Ta target.
  • a gas barrier film 103 was produced in the same manner except that a curl balance adjusting layer was formed on the clear hard coat layer 1 as follows.
  • Formation of curl balance adjustment layer 30 parts by mass of silica sol (trade name: Glasca HPC7002, manufactured by JSR Corporation) and 10 parts by mass of alkylalkoxysilane (trade name: Glasca HPC402H, manufactured by JSR Corporation) are stirred and mixed for 30 minutes, and the curl balance adjusting layer is mixed.
  • a coating solution was prepared. This coating solution was applied on the clear hard coat layer 1 with a wire bar so that the dry film thickness was 1.1 ⁇ m, and then heated at 80 ° C. for 3 minutes. Next, using a high-pressure mercury lamp, curing was performed at a dose of 0.5 J / cm 2 under air to form a curl balance adjusting layer.
  • gas barrier film 104 In the production of the gas barrier film 103, the target for forming the transition metal-containing film is changed to a metal Ta target, and the film is formed to have a thickness of 16 nm. A gas barrier film 104 was produced in the same manner except that the thickness was changed to 1.3 ⁇ m.
  • the gas barrier film 105 was produced in the same manner except that the gas barrier layer was formed as follows and the thickness of the curl balance adjusting layer was changed to 1.5 ⁇ m. did.
  • a polycrystalline Si target and a metal Nb target are used as targets, Ar and O 2 are used as process gases, and a co-sputtering method is performed by a DC method.
  • a gas barrier layer was formed by performing original co-sputtering.
  • the power supply power in the polycrystalline Si target and the power supply power in the metal Nb target were adjusted so that the oxygen partial pressure was 18% and the atomic ratio of Si and Nb in the film was the same.
  • the film formation time was set so that the layer thickness was 50 nm.
  • the permeated water amount (water vapor permeability) of each produced gas barrier film was measured to evaluate the water vapor barrier property.
  • the gas-barrier film of this invention although the measuring method of water vapor permeability is not specifically limited, In this Example, Ca method was employ
  • Vapor deposition device JEE-400, a vacuum vapor deposition device manufactured by JEOL Ltd.
  • Constant temperature and humidity oven Yamato Humidic Chamber IG47M
  • the obtained evaluation cell was stored under high temperature and high humidity of 60 ° C. and 90% RH, and the amount of corrosion of metallic calcium was determined based on the method described in JP-A-2005-283561. From this, the amount of water permeated into the cell (g / (m 2 ⁇ 24 h)) was calculated.
  • a sample obtained by depositing metallic calcium on a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample In the same manner, the cell was stored under high temperature and high humidity of 60 ° C. and 90% RH, and it was confirmed that corrosion of metallic calcium did not occur even after 1000 hours.
  • thermosetting sheet-like adhesive epoxy resin
  • Bonding was performed at a thickness of 20 ⁇ m. This was punched out to a size of 50 mm ⁇ 50 mm, then placed in a glove box and dried for 24 hours.
  • One side of a 50 mm ⁇ 50 mm non-alkali glass plate was UV cleaned. Then, Ca was vapor-deposited by the size of 20 mm x 20 mm through the mask in the center of the glass plate using the vacuum vapor deposition apparatus made from an EILS technology. The thickness of Ca was 80 nm.
  • a glass plate on which Ca has been deposited is mounted in a glove box, and the sealing resin layer surface of the gas barrier film to which the sealing resin layer is bonded is placed in contact with the Ca deposition surface of the glass plate, and bonded by vacuum lamination. did. At this time, heating at 110 ° C. was performed. Further, the adhered sample was placed on a hot plate set at 110 ° C. with the glass plate facing down, and cured for 30 minutes to produce an evaluation cell.
  • (T2 / T1) is 0.95 or more 4: (T2 / T1) is 0.90 or more and less than 0.95 3: (T2 / T1) is 0.85 or more and less than 0.90 2: ( T2 / T1) is 0.80 or more and less than 0.85 1: (T2 / T1) is 0.75 or more and less than 0.80
  • the gas barrier film of the present invention was superior in the amount of warpage, water vapor permeability, and flex resistance as compared with the gas barrier film of the comparative example.
  • the gas barrier layer has a mixed region containing a transition metal of group 5 and a non-transition metal of group 12 to 14 (M1) at least in the thickness direction. It can be seen that the curl balance adjustment layer provided on the opposite side is useful for providing a gas barrier film having high gas barrier properties and excellent productivity.
  • ⁇ Preparation of gas barrier film 201> (1) Preparation of base material Clear hard coat layer 1 (back side) on both sides of a 100 ⁇ m thick polyethylene terephthalate film (Lumirror (registered trademark) U48, abbreviated as PET film) manufactured by Toray Industries, Inc. ) And clear hard coat layer 2 (gas barrier layer forming surface side) were formed by the following method.
  • a 100 ⁇ m thick polyethylene terephthalate film Limirror (registered trademark) U48, abbreviated as PET film) manufactured by Toray Industries, Inc.
  • clear hard coat layer 2 gas barrier layer forming surface side
  • a UV curable resin manufactured by Aika Industry Co., Ltd., product number: Z731L
  • Z731L the dry layer thickness
  • the formed coating film is dried at 80 ° C., and then cured in air using a high-pressure mercury lamp under the condition of an irradiation energy amount of 0.5 J / cm 2 to clear the back side.
  • Hard coat layer 1 was formed.
  • UV curable resin “OPSTAR (registered trademark) Z7527” manufactured by JSR Corporation on the surface side of the PET film (surface on which the gas barrier layer is formed), wet coating so that the dry layer thickness is 2 ⁇ m. After coating by the method, it is dried at 80 ° C., and then cured under a condition of irradiation energy of 0.5 J / cm 2 using a high-pressure mercury lamp in the air, and a clear hard coat layer having a thickness of 2 ⁇ m on the surface side. 2 was formed.
  • a dibutyl ether solution containing 20% by mass of perhydropolysilazane (PHPS, manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6) -Dihydrohexane (TMDAH))-containing perhydropolysilazane 20% by weight dibutyl ether solution manufactured by AZ Electronic Materials Co., Ltd., NAX120-20
  • PHPS perhydropolysilazane
  • TMDAH amine catalyst
  • the above coating solution was applied by a spin coating method under a nitrogen atmosphere in a glove box so that the dry film thickness was 92 nm, and dried at 80 ° C. for 10 minutes.
  • the sample on which the film containing the non-transition metal (M1) was formed was placed in the vacuum ultraviolet irradiation apparatus shown in FIG. 4 having a Xe excimer lamp with a wavelength of 172 nm, and vacuum was applied under the condition of irradiation energy of 5.0 J / cm 2.
  • An ultraviolet irradiation treatment was performed.
  • nitrogen and oxygen were supplied into the chamber, and the oxygen concentration in the irradiation atmosphere was adjusted to 0.1% by volume.
  • the stage temperature for installing the sample was set to 80 ° C.
  • reference numeral 101 denotes an apparatus chamber, which supplies an appropriate amount of nitrogen and oxygen from a gas supply port (not shown) to the inside and exhausts it from a gas discharge port (not shown). It is possible to substantially remove water vapor from the water and maintain the oxygen concentration at a predetermined concentration.
  • Reference numeral 102 denotes a Xe excimer lamp (excimer lamp light intensity: 130 mW / cm 2 ) having a double tube structure that irradiates vacuum ultraviolet light of 172 nm
  • reference numeral 103 denotes an excimer lamp holder that also serves as an external electrode.
  • Reference numeral 104 denotes a sample stage.
  • the sample stage 104 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 101 by a moving means (not shown).
  • the sample stage 104 can be maintained at a predetermined temperature by a heating means (not shown).
  • Reference numeral 105 denotes a sample on which a polysilazane compound coating layer is formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the surface of the sample coating layer and the excimer lamp tube surface is 3 mm.
  • Reference numeral 106 denotes a light shielding plate, which prevents the application layer of the sample from being irradiated with vacuum ultraviolet rays while the Xe excimer lamp 102 is aged.
  • the energy irradiated on the surface of the sample coating layer in the vacuum ultraviolet light irradiation step was measured using a 172 nm sensor head using a UV integrating photometer: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics.
  • the sensor head is installed in the center of the sample stage 104 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 101 is vacuum ultraviolet light. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as that in the irradiation step, and measurement was performed by moving the sample stage 104 at a speed of 0.5 m / min.
  • an aging time of 10 minutes was provided after the Xe excimer lamp was turned on, and then the sample stage was moved to start the measurement.
  • the moving speed of the sample stage was adjusted to adjust the irradiation energy amount to 5.0 J / cm 2 .
  • the vacuum ultraviolet light irradiation was performed after aging for 10 minutes.
  • a film containing a transition metal was formed on the formed film containing a non-transition metal (M1) by a vapor phase method / sputtering (a magnetron sputtering apparatus manufactured by Canon Anelva, model EB1100).
  • a commercially available metal Nb target was used, and a mixed gas of Ar and O 2 was used as a process gas, and the film was formed to a thickness of 15 nm by DC sputtering.
  • the sputtering power source power was 5.0 W / cm 2 and the film forming pressure was 0.4 Pa. Further, the oxygen partial pressure was 12% under the film forming conditions. It should be noted that, after film formation using a glass substrate material in advance, the thickness change data with respect to the film formation time is taken under the film formation conditions, the thickness to be formed per unit time is calculated, The film formation time was set so that
  • a gas barrier film 202 was produced in the same manner except that the target for forming the film containing the transition metal was changed to a metal Ta target.
  • a gas barrier film 203 was produced in the same manner except that a curl balance adjusting layer was formed on the clear hard coat layer 1 as follows.
  • Formation of curl balance adjustment layer 30 parts by mass of silica sol (trade name: Glasca HPC7002, manufactured by JSR Corp.) and 10 parts by mass of alkylalkoxysilane (trade name: Glasca HPC402H, manufactured by JSR Corp.) are stirred and mixed for 30 minutes, and the curl balance adjusting layer is mixed.
  • a coating solution was prepared. This coating solution was applied on the clear hard coat layer 1 with a wire bar so that the dry film thickness was 1.0 ⁇ m, and then heated at 80 ° C. for 3 minutes. Next, using a high-pressure mercury lamp, curing was performed at a dose of 0.5 J / cm 2 under air to form a curl balance adjusting layer.
  • gas barrier film 204 In the production of the gas barrier film 203, the target for forming the film containing the transition metal is changed to a metal Ta target, and the film is formed so as to have a thickness of 16 nm. A gas barrier film 204 was produced in the same manner except that the thickness was changed to 1.3 ⁇ m.
  • the present invention can be particularly suitably used for providing a gas barrier film having high gas barrier properties and excellent productivity.

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Abstract

L'invention concerne un film doté de propriétés de barrière contre les gaz, lequel, tout en présentant d'excellentes caractéristiques de barrière contre les gaz, est excellent en termes de productivité. Le film (1) doté de propriétés de barrière contre les gaz de l'invention se caractérise en ce qu'il possède une couche (3) barrière contre les gaz située sur un substrat (2). En outre, la couche (3) barrière contre les gaz possède, au moins dans le sens de l'épaisseur, une région mixte contenant un métal de transition (M2) de famille 5 et un métal de non-transition (M1) des famille 12 à 14. 150℃. Sur le côté du substrat (2) opposé à la couche (3) barrière au gaz est située une couche (4) d'ajustement de courbe.
PCT/JP2016/084587 2015-11-24 2016-11-22 Film doté de propriétés de barrière contre les gaz et dispositif électronique mettant en oeuvre ce film WO2017090602A1 (fr)

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JP2015228663A JP2019010737A (ja) 2015-11-24 2015-11-24 ガスバリアー性フィルム及びこれを備えた電子デバイス

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014093328A (ja) * 2012-10-31 2014-05-19 Fujifilm Corp 半導体膜、半導体膜の製造方法、太陽電池、発光ダイオード、薄膜トランジスタおよび電子デバイス
JP2014151571A (ja) * 2013-02-08 2014-08-25 Konica Minolta Inc ガスバリア性フィルムおよびその製造方法、ならびに前記ガスバリア性フィルムを含む電子デバイス
JP2014201033A (ja) * 2013-04-08 2014-10-27 コニカミノルタ株式会社 ガスバリア性フィルムおよびその製造方法
JP2014201032A (ja) * 2013-04-08 2014-10-27 コニカミノルタ株式会社 ガスバリア性フィルムおよびその製造方法
JP2015003464A (ja) * 2013-06-21 2015-01-08 コニカミノルタ株式会社 ガスバリア性フィルム、その製造方法、およびこれを用いた電子デバイス
WO2015141226A1 (fr) * 2014-03-18 2015-09-24 株式会社クラレ Dispositif électronique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014093328A (ja) * 2012-10-31 2014-05-19 Fujifilm Corp 半導体膜、半導体膜の製造方法、太陽電池、発光ダイオード、薄膜トランジスタおよび電子デバイス
JP2014151571A (ja) * 2013-02-08 2014-08-25 Konica Minolta Inc ガスバリア性フィルムおよびその製造方法、ならびに前記ガスバリア性フィルムを含む電子デバイス
JP2014201033A (ja) * 2013-04-08 2014-10-27 コニカミノルタ株式会社 ガスバリア性フィルムおよびその製造方法
JP2014201032A (ja) * 2013-04-08 2014-10-27 コニカミノルタ株式会社 ガスバリア性フィルムおよびその製造方法
JP2015003464A (ja) * 2013-06-21 2015-01-08 コニカミノルタ株式会社 ガスバリア性フィルム、その製造方法、およびこれを用いた電子デバイス
WO2015141226A1 (fr) * 2014-03-18 2015-09-24 株式会社クラレ Dispositif électronique

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