WO2015119260A1 - Polysilazane modifié, solution de revêtement contenant ledit polysilazane modifié, et film barrière contre les gaz obtenu à l'aide de ladite solution de revêtement - Google Patents

Polysilazane modifié, solution de revêtement contenant ledit polysilazane modifié, et film barrière contre les gaz obtenu à l'aide de ladite solution de revêtement Download PDF

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WO2015119260A1
WO2015119260A1 PCT/JP2015/053435 JP2015053435W WO2015119260A1 WO 2015119260 A1 WO2015119260 A1 WO 2015119260A1 JP 2015053435 W JP2015053435 W JP 2015053435W WO 2015119260 A1 WO2015119260 A1 WO 2015119260A1
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sih
barrier layer
film
polysilazane
layer
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Japanese (ja)
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伊東　宏明
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コニカミノルタ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/62—Nitrogen atoms
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations

Definitions

  • the present invention relates to a modified polysilazane, a coating solution containing the modified polysilazane, and a gas barrier film produced using the coating solution. More specifically, the present invention is produced using a modified polysilazane used in an electronic device such as an organic electroluminescence (EL) element, a solar cell element, and a liquid crystal display, a coating solution containing the modified polysilazane, and the coating solution.
  • EL organic electroluminescence
  • the present invention relates to a gas barrier film.
  • a gas barrier film formed by laminating a plurality of layers including thin films of metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide on the surface of a plastic substrate or film is used to block various gases such as water vapor and oxygen.
  • metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide
  • it is widely used in packaging applications for preventing deterioration of foods, industrial products, medicines and the like.
  • a chemical deposition method in which an organic silicon compound typified by tetraethoxysilane (TEOS) is used to grow on a substrate while performing oxygen plasma oxidation under reduced pressure.
  • TEOS tetraethoxysilane
  • vapor phase methods such as a physical vapor deposition method (vacuum evaporation method or sputtering method) in which metal Si is evaporated using a semiconductor laser and deposited on a substrate in the presence of oxygen using a semiconductor laser.
  • inorganic vapor deposition methods have been preferably applied to the formation of inorganic films such as silicon oxide, silicon nitride, and silicon oxynitride, and examination of the composition range of inorganic films for obtaining good gas barrier properties. Many studies have been made on the layer structure including these inorganic films.
  • such a defect in the inorganic film causes the generation of a black spot called a dark spot that does not emit light, or the size of the dark spot grows under high temperature and high humidity. Will also affect.
  • the coating of the inorganic precursor compound solution applied on the inorganic film by the above-mentioned vapor phase method and dried By modifying the layer with heat, the defect portion of the inorganic film formed by the above-mentioned vapor phase method is effectively repaired, and further, the laminated film itself has been studied to improve the gas barrier property.
  • polysilazane as an inorganic precursor compound, studies have been made to develop a high gas barrier property by repairing the above-described defect portion.
  • Bonding of atoms is called a photon process using light energy having a wavelength of 100 to 200 nm called vacuum ultraviolet light (hereinafter also referred to as “VUV” or “VUV light”) having an energy larger than the bonding force between each atom of polysilazane.
  • VUV vacuum ultraviolet light
  • a silicon oxynitride film or a silicon oxide film can be formed at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by the action of only photons.
  • a first barrier layer formed by chemical vapor deposition on a substrate and a silicon compound such as polysilazane are applied.
  • a gas barrier film having a second barrier layer formed by irradiating a film and irradiating energy rays (for example, vacuum ultraviolet light) is disclosed.
  • the gas barrier film exhibits high barrier performance and is excellent in bending resistance, smoothness, and suitability for cutting.
  • an energy beam is applied in an atmosphere substantially free of oxygen or moisture in a coating film formed by applying a polysilazane solution added with a transition metal compound on a substrate and drying it.
  • a gas barrier film formed by irradiation for example, vacuum ultraviolet light
  • the reforming proceeds in a short time to form a high nitrogen concentration film, and high gas barrier properties are exhibited.
  • Patent Documents 1 and 2 show high gas barrier properties due to the modified surface and high gas barrier properties under general conditions, but the barrier layer by hydrolysis or the like under high temperature and high humidity. As a result, there has been a problem that the gas barrier property is rapidly lowered.
  • the present invention has been made in view of the above circumstances, and provides a modified polysilazane suitable for production of a gas barrier film excellent in storage stability, particularly storage stability under severe conditions (high temperature and high humidity conditions). With the goal.
  • Another object of the present invention is to provide a gas barrier film excellent in storage stability, particularly storage stability under severe conditions (high temperature and high humidity conditions).
  • the present inventor has intensively studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using a modified polysilazane having a ratio of SiH 3 to the sum of SiH and SiH 2 in a specific range, and the present invention has been completed.
  • a gas barrier film comprising a coating solution containing the modified polysilazane, or a substrate and a barrier layer formed using the coating solution.
  • FIG. 1 It is a schematic diagram which shows an example of the vacuum plasma CVD apparatus used for formation of the inorganic compound layer (1st barrier layer) which concerns on this invention.
  • 101 is a plasma CVD apparatus;
  • 102 is a vacuum chamber;
  • 103 is a cathode electrode;
  • 105 is a susceptor;
  • 106 is a heat medium circulation system;
  • 107 is a vacuum exhaust system;
  • 110 denotes a substrate;
  • 160 denotes a heating / cooling device.
  • FIG. 1 is a plasma CVD apparatus
  • 102 is a vacuum chamber
  • 103 is a cathode electrode
  • 105 is a susceptor
  • 106 is a heat medium circulation system
  • 107 is a vacuum exhaust system
  • 110 denotes a substrate
  • 160 denotes a heating / cooling device.
  • FIG. 1 is a plasma CV
  • 1 is a gas barrier film
  • 2 is a substrate
  • 3 is a first barrier layer
  • 31 is a production apparatus
  • 32 is a feed roller
  • 33, 34, 35, and 36 are transport rollers
  • 39 and 40 are film forming rollers
  • 41 is a gas supply pipe
  • 42 is a power source for generating plasma
  • 43 and 44 are magnetic field generators
  • 45 is a winding roller.
  • 21 indicates an apparatus chamber
  • 22 indicates a Xe excimer lamp
  • 23 indicates a holder
  • 24 indicates a sample stage
  • 25 indicates a sample
  • 26 indicates a light shielding plate.
  • the ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR [(SiH 3 ) :( SiH + SiH 2)] is 1: provide modified polysilazane 10-30.
  • the coating liquid containing the modified polysilazane of this invention and the gas-barrier film manufactured using the said coating liquid are also provided.
  • the perhydropolysilazane layer when the perhydropolysilazane layer is irradiated with energy rays (for example, vacuum ultraviolet light), the surface is modified to vitreous and exhibits high barrier properties. However, it deteriorates rapidly under severe conditions (high temperature and high humidity conditions).
  • the barrier layer (gas barrier layer) formed using polysilazane as a precursor was significantly deteriorated under severe conditions (high-temperature and high-humidity conditions) in a configuration in which the barrier layer is in the lower layer.
  • Patent Documents 1 and 2 attempts have been made to improve various characteristics including gas barrier properties of gas barrier films by various methods.
  • the methods described in Patent Documents 1 and 2 only the vicinity of the surface of the polysilazane layer is modified, and an unmodified portion remains inside. It has been found that this unmodified part is one factor that causes a significant reaction under particularly severe conditions (high temperature and high humidity conditions) to lower the gas barrier property.
  • the reaction proceeds due to the action of moisture in the atmosphere, the oxidation reaction has already progressed at the stage of irradiation with energy rays (for example, vacuum ultraviolet light), so the energy barrier cannot be sufficiently absorbed, and the optimum barrier film Is difficult or cannot be formed.
  • energy rays for example, vacuum ultraviolet light
  • modified polysilazane of the present invention is characterized by having a ratio [(SiH 3) :( SiH + SiH 2)] of the sum of SiH 3 and SiH and SiH 2 in a specific range.
  • a gas barrier film excellent in storage stability, particularly storage stability under high temperature and high humidity can be provided.
  • the present invention is not limited to the following.
  • normally used polysilazane especially perhydropolysilazane
  • has many —SiH 3 groups at the end and this —SiH 3 group becomes a reaction starting point during an operation from coating to active energy ray irradiation, and an undesirable reaction occurs. Arise.
  • the gas barrier property under severe conditions is lowered.
  • the highly reactive terminus of -SiH 3 group is a specific To be in the range of
  • an undesirable reaction (atmosphere) generated from coating to active energy ray irradiation It is possible to preferentially and efficiently carry out a desired reforming reaction (oxidation reaction of polysilazane by irradiation with active energy rays) while suppressing the reaction with moisture and oxygen therein.
  • the modified polysilazane of the present invention it is possible to produce a gas barrier film having high gas barrier properties and excellent storage stability (wet heat resistance) that suppresses / prevents deterioration of gas barrier properties particularly under high temperature and high humidity.
  • the above effect can be achieved particularly remarkably when the terminal —SiH 3 group of polysilazane is modified with a metal alkoxide and / or a metal chelate compound, and a low molecular silazane and / or a low molecular siloxane.
  • X to Y indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.
  • the modified polysilazane has SiH and / or SiH 2 and SiH 3 , and the ratio of SiH 3 measured by 29 Si-NMR to the sum of SiH and SiH 2 [(SiH 3 ) :( SiH + SiH 2 ]] (Hereinafter also simply referred to as “SiH 3 ratio”) is 1:10 to 30 (molar ratio).
  • SiH 3 ratio the ratio of SiH 3 measured by 29 Si-NMR to the sum of SiH and SiH 2 [(SiH 3 ) :( SiH + SiH 2 ]]
  • the ratio of —SiH 3 groups present at the end of the modified polysilazane is the ratio [(SiH 3 ) :( SiH + SiH 2 )] of SiH 3 measured by 29 Si-NMR and the sum of SiH and SiH 2 .
  • the barrier layer formed using the modified polysilazane of the present invention is excellent in gas barrier properties, particularly gas barrier properties under severe conditions (especially high temperature and high humidity).
  • the ratio [(SiH 3 ) :( SiH + SiH 2 )] (SiH 3 ratio) between SiH 3 and the sum of SiH and SiH 2 is measured by 29 Si-NMR, specifically Means a value measured according to the method described in.
  • the SiH 3 ratio of the modified polysilazane is 1: 10-30.
  • the SiH 3 ratio exceeds the upper limit, excessively high reactive ends (SiH 3 ) are present, and thus react with moisture in the atmosphere before irradiation with active energy rays, and gas barrier properties, particularly high temperatures. Gas barrier properties under high humidity conditions are reduced.
  • the SiH 3 ratio is below the lower limit, the polysilazane structure itself becomes unstable, resulting in an increase in low molecular components, liquid stagnation and coarse aggregation between molecules. Gas barrier properties under high humidity conditions are reduced.
  • the SiH 3 ratio of the modified polysilazane is preferably 1:12 to 28, preferably 1:15 to 25, and 1: More preferably, it is 18-24.
  • the modified polysilazane may be produced by any method as long as the polysilazane having the SiH 3 ratio as described above can be produced, but the method described in detail below can be preferably used.
  • the polysilazane is reacted with at least one selected from the group consisting of low-molecular silazanes, low-molecular siloxanes, metal alkoxide compounds and metal chelate compounds to modify the SiH 3 group so as to reduce the reactivity of the SiH 3 group in the polysilazane.
  • polysilazane low molecular silazanes and / or low-molecular-weight siloxane, and reacted with the metal alkoxide compound and / or a metal chelate compound, a SiH 3 group to lower the reactivity of the SiH 3 groups in the polysilazane It is more preferable to modify.
  • polysilazane has a silicon atom, a hydrogen atom, and a nitrogen atom.
  • the modified polysilazane of the present invention comprises (a) a polysilazane containing a silicon atom, a hydrogen atom and a nitrogen atom (hereinafter also simply referred to as “raw material polysilazane”), and (b) at least one of a low molecular silazane and a low molecular siloxane ( Hereinafter, obtained simply by reacting with at least one of “low molecular silazane / siloxane” and (c) metal alkoxide compound and metal chelate compound (hereinafter also simply referred to as “metal alkoxide / chelate compound”). Is preferred.
  • (B) low molecular silazane / siloxane and (c) a metal alkoxide / chelate compound has a high reactivity with -SiH 3 group in the raw material polysilazane, the terminal -SiH 3 group in the raw material polysilazane more efficiently Can be modified.
  • (c) metal alkoxide / chelate compound promotes the oxidation reaction of polysilazane by irradiation with active energy rays as compared with (b) low molecular weight silazane / siloxane, but has reactivity with water and oxygen in the atmosphere. high.
  • reaction point (-SiH 3 group) at the terminal of polysilazane is modified with an amount of (c) metal alkoxide / chelate compound that exhibits the desired effect of promoting oxidation reaction, and the remaining (unreacted) reaction point (-SiH 3).
  • the group) is preferably modified with (b) low molecular silazane / siloxane.
  • the modified polysilazane of the present invention comprises: (a) a polysilazane containing a silicon atom, a hydrogen atom and a nitrogen atom is reacted with at least one of (c) a metal alkoxide compound and a metal chelate compound; And more preferably obtained by reacting with at least one of low molecular siloxanes.
  • the polysilazane oxidation reaction (reforming treatment) proceeds more efficiently while suppressing / preventing reaction with moisture and oxygen in the atmosphere (undesirable reaction between application and irradiation of active energy rays). Can do.
  • modifying the SiH 3 group means a modification / reaction to reduce the reactivity (especially the reactivity with water), and at least one hydrogen atom of the SiH 3 group is replaced with another compound (eg, low molecular silazane, low molecular siloxane, metal alkoxide compound) , A metal chelate compound), and also includes coordination of the above-mentioned other compound to terminal Si, but preferably, at least one hydrogen atom of SiH 3 group is replaced with another compound (for example, , Low molecular silazane, low molecular siloxane, metal alkoxide compound, metal chelate compound).
  • (A) Polysilazane is a polymer containing at least a silicon atom, a hydrogen atom, and a nitrogen atom and having a silicon-nitrogen bond.
  • the ceramic precursor inorganic polymer such as SiO 2 , Si 3 N 4 , and both intermediate solid solutions SiO x N y having bonds such as Si—N, Si—H, and N—H in the structure. is there.
  • polysilazane used in the present invention are not particularly limited and include known ones. For example, those disclosed in paragraphs “0043” to “0058” of JP2013-022799A, paragraphs “0038” to “0056” of JP2013-226758A are appropriately adopted. Of these, perhydropolysilazane is most preferably used.
  • Polysilazane is commercially available in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as the first barrier layer forming coating solution.
  • 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 AZ Electronic Materials Co., Ltd. Is mentioned.
  • polysilazane examples include, but are not limited to, for example, a silicon alkoxide-added polysilazane obtained by reacting the polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-23827), and a glycidol reaction.
  • a silicon alkoxide-added polysilazane obtained by reacting the polysilazane with a silicon alkoxide
  • glycidol-added polysilazane Japanese Patent Laid-Open No. 6-122852
  • alcohol-added polysilazane obtained by reacting alcohol
  • 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.
  • the low molecular silazane and the low molecular siloxane are not particularly limited, but preferably, the low molecular silazane is represented by the following general formula (I):
  • X 1 , X 2 and X 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group.
  • A is an integer from 1 to 10
  • a cyclic low-molecular silazane (I) represented by the following general formula (II):
  • X 4 is a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group
  • X 5 to X 10 are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group
  • a linear low molecular weight silazane (II) represented by the following general formula (III):
  • X 11 and X 12 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group;
  • X 13 X 16 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group.
  • a low molecular weight siloxane represented by the following general formula (IV):
  • Y 1 and Y 2 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group; An integer from 1 to 10, Cyclic low molecular siloxane (IV) represented by the following general formula (V):
  • Y 3 to Y 14 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. It is cyclic low molecular siloxane (V) represented by these.
  • X 1 , X 2 and X 3 are a hydrogen atom, a substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group. is there.
  • X 1 , X 2 and X 3 may be the same or different.
  • the substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (I) is the same as the definition in the general formula (1). Omitted.
  • alkoxy group include linear or branched alkoxy groups having 1 to 8 carbon atoms.
  • the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • X 1 , X 2 and X 3 are a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or a halogen atom It is preferable that they are a hydrogen atom, a methyl group, and a methoxy group.
  • the combination of X 1 , X 2 and X 3 is not particularly limited, but X 1 and X 2 are a methyl group and a hydrogen atom, respectively, and X 3 is a methyl group; X 1 and X 2 are a methyl group X 3 is preferably a hydrogen atom.
  • a is an integer of 1 to 10, preferably 3 to 6.
  • cyclic low-molecular silazane (I) represented by the general formula (I) include the following.
  • X 4 is a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, an aryl group, a vinyl group, or a (trialkoxysilyl) alkyl group.
  • X 5 to X 10 are a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group.
  • X 4 and X 5 to X 10 may be the same or different.
  • substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (II) is represented by the general formula (1) or (I). Since the definition is the same as that in FIG. Among these, X 4 is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a vinyl group, or an alkoxy group, and more preferably a hydrogen atom.
  • X 5 to X 10 are preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a vinyl group or an alkoxy group, and more preferably a hydrogen atom, a methyl group or a vinyl group.
  • X 4 or X 5 to X 10 is a hydrogen atom.
  • chain low-molecular silazane (II) represented by the general formula (II) include the following.
  • X 11 and X 12 are a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, an aryl group, a vinyl group, or a (trialkoxysilyl) alkyl group.
  • X 13 to X 16 are a hydrogen atom, a substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group.
  • X 11 and X 12 , and X 13 to X 16 may be the same or different.
  • the substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (III) is represented by the general formula (1) or (I). Since the definition is the same as that in FIG. Of these, X 11 and X 12 represents a hydrogen atom, an alkyl group, a vinyl group having 1 to 3 carbon atoms, preferably an alkoxy group, and more preferably a hydrogen atom. X 13 to X 16 are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a vinyl group or an alkoxy group, and more preferably a methyl group or a t-butyl group.
  • chain low-molecular silazane (III) represented by the general formula (III) include the following.
  • Y 1 and Y 2 are a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, an aryl group, a vinyl group, or a (trialkoxysilyl) alkyl group.
  • Y 1 and Y 2 may be the same or different.
  • the substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (IV) is represented by the general formula (1) or (I). Since the definition is the same as that in FIG.
  • one of Y 1 and Y 2 is a hydrogen atom and the other is an alkyl group having 1 to 3 carbon atoms, a vinyl group or an alkoxy group, or both Y 1 and Y 2 have 1 to 3 carbon atoms.
  • one of Y 1 and Y 2 is a hydrogen atom and the other is an alkyl group having 1 to 3 carbon atoms, or both Y 1 and Y 2 are carbon. It is more preferably an alkyl group having 1 to 3 atoms, and one of Y 1 and Y 2 is a hydrogen atom and the other is particularly preferably an alkyl group having 1 to 3 carbon atoms.
  • b is an integer of 1 to 10, preferably 3 to 6.
  • cyclic low-molecular siloxane (IV) represented by the general formula (IV) include the following.
  • Y 3 to Y 14 are a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, an aryl group, a vinyl group, or a (trialkoxysilyl) alkyl group.
  • Y 3 to Y 14 may be the same or different.
  • the substituted or unsubstituted alkyl group, alkoxy group, halogen atom, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the general formula (V) is represented by the general formula (1) or (I). Since the definition is the same as that in FIG.
  • Y 3 to Y 14 are preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a vinyl group or an alkoxide group, and preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Is more preferable.
  • cyclic low-molecular siloxane (V) represented by the general formula (V) include the following.
  • Silazane (III) and cyclic low molecular siloxane (IV) of general formula (IV) are preferred
  • cyclic low molecular silazane (I) of general formula (I) and chain low molecular silazane (II) of general formula (II) are preferred. More preferably, compounds 2 and 3 are particularly preferable.
  • metal alkoxide compound and the metal chelate compound can efficiently form a high-performance barrier layer.
  • the metal constituting the metal alkoxide compound and the metal chelate compound is not particularly limited.
  • metal alkoxides and metal chelate compounds are beryllium (Be), boron (B), magnesium (Mg), aluminum (Al), silicon (Si), calcium (Ca), scandium (Sc), titanium (Ti), Vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), Strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), Cadmium (Cd), Indium (
  • metal alkoxides and metal chelate compounds containing aluminum (Al), titanium (Ti), iron (Fe), or copper (Cu) as a metal are more preferable in terms of high Lewis acidity.
  • the metal alkoxide compound is not particularly limited, but aluminum alkoxide is preferable from the viewpoint that a high-performance barrier layer can be formed more efficiently.
  • metal alkoxide compound examples include, for example, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-tert-butyl borate, magnesium ethoxy Magnesium ethoxy ethoxide, magnesium methoxy ethoxide, aluminum trimethoxide, aluminum triethoxide, aluminum tri n-propoxide, aluminum triisopropoxide, aluminum tri n-butoxide, aluminum tri sec-butoxide, aluminum tri tert -Butoxide, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monosec-butyrate, aluminum oxide isopropoxide trimer, al Nitric oxide octylate trimer, calcium methoxide, calcium ethoxide, calcium isopropoxide, titanium tetramethoxide, titanium tetraethoxide, titanium te
  • Silsesquioxane can also be used as the metal alkoxide compound.
  • Silsesquioxane is a siloxane-based compound whose main chain skeleton is composed of Si—O bonds, and is also called T-resin, whereas ordinary silica is represented by the general formula [SiO 2 ].
  • Silsesquioxane (also referred to as polysilsesquioxane) is a compound represented by the general formula [RSiO 1.5 ].
  • a (RSi (OR ') 3 ) compound in which one alkoxy group of tetraalkoxysilane (Si (OR') 4 ) represented by tetraethoxysilane is replaced with an alkyl group or an aryl group.
  • the polysiloxane to be synthesized, and the molecular arrangement is typically amorphous, ladder-like, or cage-like (fully condensed cage-like).
  • Silsesquioxane may be synthesized or commercially available. Specific examples of the latter include X-40-2308, X-40-9238, X-40-9225, X-40-9227, x-40-9246, KR-500, KR-510 (all of which are Shin-Etsu Chemical) SR2400, SR2402, SR2405, FOX14 (perhydrosilcelsesquioxane) (all manufactured by Toray Dow Corning), SST-H8H01 (perhydrosilcelsesquioxane) (manufactured by Gelest), etc. Is mentioned.
  • a compound having a branched alkoxy group is preferable from the viewpoint of reactivity and solubility, and a compound having a 2-propoxy group or a sec-butoxy group is more preferable.
  • More preferred metal alkoxide compounds are specifically aluminum trisec-butoxide, titanium tetraisopropoxide, or aluminum diisopropylate monosec-butyrate.
  • the metal chelate compound is not particularly limited, but is preferably a metal chelate compound having a ⁇ -diketone as a ligand from the viewpoint that a high-performance barrier layer can be formed more efficiently. That is, it is particularly preferable that the metal alkoxide compound is an aluminum alkoxide, or the metal chelate compound is a metal chelate compound having a ⁇ -diketone as a ligand.
  • Examples of ⁇ -diketone include acetylacetone, ethyl acetoacetate, 2,4-hexanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-decanedione, 2,4-tridecanedione, 5 , 5-dimethyl-2,4-hexanedione, 2,2-dimethyl-3,5-nonanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3-cyclopentanedione, Examples include 1,3-cyclohexanedione and 1-cyclohexyl-1,3-butanedione.
  • metal chelate compounds having ⁇ -diketone as a ligand include, for example, beryllium acetylacetonate, magnesium acetylacetonate, aluminum acetylacetonate, aluminum ethylacetoacetate / diisopropylate, aluminum ethylacetate Acetate di n-butyrate, aluminum diethyl acetoacetate mono n-butyrate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum trisacetylacetonate, aluminum trisethylacetoacetate, bis (ethylacetoacetate) (2,4-pentane Diato) aluminum, aluminum alkyl acetoacetate diisopropylate, calcium acetylacetonate, scan Um acetylacetonate, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, tris (2,4-pentanedionato)
  • metal chelate compounds having ⁇ -diketone as a ligand metal compounds having an acetylacetonate group or an ethylacetoacetate group are preferable. These groups are preferable because they have an interaction with the central element of the alkoxide compound due to the carbonyl structure, and thus handleability becomes easy. More preferably, a compound having a plurality of alkoxide groups, ethyl acetoacetate groups or acetylacetonate groups is more preferable from the viewpoints of reactivity and film composition.
  • More preferable metal chelate compounds are, specifically, aluminum ethyl acetoacetate diisopropylate, aluminum ethyl acetoacetate di n-butyrate, or aluminum diethyl acetoacetate mono n-butyrate, aluminum bisethyl acetoacetate monoacetyl acetonate , Titanium diisopropoxybis (acetylacetonate), bis (2,4-pentandionato) copper (II) (copper acetylacetonate), tris (2,4-pentandionato) iron (III) (iron acetyl Acetonate).
  • chelate compound having a metal alkoxide compound or ⁇ -diketone as a ligand a commercially available product or a synthesized product may be used.
  • commercially available products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), Plenact (registered trademark) AL-M (acetoalkoxyaluminum) as metal alkoxide compounds.
  • AMD aluminum diisopropylate monosec-butyrate
  • ASBD aluminum secondary butyrate
  • Plenact registered trademark
  • AL-M acetoalkoxyaluminum
  • Diisopropylate Ajinomoto Fine Chemical Co., Ltd.
  • Olga Chix series Matsumoto Fine Chemical Co., Ltd.
  • metal chelate compounds having ⁇ -diketone as a ligand include ALCH (aluminum ethyl acetoacetate diisopropylate), ALCH-TR (aluminum trisethyl acetoacetate), aluminum chelate M (aluminum alkyl acetoacetate). ⁇ Diisopropylate), aluminum chelate D (aluminum bisethyl acetoacetate monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) (above, manufactured by Kawaken Fine Chemical Co., Ltd.), ORGATIX series ( Matsumoto Fine Chemical Co., Ltd.).
  • the reaction (addition) order of (a) raw material polysilazane, (b) low molecular silazane / siloxane, and (c) metal alkoxide / chelate compound is not particularly limited, and (a) (a) raw material Even if polysilazane, (b) low molecular weight silazane / siloxane, and (c) metal alkoxide / chelate compound are mixed together and reacted; (A) (a) raw material polysilazane and (c) metal alkoxide / chelate compound (B) low molecular silazane / siloxane added and reacted; (c) (a) raw material polysilazane and (b) low molecular silazane / siloxane reacted in advance; ) Metal alkoxide / chelate compound added to react; or (d) (b) low molecular silazane / siloxane and (
  • the modified polysilazane is obtained by reacting (a) a polysilazane containing a silicon atom, a hydrogen atom and a nitrogen atom with at least one of (c) a metal alkoxide compound and a metal chelate compound, and (b) a low molecular silazane and a low molecular weight compound. It is particularly preferred that it is obtained by reacting with at least one of the siloxanes. By this reaction, gas barrier properties, particularly gas barrier properties under particularly severe conditions (high temperature and high humidity conditions) can be improved.
  • (b) the low-molecular silazane / siloxane and (c) the metal alkoxide / chelate compound are modified from the terminal side of the —SiH 3 group of the starting polysilazane. Further, (c) modification with metal alkoxide / chelate compound promotes uptake of external oxygen (that is, when irradiated with active energy rays of modified polysilazane, as compared with modification with (b) low molecular silazane and low molecular siloxane. It promotes the oxidation reaction).
  • the reactive site (-SiH 3 group) at the end of polysilazane is reacted in advance with an amount of (c) a metal alkoxide / chelate compound that exhibits a desired oxidation reaction promoting effect
  • the modified polysilazane after modifying the terminal -SiH 3 group of the raw material polysilazane with a metal alkoxide / chelate compound, the unreacted (remaining) reaction point (-SiH 3 group) is modified with (b) low molecular silazane / siloxane. It is preferable to adjust the amount (number) of —SiH 3 groups in an appropriate range.
  • the polysilazane oxidation reaction (reforming treatment) can proceed more efficiently while suppressing or preventing reaction with moisture and oxygen in the atmosphere.
  • external oxygen uptake oxidation reaction in the modified polysilazane
  • gas barrier properties particularly particularly severe conditions (high temperature and high humidity) are promoted. Under the condition), the gas barrier property can be improved more efficiently.
  • reaction (a) the reaction between (b) the low molecular silazane / siloxane and (c) the metal alkoxide / chelate compound is performed by (a) the starting polysilazane and (b) the low molecular silazane / siloxane or (c). Compared to the reaction with a metal alkoxide / chelate compound, there is a possibility that the reaction proceeds with priority.
  • the mixing ratio of (a) raw material polysilazane to (b) low molecular weight silazane / siloxane and (c) metal alkoxide / chelate compound is such that (a) terminal polysilazane terminal-SiH 3 group is (b)
  • the ratio is not particularly limited as long as the ratio can be sufficiently modified with low molecular silazane / siloxane and (c) metal alkoxide / chelate compound.
  • the total charge amount of at least one of (b) low molecular silazane and low molecular siloxane, and (c) at least one of metal alkoxide compound and metal chelate compound is (a) the number of silicon elements in the raw material polysilazane ( Si) is preferably more than 5 mol% and not more than 50 mol%, more preferably 6 to 30 mol%, more preferably 7 to 20 mol%, and more preferably 8 to 15 mol%. % Is particularly preferred. If it exceeds 5 mol%, a gas barrier film having better storage stability under high temperature and high humidity can be obtained. Moreover, if it is 50 mol% or less, the gas-barrier property of the barrier layer formed using a modified polysilazane can improve.
  • the mixing ratio of (b) low-molecular silazane / siloxane and (c) metal alkoxide / chelate compound is not particularly limited, but (b) the mixing ratio (molar ratio) of low-molecular silazane / siloxane and (c) metal alkoxide / chelating compound ) Is preferably from 1: 0.1 to 10, more preferably from 1: 0.5 to 5. Within such a range, the gas barrier film formed using the modified polysilazane can exhibit better storage stability under high temperature and high humidity.
  • the above reaction may be carried out in a solvent-free system, but is preferably carried out in a solvent.
  • the solvent is not particularly limited as long as it can dissolve (a) raw material polysilazane, (b) low molecular silazane / siloxane, and (c) metal alkoxide / chelate compound, but it can easily react with polysilazane.
  • Organic solvents that do not contain water and reactive groups (for example, hydroxyl groups or amine groups) and are inert to polysilazane are preferred, and aprotic organic solvents are more preferred.
  • the solvent is an aprotic solvent; for example, pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, solvesso, terpene, aliphatic hydrocarbons, alicyclic carbonization, etc.
  • Hydrocarbon solvents such as hydrogen and aromatic hydrocarbons; 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; Dibutyl ether, dioxane, tetrahydrofuran, mono- And aliphatic ethers such as polyalkylene glycol dialkyl ethers (diglymes) and ethers such as alicyclic ethers.
  • the said solvent may be used independently or may be used with the form of a 2 or more types of mixture. Moreover, it is preferable to reduce the oxygen concentration and water content of the solvent before use.
  • Means for reducing the oxygen concentration and water content in the solvent are not particularly limited, and conventionally known methods can be applied.
  • the concentration of the raw material polysilazane in the reaction solution is not particularly limited.
  • the modified polysilazane solution after reaction is used as it is for the production of a gas barrier film, it 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 2 to 2%. It is 50% by mass, particularly preferably 10 to 40% by mass.
  • the reaction conditions are not particularly limited as long as (a) the terminal-SiH 3 group of the starting polysilazane can be sufficiently modified with (b) low molecular silazane / siloxane and (c) metal alkoxide / chelate compound.
  • the reaction temperature preferably 30 ° C. to 100 ° C., more preferably 40 to 90 ° C., and even more preferably 50 to 80 ° C.
  • the reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 4 hours, and even more preferably 1 to 2 hours.
  • the above reaction may be performed in any atmosphere, but as described above, in consideration of reactivity with water, the reaction is preferably performed in an inert environment and substantially does not contain oxygen or moisture. More preferably, it is performed under an atmosphere.
  • the oxygen concentration in the reaction system is not particularly limited, but is preferably 0 to 200 ppm by volume, more preferably 0 to 100 ppm, and even more preferably 0 to 30 ppm by volume.
  • the water concentration (water vapor concentration) in the reaction system is not particularly limited, but is preferably 0 to 200 ppm by volume, more preferably 0 to 100 ppm, and even more preferably 0 to 30 ppm by volume.
  • the modified polysilazane of the present invention produced as described above has a small number of terminal SiH 3 groups that easily react with moisture in the atmosphere. For this reason, it is possible to preferentially advance the oxidation reaction by irradiation with active energy rays. Therefore, the modified polysilazane of the present invention is particularly useful for the production of a barrier layer excellent in gas barrier properties, particularly gas barrier properties under severe conditions (especially high temperature and high humidity), and therefore a gas barrier film.
  • the present invention also provides a gas barrier film comprising a coating solution containing the modified polysilazane of the present invention, a substrate, and a barrier layer formed using the coating solution.
  • the gas barrier film of the present invention includes a base material and a barrier layer formed of a coating solution containing the modified polysilazane of the present invention, but has a gas barrier property, particularly a gas barrier under severe conditions (especially high temperature and high humidity).
  • a gas barrier property particularly a gas barrier under severe conditions (especially high temperature and high humidity).
  • the gas barrier film comprises a substrate, an inorganic compound layer containing an inorganic compound (also referred to herein as “first barrier layer”), and the modified polysilazane of the present invention.
  • a barrier layer also referred to as a “second barrier layer” in this specification
  • the gas barrier film of the present invention preferably has a substrate, a first barrier layer, and a second barrier layer in this order.
  • the gas barrier film may further include other members.
  • the gas barrier film of the present invention is, for example, between the base material and the first barrier layer, between the first barrier layer and the second barrier layer, on the second barrier layer, or on the first barrier. You may have another member in the other surface of the base material in which the layer and the 2nd barrier layer are not formed.
  • the other members are not particularly limited, and members used for conventional gas barrier films can be used similarly or appropriately modified. Specific examples include an intermediate layer, a protective layer, a smooth layer, an anchor coat layer, a bleed-out prevention layer, a desiccant layer having moisture adsorbability, and a functionalized layer of an antistatic layer.
  • the gas barrier property having the first barrier layer and the second barrier layer may be formed on one surface of the substrate, or may be formed on both surfaces of the substrate.
  • the gas barrier unit may include a layer that does not necessarily have a gas barrier property.
  • a plastic film or a plastic sheet is preferably used as a substrate, and a film or sheet made of a colorless and transparent resin is more preferably used.
  • the plastic film used is not particularly limited as long as it is a film that can hold the second barrier layer and, if necessary, the first barrier layer, etc., and can be appropriately selected according to the purpose of use. it can.
  • plastic film examples include polyester resins such as polyethylene terephthalate (PET), methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, Polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene
  • thermoplastic resins such as a ring-modified polycarbonate resin, an alicyclic modified polycarbonate resin, a fluorene ring-modified polyester resin, and an acryloyl compound.
  • the substrates disclosed in paragraphs “0056” to “0075” of JP2012-116101A, paragraphs “0125” to “0131” of JP2013-226758A, etc. are also appropriately employed. Is done.
  • the thickness of the base material used for the gas barrier film according to the present invention is not particularly limited because it is appropriately selected depending on the application, but is typically 1 to 800 ⁇ m, preferably 10 to 200 ⁇ m.
  • These plastic films may have functional layers such as a transparent conductive layer, a primer layer, and a clear hard coat layer.
  • As the functional layer in addition to those described above, those described in paragraph numbers “0036” to “0038” of JP-A-2006-289627 can be preferably used.
  • the substrate preferably has a high surface smoothness.
  • the surface smoothness those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the barrier layer is provided, may be polished to improve smoothness.
  • various known treatments for improving adhesion such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, and smoothing described later. Layer stacking or the like may be performed, and it is preferable to combine the above treatments as necessary.
  • the inorganic compound layer (first barrier layer) formed on the upper part of the substrate contains an inorganic compound.
  • the inorganic compound is not particularly limited, and examples thereof include metal oxides, metal nitrides, metal carbides, metal oxynitrides, and metal oxycarbides.
  • oxides, nitrides, carbides, oxynitrides or oxycarbides containing one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta in terms of gas barrier performance are preferably used, and an oxide, nitride or oxynitride of a metal selected from Si, Al, In, Sn, Zn and Ti is more preferable, and in particular, an oxide of at least one of Si and Al, Nitride or oxynitride is preferred.
  • suitable inorganic compounds include composites such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, aluminum oxide, titanium oxide, or aluminum silicate. You may contain another element as a secondary component.
  • the content of the inorganic compound contained in the first barrier layer is not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, and 95% by mass in the first barrier layer. More preferably, it is more preferably 98% by mass or more, and most preferably 100% by mass (that is, the first barrier layer is made of an inorganic compound).
  • the first barrier layer contains an inorganic compound and thus has a gas barrier property.
  • the gas barrier property of the first barrier layer is calculated using a laminate in which the first barrier layer is formed on the substrate, the water vapor transmission rate (WVTR) is 0.1 g / (m 2 ⁇ day). Or less, more preferably 0.01 g / (m 2 ⁇ day) or less.
  • the method for forming the first barrier layer is not particularly limited, but a vacuum film-forming method such as physical vapor deposition (PVD method) or chemical vapor deposition (CVD), or a liquid containing an inorganic compound, preferably A method of modifying and forming a coating film formed by applying a liquid containing a silicon compound (hereinafter also simply referred to as a coating method) is preferred, and a physical vapor deposition method or a chemical vapor deposition method is more preferred. .
  • PVD method physical vapor deposition
  • CVD chemical vapor deposition
  • the physical vapor deposition method is a method of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method.
  • a target material for example, a thin film such as a carbon film
  • Examples thereof include a DC sputtering method, an RF sputtering method, an ion beam sputtering method, and a magnetron sputtering method, a vacuum deposition method, and an ion plating method.
  • Sputtering is a method in which a target is placed in a vacuum chamber, a rare gas element (usually argon) ionized by applying a high voltage is collided with the target, and atoms on the target surface are ejected and adhered to the substrate.
  • a reactive sputtering method may be used in which an inorganic layer is formed by causing nitrogen and oxygen gas to flow into the chamber to react nitrogen and oxygen with an element ejected from the target by argon gas. .
  • the chemical vapor deposition method (Chemical Vapor Deposition, CVD method) is a method of depositing a film by supplying a source gas containing a target thin film component onto a substrate and performing a chemical reaction on the surface of the substrate or in the gas phase. It is. In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like.
  • Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The method etc. are mentioned. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of film forming speed and processing area.
  • the first barrier layer preferably contains carbon, silicon, and oxygen as constituent elements.
  • a more preferable form is a layer that satisfies the following requirements (i) to (iii).
  • the following requirements (i) to (iii) are also referred to as “requirement (i)”, “requirement (ii)”, and “requirement (iii)”, respectively.
  • the first barrier layer is based on (i) the distance (L) from the surface of the first barrier layer in the film thickness direction of the first barrier layer and the total amount of silicon atoms, oxygen atoms, and carbon atoms.
  • Silicon distribution curve showing the relationship with the ratio of the amount of silicon atoms (silicon atomic ratio), the ratio of the amount of oxygen atoms to the total amount of L and silicon atoms, oxygen atoms, and carbon atoms (oxygen atomic ratio)
  • the carbon distribution curve showing the relationship between the L and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon).
  • the film thickness of the barrier layer In the region of 90% or more (upper limit: 100%) of the film thickness of the barrier layer, (oxygen atomic ratio), (silicon atomic ratio), (carbon atomic ratio) increase in this order (atomic ratio is O> Si> C) is preferred.
  • the gas barrier property and flexibility of the obtained gas barrier film can be improved.
  • the relationship among the above (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) is at least 90% or more (upper limit) of the film thickness of the first barrier layer. : 100%), and more preferably at least 93% or more (upper limit: 100%).
  • at least 90% or more of the film thickness of the first barrier layer does not have to be continuous in the first barrier layer, and simply satisfies the above-described relationship at 90% or more. Good.
  • the first barrier layer preferably has (ii) the carbon distribution curve has at least two extreme values.
  • the first barrier layer preferably has at least three extreme values in the carbon distribution curve, and more preferably has at least four extreme values, but may have five or more extreme values.
  • the extreme value of the carbon distribution curve is two or more, the gas barrier property when the obtained gas barrier film is bent can be improved.
  • the upper limit of the extreme value of the carbon distribution curve is not particularly limited. For example, it is preferably 30 or less, more preferably 25 or less, but the number of extreme values is also caused by the film thickness of the first barrier layer. Therefore, it cannot be specified in general.
  • the first barrier in the film thickness direction of the first barrier layer at one extreme value of the carbon distribution curve and an extreme value adjacent to the extreme value is preferably 200 nm or less, more preferably 100 nm or less, and 75 nm. It is particularly preferred that With such a distance between extreme values, a portion having a high carbon atom ratio (maximum value) exists in the first barrier layer at an appropriate period, so that appropriate flexibility is imparted to the first barrier layer. In addition, the generation of cracks when the gas barrier film is bent can be more effectively suppressed / prevented.
  • extreme value means a maximum value or a minimum value of an atomic ratio of an element to a distance (L) from the surface of the first barrier layer in the film thickness direction of the first barrier layer. That means.
  • maximum value means that the atomic ratio value of an element (oxygen, silicon, or carbon) changes from increasing to decreasing when the distance from the surface of the first barrier layer is changed.
  • the distance from the surface of the first barrier layer in the film thickness direction of the first barrier layer from the point is further changed within the range of 4 to 20 nm, rather than the atomic ratio value of the element at that point. This is the point where the atomic ratio value of the element at the position decreases by 3 at% or more.
  • the atomic ratio value of the element is reduced by 3 at% or more in any range when changing in the range of 4 to 20 nm.
  • the “minimum value” means that the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from a decrease to an increase when the distance from the surface of the first barrier layer is changed. The distance from the surface of the first barrier layer in the film thickness direction of the first barrier layer from the point is further changed within the range of 4 to 20 nm, rather than the value of the atomic ratio of the element at that point. This is the point at which the value of the atomic ratio of the element at the position increases by 3 at% or more.
  • the atomic ratio value of the element when changing in the range of 4 to 20 nm, the atomic ratio value of the element only needs to increase by 3 at% or more in any range.
  • the lower limit of the distance between the extreme values in the case of having at least three extreme values is particularly high because the smaller the distance between the extreme values, the higher the effect of suppressing / preventing crack generation when the gas barrier film is bent.
  • the thickness is preferably 10 nm or more, and more preferably 30 nm or more.
  • the first barrier layer has (iii) an absolute value of a difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve (hereinafter, also simply referred to as “C max ⁇ C min difference”) of 3 at. % Or more is preferable.
  • C max ⁇ C min difference an absolute value of a difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve
  • the C max ⁇ C min difference is more preferably 5 at% or more, further preferably 7 at% or more, and particularly preferably 10 at% or more.
  • the “maximum value” is the atomic ratio of each element that is maximum in the distribution curve of each element, and is the highest value among the maximum values.
  • the “minimum value” is the atomic ratio of each element that is the minimum in the distribution curve of each element, and is the lowest value among the minimum values.
  • the upper limit of the C max -C min difference is not particularly limited, but it is preferably 50 at% or less in consideration of the effect of suppressing / preventing crack generation during bending of the gas barrier film, and is preferably 40 at% or less. It is more preferable that
  • the oxygen distribution curve of the first barrier layer preferably has at least one extreme value, more preferably has at least two extreme values, and further preferably has at least three extreme values.
  • the oxygen distribution curve has at least one extreme value
  • the gas barrier property when the obtained gas barrier film is bent is further improved as compared with a gas barrier film having no extreme value.
  • the upper limit of the extreme value of the oxygen distribution curve is not particularly limited, but is preferably 20 or less, more preferably 10 or less, for example. Even in the number of extreme values of the oxygen distribution curve, there is a portion caused by the film thickness of the first barrier layer, and it cannot be defined unconditionally.
  • one extreme value of the oxygen distribution curve and the first barrier layer in the thickness direction of the first barrier layer at the extreme value adjacent to the extreme value is preferably 200 nm or less, and more preferably 100 nm or less. With such a distance between extreme values, the occurrence of cracks during bending of the gas barrier film can be more effectively suppressed / prevented.
  • the lower limit of the distance between the extreme values in the case of having at least three extreme values is not particularly limited, but considering the improvement effect of crack generation suppression / prevention when the gas barrier film is bent, the thermal expansion property, etc.
  • the thickness is preferably 10 nm or more, and more preferably 30 nm or more.
  • the silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination.
  • XPS X-ray photoelectron spectroscopy
  • rare gas ion sputtering such as argon in combination.
  • XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample.
  • a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).
  • the etching time is the distance (L from the surface of the first barrier layer in the film thickness direction of the first barrier layer in the film thickness direction). ) From the relationship between the etching rate and the etching time employed in the XPS depth profile measurement as “the distance from the surface of the first barrier layer in the film thickness direction of the first barrier layer”. The calculated distance from the surface of the first barrier layer can be employed.
  • the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve can be prepared under the following measurement conditions.
  • Etching ion species Argon (Ar + ) Etching rate (SiO 2 thermal oxide equivalent value): 0.05 nm / sec Etching interval (SiO 2 equivalent value): 10 nm
  • X-ray photoelectron spectrometer Model name "VG Theta Probe", manufactured by Thermo Fisher Scientific Irradiation X-ray: Single crystal spectroscopy AlK ⁇ X-ray spot and its size: 800 ⁇ 400 ⁇ m oval.
  • the film thickness (dry film thickness) of the first barrier layer formed by the plasma CVD method is not particularly limited.
  • the film thickness per layer of the first barrier layer is preferably 20 to 3000 nm, more preferably 50 to 2500 nm, and particularly preferably 100 to 1000 nm.
  • the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending.
  • each first barrier layer has the film thickness as described above.
  • the first barrier layer is in the film surface direction (parallel to the surface of the first barrier layer).
  • Direction is preferably substantially uniform.
  • the fact that the first barrier layer is substantially uniform in the film surface direction means that the oxygen distribution curve and the carbon are measured at any two measurement points on the film surface of the first barrier layer by XPS depth profile measurement.
  • the distribution curve and the oxygen carbon distribution curve are created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the atomic ratio of carbon in each carbon distribution curve The absolute value of the difference between the maximum value and the minimum value is the same or within 5 at%.
  • the carbon distribution curve is substantially continuous.
  • the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously.
  • the carbon distribution curve is calculated from the etching rate and the etching time. The distance (x, unit: nm) from the surface of the first barrier layer in the film thickness direction of at least one layer of the first barrier layer and the atomic ratio of carbon (C, unit: at%) ), The condition expressed by the following formula 1 is satisfied.
  • the first barrier layer that satisfies all of the above conditions (i) to (iii) may include only one layer, or may include two or more layers. Further, when two or more such first barrier layers are provided, the materials of the plurality of first barrier layers may be the same or different.
  • the method for forming the first barrier layer is not particularly limited, and the conventional method and the method can be applied in the same manner or appropriately modified.
  • the first barrier layer is preferably a chemical vapor deposition (CVD) method, particularly a plasma chemical vapor deposition method (plasma CVD, PECVD (plasma-enhanced chemical vapor deposition), hereinafter simply referred to as “plasma CVD method”).
  • CVD chemical vapor deposition
  • PECVD plasma-enhanced chemical vapor deposition
  • the plasma CVD method may be a Penning discharge plasma type plasma CVD method.
  • plasma discharge in a space between a plurality of film forming rollers it is preferable to generate plasma discharge in a space between a plurality of film forming rollers.
  • a pair of film forming rollers is used, and each of the pair of film forming rollers is used. More preferably, a substrate is placed and discharged between a pair of film forming rollers to generate plasma.
  • the film formation rate can be doubled compared to the plasma CVD method without using any roller, and since it is possible to form a film having a structure that is substantially the same, it is possible to at least double the extreme value in the carbon distribution curve, It is possible to efficiently form a layer that satisfies all of the above conditions (i) to (iii).
  • the film forming gas used in such a plasma CVD method preferably contains an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation.
  • the first barrier layer is preferably a layer formed by a continuous film formation process.
  • the gas barrier film according to the present invention preferably has the first barrier layer formed on the surface of the substrate by a roll-to-roll method from the viewpoint of productivity.
  • an apparatus that can be used when the first barrier layer is manufactured by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source. It is preferable that the apparatus has a configuration capable of discharging between the film forming rollers. For example, in the case where the manufacturing apparatus shown in FIG. 2 is used, a roll-to-roll method using a plasma CVD method is used. Can also be manufactured.
  • FIG. 2 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing the first barrier layer by this manufacturing method.
  • the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.
  • the manufacturing apparatus 31 shown in FIG. 2 includes a delivery roller 32, transport rollers 33, 34, 35, and 36, film formation rollers 39 and 40, a gas supply pipe 41, a plasma generation power source 42, and a film formation roller 39. And magnetic field generators 43 and 44 installed inside 40 and a winding roller 45.
  • a vacuum chamber (not shown).
  • the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.
  • each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes. 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge into the space between the film forming roller 39 and the film forming roller 40 by supplying electric power from the plasma generating power source 42. Plasma can be generated in the space between the film roller 39 and the film formation roller 40. In this way, when the film forming roller 39 and the film forming roller 40 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes.
  • the first barrier layer 3 can be formed on the surface of the substrate 2 by the CVD method, and the first barrier layer 3 is formed on the surface of the substrate 2 on the film formation roller 39. While the first barrier layer component is deposited, the first barrier layer component can be deposited on the surface of the substrate 2 also on the film forming roller 40, so that the first barrier is formed on the surface of the substrate 2. A layer can be formed efficiently.
  • magnetic field generators 43 and 44 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.
  • the magnetic field generators 43 and 44 provided on the film forming roller 39 and the film forming roller 40 are respectively a magnetic field generating device 43 provided on one film forming roller 39 and a magnetic field generating device provided on the other film forming roller 40. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between them and the magnetic field generators 43 and 44 form a substantially closed magnetic circuit. By providing such magnetic field generators 43 and 44, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell in the vicinity of the opposing surface of each film forming roller 39 and 40, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.
  • the magnetic field generators 43 and 44 provided in the film forming roller 39 and the film forming roller 40 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 43 and the other magnetic field generator. It is preferable to arrange the magnetic poles so that the magnetic poles facing to 44 have the same polarity.
  • By providing such magnetic field generators 43 and 44 the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force of each of the magnetic field generators 43 and 44 are opposed.
  • a racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained.
  • the material 2 is excellent in that the first barrier layer 3 that is a vapor deposition film can be efficiently formed.
  • the film formation roller 39 and the film formation roller 40 known rollers can be used as appropriate. As such film forming rollers 39 and 40, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, the diameter of the film forming rollers 39 and 40 is preferably in the range of 300 to 1000 mm ⁇ , particularly in the range of 300 to 700 mm ⁇ , from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mm ⁇ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated and it is possible to avoid applying the total amount of heat of the plasma discharge to the substrate 2 in a short time. It is preferable because damage to the material 2 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mm ⁇ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.
  • the base material 2 is disposed on a pair of film forming rollers (the film forming roller 39 and the film forming roller 40) so that the surfaces of the base material 2 face each other.
  • the base material 2 By disposing the base material 2 in this manner, when the plasma is generated by performing discharge in the facing space between the film formation roller 39 and the film formation roller 40, the base existing between the pair of film formation rollers is present.
  • Each surface of the material 2 can be formed simultaneously. That is, according to such a manufacturing apparatus, the first barrier layer component is deposited on the surface of the base material 2 on the film forming roller 39 by the plasma CVD method, and the first film forming roller 40 further performs the first operation. Therefore, it is possible to efficiently form the first barrier layer on the surface of the substrate 2.
  • the winding roller 45 is not particularly limited as long as it can wind the gas barrier film 1 in which the first barrier layer 3 is formed on the substrate 2, and a known roller is appropriately used. Can be used.
  • gas supply pipe 41 and the vacuum pump those capable of supplying or discharging the raw material gas at a predetermined speed can be appropriately used.
  • the gas supply pipe 41 as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 39 and the film formation roller 40, and is a vacuum as a vacuum exhaust means.
  • a pump (not shown) is preferably provided on the other side of the facing space.
  • the plasma generating power source 42 a known power source of a plasma generating apparatus can be used as appropriate.
  • a plasma generating power supply 42 supplies power to the film forming roller 39 and the film forming roller 40 connected thereto, and makes it possible to use these as counter electrodes for discharge.
  • Such a plasma generating power source 42 can perform plasma CVD more efficiently, and can alternately reverse the polarity of the pair of film forming rollers (AC power source or the like). Is preferably used.
  • the plasma generating power source 42 can perform plasma CVD more efficiently, the applied power can be set to 100 W to 10 kW, and the AC frequency can be set to 50 Hz to 500 kHz. More preferably, it is possible to do this.
  • the magnetic field generators 43 and 44 known magnetic field generators can be used as appropriate.
  • the base material 2 in addition to the base material used in the present invention, a material in which the first barrier layer 3 is previously formed can be used. As described above, by using the substrate 2 in which the first barrier layer 3 is formed in advance, the thickness of the first barrier layer 3 can be increased.
  • the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the transport of the film (base material) By appropriately adjusting the speed, the first barrier layer according to the present invention can be produced. That is, using the manufacturing apparatus 31 shown in FIG. 2, a discharge is generated between the pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber.
  • the film-forming gas (raw material gas or the like) is decomposed by plasma, and the first barrier layer 3 is formed on the surface of the base material 2 on the film-forming roller 39 and on the surface of the base material 2 on the film-forming roller 40.
  • a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axes of the film forming rollers 39 and 40, and the plasma is converged on the magnetic field.
  • the base material 2 passes the point A of the film forming roller 39 and the point B of the film forming roller 40 in FIG. 2, the maximum value of the carbon distribution curve is formed in the first barrier layer.
  • the base material 2 passes the points C1 and C2 of the film forming roller 39 and the points C3 and C4 of the film forming roller 40 in FIG. A local minimum is formed. For this reason, five extreme values are usually generated for two film forming rollers. Further, the distance between the extreme values of the first barrier layer (the surface of the first barrier layer in the thickness direction of the first barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value) (The absolute value of the difference in distance (L) from) can be adjusted by the rotation speed of the film forming rollers 39 and 40 (the conveyance speed of the substrate). In such film formation, the substrate 2 is conveyed by the delivery roller 32, the film formation roller 39, and the like, respectively, so that the surface of the substrate 2 is formed by a roll-to-roll continuous film formation process. First barrier layer 3 is formed.
  • a raw material gas, a reactive gas, a carrier gas, or a discharge gas can be used alone or in combination of two or more.
  • the source gas in the film forming gas used for forming the first barrier layer 3 can be appropriately selected and used according to the material of the first barrier layer 3 to be formed.
  • a source gas for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used.
  • organosilicon compounds examples include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane.
  • HMDSO hexamethyldisiloxane
  • HMDS hexamethyldisilane
  • 1,1,3,3-tetramethyldisiloxane vinyltrimethylsilane
  • methyltrimethylsilane hexamethyldisilane.
  • Methylsilane dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • phenyltrimethoxysilane methyltriethoxy
  • Examples include silane and octamethylcyclotetrasiloxane.
  • hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of the handling properties of the compound and the gas barrier properties of the obtained first barrier layer.
  • organosilicon compounds can be used alone or in combination of two or more.
  • organic compound gas containing carbon examples include methane, ethane, ethylene, and acetylene.
  • an appropriate source gas is selected according to the type of the first barrier layer 3.
  • a reactive gas may be used in addition to the raw material gas.
  • a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used.
  • a reaction gas for forming an oxide for example, oxygen or ozone can be used.
  • a reactive gas for forming nitride nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.
  • a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber.
  • a discharge gas may be used as necessary in order to generate plasma discharge.
  • carrier gas and discharge gas known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon; hydrogen can be used.
  • the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary to completely react the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. It is excellent in that excellent barrier properties and flex resistance can be obtained by forming the first barrier layer 3 by not excessively increasing the ratio of the reaction gas. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.
  • the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 Pa to 50 Pa.
  • an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used.
  • the power applied to the power source can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, and the like. It is preferable to be in the range. If such an applied power is 100 W or more, the generation of particles can be sufficiently suppressed. On the other hand, if the applied power is 10 kW or less, the amount of heat generated at the time of film formation can be suppressed. An increase in surface temperature can be suppressed. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.
  • the conveyance speed (line speed) of the base material 2 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is in the range of 5 to 20 m / min. If the line speed is 0.25 m / min or more, generation of wrinkles due to heat in the substrate can be effectively suppressed. On the other hand, if it is 100 m / min or less, it is excellent at the point which can ensure sufficient film thickness as a 1st barrier layer, without impairing productivity.
  • a plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. 2 as the first barrier layer according to the present invention.
  • the film is formed by the above. This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode. This is because it is possible to efficiently manufacture the first barrier layer in which the barrier performance is compatible.
  • Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.
  • the first barrier layer according to the present invention is a method (coating method) formed by modifying a coating film formed by applying a liquid containing an inorganic compound, preferably a liquid containing a silicon compound, for example. It may be formed.
  • a liquid containing an inorganic compound preferably a liquid containing a silicon compound, for example. It may be formed.
  • the silicon compound will be described as an example of the inorganic compound, but the inorganic compound is not limited to the silicon compound.
  • the silicon compound is not particularly limited as long as a coating solution containing a silicon compound can be prepared.
  • perhydropolysilazane organopolysilazane, silsesquioxane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, Tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, dimethyldivinylsilane, dimethyl Ethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-
  • polysilazane such as perhydropolysilazane and organopolysilazane; polysiloxane such as silsesquioxane, etc. are preferable in terms of film formation, fewer defects such as cracks, and less residual organic matter, and high gas barrier performance.
  • Polysilazane is more preferable, and perhydropolysilazane is particularly preferable because the barrier performance is maintained even when bent and under high temperature and high humidity conditions.
  • the polysilazane is the same as that described in the modified polysilazane, and the description thereof is omitted here.
  • the content of polysilazane in the first barrier layer before the modification treatment may be 100% by mass when the total mass of the first barrier layer is 100% by mass.
  • the content of polysilazane in the layer is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass or less. More preferably, it is 70 mass% or more and 95 mass% or less.
  • the method for forming the first barrier layer by the application method as described above is not particularly limited, and a known method can be applied. However, the first barrier layer formation containing a silicon compound and, if necessary, a catalyst in an organic solvent is possible. It is preferable to apply the coating liquid for coating by a known wet coating method, evaporate and remove the solvent, and then perform a modification treatment.
  • the solvent for preparing the first barrier layer forming coating solution is not particularly limited as long as it can dissolve the silicon compound, but water and reactive groups (for example, hydroxyl group) that easily react with the silicon compound.
  • the solvent is an aprotic solvent; for example, pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, solvesso, terpene, aliphatic hydrocarbons, alicyclic carbonization, etc.
  • Hydrocarbon solvents such as hydrogen and aromatic hydrocarbons; 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; Dibutyl ether, dioxane, tetrahydrofuran, mono- And aliphatic ethers such as polyalkylene glycol dialkyl ethers (diglymes) and ethers such as alicyclic ethers.
  • the solvent is selected according to purposes such as the solubility of the silicon compound 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 the silicon compound in the first barrier layer-forming coating solution 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, particularly preferably 10 to 40% by mass.
  • the first barrier layer forming coating solution preferably contains a catalyst in order to promote reforming.
  • 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 the silicon compound. By setting the amount of the catalyst to be in this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.
  • a sol-gel method can be used for forming the first barrier layer.
  • the coating solution used when forming the modified layer by the sol-gel method preferably contains a silicon compound and at least one of a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer.
  • Method for applying first barrier layer forming coating solution As a method for applying the first barrier layer forming coating solution, a conventionally known appropriate wet coating method may be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
  • the coating thickness can be appropriately set according to the purpose.
  • the coating thickness per first barrier layer is preferably about 10 nm to 10 ⁇ m after drying, more preferably 15 nm to 1 ⁇ m, and further preferably 20 to 500 nm. preferable. If the film thickness is 10 nm or more, sufficient barrier properties can be obtained, and if it is 10 ⁇ m or less, stable coating properties can be obtained during layer formation, and high light transmittance can be realized.
  • a solvent such as an organic solvent contained in the coating film can be removed. At this time, all of the solvent contained in the coating film may be dried or may be partially left. Even when a part of the solvent is left, a suitable first barrier 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 modification treatment of the first barrier layer formed by the coating method in the present invention refers to a conversion reaction of a silicon compound to silicon oxide, silicon oxynitride, or the like.
  • the gas barrier film as a whole has gas barrier properties. This refers to a process for forming an inorganic thin film at a level that can contribute to the expression of (water vapor permeability of 1 ⁇ 10 ⁇ 3 g / m 2 ⁇ day or less).
  • the conversion reaction of the silicon compound to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method.
  • Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment.
  • the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment).
  • the treatment by the vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds atoms with only photons called photon processes.
  • This is a method of forming a silicon oxide film 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 by action.
  • the radiation source in the present invention may be any radiation source that emits light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator having a maximum emission at about 172 nm (eg, Xe excimer lamp), and has an emission line at about 185 nm.
  • Excimer radiator having a maximum emission at about 172 nm (eg, 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 target 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 ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out 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, more preferably 50 to 10,000 volume ppm. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.
  • 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. preferably, further preferably at 50mW / cm 2 ⁇ 160mW / cm 2. If it is 1 mW / cm 2 or more, sufficient reforming efficiency is obtained, and if it is 10 W / cm 2 or less, it is difficult to cause ablation in the coating film and damage the substrate.
  • Irradiation energy amount of the VUV in the coated surface it preferably from 10 ⁇ 10000mJ / cm 2, more preferably 100 ⁇ 8000mJ / cm 2, a 200 ⁇ 6000mJ / cm 2 Is more preferable. If it is 10 mJ / cm 2 or more, the modification can proceed sufficiently. If it is 10,000 mJ / cm 2 or less, cracking due to over-reformation and thermal deformation of the substrate are unlikely to occur.
  • the vacuum ultraviolet light used for reforming may be generated by plasma formed in a gas containing at least one of 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 gas barrier film obtained by the method of the present invention has a barrier layer (second barrier layer) formed using the modified polysilazane of the present invention, and preferably the modified polysilazane of the present invention on the first barrier layer.
  • a barrier layer (second barrier layer) formed using hereinafter although the preferable form of this invention in which the barrier layer (2nd barrier layer) formed using the modified polysilazane of this invention is provided on the first barrier layer is described, the present invention is limited to the following form. It is not something.
  • the first barrier layer may be omitted, and even in this case, the following form can be appropriately modified and applied.
  • the composition of the second barrier layer provided on the first barrier layer is not particularly limited, but it contains at least silicon atoms and oxygen atoms, and the abundance ratio of oxygen atoms to silicon atoms (O / Si) is 1.
  • the abundance ratio of nitrogen to silicon atoms (N / Si) is more preferably 0 to 0.4.
  • the abundance ratio of oxygen atoms to silicon atoms (O / Si) is 1.4 to 2.2” means that the depth of the second barrier layer measured by the apparatus and method described later. This also means that there is no portion where O / Si shows a value less than 1.4 or more than 2.2.
  • the abundance ratio of nitrogen atoms to silicon atoms (N / Si) is 0 to 0.4” means any depth of the second barrier layer measured by the apparatus and method described later. , N / Si means that there is no portion showing a value exceeding 0.4.
  • the second barrier layer reacts with moisture under high temperature and high humidity, and the barrier property is greatly reduced. Highly effective in preventing On the other hand, if the ratio is 2.2 or less, the ratio of silanol groups (Si—OH) present in the molecule decreases, and thus higher barrier properties can be obtained.
  • the O / Si is more preferably 1.5 to 2.1, and still more preferably 1.7 to 2.0.
  • the second barrier layer reacts with moisture under high temperature and high humidity, and the barrier property decreases.
  • the effect to prevent is high.
  • the N / Si is more preferably 0 to 0.3, and further preferably 0 to 0.2.
  • the O / Si and the N / Si can be measured by the following method. That is, the composition profile of the second barrier layer can be obtained by combining an Ar sputter etching apparatus and X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the profile distribution in the depth direction can be calculated by film processing by a FIB (focused ion beam) processing apparatus and by obtaining the actual film thickness by TEM (transmission electron microscope) and making it correspond to the XPS result.
  • FIB focused ion beam
  • the difference from the average value of the abundance ratio is preferably 0.4 or less.
  • the average value of the abundance ratio of oxygen atoms to silicon atoms in the region from the outermost surface to a depth of 10 nm, and the average value of the abundance ratio of oxygen atoms to silicon atoms in a region where the depth from the outermost surface exceeds 10 nm are: It can be calculated by a method combining the Ar sputter etching apparatus described above and X-ray photoelectron spectroscopy (XPS).
  • the second barrier layer may be formed by any method as long as it is formed using the coating solution of the modified polysilazane of the present invention, and a known method can be applied in the same manner or appropriately modified.
  • the method for forming the second barrier layer is not particularly limited, but a second barrier layer forming coating solution containing a modified polysilazane, preferably a modified polysilazane, and, if necessary, a catalyst or an additive compound in an organic solvent. Is preferably applied by a known wet coating method, the solvent is evaporated and removed, and then a modification treatment is performed by irradiation with active energy rays.
  • the second barrier layer is obtained by applying (i) a coating solution containing the modified polysilazane of the present invention (second coating solution for forming a barrier layer) on the inorganic compound layer (first barrier layer) and drying. It is preferable that the precursor layer be formed by further modifying (ii) the precursor layer by irradiation with active energy rays.
  • a precursor layer (coating film) is formed by applying and drying a coating solution (second barrier layer forming coating solution) on the inorganic compound layer.
  • the coating solution (second barrier layer forming coating solution) is prepared by dissolving modified polysilazane in a solvent.
  • the solvent constituting the coating solution of the modified polysilazane is not particularly limited as long as it can dissolve the modified polysilazane, but water and a reactive group (for example, a hydroxyl group, or easily reacting with the modified polysilazane).
  • An organic solvent that does not contain 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, pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, solvesso, terpene, aliphatic hydrocarbons, alicyclic carbonization, etc.
  • Hydrocarbon solvents such as hydrogen and aromatic hydrocarbons; 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; Dibutyl ether, dioxane, tetrahydrofuran, mono- And aliphatic ethers such as polyalkylene glycol dialkyl ethers (diglymes) and ethers such as alicyclic ethers.
  • the said solvent may be used independently or may be used with the form of a 2 or more types of mixture. Moreover, it is preferable to reduce the oxygen concentration and water content of the solvent before use.
  • Means for reducing the oxygen concentration and water content in the solvent are not particularly limited, and conventionally known methods can be applied.
  • the concentration of the modified polysilazane in the coating solution of the modified polysilazane 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 2 to 50% by mass. Particularly preferred is 10 to 40% by mass.
  • the modified polysilazane coating solution of the present invention may contain polysilazane as described above in addition to the modified polysilazane, but preferably contains only modified polysilazane as an active ingredient.
  • the modified polysilazane of the present invention is preferably modified with a metal alkoxide / chelate compound or a low-molecular silazane / siloxane that promotes external oxygen uptake.
  • the —SiH 3 group and the metal alkoxide / chelate compound in the modified polysilazane are highly reactive with moisture. For this reason, it is preferable to perform in the preparation process of a coating liquid in an environment with low oxygen and water vapor
  • a coating solution by dissolving modified polysilazane in a solvent in an environment where the oxygen concentration is 200 ppm by volume or less and the water vapor concentration is 100 ppm by volume or less.
  • the reaction of the modified polysilazane proceeds by absorption of vacuum ultraviolet light ( ⁇ 230 nm), and a dense barrier layer is formed.
  • the modified polysilazane reacts with oxygen and moisture in the environment at the stage of preparing the coating solution, the oxidation reaction has already progressed at the stage of irradiation with vacuum ultraviolet light, so that the vacuum ultraviolet light is sufficiently absorbed. Not absorbed.
  • Si—N of the modified polysilazane absorbs vacuum ultraviolet light, but when Si—N of the modified polysilazane reacts to become Si—O, it is stabilized in terms of energy, so that it does not absorb vacuum ultraviolet light. Conceivable.
  • the second barrier layer forming coating solution is prepared in an environment where the oxygen concentration is 200 ppm by volume or less and the water vapor concentration is 100 ppm by volume or less, the reaction between polysilazane and oxygen or moisture during preparation is suppressed. Can do. As a result, vacuum ultraviolet light can be effectively absorbed, so that Si—N remaining in the barrier layer after irradiation with vacuum ultraviolet light can be reduced.
  • the oxidation reaction of the modified polysilazane in a coating liquid may advance excessively by the oxygen in the environment at the time of liquid preparation. If the water vapor concentration exceeds 100 ppm by volume, the oxidation reaction of the modified polysilazane in the coating solution may proceed excessively due to the action of moisture.
  • the coating solution is prepared in an environment where the oxygen concentration is more preferably 0 to 100 ppm by volume, and even more preferably 0 to 30 ppm by volume. Further, it is carried out in an environment where the water vapor concentration is more preferably 0 to 50 ppm by volume, and still more preferably 0 to 30 ppm by volume.
  • Such an environment can be realized by preparing preparation equipment such as a glove box in which the oxygen concentration and water vapor concentration are controlled.
  • a dry inert gas is preferably used as the gas that satisfies the atmosphere and is used when the second barrier layer forming coating solution is prepared.
  • the inert gas include nitrogen, argon, helium and the like, but dry nitrogen gas is particularly preferable from the viewpoint of cost.
  • the oxygen concentration can be adjusted by measuring the flow rates of oxygen gas and inert gas introduced into the preparation equipment such as a glove box and changing the flow rate ratio.
  • the water vapor concentration in the atmosphere can be lowered by drying using a desiccant such as molecular sieves, for example. Further, the oxygen concentration in the atmosphere can be lowered by means of, for example, reacting with a metal copper catalyst or the like, or adsorbing it to an oxygen scavenger.
  • the coating solution prepared in this manner is applied onto the first barrier layer to form a coating film, and the coating film is irradiated with vacuum ultraviolet rays for modification treatment to produce a gas barrier film.
  • the second barrier layer forming coating solution preferably contains a catalyst in order to promote reforming.
  • 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.
  • an amine catalyst it is preferable to use an amine catalyst.
  • 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 the modified polysilazane. By setting the amount of the catalyst to be in this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.
  • the amine catalyst can also serve as the additive compound.
  • 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 especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.
  • the coating liquid (second barrier layer forming coating liquid) obtained above is preferably applied onto the first barrier layer to form a coating film.
  • a conventionally known appropriate wet coating method may be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
  • the coating thickness can be appropriately set according to the purpose.
  • the coating thickness (thickness after drying) per second barrier layer is preferably about 10 nm to 10 ⁇ m, more preferably 15 nm to 1 ⁇ m, and more preferably 20 to 500 nm. Further preferred. If the film thickness is 10 nm or more, sufficient barrier properties can be obtained, and if it is 10 ⁇ m or less, stable coating properties can be obtained during layer formation, and high light transmittance can be realized.
  • the atmosphere for applying the coating solution may be any conditions such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, a reduced pressure atmosphere in which the oxygen concentration is controlled, etc.
  • an inert gas atmosphere in which the oxygen concentration is controlled to 200 volume ppm or less and the water vapor concentration is controlled to 100 volume ppm or less.
  • a solvent such as an organic solvent contained in the coating film can be removed. At this time, all of the solvent contained in the coating film may be dried or may be partially left. Even when a part of the solvent is left, a suitable second barrier 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.
  • 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 in which the oxygen concentration is controlled.
  • a coating solution is prepared. As in the step, it is preferable to carry out in an inert gas atmosphere in which the oxygen concentration is controlled to 200 volume ppm or less and the water vapor concentration is controlled to 100 volume ppm or less.
  • the coating film obtained as described below is subjected to a modification treatment by irradiating it with vacuum ultraviolet rays, but the transmittance of light at 172 nm of the coating film immediately before irradiation with vacuum ultraviolet rays is preferably 20% or less, It is more preferably 15% or less, and further preferably 10% or less. This is because by having sufficient absorption with respect to vacuum ultraviolet light, modification by vacuum ultraviolet light proceeds and a dense barrier layer is formed.
  • the lower limit of the transmittance of light at 172 nm of the coating film immediately before irradiation with vacuum ultraviolet rays is not particularly limited, but is substantially 0.1% or more. The value measured by the method described in the Examples is adopted as the light transmittance of 172 nm of the coating film.
  • the precursor layer (coating film) obtained in the above step (i) is irradiated with active energy rays such as ultraviolet rays, electron beams, X rays, ⁇ rays, ⁇ rays, ⁇ rays, neutron rays,
  • active energy rays such as ultraviolet rays, electron beams, X rays, ⁇ rays, ⁇ rays, ⁇ rays, neutron rays,
  • active energy rays such as ultraviolet rays, electron beams, X rays, ⁇ rays, ⁇ rays, ⁇ rays, neutron rays.
  • any commonly used active energy ray generator can be used, but a vacuum ultraviolet ray generator is preferably used.
  • the method described in (ultraviolet irradiation process) in the section of the “first barrier layer” can be applied.
  • the method and conditions described in the “ultraviolet irradiation treatment” section of the above “first barrier layer” can be applied also in this step (ii), and thus will be omitted.
  • Vacuum ultraviolet irradiation is not particularly limited.
  • the modified polysilazane of the present invention is modified with a metal alkoxide / chelate compound that promotes external oxygen uptake. For this reason, it is important to supply oxygen from the surface of the coating film, and it is preferable to carry out under conditions where oxygen is present rather than a completely inert gas atmosphere.
  • vacuum ultraviolet irradiation is preferably performed in an atmosphere having an oxygen concentration of 200 to 10,000 ppm by volume. That is, in the step (ii), the modification treatment is preferably performed by irradiation with vacuum ultraviolet rays having a wavelength of 230 nm or less in an atmosphere having an oxygen concentration of 200 to 10,000 volume ppm.
  • the oxygen concentration at the time of vacuum ultraviolet irradiation is 500 to 5,000 volume ppm, and more preferably 700 to 2,000 volume ppm. If the oxygen concentration is 200 ppm by volume or more, oxygen is supplied during vacuum ultraviolet irradiation, the reaction between the metal compound and polysilazane is sufficiently promoted, and as carbon dioxide derived from the metal compound, nitrogen oxide derived from polysilazane, and ammonia Released outside the system.
  • the second coating liquid for forming the barrier layer contains a metal compound, if there is a large proportion of carbon atoms derived from the metal compound remaining in the barrier layer, the gas barrier property may decrease, but it reacts with oxygen.
  • the gas barrier property of the barrier layer obtained by being released out of the system as carbon dioxide can be improved.
  • vacuum ultraviolet rays are absorbed by oxygen, a decrease in efficiency in the vacuum ultraviolet irradiation process can be suppressed by carrying out in an atmosphere having an oxygen concentration of 10,000 ppm by volume or less.
  • the irradiation with vacuum ultraviolet rays is performed in a state where the water vapor concentration is as low as possible.
  • the water vapor concentration at the time of vacuum ultraviolet irradiation is preferably 1000 ppm by volume or less, and more preferably 200 ppm by volume or less.
  • the vacuum ultraviolet irradiation is not particularly limited, but is preferably performed by controlling the temperature of the coating film at 50 to 120 ° C.
  • the temperature of the coating film at the time of irradiation with vacuum ultraviolet rays is more preferably 60 to 100 ° C., further preferably 70 to 90 ° C.
  • the reaction between the metal compound and polysilazane is sufficiently accelerated, the gas barrier property is excellent, and the gas barrier property is excellent in storage stability under high temperature and high humidity. A film can be obtained.
  • the temperature of the coating film at the time of vacuum ultraviolet irradiation is 120 ° C.
  • the specific means for controlling the temperature of the coating film is not particularly limited, and a conventionally known method can be appropriately used. Furthermore, it is more preferable to control the temperature of the atmosphere at the time of vacuum ultraviolet irradiation to the above range. A means for controlling the temperature of the atmosphere is not particularly limited, and a conventionally known method can be appropriately used.
  • the illuminance of the vacuum ultraviolet light on the surface of the coating film formed from the second barrier layer forming coating solution is preferably 1 mW / cm 2 to 10 W / cm 2 , and 30 mW / cm 2. more preferably 2 ⁇ 200mW / cm 2, further preferably at 50mW / cm 2 ⁇ 160mW / cm 2. If it is 1 mW / cm 2 or more, sufficient reforming efficiency is obtained, and if it is 10 W / cm 2 or less, it is difficult to cause ablation in the coating film and damage the substrate.
  • the amount of irradiation energy (integrated light amount) of vacuum ultraviolet rays on the coating film surface formed from the second barrier layer forming coating solution is preferably 10 to 10000 mJ / cm 2 , and preferably 100 to 8000 mJ / cm 2 . More preferably, it is 200 to 6000 mJ / cm 2 . If it is 10 mJ / cm 2 or more, the modification can proceed sufficiently. If it is 10,000 mJ / cm 2 or less, cracking due to over-reformation and thermal deformation of the substrate are unlikely to occur.
  • the film density of the second barrier layer can be appropriately set according to the purpose.
  • the film density of the second barrier layer is preferably in the range of 1.5 to 2.6 g / cm 3 . If it is the said range, the density of a film
  • the second barrier layer may be a single layer or a laminated structure of two or more layers.
  • each second barrier layer may have the same composition or a different composition.
  • the gas barrier film of the present invention may have an intermediate layer between the first barrier layer and the second barrier layer for the purpose of stress relaxation and the like.
  • a method of forming the intermediate layer a method of forming a polysiloxane modified layer can be applied.
  • a coating liquid containing polysiloxane is applied on the first barrier layer by a wet coating method and dried, and then the coating film obtained by drying is irradiated with vacuum ultraviolet light.
  • This is a method of forming an intermediate layer.
  • the intermediate layer is not particularly limited, and can be applied in the same manner or appropriately modified as the intermediate layer described in, for example, Japanese Patent Application Laid-Open Nos. 2014-151571 and 2014-046272.
  • the coating solution used for forming the intermediate layer preferably contains polysiloxane and an organic solvent.
  • the polysiloxane applicable to the formation of the intermediate layer is not particularly limited, and conventionally known compounds such as those described in JP2014-151571A, JP2014-046272A, and the like are used. can do.
  • a protective layer containing an organic compound may be provided on the second barrier layer.
  • an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group is preferably used.
  • the protective layer is not particularly limited, and can be applied, for example, in the same manner or appropriately modified as the protective layer described in JP2014-151571A, JP2014-046272A, and the like.
  • the gas barrier film of the present invention may have a desiccant layer (moisture adsorption layer).
  • the material used for the desiccant layer include calcium oxide and organometallic oxide.
  • calcium oxide what was disperse
  • the organic metal oxide OleDry (registered trademark) series manufactured by Futaba Electronics Co., Ltd. or the like can be used.
  • the gas barrier film of the present invention may have a smooth layer (underlayer, primer layer) between the surface of the substrate having the barrier layer, preferably between the substrate and the first barrier layer.
  • the smooth layer is provided in order to flatten the rough surface of the substrate on which the protrusions and the like exist, or to fill the unevenness and pinholes generated in the barrier layer with the protrusions on the substrate and to flatten the surface.
  • Such a smooth layer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer. That is, it is preferable that the gas barrier film of the present invention further has a smooth layer containing a carbon-containing polymer between the substrate and the first barrier layer.
  • the smooth layer also contains a carbon-containing polymer, preferably a curable resin.
  • the curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material or the like with an active energy ray such as an ultraviolet ray to be cured is heated. And thermosetting resins obtained by curing. These curable resins may be used alone or in combination of two or more.
  • the smooth layer is not particularly limited, and can be applied, for example, as the smooth layer described in JP-A No. 2014-151571, JP-A No. 2014-046272, or the like as appropriate.
  • an anchor coat layer On the surface of the base material according to the present invention, an anchor coat layer may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion).
  • the anchor coat agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene / vinyl alcohol resin, vinyl-modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. Can be used alone or in combination of two or more.
  • a commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., “X-12-2400” in 3% isopropyl alcohol) can be used.
  • the above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is coated by drying and removing the solvent, diluent, etc. Can do.
  • the application amount of the anchor coating agent is preferably about 0.1 to 5 g / m 2 (dry state).
  • a commercially available base material with an easy-adhesion layer may be used.
  • 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.
  • the thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 ⁇ m.
  • the gas barrier film of the present invention can further have a bleed-out preventing layer.
  • the bleed-out prevention layer has a smooth layer for the purpose of suppressing the phenomenon of unreacted oligomers moving from the base material to the surface when the film having the smooth layer is heated and contaminating the contact surface.
  • the bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.
  • Compounds that can be included in the bleed-out prevention layer include polyunsaturated organic compounds having two or more polymerizable unsaturated groups in the molecule, or one polymerizable unsaturated group in the molecule.
  • Hard coat agents such as unitary unsaturated organic compounds can be mentioned.
  • the bleed-out prevention layer is not particularly limited, and can be applied, for example, as the bleed-out prevention layer described in JP-A No. 2014-151571, JP-A No. 2014-046272, or the like or appropriately modified.
  • the gas barrier film according to the present invention can be continuously produced and wound into a roll form (so-called roll-to-roll production). In that case, it is preferable to stick and wind up a protective sheet on the surface in which the barrier layer was formed.
  • a protective sheet is applied in a place with a high degree of cleanliness. It is very effective to prevent the adhesion of dust. In addition, it is effective for preventing scratches on the surface of the barrier layer that enters during winding.
  • the protective sheet is not particularly limited, and general “protective sheet” and “release sheet” having a configuration in which a weakly adhesive layer is provided on a resin substrate having a thickness of about 100 ⁇ m can be used.
  • the water vapor permeability of the gas barrier film produced by the method of the present invention is preferably as low as possible. For example, it is preferably 1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 5 g / m 2 ⁇ day, and preferably 1 ⁇ 10. -4 to 1 ⁇ 10 -5 g / m 2 ⁇ day is more preferable.
  • the water vapor transmission rate is a value measured by the method described in Examples described later.
  • the gas barrier film produced by the method of the present invention can be preferably used for a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air.
  • the device include electronic devices such as an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device. That is, the present invention also provides an organic EL device having the gas barrier film of the present invention.
  • the gas barrier film produced by the method of the present invention can also be used for device film sealing. That is, it is a method of providing the gas barrier film of the present invention on the surface of the device itself as a support.
  • the device may be covered with a protective layer before providing the gas barrier film.
  • the gas barrier film produced by the method of the present invention can also be used as a device substrate or a film for sealing by a solid sealing method.
  • the solid sealing method is a method in which after a protective layer is formed on a device, an adhesive layer and a gas barrier film are stacked and cured.
  • an adhesive agent A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.
  • Organic EL device Examples of organic EL elements using a gas barrier film are described in detail in JP-A-2007-30387.
  • the reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a ⁇ / 4 plate, and a polarizing film in order from the bottom.
  • the gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
  • the transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a ⁇ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a ⁇ / 4 plate, and a polarization It has a structure consisting of a film. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
  • the type of the liquid crystal cell is not particularly limited, but more preferably a TN type (Twisted Nematic), an STN type (Super Twisted Nematic), a HAN type (Hybrid Aligned Nematic), a VA type (Vertical Alignment), an EC type, a B type.
  • TN type Transmission Nematic
  • STN type Super Twisted Nematic
  • HAN type Hybrid Aligned Nematic
  • VA Very Alignment
  • an EC type a B type.
  • OCB type Optically Compensated Bend
  • IPS type In-Plane Switching
  • CPA type Continuous Pinwheel Alignment
  • the gas barrier film of the present invention can also be used as a sealing film for solar cell elements.
  • the gas barrier film of the present invention is preferably sealed so that the barrier layer is closer to the solar cell element.
  • the solar cell element in which the gas barrier film of the present invention is preferably used is not particularly limited. For example, it is a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, or a tandem structure type.
  • Amorphous silicon-based solar cell elements III-V group compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI group compound semiconductor solar cell elements such as cadmium tellurium (CdTe), I-III- such as copper / indium / selenium (so-called CIS), copper / indium / gallium / selenium (so-called CIGS), copper / indium / gallium / selenium / sulfur (so-called CIGS), etc.
  • Group VI compound semiconductor solar cell element dye-sensitized solar cell element, organic solar cell element, etc. And the like.
  • the solar cell element is a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur.
  • CIS system copper / indium / selenium system
  • CIGS system copper / indium / gallium / selenium system
  • sulfur copper / indium / gallium / selenium / sulfur.
  • a group I-III-VI compound semiconductor solar cell element such as a system (so-called CIGSS system) is preferable.
  • the gas barrier film of the present invention can also be used as an optical member.
  • the optical member include a circularly polarizing plate.
  • a circularly polarizing plate can be produced by laminating a ⁇ / 4 plate and a polarizing plate using the gas barrier film in the present invention as a substrate. In this case, the lamination is performed so that the angle formed by the slow axis of the ⁇ / 4 plate and the absorption axis of the polarizing plate is 45 °.
  • a polarizing plate one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used.
  • MD longitudinal direction
  • those described in JP-A-2002-865554 can be suitably used. .
  • a film forming gas mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (which also functions as a discharge gas) as a source gas
  • HMDSO hexamethyldisiloxane
  • oxygen gas which also functions as a discharge gas
  • a gas barrier thin film inorganic compound layer, first barrier layer
  • the thickness of the inorganic compound layer was 150 nm. It was confirmed that the inorganic compound layer formed as described above contains carbon, silicon, and oxygen as constituent elements and satisfies the requirements (i) to (iii).
  • PHPS non-catalytic perhydropolysilazane
  • 29 Si-NMR measurement is performed as follows. Specifically, in the 29 Si-NMR measurement result, it is attributed to SiH and SiH 2 observed in the vicinity of ⁇ 35 ppm when the area of the peak attributed to SiH 3 observed in the vicinity of ⁇ 50 ppm is 1. The ratio of the peak areas is the SiH 3 ratio.
  • the measurement is performed using a 500 MHz NMR apparatus manufactured by JEOL Ltd. using an NMR tube tube for 29 Si measurement and using heavy benzene as a solvent.
  • the coating solution obtained above is formed on the inorganic compound layer with a spin coater so that the thickness (dry film thickness) is 80 nm, left for 2 minutes, and then heated on an 80 ° C. hot plate. Additional heat treatment was performed for 1 minute to form a polysilazane coating film (precursor layer).
  • a vacuum ultraviolet ray irradiation treatment is performed so that a vacuum ultraviolet ray of 172 nm becomes 6000 mJ / cm 2 according to the following method.
  • the gas barrier film 101 was produced.
  • SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured in the same manner as described above, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (1) is read as SiH 3 ratio of the barrier layer (second barrier layer).
  • reference numeral 21 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.
  • vacuum ultraviolet irradiation was performed with the oxygen concentration adjusted to 1,000 ppm by volume.
  • the oxygen concentration in the chamber was measured using an oxygen concentration meter (zirconia oxygen concentration meter LC-450A manufactured by Toray Engineering Co., Ltd.).
  • Reference numeral 22 denotes an Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm
  • reference numeral 23 denotes an excimer lamp holder that also serves as an external electrode.
  • Reference numeral 24 denotes a sample stage. The sample stage 24 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 21 by a moving means (not shown). The sample stage 24 can be maintained at a predetermined temperature by a heating means (not shown). Here, it was set to 100 ° C.
  • Reference numeral 25 denotes a sample on which a polysilazane coating film is formed.
  • Reference numeral 26 denotes a light shielding plate, which prevents the application layer of the sample from being irradiated with vacuum ultraviolet light during aging of the Xe excimer lamp 22.
  • the energy irradiated to the coating film surface in the vacuum ultraviolet irradiation process was measured using a 172 nm sensor head using a UV integrating light meter: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics Co., Ltd.
  • the sensor head is placed in the center of the sample stage 24 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 6 mm, and the atmosphere in the apparatus chamber 21 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 measurement was performed by moving the sample stage 24 at a speed of 0.5 m / min (V in FIG. 3).
  • 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 irradiation speed was adjusted to 6000 mJ / cm 2 by adjusting the moving speed of the sample stage.
  • the vacuum ultraviolet irradiation was performed after aging for 10 minutes as in the case of irradiation energy measurement.
  • Comparative Example 2 Production of gas barrier film 102
  • ALCH Korean Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate
  • a gas barrier film 102 was produced in the same manner as in Comparative Example 1 except that the coating liquid (2) prepared by stirring and reacting at 80 ° C. for 1 hour and then cooling was used.
  • the said reaction was performed in the atmosphere whose water vapor
  • the oxygen concentration in the reaction system was measured using an oxygen concentration meter (zirconia type oxygen concentration meter LC-450A manufactured by Toray Engineering Co., Ltd.).
  • the water vapor concentration in the reaction system was determined by measuring the dew point using a dew point meter (manufactured by Vaisala, DMT type dew point meter), and obtaining the water vapor concentration from the measured dew point.
  • Comparative Example 3 Production of gas barrier film 103
  • ALCH aluminum ethyl acetoacetate diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.
  • ALCH aluminum ethyl acetoacetate diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.
  • a gas barrier film 103 was produced in the same manner as in Comparative Example 1 except that the coating liquid (3) prepared by stirring and reacting at 80 ° C. for 1 hour and then cooling was used. .
  • the said reaction was performed in the atmosphere whose water vapor
  • Example 1 Production of gas barrier film 104)
  • ALCH Korean Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate
  • a gas barrier film 104 was produced in the same manner as in Comparative Example 1 except that the coating liquid (4) prepared by further stirring and reacting at 80 ° C. for 1 hour and then cooling was used in addition to the liquid (1). .
  • the said reaction was performed in the atmosphere whose water vapor
  • Example 2 Production of gas barrier film 105)
  • AMD Korean Fine Chemical Co., Ltd., aluminum diisopropylate monosecondary butyrate
  • a gas barrier film 105 was produced in the same manner as in Comparative Example 1 except that the coating liquid (5) prepared by stirring and reacting at 80 ° C. for 1 hour and then cooling was used. .
  • the said reaction was performed in the atmosphere whose water vapor
  • Example 3 Production of gas barrier film 106
  • aluminum chelate D produced by Kawaken Fine Chemical Co., Ltd., aluminum bisethyl acetoacetate / monoacetylacetonate
  • the coating solution (6) prepared by further stirring and reacting at 80 ° C. for 1 hour and then cooling was used. 106 was produced.
  • the said reaction was performed in the atmosphere whose water vapor
  • Example 4 Production of gas barrier film 107) [Formation of inorganic compound layer (first barrier layer) (plasma CVD method)] In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
  • TDAH 1,6-diaminohexane
  • NAX120-20 1,6-diaminohexane
  • the coating solution (7-1) thus prepared ALCH (Aluminum ethyl acetoacetate diisopropylate, manufactured by Kawaken Fine Chemical Co., Ltd.) is used in an amount of 5 mol% based on the number of Si elements in perhydropolysilazane. After that, the mixture was further reacted with stirring at 80 ° C. for 1 hour and then cooled to prepare a coating solution (7-2). Next, Compound 1 having the following structure was further added to this coating solution (7-2) in an amount of 5 mol% with respect to the number of Si elements of perhydropolysilazane, and then stirred at 80 ° C. for 1 hour. After cooling, a coating solution (7-3) was prepared.
  • ALCH Aligninum ethyl acetoacetate diisopropylate, manufactured by Kawaken Fine Chemical Co., Ltd.
  • a gas barrier film 107 was produced in the same manner as in Comparative Example 1, except that the coating liquid (7-3) prepared as described above was used instead of the coating liquid (1). .
  • the said reaction was performed in the atmosphere whose water vapor
  • the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (7) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
  • Example 5 to 11 Production of gas barrier films 108 to 114
  • gas barrier films 108 to 114 were produced in the same manner as in Example 4, except that compounds 2 to 8 having the following structures were used instead of compound 1, respectively.
  • the said reaction was performed in the atmosphere whose water vapor
  • the ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane in each coating solution was prepared in this example [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1.
  • the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of each polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solutions shown in Table 1 is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
  • Example 12 Production of gas barrier film 115
  • a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
  • a solution of 20% by mass of perhydropolysilazane containing 5% by mass of 1,6-diaminohexane (TMDAH) manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20
  • TDAH 1,6-diaminohexane
  • NAX120-20 1,6-diaminohexane
  • the coating solution (8-1) thus prepared AMD (aluminum diisopropylate monosecondary butyrate manufactured by Kawaken Fine Chemical Co., Ltd.) is used in an amount of 5 mol% with respect to the number of Si elements in perhydropolysilazane. After further addition, the mixture was allowed to react with stirring at 80 ° C. for 1 hour and then cooled to prepare a coating solution (8-2). Next, the compound 1 is further added to the coating solution (8-2) in an amount of 5 mol% with respect to the number of Si elements of perhydropolysilazane, and then stirred at 80 ° C. for 1 hour and then cooled. Thus, a coating solution (8-3) was prepared.
  • AMD aluminum diisopropylate monosecondary butyrate manufactured by Kawaken Fine Chemical Co., Ltd.
  • a gas barrier film 115 was produced in the same manner as in Comparative Example 1, except that the coating liquid (8-3) prepared as described above was used instead of the coating liquid (1). .
  • the said reaction was performed in the atmosphere whose water vapor
  • the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (8-3) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
  • Example 13 to 14 Production of gas barrier films 116 to 117
  • gas barrier films 116 to 117 were produced in the same manner as in Example 12 except that the compounds 3 and 5 were used instead of the compound 1, respectively.
  • the said reaction was performed in the atmosphere whose water vapor
  • the ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane in each coating solution was prepared in this example [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1.
  • SiH 3 ratio of the obtained barrier layer (second barrier layer) When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solutions shown in Table 1 is replaced with SiH 3 ratio of the corresponding barrier layer (second barrier layer).
  • Example 15 Production of gas barrier film 118
  • a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
  • a solution of 20% by mass of perhydropolysilazane containing 5% by mass of 1,6-diaminohexane (TMDAH) manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20
  • TDAH 1,6-diaminohexane
  • NAX120-20 1,6-diaminohexane
  • the coating solution (9-1) was prepared so that the ratio was 2.7% by mass.
  • the coating solution (9-1) thus prepared aluminum chelate D (produced by Kawaken Fine Chemical Co., Ltd., aluminum bisethylacetoacetate / monoacetylacetonate) was added in an amount of 5 mol with respect to the number of Si elements in perhydropolysilazane. % was added, followed by stirring and reaction at 80 ° C. for 1 hour, followed by cooling to prepare a coating solution (9-2).
  • the compound 1 is further added to the coating solution (9-2) in an amount of 5 mol% with respect to the number of Si elements of perhydropolysilazane, followed by stirring at 80 ° C. for 1 hour and cooling.
  • a coating solution (9-3) was prepared.
  • a gas barrier film 118 was produced in the same manner as in Comparative Example 1 except that the coating liquid (9-3) prepared as described above was used instead of the coating liquid (1). .
  • the said reaction was performed in the atmosphere whose water vapor
  • the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (9-3) is replaced with SiH 3 ratio of the barrier layer (second barrier layer).
  • Example 16 to 17 Production of gas barrier films 119 to 120
  • gas barrier films 119 to 120 were produced in the same manner as in Example 15 except that the compounds 3 and 5 were used instead of the compound 1, respectively.
  • the said reaction was performed in the atmosphere whose water vapor
  • the ratio of the sum of the SiH 3 and SiH and SiH 2 as measured by 29 Si-NMR of the modified polysilazane in each coating solution was prepared in this example [(SiH 3) :( SiH + SiH 2)], Measurements were made in the same manner as in Comparative Example 1, and the results are shown in Table 1.
  • SiH 3 ratio of the obtained barrier layer (second barrier layer) When the SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solutions shown in Table 1 is replaced with SiH 3 ratio of the corresponding barrier layer (second barrier layer).
  • Example 18 Production of gas barrier film 121) [Formation of inorganic compound layer (first barrier layer) (plasma CVD method)] In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
  • TDAH 1,6-diaminohexane
  • NAX120-20 1,6-diaminohexane
  • the above compound 3 was further added in an amount of 5 mol% with respect to the number of Si elements of perhydropolysilazane, and then stirred at 80 ° C. for 1 hour. After cooling, a coating solution (10-2) was prepared. Next, ALCH (produced by Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate) was further added to this coating solution (10-2) in an amount of 5 mol% with respect to the number of Si elements in perhydropolysilazane. Then, the mixture was allowed to react with stirring at 80 ° C. for 1 hour and then cooled to prepare a coating solution (10-3).
  • ALCH produced by Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate
  • a gas barrier film 121 was produced in the same manner as in Comparative Example 1, except that the coating liquid (10-3) prepared as described above was used instead of the coating liquid (1). .
  • the said reaction was performed in the atmosphere whose water vapor
  • the obtained barrier layer (second barrier layer) was measured for SiH 3 ratio showed values similar to SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (10-3) is read as SiH 3 ratio of the barrier layer (second barrier layer).
  • Example 19 Production of gas barrier film 122) [Formation of inorganic compound layer (first barrier layer) (plasma CVD method)] In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
  • TDAH methyl-1,6-diaminohexane
  • NAX120-20 methyl-1,6-diaminohexane
  • the above-described coating solution was further added with each of the compound 3 and ALCH in an amount of 5 mol% based on the number of Si elements in perhydropolysilazane. After stirring and reacting at 80 ° C. for 1 hour, the mixture was cooled to prepare a coating solution (11-3). In addition, the said reaction was performed in the atmosphere whose water vapor
  • a gas barrier film 122 was produced in the same manner as in Comparative Example 1 except that the coating liquid (11-3) prepared as described above was used instead of the coating liquid (1).
  • the coating liquid (11-3) prepared as described above was used instead of the coating liquid (1).
  • SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (11-3) is read as SiH 3 ratio of the barrier layer (second barrier layer).
  • Example 20 Production of gas barrier film 123) [Formation of inorganic compound layer (first barrier layer) (plasma CVD method)] In the same manner as in Comparative Example 1, a gas barrier thin film (inorganic compound layer, first barrier layer) having a thickness of 150 nm was formed on a substrate by plasma CVD.
  • TDAH 1,6-diaminohexane
  • NAX120-20 1,6-diaminohexane
  • the coating liquid (12-1) thus prepared was mixed with ALCH (aluminum ethyl acetoacetate diisopropylate) manufactured by Kawaken Fine Chemical Co., Ltd. and the above compound 3 with respect to the number of Si elements in perhydropolysilazane. After further adding in an amount of 5 mol%, the mixture was reacted with stirring at 80 ° C. for 1 hour and then cooled to prepare a coating solution (12-2).
  • ALCH aluminum ethyl acetoacetate diisopropylate
  • a gas barrier film 123 was produced in the same manner as in Comparative Example 1, except that the coating liquid (12-2) prepared as described above was used instead of the coating liquid (1). .
  • the above reaction was performed in an atmosphere having a water vapor concentration and an oxygen concentration of 10 ppm by volume or less.
  • SiH 3 ratio of the obtained barrier layer (second barrier layer) was measured, it showed a value similar to the SiH 3 ratio of the polysilazane-containing coating solution. Therefore, SiH 3 ratio of the coating solution shown in Table 1 (12-2) is read as SiH 3 ratio of the barrier layer (second barrier layer).
  • Vapor deposition device JEOL Ltd., vacuum vapor deposition device JEE-400 Constant temperature and humidity oven: Yamato Humidic Chamber IG47M (raw materials) Metal that reacts with water and corrodes: Calcium (granular) Water vapor impermeable metal: Aluminum ( ⁇ 3-5mm, granular) (Preparation of water vapor barrier property evaluation sample)
  • a vacuum vapor deposition device vacuum vapor deposition device JEE-400 manufactured by JEOL Ltd.
  • calcium metal was deposited on the surface of the second barrier layer of the produced gas barrier film in a size of 12 mm ⁇ 12 mm through a mask. At this time, the deposited film thickness was set to 80 nm.
  • the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet and temporarily sealed.
  • the vacuum state is released, and it is immediately transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum vapor-deposited surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX Corporation).
  • the water vapor barrier property evaluation sample was produced by irradiating ultraviolet rays to cure and adhere the resin to perform main sealing.
  • the obtained sample was stored at a high temperature and high humidity of 85 ° C. and 85% RH, and the state in which the metal calcium was corroded with respect to the storage time was observed. Observation was obtained by linearly interpolating the time when the area where metal calcium was corroded with respect to the metal calcium deposition area of 12 mm ⁇ 12 mm to 50% from the observation results, and the water vapor transmission rate WVTR (g / m 2 / g from the amount of deteriorated calcium. day).
  • the gas barrier film produced according to the examples of the present invention hardly deteriorates in gas barrier property due to composition change even after being exposed to high temperature and high humidity for a long time. I understand.
  • first electrode layer A 150-nm-thick ITO (indium tin oxide) film formed by sputtering on an alkali-free glass was patterned by photolithography to form a first electrode layer. The pattern was such that the light emission area was 50 mm square.
  • a coating liquid for forming a hole transport layer shown below is extrusion-coated in an environment of 25 ° C. and a relative humidity of 50% RH. After coating, the substrate was dried and heated under the following conditions to form a hole transport layer. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.
  • the gas barrier film was subjected to cleaning surface modification using a low-pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm 2 and a distance of 10 mm.
  • the charge removal treatment was performed using a static eliminator with weak X-rays.
  • PEDOT / PSS polystyrene sulfonate
  • Baytron P AI 4083 manufactured by Bayer
  • ⁇ Drying and heat treatment conditions After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment.
  • the back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.
  • the following coating solution for forming a white light emitting layer is applied by an extrusion coater under the following conditions, followed by drying and heat treatment under the following conditions to form a light emitting layer. did.
  • the white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.
  • ⁇ White luminescent layer forming coating solution> As a host material, 1.0 g of a compound represented by the following chemical formula HA, 100 mg of a compound represented by the following chemical formula DA as a dopant material, and 0.1 mg of a compound represented by the following chemical formula DB as a dopant material. 2 mg of a compound represented by the following chemical formula DC as a dopant material was dissolved in 0.2 mg and 100 g of toluene to prepare a white light emitting layer forming coating solution.
  • the coating process is performed in an atmosphere with a nitrogen gas concentration of 99% or more, the coating temperature is 25 ° C., and the coating speed is 1 m. / Min.
  • ⁇ Drying and heat treatment conditions After applying the white light emitting layer forming coating solution, the solvent was removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., and then a temperature of 130 ° C. A heat treatment was performed to form a light emitting layer.
  • the following electron transport layer forming coating solution was applied by an extrusion coater under the following conditions, and then dried and heat-treated under the following conditions to form an electron transport layer.
  • the coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.
  • the coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.
  • the electron transport layer was prepared by dissolving a compound represented by the following chemical formula EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating solution for forming an electron transport layer.
  • An electron injection layer was formed on the electron transport layer formed above.
  • the substrate was put into a decompression chamber and decompressed to 5 ⁇ 10 ⁇ 4 Pa.
  • cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.
  • Aluminum is used as the second electrode forming material on the electron injection layer formed as described above, except for the portion that becomes the extraction electrode of the first electrode 22 under a vacuum of 5 ⁇ 10 ⁇ 4 Pa, A mask pattern was formed by vapor deposition so as to have an extraction electrode so that the light emission area was 50 mm square, and a second electrode having a thickness of 100 nm was laminated.
  • thermosetting adhesive containing bisphenol A diglycidyl ether (DGEBA), dicyandiamide (DICY) and an epoxy adduct curing accelerator was used as the thermosetting adhesive.
  • the gas barrier film is closely attached and arranged so that the extraction electrode (including the extraction electrodes of the first electrode and the second electrode) patterned on the first electrode is exposed, and the vacuum laminator is Used tightly sealed. After sealing, post-curing treatment was performed at 110 ° C. for 15 minutes to produce an organic EL element.
  • the gas barrier film produced according to the example of the present invention has the effect of reducing the occurrence of dark spots by using it as a sealing film for organic EL elements, and has a very high gas barrier property.

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Abstract

　L'invention concerne un procédé de production d'un film barrière contre les gaz présentant une stabilité d'entreposage exceptionnelle, en particulier une stabilité d'entreposage dans des conditions rigoureuses (conditions de température élevée ou de forte humidité). Ce polysilazane modifié présente un rapport ((SiH3:(SiH+SiH2)) de SiH3 et le total de SiH et SiH2 de 1:10 à 30, tel que mesuré par 29Si-NMR.
PCT/JP2015/053435 2014-02-07 2015-02-06 Polysilazane modifié, solution de revêtement contenant ledit polysilazane modifié, et film barrière contre les gaz obtenu à l'aide de ladite solution de revêtement WO2015119260A1 (fr)

Priority Applications (2)

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CN201580006849.2A CN105939959A (zh) 2014-02-07 2015-02-06 改性聚硅氮烷、含有该改性聚硅氮烷的涂布液及使用该涂布液而制造的气体阻隔性膜
JP2015561067A JPWO2015119260A1 (ja) 2014-02-07 2015-02-06 変性ポリシラザン、当該変性ポリシラザンを含む塗布液および当該塗布液を用いて製造されるガスバリア性フィルム

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TWI756475B (zh) * 2017-10-06 2022-03-01 日商東京威力科創股份有限公司 抑制粒子產生之方法及真空裝置
CN112480817B (zh) * 2020-11-26 2021-11-30 徐玲 一种可热固化、湿气固化或uv固化的防腐组合物
CN113105663A (zh) * 2021-04-13 2021-07-13 中山大学 一种具有透明硅氧化物涂层的高阻隔生物可降解薄膜及其制备方法

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