WO2016009801A1 - Film barrière aux gaz et dispositif électronique - Google Patents

Film barrière aux gaz et dispositif électronique Download PDF

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WO2016009801A1
WO2016009801A1 PCT/JP2015/068227 JP2015068227W WO2016009801A1 WO 2016009801 A1 WO2016009801 A1 WO 2016009801A1 JP 2015068227 W JP2015068227 W JP 2015068227W WO 2016009801 A1 WO2016009801 A1 WO 2016009801A1
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layer
gas barrier
film
anchor coat
coat layer
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PCT/JP2015/068227
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English (en)
Japanese (ja)
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森　孝博
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コニカミノルタ株式会社
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Priority to KR1020167036284A priority Critical patent/KR101905298B1/ko
Priority to CN201580038447.0A priority patent/CN106536192B/zh
Priority to JP2016534345A priority patent/JPWO2016009801A1/ja
Publication of WO2016009801A1 publication Critical patent/WO2016009801A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of 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; Derivatives of such polymers
    • C08J2483/16—Characterised by the use of 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; Derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

  • the present invention relates to a gas barrier film and an electronic device.
  • 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 for packaging of articles that require the use of, for example, packaging for preventing deterioration of foods, industrial products, pharmaceuticals, and the like.
  • gas barrier films used for sealing organic EL devices are required to have high barrier properties and flexibility.
  • a bottom emission type organic EL device using a gas barrier film as a substrate is required to have a gas barrier property with a very high glass level, and in-plane uniformity of the gas barrier property (a portion having a low barrier property in a spot shape). Is not required).
  • the gas barrier layer of such a gas barrier film has been formed by a plasma CVD method (see, for example, Patent Document 1).
  • a plasma CVD method see, for example, Patent Document 1
  • the gas barrier layer was formed by plasma CVD using high plasma excitation power, it was found that the substrate surface was subject to an energy load during film formation, and the gas barrier layer was likely to be damaged.
  • such a gas barrier film is used as a substrate of an organic EL device, many dark spots are generated, and thus it has been demanded to improve damage to the base material and the gas barrier layer.
  • Patent Document 2 discloses an undercoat layer having a high inorganic component ratio, which is formed by applying and drying a coating solution containing a silane coupling agent as a main component.
  • Patent Document 3 discloses an undercoat layer mainly composed of an inorganic component formed by applying dialkoxysilane to polysilazane (PHPS) and applying and drying the mixed application liquid as an undercoat layer of the vapor deposition barrier layer.
  • PHPS dialkoxysilane to polysilazane
  • Patent Document 4 at least a part is modified by irradiating a polysilazane film formed by applying and drying a coating liquid containing polysilazane on a lower portion of a gas barrier layer formed by a vacuum film-forming method by drying.
  • a polysilazane film formed by applying and drying a coating liquid containing polysilazane on a lower portion of a gas barrier layer formed by a vacuum film-forming method by drying is disclosed.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a gas barrier film having high gas barrier properties and in-plane uniformity of gas barrier properties. Another object of the present invention is to provide an electronic device excellent in durability in a high temperature and high humidity environment.
  • an anchor coat layer obtained by applying energy to a layer containing polysilazane and modifying the substrate, and a gas barrier layer in contact with the anchor coat layer and formed by a vacuum film formation method in this order.
  • the present invention finds that the above problem can be solved by a gas barrier film in which the product of the thickness of the anchor coat layer and the atomic ratio of nitrogen atoms to silicon atoms in the entire anchor coat layer is a specific value or less. It came to complete.
  • the above-described problem of the present invention is a gas barrier film having, in this order, an anchor coat layer and a gas barrier layer that is in contact with the anchor coat layer and is formed by a vacuum film forming method on the base material.
  • the coat layer is a layer obtained by applying energy to the polysilazane-containing layer and performing a modification treatment.
  • the thickness of the anchor coat layer is A (nm), and the anchor coat layer has a total thickness of silicon atoms. This is achieved by a gas barrier film where A ⁇ B ⁇ 60, where B is the atomic ratio of nitrogen atoms (N / Si).
  • the present invention is a gas barrier film having, in this order, an anchor coat layer and a gas barrier layer that is in contact with the anchor coat layer and formed by a vacuum film formation method on a base material, wherein the anchor coat layer comprises polysilazane.
  • the layer containing the carbon atom is obtained by applying energy to the layer, and the thickness of the anchor coat layer is A (nm), and the atomic ratio of nitrogen atoms to silicon atoms in the entire anchor coat layer A gas barrier film where A ⁇ B ⁇ 60, where B is N / Si (hereinafter also referred to simply as N / Si ratio).
  • the gas barrier film of the present invention has high gas barrier properties and excellent in-plane uniformity of gas barrier properties. Moreover, the electronic device having the gas barrier film of the present invention is excellent in durability in a high temperature and high humidity environment.
  • the gas barrier film of the present invention is characterized in that A ⁇ B ⁇ 60 when the thickness of the anchor coat layer is A (nm) and the N / Si ratio of the entire anchor coat layer is B.
  • the gas barrier film having such a configuration has high gas barrier properties and in-plane uniformity of gas barrier properties.
  • the present invention is not limited to the following.
  • the condition A ⁇ B to be satisfied by the anchor coat layer of the gas barrier film according to the present invention indirectly indicates the amount of nitrogen contained in the anchor coat layer, and the larger the value, the more included in the anchor coat layer. Indicates that the amount of nitrogen is large. By controlling this value, the amount of outgas generated can be suppressed. Therefore, it is possible to obtain a gas barrier film having high gas barrier properties and in-plane uniformity of gas barrier properties by suppressing the generation of defects during the film formation process of the gas barrier layer.
  • the anchor coat layer is formed by applying an energy such as vacuum ultraviolet light to the layer containing polysilazane and performing a modification treatment. For this reason, an unmodified region containing more nitrogen and hydrogen tends to remain on the base material side of the anchor coat layer where the energy such as vacuum ultraviolet light is difficult to reach compared to the vicinity of the surface.
  • the surface modification of the anchor coat layer When the surface modification of the anchor coat layer has already progressed sufficiently, it has a high gas barrier property, so the escape path of the generated outgas is only on the substrate side. However, since it is under vacuum, outgas is difficult to escape, and outgas bubbles are generated between the base material and the anchor coat layer, causing defects in the gas barrier layer and the anchor coat layer. As a result, the gas barrier property of the gas barrier film is lowered, and a portion having a low gas barrier property is generated in a spot shape.
  • the amount of outgas generated between the anchor coat layer and the substrate is reduced by setting the value of A ⁇ B to a predetermined value or less, that is, by reducing the amount of nitrogen contained in the anchor coat layer.
  • the generation of bubbles can be suppressed.
  • the gas barrier film of the present invention has high gas barrier properties and in-plane uniformity of gas barrier properties.
  • 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%.
  • Examples of the base material used in the gas barrier film of the present invention include a metal substrate such as silicon, a glass substrate, a ceramic substrate, a plastic film, and the like, and a plastic film is preferably used.
  • the plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a barrier layer, a clear hard coat layer, and the like, and can be appropriately selected according to the purpose of use.
  • Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide.
  • Resin Cellulose acylate resin, Polyurethane resin, Polyether ether ketone resin, Polycarbonate resin, Alicyclic polyolefin resin, Polyarylate resin, Polyether sulfone resin, Polysulfone resin, Cycloolefin copolymer, Fluorene ring modified polycarbonate resin, Alicyclic Examples thereof include thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.
  • the anchor coat layer is a layer obtained by applying a coating solution containing a polysilazane compound on a substrate and applying energy to the resulting polysilazane-containing layer for modification treatment.
  • a ⁇ B ⁇ 60 where A (nm) is the thickness of the anchor coat layer and B is the N / Si ratio of the entire anchor coat layer.
  • the anchor coat layer may be a single layer or a laminated structure of two or more layers.
  • the lower limit of A ⁇ B may be 0 or more, but is preferably 3 or more, more preferably 10 or more from the viewpoint of improving gas barrier properties.
  • the upper limit of AxB is 60 or less from a viewpoint of the above-mentioned outgas generation
  • the anchor coat layer may be a single layer or a laminated structure of two or more layers.
  • the respective anchor coat layers may have the same composition or different compositions.
  • the upper limit of the thickness (A) of the anchor coat layer when the energy is applied to the layer containing polysilazane as described later, the energy reaches the polysilazane on the substrate side for modification. From the viewpoint of sufficiently proceeding, it is preferably 1000 nm or less, more preferably 500 nm or less, still more preferably 300 nm or less, even more preferably less than 150 nm, and particularly preferably 120 nm or less.
  • the lower limit value of the thickness of the anchor coat layer is preferably 5 nm or more from the viewpoint of preventing the base material from being damaged by plasma irradiation or the like during vacuum film formation or suppressing the generation of bubbles. More preferably, it is 30 nm or more, and further preferably 40 nm or more.
  • the thickness of the anchor coat layer can be measured by observing the cross section of the layer with a transmission electron microscope (TEM).
  • the N / Si ratio (B) of the anchor coat layer is preferably 0.01 to 0.40, more preferably 0.05 to 0.30, and preferably 0.1 to 0.25. More preferably it is. If it is this range, the value of AxB can be made into a preferable range, having a preferable function as the above-mentioned anchor coat layer.
  • a ⁇ B ⁇ 60 is satisfied for each layer.
  • the method for adjusting the N / Si ratio of the anchor coat layer is not particularly limited. For example, (1) a method for reducing the N / Si ratio during the modification treatment of the polysilazane-containing layer, and (2) polysilazane. A method of performing aging after the modification treatment of the layer containing, (3) a method of performing additional excimer modification treatment after the modification treatment of the layer containing polysilazane, and (4) modifying the layer in which the aluminum compound is added to polysilazane. And the like.
  • an anchor coating layer satisfying A ⁇ B ⁇ 60 can be efficiently obtained, and high gas barrier properties and in-plane uniformity of gas barrier properties can be obtained.
  • the gas barrier film which has can be obtained efficiently.
  • the film thickness of the layer containing polysilazane Is a thin layer of about 10 to 130 nm.
  • the thickness of the polysilazane-containing layer When the thickness of the polysilazane-containing layer is reduced, energy such as excimer light reaches the substrate side during the modification treatment, and in the range of 110 to 150 nm in particular, the energy is based on energy.
  • the modification progresses greatly because it reaches the material surface significantly.
  • the polysilazane layer has a high absorptivity of the excimer light when excimer light having a wavelength of 172 nm is used, for example, it absorbs about 90% at a thickness of 120 nm.
  • the N / Si ratio can be greatly reduced from 0.8 before the modification. This is thought to be due to the fact that the excimer light reaches the substrate surface, the moisture contained in the substrate surface is released, and using this as an oxygen source, the nitrogen of the polysilazane is replaced by oxygen and the reforming proceeds.
  • the thickness of the polysilazane-containing layer can be reduced and the composition of the substrate surface can be changed to further improve the properties.
  • a layer containing inorganic fine particles having crystal water is formed between the layer containing polysilazane and the substrate.
  • the inorganic fine particles having crystal water are not particularly limited.
  • Barium, indium oxide, tin oxide, lead oxide and the like can be mentioned.
  • silicon oxide is preferable, and colloidal silica is more preferable.
  • Such inorganic fine particles may be contained in a clear hard coat layer coating solution that can be provided on the surface of the substrate.
  • a commercially available product can be used.
  • an OPSTAR (registered trademark) series manufactured by JSR Corporation a compound obtained by bonding an organic compound having a polymerizable unsaturated group to silica fine particles. Containing coating liquid).
  • the film thickness of the polysilazane-containing layer in this embodiment is preferably 40 to 130 nm from the viewpoint of allowing oxidation to proceed to a preferred N / Si ratio with moisture supplied from the substrate side during the modification treatment. 60 to 120 nm is preferable.
  • the amine catalyst can be contained in an amount of 1 to 5% by mass relative to polysilazane.
  • the film thickness of the polysilazane layer in this embodiment is preferably 40 to 500 nm, more preferably 60 to 400 nm, from the viewpoint that oxidation proceeds to a preferable N / Si ratio.
  • the modification process is divided into multiple times Is preferable because the N / Si ratio can be greatly reduced.
  • the number of reforming treatments is preferably 2 to 10 times.
  • the interval between the reforming processes is preferably 6 hours or more, and more preferably 12 hours or more.
  • the upper limit of the interval when performing the twice reforming treatment is not particularly limited, but is preferably within 7 days from the viewpoint of process cost and the above-mentioned aging effect.
  • the film thickness of the polysilazane-containing layer in this embodiment is preferably 40 to 500 nm, more preferably 60 to 400 nm, from the viewpoint that oxidation proceeds to a preferable N / Si ratio.
  • Examples of the aluminum compound include, for example, aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum tri-sec-butoxide, aluminum tri-tert-butoxide.
  • the content of the aluminum compound is preferably 0.01 to 0.2 as the Al / Si element ratio.
  • the thickness of the layer obtained by adding aluminum to polysilazane is preferably 40 to 500 nm, more preferably 60 to 400 nm, from the viewpoint of sufficiently progressing modification of polysilazane.
  • the N / Si ratio of the anchor coat layer as a whole can be obtained by measuring by the following method using XPS (photoelectron spectroscopy) analysis.
  • the XPS analysis in the present invention was performed under the following conditions, but even if the apparatus and measurement conditions are changed, any measurement method that conforms to the gist of the present invention can be applied without any problem.
  • the measurement method according to the gist of the present invention is mainly the resolution in the thickness direction, and the etching depth per measurement point (corresponding to the conditions of the following sputter ion and depth profile) is 1 to 15 nm.
  • the thickness is preferably 1 to 10 nm.
  • the etching depth (etching rate) per measurement point corresponds to about 2.8 nm in terms of SiO 2 .
  • ⁇ XPS analysis conditions >> ⁇ Equipment: ULVAC-PHI QUANTERASXM ⁇ X-ray source: Monochromatic Al-K ⁇ Measurement area: Si2p, C1s, N1s, O1s ⁇ Sputtering ion: Ar (2 keV) Depth profile: repeats measurement after sputtering for a certain time. In one measurement, the sputtering time is adjusted so as to be about 2.8 nm in terms of SiO 2. Quantification: The background was obtained by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. For data processing, MultiPak manufactured by ULVAC-PHI was used.
  • the anchor coat layer according to the present invention is formed by applying energy to a coating film formed by applying a coating liquid containing polysilazane since the defects such as film formability and cracks are few (coating film) Forming method).
  • a coating film formed by applying a coating liquid containing polysilazane since the defects such as film formability and cracks are few (coating film) Forming method will be described.
  • polysilazane examples include perhydropolysilazane, organopolysilazane, and the like, but perhydropolysilazane is preferable because it contains little residual organic matter.
  • Polysilazane is a polymer having a silicon-nitrogen bond, such as SiO 2 , Si 3 N 4 having a bond such as Si—N, Si—H, or N—H, and ceramics such as both intermediate solid solutions SiO x N y. It is a precursor inorganic polymer.
  • the polysilazane preferably has the following structure.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. .
  • R 1 , R 2 and R 3 may be the same or different.
  • examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms.
  • the aryl group include aryl groups having 6 to 30 carbon atoms.
  • non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group , Condensed polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc.
  • non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, nap
  • the (trialkoxysilyl) alkyl group includes an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specific examples include 3- (triethoxysilyl) propyl group and 3- (trimethoxysilyl) propyl group.
  • the substituent optionally present in R 1 to R 3 is not particularly limited, and examples thereof include an alkyl group, a halogen atom, a hydroxyl group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO 3 H), a carboxyl group (—COOH), a nitro group (—NO 2 ) and the like. Note that the optionally present substituent is not the same as R 1 to R 3 to be substituted. For example, when R 1 to R 3 are alkyl groups, they are not further substituted with an alkyl group.
  • R 1 , R 2 and R 3 are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.
  • n is an integer
  • the polysilazane having the structure represented by the general formula (I) is determined to have a number average molecular weight of 150 to 150,000 g / mol. preferable.
  • one of preferred embodiments is perhydropolysilazane in which all of R 1 , R 2 and R 3 are hydrogen atoms.
  • the anchor coat layer formed from such polysilazane has high density.
  • polysilazane has a structure represented by the following general formula (II).
  • R 1 ′ , R 2 ′ , R 3 ′ , R 4 ′ , R 5 ′ and R 6 ′ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group.
  • R 1 ′ , R 2 ′ , R 3 ′ , R 4 ′ , R 5 ′ and R 6 ′ may be the same or different.
  • the substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.
  • n ′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined to have a number average molecular weight of 150 to 150,000 g / mol. It is preferred that Note that n ′ and p may be the same or different.
  • R 1 ′ , R 3 ′ and R 6 ′ each represent a hydrogen atom, and R 2 ′ , R 4 ′ and R 5 ′ each represent a methyl group;
  • R 1 ' , R 3' and R 6 ' each represents a hydrogen atom, R 2' , R 4 ' each represents a methyl group, and R 5' represents a vinyl group;
  • R 1 ' , R 3' , R 4 A compound in which ' and R 6' each represent a hydrogen atom and R 2 ' and R 5' each represents a methyl group is preferred.
  • polysilazane has a structure represented by the following general formula (III).
  • R 1 ′′ , R 2 ′′ , R 3 ′′ , R 4 ′′ , R 5 ′′ , R 6 ′′ , R 7 ′′ , R 8 ′′ and R 9 ′′ are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, wherein R 1 ′′ , R 2 ′′ , R 3 ′′ , R 4 ′′ , R 5 ′′ , R 6 ′′ , R 7 ′′ , R 8 ′′ and R 9 ′′ may be the same or different.
  • the substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.
  • n ′′, p ′′ and q are integers, and the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. It is preferable to be determined as follows. Note that n ′′, p ′′, and q may be the same or different.
  • R 1 ′′ , R 3 ′′ and R 6 ′′ each represent a hydrogen atom
  • R 2 ′′ , R 4 ′′ , R 5 ′′ and R 8 ′′ each represent a methyl group.
  • R 9 ′′ represents a (triethoxysilyl) propyl group
  • R 7 ′′ represents an alkyl group or a hydrogen atom.
  • the organopolysilazane in which a part of the hydrogen atom portion bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material as a base by having an alkyl group such as a methyl group and is hard.
  • the ceramic film made of brittle polysilazane can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. For this reason, these perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.
  • Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings.
  • the number average molecular weight (Mn) is about 600 to 2000 (polystyrene conversion), and there are liquid or solid substances, and the state varies depending on the molecular weight.
  • Polysilazane is commercially available in a solution in an organic solvent, and a commercially available product may be used as it is as a coating solution for forming an anchor coat layer, or a plurality of commercially available products may be used in combination. Moreover, you may dilute and use a commercial item with a suitable solvent. 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.
  • the content of polysilazane in the anchor coat layer before application of energy can be 100% by mass when the total weight of the anchor coat layer is 100% by mass.
  • the content of polysilazane in the anchor coat 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 solvent for preparing the coating solution for forming the anchor coat layer is not particularly limited as long as it can dissolve polysilazane, but water and reactive groups (for example, hydroxyl group or amine) that easily react with polysilazane.
  • the solvent is an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, terpenes, etc.
  • Hydrogen solvents Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like.
  • the solvent is selected according to purposes such as the solubility of 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 polysilazane in the coating solution for forming the anchor coat layer is not particularly limited, and varies depending on the thickness of the anchor coat layer and the pot life of the coating solution, but is preferably 1 to 80% by mass, more preferably 5 to 50% by mass. %, More preferably 10 to 40% by mass.
  • the anchor coat layer forming coating solution preferably contains a catalyst in order to promote modification.
  • 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 addition amount of the catalyst within this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, decrease in film density, increase in film defects, and the like.
  • the following additives can be used in the anchor coat layer forming coating solution 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 layer containing polysilazane can be formed by applying the above-described coating liquid for forming an anchor coat layer on a substrate.
  • a coating method a conventionally known appropriate wet coating method can be adopted. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, die coating method, gravure printing method and the like. It is done.
  • the coating thickness can be appropriately selected according to the thickness of the anchor coat layer.
  • the coating film After applying the coating solution, it is preferable to dry the coating film.
  • the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable anchor coat 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.
  • a known method can be appropriately selected and applied.
  • Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment.
  • modification by heat treatment since a high temperature of 450 ° C. or higher is required, adaptation is difficult for flexible substrates such as plastic. For this reason, it is preferable to perform the heat treatment in combination with other reforming treatments.
  • a plasma treatment capable of a conversion reaction at a lower temperature or a conversion reaction by ultraviolet irradiation treatment is preferable.
  • a known method can be used as the plasma treatment that can be used as the modification treatment, and an atmospheric pressure plasma treatment or the like can be preferably used.
  • the atmospheric pressure plasma CVD method which performs plasma CVD processing near atmospheric pressure, does not need to be reduced in pressure and is more productive than the plasma CVD method under vacuum.
  • the film speed is high, and further, under a high pressure condition under atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free process is very short, so that a very homogeneous film can be obtained.
  • nitrogen gas or a gas containing Group 18 atoms of the long-period periodic table specifically helium, neon, argon, krypton, xenon, radon, or the like is used.
  • nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.
  • UV irradiation treatment As one of the modification treatment methods, treatment by ultraviolet irradiation is preferable. Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures It is.
  • This UV irradiation heats the base material and excites and activates O 2 and H 2 O that contribute to ceramics conversion (silica conversion), UV absorbers, and polysilazanes themselves, thus promoting the conversion of polysilazanes into ceramics.
  • the resulting anchor coat layer becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.
  • any commonly used ultraviolet ray generator can be used.
  • the ultraviolet ray referred to in the present invention generally refers to an electromagnetic wave having a wavelength of 10 to 400 nm, but in the case of an ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, it is preferably 210 to 375 nm. Use ultraviolet light.
  • the irradiation intensity and the irradiation time are set within a range in which the substrate carrying the irradiated anchor coat layer is not damaged.
  • a 2 kW (80 W / cm ⁇ 25 cm) lamp is used, and the strength of the base material surface is 20 to 300 mW / cm 2 , preferably 50 to 200 mW / cm.
  • the distance between the base material and the ultraviolet irradiation lamp is set so as to be 2, and irradiation can be performed for 0.1 seconds to 10 minutes.
  • the substrate temperature during ultraviolet irradiation treatment is 150 ° C. or more
  • the properties of the substrate are impaired, such as deformation of the substrate or deterioration of its strength.
  • a modification treatment at a higher temperature is possible.
  • the substrate temperature at the time of ultraviolet irradiation there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate.
  • Examples of such ultraviolet ray generating means include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. Manufactured by M.D. Com Co., Ltd.), UV light laser, and the like, but are not particularly limited.
  • the layer containing polysilazane with the generated ultraviolet ray from the viewpoint of achieving efficiency improvement and uniform irradiation, the layer containing polysilazane is reflected after reflecting the ultraviolet ray from the generation source with a reflector. It is preferable to apply.
  • UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used.
  • a laminate having a polysilazane-containing layer on its surface can be processed in an ultraviolet baking furnace equipped with an ultraviolet source as described above.
  • the ultraviolet baking furnace itself is generally known.
  • an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used.
  • the laminated body which has the layer containing polysilazane on the surface is a long film form, it irradiates with an ultraviolet-ray continuously in the drying zone equipped with the above ultraviolet ray generation sources, conveying this. Can be made into ceramics.
  • the time required for the ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the base material used and the layer containing polysilazane.
  • the most preferable modification treatment method for the anchor coat layer is a 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)
  • 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 perform in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of irradiation with vacuum ultraviolet rays is preferably 10 to 20,000 volume ppm (0.001 to 2 volume%), and preferably 50 to 10,000 volume ppm (0.005 to 1 volume%). More preferably. 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 layer containing polysilazane is preferably 1 mW / cm 2 to 10 W / cm 2 , and 30 mW / cm 2 to 200 mW / cm 2. It is more preferable, further preferably a 50mW / cm 2 ⁇ 160mW / cm 2. If it is less than 1 mW / cm 2, there is a concern that the reforming efficiency is greatly reduced. If it exceeds 10 W / cm 2 , there is a concern that the coating film may be ablated or the substrate may be damaged.
  • the amount of irradiation energy (irradiation amount) of vacuum ultraviolet rays on the coating surface is preferably 100 mJ / cm 2 to 50 J / cm 2 , more preferably 200 mJ / cm 2 to 20 J / cm 2 , and 500 mJ / cm 2. More preferably, it is 2 to 10 J / cm 2 . If it is 100 mJ / cm 2 or more, it is possible to avoid insufficient modification, and if it is 50 J / cm 2 or less, generation of cracks due to excessive modification and thermal deformation of the substrate can be prevented.
  • the irradiation with vacuum ultraviolet rays may be performed in a plurality of times. In that case, it is preferable to irradiate so that the total amount of irradiation energy is within the above range.
  • the vacuum ultraviolet light used may be generated by plasma formed of a gas containing at least one of CO, CO 2 and CH 4 .
  • the gas containing at least one of CO, CO 2 and CH 4 hereinafter also referred to as carbon-containing gas
  • the carbon-containing gas may be used alone, but carbon containing rare gas or H 2 as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.
  • the gas barrier film according to the present invention has a gas barrier layer which is in contact with the anchor coat layer and formed by a vacuum film formation method on the anchor coat layer.
  • PVD method physical vapor deposition method
  • CVD method chemical vapor deposition method
  • 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.
  • 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.
  • CVD method for the purpose of activating the chemical reaction, there are methods for generating plasma and the like, and well-known CVD methods such as a thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method and the like can be mentioned.
  • a vacuum plasma CVD method it is preferable to apply a vacuum plasma CVD method from the viewpoints of film formation speed, processing area, flexibility of the obtained gas barrier layer, and gas barrier properties.
  • silicon oxide is generated.
  • highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.
  • FIG. 1 and 2 are schematic configuration diagrams showing an example of a film forming apparatus.
  • the film forming apparatus 101 illustrated in FIG. 2 has a basic structure in which two film forming apparatuses 100 illustrated in FIG. 1 are joined in tandem.
  • the case where the gas barrier layer is formed will be described using the film forming apparatus illustrated in FIG. 2 as an example.
  • the description regarding the film forming apparatus illustrated in FIG. 2 is the same as the description regarding the film forming apparatus illustrated in FIG. However, it is considered as appropriate.
  • the film forming apparatus 101 includes a delivery roll 10, transport rolls 11 to 14, first, second, third and fourth film forming rolls 15, 16, 15 ′, 16 ′, Take-off roll 17, gas supply pipes 18, 18 ', plasma generation power sources 19, 19', magnetic field generators 20, 21, 20 ', 21', vacuum chamber 30, vacuum pumps 40, 40 ' And a control unit 41.
  • the delivery roll 10, the transport rolls 11 to 14, the first, second, third and fourth film forming rolls 15, 16, 15 ′, 16 ′ and the take-up roll 17 are accommodated in the vacuum chamber 30.
  • the delivery roll 10 feeds the base material 1 a installed in a state of being wound in advance toward the transport roll 11.
  • the delivery roll 10 is a cylindrical roll extending in a direction perpendicular to the paper surface, and is wound around the delivery roll 10 by rotating counterclockwise (see an arrow in FIG. 2) by a drive motor (not shown).
  • the base material 1a is sent out toward the transport roll 11.
  • the transport rolls 11 to 14 are cylindrical rolls configured to be rotatable around a rotation axis substantially parallel to the delivery roll 10.
  • the transport roll 11 is a roll for transporting the base material 1 a from the feed roll 10 to the film forming roll 15 while applying an appropriate tension to the base material 1 a.
  • the transport rolls 12 and 13 are rolls for transporting the base material 1 b from the film forming roll 15 to the film forming roll 16 while applying an appropriate tension to the base material 1 b formed by the film forming roll 15.
  • the transporting rolls 12 ′ and 13 ′ are for supplying the base material 1e from the film forming roll 15 ′ to the film forming roll 16 ′ while applying an appropriate tension to the base material 1e formed by the film forming roll 15 ′. It is a roll of.
  • the transport roll 14 is a roll for transporting the base material 1 c from the film forming roll 16 to the take-up roll 17 while applying an appropriate tension to the base material 1 c formed by the film forming roll 16 ′. .
  • the first film-forming roll 15 and the second film-forming roll 16 are a pair of film-forming rolls having a rotation axis substantially parallel to the delivery roll 10 and facing each other at a predetermined distance.
  • the third film-forming roll 15 ′ and the fourth film-forming roll 16 ′ have a rotation axis that is substantially parallel to the delivery roll 10, and are formed by a pair of film-forming rolls that are opposed to each other by a predetermined distance. is there.
  • the film forming roll 16 forms the substrate 1b and conveys the substrate 1d to the film forming roll 15 'while applying an appropriate tension to the formed substrate 1d.
  • the film forming roll 16 ′ forms the base material 1 e and transports the base material 1 c to the transport roll 14 while applying an appropriate tension to the formed base material 1 c.
  • the separation distance between the first film-forming roll 15 and the second film-forming roll 16 is a distance connecting the point A and the point B, and the third film-forming roll 15 ′ and the second film-forming roll.
  • the separation distance from the roll 16 ′ is a distance connecting the point A ′ and the point B ′.
  • the first to fourth film forming rolls 15, 16, 15 ′, 16 ′ are discharge electrodes formed of a conductive material, and the first film forming roll 15, the second film forming roll 16, and the third film forming roll.
  • the 15 ′ and the fourth film forming roll 16 ′ are insulated from each other.
  • the materials and configurations of the first to fourth film forming rolls 15, 16, 15 ', 16' can be appropriately selected so as to achieve a desired function as an electrode.
  • first to fourth film forming rolls 15, 16, 15 ', 16' may be independently temperature controlled.
  • the temperature of the first to fourth film forming rolls 15, 16, 15 ′, 16 ′ is not particularly limited, but is, for example, ⁇ 30 to 100 ° C., which exceeds the glass transition temperature of the substrate 1a. If the temperature is set too high, the substrate may be deformed by heat.
  • Magnetic field generators 20, 21, 20 'and 21' are installed inside the first to fourth film forming rolls 15, 16, 15 'and 16', respectively.
  • the first film forming roll 15 and the second film forming roll 16 are supplied with a plasma generating power source 19, and the third film forming roll 15 ′ and the fourth film forming roll 16 ′ are supplied with a plasma generating power supply 19 ′.
  • a generating high frequency voltage is applied.
  • An electric field is formed in the film, and discharge plasma of the film forming gas supplied from the gas supply pipe 18 or 18 'is generated.
  • the voltage applied by the plasma generating power supply 19 and the voltage applied by the plasma generating power supply 19 ′ may be the same or different.
  • the power source frequency of the plasma generating power source 19 or 19 ′ can be arbitrarily set, but the apparatus of this configuration is, for example, 60 to 100 kHz, and the applied power is, for example, 1 to 1 with respect to an effective film forming width of 1 m. 10 kW.
  • the take-up roll 17 has a rotating shaft substantially parallel to the feed roll 10 and takes up the base material 1c and stores it in a roll shape.
  • the take-up roll 17 takes up the substrate 1c by rotating counterclockwise by a drive motor (not shown) (see the arrow in FIG. 2).
  • the substrate 1a fed from the feed roll 10 is wound around the transport rolls 11 to 14 and the first to fourth film forming rolls 15, 16, 15 ′ and 16 ′ between the feed roll 10 and the take-up roll 17. It is conveyed by rotation of each of these rolls while maintaining an appropriate tension by being applied.
  • the conveyance direction of the substrates 1a, 1b, 1c, 1d, and 1e (hereinafter, the substrates 1a, 1b, 1c, 1d, and 1e are also collectively referred to as “substrates 1a to 1e”) is indicated by arrows. .
  • the conveyance speed (line speed) of the base materials 1a to 1e (for example, the conveyance speed at the points C and C ′ in FIG.
  • the conveyance speed is adjusted by controlling the rotation speeds of the drive motors of the delivery roll 10 and the take-up roll 17 by the control unit 41. When the conveyance speed is decreased, the thickness of the formed region is increased.
  • the transport direction of the base materials 1a to 1e is set to a direction (hereinafter referred to as a reverse direction) opposite to a direction indicated by an arrow in FIG. 2 (hereinafter referred to as a forward direction).
  • a gas barrier film forming step can also be performed.
  • the control unit 41 rotates the rotation direction of the drive motors of the feed roll 10 and the take-up roll 17 in the direction opposite to that described above in a state where the substrate 1c is taken up by the take-up roll 17. Control to do.
  • the substrate 1c fed from the take-up roll 17 is transported between the feed roll 10 and the take-up roll 17 between the transport rolls 11 to 14, the first to fourth film forming rolls 15, 16, While being wound around 15 'and 16', appropriate tension is maintained, and the rolls are conveyed in the reverse direction by rotation of these rolls.
  • the base material 1a is transported in the forward direction and the reverse direction, and the film forming unit S or the film forming unit S ′ is reciprocated to form a gas barrier layer.
  • the (film) step can be repeated multiple times.
  • the gas supply pipes 18 and 18 ′ supply a film forming gas such as a plasma CVD source gas into the vacuum chamber 30.
  • the gas supply pipe 18 has a tubular shape extending in the same direction as the rotation axes of the first film forming roll 15 and the second film forming roll 16 above the film forming section S, and is provided at a plurality of locations. A film forming gas is supplied to the film forming part S from the opened opening.
  • the gas supply pipe 18 ′ has a tubular shape extending above the film forming section S ′ in the same direction as the rotation axes of the third film forming roll 15 ′ and the fourth film forming roll 16 ′.
  • the film forming gas is supplied to the film forming part S ′ from the openings provided at a plurality of locations.
  • the film forming gas supplied from the gas supply pipe 18 and the film forming gas supplied from the gas supply pipe 18 ' may be the same or different. Further, the supply gas pressure supplied from these gas supply pipes may be the same or different.
  • a silicon compound can be used as the source gas.
  • the silicon compound include hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, and diethylsilane.
  • the compounds described in paragraph “0075” of JP-A-2008-056967 can also be used.
  • HMDSO is preferably used in the formation of the gas barrier layer from the viewpoint of easy handling of the compound and high gas barrier properties of the resulting gas barrier film. Two or more of these silicon compounds may be used in combination.
  • the source gas may contain monosilane in addition to the silicon compound.
  • a reactive gas may be used in addition to the source gas.
  • a gas that reacts with the raw material gas to become a silicon compound such as oxide or nitride is selected.
  • a reactive gas for forming an oxide as a thin film for example, oxygen gas or ozone gas can be used. In addition, you may use these reaction gas in combination of 2 or more type.
  • a carrier gas may be further used to supply the source gas into the vacuum chamber 30.
  • a discharge gas may be further used to generate plasma.
  • a carrier gas and the discharge gas for example, a rare gas such as argon, hydrogen, or nitrogen is used.
  • the magnetic field generators 20 and 21 are members that form a magnetic field in the film forming unit S between the first film forming roll 15 and the second film forming roll 16, and the magnetic field generating apparatuses 20 ′ and 21 ′ are similarly configured. It is a member that forms a magnetic field in the film forming section S ′ between the third film forming roll 15 ′ and the fourth film forming roll 16 ′. These magnetic field generators 20, 20 ', 21, 21' do not follow the rotation of the first to fourth film forming rolls 15, 16, 15 ', 16', but are stored at predetermined positions.
  • the vacuum chamber 30 maintains the decompressed state by sealing the delivery roll 10, the transport rolls 11 to 14, the first to fourth film forming rolls 15, 16, 15 ', 16', and the take-up roll 17.
  • the pressure (degree of vacuum) in the vacuum chamber 30 can be adjusted as appropriate according to the type of source gas.
  • the pressure of the film forming part S or S ′ is preferably 0.1 to 50 Pa.
  • the vacuum pumps 40 and 40 ′ are communicably connected to the control unit 41 and appropriately adjust the pressure in the vacuum chamber 30 in accordance with a command from the control unit 41.
  • the control unit 41 controls each component of the film forming apparatus 101.
  • the control unit 41 is connected to the drive motors of the feed roll 10 and the take-up roll 17 and adjusts the conveyance speed of the substrate 1a by controlling the rotation speed of these drive motors. Moreover, the conveyance direction of the base material 1a is changed by controlling the rotation direction of the drive motor.
  • the control unit 41 is connected to a film-forming gas supply mechanism (not shown) so as to be communicable, and controls the supply amount of each component gas of the film-forming gas.
  • the control unit 41 is communicably connected to the plasma generation power sources 19 and 19 ′ and controls the output voltage and output frequency of the plasma generation power source 19. Further, the control unit 41 is communicably connected to the vacuum pumps 40 and 40 ′, and controls the vacuum pump 40 so as to maintain the inside of the vacuum chamber 30 in a predetermined reduced pressure atmosphere.
  • the control unit 41 includes a CPU (Central Processing Unit), a HDD (Hard Disk Drive), a RAM (Random Access Memory), and a ROM (Read Only Memory).
  • the HDD stores a software program describing a procedure for controlling each component of the film forming apparatus 101 and realizing a method for producing a gas barrier film.
  • the software program is loaded into the RAM and sequentially executed by the CPU.
  • the ROM stores various data and parameters used when the CPU executes the software program.
  • the gas barrier layer may be a single layer or a laminated structure of two or more layers.
  • the gas barrier layers may have the same composition or different compositions.
  • the gas barrier layer formed by the vacuum film formation method according to the present invention preferably has a composition distribution region having a high density in the thickness direction of the gas barrier layer and a high carbon concentration. That is, the gas barrier layer preferably has a region having a composition distribution represented by SiC x in the thickness direction, where x is 0.8 to 1.2. More preferably, x is 0.9 to 1.1. By having a region having such a composition, the gas barrier property can be further improved.
  • the measurement of the composition distribution in the thickness direction of the gas barrier layer and the measurement of the thickness of the region can be performed by XPS analysis employing the same conditions as the measurement of the N / Si ratio of the entire anchor coat layer.
  • the lower limit of the thickness of the region where the composition is represented by SiC x and where x is 0.8 to 1.2 is not particularly limited because it varies depending on the application. From the viewpoint of improving the properties, it is preferably 1 nm or more, more preferably 30 nm or more, still more preferably 50 nm or more, and even more preferably 90 nm or more.
  • the upper limit is also not particularly limited because it varies depending on the application, but is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less from the viewpoint of ensuring optical characteristics.
  • the thickness of the region in which the composition is represented by SiC x, where x is 0.8 to 1.2, is, for example, the amount and ratio of the film-forming raw material and oxygen supplied, It is possible to control by appropriately combining the conveyance speed, the number of times of film formation, and the like.
  • the formation of the gas barrier layer is shown by (2) a method of performing aging after the modification treatment of the layer containing polysilazane, or (3) a method of performing an additional modification treatment after the modification treatment of the layer containing polysilazane.
  • the sample that has not been subjected to the composition adjustment processing of the N / Si ratio of the anchor coat layer is preferably performed within 1 to 2 days after the formation of the anchor coat layer.
  • the sample subjected to the anchor coat layer composition adjustment treatment is preferably performed within 1 to 2 days after the adjustment of the N / Si ratio.
  • the thickness of the gas barrier layer (the total thickness in the case of a laminated structure of two or more layers) is not particularly limited, but is preferably 5 to 1000 nm, more preferably 20 to 500 nm, and more preferably 50 to 300 nm. More preferably it is. If it is this range, the advantage of coexistence of productivity and gas barrier property will be acquired.
  • the thickness of the gas barrier layer can be measured by TEM observation.
  • the formation and modification treatment of the polysilazane-containing layer further provided on the gas barrier layer can be performed by the same method as the formation of the anchor coat layer.
  • the type of polysilazane used is preferably perhydropolysilazane because it has a small amount of residual organic matter.
  • the energy is preferably applied by irradiation with vacuum ultraviolet light from the viewpoint that the modification treatment can be performed at a relatively low temperature.
  • the thickness of the layer obtained by modifying the layer containing polysilazane further provided on the gas barrier layer is also preferably within the preferable range as the thickness of the anchor coat layer.
  • a layer obtained by modifying such a layer containing polysilazane on the gas barrier layer is a gas barrier property, in-plane uniformity of the gas barrier property, or durability of an electronic device in a high temperature and high humidity environment. Can be further improved.
  • a clear hard coat layer may be provided on the substrate.
  • the clear hard coat layer improves adhesion between the base material and the anchor coat layer, relieves internal stress caused by the difference in expansion and contraction between the base material and the anchor coat layer under high temperature and high humidity, and a base material on which the anchor coat layer is provided It is possible to provide functions such as flattening and prevention of bleeding out of low molecular weight components such as monomers and oligomers from the substrate.
  • an antiblock function can also be provided by giving the surface of a clear hard-coat layer a little roughness.
  • the clear hard coat layer may be provided between the base material and the anchor coat layer, or may be provided on the surface opposite to the surface having the gas barrier layer of the base material.
  • it is preferably provided on the surface opposite to the surface having the gas barrier layer of the base material from the viewpoint of preventing bleeding out, and more preferably clear hard having an anti-block function. It is a coat layer.
  • Such a clear hard coat layer is basically produced by curing a photosensitive material or a thermosetting material.
  • the gas barrier film of the present invention may have a bleed-out preventing layer on the surface of the substrate opposite to the surface on which the anchor coat layer is provided.
  • the bleed-out prevention layer is used for the purpose of suppressing the phenomenon that unreacted oligomers migrate from the film to the surface and contaminate the contact surface when the film is heated. It is provided on the surface opposite to the provided surface.
  • the bleed-out prevention layer may basically have the same configuration as the clear hard coat layer as long as it has this function.
  • the gas barrier film of the present invention can be preferably applied to a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. That is, this invention provides the electronic device containing the gas barrier film of this invention, and the electronic device main body formed on this gas barrier film.
  • Examples of the electronic device body used in the electronic device of the present invention include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. be able to.
  • the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.
  • Anode / light emitting layer / cathode (2) Anode / hole transport layer / light emitting layer / cathode (3) Anode / light emitting layer / electron transport layer / cathode (4) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode (5) Anode / anode buffer layer (hole injection layer) / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode (anode)
  • an electrode material made of a metal, an alloy, an electrically conductive compound or a mixture thereof having a high work function (4 eV or more) is preferably used.
  • electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • ITO indium tin oxide
  • ZnO ZnO
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • these electrode materials may be formed as a thin film by a method such as vapor deposition or sputtering, and the thin film may be formed into a desired shape pattern by photolithography, or if the pattern accuracy is not required (The pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered.
  • the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness of the anode depends on the material, but is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • cathode As the cathode in the organic EL element, a material having a small work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof is used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are suitable as the cathode.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as a cathode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness of the cathode is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm. In order to transmit the emitted light, if either the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.
  • a transparent transparent or semi-transparent cathode is produced by producing the conductive transparent material mentioned in the explanation of the anode on the metal.
  • the injection layer includes an electron injection layer and a hole injection layer.
  • An electron injection layer and a hole injection layer are provided as necessary, and between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport. Exist between the layers.
  • An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance.
  • Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).
  • anode buffer layer hole injection layer
  • Examples thereof include a phthalocyanine buffer layer typified by phthalocyanine, an oxide buffer layer typified by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
  • cathode buffer layer (electron injection layer) The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium Metal buffer layer typified by aluminum and aluminum, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. Is mentioned.
  • the buffer layer (injection layer) is preferably a very thin film, and although it depends on the material, the film thickness is preferably in the range of 0.1 nm to 5 ⁇ m.
  • the light emitting layer in the organic EL element is a layer that emits light by recombination of electrons and holes injected from the electrode (cathode, anode) or electron transport layer, hole transport layer, and the light emitting portion is the light emitting layer. It may be in the layer or the interface between the light emitting layer and the adjacent layer.
  • the light emitting layer of the organic EL device preferably contains the following dopant compound (light emitting dopant) and host compound (light emitting host). Thereby, the luminous efficiency can be further increased.
  • Luminescent dopant There are two types of luminescent dopants: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.
  • fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes. Stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.
  • the phosphorescent dopant preferably a complex compound containing a metal of Group 8, Group 9, or Group 10 in the periodic table of elements, more preferably an iridium compound or an osmium compound, Of these, iridium compounds are the most preferred.
  • the light emitting dopant may be used by mixing a plurality of kinds of compounds.
  • the light emitting host is not particularly limited in terms of structure, but is typically a basic skeleton such as a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, or an oligoarylene compound.
  • a carboline derivative or a diazacarbazole derivative herein, a diazacarbazole derivative is one in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom
  • carboline derivatives, diazacarbazole derivatives and the like are preferably used.
  • the light emitting layer can be formed by forming the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method.
  • the thickness of the light emitting layer is not particularly limited, but is usually selected in the range of 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • This light emitting layer may have a single layer structure in which the dopant compound and the host compound are one kind or two or more kinds, or may have a laminated structure made up of a plurality of layers having the same composition or different compositions.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer.
  • the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has either hole injection or transport or electron barrier properties, and may be either organic or inorganic.
  • triazole derivatives oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives
  • Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • the above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.
  • the hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can.
  • the thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the hole transport layer may have a single layer structure composed of one or more of the above materials.
  • the electron transport layer is made of an electron transport material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer.
  • the electron transport layer can be provided as a single layer or a plurality of layers.
  • the electron transport material only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and the material can be selected and used from conventionally known compounds. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq3), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material.
  • metal-free or metal phthalocyanine or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material.
  • inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the electron transport material.
  • the electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method.
  • the thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the electron transport layer may have a single layer structure composed of one or more of the above materials.
  • organic EL element a method for producing an organic EL element composed of an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.
  • a thin film made of a desired electrode material for example, an anode material
  • a gas barrier film by a method such as vapor deposition, sputtering, or plasma CVD so as to have a film thickness of 1 ⁇ m or less, preferably 10 to 200 nm.
  • an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, which are organic EL element materials, is formed thereon.
  • a method for forming this organic compound thin film there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method), etc., but a homogeneous film is easily obtained and pinholes are not easily generated. From the point of view, the vacuum deposition method, the spin coating method, the ink jet method, and the printing method are particularly preferable. Further, different film forming methods may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 10 ⁇ 6 to 10 ⁇ 2 Pa, and a vapor deposition rate of 0.01 to It is desirable to select appropriately within a range of 50 nm / second, a substrate temperature of ⁇ 50 to 300 ° C., and a film thickness of 0.1 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 ⁇ m or less, preferably in the range of 50 to 200 nm, and a cathode is provided.
  • a desired organic EL element can be obtained.
  • this organic EL element For the production of this organic EL element, it is preferable to produce the anode and the hole injection layer to the cathode consistently by a single vacuum, but it may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere. In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order.
  • a DC voltage is applied to the multicolor display device (organic EL panel) having the organic EL element thus obtained, a voltage of about 2 to 40 V is applied with the positive polarity of the anode and the negative polarity of the cathode. Then luminescence can be observed.
  • An alternating voltage may be applied.
  • the alternating current waveform to be applied may be arbitrary.
  • Substrate 1 A 100 ⁇ m-thick polyethylene terephthalate film (Lumirror (registered trademark) (U48), manufactured by Toray Industries, Inc.) with easy adhesion treatment on both sides has a thickness of 0.
  • a substrate 1 was formed by forming a clear hard coat layer having an antiblock function of 5 ⁇ m. That is, a UV curable resin (manufactured by Aika Kogyo Co., Ltd., product number: Z731L) was applied so as to have a dry film thickness of 0.5 ⁇ m, and then dried at 80 ° C. Then, using a high-pressure mercury lamp in the air. Curing was performed under the condition of an irradiation energy amount of 0.5 J / cm 2 .
  • Substrate 2 A clear hard coat layer having a thickness of 2 ⁇ m was formed on the surface of the substrate 1 on the side where the gas barrier layer was to be formed as follows.
  • a UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a dry film thickness of 2 ⁇ m, dried at 80 ° C., and then irradiated with a high-pressure mercury lamp in air. Curing was performed under the condition of 0.5 J / cm 2 .
  • the anchor coat layer was formed by applying a coating solution as shown below to form a coating film, and then performing modification by irradiation with vacuum ultraviolet rays.
  • the coating solution was prepared as follows.
  • Coating solution 1 A dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials, NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6- Dihydrohexane containing 20% by weight of dihydrohexane containing diaminohexane (TMDAH) (AZ Electronic Materials Co., Ltd., NAX120-20) was mixed at a ratio of 4: 1 (mass ratio), and further dried film A coating solution was prepared by appropriately diluting with dibutyl ether to adjust the thickness.
  • TMDAH diaminohexane
  • Coating solution 2 Aluminum ethyl acetoacetate diisopropylate (ALCH) is added to polysilazane so that the Al / Si ratio is 0.05 when preparing the coating solution 1, and the mixture is heated at room temperature (25 ° C.) for 6 hours. A coating solution was prepared by stirring.
  • a coating solution was prepared by stirring.
  • Coating solution 3 Commercially available polysiloxane coating agent: Glasca (manufactured by JSR Corporation) was used.
  • Thickness after drying the obtained coating liquid on the surface opposite to the surface on which the clear hard coat layer having the antiblock function of the substrate 1 is formed, or on the clear hard coat layer of the substrate 2 was applied by a die coating method so as to have a thickness as shown in Table 1 below, and dried in air at a temperature shown in Table 1 below (dew point 5 ° C.) for 2 minutes.
  • the coating film obtained by drying was subjected to a vacuum ultraviolet ray irradiation treatment (modification treatment) using a Xe excimer lamp having a wavelength of 172 nm in a nitrogen atmosphere under the conditions shown in Table 1 below, and an anchor coat layer. Formed.
  • composition adjustment treatment of the anchor coat layer shown in Table 2 below was performed on the coating film.
  • the layer containing polysilazane was modified under the following conditions.
  • the film thickness of the anchor coat layer was determined by observing the cross section of the layer with a TEM.
  • a gas barrier layer was formed on the anchor coat layer by a vacuum plasma CVD method.
  • a roll-to-roll type CVD film forming apparatus in which two apparatuses each having a film forming unit composed of opposing film forming rolls shown in FIG. 2 are connected (having a first film forming unit and a second film forming unit) was used.
  • the effective film formation width is 1000 mm, and the film formation conditions are: conveyance speed, supply amount of source gas (HMDSO) of each of the first film formation unit and the second film formation unit, supply amount of oxygen gas, degree of vacuum, applied power, The frequency was adjusted by the frequency of the power supply and the number of film formation (number of passes of the apparatus).
  • the substrate In contrast to the first pass, the substrate is transported in the direction of rewinding the substrate in the second pass.
  • the first film forming unit passes through the first film forming unit, and the component that passes next.
  • the film part was used as the second film forming part.
  • the power supply frequency was 84 kHz, and the film forming roll temperatures were all 30 ° C.
  • the film thickness was determined by cross-sectional TEM observation.
  • the formation of the gas barrier layer was performed within 1 to 2 days after the anchor coat layer was applied to the samples that were not subjected to the composition adjustment treatment of the anchor coat layer.
  • the samples subjected to the anchor coat layer composition adjustment treatment represented by M1, M2 and M3 were performed within 1 to 2 days after the composition adjustment treatment.
  • any one of the three types of CVD 1 to 3 having a composition distribution region represented by SiC x and having different thicknesses where x is 0.8 to 1.2 is used. Layers were deposited. Table 3 shows the deposition conditions of each gas barrier layer, the thickness of the gas barrier layer, and the thickness of the region represented by SiC x where x is 0.8 to 1.2.
  • a gas barrier film was produced by combining the above conditions.
  • the gas barrier films of Comparative Examples 1 to 7 and Examples 1 to 11 were subjected to “Evaluation of the number of defects in the gas barrier layer” described later.
  • Comparative Examples 8 to 12 and Examples 12 to 18 an organic EL element was produced on a gas barrier film, and “dark spot (DS) evaluation of organic EL device” described later was performed.
  • Example 3 A gas barrier film (Sample No. 3) was produced in the same manner as in Comparative Example 2 except that the resin base material 2 was used and the anchor coat layer was formed under the conditions of U2 in Table 1 above.
  • Comparative Example 4 A gas barrier film (sample No. 4) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U3 in Table 1 above.
  • Example 5 A gas barrier film (Sample No. 5) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U8 in Table 1 above.
  • Example 6 A gas barrier film (Sample No. 6) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U9 in Table 1 above.
  • Example 1 A gas barrier film (Sample No. 7) was produced in the same manner as in Comparative Example 2 except that the composition adjustment treatment M2 of the anchor coat layer was performed during the modification treatment of the layer containing polysilazane.
  • Example 2 A gas barrier film (Sample No. 8) was produced in the same manner as in Comparative Example 3 except that the composition adjustment treatment M1 of the anchor coat layer was performed during the modification treatment of the layer containing polysilazane.
  • Example 3 A gas barrier film (Sample No. 9) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U4 in Table 1 above.
  • Example 4 A gas barrier film (Sample No. 10) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U5 in Table 1 above.
  • Example 5 A gas barrier film (Sample No. 11) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U6 in Table 1 above.
  • Example 6 A gas barrier film (Sample No. 12) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U7 in Table 1 above.
  • Example 7 A gas barrier film (Sample No. 13) was produced in the same manner as in Example 3 except that the gas barrier layer was changed to CVD1.
  • Example 8 A gas barrier film (Sample No. 14) was produced in the same manner as in Example 3 except that the gas barrier layer was changed to CVD3.
  • Example 7 A gas barrier film (Sample No. 15) was produced in the same manner as in Comparative Example 3 except that the gas barrier layer was changed to CVD1.
  • Example 9 A gas barrier film (Sample No. 16) was produced in the same manner as in Comparative Example 3 except that the anchor coat layer was formed under the conditions of U10 in Table 1 above.
  • Example 10 A gas barrier film (sample No. 17) was formed in the same manner as in Example 4 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. Produced.
  • Example 11 In Comparative Example 3, the gas barrier film (Sample No. 18) was prepared in the same manner as Comparative Example 3 except that the anchor coat layer composition adjustment treatment M3 was performed during the modification treatment of the polysilazane-containing layer. Produced.
  • Example 9 A gas barrier film (Sample No. 20) was formed in the same manner as in Comparative Example 3 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. Produced.
  • Example No. 21 A gas barrier film (Sample No. 21) was produced in the same manner as in Comparative Example 9 except that the anchor coat layer was formed under the conditions of U3 in Table 1 above.
  • Example 12 A gas barrier film (Sample No. 22) was produced in the same manner as in Example 1 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. did.
  • Example No. 23 A gas barrier film (sample No. 23) was produced in the same manner as in Comparative Example 5 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. did.
  • Example 13 A gas barrier film (sample No. 24) was prepared in the same manner as in Example 3 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 and the modification treatment was performed. did.
  • Example 14 A gas barrier film (sample No. 25) was produced in the same manner as in Example 4 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. did.
  • Example 15 A gas barrier film (sample No. 26) was prepared in the same manner as in Example 5 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 and the reforming treatment was performed. did.
  • Example 16 A gas barrier film (sample No. 27) was prepared in the same manner as in Example 6 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 and the modification treatment was performed. did.
  • Example 17 A gas barrier film (Sample No. 28) was produced in the same manner as in Example 7 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. did.
  • Example 12 A gas barrier film (sample No. 29) was produced in the same manner as in Comparative Example 7 except that a layer containing polysilazane was further formed on the gas barrier layer under the conditions of U2 in Table 1 above and the modification treatment was performed. did.
  • Example 18 A gas barrier film (Sample No. 30) was produced in the same manner as in Comparative Example 7 except that the composition adjustment treatment M2 was performed during the modification treatment of the layer containing polysilazane.
  • evaluation methods ⁇ Evaluation of number of defects in gas barrier layer by vacuum film formation>
  • evaluation elements having a Ca vapor deposition area of 50 mm were produced.
  • the number of Ca corrosion points of 100 ⁇ m or more was determined in terms of a circle-equivalent diameter generated when stored at 85 ° C. and 85% RH for 6 hours.
  • Each gas barrier film measured as described above was evaluated by the number of Ca corrosion points and ranked as follows. In addition, if the number of Ca corrosion points is 19 or less ( ⁇ evaluation or more), it means that it has high gas barrier properties and excellent in-plane uniformity of gas barrier properties, and there is no problem in practical use, and it is a pass product. It is.
  • the gas barrier films of the examples are Sample 1 without an anchor coat layer, Samples 2 to 5 with A ⁇ B> 60, and Sample 15, and an anchor coat layer formed by modifying polysiloxane. It was found that the film 6 had high gas barrier properties and excellent in-plane uniformity of gas barrier properties as compared to the sample 6 formed.
  • a bottom emission type organic electroluminescence device (organic EL device) is produced by the following method so that the area of the light emitting region is 5 cm ⁇ 5 cm. did.
  • the gas barrier film is fixed to a substrate holder of a commercially available vacuum deposition apparatus, compound 118 is placed in a resistance heating boat made of tungsten, and the substrate holder and the heating boat are attached in the first vacuum chamber of the vacuum deposition apparatus. It was. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.
  • the heating boat containing the compound 118 was energized and heated, and the deposition rate was 0.1 nm / second to 0.2 nm / second.
  • the underlayer of the first electrode was provided with a thickness of 10 nm.
  • the base material formed up to the base layer was transferred to the second vacuum chamber while being vacuumed, and after the pressure in the second vacuum chamber was reduced to 4 ⁇ 10 ⁇ 4 Pa, the heating boat containing silver was energized and heated.
  • a first electrode made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second.
  • compound A-3 blue light-emitting dopant
  • compound A-1 green light-emitting dopant
  • compound A-2 red light-emitting dopant
  • compound H-1 host compound
  • the deposition rate was changed depending on the location so that it was linearly from 35% by weight to 5% by weight.
  • Compound A-1 and Compound A-2 each had a concentration of 0.2% by weight without depending on the film thickness.
  • the compound H-1 was co-deposited to a thickness of 70 nm by changing the deposition rate depending on the location so that it was 64.6 wt% to 94.6 wt%.
  • a light emitting layer was formed.
  • the compound ET-1 was deposited to a thickness of 30 nm to form an electron transport layer, and further potassium fluoride (KF) was formed to a thickness of 2 nm. Furthermore, aluminum 110nm was vapor-deposited and the 2nd electrode was formed.
  • KF potassium fluoride
  • compound 118 The compound 118, compound HT-1, compounds A-1 to A-3, compound H-1, and compound ET-1 are the compounds shown below.
  • the sample was placed in a decompression device, and pressed at 90 ° C. under a reduced pressure of 0.1 MPa, pressed against the superposed base material and the sealing member, and held for 5 minutes. Subsequently, the sample was returned to an atmospheric pressure environment and further heated at 120 ° C. for 30 minutes to cure the adhesive.
  • the sealing step is performed under atmospheric pressure and in a nitrogen atmosphere with a water content of 1 ppm or less, in accordance with JIS B 9920: 2002.
  • the measured cleanliness is class 100, the dew point temperature is ⁇ 80 ° C. or less, and the oxygen concentration is 0. It was performed at an atmospheric pressure of 8 ppm or less.
  • the description regarding formation of the lead-out wiring from an anode and a cathode is abbreviate
  • the organic EL device obtained as described above was energized for 100 hours in an environment of 85 ° C. and 85% RH, issued and photographed, and the size and number of dark spots were measured from the photograph image.
  • the number of dark spots 300 ⁇ m or more was obtained.
  • the number of dark spots was converted to an issue area of 100 cm 2 and ranked as follows.
  • the number of dark spots is 19 or less ( ⁇ evaluation or more)
  • the number of dark spots is 19 or less ( ⁇ evaluation or more), there is no problem in actual use and the product is acceptable.
  • the organic EL element samples 22 and 24-28 having the gas barrier films of Examples in which the anchor coat layer satisfies A ⁇ B ⁇ 60 showed good results in the dark spot evaluation in a high temperature and high humidity environment.
  • a modified layer of polysilazane is further provided on the gas barrier layer (samples 20 and 21), and the composition is SiC. Even if the thickness of the region of the gas barrier layer in which x is 0.8 to 1.2 (sample 29) is increased (sample 29), the composition distribution is represented by x. Spots were observed, indicating that the durability was poor.

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Abstract

L'invention concerne un film barrière aux gaz qui a de bonnes propriétés de barrière aux gaz et une excellente uniformité dans le plan de propriétés de barrière aux gaz. En outre, l'invention concerne un dispositif électronique qui a une excellente durabilité dans des environnements à haute température et haute humidité. Ce film barrière aux gaz comprend, sur un substrat, une couche de revêtement d'ancrage et une couche de barrière aux gaz, dans cet ordre, où la couche de barrière aux gaz est en contact avec la couche de revêtement d'ancrage et est formée par dépôt sous vide. Cette couche de revêtement d'ancrage est obtenue par un processus de reformage qui consiste à appliquer de l'énergie à une couche contenant du polysilizane et, en définissant A (nm) comme l'épaisseur de la couche de revêtement d'ancrage, et B le rapport atomique (N/Si) des atomes d'azote par rapport aux atomes de silicium dans toute la couche de revêtement d'ancrage, la relation A×B ≦ 60 est respectée.
PCT/JP2015/068227 2014-07-14 2015-06-24 Film barrière aux gaz et dispositif électronique WO2016009801A1 (fr)

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KR101905298B1 (ko) 2018-10-05
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JPWO2016009801A1 (ja) 2017-04-27

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