WO2017014246A1 - Film de barrière contre les gaz et son procédé de production - Google Patents

Film de barrière contre les gaz et son procédé de production Download PDF

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Publication number
WO2017014246A1
WO2017014246A1 PCT/JP2016/071322 JP2016071322W WO2017014246A1 WO 2017014246 A1 WO2017014246 A1 WO 2017014246A1 JP 2016071322 W JP2016071322 W JP 2016071322W WO 2017014246 A1 WO2017014246 A1 WO 2017014246A1
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Prior art keywords
gas barrier
layer
atom
metal
region
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PCT/JP2016/071322
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English (en)
Japanese (ja)
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森　孝博
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コニカミノルタ株式会社
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Priority to JP2017529914A priority Critical patent/JPWO2017014246A1/ja
Publication of WO2017014246A1 publication Critical patent/WO2017014246A1/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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.
  • Gas barrier films are used as substrate films and sealing films in flexible electronic devices, particularly flexible organic EL devices.
  • the gas barrier film used for these is required to have high gas barrier properties.
  • a gas barrier film is manufactured by forming an inorganic barrier layer on a base film by a vapor deposition method such as vapor deposition, sputtering, or CVD.
  • a manufacturing method for forming a gas barrier layer by applying energy to a precursor layer formed by applying a solution on a substrate has been studied.
  • studies using a polysilazane compound as a precursor have been widely conducted, and studies are being conducted as a technique that achieves both high productivity by coating and gas barrier properties.
  • the modification of the polysilazane layer using excimer light having a wavelength of 172 nm has attracted attention.
  • a solution containing polysilazane and a catalyst is applied onto a substrate, and then the solvent is removed to form a polysilazane layer.
  • the gas barrier layer formed by modifying polysilazane described in the above Japanese translation of PCT publication No. 2009-503157 (US Patent Application Publication No. 2010/1666977) with excimer light has a low temperature of about 40 ° C.
  • the gas barrier property is good, it has been found that the gas barrier property decreases with time in a very severe environment of high temperature and high humidity such as 80 ° C. and 85% RH.
  • JP-T-2009-503157 US Patent Application Publication No. 2010/1666977
  • JP-T-2009-503157 US Patent Application Publication No. 2010/1666977
  • an object of the present invention is to provide a gas barrier film excellent in durability in a high temperature and high humidity environment.
  • Another object of the present invention is to provide a method for producing a gas barrier film excellent in productivity and production stability.
  • a gas barrier film having a gas barrier layer containing a silicon atom, a metal M1 other than silicon, an element M2 other than silicon and the metal M1, and an oxygen atom on a resin substrate.
  • the ratio of the amount of the silicon atom to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer is [Si] (unit: atom %), And the ratio of the amount of the metal M1 to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer [M1] (unit: atom) %) And the element relative to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer.
  • a method for producing the gas barrier film wherein the first layer containing the silicon atom, the element M2, and the oxygen atom is formed on the resin base material. And a step of forming a second layer containing the metal M1 and the oxygen atom on the first layer.
  • FIG. 1 is a schematic cross-sectional view of a vacuum ultraviolet irradiation apparatus used in the examples, 1 is an apparatus chamber, 2 is a Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet light of 172 nm, and 3 also serves as an external electrode.
  • An excimer lamp holder, 4 is a sample stage, 5 is a sample on which a polysilazane compound coating layer is formed, 6 is a light shielding plate, and V is a moving speed of the sample stage.
  • the present invention is a gas barrier film having, on a resin substrate, a gas barrier layer containing a silicon atom, a metal M1 other than silicon, an element M2 other than silicon and the metal M1, and an oxygen atom,
  • the ratio of the amount of the silicon atom to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer is [Si] (unit: atom%)
  • the ratio of the amount of the metal M1 to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer is [M1] (unit: atom%)
  • Ratio of the amount of the element M2 to the total amount of the silicon atom, the metal M1, the element M2, the oxygen atom, the nitrogen atom, and the carbon atom in the gas barrier layer Is [M2] (unit: atom%), from the resin substrate side, the region (C)
  • the gas barrier film of the present invention having such a configuration is excellent in durability in a high temperature and high humidity environment. Moreover, the manufacturing method of the gas barrier film of this invention is excellent in productivity and production stability.
  • Area (A) is an area where a lot of metal M1 exists. It has been found that when the region (A) satisfies the relationship of the above formula (a), the region (A) has a property of being excellent in scratch resistance as compared with a region made of an oxide or oxynitride containing silicon (Si) as a main component. . Then, by arranging the region (A) among the regions (A) to (C) on the side farthest from the resin base material, it functions as a protective layer in the gas barrier film manufacturing process and deteriorates the gas barrier property. It has the effect of suppressing.
  • the region (B) is a region having a high gas barrier property.
  • a compound having a bond between Si and the metal M1 hereinafter also referred to as Si-M1 bond
  • Si-M1 bond a compound having a bond between Si and the metal M1
  • Si-M1 bond a compound having a bond between Si and the metal M1
  • Si-M1 bond a compound having a bond between Si and the metal M1
  • Si-M1 bond a compound having a bond between Si and the metal M1 (hereinafter also referred to as Si-M1 bond)
  • the region (B) where the Si-M1 bond is formed has higher moisture and heat resistance than SiO 2
  • the region (B) has excellent durability to maintain a good gas barrier property even when stored in a high temperature and high humidity environment.
  • the element M2 may exist in the region (B), it is considered that the element M2 inhibits the formation of the Si-M1 bond.
  • the region (C) closest to the resin base material is a region mainly containing silicon but containing a relatively large amount of the element M2.
  • the region (C) contains a relatively large amount of the element M2, that is, by satisfying the relationship of the above formula (c), composition change when stored in a high temperature and high humidity environment is suppressed, and durability in a high temperature and high humidity environment is achieved. Excellent in properties. Moreover, it has the effect of reducing the unevenness
  • the composition stability is hardly changed and the production stability becomes stable. It also has excellent productivity.
  • X to Y indicating a range means “X or more and Y or less”.
  • measurement of operation and physical properties is performed under the conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.
  • resin substrate Specific examples of the resin substrate according to the present invention include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, and polyamideimide resin.
  • resin substrates can be used alone or in combination of two or more.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • alicyclic 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.
  • the resin 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.
  • an opaque material can be used as the plastic film.
  • the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.
  • the resin base material listed above may be an unstretched film or a stretched film.
  • the resin substrate can be produced by a conventionally 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 resin 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 may be combined as necessary. May go.
  • the resin base material may be subjected to an easy adhesion treatment.
  • the resin substrate may be a single layer or a laminated structure of two or more layers.
  • the resin base materials may be the same type or different types.
  • the thickness of the resin base material 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, and more preferably 20 to 150 ⁇ m.
  • the gas barrier film of the present invention has a gas barrier layer containing a silicon atom, a metal M1 other than silicon, an element M2 other than silicon and metal M1, and an oxygen atom.
  • the gas barrier layer may further contain nitrogen atoms.
  • Metal M1 The metal M1 other than silicon is not particularly limited, but a transition metal is preferable.
  • the transition metal refers to a Group 3 element to a Group 11 element in the long-period periodic table, and more specifically, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr ), Manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc) ), Ruthenium (Ru), palladium (Pd), silver (Ag), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu) ), Gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), yt
  • Nb, Ta, V, Zr, Ti, Hf, Y, La, or Ce is preferable as M1 from the viewpoint that a good gas barrier property can be obtained. Furthermore, among these, it is considered from the various examination results that Nb, Ta, and V, which are metals of Group 5 of the long-period periodic table, are likely to be bonded to Si contained in the gas barrier layer. Further preferably, it can be used.
  • the metal M1 is a Group 5 metal (particularly Nb)
  • the metal M1 is particularly preferably Nb or Ta from which a compound with good transparency can be obtained.
  • element M2 examples include elements other than silicon and metal M1, and at least one element selected from the group consisting of elements of Group 1 to Group 14 of the long-period periodic table.
  • element M2 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), etc.
  • At least one selected from the group consisting of boron (B), aluminum (Al), titanium (Ti), and zirconium (Zr) is more preferable, and aluminum (Al) and boron (B) are more preferable.
  • Aluminum (Al) is particularly preferable.
  • the moisture and heat resistance of the gas barrier film can be further improved.
  • the element M2 may be used independently and 2 or more types may be used together.
  • the gas barrier layer contains silicon atoms, metals M1, elements M2, and oxygen atoms by performing XPS (X-ray Photoelectron Spectroscopy) composition analysis of the gas barrier layer as follows. Can do.
  • ⁇ XPS analysis conditions >> ⁇ Device: QUANTERASXM manufactured by ULVAC-PHI ⁇ X-ray source: Monochromatic Al-K ⁇ ⁇ Sputtering ion: Ar (2 keV) Depth profiles: in terms of SiO 2 sputter thickness, repeat the measurement at a predetermined thickness intervals, - obtaining the depth depth profile Quantification relative sensitivity coefficients background determined by Shirley method, from the peak area obtained Quantified using the method. For data processing, MultiPak manufactured by ULVAC-PHI was used. The elements to be analyzed were Si, metal M1, element M2, O, N, and C.
  • the measurement resolution (predetermined thickness interval) of the depth profile may be 3 nm or less, 2 nm or less, or 1 nm or less. In the embodiment of the present invention, the measurement resolution of the depth profile is 1 nm.
  • the gas barrier layer according to the present invention includes, from the resin substrate side, a region (C) that satisfies the above formula (c), a region (B) that satisfies the above formula (b), and a region (A) that satisfies the above formula (a). In this order.
  • the region (A) is a region that satisfies the above formula (a).
  • the thickness of the region (A) is preferably 1 nm or more from the viewpoint that a certain amount of thickness is necessary to function as a protective layer and from the viewpoint of obtaining a visible light reflectance suitable as a film for optical applications. It is 15 nm or less, more preferably 3 nm or more and 10 nm or less.
  • the thickness of the region (A) can be measured by the following method using XPS composition analysis.
  • the starting point is the measurement point where [M1]> [Si] ⁇ [M2], and [Si] ⁇ [M1]>
  • the region up to the measurement point immediately before the measurement point that is [M2] is defined as the region (A).
  • the sputtering depth in terms of SiO 2 with respect to one measurement point is d (unit: nm)
  • the number of measurement points (A) n measured as the region (A) is multiplied by d [(A).
  • n ⁇ d (nm)] is the thickness of the region (A).
  • the thickness of the regions (A) to (C), and [B] and [C] described later can be measured by the XPS composition analysis described above.
  • the region (B) is a region that satisfies the above formula (b).
  • the thickness of the region (B) is preferably 5 nm or more and 50 nm or less, more preferably 10 nm or more and 30 nm or less, from the viewpoint of gas barrier properties and productivity.
  • the thickness of the region (B) can be measured by the following method using XPS composition analysis.
  • the starting point is [Si] ⁇ [M1]> [M2], and [Si]> [M2] ⁇
  • the region (B) is defined up to the measurement point immediately before the measurement point that becomes [M1].
  • the sputtering depth in terms of SiO 2 for one measurement point is d (unit: nm)
  • the number of measurement points (B) n measured as the region (B) is multiplied by d [(B).
  • n ⁇ d (nm)] is the thickness of the region (B).
  • the region (C) is a region that satisfies the above formula (c).
  • the thickness of the region (C) is preferably 1 nm or more and 500 nm or less, more preferably 10 nm or more and 200 nm or less, from the viewpoint of reducing durability in a high temperature and high humidity environment and unevenness of the resin base material.
  • the thickness of the region (C) can be measured by the following method using XPS composition analysis.
  • the measurement point originated from the surface of the resin base material, starting from the measurement point where [Si]> [M2] ⁇ [M1] was first established.
  • a region (C) is defined up to the measurement point immediately before the measurement point at which the measurement point (measurement point due to the surface of the other layer when another layer is provided between the gas barrier layer and the resin base material) is obtained. To do.
  • the definition of the depth range is calculated in the same way as above. Whether or not the measurement point is due to the surface of the resin substrate (measurement point due to the surface of the other layer) is appropriately determined from the composition of the resin substrate (other layer) used.
  • the mechanism of [C]> [B] is not clear, but is estimated as follows.
  • the first layer formed by the coating method is originally [M2] / [Si] is the thickness of the first layer. It is constant over the entire area of direction.
  • the metal M1 in the second layer diffuses into the first layer while extracting oxygen from the first layer.
  • the first layer has an oxygen deficient composition, it is considered that a Si-M1 bond or a Si-M2 bond is formed.
  • the Si-M1 bond is easier to form than the Si-M2 bond, the Si-M2 bond is formed preferentially, and the phenomenon that Si diffuses into the second layer also occurs.
  • a layer containing a mixed oxide as a main component and having a reduced M2 content is formed on the surface layer side.
  • a region where [Si] ⁇ [M2] is the region (B).
  • [B] is preferably 0 to 0.2, more preferably 0 to 0.1.
  • [C] is preferably 0.001 to 0.5, and more preferably 0.002 to 0.2.
  • [C] / [B] is preferably 1.2 to 20, and more preferably 1.5 to 10.
  • Examples of the method for obtaining a gas barrier film satisfying the relationship [C]> [B] include the following method for producing a gas barrier film of the present invention. In the manufacturing method described later, this can be achieved by laminating the second layer containing the metal M1 on the first layer containing Si and the element M2 by a specific method. Specifically, the lamination is preferably performed under the condition that the metal M1 is oxygen deficient (a state where the amount of oxygen or nitrogen bonded to the maximum valence of the metal M1 is insufficient). When the metal M1 is laminated under conditions that cause oxygen vacancies, a bond is formed between the Si contained in the first layer and the metal M1 contained in the second layer (because the Si and the metal M1 are likely to form a bond). Conceivable).
  • the first layer of Si diffuses into the second layer, and the second layer of metal M1 diffuses into the first layer.
  • the element M2 in the first layer is less likely to form a bond with the metal M1 than Si, and thus the element M2 is difficult to diffuse to the second layer side.
  • the gas-barrier film which satisfy
  • [Si] [M1].
  • [Si] and [M1] at the boundary between the region (A) and the region (B) are preferably 10 atom% or more and 25 atom% or less, and 12 atom% or more and 20 atom% or less from the viewpoint of good gas barrier properties. It is more preferable that
  • [M1] [M2] at the boundary between the region (B) and the region (C).
  • [M1] and [M2] at the boundary between the region (B) and the region (C) are preferably 0 atom% or more and 15 atom% or less, and preferably 0 atom% or more and 5 atom% or less from the viewpoint of good heat and moisture resistance. It is preferable that it is 0 atm% or more and 1 atom% or less.
  • [Si] and [M1] at the boundary between the region (A) and the region (B), and [M1] and [M2] at the boundary between the region (B) and the region (C) are the first layer.
  • the [M2] / [Si] ratio and the film formation conditions of the second layer can be controlled.
  • the region (B) of the gas barrier layer has the following condition ⁇ B> when oxygen is O, nitrogen is N, and the composition of the gas barrier layer is SiM1 x O y N z. It is preferable to satisfy.
  • the above condition ⁇ B> indicates that the gas barrier layer contains the oxygen deficient composition of the complex oxide of Si and the metal M1 over a predetermined thickness.
  • the composition of the composite oxide of Si and metal M1 according to the present invention is represented by SiM1 x O y N z .
  • the composite oxide may partially include a nitride structure.
  • the maximum valence of Si is 4, the maximum valence of metal M1 is b, the valence of O is 2, and the valence of N is 3.
  • both Si and metal M1 are bonded to either O or N. Will be.
  • the composite valence calculated by weighted averaging the maximum valence of each element according to the abundance ratio of each element is “maximum valence”. It shall be adopted as the value of b.
  • the region [b] is a region satisfying x ⁇ 1.
  • the region [b] satisfying this condition is considered to contribute to the improvement of the gas barrier property.
  • the region [b] preferably includes a region satisfying 0.5 ⁇ x ⁇ 1. It is more preferable to include a region that satisfies 6 ⁇ x ⁇ 1, and it is further preferable to include a region that satisfies 0.7 ⁇ x ⁇ 1.
  • the region [b] satisfying (2y + 3z) / (4 + bx) ⁇ 1.0 is present, the effect of improving the gas barrier property is exhibited, but the region [b] Preferably satisfies (2y + 3z) / (4 + bx) ⁇ 0.98, more preferably satisfies (2y + 3z) / (4 + bx) ⁇ 0.95, and (2y + 3z) / (4 + bx) ⁇ 0. More preferably, 92 is satisfied.
  • the value of (2y + 3z) / (4 + bx) in the region [b] decreases, the effect of improving the gas barrier property increases, but the absorption with visible light also increases.
  • (2y + 3z) / (4 + bx) ⁇ 0.7 is preferable, and (2y + 3z) / (4 + bx) ⁇ 0.75. Is more preferable, and (2y + 3z) / (4 + bx) ⁇ 0.8 is more preferable.
  • the thickness of the region [b] where good gas barrier properties can be obtained is preferably 2 nm or more, more preferably 3 nm or more, and more preferably 4 nm or more as the sputtering thickness in terms of SiO 2. More preferably, it is more preferably 5 nm or more.
  • the manufacturing method of the gas barrier film of the present invention is not particularly limited, (1) a step of forming a first layer containing a silicon atom, an element M2, and an oxygen atom on a resin substrate; (2) the first And a step of forming a second layer containing metal M1 and oxygen atoms on one layer.
  • Step of forming first layer As a method of forming the first layer containing silicon atoms, element M2, and oxygen atoms, a method including vapor phase film-forming or applying and drying a coating liquid containing a compound containing polysilazane and element M2 (Hereinafter, also simply referred to as a coating method). Among these, the coating method is preferable from the viewpoint of productivity.
  • the vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, and ion plating, plasma CVD (chemical), and the like. Examples thereof include chemical vapor deposition methods such as vapor deposition method and ALD (Atomic Layer Deposition). Among them, the physical vapor deposition method is preferable and the sputtering method is more preferable because the film formation is possible without damaging the lower layer and the productivity is high.
  • bipolar sputtering, magnetron sputtering, dual magnetron (DMS) sputtering 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.
  • RF high frequency
  • 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 By controlling the sputtering phenomenon so as to be in the transition region, a metal oxide film can be formed at a high film formation speed, which is preferable.
  • a thin film of an element M2 oxide can be formed by using a target containing the element M2 as a target and further introducing oxygen into the process gas.
  • an oxide target of the element M2 can be used.
  • the inert gas used for the process gas He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used.
  • a thin film such as an oxide, nitride, nitride oxide, or carbonate of the element M2 can be formed.
  • 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, film material, film thickness, and the like.
  • Examples of the target including the element M2 include a plurality of targets described in, for example, JP 2000-026961 A, JP 2009-215651 A, JP 2003-160862 A, JP 2012-007218 A, and the like. A target containing any of these elements can be used.
  • (1-2) Coating Method Another method for forming the first layer includes a method of coating and drying a coating solution containing polysilazane and a compound containing the element M2.
  • Polysilazane is a polymer having a silicon-nitrogen bond, such as SiO 2 , Si 3 N 4 having a bond such as Si—N, Si—H, or N—H, and ceramics such as both intermediate solid solutions SiO x N y. It is a precursor inorganic polymer.
  • the polysilazane preferably has the following structure.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . At this time, R 1 , R 2 and R 3 may be the same or different.
  • n is an integer
  • the polysilazane having the structure represented by the general formula (I) is determined to have a number average molecular weight of 150 to 150,000 g / mol. Is preferred.
  • one of preferred embodiments is perhydropolysilazane in which all of R 1 , R 2 and R 3 are hydrogen atoms.
  • polysilazane has a structure represented by the following general formula (II).
  • R 1 ′ , R 2 ′ , R 3 ′ , R 4 ′ , R 5 ′ and R 6 ′ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group.
  • R 1 ′ , R 2 ′ , R 3 ′ , R 4 ′ , R 5 ′ and R 6 ′ may be the same or different.
  • n ′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined to have a number average molecular weight of 150 to 150,000 g / mol. It is preferred that Note that n ′ and p may be the same or different.
  • R 1 ′ , R 3 ′ and R 6 ′ each represent a hydrogen atom, and R 2 ′ , R 4 ′ and R 5 ′ each represent a methyl group;
  • R 1 ' , R 3' and R 6 ' each represents a hydrogen atom, R 2' , R 4 ' each represents a methyl group, and R 5' represents a vinyl group;
  • R 1 ' , R 3' , R 4 A compound in which ' and R 6' each represent a hydrogen atom and R 2 ' and R 5 ' each represents a methyl group is preferred.
  • polysilazane has a structure represented by the following general formula (III).
  • R 1 ′′ , R 2 ′′ , R 3 ′′ , R 4 ′′ , R 5 ′′ , R 6 ′′ , R 7 ′′ , R 8 ′′ and R 9 ′′ are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, wherein R 1 ′′ , R 2 ′′ , R 3 ′′ , R 4 ′′ , R 5 ′′ , R 6 ′′ , R 7 ′′ , R 8 ′′ and R 9 ′′ may be the same or different.
  • n ′′, p ′′ and q are integers, and the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. It is preferable to be determined as follows. Note that n ′′, p ′′, and q may be the same or different.
  • R 1 ′′ , R 3 ′′ and R 6 ′′ each represent a hydrogen atom
  • R 2 ′′ , R 4 ′′ , R 5 ′′ and R 8 ′′ each represent a methyl group.
  • R 9 ′′ represents a (triethoxysilyl) propyl group
  • R 7 ′′ represents an alkyl group or a hydrogen atom.
  • the organopolysilazane in which a part of the hydrogen atom portion bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material as a base by having an alkyl group such as a methyl group and is hard.
  • the ceramic film made of brittle polysilazane can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. For this reason, these perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.
  • Perhydropolysilazane is preferably exemplified as polysilazane. Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The number average molecular weight (Mn) is about 600 to 2000 (polystyrene conversion), and there are liquid or solid substances, and the state varies depending on the molecular weight.
  • Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a coating solution for forming the first layer.
  • examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, and SP140 manufactured by Merck Co., Ltd. . These polysilazane solutions can be used alone or in combination of two or more.
  • polysilazane examples include, but are not limited to, for example, a silicon alkoxide-added polysilazane obtained by reacting the above polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-238827), a glycidol reacted Glycidol-added polysilazane (Japanese Patent Laid-Open No. 6-122852) obtained by reaction, alcohol-added polysilazane obtained by reacting alcohol (Japanese Patent Laid-Open No.
  • metal carboxylate obtained by reacting metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal obtained by adding metal fine particles Fine particle added policy Zhang such (JP-A-7-196986), and a polysilazane ceramic at low temperatures.
  • Examples of the compound containing the element M2 used in the coating method include, for example, aluminum isopropoxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, Aluminum tri-n-butylate, aluminum tri-sec-butylate, aluminum ethyl acetoacetate diisopropylate, acetoalkoxy aluminum diisopropylate, calcium isopropylate, titanium tetraisopropoxide (titanium (IV) isopropylate), zirconium tetraacetylacetate Nate, aluminum diisopropylate monoaluminum tert-butylate, aluminum trisethyl acetoacetate, Luminium oxide isopropoxide trimer, zirconium (IV) isopropylate, tris (2,4-pentanedionato) titanium (V), tetrakis
  • the compound containing the element M2 is preferably a metal alkoxide compound, and among the metal alkoxide compounds, a compound having a branched alkoxy group is more preferable from the viewpoint of reactivity, solubility, and the like, a 2-propoxy group, or More preferred is a compound having a sec-butoxy group. Moreover, the compound which has an ethoxy group from a viewpoint of gas barrier performance, adhesiveness, etc. is more preferable.
  • metal alkoxide compounds having an acetylacetonate group are also preferred.
  • the acetylacetonate group is preferable because it has an interaction with the central element of the alkoxide compound due to the carbonyl structure, so that handling is easy.
  • a compound having a plurality of alkoxide groups or acetylacetonate groups is more preferable from the viewpoint of reactivity and film composition.
  • metal alkoxide compound a commercially available product or a synthetic product may be used.
  • commercially available products include, for example, AMD (aluminum diisopropylate mono-sec-butylate), ASBD (aluminum sec-butylate), ALCH (aluminum ethyl acetoacetate diisopropylate), ALCH-TR (aluminum tris) Ethyl acetoacetate), aluminum chelate M (aluminum alkyl acetoacetate / diisopropylate), aluminum chelate D (aluminum bisethylacetoacetate / monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) , Kawaken Fine Chemical Co., Ltd.), Preneact (registered trademark) AL-M (acetoalkoxyaluminum diisopropylate, Ajinomoto Fine Chemical Co., Ltd.), Olga Ts
  • the coating liquid containing polysilazane inert gas atmosphere. This is to prevent the metal alkoxide compound from reacting with moisture and oxygen in the atmosphere and causing intense oxidation.
  • the solvent for preparing the coating solution for forming the first layer is not particularly limited as long as it can dissolve the compound containing polysilazane and the element M2, but water and reactive groups that easily react with polysilazane (for example, an organic solvent that does not contain a hydroxyl group or an amine group and is inert to polysilazane is preferable, and an aprotic organic solvent is more preferable.
  • the solvent is an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, terpenes, etc.
  • aprotic solvent for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, terpenes, etc.
  • Hydrogen solvents Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like.
  • the solvent is selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.
  • the concentration of polysilazane in the coating solution for forming the first layer is not particularly limited and varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 1 to 80% by mass, more preferably 5 to 50% by mass, More preferably, it is 10 to 40% by mass.
  • the coating solution for forming the first layer preferably contains a catalyst from the viewpoint of promoting modification by vacuum ultraviolet rays.
  • a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, Amine catalysts such as N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds.
  • the concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on polysilazane.
  • concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on polysilazane.
  • the following additives may be used as necessary.
  • cellulose ethers, cellulose esters for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc.
  • natural resins for example, rubber, rosin resin, etc., synthetic resins
  • Aminoplasts particularly urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyester resins or modified polyester resins, epoxy resins, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.
  • a method of applying the first layer forming coating solution a conventionally known appropriate wet coating method may be employed. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, die coating method, gravure printing method and the like. It is done.
  • the coating thickness can be appropriately set according to the preferred thickness and purpose.
  • the coating film After applying the coating solution, it is preferable to dry the coating film.
  • the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable first layer can be obtained. The remaining solvent can be removed later.
  • the drying temperature of the coating film varies depending on the substrate to be applied, but is preferably 50 to 200 ° C.
  • the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat.
  • the temperature can be set by using a hot plate, oven, furnace or the like.
  • the drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes.
  • the drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.
  • the manufacturing method may include a step of removing moisture from the coating film obtained by applying the first layer forming coating solution.
  • a form of dehumidification while maintaining a low humidity environment is preferable. Since the humidity in the low humidity environment varies depending on the temperature, the relationship between the temperature and the humidity shows a preferable form by the definition of the dew point temperature.
  • the preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), the more preferable dew point temperature is ⁇ 5 ° C. or lower (temperature 25 ° C./humidity 10%), and the time for maintaining is the thickness of the first layer It is preferable to set appropriately.
  • the dew point temperature is ⁇ 5 ° C. or lower and the maintaining time is 1 minute or longer.
  • the lower limit of the dew point temperature is not particularly limited, but is usually ⁇ 50 ° C. or higher, and preferably ⁇ 40 ° C. or higher. This is a preferred form from the viewpoint of promoting the dehydration reaction of the first layer converted to silanol by removing water before or during the reforming treatment.
  • the second layer may be formed continuously.
  • the first layer is irradiated with vacuum ultraviolet rays to form polysilazane silicon oxynitride, etc. It is preferable to carry out the conversion reaction into If the first layer containing the element M2 is formed, the composition of the gas barrier layer that is finally obtained by storage over time until the second layer is formed can be suppressed without irradiation with vacuum ultraviolet rays. , Productivity and production stability are improved.
  • the composition of the gas barrier layer finally obtained is hardly changed compared to a production method having no storage step, and production stability is further improved. Therefore, in actual production, there are fewer restrictions on the coating process, the modification process, and the like, and there are fewer restrictions on the substrate conveyance speed in the coating process, the modification process, etc., and the productivity is further improved.
  • UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used.
  • it can be processed in an ultraviolet baking furnace equipped with an ultraviolet ray generation source.
  • the ultraviolet baking furnace itself is generally known.
  • an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used.
  • the object when it is a long film, it can be converted to ceramics by continuously irradiating ultraviolet rays in a drying zone equipped with the ultraviolet ray generation source as described above while being conveyed.
  • the time required for ultraviolet irradiation depends on the resin substrate used and the composition and concentration of the first layer, but is preferably 0.1 second to 10 minutes, more preferably 0.5 seconds to 3 minutes.
  • Excimer irradiation treatment uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds the atoms only to photons called photon processes.
  • a film containing silicon oxynitride is formed at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly.
  • the vacuum ultraviolet ray source in the present invention may be any source that generates light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator (for example, Xe excimer lamp) having a maximum emission at about 172 nm, and an emission line at about 185 nm.
  • Excimer radiator for example, Xe excimer lamp
  • the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.
  • the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.
  • ⁇ Excimer lamps have high light generation efficiency and can be lit with low power.
  • light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the irradiation object is suppressed.
  • it is suitable for flexible film materials such as PET that are easily affected by heat.
  • Oxygen is required for the reaction at the time of vacuum ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease.
  • it is preferably performed in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of irradiation with vacuum ultraviolet rays is preferably 10 to 20,000 volume ppm (0.001 to 2 volume%), and preferably 50 to 10,000 volume ppm (0.005 to 1 volume%). More preferably.
  • the water vapor concentration during the conversion process is preferably in the range of 1,000 to 4,000 volume ppm.
  • the gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays is preferably a dry inert gas, and particularly preferably dry nitrogen gas from the viewpoint of cost.
  • the oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.
  • the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane coating is preferably 1 mW / cm 2 to 10 W / cm 2 , more preferably 30 mW / cm 2 to 200 mW / cm 2. and further preferably 50mW / cm 2 ⁇ 160mW / cm 2. If it is 1 mW / cm 2 or more, the reforming efficiency is improved, and if it is 10 W / cm 2 or less, ablation that can occur in the coating film and damage to the substrate can be reduced.
  • the amount of irradiation energy (irradiation amount) of vacuum ultraviolet rays on the surface of the coating film is preferably 0.1 J / cm 2 or more and less than 1 J / cm 2 , preferably 0.2 to 0.8 J / cm 2. more preferably cm 2. If the amount of irradiation energy is within this range, even if it has a step of storing in a high-temperature and high-humidity environment between the formation of the first layer and the formation of the second layer, it is finally obtained.
  • the composition of the gas barrier layer hardly changes, and the production stability is further improved. Further, in actual production, there are fewer restrictions on the coating process and the modification process, and there are fewer restrictions on the substrate conveyance speed in the coating process and the modification process, and the productivity is further improved.
  • the vacuum ultraviolet ray used may be generated by plasma formed of a gas containing at least one of CO, CO 2 and CH 4 .
  • the gas containing at least one of CO, CO 2 and CH 4 hereinafter also referred to as carbon-containing gas
  • the carbon-containing gas may be used alone, but carbon containing rare gas or H 2 as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.
  • the content of the element M2 in the first layer is preferably 0.001 to 50% by mass, and more preferably 0.1 to 40% by mass with respect to the mass of the entire first layer.
  • the content of the element M2 in the first layer is preferably 5 to 20 mol%, more preferably 5 to 10 mol% with respect to 100 mol% of silicon (Si).
  • the thickness of the first layer formed as described above is preferably 10 to 500 nm, and more preferably 30 to 300 nm.
  • the method for forming the second layer containing the metal M1 and oxygen atoms is preferably a vapor deposition method from the viewpoint of easily forming the regions (A) and (B).
  • the vapor deposition method is not particularly limited, and specific examples include the method described in (1-1) above.
  • 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, a transition metal compound thin film such as an oxide, nitride, nitride oxide, or carbonate of metal M1 can be formed. Examples of film formation conditions in the vapor phase film formation method include applied power, discharge current, discharge voltage, time, and the like. These may be appropriately selected according to the apparatus used, the material of the film, the film thickness, and the like. it can.
  • a target containing an oxide of metal M1 is preferable.
  • a sputtering method used as a target containing an oxide of the metal M1 is preferable because the film formation rate is higher and the productivity is higher.
  • the set thickness of the second layer is preferably 1.5 to 30 nm, and preferably 3 to 20 nm.
  • An anchor coat layer may be formed on the surface of the resin substrate on the side where the gas barrier layer according to the present invention is formed for the purpose of improving the adhesion between the resin substrate and the gas barrier layer.
  • polyester resins As anchor coating agents used for the anchor coat layer, polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, alkyl titanates, etc. are used alone Or in combination of two or more.
  • the above-mentioned anchor coating agent is coated on the support 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 be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition.
  • a vapor phase 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 phase method, the gas generated from the substrate side is blocked to some extent.
  • an anchor coat layer can be formed for the purpose of 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 hard coat layer may be provided on the surface (one side or both sides) of the resin substrate.
  • the material contained in the hard coat layer include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because it is easy to mold.
  • 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 functional resin, ie, a 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. You may use the commercially available resin base material in which the hard-coat layer is formed previously.
  • the thickness of the hard coat layer is preferably from 0.1 to 15 ⁇ m, more preferably from 0.5 to 5 ⁇ m, from the viewpoint of smoothness and bending resistance.
  • the gas barrier film of the present invention may have a smooth layer between the resin substrate and the gas barrier layer.
  • the smooth layer used in the present invention flattens the rough surface of the resin base material where protrusions and the like exist, or flattens the unevenness and pinholes generated in the transparent inorganic compound layer by the protrusions existing on the resin base material.
  • Such a smooth layer is basically produced by curing a photosensitive material or a thermosetting material.
  • the photosensitive material for the smooth layer examples include a resin composition containing an acrylate compound having a radical-reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, and urethane acrylate. And a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. Specifically, 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 resistant epoxy resin), various silicon resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG manufactured by Nittobo Co., Ltd.
  • Examples include coats, thermosetting urethane resins composed of acrylic polyols and isocyanate prepolymers, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicon resins.
  • an epoxy resin-based material having heat resistance is particularly preferable.
  • the method for forming the smooth layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, a dip method, or a dry coating method such as an evaporation method.
  • a wet coating method such as a spin coating method, a spray method, a blade coating method, a dip method, or a dry coating method such as an evaporation method.
  • 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 formability and preventing the generation of pinholes in the film.
  • the thickness of the smooth layer is preferably in the range of 1 to 10 ⁇ m and more preferably in the range of 2 to 7 ⁇ m from the viewpoint of improving the heat resistance of the film and facilitating balance adjustment of the optical properties of the film.
  • the smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601: 2001, and the 10-point average roughness Rz is preferably 10 nm or more and 30 nm or less. If it is this range, even if it is a case where a gas barrier layer is apply
  • the gas barrier film according to 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.
  • the electronic device examples include an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device is preferably an organic EL element or a solar cell, and more preferably an organic EL element.
  • organic EL element organic electroluminescence element
  • LCD liquid crystal display element
  • PV solar cell
  • resin base material As the resin base material, a 100 ⁇ m-thick polyethylene terephthalate film (Lumirror (registered trademark) (U48), manufactured by Toray Industries, Inc.) with easy adhesion treatment on both surfaces was used. A clear hard coat layer having a thickness of 0.5 ⁇ m and having an antiblock function was formed on the surface of the resin substrate opposite to the surface on which the gas barrier layer was formed. That is, a UV curable resin (manufactured by Aika Kogyo Co., Ltd., product number: Z731L) was applied on a resin substrate so that the dry film thickness was 0.5 ⁇ m, and then dried at 80 ° C., and then under high pressure in the 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 substrate 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 film thickness of 2 ⁇ m, then dried at 80 ° C., and then using a high-pressure mercury lamp in the air. Then, curing was performed under the condition of an irradiation energy amount of 0.5 J / cm 2 . In this way, a resin substrate with a clear hard coat layer was obtained.
  • this resin substrate with a clear hard coat layer is simply referred to as a resin substrate for convenience.
  • Example 1-1 to 1-3 Comparative Examples 1-1 to 1-4
  • the first layer and the second layer were formed as follows to produce a gas barrier film.
  • a first layer was formed on one surface of the resin base material using a magnetron sputtering apparatus (manufactured by Canon Anelva Co., Ltd .: Model EB1100).
  • the following targets and film formation conditions were used as targets, Ar and O 2 were used as process gases, and film formation was performed by DC sputtering.
  • the sputtering power source power was 5.0 W / cm 2 and the film forming pressure was 0.4 Pa.
  • the composition was adjusted by adjusting the oxygen partial pressure.
  • the condition of the composition is determined by adjusting the oxygen partial pressure, and the condition in which the composition near the depth of 10 nm from the surface layer becomes the target composition is found. Applied.
  • film thickness change data with respect to the film formation time is obtained in the range of 100 to 300 nm, the film formation time per unit time is calculated, and then the film formation time is set to the set film thickness. The film thickness was adjusted by setting.
  • T1 A silicon target containing no M2 was produced by the method described in Comparative Example 1 of JP2012-007218A. However, the target shape was a plate shape; T2: A target containing 1.5% by mass of boron with respect to silicon as M2 was produced by the method described in Example 1 of JP2012-007218A. However, the target shape was a plate shape; T3: According to the same method as that of the target 1 of the present invention described in “Aspects of the Invention” of JP-A-2003-160862, M2 contains 5% by mass of aluminum, 12% by mass of phosphorus, and the balance (almost 95 A target having a mass%) of silicon was produced. Since the phosphorus content was very small, no analysis was performed on phosphorus in the composition analysis described below.
  • T1-1 T1 was used as a target, and in the above XPS analysis, the oxygen partial pressure was adjusted so that the composition of the layer was SiO 2 . Also, the film formation time was set so that the film thickness was 120 nm; T1-2: Performed in the same manner as T1-1 except that the film formation time was set so that the film thickness was 100 nm; T2-1: Performed in the same manner as T1-1 except that T2 was used as a target and the film formation time was set to 120 nm in the T2 condition determination; T2-2: The same as T2-1, except that the film formation time was set so that the film thickness was 100 nm; T3-1: Performed in the same manner as T1-1 except that T3 was used as a target and a film formation time was set at which the film thickness was 120 nm in the T3 condition determination; T3-2: Performed in the same manner as T3-1 except that the film formation time was set so that the film thickness was 100 nm.
  • a second layer was formed on the first layer.
  • the same apparatus as that used for film formation of the first layer was used, and the film composition and film thickness were set by the same method as that for film formation of the first layer.
  • ⁇ Target> T4 A commercially available oxygen-deficient niobium oxide target was used. The composition was Nb 12 O 29 .
  • T4 was used as a target, and the oxygen partial pressure was 12%. Also, the film formation time was set so that the film thickness was 15 nm; T4-2: Performed in the same manner as T4-1 except that the film formation time was set so that the film thickness was 10 nm; T4-3: Performed in the same manner as T4-1 except that the film formation time was set so that the film thickness was 5 nm.
  • Example 2-1 to 2-15 Comparative Examples 2-1 to 2-7
  • the first layer and the second layer were formed as follows to produce a gas barrier film.
  • the coating liquid (S1 to S9) containing polysilazane as shown below is applied on one surface of the resin substrate, dried to form a coating film, and then modified by vacuum ultraviolet irradiation under the conditions shown below
  • the first layer was formed (S1-1, S2-1, S2-3 to 9-1) or without modification (S1-2, S2-2).
  • the coating solution (S1 to S9) was applied on the resin base material by spin coating so as to have a dry film thickness shown in Table 2 below, and dried at 80 ° C. for 2 minutes.
  • vacuum ultraviolet irradiation treatment was performed on the dried coating film under the film forming conditions shown in Table 2 using the vacuum ultraviolet irradiation apparatus of FIG. 1 having an 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.
  • reference numeral 1 denotes an apparatus chamber, which supplies appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) to the inside and exhausts gas from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber.
  • the oxygen concentration can be maintained at a predetermined concentration.
  • 2 is an Xe excimer lamp having a double tube structure that irradiates 172 nm vacuum ultraviolet light (excimer lamp light intensity: 130 mW / cm 2 )
  • 3 is an excimer lamp holder that also serves as an external electrode
  • 4 is a sample stage.
  • the sample stage 4 can reciprocate horizontally in the apparatus chamber 1 at a predetermined speed (V in FIG. 1) by a moving means (not shown).
  • the sample stage 4 can be maintained at a predetermined temperature by a heating means (not shown).
  • Reference numeral 5 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 6 denotes a light-shielding plate which prevents the application of the sample from being irradiated with vacuum ultraviolet rays during aging of the Xe excimer lamp 2.
  • the energy applied to the surface of the sample coating layer in the vacuum ultraviolet irradiation step was measured using a 172 nm sensor head using an ultraviolet integrated light meter (C8026 / H8025 UV POWER METER) manufactured by Hamamatsu Photonics Co., Ltd.
  • the sensor head is installed in the center of the sample stage 4 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 1 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as in the process, and the sample stage 4 was moved at a speed of 0.5 m / min for measurement.
  • 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 amount of irradiation energy shown in Table 2 was adjusted by adjusting the moving speed of the sample stage.
  • the vacuum ultraviolet irradiation was performed after aging for 10 minutes.
  • ⁇ Coating solution> S1 Dibutyl ether solution containing 20% by mass of perhydropolysilazane (Merck Co., Ltd., NN120-20) and amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH) ) And a dibutyl ether solution of 20% by mass of perhydropolysilazane (manufactured by Merck & Co., Inc., NAX120-20) at a ratio of 4: 1 (mass ratio), and further a solid content concentration of 3% by mass with dibutyl ether.
  • the coating solution S1 was prepared by dilution.
  • the coating solution was prepared in a glove box.
  • S2 An aluminum compound solution was prepared by diluting aluminum ethyl acetoacetate diisopropylate with dibutyl ether so that the solid concentration was 3% by mass. S1 and the aluminum compound solution are mixed so that the Al / Si atomic ratio is 0.01, heated to 80 ° C. with stirring, held at 80 ° C. for 2 hours, and then gradually lowered to room temperature (25 ° C.). Chilled.
  • a coating solution S2 was prepared;
  • S3 A coating solution S3 was prepared in the same manner as S2, except that S1 and the aluminum compound solution prepared in S2 were mixed so that the Al / Si atomic ratio was 0.1;
  • S4 Coating solution S4 was prepared in the same manner as S2, except that S1 and the aluminum compound solution prepared in S2 were mixed so that the Al / Si atomic ratio was 0.15;
  • S5 A coating solution S5 was prepared in the same manner as S2, except that S1 and the aluminum compound solution prepared in S2 were mixed so that the Al / Si atomic ratio was 0.005;
  • S6 Coating solution S6 was prepared in the same manner as S2, except that S1 and the aluminum compound solution prepared in S2 were mixed so that the Al / Si atomic ratio was 0.03;
  • S7 A boron compound solution was prepared by diluting triisopropyl borate with dibutyl ether so that the solid concentration was 3% by mass.
  • S1 and boron compound solution are mixed so that the B / Si atomic ratio is 0.01, heated to 80 ° C. with stirring, held at 80 ° C. for 2 hours, and then gradually brought to room temperature (25 ° C.). Chilled.
  • a coating solution S7 was prepared;
  • S1 and the titanium compound liquid were mixed so that the Ti / Si atomic ratio was 0.01, the temperature was raised to 80 ° C. with stirring, the temperature was maintained at 80 ° C. for 2 hours, and then gradually increased to room temperature (25 ° C.). Chilled.
  • a coating solution S8 was prepared;
  • S9 A zirconium compound solution was prepared by diluting zirconium tetraacetylacetonate with dibutyl ether so that the solid concentration was 3% by mass.
  • S1 and the zirconium compound liquid were mixed so that the Zr / Si atomic ratio was 0.01, the temperature was raised to 80 ° C. with stirring, the temperature was maintained at 80 ° C. for 2 hours, and then gradually increased to room temperature (25 ° C.). Chilled.
  • a coating solution S9 was prepared; ⁇ Film formation conditions> S1-1: Using the coating solution S1, coating and drying were performed according to the above-described method so that the dry film thickness was 100 nm.
  • a second layer was formed on the first layer.
  • a magnetron sputtering apparatus (Canon Anelva Co., Ltd .: Model EB1100) was used, and the film composition and film thickness were set by the same method.
  • T4 A commercially available oxygen-deficient niobium oxide target was used.
  • the composition was Nb 12 O 29 ;
  • T5 A commercially available Ta target was used.
  • T4 T4 was used as a target, and the oxygen partial pressure was set to 12% by volume. Also, the film formation time was set so that the film thickness was 15 nm; T4-2: Performed in the same manner as T4-1 except that the film formation time was set so that the film thickness was 10 nm; T4-3: Performed in the same manner as T4-1 except that the film formation time was set so that the film thickness was 5 nm; T4-4: The same as T4-1 except that the film formation time was set so that the film thickness was 2 nm; T4-5: The same as T4-1, except that the film formation time was set so that the film thickness was 1 nm; T4-6: Film formation was performed without introducing oxygen using T4 as a target.
  • the film formation time was set so that the film thickness was 5 nm; T4-7: The same as T4-6, except that the film formation time was set so that the film thickness was 2 nm; T5-1: T5 was used as a target, and the oxygen partial pressure was 18% by volume. The film formation time was set so that the film thickness was 15 nm.
  • the thickness of the regions (A) to (C), the Si ratio at the boundary between the regions (A) and (B), the composition of the region (b), the regions (B) and (C) The M1 ratio, [B], and [C] at the boundary were measured.
  • Samples stored for 24 hours in a high-temperature and high-humidity environment of 85 ° C. and 85% RH with the gas barrier layer exposed were prepared, and Ca method evaluation cells were prepared. That is, three types of samples for gas barrier property evaluation were prepared.
  • thermosetting sheet-like adhesive epoxy resin
  • Ca was vapor-deposited with a size of 20 mm ⁇ 20 mm through a mask in the center of the glass plate using a vacuum vapor deposition apparatus manufactured by ALS Technology.
  • the thickness of Ca was 80 nm.
  • the glass plate on which Ca was vapor-deposited was taken out into the glove box, placed so that the sealing resin layer surface of the barrier film to which the sealing resin layer was bonded and the Ca vapor-deposited 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.
  • a sample using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample was similarly 85. It was stored in a high-temperature and high-humidity environment at 85 ° C. and it was confirmed that no corrosion of metallic calcium occurred even after 100 hours.
  • the transmission density was measured using the evaluation cell.
  • a black and white transmission density meter TM-5 manufactured by Konica Minolta Co., Ltd. was used for transmission density measurement.
  • the transmission density was measured at any four points in the cell, and the average value was calculated. The same applies hereinafter.
  • the evaluation cell After measuring the initial value of the transmission density of each evaluation cell, the evaluation cell is stored in an 85 ° C. and 85% RH environment, and is observed every 1 hour, 5 hours, 10 hours, and thereafter every 5 hours. The transmission density was measured. The observation time when the transmission density became less than 50% of the initial value was determined, and evaluated using the following indices.
  • Indicator Time for transmission density to be less than 50% 0: less than 1 hour 1: 1 to less than 5 hours 2: 5 to 10 hours 3: 10 to 25 hours 4: 25 to 50 hours 5:50 Over time.
  • compositions and evaluation results of Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-4 are shown in Table 1 and Table 2 below.
  • Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2 The composition and evaluation results of ⁇ 7 are shown in Table 3 and Table 4 below, respectively. “No film formation” in the film formation condition column for the second layer in Tables 1 and 3 indicates that the second layer was not formed.
  • the gas barrier layer composition of Table 4 is the result of measuring about the sample which formed the 2nd layer, after storing for 24 hours in 20 degreeC50% RH environment after 1st layer formation.
  • the gas barrier films of Examples 1-1 to 1-3 and Examples 2-1 to 2-15 have gas barrier properties even after being stored in a high temperature and high humidity environment. It turns out that it is hard to deteriorate and is excellent in durability.
  • the second layer is formed afterwards regardless of the change in the storage environment after the first layer is formed.
  • a gas barrier film having excellent gas barrier properties can be obtained. That is, the production method according to the present invention is excellent in production stability and productivity.

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Abstract

La présente invention concerne un film de barrière contre les gaz qui comprend, sur une base de résine, une couche de barrière contre les gaz qui contient des atomes de silicium, un métal M1 autre que le silicium, un élément M2 autre que le silicium et le métal M1, et des atomes d'oxygène. Si [Si] (% atome) est le rapport de la quantité des atomes de silicium à la quantité totale des atomes de silicium, du métal M1, de l'élément M2, des atomes d'oxygène, des atomes d'azote et des atomes de carbone dans la couche de barrière contre les gaz, [M1] (% atome) est le rapport de la quantité du métal M1 à la quantité totale des atomes de silicium, du métal M1, de l'élément M2, des atomes d'oxygène, des atomes d'azote et des atomes de carbone dans la couche de barrière contre les gaz, et [M2] (% atome) est le rapport de la quantité de l'élément M2 à la quantité totale des atomes de silicium, du métal M1, de l'élément M2, des atomes d'oxygène, des atomes d'azote et des atomes de carbone dans la couche de barrière contre les gaz, ce film de barrière contre les gaz présente séquentiellement une région (C) qui satisfait à la formule (c), une région (B) qui satisfait à la formule (b) et une région (A) qui satisfait à la formule (a) dans cet ordre, à partir du côté de la base de résine.
PCT/JP2016/071322 2015-07-23 2016-07-20 Film de barrière contre les gaz et son procédé de production WO2017014246A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013157515A1 (fr) * 2012-04-19 2013-10-24 コニカミノルタ株式会社 Procédé de fabrication de film conducteur transparent, film conducteur transparent et dispositif électronique
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
WO2015002156A1 (fr) * 2013-07-01 2015-01-08 コニカミノルタ株式会社 Film barrière contre les gaz et son procédé de production, et dispositif électronique utilisant un tel film
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
JP2015033764A (ja) * 2013-08-07 2015-02-19 コニカミノルタ株式会社 ガスバリア性フィルム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013157515A1 (fr) * 2012-04-19 2013-10-24 コニカミノルタ株式会社 Procédé de fabrication de film conducteur transparent, film conducteur transparent et dispositif électronique
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
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
WO2015002156A1 (fr) * 2013-07-01 2015-01-08 コニカミノルタ株式会社 Film barrière contre les gaz et son procédé de production, et dispositif électronique utilisant un tel film
JP2015033764A (ja) * 2013-08-07 2015-02-19 コニカミノルタ株式会社 ガスバリア性フィルム

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