WO2017110463A1 - Film barrière contre des gaz et procédé pour sa fabrication - Google Patents

Film barrière contre des gaz et procédé pour sa fabrication Download PDF

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Publication number
WO2017110463A1
WO2017110463A1 PCT/JP2016/086305 JP2016086305W WO2017110463A1 WO 2017110463 A1 WO2017110463 A1 WO 2017110463A1 JP 2016086305 W JP2016086305 W JP 2016086305W WO 2017110463 A1 WO2017110463 A1 WO 2017110463A1
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Prior art keywords
gas barrier
transition metal
barrier layer
layer
barrier film
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PCT/JP2016/086305
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English (en)
Japanese (ja)
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圭一 須川
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コニカミノルタ株式会社
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Priority to JP2017557853A priority Critical patent/JPWO2017110463A1/ja
Publication of WO2017110463A1 publication Critical patent/WO2017110463A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • 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

Definitions

  • the present invention relates to a gas barrier film and a method for producing the same. More specifically, the present invention relates to a gas barrier film having high durability even in a high temperature and high humidity environment, and having high resistance to damage caused by winding even in roll-to-roll production, and a method for producing the same.
  • gas barrier film having a structure (hereinafter referred to as a gas barrier film in the present application) has been used.
  • a gas barrier layer is formed on a resin base material by a plasma CVD method (also referred to as a chemical vapor deposition method or a chemical vapor deposition method).
  • a plasma CVD method also referred to as a chemical vapor deposition method or a chemical vapor deposition method.
  • a surface treatment modification treatment
  • a coating liquid containing polysilazane as a main component onto a substrate
  • the present invention has been made in view of the above-mentioned problems and situations, and the solution is to have high durability even in a high-temperature and high-humidity environment, and high resistance to damage caused by winding even in roll-to-roll manufacturing. It is to provide a gas barrier film and a manufacturing method thereof.
  • the present inventor has a gas barrier film having at least a first gas barrier layer and a second gas barrier layer in this order on a substrate in the process of examining the cause of the above-mentioned problem.
  • the first gas barrier layer contains a non-transition metal
  • the second gas barrier layer contains a transition metal
  • the arithmetic average roughness of the surface of the second gas barrier layer The gas barrier film in which Ra is within a specific range has a high durability even in a high-temperature and high-humidity environment, and even in roll-to-roll manufacturing, a gas barrier film having high resistance to damage caused by winding can be obtained. I found it.
  • a gas barrier film having at least a first gas barrier layer and a second gas barrier layer in this order on a substrate,
  • the first gas barrier layer contains a non-transition metal;
  • the second gas barrier layer contains a transition metal, and the arithmetic mean roughness Ra of the surface of the second gas barrier layer is in the range of 1.0 to 20.0 nm. Gas barrier film.
  • the mixed region where the value (M2 / M1) of the atomic number ratio of the transition metal (M2) to the transition metal (M1) is in the range of 0.02 to 49 is continuously 5 nm or more in the thickness direction.
  • the mixed region contains at least one of the non-transition metal or a compound derived from the non-transition metal and a mixture of the transition metal or a compound derived from the transition metal or a composite oxide.
  • Item 3. A gas barrier film according to item 2.
  • Item 4 The gas barrier film according to Item 2 or 3, wherein the composition of the mixed region further contains oxygen.
  • the arithmetic mean roughness Ra of the surface of the first gas barrier layer is in the range of 1.0 to 20.0 nm, according to any one of items 1 to 6, Gas barrier film.
  • transition metal according to any one of items 1 to 7, wherein the transition metal is at least one selected from niobium (Nb), tantalum (Ta), and vanadium (V). Gas barrier film.
  • step of forming the first gas barrier layer includes a step of applying a polysilazane-containing coating solution and performing a modification treatment.
  • Item 12 The method for producing a gas barrier film according to Item 10 or 11, wherein the step of etching and the step of forming the second gas barrier layer are performed in a vacuum film forming apparatus.
  • the inventor forms a first gas barrier layer containing a non-transition metal (M1) such as Si, and further stacks a layer containing a transition metal (M2) such as Nb.
  • M1 non-transition metal
  • M2 transition metal
  • a region containing a mixture or composite oxide of transition metal (M1) and transition metal (M2) (hereinafter referred to as “mixed region” in the present application) is formed, and further, the mixed region has an oxygen-deficient composition. It has been found that the gas barrier properties of the entire barrier film are remarkably improved.
  • the present inventor further improved the overall gas barrier property by roughening the surface of the first gas barrier layer so as to have a specific range of roughness.
  • the present inventors have found that the gas barrier property has high durability even under, and that, in roll-to-roll manufacturing, it is possible to impart high resistance to gas barrier property damage due to winding.
  • the layer thickness of the second gas barrier layer within a specific range, the surface of the second gas barrier layer is roughened along the rough surface state of the surface of the first gas barrier layer, It is presumed that the damage resistance (resistance to scratches, cracks, etc.) to the gas barrier property due to conveyance and winding is improved when manufacturing by roll-to-roll.
  • the gas barrier property may be deteriorated due to damage in the course of roughening.
  • the first gas barrier layer is mainly roughened. Since the treatment is performed, it is presumed that the gas barrier property of the entire gas barrier film does not deteriorate.
  • Sectional drawing which shows the structure of the gas barrier film of this invention Graph for explaining element profile and mixed region when composition distribution of silicon and transition metal in thickness direction of gas barrier layer is analyzed by XPS method
  • the gas barrier film of the present invention is a gas barrier film having at least a first gas barrier layer and a second gas barrier layer in this order on a substrate, wherein the first gas barrier layer is a non-transition metal.
  • the second gas barrier layer contains a transition metal, and the arithmetic mean roughness Ra of the surface of the second gas barrier layer is in the range of 1.0 to 20.0 nm.
  • the non-transition metal (M1) is provided at least in the thickness direction between the first gas barrier layer and the second gas barrier layer from the viewpoint of manifesting the effects of the present invention.
  • the transition metal (M2) -containing region the value of the atomic ratio of the transition metal (M2) to the non-transition metal (M1) (M2 / M1) is in the range of 0.02 to 49 It is preferable that the mixed region is continuously 5 nm or more in the thickness direction from the viewpoint of excellent durability and scratch resistance and improving gas barrier properties.
  • the mixed region preferably contains at least one of a mixture derived from the non-transition metal or the compound derived from the non-transition metal and a compound derived from the transition metal or the transition metal or a composite oxide, Furthermore, it is preferable that oxygen is further contained in the composition of the mixed region.
  • composition of the mixed region is expressed by the chemical composition formula (1), it is excellent in durability and scratch resistance, and gas barrier properties that at least a part of the mixed region satisfies the relational expression (2). From the viewpoint of improving the ratio.
  • the layer thickness of the second gas barrier layer is preferably in the range of 1 to 30 nm because the surface roughness of the first gas barrier layer is expressed as it is, and the first gas barrier layer is preferable.
  • the arithmetic average roughness Ra of the surface of the barrier layer is preferably in the range of 1.0 to 20.0 nm, since it is possible to impart an appropriate surface roughness to the gas barrier film surface.
  • the non-transition metal is silicon (Si) derived from polysilazane, and the transition metal is at least one selected from niobium (Nb), tantalum (Ta), and vanadium (V). From the viewpoint of significantly improving the properties.
  • the manufacturing method of the gas barrier film which manufactures the gas barrier film of this invention is the process of forming the said 1st gas barrier layer on a elongate base film,
  • the said elongate base film is roll-shaped.
  • the step of forming the first gas barrier layer includes a step of applying and modifying a polysilazane-containing coating solution, and the step of etching and the step of forming the second gas barrier layer. From the viewpoint of improving productivity, it is a preferable manufacturing method to be performed in a vacuum film forming apparatus.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the gas barrier film of the present invention is a gas barrier film having at least a first gas barrier layer and a second gas barrier layer in this order on a substrate, wherein the first gas barrier layer is a non-transition metal.
  • the second gas barrier layer contains a transition metal, and the arithmetic mean roughness Ra of the surface of the second gas barrier layer is in the range of 1.0 to 20.0 nm. It is characterized by.
  • second gas barrier layer surface means, in addition to the general meaning of “surface”, when the second gas barrier layer is in contact with another layer, the boundary surface with the other layer is defined. Including meaning.
  • the arithmetic average roughness Ra according to the present invention is a surface roughness defined by JIS B0601: 2001, and is a value that can be measured using, for example, a non-contact three-dimensional micro surface shape measurement system (WYKO manufactured by Veeco). is there.
  • the mixed region where the value (M2 / M1) of the atomic ratio of the transition metal (M2) to the non-transition metal (M1) is in the range of 0.02 to 49 is continuously 5 nm or more in the thickness direction. It is preferable from the viewpoint of developing a high gas barrier property.
  • the mixed region is composed of a plurality of regions having different chemical compositions of components in at least the thickness direction of the gas barrier film, and at least one of the plurality of regions contains a non-transition metal.
  • the mixed region includes a state in which the constituent components of the first gas barrier layer and the second gas barrier layer are mixed without being chemically bonded to each other, but the non-transition metal and the transition metal are mutually mixed. It is preferable to form a complex oxide that is chemically bonded to.
  • Composite oxide refers to a compound (oxide) formed by chemically bonding the constituent components of the first gas barrier layer and the second gas barrier layer to each other.
  • it refers to a compound having a chemical structure in which a non-transition metal and a transition metal form a chemical bond directly or through an oxygen atom.
  • the mixed region contains a non-transition metal, a transition metal, and oxygen. Further, the mixed region preferably includes at least one of a mixture of a transition metal oxide and a non-transition metal oxide, or a composite oxide of a transition metal and a non-transition metal. More preferably, a composite oxide of a transition metal and a non-transition metal is contained.
  • a composite formed by physically bonding the constituent components of the first gas barrier layer and the second gas barrier layer to each other by intermolecular interaction or the like according to the present invention is also related to the present invention. It is included in “complex oxide”.
  • composition of the mixed region is expressed by the chemical composition formula (1), it is preferable that at least a part of the mixed region satisfies the condition defined by the relational expression (2).
  • the gas barrier property of the gas barrier film of the present invention was measured by a method according to JIS K 7129-1992 when calculated with a laminate in which the gas barrier layer was formed on a substrate. It is preferably a gas barrier film having a water vapor permeability of 0.01 g / m 2 ⁇ 24 h or less in an environment of 90 ° C. and 2 ⁇ RH, and further measured by a method according to JIS K 7126-2006. In addition, the oxygen permeability under an environment of 85 ° C.
  • RH is 1 ⁇ 10 ⁇ 3 mL / m 2 ⁇ 24 h ⁇ atm or less, and the water vapor permeability is 1 ⁇ 10 ⁇ 3 g / m 2 ⁇ 24 h or less.
  • High gas barrier properties are preferred.
  • FIG. 1 is a sectional view showing the structure of the gas barrier film of the present invention.
  • the first gas barrier layer 2 and the second gas barrier layer 3 are laminated on the substrate 1, and the mixed region 4 is formed therebetween.
  • a functional layer such as an undercoat layer (also referred to as an anchor layer in the present invention), a hard coat layer, or the like may be formed between the substrate 1 and the first gas barrier layer 2.
  • an adhesion layer that improves adhesion with other functional layers (for example, a quantum dot resin layer) may be formed.
  • a backcoat layer or the like may be formed on the surface of the substrate opposite to the side where the gas barrier layer is disposed.
  • Substrate As the substrate according to the present invention, specifically, application of glass or a resin film is preferable, and when flexibility is required, a resin film is preferable.
  • Preferred resins include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, and cellulose acylate resin.
  • the base material is preferably made of a material having heat resistance. Specifically, a base material having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and a glass transition temperature (Tg) of 100 ° C. or more and 300 ° C. or less is used.
  • the base material satisfies the requirements for use as a laminated film for electronic parts and displays. That is, when the gas barrier layer according to the present invention is used for these applications, the substrate may be exposed to a process of 150 ° C. or higher. In this case, when the linear expansion coefficient of the base material exceeds 100 ppm / K, the substrate dimensions are not stable when flowing through the temperature process as described above, and the barrier performance deteriorates due to thermal expansion and contraction. Or, the problem that it cannot withstand the heat process is likely to occur. If it is less than 15 ppm / K, the film may break like glass and the flexibility may deteriorate.
  • Polyolefin for example, ZEONOR (registered trademark) 1600: 160 ° C, manufactured by Nippon Zeon Co., Ltd.
  • polyarylate PAr: 210 ° C
  • polyethersulfone PES: 220 ° C
  • polysulfone PSF: 190 ° C
  • cycloolefin copolymer COC: Compound described in JP-A No. 2001-150584: 162 ° C.
  • polyimide for example, Neoprim (registered trademark): 260 ° C.
  • the substrate is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.
  • the light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.
  • the above-mentioned base material may be an unstretched film or a stretched film.
  • the said base material can be manufactured by a conventionally well-known general method. Regarding the method for producing these base materials, the items described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 can be appropriately employed.
  • the surface of the substrate may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and the above treatments are performed in combination as necessary. It may be. Moreover, you may perform an easily bonding process to a base material.
  • the base material may be a single layer or a laminated structure of two or more layers.
  • the respective substrates may be the same type or different types.
  • the thickness of the substrate according to the present invention (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m.
  • Gas barrier layer [2.1] Outline of gas barrier layer and mixing region
  • the gas barrier film of the present invention comprises at least a first gas barrier layer and a second gas barrier layer in this order on a substrate.
  • the non-transition metal refers to a non-transition metal (M1) selected from the metals of Group 12 to Group 14 of the long-period periodic table, which includes “a compound of non-transition metal”, for example, an oxide Nitride, oxynitride, and oxycarbide, particularly preferably an oxide.
  • the transition metal (M2) refers to a metal selected from Group 3 elements to Group 11 elements of the long-period periodic table, which includes “transition metal compounds” such as oxides, nitrides, An oxynitride and an oxycarbide are mentioned, and an oxide is particularly preferable.
  • the non-transition metal (M1) selected from the metals of Group 12 to Group 14 of the long periodic table is not particularly limited, and any metal of Groups 12 to 14 can be used alone or in combination.
  • any metal of Groups 12 to 14 can be used alone or in combination.
  • Si, Al, Zn, In, and Sn can be used.
  • M1 preferably contains Si, Sn or Zn, more preferably contains Si, and particularly preferably Si alone.
  • the transition metal (M2) selected from Group 3 to Group 11 elements in the long-period periodic table is not particularly limited, and any transition metal can be used alone or in combination.
  • transition metals include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, and Pm. , Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, and Au.
  • transition metal (M2) examples include Nb, Ta, V, Zr, Ti, Hf, Y, La, and Ce.
  • Nb, Ta, and V which are Group 5 elements, are considered to be preferably used because they are likely to be bonded to the non-transition metal (M1) contained in the gas barrier layer. be able to.
  • the transition metal (M2) is a Group 5 element (for example, Nb) and the above-described non-transition metal (M1) is Si
  • a significant gas barrier property improvement effect can be obtained. This is considered to be because the bond between Si and the Group 5 element (for example, 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 layer thickness of the gas barrier layer is not particularly limited, but is preferably 5 to 1000 nm. If it is such a range, it will be excellent in high gas barrier performance, bending resistance, and cutting processability.
  • the gas barrier layer may be composed of two or more adjacent layers.
  • the “mixed region” according to the present invention is selected from a non-transition metal (M1) selected from metals of Groups 12 to 14 and metals of Groups 3 to 11 of the long-period periodic table.
  • the region containing the transition metal (M2), and the ratio of the number of atoms of the transition metal (M2) to the non-transition metal (M1) (M2 / M1) is in the range of 0.02 to 49. This is a region having a certain mixed region of 5 nm or more continuously in the thickness direction.
  • the mixed region includes (1) a plurality of regions having different chemical compositions of components in at least the thickness direction of the gas barrier layer, and one of the plurality of regions includes a non-transition metal or a compound thereof.
  • the transition metal is contained in the other region directly or indirectly facing the one region, the main component a of the first gas barrier layer and the second The area
  • the composition of at least a part of the mixed region is preferably a non-stoichiometric composition in which oxygen is deficient.
  • the oxygen deficient composition is defined by the following relational expression (2) when at least a part of the composition of the mixed region is expressed by the following chemical composition formula (1). It is defined as satisfying the condition.
  • 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 certain mixed region is used.
  • the mixed region is further reduced.
  • it is guessed that the high-density structure of a metal compound is formed in the said mixed region, and contributes to high gas barrier property.
  • composition represented by the chemical composition formula (1) is simply referred to as the composition of the composite region.
  • the composition in the composite region of the non-transition metal (M1) and the transition metal (M2) according to the present invention is represented by (M1) (M2) x O y N z .
  • the composition of the composite region may partially include a nitride structure, and it is more preferable to include 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.
  • the composition of the composite region including a part of the nitride
  • (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 weighted averaging with the existence ratio is adopted as the values of a and b of the “maximum valence”.
  • the mixed region is a region where the value of x satisfies 0.02 ⁇ x ⁇ 49 (0 ⁇ y, 0 ⁇ z). This is defined as a region in which the value of the number ratio of transition metal (M2) / non-transition metal (M1) is in the range of 0.02 to 49 and the thickness is 5 nm or more. It is the same definition as that. In this region, since both the non-transition metal (M1) and the transition metal (M2) are involved in the direct bonding between the metals, a mixed region that satisfies this condition exists in a thickness of a predetermined value or more (5 nm). Therefore, it is thought that it contributes to the improvement of gas barrier properties.
  • the mixed region is a region satisfying 0.1 ⁇ x ⁇ 10. It is preferable to include 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 thickness of the mixed region that provides good gas barrier properties is 5 nm or more as the sputtering thickness in terms of SiO 2 , and this thickness is preferably 8 nm or more, preferably 10 nm or more. More preferably, it is 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.
  • the gas barrier layer having the above-described configuration exhibits an extremely 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 Regarding the mixed region of the gas barrier layer according to the present invention, the composition distribution in the first gas barrier layer and the second gas barrier layer, the thickness of each region, etc., X-ray photoelectric spectroscopy (X- ray Photoelectron Spectroscopy (abbreviation: XPS).
  • 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 of each element (unit: atom%) and the horizontal axis as the etching time (sputtering time).
  • the etching time is generally 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, As 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 employed in the XPS depth profile measurement Can be adopted.
  • 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 was determined 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), oxygen (O), nitrogen (N), and carbon (C).
  • the composition ratio is calculated from the obtained data, the non-transition metal (M1) and the transition metal (M2) coexist, and the value of the atomic ratio of the transition metal (M2) / non-transition metal (M1) is , 0.02 to 49 is obtained, this is defined as a mixed region, and its thickness is obtained.
  • the thickness of the mixed region represents the sputter depth in XPS analysis in terms of SiO 2 .
  • the thickness of the mixed region when the thickness of the mixed region is 5 nm or more, it is determined as “mixed region”. From the viewpoint of gas barrier properties, there is no upper limit of the thickness in the mixed region, but from the viewpoint of optical characteristics. Therefore, it is preferably in the range of 5 to 100 nm, more preferably in the range of 8 to 50 nm, and still more preferably in the range of 10 to 30 nm.
  • FIG. 2 is a graph for explaining the element profile and the mixed region when the composition distribution of the non-transition metal and the transition metal in the thickness direction of the gas barrier layer is analyzed by the XPS method.
  • elemental analysis of the 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 (the left end of the graph), and the horizontal axis represents the sputter. It is the graph which showed the content rate (atom%) of a non-transition metal (M1) and a transition metal (M2) on the vertical axis
  • a first gas barrier layer having an elemental composition mainly composed of a non-transition metal (M1, eg, Si) as a metal is shown, and a transition metal (M2, eg, niobium) is shown as a metal on the left side in contact therewith.
  • a second gas barrier layer having an elemental composition mainly composed of is shown.
  • the mixed region is a region in which the value of the atomic ratio of transition metal (M2) / non-transition metal (M1) is indicated by an elemental composition within a range of 0.02 to 49, and the mixed gas region of the first gas barrier layer.
  • Method for forming mixed region As the mixed region forming method, as described above, when forming the first gas barrier layer and the second gas barrier layer, the formation conditions of the first gas barrier layer and the second gas barrier are adjusted. A method of forming a mixed region with the barrier layer is preferable.
  • the first gas barrier layer is formed by, for example, a vapor deposition method, for example, the ratio of the non-transition metal (M1) and oxygen in the deposition raw material, the inert gas and the reactive gas during the deposition And one or more conditions selected from the group consisting of the ratio of the above, 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 By doing so, a mixed region can be formed.
  • a mixed region can be formed by appropriately adjusting the selection of materials, coating solution conditions, coating conditions, and the like.
  • the second gas barrier layer is formed by a vapor deposition method, for example, the ratio of the non-transition metal (M1) and transition metal (M2) to oxygen in the film-forming raw material, the inert gas during film formation And one or more selected from the group consisting of the ratio of the reactive gas to the reactive gas, 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
  • M1 and M2 transition metal
  • the mixed region can be formed by adjusting the conditions.
  • the formation conditions of the method for forming the first gas barrier layer and the second gas barrier layer can be appropriately adjusted and controlled.
  • a desired thickness can be obtained by controlling the deposition time.
  • a method of directly forming a mixed region of a non-transition metal and a transition metal is also preferable.
  • a method for directly forming the mixed region it is preferable to use a known co-evaporation method.
  • 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 a composite of a non-transition metal
  • M2 transition metal
  • One-way sputtering using a composite target having a composition of the region as a sputtering target may be used.
  • 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
  • a method for producing these sputtering targets and a method for producing a thin film having a composition of a composite region using these sputtering targets for example, JP 2000-160331 A, JP 2004-068109 A, and the like. Reference can be made to the descriptions in Japanese Unexamined Patent Publication No. 2013-047361.
  • 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 film forming process.
  • One or two 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 are exemplified, and these film formation conditions (preferably oxygen content)
  • these film formation conditions preferably oxygen content
  • 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
  • First Gas Barrier Layer Formation of Non-Transition Metal (M1) Containing Layer
  • the layer containing the non-transition metal (M1) according to the present invention is As described above, it is more preferable that Si is contained, and it is particularly preferable that Si is contained alone.
  • the method for forming the first gas barrier layer according to the present invention is not particularly limited, and for example, a vapor deposition method can be used by a known method.
  • the vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assist vapor deposition, plasma CVD (chemical vapor deposition), and ALD. Examples thereof include a chemical vapor deposition (CVD) method such as an (Atomic Layer Deposition) method.
  • PVD physical vapor deposition
  • the layer containing the non-transition metal (M1) is preferably a layer containing polysilazane or a modified polysilazane, and the polysilazane modified body is applied to the coating liquid containing polysilazane in the present invention. It is more preferable that it is a layer formed by coating on such a substrate and irradiating with vacuum ultraviolet light because a gas barrier layer having excellent gas properties and excellent optical properties such as transmittance can be obtained. .
  • the number of layers to be formed is not particularly limited, and may be at least one layer, and may be a plurality of layers.
  • the reforming treatment is preferably a vacuum ultraviolet light irradiation treatment.
  • the gas barrier layer exhibits a gas barrier property by a modification treatment such as irradiation with vacuum ultraviolet light.
  • a coating solution containing polysilazane can be applied by a known wet coating method and subjected to a modification treatment to form a layer that becomes a part of the gas barrier layer.
  • the “polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond in the structure and serving as a precursor of silicon oxynitride, and one having a structure of the following general formula (1) is preferably used. .
  • each of R 1 , R 2 , and R 3 represents 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.
  • perhydropolysilazane in which all of R 1 , R 2 and R 3 are hydrogen atoms is particularly preferable from the viewpoint of the denseness as a film of the obtained gas barrier layer.
  • Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and the commercially available product can be used as a polysilazane-containing coating solution as it is.
  • Examples of commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials.
  • paragraphs “0024” to “0040” of JP2013-255910A, paragraphs “0037” to “0043” of JP2013-188942A, and JP2013-2013A are known. No. 151123, paragraphs “0014” to “0021”, JP 2013-052569 A paragraphs “0033” to “0045”, JP 2013-129557 A paragraphs “0062” to “0075”, JP 2013 It can be adopted with reference to paragraphs “0037” to “0064” of Japanese Patent No. 226758.
  • the coating liquid containing polysilazane is performed in a nitrogen atmosphere, for example, in a glove box in order to suppress deterioration of the electronic device due to oxygen or water vapor.
  • Any appropriate method can be adopted as a method of applying the coating liquid containing polysilazane. Specific examples include spin coating, roll coating, flow coating, ink jet, spray coating, printing, dip coating, cast film formation, bar coating, and gravure printing.
  • After applying the coating solution it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed.
  • the formation method refer to paragraphs “0058” to “0064” of JP-A-2014-151571, paragraphs “0052” to “0056” of JP-A-2011-183773, etc., which are conventionally known. Can do.
  • the modification treatment refers to a conversion reaction of polysilazane to silicon oxide or silicon oxynitride.
  • the reforming process is performed under a nitrogen atmosphere such as in a glove box or under reduced pressure.
  • a known method based on the conversion reaction of polysilazane can be selected.
  • a conversion reaction using plasma, ozone, or ultraviolet light that can be converted at a low temperature is preferable.
  • Conventionally known methods can be used for plasma and ozone.
  • a layer containing a non-transition metal (M1) is formed by providing a coating film of a polysilazane-containing liquid and irradiating it with vacuum ultraviolet light (also referred to as VUV) having a wavelength of 200 nm or less. It is preferable to do.
  • VUV vacuum ultraviolet light
  • the layer thickness is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm.
  • the entire layer may be a modified layer, but the thickness of the modified layer subjected to the modification treatment is preferably 1 to 50 nm, and more preferably 1 to 10 nm.
  • the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane layer coating film is preferably in the range of 30 to 200 mW / cm 2 , and in the range of 50 to 160 mW / cm 2 . It is more preferable that By setting the illuminance of the vacuum ultraviolet light to 30 mW / cm 2 or more, the reforming efficiency can be sufficiently improved, and when it is 200 mW / cm 2 or less, the rate of damage to the coating film is extremely suppressed, It is preferable because damage to the device can be reduced.
  • the amount of irradiation energy of vacuum ultraviolet light on the polysilazane layer coating surface is preferably in the range of 0.01 to 0.9 J / cm 2 , and 0.05 to 0.5 J / Cm 2 is more preferable from the viewpoint of reducing damage to the device.
  • the vacuum ultraviolet light source Since vacuum ultraviolet light is absorbed by oxygen, the efficiency in the vacuum ultraviolet light irradiation process is likely to decrease. Therefore, it is preferable to perform the irradiation with vacuum ultraviolet light in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration at the time of vacuum ultraviolet light irradiation is preferably in the range of 10 to 10,000 ppm, more preferably in the range of 50 to 5000 ppm, further preferably in the range of 80 to 4500 ppm, and most preferably in the range of 100 to 1000 ppm. is there.
  • a heat treatment can also be used for the reforming treatment.
  • the heating conditions are preferably in the range of 50 to 300 ° C., more preferably in the range of 70 to 200 ° C., preferably 0.005 to 60 minutes, more preferably 0.01 to 10 minutes.
  • condensation is performed and a modified product can be formed.
  • the heat treatment for example, a method of heating a coating film by contacting a substrate with a heating element such as a heat block, a method of heating an atmosphere with an external heater such as a resistance wire, an infrared region such as an IR heater
  • a heating element such as a heat block
  • an external heater such as a resistance wire
  • an infrared region such as an IR heater
  • the temperature of the coating film during the heat treatment is preferably adjusted as appropriate within a range of 50 to 250 ° C, and more preferably within a range of 50 to 120 ° C.
  • the heating time is preferably within a range of 1 second to 10 hours, and more preferably within a range of 10 seconds to 1 hour.
  • the gas barrier layer according to the present invention is preferably formed using polysilazane, particularly preferably perhydropolysilazane, as a precursor, but the gas barrier layer as the final product is a layer formed of polysilazane. It can be proved by analyzing by the following method.
  • the measurement point is 80% or more with respect to the thickness of the formed gas barrier layer.
  • the composition of y is in the range of ⁇ 2% of (0.8 ⁇ x / 3), it can be estimated that the layer is a gas barrier layer formed from perhydropolysilazane. It becomes.
  • the coating liquid for forming the layer containing the non-transition metal (M1) includes at least an additive element (selected from the group consisting of elements of Group 1 to Group 14 of the long-period periodic table) 1 element) can be contained.
  • additive elements 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), potassium (K ), Calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), germanium (Ge) and the like. .
  • the layer containing the non-transition metal (M1) according to the present invention is preferably formed by applying and drying a coating liquid containing polysilazane and an aluminum compound or polysilazane and a boron compound.
  • 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.
  • Examples of the boron compound include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-tert-butyl borate and the like.
  • aluminum compounds are preferred.
  • 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 element in the layer containing the non-transition metal (M1) is preferably 0.1 to 20 mol% with respect to 100 mol% of silicon (Si). More preferably, it is 0.5 to 10 mol%.
  • the method for producing a gas barrier film for producing the gas barrier film of the present invention comprises the first gas barrier on a long substrate film. A step of forming a layer, a step of winding the long base film into a roll shape to form a roll body, an unwinding of the long base film from the roll body, and the first gas barrier A step of etching the surface of the layer, and then a step of forming the second gas barrier layer.
  • the step of forming the first gas barrier layer preferably includes a step of applying a polysilazane-containing coating solution and performing a modification treatment.
  • the etching process and the second gas barrier layer forming process be performed in a vacuum film forming apparatus from the viewpoint of improving productivity.
  • the second gas barrier layer contains a transition metal oxide, and the arithmetic average roughness Ra of the gas barrier layer surface is in the range of 1.0 to 20.0 nm.
  • the adhesion area with the second gas barrier layer is increased, and a stronger laminated structure is formed.
  • the damage (peeling, cracks, etc.) during the roughening treatment to the second gas barrier layer can be avoided, the surface of the second gas barrier layer is roughened after the first gas barrier layer is formed in the present invention. Is preferred.
  • the surface roughening method is not particularly limited.
  • a sandblasting method a method of forming a resin containing a matting agent, a method of forming a plurality of types of resin precursors or resins by phase separation, and physical etching.
  • Method, chemical etching method, mold transfer method, etc. but since the physical etching method can be performed in the vacuum film forming apparatus together with the step of forming the second gas barrier layer, preferable.
  • a dry etching technique such as planar plasma etching (PPE) or reactive ion etching (RIE) from the viewpoint of fine processing, and it is preferable to use reactive ion etching (RIE).
  • PPE planar plasma etching
  • RIE reactive ion etching
  • RIE reactive ion etching
  • Argon, oxygen, nitrogen, and hydrogen can be used as the gas species for performing the roughening treatment by RIE. These gases may be used alone, or two or more kinds of gases may be mixed and used. Moreover, you may process continuously using two processor.
  • the processing conditions indicated by the processing speed, energy level, and the like can be set as appropriate according to the type of gas barrier layer, the roughened state, the discharge device characteristics, etc., and the plasma self-bias value ranges from 200 to 2000V.
  • Ed Plasma density ⁇ Ed value defined by processing time is preferably in the range of 100 to 10000 V ⁇ s ⁇ m ⁇ 2 , and even a slightly lower value expresses surface irregularities that affect a certain degree of adhesion. However, the advantage is slightly lower than that of untreated products. On the other hand, if the value is high, the gas barrier layer surface is deteriorated due to excessively strong treatment, resulting in a decrease in adhesion.
  • the flow rate differs depending on the pump performance, the mounting position, and the like, so that the flow rate differs depending on the application, base material, and device characteristics.
  • a mixed gas of argon / oxygen 3/1 is used as a processing gas in the vacuum film forming apparatus.
  • the first gas barrier is used under the processing conditions in which power is supplied to the electrode from a high frequency power source having a frequency of 13.56 HMz to generate low temperature plasma, the self-bias value is 800 V, and the Ed value is 450 V ⁇ s / m 2. This is possible by forming the layer surface by reactive ion etching.
  • Second Gas Barrier Layer Formation of Transition Metal (M2) Containing Layer
  • the transition metal (M2) according to the present invention is an element of Group 3 to Group 11 of the long-period periodic table. From the viewpoint of obtaining good gas barrier properties as described above, Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce and the like can be mentioned, and among these, Nb which is a Group 5 element in particular , Ta and V can be preferably used because they are considered to easily bond to the non-transition metal (M1) contained in the gas barrier layer.
  • the formation of the layer containing the transition metal (M2) according to the present invention is not particularly limited.
  • the use of a conventionally known vapor deposition method using an existing thin film deposition technique makes the mixed region efficient. It is preferable from a viewpoint of forming.
  • the vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assist vapor deposition, plasma CVD (chemical vapor deposition), and ALD. Examples thereof include a chemical vapor deposition (CVD) method such as an (Atomic Layer Deposition) method. Among these, it is possible to form a film without damaging the functional element, and since it has high productivity, it is preferably formed by a physical vapor deposition (PVD) method, and more preferably formed by a sputtering method. .
  • 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 also 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.
  • Ar is preferably used.
  • a thin film of a non-transition metal (M1) and transition metal (M2) composite oxide, nitride oxide, oxycarbide, or the like is formed. be able to.
  • film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, the material of the film, the layer thickness, and the like.
  • the sputtering method may be multi-source simultaneous sputtering using a plurality of sputtering targets including a transition metal (M2) alone or its oxide.
  • 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 Reference can be made to the descriptions in Japanese Patent Application Laid-Open No. 2013-047361.
  • 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 film forming process.
  • One or two 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 are exemplified, and these film formation conditions (preferably oxygen content)
  • these film formation conditions preferably oxygen content
  • the layer thickness of the second gas barrier layer reflects the arithmetic average roughness of the surface of the first gas barrier layer on the arithmetic average roughness of the surface of the second gas barrier layer, and the thickness of the second gas barrier layer surface
  • the arithmetic average roughness Ra in the range of 1.0 to 20.0 nm
  • the layer thickness is in the range of 1 to 30 nm, the mixed region according to the present invention can be formed, and the arithmetic average roughness range can be realized.
  • the upper limit is preferably 30 nm.
  • Anchor layer In the present invention, at least one anchor layer and a laminate of the first gas barrier layer and the second gas barrier layer are laminated on a substrate. From the viewpoint of improving adhesion between the base material and the gas barrier layer, preventing damage or defects of the layer due to mechanical or thermal stress to the gas barrier layer in use environment fluctuation, and suppressing deterioration of the gas barrier property. It is an aspect.
  • the anchor layer used in the present invention is preferably an organic polymer layer containing a resin.
  • the resin used include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, and epoxy resin.
  • Modified styrene resin, modified silicone resin, alkyl titanate and the like can be used alone or in combination of two or more.
  • a polymerizable composition containing the following polymerizable compound, a silane coupling agent, and a polymerization initiator may be formed into a layer and then cured.
  • the polymerizable composition in the present invention, it can be formed by applying the polymerizable composition on a substrate.
  • Arbitrary appropriate methods may be employ
  • After applying the coating solution it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed.
  • the formation method refer to paragraphs “0058” to “0064” of JP-A-2014-151571, paragraphs “0052” to “0056” of JP-A-2011-183773, etc., which are conventionally known. Can do.
  • an ink jet method using the composition can be preferably applied.
  • the ink jet method can be adopted with reference to the technical contents described in International Publication No. 2014/176365, International Publication No. 2015/100375, International Publication No. 2015/112454, and the like.
  • a vapor phase film forming method such as a known flash vapor deposition method can be used.
  • a polymerizable composition containing a polymerizable compound, a silane coupling agent, and a polymerization initiator may be volatilized by heating in a reduced pressure atmosphere to form a deposited film on a substrate, an electrode layer, or an organic functional layer. preferable.
  • a base material and an organic functional layer formed thereon are installed in a vacuum apparatus, and the polymerizable composition is placed in a heating boat installed in the vacuum apparatus, and the polymerization is performed under a reduced pressure of about 10 Pa.
  • the vapor-deposited film can be formed to have a desired layer thickness while heating the composition to about 200 ° C. and covering the base material and the organic functional layer.
  • the obtained deposited film is irradiated with ultraviolet rays using a high-pressure mercury lamp or the like in a vacuum environment, and the deposited polymerizable composition is cured to form an anchor layer.
  • the polymerizable compound used in the present invention is a compound having an ethylenically unsaturated bond at the terminal or side chain, or a compound having epoxy or oxetane at the terminal or side chain. Of these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred. Examples of the compound having an ethylenically unsaturated bond at the terminal or side chain include (meth) acrylate compounds, acrylamide compounds, styrene compounds, maleic anhydride and the like, with (meth) acrylate compounds being preferred.
  • (meth) acrylate compound As the (meth) acrylate compound, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like are preferable.
  • styrene compound styrene, ⁇ -methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.
  • silane coupling agent examples include halogen-containing silane coupling agents (2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxy).
  • Silane epoxy group-containing silane coupling agents [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxy Cyclohexyl) propyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, etc.], amino Group-containing silane coupling agent (2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- [N- (2-aminoethyl) amino] ethyltrimethoxysi
  • silane coupling agents (2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agents (vinyltrimethoxysilane, vinyl) Triethoxysilane) (Meth) acryloyl group-containing silane coupling agent (2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyl Oxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, etc.).
  • the silane coupling agent ((meth) acryloyl group containing silane coupling
  • acryloyl group-containing silane coupling agents include 1,3-bis (acryloyloxymethyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (methacryloyloxymethyl). ) -1,1,3,3-tetramethyldisilazane, 1,3-bis ( ⁇ -acryloyloxypropyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis ( ⁇ -methacryloyl) Oxypropyl) -1,1,3,3-tetramethyldisilazane, acryloyloxymethylmethyltrisilazane, methacryloyloxymethylmethyltrisilazane, acryloyloxymethylmethyltetrasilazane, methacryloyloxymethylmethyltetrasilazane, acryloyloxymethylmethylpolysilazane , Methacryloyloxy Methylmethylpolysilazane ,
  • silane coupling agent used in the present invention the compounds shown below are preferably used.
  • the synthesis method of the silane coupling agent reference can be made to JP-A-2009-67778.
  • the polymerizable composition in the present invention usually contains a polymerization initiator.
  • a polymerization initiator When a polymerization initiator is used, its content is preferably 0.1 mol% or more, more preferably 0.5 to 2 mol% of the total amount of compounds involved in the polymerization. By setting it as such a composition, the polymerization reaction via an active component production
  • photopolymerization initiators are Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, etc.) commercially available from BASF Japan.
  • Darocur series eg, Darocur TPO, Darocur 1173, etc.
  • Quantacure PDO eg, Ezacure TZM, Ezacure TZT, Ecure TZT, Ecure TZT, Ecure TZT, Ecure Etc.
  • a polymerizable composition containing a silane coupling agent, a polymerizable compound, and a polymerization initiator is cured with light (for example, ultraviolet rays), electron beams, or heat rays, but is preferably cured with light. .
  • light for example, ultraviolet rays
  • electron beams or heat rays
  • the hydrolysis reaction of the silane coupling agent proceeds, the polymerizable composition is effectively cured, and the film is formed without damaging the base material or the organic functional layer. Can do.
  • the light to be irradiated is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp.
  • the radiation energy is preferably 0.1 J / cm 2 or more, 0.5 J / cm 2 or more is more preferable.
  • a (meth) acrylate compound is employed as the polymerizable compound, polymerization inhibition is caused by oxygen in the air, so that it is preferable to reduce the oxygen concentration or oxygen partial pressure during polymerization.
  • the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less.
  • the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less.
  • the anchor layer used in the present invention is preferably smooth and has high film hardness.
  • the smoothness of the anchor layer is preferably less than 1 nm as an average roughness (Ra value) of 1 ⁇ m square, and more preferably less than 0.5 nm.
  • the polymerization rate of the monomer is preferably 85% or more, more preferably 88% or more, still more preferably 90% or more, and particularly preferably 92% or more.
  • the polymerization rate here means the ratio of the reacted polymerizable group among all the polymerizable groups (for example, acryloyl group and methacryloyl group) in the monomer mixture.
  • the polymerization rate can be quantified by an infrared absorption method.
  • the layer thickness of the anchor layer is not particularly limited, but if it is too thin, it will be difficult to obtain a uniform layer thickness, and if it is too thick, cracks will be generated due to external force and gas barrier properties will be reduced. From this viewpoint, the thickness of the organic layer is preferably 50 to 2000 nm, more preferably 200 to 1500 nm.
  • the surface of the anchor layer is required to be free of foreign matters such as particles and protrusions.
  • the anchor layer is preferably formed in a clean room.
  • the degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.
  • the organic layer has a high hardness. When the hardness of the organic layer is high, the inorganic layer is smoothly formed, and as a result, the barrier ability is improved.
  • the hardness of the organic layer can be expressed as a microhardness based on the nanoindentation method.
  • the microhardness of the organic layer is preferably 100 N / mm or more, and more preferably 150 N / mm or more.
  • Adhesion layer On the gas barrier layer of the gas barrier film of the present invention, it is preferable to provide an adhesion layer for enhancing the adhesion with the QD-containing resin layer constituting the QD film described later.
  • adhesion layer it is preferable to form an adhesion layer containing an organosilicon compound having a polymerizable group, and the thickness of the adhesion layer is preferably 5 nm or less.
  • the organosilicon compound having a polymerizable group is not particularly limited, but is preferably a silane coupling agent such as a halogen-containing silane coupling agent (2-chloroethyltrimethoxysilane, 2-chloroethyl).
  • a silane coupling agent such as a halogen-containing silane coupling agent (2-chloroethyltrimethoxysilane, 2-chloroethyl).
  • silane coupling agents containing (meth) acryloyl groups are preferred.
  • Examples of the (meth) acryloyl group-containing silane coupling agent include 1,3-bis (acryloyloxymethyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (methacryloyloxymethyl) -1, 1,3,3-tetramethyldisilazane, 1,3-bis ( ⁇ -acryloyloxypropyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis ( ⁇ -methacryloyloxypropyl)- 1,1,3,3-tetramethyldisilazane, acryloyloxymethylmethyltrisilazane, methacryloyloxymethylmethyltrisilazane, acryloyloxymethylmethyltetrasilazane, methacryloyloxymethylmethyltetrasilazane, acryloyloxymethylmethylpolysilazane, methacryloyloxymethyl Methylpo Risilazane
  • Examples of commercially available (meth) acryloyl group-containing silane coupling agents include KBM-5103, KBM-502, KBM-503, KBE-502, KBE-503, and KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.). Can be mentioned.
  • One of these (meth) acryloyl group-containing silane coupling agents may be used alone, or two or more thereof may be used in combination.
  • the silane coupling agent used in the present invention the compound represented by the above [Chemical Formula 2] is preferably used.
  • the adhesion layer can be formed by applying a polymerizable composition.
  • a solution prepared by dissolving the (meth) acryloyl group-containing compound in an appropriate solvent is applied to the surface of the gas barrier layer and dried.
  • the method to make is illustrated.
  • a suitable photopolymerization initiator is added to the solution, and the coating obtained by applying the solution and drying is subjected to a light irradiation treatment, and a part of the (meth) acryloyl group-containing compound. May be polymerized to form a polymerizable polymer.
  • Arbitrary appropriate methods may be employ
  • the film can be formed by a vapor deposition method, and the vapor deposition method can be used by a known method.
  • the vapor deposition method is not particularly limited.
  • physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, ion assisted vapor deposition, plasma CVD, ALD (Atomic Layer Deposition). ) Method and the like.
  • PVD physical vapor deposition
  • sputtering vapor deposition, ion plating, ion assisted vapor deposition, plasma CVD, ALD (Atomic Layer Deposition).
  • ALD Atomic Layer Deposition
  • the thickness of the adhesion layer is sufficient to exhibit an adhesion effect, and is preferably 5 nm or less from the viewpoint of thinning.
  • the thickness of the adhesion layer can be measured by a transmission electron microscope (TEM).
  • a surface treatment step between the gas barrier layer and the adhesion layer is added, and the surface treatment step is performed with the apparatus used for forming the gas barrier layer after forming the gas barrier layer. From the viewpoint of productivity.
  • a known method can be applied to the surface treatment step, and corona treatment, plasma treatment, sputtering treatment, flame treatment, and the like can be employed.
  • oxygen plasma treatment includes a resin base material and a gas barrier layer. Can be reduced, and can be carried out continuously with the apparatus used for forming the gas barrier layer, which is preferable in production.
  • the gas barrier film of the present invention is suitably used for various electronic devices.
  • the gas barrier film of this invention has the outstanding gas barrier property, it can be used suitably for a quantum dot containing resin film and an organic electroluminescent element (OLED).
  • QD Quantum Dot-Containing Resin Layer
  • resin which are main components of the quantum dot-containing resin layer, will be described.
  • Quantum dots semiconductor nanoparticles exhibiting a quantum confinement effect with a nanometer-sized semiconductor material are also referred to as “quantum dots”.
  • 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 dots contained in the quantum dot-containing resin layer may be known, and can be generated using any method known to those skilled in the art.
  • suitable QDs and methods for forming suitable QDs include US Pat. No. 6,225,198, US 2002/0066401, US Pat. No. 6,207,229, US Pat. No. 6,322,901. Description, 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 Can be mentioned.
  • Quantum dots are generated from any suitable material, preferably an inorganic material, and 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 quantum dot content resin layer as a binder holding a quantum dot.
  • resin can be used for a quantum dot content resin layer as a binder holding a quantum dot.
  • acrylic resins such as ketone imide, polyamide resin, fluororesin, nylon, and polymethyl methacrylate.
  • the quantum dot-containing resin layer preferably has a thickness in the range of 50 to 200 ⁇ m.
  • the optimum amount of quantum dots in the quantum dot-containing resin layer varies depending on the compound used, but is generally preferably in the range of 15 to 60% by volume.
  • Organic EL device includes, for example, an anode, a first organic functional layer group, a light emitting layer, a second organic functional layer group, and a cathode laminated on the gas barrier layer of the present invention. It is preferable that it is comprised.
  • the first organic functional layer group includes, for example, a hole injection layer, a hole transport layer, an electron blocking layer, and the like
  • the second organic functional layer group includes, for example, a hole blocking layer, an electric transport layer, and an electron injection layer. Etc.
  • Each of the first organic functional layer group and the second organic functional layer group may be composed of only one layer, or the first organic functional layer group and the second organic functional layer group may not be provided.
  • the organic EL element may have a non-ode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode (ii) Anode / hole injection transport layer / light emitting layer / hole blocking layer / electron injection transport layer / cathode (iii) Anode / Hole injection / transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron injection transport layer / cathode (iv) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / Cathode (v) Anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode (vi) Anode / hole injection layer / hole transport layer / electron blocking Layer / light emitting layer / hole blocking layer / electron transporting layer / electron injecting layer / cathode Furthermore, the organic
  • the intermediate layer may be a charge generation layer or a multi-photon unit configuration.
  • organic EL elements applicable to the present invention, see, for example, JP2013-157A. No. 634, JP 2013-168552 A, JP 2013-177361 A, JP 2013-187411 A, JP 2013-191644 A, JP 2013-191804 A, JP 2013-225678 A.
  • Example 1 ⁇ Preparation of gas barrier film 101>
  • resin base material a polyethylene terephthalate film roll (Lumilar (registered trademark) (U48), manufactured by Toray Industries, Inc.) having a thickness of 100 ⁇ m and a length of 1000 m and subjected to easy adhesion treatment on both surfaces was used.
  • a UV curable resin manufactured by Aika Kogyo Co., Ltd., product number: Z731L was applied on a resin base material so that the dry layer thickness was 0.5 ⁇ m, and then dried at 80 ° C., and then under high pressure in air. Curing was performed using a mercury lamp under the condition of an irradiation energy amount of 0.5 J / cm 2 .
  • a clear hard coat layer having a thickness of 2 ⁇ m was formed on the surface of the resin base on the side where the gas barrier layer is to be formed as follows.
  • a UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a resin substrate so as to have a dry layer thickness of 2 ⁇ m, dried at 80 ° C., and then using a high-pressure mercury lamp in the air. It was cured under conditions of irradiation energy 0.5 J / cm 2 Te. In this way, a resin base roll with a clear hard coat layer was obtained.
  • this resin substrate with a clear hard-coat layer is only used as a base material for convenience.
  • the first gas barrier layer is formed by the following procedure.
  • the first gas barrier layer containing a non-transition metal (M1): silica (Si) derived from perhydropolysilazane (PHPS) having a layer thickness of 250 nm is formed. Formed.
  • a dibutyl ether solution of 20% by mass of perhydropolysilazane manufactured by AZ Electronic Materials Co., Ltd., NAX120-20
  • a coating solution was prepared by appropriately diluting with dibutyl ether.
  • the above coating solution was applied to the surface of the clear hard coat layer of the resin substrate by spin coating so that the dry layer thickness was 250 nm, and dried at 80 ° C. for 2 minutes.
  • vacuum ultraviolet light irradiation treatment was performed on the dried coating film under a condition of irradiation energy of 6 J / cm 2 using a vacuum ultraviolet light irradiation apparatus having a Xe excimer lamp with a wavelength of 172 nm.
  • the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume.
  • the stage temperature for installing the sample was set to 80 ° C.
  • the second gas barrier layer was formed by a vapor phase method / sputtering.
  • a sputtering apparatus a magnetron sputtering apparatus (manufactured by Canon Anelva: Model EB1100) is used, and a second gas barrier containing a transition metal: niobium (Nb) having a layer thickness of 5 nm in a roll-to-roll system according to the following procedure A layer was obtained.
  • the resin base material was wound into a roll shape, a roll body was produced, and a gas barrier film 101 was produced.
  • the following targets were used, and Ar and O 2 were used as process gases, and film formation was performed by an RF method using a magnetron sputtering apparatus.
  • the sputtering power source power was 5.0 W / cm 2 and the film forming pressure was 0.4 Pa.
  • the oxygen partial pressure was adjusted to 20%. It should be noted that, after film formation using a glass substrate in advance, data on the layer thickness change with respect to the film formation time was obtained under each film formation condition, and after calculating the layer thickness formed per unit time, the set layer thickness The film formation time was set so that
  • T1 A commercially available oxygen-deficient niobium oxide target was used.
  • the composition was Nb 12 O 29 .
  • ⁇ Preparation of gas barrier film 102> In the production of the gas barrier film 101, after forming the first gas barrier layer, a winding roll body was produced in a roll shape. Next, a gas barrier film 102 was produced in the same manner except that the resin base material on which the first gas barrier layer was formed was unwound from the roll body and the surface was subjected to the etching treatment.
  • a gas barrier film 103 was produced in the same manner as in the production of the gas barrier film 102 except that the etching treatment was performed by the following plasma CVD method (indicated as method (2) in Table 1).
  • the surface of the first gas barrier layer is etched by the plasma CVD process under the following conditions on the resin base material on which the first gas barrier layer is formed under the following plasma CVD conditions. did.
  • the etching conditions were appropriately adjusted after conducting a preliminary test so that the arithmetic average roughness of the second gas barrier layer surface was 1.0 nm.
  • gas barrier films 113 and 114 were produced in the same manner except that the following target was used to form the second gas barrier layer.
  • a gas barrier film 113 was produced using a commercially available metal thallium (Ta) target with a DC method and an oxygen partial pressure of 20%.
  • T3 Using a commercially available metal vanadium (V) target, a film was formed with a DC method and an oxygen partial pressure of 20%, and a gas barrier film 114 was produced.
  • V metal vanadium
  • gas barrier films 115 and 116 were produced in the same manner except that the etching treatment was not performed on the first gas barrier layer.
  • a gas barrier film 117 was produced in the same manner except that the film was not wound into a roll and was not etched.
  • MultiPak manufactured by ULVAC-PHI was used.
  • the analyzed elements are Si, Nb, Ta, Al, O, N, and C.
  • the composition of the gas barrier layer can be represented by (Si) (Nb) x O y N z from the data obtained from the XPS composition analysis.
  • Si as a non-transition metal
  • Nb as a transition metal coexist in the interface region between the first layer and the second layer
  • the transition metal Nb / Si A region where the value x of the atomic number ratio is in the range of 0.02 ⁇ x ⁇ 49 and 5 nm or more continuously in the thickness direction is defined as a “mixed region”, and the presence or absence of the region is described in the table.
  • the Ca method evaluation sample (type evaluated by permeation concentration) prepared as described below was stored in a 60 ° C. and 90% RH environment, and the corrosion rate of Ca was observed at regular intervals. 1 hour, 5 hours, 10 hours, 20 hours, and thereafter, observation and transmission density measurement (average of 4 points) every 20 hours, and when the measured transmission density is less than 50% of the initial transmission density value Was used as an indicator of gas barrier properties.
  • the transmission density measured in storage for 1000 hours was 50% or more of the initial value of transmission density, it was set to 1000 hours or more.
  • thermosetting sheet adhesive epoxy resin
  • a thermosetting sheet adhesive epoxy resin
  • One side of a 50 mm ⁇ 50 mm non-alkali glass plate was UV cleaned.
  • 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.
  • the Ca-deposited glass plate was taken out into the glove box, placed so that the sealing resin layer surface of the gas barrier film to which the sealing resin layer was bonded and the Ca deposition surface of the glass plate were in contact, and adhered by vacuum lamination. 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.
  • the gas barrier film having the constitution of the present invention was a gas barrier film in which the gas barrier property was remarkably improved as compared with the comparative example.
  • the gas barrier film having the constitution of the present invention has high resistance to deterioration of the gas barrier property due to damage even when a winding roll body is formed in a roll shape or unwound from the roll body.
  • the gas barrier film of the present invention has high durability even in a high-temperature and high-humidity environment, and in roll-to-roll manufacturing, a gas barrier film that is highly resistant to damage caused by winding, and an organic electro where high gas barrier properties are required. Suitable for luminescence elements.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

La présente invention vise à procurer : un film barrière contre des gaz ayant une durée de vie élevée même dans un environnement à haute température et à humidité élevée, et ayant une résistance élevée contre des détériorations provoquées par l'enroulement dans une fabrication rouleau à rouleau; et un procédé pour fabriquer le film barrière contre des gaz. À cet effet, l'invention porte sur un film barrière contre des gaz, lequel film a au moins une première couche barrière contre des gaz et une seconde couche barrière contre des gaz, selon la séquence énumérée, sur un substrat, la première couche barrière contre des gaz contenant un métal de non transition, la seconde couche barrière contre des gaz contenant un métal de transition, et la rugosité moyenne arithmétique Ra de la surface de la seconde couche barrière contre des gaz étant dans la plage de 1,0 à 20,0 nm.
PCT/JP2016/086305 2015-12-22 2016-12-07 Film barrière contre des gaz et procédé pour sa fabrication WO2017110463A1 (fr)

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Cited By (1)

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WO2016208237A1 (fr) * 2015-06-24 2016-12-29 コニカミノルタ株式会社 Film barrière contre les gaz, élément électroconducteur transparent, élément électroluminescent organique, procédé pour fabriquer un film barrière contre les gaz, procédé pour fabriquer un élément électroconducteur transparent, et procédé pour fabriquer un élément électroluminescent organique

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JP7266810B2 (ja) 2017-09-05 2023-05-01 エリコン サーフェス ソリューションズ アーゲー、 プフェフィコン Ａｌ富化ＡｌＴｉＮ系膜
US11965234B2 (en) 2017-09-05 2024-04-23 Oerlikon Surface Solutions Ag, Pfäffikon Al-rich AlTin-based films

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