WO2015105188A1 - Gas barrier film and electronic device comprising same - Google Patents
Gas barrier film and electronic device comprising same Download PDFInfo
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- WO2015105188A1 WO2015105188A1 PCT/JP2015/050535 JP2015050535W WO2015105188A1 WO 2015105188 A1 WO2015105188 A1 WO 2015105188A1 JP 2015050535 W JP2015050535 W JP 2015050535W WO 2015105188 A1 WO2015105188 A1 WO 2015105188A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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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
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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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
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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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
- C08J7/048—Forming gas barrier coatings
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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
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/04—Treatment by energy or chemical effects using liquids, gas or steam
- B32B2310/0445—Treatment by energy or chemical effects using liquids, gas or steam using gas or flames
- B32B2310/0463—Treatment by energy or chemical effects using liquids, gas or steam using gas or flames other than air
- B32B2310/0481—Ozone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
- B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
- B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
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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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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 including the same.
- a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used for packaging articles in the fields of food, medicine, etc. It is used for.
- a gas barrier film By using the gas barrier film, it is possible to prevent alteration of the article due to gas such as water vapor or oxygen.
- a gas barrier film having a high gas barrier property for example, a coating liquid containing polysilazane is applied on a substrate such as polyethylene terephthalate (PET), and the obtained polysilazane coating film is modified.
- a gas barrier film having a gas barrier layer containing the resulting polysilazane modified product is known (see, for example, Patent Document 1).
- the gas barrier film is formed by a so-called wet film forming method, and generally has a high gas barrier property since a uniform coating film is obtained.
- a film is bonded to carrier glass or the like, and a device is formed by sequentially forming a functional layer or the like on the film by roll-to-roll or the like, and finally the device is formed from carrier glass or the like.
- a so-called device forming process of separation is preferably employed because of its excellent productivity.
- the process may be exposed to a high temperature environment of 300 ° C. or higher, and the film to be used needs to have heat resistance.
- a polyimide base material is mentioned as a film provided with such heat resistance.
- the conventional gas barrier film mainly uses a thermoplastic resin such as PET, it cannot be applied to a device forming process exposed to a high temperature environment.
- an object of the present invention is to provide a gas barrier film that can be suitably applied to a device formation process.
- the inventor used a polyimide base material as a base material, applied a gas barrier layer containing a polysilazane modified product obtained by modifying polysilazane as a gas barrier layer, and adhered the polyimide base material and the gas barrier layer. It has been found that the above-mentioned problems can be solved by setting the strength to a certain level or more, and the present invention has been completed.
- the gas barrier film according to this embodiment has a polyimide base material and a gas barrier layer containing a polysilazane modified product.
- the adhesive strength of a polyimide base material and a gas barrier layer is 1.3 N / cm or more, Preferably it is 2.7 N / cm or more, More preferably, it is 4 N / cm or more, More preferably, it is 5 N / cm or more.
- the adhesive strength between the polyimide base material and the gas barrier layer is 1.3 N / cm or more, formation of an insulating film formed on the barrier surface is facilitated, and the value as a heat resistant base material having a barrier property is recognized.
- the adhesive strength of a polyimide base material and a barrier layer is 50 N / cm or less, More preferably, it is 40 N / cm or less. When it is larger than 50 N / cm, it becomes difficult to smoothly transport various production lines, leading to problems in the manufacturing apparatus and a decrease in productivity.
- the polyimide base material generally has excellent heat resistance, it can withstand high temperature exposure in the device forming process and can be used in the device forming process.
- the polyimide substrate has very low adhesion to the gas barrier layer containing the polysilazane modified product in a high temperature environment. Therefore, when a gas barrier film including a polyimide base material and the gas barrier layer is applied to a device forming process, the polyimide base material and the gas barrier layer are peeled off when the device is separated from the carrier glass during the process or after the device formation. sell. As a result, a desired device cannot be formed.
- the gas barrier film according to the present embodiment has a high adhesion strength even in a high temperature environment because the gas barrier layer containing the polyimide base material and the polysilazane modified product has a high adhesion strength. Can be prevented. As a result, it can be suitably applied to a device formation process.
- adheresive strength between the polyimide base material and the gas barrier layer means the adhesive strength between the polyimide base material and the gas barrier layer. Therefore, even if another layer (for example, an adhesive layer) is interposed between the polyimide substrate and the gas barrier layer, the other layer (for example, other layer) is provided on the surface opposite to the surface on which the polyimide substrate is disposed. Even if the gas barrier layer is present, the adhesive force between the polyimide base material and the gas barrier layer is referred to as “adhesive strength between the polyimide base material and the gas barrier layer”. At this time, in this specification, the value measured by the method described in the examples is adopted as the value of “adhesive strength between the polyimide base material and the gas barrier layer”.
- the water vapor permeability of the gas barrier film is preferably 0.01 g / (m 2 ⁇ 24 h) or less, and more preferably 0.0001 g / (m 2 ⁇ 24 h) or less.
- a value measured by a method based on JIS K 7129-1992 is adopted as the value of “water vapor permeability”. Measurement conditions are temperature: 60 ⁇ 0.5 ° C. and relative humidity (RH): 90 ⁇ 2%.
- the polyimide substrate is generally a resin film obtained by polymerizing a monomer containing tetracarboxylic dianhydride and diamine.
- the tetracarboxylic dianhydride is not particularly limited, and examples thereof include aliphatic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides.
- Examples of the aliphatic tetracarboxylic dianhydride include bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane.
- aromatic tetracarboxylic dianhydride examples include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3 , 3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, m-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 4,4 ′-(2,2- Hexafluoroisopropylene) diphthalic dianhydride, 2,2′-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis
- aromatic tetracarboxylic dianhydrides are preferable from the viewpoint of obtaining a polyimide base material having excellent chemical and physical properties, and biphenyltetracarboxylic dianhydrides. More preferably, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3, More preferably, it is 4′-biphenyltetracarboxylic dianhydride.
- tetracarboxylic dianhydrides may be used alone or in combination of two or more.
- the diamine is not particularly limited, and examples thereof include aliphatic diamines and aromatic diamines.
- aliphatic diamine examples include diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, diaminodecane, diaminoundecane, diaminododecane, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,2 -Diaminocyclohexane, 3-methyl-1,4-diaminocyclohexane, 3-methyl-, 3-aminomethyl-, 5,5-dimethylcyclohexylamine, 1,3-bisaminomethylcyclohexane, bis (4,4'- Aminocyclohexyl) methane, bis (3,3′-methyl-4,4′-aminocyclohexyl) methane, bis (aminomethyl) norbornane, bis (aminomethyl
- aromatic diamine examples include p-phenylenediamine, metaphenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4, 4'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4-aminophenyl) sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'- Diaminobenzanilide, 1,4-bis (4-amin
- aromatic diamines are preferable and p-phenylenediamine is more preferable from the viewpoint of obtaining a polyimide base material having excellent chemical and physical properties.
- the above diamines may be used alone or in combination of two or more.
- the polyimide base material is a polymer containing biphenyltetracarboxylic dianhydride and p-phenylenediamine as monomers because there is no volatile component that damages the barrier film when the film is exposed to high temperatures. It is preferable.
- the polyimide base material can be obtained by polymerizing a monomer containing tetracarboxylic dianhydride and diamine. More specifically, (1) a polyamic acid is synthesized by reacting tetracarboxylic dianhydride and diamine in an organic solvent, and (2) a polyimide substrate is produced by imidizing the obtained polyamic acid. can do.
- a polyamic acid can be synthesized by reacting a tetracarboxylic dianhydride and a diamine in an organic solvent.
- the reaction is preferably performed by dissolving diamine in an organic solvent and gradually adding tetracarboxylic dianhydride while stirring the obtained diamine solution.
- the organic solvent that can be used is not particularly limited, but amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide; ⁇ -butyrolactone, Cyclic ester solvents such as ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyrolactone; carbonate solvents such as ethylene carbonate and propylene carbonate; glycol solvents such as triethylene glycol; Phenolic solvents such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol; acetophenone; 1,3-dimethyl-2-imidazolidinone; sulfolane; dimethyl sulfoxide and the like.
- amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide
- the molar ratio of tetracarboxylic dianhydride and diamine used in the reaction can be appropriately set according to the viscosity of the polyamic acid, but it should be 0.90 to 1.10. Is more preferable, and 0.95 to 1.05 is more preferable.
- the reaction temperature is preferably 0 to 100 ° C.
- the reaction time is preferably 1 to 72 hours.
- a polyimide substrate can be produced by imidizing the polyamic acid obtained in (1) above.
- the polyimide substrate can be produced by casting a solution containing polyamic acid on a support and heating.
- the solution containing the polyamic acid contains a polyamic acid and an organic solvent. If necessary, it may further contain an imidization catalyst, an organic phosphorus-containing compound, inorganic fine particles and the like.
- polyamic acid those obtained in the above (1) are used. Under the present circumstances, polyamic acid may be used independently or may be used in combination of 2 or more type.
- the content of polyamic acid is preferably 10 to 30% by mass with respect to the total amount of the solution containing polyamic acid.
- the imidization catalyst has a function of improving the physical properties (elongation, end tear resistance, etc.) of the polyimide film.
- a substituted or unsubstituted nitrogen-containing heterocyclic compound and this N-oxide compound substituted or unsubstituted amino acid compound; Aromatic hydrocarbon compound which has a hydroxyl group; Aromatic heterocyclic Compounds.
- Specific imidization catalysts include 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methylbenzimidazole, Examples thereof include N-benzyl-2-methylimidazole, isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n-propylpyridine and the like.
- the amount of the imidization catalyst used is preferably 0.01 to 2 equivalents, more preferably 0.02 to 1 equivalents relative to the amic acid unit of the polyamic acid.
- the organic phosphorus-containing compound is not particularly limited, but is monocaproyl phosphate ester, monooctyl phosphate ester, monolauryl phosphate ester, monomyristyl phosphate ester, monocetyl phosphate ester, monostearyl phosphate ester, triethylene Monophosphate ester of glycol monotridecyl ether, monophosphate ester of tetraethylene glycol monolauryl ether, monophosphate ester of diethylene glycol monostearyl ether, dicaproyl phosphate ester, dioctyl phosphate ester, dicapryl phosphate ester, dilauryl phosphate ester, dimyristyl Phosphate, dicetyl phosphate, distearyl phosphate, diethylene phosphate of tetraethylene glycol mononeopentyl ether Steal, phosphate esters such as diethylene ester of triethylene glycol monotridecyl ether
- Amine salts include ammonia, monomethylamine, monoethylamine, monopropylamine, monobutylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, monoethanolamine, diethanolamine, triamine.
- Examples include amine salts such as ethanolamine. These organic phosphorus-containing compounds may be used alone or in combination of two or more.
- the inorganic fine particles are not particularly limited, but inorganic oxide powders such as fine particle titanium dioxide powder, silicon dioxide (silica) powder, magnesium oxide powder, aluminum oxide (alumina) powder, and zinc oxide powder; fine particle nitriding Examples thereof include inorganic nitride powders such as silicon powder and titanium nitride powder; inorganic carbide powders such as silicon carbide powder; inorganic salt powders such as particulate calcium carbonate powder, calcium sulfate powder and barium sulfate powder. These inorganic fine particles may be used alone or in combination of two or more. In addition, in order to disperse
- the support for casting a solution containing polyamic acid is not particularly limited, and a known support such as a stainless steel substrate or a stainless steel belt can be used. At this time, the support is preferably smooth.
- the support is preferably an endless support such as an endless belt from the viewpoint of enabling continuous production.
- the method for casting the solution containing polyamic acid is not particularly limited, but is preferably extrusion coating or melt coating.
- a solution containing a surface treatment agent may be applied to one side or both sides of the obtained self-supporting coating film as necessary.
- the process of the polyimide base material by the said surface treating agent is not contained in the "surface treatment of a polyimide base material" mentioned later.
- the solution containing the surface treatment agent contains a surface treatment agent and an organic solvent.
- the surface treatment agent is not particularly limited, but silane coupling agents, borane coupling agents, aluminum coupling agents, aluminum chelating agents, titanate coupling agents, iron coupling agents, copper coupling agents and the like. Can be mentioned. Of these, silane coupling agents and titanate coupling agents are preferably used.
- the silane coupling agent is not particularly limited, but epoxy such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.
- Silane coupling agents vinyl silane coupling agents such as vinyltrichlorosilane, vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane; acrylic silane cups such as ⁇ -methacryloxypropyltrimethoxysilane Ring agent: N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -Aminopropyl Examples include aminosilane coupling agents such as trimethoxysilane; ⁇ -mercaptopropyltrimethoxysilane, ⁇ -chloropropyltrimethoxysilane, and the like.
- the titanate coupling agent is not particularly limited, but is isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctyl phosphite) titanate, tetra ( 2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyltricumyl Examples thereof include phenyl titanate.
- an aminosilane coupling agent such as ⁇ -aminopropyl-triethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyl-triethoxysilane, N- (aminocarbonyl).
- the above-mentioned surface treatment agents may be used alone or in combination of two or more.
- the content of the surface treatment agent in the solution containing the surface treatment agent is not particularly limited, but is preferably 0.5% by mass or more with respect to the total amount of the solution containing the surface treatment agent, and is 1 to 100% by mass. More preferred is 3 to 60% by mass, still more preferred is 5 to 55% by mass.
- the organic solvent may be the same as the organic solvent used for the synthesis of the polyamic acid described above.
- Examples of the coating method having a self-supporting solution containing a surface treatment agent include a gravure coating method, a spin coating method, a silk screen method, a dip coating method, a spray coating method, a bar coating method, and a knife coating method. And a known coating method such as a roll coating method, a blade coating method, and a die coating method.
- the amount of application of the solution containing the surface treatment agent to the coating film having self-supporting property is not particularly limited, but is preferably 1 to 50 g / m 2 , more preferably 2 to 30 g / m 2. Particularly preferred is 3 to 20 g / m 2 .
- imidation of polyamic acid is performed by heating the obtained coating film having self-supporting property, or the coating film obtained by applying a solution containing the coating film having self-supporting property and the surface treatment agent. And a polyimide substrate can be produced.
- the heating temperature for imidization is not particularly limited as long as imidization proceeds, but it is preferably 100 to 550 ° C, more preferably 100 to 400 ° C.
- the heating is preferably performed stepwise.
- the heating is performed at 100 to 170 ° C. as the primary heat treatment, the heating is performed at 170 to 220 ° C. as the second heat treatment, and 220 is performed as the third heat treatment.
- Heating at ⁇ 400 ° C. and heating at 400 ⁇ 550 ° C. can be performed as the fourth heat treatment.
- the film When heating, the film may be stretched as necessary. Thereby, physical properties, such as a thermal expansion coefficient of a polyimide base material, can be controlled suitably.
- the stretching method may be biaxial stretching such as sequential biaxial stretching and simultaneous biaxial stretching, or uniaxial stretching.
- the draw ratio is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.
- the imidation of the polyamic acid can be performed by chemical imidation instead of or in addition to the above heating.
- a solution obtained by further adding a dehydrating agent and a catalyst to the solution containing the polyamic acid described above is cast on a support and heated. It can be carried out.
- the dehydrating agent is not particularly limited, and examples thereof include aliphatic acid anhydrides, aromatic acid anhydrides, alicyclic acid anhydrides, and heterocyclic acid anhydrides. Specific examples include acetic anhydride, propionic anhydride, butyric anhydride, formic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, picolinic anhydride, and the like. Of these, acetic anhydride is preferably used. In addition, the said dehydrating agent may be used independently or may be used in combination of 2 or more type.
- the addition amount of the dehydrating agent is preferably 0.5 mol or more per 1 mol of the amic acid bond of the polyamic acid.
- the catalyst is not particularly limited, and examples thereof include aliphatic tertiary amines, aromatic tertiary amines, and heterocyclic tertiary amines. Specific examples include trimethylamine, triethylamine, dimethylaniline, pyridine, ⁇ -picoline, isoquinoline, quinoline and the like. Of these, isoquinoline is preferably used.
- the amount of the catalyst added is preferably 0.1 mol or more with respect to 1 mol of the amic acid bond of the polyamic acid.
- the polyimide base material can be produced by casting and heating to the support in the same manner as described above.
- polyimide base material you may use the well-known polyimide base material manufactured by making tetracarboxylic dianhydride and diisocyanate react, for example besides what was mentioned above.
- the film thickness of the polyimide base material is preferably 5 to 500 ⁇ m, more preferably 25 to 250 ⁇ m.
- the linear expansion coefficient of the polyimide base material is preferably 20 ppm / K or less, and more preferably 10 ppm / K or less.
- a gas barrier film is applied to an electronic device such as a liquid crystal display device (LCD panel) such that the linear expansion coefficient of the polyimide base material is 20 ppm / K or less, the occurrence of color misregistration with respect to environmental temperature changes, etc. It is preferable because deformation can be suppressed.
- the value measured by the following method shall be employ
- the polyimide base material preferably has a visible light (400 to 700 nm) light transmittance of 80% or more, and more preferably 90% or more.
- a visible light (400 to 700 nm) light transmittance 80% or more
- a gas barrier film is applied to an electronic device such as a liquid crystal display (LCD panel)
- LCD panel liquid crystal display
- light transmittance means a spectrophotometer (visible ultraviolet spectrophotometer UV-2500PC: manufactured by Shimadzu Corporation), which uses visible light in accordance with the ASTM D-1003 standard. It means the average transmittance in the visible light range, which is calculated by measuring the total transmitted light amount with respect to the incident light amount.
- the polyimide base material has a 10-point average surface roughness Rz defined by JIS B 0601 (2001) of preferably 1 to 1500 nm, more preferably 5 to 400 nm, and further preferably 300 to 350 nm. preferable.
- the polyimide base material preferably has a center line average roughness Ra defined by JIS B 0601 (2001) of 0.5 to 12 nm, and more preferably 1 to 8 nm. It is preferable that Rz and Ra are within the above ranges since the coating property of the coating liquid is improved. If necessary, the polyimide base material may be polished on one side or both sides to improve smoothness.
- the elastic modulus of the polyimide base material is preferably 1 GPa or more, more preferably 2 to 10 GPa. It is preferable for the elastic modulus of the polyimide base material to be 1 GPa or more because it has high dimensional stability and can be suitably applied to a device formation step. In the present specification, a value measured in accordance with ASTM D882-97 is adopted as the value of “elastic modulus”.
- the gas barrier layer contains a polysilazane modified product.
- additives such as amine catalysts and metal catalysts may be included as necessary.
- the film thickness of the gas barrier layer is preferably 10 to 500 nm, and more preferably 20 to 300 nm.
- the thickness of the gas barrier layer is preferably 10 nm or more, since the thickness can be made uniform and high gas barrier properties can be obtained.
- it is preferable that the thickness of the gas barrier layer is 500 nm or less because cracks can be suppressed.
- the water vapor permeability of the gas barrier layer is preferably 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less, and more preferably 1 ⁇ 10 ⁇ 4 g / (m 2 ⁇ 24 h) or less.
- the polysilazane modified product means a modified product obtained by modifying polysilazane.
- the polysilazane modified product contains silicon oxide obtained by modifying polysilazane.
- silicon nitride and / or silicon oxynitride obtained by modifying polysilazane may be included.
- Polysilazane is a polymer having a bond such as Si—N, Si—H, or NH in its structure.
- the polysilazane is not particularly limited, but it is preferably a compound that is converted to silica by being ceramicized at a relatively low temperature in consideration of performing the modification treatment, for example, as described in JP-A-8-112879.
- a compound having a main skeleton composed of units represented by the following general formula is preferable.
- R 1 , R 2 , and R 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group. .
- the polysilazane is particularly preferably perhydropolysilazane (hereinafter, also referred to as “PHPS”) in which all of R 1 , R 2 , and R 3 are hydrogen atoms from the viewpoint of the denseness of the resulting gas barrier layer.
- PHPS perhydropolysilazane
- Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and may be a liquid or solid substance depending on the molecular weight.
- Mn number average molecular weight
- a commercially available product may be used, and examples of the commercially available product include NN120, NN110, NAX120, NAX110, NL120A, NL110A, NL150A, NP110, NP140 (manufactured by AZ Electronic Materials Co., Ltd.). .
- a silicon alkoxide-added polysilazane obtained by reacting a polysilazane represented by the above general formula with a silicon alkoxide (for example, JP-A-5-238827), glycidol is reacted.
- glycidol-added polysilazane eg, JP-A-6-122852
- alcohol-added polysilazane eg, JP-A-6-240208
- metal carboxylate Metal silicic acid salt-added polysilazane for example, JP-A-6-299118
- acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex
- metal Add fine particles The resulting metal particles added polysilazane (e.g., JP-A-7-196986 publication), and the like.
- Polysilazane is converted by modification to produce silicon oxide.
- the modification mechanism of polysilazane to silicon oxide includes modification of polysilazane by hydrolysis of water. Specifically, the Si—N bond of polysilazane is hydrolyzed with water, whereby the polymer main chain is cleaved to form Si—OH. When two Si—OH are dehydrated and condensed under the reforming conditions, Si—O—Si bonds are formed and cured to produce silicon oxide.
- modification to silicon oxide by the direct oxidation of polysilazane can occur together with or instead of the modification mechanism to silicon oxide.
- polysilazane is irradiated with vacuum ultraviolet light
- H or N in the polysilazane is directly replaced with O by vacuum ultraviolet light
- ozone activated by the vacuum ultraviolet light, active oxygen, or the like that is, Forming Si—O—Si bonds (without going through silanol) and curing results in silicon oxide (photon action called photon process).
- modification to silicon nitride and / or silicon oxynitride may occur in addition to or instead of modification of the polysilazane to silicon oxide by direct oxidation.
- the Si—H bond or N—H bond in the polysilazane is relatively easily broken by excitation or the like, and recombines as Si—N in an inert atmosphere. Thereby, silicon nitride and silicon oxynitride can be generated.
- VUV light ultraviolet light having a high energy with a wavelength of 200 nm or less.
- the gas barrier layer may contain an amine catalyst and / or a metal catalyst.
- the amine catalyst is not particularly limited, but N, N-dimethylethanolamine, N, N-diethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′-tetra And methyl-1,3-diaminopropane and N, N, N ′, N′-tetramethyl-1,6-diaminohexane.
- the metal catalyst is not particularly limited, and examples thereof include platinum compounds such as platinum acetylacetonate, palladium compounds such as palladium propionate, and rhodium compounds such as rhodium acetylacetonate.
- the modification of polysilazane can be promoted by adding the amine catalyst and the metal catalyst.
- a gas barrier layer containing the modified polysilazane is disposed on the polyimide substrate.
- two or more gas barrier layers may be laminated (that is, a substrate-gas barrier layer-gas barrier layer, etc.).
- another gas barrier layer may be formed on the surface of the gas barrier layer (that is, base material-gas barrier layer-other gas barrier layer).
- two or more other gas barrier layers may be laminated (ie, base material-gas barrier layer-other gas barrier layer-other gas barrier layer, etc.).
- the other gas barrier layer is not particularly limited, and may be a known gas barrier layer, for example, a gas barrier layer formed by a dry film forming method.
- the gas barrier layer formed by the dry film forming method includes zinc disulfide, aluminum oxide, indium oxide, tin oxide, gallium oxide, indium tin oxide (ITO), aluminum-added zinc oxide (AZO), and zinc-tin composite oxide.
- Inorganic materials such as (ZTO), aluminum nitride, and silicon carbide may be included.
- the film thickness of the gas barrier layer formed by the dry film forming method is preferably 10 to 500 nm, and more preferably 20 to 300 nm.
- the water vapor permeability of the gas barrier layer formed by the dry film formation method is preferably 0.1 g / (m 2 ⁇ 24 h) or less, preferably 0.0001 to 0.01 g / (m 2 ⁇ 24 h). More preferably.
- the gas barrier layer containing the polysilazane modified product according to the present embodiment is preferably provided with an adhesive means in order to realize high adhesive strength with the polyimide base material.
- the adhesive means is not particularly limited as long as the adhesive strength is improved, and examples thereof include arrangement of an adhesive layer and surface treatment of a polyimide base material. These bonding means may be used alone or in combination of two or more.
- the adhesive layer is usually disposed between the polyimide substrate and the gas barrier layer.
- the adhesive layer the adhesive strength of a polyimide base material and a gas barrier layer can improve.
- the adhesive layer includes an adhesive.
- examples of the adhesive include metal oxides and chemically reactive adhesives.
- metal oxide examples include aluminum oxide such as aluminum oxide (Al 2 O 3 ); titanium oxide such as titanium oxide (TiO 2 ); tin oxide such as tin oxide (SnO 2 ); cerium oxide (CeO 2). ) And the like; zinc oxides such as zinc oxide (ZnO); and silicon oxides such as silicon oxide (SiO 2 ). These metal oxides may be used alone or in combination of two or more.
- a contact bonding layer using a metal oxide when forming a contact bonding layer using a metal oxide, it can usually be performed by a physical vapor deposition method, a chemical vapor deposition method, or these combinations.
- Examples of the physical vapor deposition method include vapor deposition methods such as resistance heating method, electron beam vapor deposition method, molecular beam epitaxy method; ion plating method; sputtering method and the like.
- Examples of the chemical vapor deposition include thermal CVD, catalytic chemical vapor deposition, photo CVD, and plasma CVD.
- the chemical reaction type adhesive includes a bone agent, a binder, and a curing agent, and is mainly classified into a silicate type adhesive, a phosphate type adhesive, and a colloidal silica type adhesive.
- oxides, nitrides or carbides having high fire resistance such as alumina, silica, zirconia, spinel and the like can be used as the bone agent.
- alkali metal silicate can be used as the binder.
- metal oxides such as ZnO and MgO, hydroxides, phosphates, borates, silicofluorides, and the like can be used.
- the same adhesive as the silicate adhesive can be used as a bone agent.
- the binder metal phosphates such as aluminum phosphate and magnesium phosphate can be used.
- metal oxide, magnesium silicate, strontium titanate, or the like can be used as the curing agent.
- colloidal silica-based adhesive the same silicate-based adhesive as that described above can be used.
- binder colloidal silica (particle size: 10 to 100 ⁇ m) can be used.
- a metal oxide or the like can be used as the curing agent.
- a metal oxide it is preferable to use a metal oxide, and it is more preferable to use aluminum oxide, titanium oxide, tin oxide, cerium oxide, or zinc oxide.
- the film thickness of the adhesive layer is preferably 50 nm or less, and more preferably 5 to 30 nm. Note that the film thickness of the adhesive layer is preferably a thin film, and therefore does not show or hardly shows gas barrier properties.
- the surface of the polyimide base material is preferably surface-treated.
- Specific examples of the surface treatment include corona treatment, plasma treatment, UV ozone treatment, and excimer treatment, preferably plasma treatment, UV ozone treatment, and excimer treatment.
- the surface of the polyimide base material can be modified and cleaned.
- an active group such as a hydroxyl group, a carboxy group, or an amino group can be introduced on the surface of the polyimide substrate.
- the wettability can be improved by the washing.
- the bonding strength and adhesion with the gas barrier layer disposed on the polyimide base material can be improved, and the adhesive strength between the polyimide base material and the gas barrier layer can be improved.
- the adhesive strength between the polyimide base material and the gas barrier can be improved by an anchor effect or the like.
- Corona treatment is a method for surface modification using corona discharge that is excited by applying an alternating high voltage to a pair of electrodes in an atmospheric pressure state.
- Plasma treatment is a method in which oxygen gas or a mixed gas of oxygen gas and inert gas is ionized by arc discharge, and surface modification is performed using the plasma gas generated thereby.
- inert gas examples include nitrogen gas, argon gas, and helium gas.
- a device such as direct current glow discharge, high frequency discharge, or microwave discharge can be used.
- the supply amount of oxygen gas is preferably 1 to 50 sccm (0 ° C., 1 atm standard), more preferably 10 to 30 sccm.
- the vacuum degree of the vacuum chamber is preferably 0.5 to 50 Pa, and more preferably 1 to 10 Pa.
- the applied power from the plasma generation power source is preferably 50 to 500 W.
- the frequency of the power source for generating plasma is preferably 5 to 50 kHz, and more preferably 10 to 20 kHz.
- UV ozone treatment is a method in which ultraviolet rays (UV) are irradiated, oxygen in the air is converted into ozone, and surface modification is performed using ozone and ultraviolet rays.
- UV ultraviolet rays
- the light source used for UV ozone treatment includes a low-pressure mercury lamp (185 nm, 254 nm).
- the irradiation time is preferably 0.5 to 30 minutes, and more preferably 0.5 to 10 minutes.
- Excimer treatment is a method in which excimer light is irradiated, oxygen in the air is converted to ozone, and surface modification is performed using ozone and excimer light.
- Examples of the light source used for the excimer treatment include a Xe excimer lamp (172 nm), a krypton lamp (146 nm), and an argon lamp (126 nm). Among these, it is preferable to use a Xe excimer lamp.
- the illuminance is preferably 1 mW / cm 2 to 100 kW / cm 2 , and more preferably 100 mW / cm 2 to 10 W / cm 2 .
- the exposure integrated amount is preferably 10 to 1000 mJ / cm 2 , and more preferably 50 to 500 mJ / cm 2 .
- the irradiation time is preferably 0.1 to 500 seconds, and more preferably 0.1 to 60 seconds.
- the manufacturing method of a gas barrier film includes the process of forming a gas barrier layer on a polyimide base material. In addition, as needed, the process of preparing a base material, the process of forming an contact bonding layer, the process of forming another gas barrier layer, etc. are included.
- the method for producing a gas barrier film includes a step of preparing a substrate, a step of forming an adhesive layer, a step of forming a gas barrier layer, and a step of forming another gas barrier layer in this order.
- This step includes preparing a polyimide substrate. If necessary, a surface treatment of the polyimide base material may be included.
- Preparation of a polyimide base material can be performed by manufacturing a polyimide base material itself. Moreover, you may purchase commercially available polyimide.
- the method for producing the polyimide base material is not particularly limited, and the above description can be appropriately referred to.
- a surface treatment of the polyimide substrate can be performed.
- the surface treatment include plasma treatment, UV ozone treatment, and excimer treatment as described above.
- the specific surface treatment method is not particularly limited, and a known technique can be used. For example, the above description can be referred to appropriately.
- Step of forming an adhesive layer This step includes forming an adhesive layer on the polyimide substrate.
- the method for forming the adhesive layer a known method can be appropriately employed depending on the adhesive to be used.
- an adhesive layer can be formed by physical vapor deposition or chemical vapor deposition.
- the adhesive layer can be formed by applying the chemically reactive adhesive on the polyimide substrate, drying and heating.
- Step of forming gas barrier layer This step includes applying a coating liquid containing polysilazane to a polyimide base material (on the adhesive layer when an adhesive layer is formed on the polyimide base material), and modifying the polysilazane. Thereby, the gas barrier layer containing the polysilazane modified product is formed.
- coating liquid containing polysilazane contains polysilazane and a solvent.
- additives such as an amine catalyst and a metal catalyst may be included as necessary.
- Polysilazane Polysilazane can be used in the same manner as described above, and the description thereof is omitted here.
- the content of polysilazane in the coating solution varies depending on the desired film thickness of the gas barrier layer, the pot life of the coating solution, etc., but is preferably 0.2 to 35% by mass with respect to the total amount of the coating solution.
- the solvent is not particularly limited as long as it does not react with polysilazane, and a known solvent can be used.
- a known solvent can be used.
- Specific examples include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons; ether solvents such as aliphatic ethers and alicyclic ethers.
- the hydrocarbon solvent include pentane, hexane, cyclohexane, toluene, xylene, solvesso, turben, methylene chloride, trichloroethane, and the like.
- Examples of ether solvents include dibutyl ether, dioxane, and tetrahydrofuran. These solvents can be used alone or in admixture of two or more.
- Amine catalyst and metal catalyst As the amine catalyst and the metal catalyst, the same ones as described above can be used, so that the description thereof is omitted here.
- the coating solution contains an amine catalyst and / or a metal catalyst
- the amine catalyst and / or metal catalyst is preferably contained in an amount of 0.1 to 10% by mass with respect to polysilazane.
- the amine catalyst is more preferably contained in an amount of 0.5 to 5% by mass based on the polysilazane from the viewpoint of improving the coating property and shortening the reaction time.
- the content of the amine catalyst is preferably less than 2% by mass with respect to polysilazane. It is preferable that the content of the amine catalyst is less than 2% by mass because components that do not contribute to the gas barrier property itself in the gas barrier layer are reduced and high gas barrier property is obtained. Further, when heating is included in the polysilazane modification method described later, the entire coating film is modified. Therefore, in such a case, when the content of the amine catalyst is less than 2% by mass, the modification rate of the polysilazane is reduced, and the modification proceeds while following the base material. Since the gas barrier layer tends to take a thermodynamically stable form, the adhesion between the polyimide base material and the gas barrier layer is improved, and the occurrence of cracks in the gas barrier layer can be prevented.
- a coating liquid is apply
- a coating liquid can be apply
- a coating method of the coating solution a known method can be adopted as appropriate. Specific examples include spin coating methods, roll coating methods, flow coating methods, ink jet methods, spray coating methods, printing methods, dip coating methods, cast film forming methods, bar coating methods, and gravure printing methods.
- the coating amount of the coating liquid is not particularly limited, but can be appropriately adjusted so as to have the desired thickness of the gas barrier layer.
- Modification of polysilazane The modification method of polysilazane is not particularly limited, and a known method can be applied. Specific methods for modifying polysilazane include ultraviolet light irradiation, plasma irradiation, heating, and combinations thereof.
- the irradiation of the ultraviolet light can be performed by irradiating the ultraviolet light by a known method.
- Polysilazane can be modified by irradiation with ultraviolet light.
- irradiation with ultraviolet light includes setting an environment in which ultraviolet light is irradiated onto a coating film obtained by applying a coating liquid. Therefore, “irradiation with ultraviolet light” includes standing the coating film in an environment such as a fluorescent lamp or a yellow lamp. Of these, irradiation with ultraviolet light is preferably performed in an oxidizing gas atmosphere and in a low humidity environment.
- the wavelength of the ultraviolet light to be irradiated is not particularly limited, but is preferably 10 to 450 nm, more preferably 100 to 300 nm, further preferably 100 to 200 nm, and particularly preferably 100 to 180 nm. preferable.
- the ultraviolet light to be irradiated is preferably vacuum ultraviolet light (ultraviolet light having a wavelength of 200 nm or less) from the viewpoint of proceeding the conversion reaction at a lower temperature and in a shorter time.
- the polysilazane is directly oxidized without passing through silanol by irradiation with vacuum ultraviolet light (the action of photons called a photon process), there is little volume change in the oxidation process, and the defect density is high.
- a film containing a small amount of silicon oxide, silicon nitride, silicon oxynitride, or the like can be obtained.
- ozone or active oxygen having high oxidation ability is generated from oxygen or the like present in the reaction atmosphere, and polysilazane reforming treatment can be performed by the ozone or active oxygen.
- denser films such as silicon oxide, silicon nitride, and silicon oxynitride can be obtained. Therefore, the gas barrier layer obtained by modifying polysilazane by irradiation with vacuum ultraviolet light can have high barrier properties.
- the ultraviolet light source is not particularly limited, a low-pressure mercury lamp, a deuterium lamp, a xenon excimer lamp, a metal halide lamp, an excimer laser, or the like can be used. Further, as described above, a fluorescent lamp, a yellow lamp, or the like may be used. Among these, it is preferable to use a rare gas excimer lamp such as a xenon excimer lamp.
- the oxygen concentration during vacuum ultraviolet light irradiation is preferably 0.5% by volume or less, and more preferably 0.1% by volume or less. It is preferable that the oxygen concentration be 0.5% by volume or less because the replacement time between the atmosphere and oxygen can be shortened.
- the method for adjusting the oxygen concentration and the water vapor concentration is not particularly limited, and examples thereof include a method of reducing the pressure in the apparatus and a method of gas flow. Among these, it is preferable to adjust the oxygen concentration and the water vapor concentration by a method of reducing the pressure in the apparatus.
- the pressure is reduced from atmospheric pressure to 100 Pa or less, more preferably 20 Pa or less using a vacuum pump.
- an environment excited by plasma can be obtained by introducing a predetermined gas and setting a predetermined pressure.
- polysilazane can be modified by the heating.
- the heating method is not particularly limited, and the method of heating the coating film by contacting the substrate with a heating element such as a heat block, the method of heating the atmosphere by an external heater such as a resistance wire, and the like of an IR heater And a method using light in the infrared region. Moreover, it is good also as a high temperature environment in a device formation process. That is, a film in which at least a part of the polysilazane in the gas barrier layer is not modified may be manufactured and applied to the device forming process, and at least a part of the unmodified polysilazane may be modified in the process. These methods can be appropriately selected from the viewpoint of the smoothness of the coating film.
- the temperature of the heat treatment is not particularly limited, but is preferably 50 to 200 ° C, more preferably 80 to 150 ° C.
- the heating time is preferably 1 second to 10 hours, more preferably 10 seconds to 1 hour.
- the modification of polysilazane is preferably a combination of ultraviolet light irradiation or plasma irradiation and heat treatment. Modification can be promoted by combining ultraviolet irradiation or plasma irradiation and heat treatment.
- the film thickness, density, etc. of the gas barrier layer obtained by the above modification treatment are the coating conditions, the intensity of ultraviolet light, the irradiation time, the wavelength (light energy density), the irradiation method, the plasma irradiation method, the gas type, and the pressure. It is possible to control by appropriately selecting the frequency of the power source, the input power density, the heating temperature, and the like.
- the film thickness, density, etc. of the gas barrier layer can be controlled by appropriately selecting the irradiation method of ultraviolet light from continuous irradiation, irradiation divided into a plurality of times, and so-called pulse irradiation, etc., in which the plurality of times of irradiation is short. sell.
- the extent of the modification treatment can be confirmed by determining each atomic composition ratio of silicon (Si) atoms, nitrogen (N) atoms, oxygen (O) atoms, etc. by XPS surface analysis of the formed gas barrier layer. .
- the modification of polysilazane does not occur only at the time of the above-mentioned heating, ultraviolet light irradiation, or plasma irradiation, but can occur after the coating liquid is applied on the polyimide substrate.
- a polysilazane modified product containing silicon oxide can be obtained by modifying polysilazane by methods such as ultraviolet light irradiation, plasma irradiation, heating, and combinations thereof.
- the modification includes irradiation with vacuum ultraviolet light
- a polysilazane modified product containing silicon nitride and / or silicon oxynitride together with silicon oxide can be obtained.
- the step of forming another gas barrier layer includes forming another gas barrier layer on the gas barrier layer containing the polysilazane modified product.
- the other gas barrier layer is not particularly limited as described above, and examples thereof include a known gas barrier layer, for example, a gas barrier layer formed by a dry film forming method.
- a method of forming another gas barrier layer by a dry film forming method will be described.
- the dry film forming method examples include physical vapor deposition and chemical vapor deposition.
- the physical vapor deposition method is a method in which a thin film of a target substance is deposited on the surface of the substance by a physical method in a gas phase, and a vapor deposition method (resistance heating method, electron beam vapor deposition method, molecular beam epitaxy method). , Ion plating method, sputtering method and the like.
- the chemical vapor deposition method is a method in which a raw material gas containing a target thin film component is supplied onto a substrate or the like, and the film is formed by a chemical reaction on the substrate surface or in the gas phase. It refers to a method of deposition, and examples include thermal CVD, catalytic chemical vapor deposition, photo CVD, and plasma CVD. Of these, the sputtering method and the plasma CVD method are preferably used, and the plasma CVD method is more preferably used.
- a plasma discharge in a space between a plurality of film forming rollers it is preferable to generate a plasma discharge in a space between a plurality of film forming rollers.
- a pair of film forming rollers is used, and a film is applied to each of the pair of film forming rollers. More preferably, the plasma is generated by discharging between the pair of film forming rollers.
- the plasma is generated by discharging between the pair of film forming rollers.
- the film formation rate can be doubled, and a film having a substantially identical structure can be formed.
- the film forming gas used in such a plasma CVD method preferably contains an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation.
- the other gas barrier layer formed by the dry film forming method is preferably a layer formed by a continuous film forming process.
- an apparatus that can be used when forming another gas barrier layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source. It is preferable that the apparatus has a configuration capable of discharging between the film forming rollers. For example, when the manufacturing apparatus shown in FIG. 1 is used, a roll-to-roll operation is performed using the plasma CVD method. It is also possible to manufacture by a method.
- FIG. 1 is a schematic view showing an example of a manufacturing apparatus that can be suitably used for forming a gas barrier layer by this method.
- the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.
- the 1 includes a feed roller 32, transport rollers 33, 34, 35, and 36, film forming rollers 39 and 40, a gas supply pipe 41, a plasma generating power source 42, and a film forming roller 39. And magnetic field generators 43 and 44 installed inside 40 and a winding roller 45.
- a manufacturing apparatus at least the film forming rollers 39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic field generating apparatuses 43 and 44 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.
- the gas barrier layer can be formed by appropriately adjusting the transport speed. That is, using the manufacturing apparatus 31 shown in FIG. 1, a discharge is generated between a pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber.
- the film forming gas (raw material gas or the like) is decomposed by plasma, and the gas barrier layer is formed on the surface of the base material on the film forming roller 39 and the surface of the base material on the film forming roller 40 by plasma CVD. It is formed by.
- the substrate and the like are conveyed by the delivery roller 32 and the film formation roller 39, respectively, so that they are formed on the surface of the substrate and the like by a roll-to-roll continuous film formation process.
- a gas barrier layer is formed.
- a raw material gas, a reactive gas, a carrier gas, or a discharge gas can be used alone or in combination of two or more.
- the source gas in the film-forming gas used for forming the other gas barrier layer can be appropriately selected and used according to the material of the other gas barrier layer to be formed.
- a source gas for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used.
- organosilicon compounds examples include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane.
- HMDSO hexamethyldisiloxane
- HMDS hexamethyldisilane
- 1,1,3,3-tetramethyldisiloxane vinyltrimethylsilane
- methyltrimethylsilane hexamethyldisilane.
- Methylsilane dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy
- TMOS tetramethoxysilane
- TEOS tetraethoxysilane
- phenyltrimethoxysilane methyltriethoxy
- Examples include silane and octamethylcyclotetrasiloxane.
- hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of other gas barrier layers obtained.
- organosilicon compounds can be used alone or in combination of two or more.
- organic compound gas containing carbon examples include methane, ethane, ethylene, and acetylene.
- an appropriate source gas is selected according to the type of the gas barrier layer.
- a reactive gas may be used in addition to the raw material gas.
- a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used.
- a reaction gas for forming an oxide for example, oxygen or ozone can be used.
- a reactive gas for forming nitride nitrogen and ammonia can be used, for example. These reaction gases can be used alone or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a reaction gas for forming a nitride can be used in combination.
- a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber.
- a discharge gas may be used as necessary in order to generate plasma discharge.
- carrier gas and discharge gas known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon; hydrogen can be used.
- the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary to completely react the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. By not making the ratio of the reaction gas excessive, it is excellent in that excellent barrier properties and bending resistance can be obtained by the other gas barrier layers to be formed. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.
- the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 Pa to 50 Pa.
- an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used.
- the power applied to the power source can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, and the like. It is preferable to be in the range. If such applied power is 100 W or more, generation of particles can be sufficiently suppressed, and if it is 10 kW or less, the amount of heat generated during film formation can be suppressed, and the film surface during film formation can be suppressed. It is possible to suppress an increase in temperature. Therefore, it is excellent in that wrinkles can be prevented during film formation without losing heat to the film.
- other gas barrier layers are formed by plasma CVD using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. To do.
- This is excellent in flexibility (flexibility) and mechanical strength, especially in roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode.
- Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.
- the electronic device containing an electronic device main body and the above-mentioned gas barrier film is provided.
- the electronic device body is not particularly limited, and examples thereof include known electronic device bodies to which a gas barrier film can be applied.
- a solar cell (PV), a liquid crystal display element (LCD), an organic electroluminescence (EL) element, etc. are mentioned.
- the organic EL element can have a substrate, a negative electrode, an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer, a positive electrode, and the like.
- the gas barrier film described above can be used as a substrate, a sealing material, and the like.
- a base material when used for a solar cell, for example, it can be applied as a resin support in which a transparent conductive thin film such as ITO is provided as a transparent electrode on a gas barrier film.
- the gas barrier film is incorporated in the electronic device body.
- a sealing material for example, an electronic device in which a liquid crystal display element is sealed can be obtained.
- the gas barrier film according to the present invention is preferably used for sealing an electronic device body as a sealing material.
- Example 1 ⁇ Manufacture of gas barrier film> [Example 1]
- Substrate UPILEX-50SGA polyimide film, manufactured by Ube Industries, Ltd.
- substrates having the same size were used.
- UV-1 manufactured by Samco Corporation
- the substrate surface is subjected to ozone treatment for 3 minutes (substrate temperature: 80 ° C., supply gas: air) to treat the surface of the substrate. Went.
- a coating liquid containing polysilazane was prepared as follows.
- an uncatalyzed perhydropolysilazane 20 wt% dibutyl ether solution (NN120-20, manufactured by AZ Electronic Materials Co., Ltd.) was converted into an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diamino). Hexane) was mixed with a 20% by weight dibutyl ether solution (NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.) containing 5% by weight of perhydropolysilazane.
- a coating liquid containing polysilazane was prepared as a dibutyl ether solution containing 1 wt% of the amine catalyst with respect to perhydropolysilazane.
- the prepared coating liquid containing polysilazane was applied to a surface-treated polyimide base material to form a coating film. At this time, the application was performed immediately after the surface treatment of the substrate.
- a coating liquid containing polysilazane was applied onto the surface-treated substrate by spin coating, and then dried at 80 ° C. for 1 minute to form a coating film.
- the obtained coating film was irradiated with vacuum ultraviolet (VUV) light having a main peak emission wavelength of 172 nm under the following conditions to form a gas barrier layer containing a polysilazane modified product having a thickness of 250 nm.
- VUV vacuum ultraviolet
- Vacuum ultraviolet (VUV light) irradiation treatment conditions Vacuum ultraviolet irradiation device: Stage movable xenon excimer irradiation device (MD excimer, MECL-M-1-200) Illuminance: 140 mW / cm 2 (172 nm) Stage temperature: 100 ° C Processing environment: Under dry nitrogen gas atmosphere Oxygen concentration in processing environment: 0.1% by volume Stage movable speed and number of times of conveyance: 15 times of conveyance at 10 mm / second Excimer light exposure integrated amount: 6500 mJ / cm 2 .
- the sample was installed so that the gap (Gap) between the lamp and the sample was 3 mm. Further, the irradiation time was changed by adjusting the movable speed of the movable stage. Regarding the adjustment of oxygen concentration during irradiation with vacuum ultraviolet rays (VUV light), the flow rate of nitrogen gas and oxygen gas introduced into the irradiation chamber is measured with a flow meter, and the nitrogen gas / oxygen gas flow ratio of the gas introduced into the chamber is measured. It was adjusted by controlling.
- VUV light vacuum ultraviolet rays
- gas barrier layer (second layer) A gas barrier layer (second layer) having a thickness of 40 nm was formed on the gas barrier layer (first layer) by the same method as in (2) above. Further, heat treatment was performed at 250 ° C. for 60 minutes to produce a gas barrier film in which a polyimide substrate (ozone treatment) -gas barrier layer-gas barrier layer was laminated in this order.
- the peeling strength of the polyimide base material and the gas barrier film (first layer) was measured according to the 180 degree peeling method of JIS Z0237: 2009.
- a predetermined adhesive tape was attached to the outermost gas barrier layer (second gas barrier layer) of the produced gas barrier film.
- the end of the tape was pulled at a speed of 30 mm / min using FGS-50E (manufactured by Nidec Shinpo Co., Ltd.), which is an electric vertical force gauge stand, and the polyimide base material, the gas barrier layer, It was confirmed whether or not.
- the peel strength was measured according to the type of pressure-sensitive adhesive tape used.
- the used adhesive tape is as follows; (A) Sealing masking tape No. 2541 (Adhesive strength: 1.3 N / cm, manufactured by Nichiban Co., Ltd.) (B) Cellotape (registered trademark) No. 5511 (Adhesive strength: 2.7 N / cm, manufactured by Nichiban Co., Ltd.) (C) Cellotape (registered trademark) No. 405AP-24 (Adhesive strength: 4 N / cm, manufactured by Nichiban Co., Ltd.) (D) Polysper tape (5.9 N / m, manufactured by Sekisui Chemical Co., Ltd.).
- the obtained gas barrier film did not peel off the polyimide substrate and the gas barrier film with the adhesive tape (a), but peeled off with the adhesive tape (b). Therefore, the adhesive strength is more than 1.3 N / cm and less than 2.7 N / cm.
- Base material 40 ⁇ m thick neoprim (polyimide film, polyimide consisting of cyclohexanetetracarboxylic acid or cyclohexanetetracarboxylic dianhydride and pyromellitic acid or pyromellitic dianhydride, manufactured by Mitsubishi Gas Chemical Co., Ltd.) used.
- neoprim polyimide film, polyimide consisting of cyclohexanetetracarboxylic acid or cyclohexanetetracarboxylic dianhydride and pyromellitic acid or pyromellitic dianhydride, manufactured by Mitsubishi Gas Chemical Co., Ltd.
- Excimer treatment was performed by irradiating the substrate surface with excimer light in the presence of oxygen using a stage movable xenon excimer irradiation device (MDCL-M-1-200, manufactured by MD Excimer).
- MDCL-M-1-200 stage movable xenon excimer irradiation device
- Vacuum ultraviolet (VUV light) irradiation treatment conditions Vacuum ultraviolet irradiation device: Stage movable xenon excimer irradiation device (MD excimer, MECL-M-1-200) Illuminance: 140 mW / cm 2 (172 nm) Stage temperature: 100 ° C Processing environment: Under dry nitrogen gas atmosphere Oxygen concentration in processing environment: 0.1% by volume Stage movable speed and number of times of conveyance: 2 times of conveyance at 20 mm / sec. Excimer light exposure integrated amount: 500 mJ / cm 2 .
- Gas Barrier Layer Two gas barrier layers were formed on a polyimide base material by the same method as in Example 1 immediately after the surface treatment of the base material.
- Kapton having a thickness of 50 ⁇ m (polyimide film having pyromellitic dianhydride and 4,4′-diaminodiphenyl ether as monomer components, manufactured by Toray DuPont Co., Ltd.) was used as a substrate.
- the obtained gas barrier film has a structure in which a polyimide base material (excimer treatment), a gas barrier layer, and a gas barrier layer are laminated in this order.
- Example 4 Base material UPILEX 25-50S (polyimide film, manufactured by Ube Industries, Ltd.) having a thickness of 40 ⁇ m was used as the base material.
- Oxygen plasma treatment was performed at 200 W for 2 minutes using a plasma dry cleaner PC-300 (manufactured by Samco Corporation) (amount of oxygen gas supplied: 5 sccm (0 ° C., 1 atm standard), vacuum degree of vacuum chamber: 1 Pa).
- Gas Barrier Layer Two gas barrier layers were formed on a polyimide base material by the same method as in Example 1 immediately after the surface treatment of the base material.
- Kapton having a thickness of 50 ⁇ m (polyimide film having pyromellitic dianhydride and 4,4′-diaminodiphenyl ether as monomer components, manufactured by Toray DuPont Co., Ltd.) was used as a substrate.
- the obtained gas barrier film has a structure in which a polyimide base material (oxygen plasma treatment), a gas barrier layer, and a gas barrier layer are laminated in this order.
- Base material UPILEX-505SGA (polyimide film, manufactured by Ube Industries, Ltd.) having a thickness of 40 ⁇ m was used as a base material.
- the corona treatment of the substrate surface was performed.
- AGI-080 manufactured by Kasuga Denki Co., Ltd. was used as the corona discharge device, the gap between the discharge-like electrode of the corona discharge treatment device and the film surface was set to 1 mm, and the surface for 10 seconds under the condition of a treatment output of 600 mW / cm 2. Corona treatment was performed.
- Gas Barrier Layer Two gas barrier layers were formed on a polyimide base material by the same method as in Example 1 immediately after the surface treatment of the base material.
- Example 7 Substrate UPILEX-50SGA (polyimide film, manufactured by Ube Industries, Ltd.) having a thickness of 50 ⁇ m was used as a substrate.
- TiO 2 titanium oxide
- Example 8 A gas barrier film was produced in the same manner as in Example 7 except that an Al 2 O 3 film (thickness 30 nm) was formed as an adhesive layer.
- the obtained gas barrier film has a structure in which a polyimide base material (excimer treatment) -adhesion layer (TiO 2 ) -gas barrier layer-gas barrier layer are laminated in this order.
- Example 9 Substrate UPILEX-50SGA (polyimide film, manufactured by Ube Industries, Ltd.) having a thickness of 50 ⁇ m was used as a substrate.
- Source gas supply 50 sccm (Standard Cubic Centimeter per Minute, 0 ° C, 1 atm standard)
- Oxygen gas supply amount 500 sccm (0 ° C., 1 atm standard)
- Degree of vacuum in the vacuum chamber 3Pa
- Applied power from the power source for plasma generation 0.8 kW
- Frequency of power source for plasma generation 70 kHz
- Film conveyance speed 1.0 m / min.
- Base material Kapton having a thickness of 50 ⁇ m (a polyimide film having pyromellitic dianhydride and 4,4′-diaminodiphenyl ether as monomer components, manufactured by Toray DuPont Co., Ltd.) was used as the base material.
- the gas barrier films according to the examples all have high adhesive strength, and even when applied to the device forming process, the gas barrier layer does not peel off from the polyimide substrate, and the device forming process. It was found that the present invention can be suitably applied to.
- the gas barrier films of Examples 1 to 10 had a water vapor permeability (WVTR) calculated by the Ca corrosion method of 0.1 g / (m 2 ⁇ 24 h) or less.
- WVTR water vapor permeability
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Abstract
Description
(2)前記ポリイミド基材および前記ガスバリア層の接着強度が、4N/cm以上である、(1)に記載のガスバリア性フィルム;
(3)前記ポリイミドが、ビフェニルテトラカルボン酸二無水物およびp-フェニレンジアミンをモノマーとして含む重合体である、(1)または(2)に記載のガスバリア性フィルム;
(4)前記ポリイミド基材および前記ガスバリア層の間に、接着層を有する、(1)~(3)のいずれか1つに記載のガスバリア性フィルム;
(5)前記ポリイミド基材の表面が、プラズマ処理、UVオゾン処理、またはエキシマ処理されてなる、(1)~(4)のいずれか1つに記載のガスバリア性フィルム;
(6)前記ポリシラザン改質物が、真空紫外光で改質処理されたものである、(1)~(5)のいずれか1つに記載のガスバリア性フィルム;
(7)電子デバイス本体と、(1)~(6)のいずれか1つに記載のガスバリア性フィルムとを含む、電子デバイス。 (1) A gas barrier film having a polyimide base material and a gas barrier layer containing a polysilazane modified product, wherein the adhesive strength of the polyimide base material and the gas barrier layer is 1.3 N / cm or more;
(2) The gas barrier film according to (1), wherein the adhesive strength of the polyimide base material and the gas barrier layer is 4 N / cm or more;
(3) The gas barrier film according to (1) or (2), wherein the polyimide is a polymer containing biphenyltetracarboxylic dianhydride and p-phenylenediamine as monomers.
(4) The gas barrier film according to any one of (1) to (3), which has an adhesive layer between the polyimide substrate and the gas barrier layer;
(5) The gas barrier film according to any one of (1) to (4), wherein the surface of the polyimide base material is subjected to plasma treatment, UV ozone treatment, or excimer treatment;
(6) The gas barrier film according to any one of (1) to (5), wherein the polysilazane-modified product is modified with vacuum ultraviolet light;
(7) An electronic device comprising an electronic device main body and the gas barrier film according to any one of (1) to (6).
本形態に係るガスバリア性フィルムは、ポリイミド基材と、ポリシラザン改質物を含むガスバリア層と、を有する。この際、ポリイミド基材およびガスバリア層の接着強度は、1.3N/cm以上、好ましくは2.7N/cm以上、より好ましくは4N/cm以上、さらに好ましくは5N/cm以上である。ポリイミド基材およびガスバリア層の接着強度が1.3N/cm以上であることで、バリア表面に形成される絶縁膜の形成が容易となり、バリア性を有する耐熱基材としての価値が認められる。また、ポリイミド基材およびバリア層の接着強度は50N/cm以下、より好ましくは40N/cm以下である。50N/cmよりも大きいと種々の製造ライン搬送時にスムーズに搬送することが困難になり、製造装置の不具合や生産性の低下につながる。 <Gas barrier film>
The gas barrier film according to this embodiment has a polyimide base material and a gas barrier layer containing a polysilazane modified product. Under the present circumstances, the adhesive strength of a polyimide base material and a gas barrier layer is 1.3 N / cm or more, Preferably it is 2.7 N / cm or more, More preferably, it is 4 N / cm or more, More preferably, it is 5 N / cm or more. When the adhesive strength between the polyimide base material and the gas barrier layer is 1.3 N / cm or more, formation of an insulating film formed on the barrier surface is facilitated, and the value as a heat resistant base material having a barrier property is recognized. Moreover, the adhesive strength of a polyimide base material and a barrier layer is 50 N / cm or less, More preferably, it is 40 N / cm or less. When it is larger than 50 N / cm, it becomes difficult to smoothly transport various production lines, leading to problems in the manufacturing apparatus and a decrease in productivity.
ポリイミド基材は、一般に、テトラカルボン酸二無水物およびジアミンを含むモノマーを重合して得られる樹脂フィルムである。 [Polyimide substrate]
The polyimide substrate is generally a resin film obtained by polymerizing a monomer containing tetracarboxylic dianhydride and diamine.
ポリアミック酸は、テトラカルボン酸二無水物およびジアミンを有機溶媒中で反応させることにより合成することができる。当該反応は、ジアミンを有機溶剤に溶解し、得られたジアミン溶液を撹拌しながらテトラカルボン酸二無水物を徐々に添加することにより行うことが好ましい。 (1) Synthesis of polyamic acid A polyamic acid can be synthesized by reacting a tetracarboxylic dianhydride and a diamine in an organic solvent. The reaction is preferably performed by dissolving diamine in an organic solvent and gradually adding tetracarboxylic dianhydride while stirring the obtained diamine solution.
上記(1)で得られたポリアミック酸をイミド化することによりポリイミド基材を製造することができる。 (2) Production of polyimide substrate A polyimide substrate can be produced by imidizing the polyamic acid obtained in (1) above.
ガスバリア層は、ポリシラザン改質物を含む。その他必要に応じてアミン触媒および金属触媒等の添加剤を含んでいてもよい。 [Gas barrier layer]
The gas barrier layer contains a polysilazane modified product. In addition, additives such as amine catalysts and metal catalysts may be included as necessary.
ポリシラザン改質物とは、ポリシラザンを改質することによって得られる改質物を意味する。 (Polysilazane modified product)
The polysilazane modified product means a modified product obtained by modifying polysilazane.
ポリシラザンは、その構造内にSi-N、Si-H、N-H等の結合を有するポリマーである。 Polysilazane Polysilazane is a polymer having a bond such as Si—N, Si—H, or NH in its structure.
ポリシラザンは改質により転化して酸化ケイ素を生じる。 Modification Polysilazane is converted by modification to produce silicon oxide.
ガスバリア層は、アミン触媒および/または金属触媒を含んでいてもよい。 (Amine catalyst and metal catalyst)
The gas barrier layer may contain an amine catalyst and / or a metal catalyst.
ポリシラザン改質物を含むガスバリア層はポリイミド基材上に配置される。この際、ガスバリア層は2層以上が積層されていてもよい(すなわち、基材-ガスバリア層-ガスバリア層等)。また、ガスバリア層の表面にさらに他のガスバリア層が形成されていてもよい(すなわち、基材-ガスバリア層-他のガスバリア層)。この際、他のガスバリア層はさらに2層以上が積層されていてもよい(すなわち、基材-ガスバリア層-他のガスバリア層-他のガスバリア層等)。 (Form of gas barrier layer)
A gas barrier layer containing the modified polysilazane is disposed on the polyimide substrate. At this time, two or more gas barrier layers may be laminated (that is, a substrate-gas barrier layer-gas barrier layer, etc.). Further, another gas barrier layer may be formed on the surface of the gas barrier layer (that is, base material-gas barrier layer-other gas barrier layer). At this time, two or more other gas barrier layers may be laminated (ie, base material-gas barrier layer-other gas barrier layer-other gas barrier layer, etc.).
本形態に係るポリシラザン改質物を含むガスバリア層は、ポリイミド基材との間で高い接着強度を実現するために、接着手段を設けることが好ましい。 [Adhesion means]
The gas barrier layer containing the polysilazane modified product according to the present embodiment is preferably provided with an adhesive means in order to realize high adhesive strength with the polyimide base material.
接着層は、通常、ポリイミド基材およびガスバリア層の間に配置される。当該接着層により、ポリイミド基材およびガスバリア層の接着強度が向上しうる。 (Adhesive layer placement)
The adhesive layer is usually disposed between the polyimide substrate and the gas barrier layer. By the said adhesive layer, the adhesive strength of a polyimide base material and a gas barrier layer can improve.
ポリイミド基材の表面は、表面処理されることが好ましい。具体的な表面処理としては、コロナ処理、プラズマ処理、UVオゾン処理、エキシマ処理、好ましくはプラズマ処理、UVオゾン処理、エキシマ処理等が挙げられる。 (Surface treatment of polyimide substrate)
The surface of the polyimide base material is preferably surface-treated. Specific examples of the surface treatment include corona treatment, plasma treatment, UV ozone treatment, and excimer treatment, preferably plasma treatment, UV ozone treatment, and excimer treatment.
コロナ処理は、大気圧状態において、一対の電極に交流の高電圧を印加して励起されるコロナ放電を利用して表面改質を行う方法である。 Corona treatment Corona treatment is a method for surface modification using corona discharge that is excited by applying an alternating high voltage to a pair of electrodes in an atmospheric pressure state.
プラズマ処理は、酸素ガスまたは酸素ガスおよび不活性ガスの混合ガスを、アーク放電により電離させ、これにより生じるプラズマガスを利用して表面改質を行う方法である。 Plasma treatment Plasma treatment is a method in which oxygen gas or a mixed gas of oxygen gas and inert gas is ionized by arc discharge, and surface modification is performed using the plasma gas generated thereby.
UVオゾン処理は、紫外線(UV)を照射し、空気中の酸素をオゾンに変換し、オゾンおよび紫外線を利用して表面改質を行う方法である。 UV ozone treatment UV ozone treatment is a method in which ultraviolet rays (UV) are irradiated, oxygen in the air is converted into ozone, and surface modification is performed using ozone and ultraviolet rays.
エキシマ処理は、エキシマ光を照射し、空気中の酸素をオゾンに変換し、オゾンおよびエキシマ光を利用して表面改質を行う方法である。 Excimer treatment Excimer treatment is a method in which excimer light is irradiated, oxygen in the air is converted to ozone, and surface modification is performed using ozone and excimer light.
ガスバリア性フィルムの製造方法は、ポリイミド基材上にガスバリア層を形成する工程を含む。その他、必要に応じて、基材を準備する工程、接着層を形成する工程、他のガスバリア層を形成する工程等を含む。 <Method for producing gas barrier film>
The manufacturing method of a gas barrier film includes the process of forming a gas barrier layer on a polyimide base material. In addition, as needed, the process of preparing a base material, the process of forming an contact bonding layer, the process of forming another gas barrier layer, etc. are included.
本工程は、ポリイミド基材を準備することを含む。必要に応じて、ポリイミド基材の表面処理を含んでいてもよい。 [Process for preparing polyimide base material]
This step includes preparing a polyimide substrate. If necessary, a surface treatment of the polyimide base material may be included.
ポリイミド基材の準備は、自らポリイミド基材を製造することにより行われうる。また、市販のポリイミドを購入してもよい。 (Preparation of polyimide substrate)
Preparation of a polyimide base material can be performed by manufacturing a polyimide base material itself. Moreover, you may purchase commercially available polyimide.
ポリイミド基材およびガスバリア層間の接着強度を制御するために、ポリイミド基材の表面処理が行われうる。当該表面処理としては、上述のように、プラズマ処理、UVオゾン処理、またはエキシマ処理等を挙げることができる。具体的な表面処理方法としては、特に制限されず公知の技術を用いることができ、例えば、上述の記載が適宜参照されうる。 (Surface treatment of polyimide substrate)
In order to control the adhesive strength between the polyimide substrate and the gas barrier layer, a surface treatment of the polyimide substrate can be performed. Examples of the surface treatment include plasma treatment, UV ozone treatment, and excimer treatment as described above. The specific surface treatment method is not particularly limited, and a known technique can be used. For example, the above description can be referred to appropriately.
本工程は、ポリイミド基材上に接着層を形成することを含む。 [Step of forming an adhesive layer]
This step includes forming an adhesive layer on the polyimide substrate.
本工程は、ポリシラザンを含む塗布液を、ポリイミド基材(ポリイミド基材上に接着層が形成されている場合には、接着層上)に塗布し、前記ポリシラザンを改質することを含む。これにより、ポリシラザン改質物を含むガスバリア層が形成される。 [Step of forming gas barrier layer]
This step includes applying a coating liquid containing polysilazane to a polyimide base material (on the adhesive layer when an adhesive layer is formed on the polyimide base material), and modifying the polysilazane. Thereby, the gas barrier layer containing the polysilazane modified product is formed.
ポリシラザンを含む塗布液(以下、単に「塗布液」とも称する)は、ポリシラザンおよび溶媒を含む。その他必要に応じて、アミン触媒および金属触媒等の添加剤を含んでいてもよい。 (Coating liquid containing polysilazane)
The coating liquid containing polysilazane (hereinafter also simply referred to as “coating liquid”) contains polysilazane and a solvent. In addition, additives such as an amine catalyst and a metal catalyst may be included as necessary.
ポリシラザンは上述のものと同様のものが用いられうることからここでは説明を省略する。 Polysilazane Polysilazane can be used in the same manner as described above, and the description thereof is omitted here.
溶媒としては、ポリシラザンと反応するものでなければ特に制限はなく、公知の溶媒が用いられうる。具体的には、脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素、ハロゲン化炭化水素等の炭化水素系溶媒;脂肪族エーテル、脂環式エーテル等のエーテル系溶媒が挙げられる。より詳細には、炭化水素溶媒としては、ペンタン、ヘキサン、シクロヘキサン、トルエン、キシレン、ソルベッソ、ターベン、塩化メチレン、トリクロロエタン等が挙げられる。また、エーテル系溶媒としては、ジブチルエーテル、ジオキサン、テトラヒドロフラン等が挙げられる。これらの溶媒は単独で、または2種以上を混合して用いられうる。 Solvent The solvent is not particularly limited as long as it does not react with polysilazane, and a known solvent can be used. Specific examples include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons; ether solvents such as aliphatic ethers and alicyclic ethers. More specifically, examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, toluene, xylene, solvesso, turben, methylene chloride, trichloroethane, and the like. Examples of ether solvents include dibutyl ether, dioxane, and tetrahydrofuran. These solvents can be used alone or in admixture of two or more.
アミン触媒および金属触媒としては上述のものと同様のものが用いられうることからここでは説明を省略する。 Amine catalyst and metal catalyst As the amine catalyst and the metal catalyst, the same ones as described above can be used, so that the description thereof is omitted here.
塗布においては、塗布液を基材上に塗布し、塗膜を形成する。なお、基材が接着層を有する場合には、塗布液は接着層上に塗布されうる。 (Application)
In application | coating, a coating liquid is apply | coated on a base material and a coating film is formed. In addition, when a base material has an adhesive layer, a coating liquid can be apply | coated on an adhesive layer.
ポリシラザンの改質方法は特に制限されず、公知の方法が適用されうる。具体的なポリシラザンの改質方法としては、紫外光の照射、プラズマ照射、加熱、およびこれらの組み合わせ等が挙げられる。 (Modification of polysilazane)
The modification method of polysilazane is not particularly limited, and a known method can be applied. Specific methods for modifying polysilazane include ultraviolet light irradiation, plasma irradiation, heating, and combinations thereof.
他のガスバリア層を形成する工程は、ポリシラザン改質物を含むガスバリア層等の上に、他のガスバリア層を形成することを含む。 [Step of forming another gas barrier layer]
The step of forming another gas barrier layer includes forming another gas barrier layer on the gas barrier layer containing the polysilazane modified product.
他のガスバリア層としては、上述のように特に制限されないが、公知のガスバリア層、例えば、乾式成膜法により形成されるガスバリア層が挙げられる。以下においては、乾式成膜法により他のガスバリア層を形成する方法について説明する。 (Other gas barrier layers)
The other gas barrier layer is not particularly limited as described above, and examples thereof include a known gas barrier layer, for example, a gas barrier layer formed by a dry film forming method. Hereinafter, a method of forming another gas barrier layer by a dry film forming method will be described.
乾式製膜法としては、物理気相成長法および化学気相成長法が挙げられる。物理気相成長法とは、気相中で物質の表面に物理的手法により目的とする物質の薄膜を堆積する方法をいい、蒸着法(抵抗加熱法、電子ビーム蒸着法、分子線エピタキシー法)、イオンプレーティング法、スパッタ法等が挙げられる。一方、化学気相成長法(化学蒸着法、CVD法)とは、基材等の上に、目的とする薄膜の成分を含む原料ガスを供給し、基板表面または気相における化学反応により膜を堆積させる方法をいい、熱CVD法、触媒化学気相成長法、光CVD法、プラズマCVD法等が挙げられる。これらのうち、スパッタ法、プラズマCVD法を用いることが好ましく、プラズマCVD法を用いることがより好ましい。 (Dry film forming method)
Examples of the dry film forming method include physical vapor deposition and chemical vapor deposition. The physical vapor deposition method is a method in which a thin film of a target substance is deposited on the surface of the substance by a physical method in a gas phase, and a vapor deposition method (resistance heating method, electron beam vapor deposition method, molecular beam epitaxy method). , Ion plating method, sputtering method and the like. On the other hand, the chemical vapor deposition method (chemical vapor deposition method, CVD method) is a method in which a raw material gas containing a target thin film component is supplied onto a substrate or the like, and the film is formed by a chemical reaction on the substrate surface or in the gas phase. It refers to a method of deposition, and examples include thermal CVD, catalytic chemical vapor deposition, photo CVD, and plasma CVD. Of these, the sputtering method and the plasma CVD method are preferably used, and the plasma CVD method is more preferably used.
本発明の一形態によれば、電子デバイス本体と、上述のガスバリア性フィルムとを含む電子デバイスが提供される。 <Electronic device>
According to one form of this invention, the electronic device containing an electronic device main body and the above-mentioned gas barrier film is provided.
電子デバイス本体としては、特に制限されず、ガスバリア性フィルムが適用されうる公知の電子デバイス本体が挙げられる。例えば、太陽電池(PV)、液晶表示素子(LCD)、有機エレクトロルミネッセンス(EL)素子等が挙げられる。これらの電子デバイス本体の構成についても、特に制限はなく、公知の構成を有しうる。例えば、有機EL素子は、基板、陰電極、電子注入層、電子輸送層、発光層、正孔輸送層、正孔注入層、陽電極等を有しうる。 [Electronic device body]
The electronic device body is not particularly limited, and examples thereof include known electronic device bodies to which a gas barrier film can be applied. For example, a solar cell (PV), a liquid crystal display element (LCD), an organic electroluminescence (EL) element, etc. are mentioned. There is no restriction | limiting in particular also about the structure of these electronic device main bodies, It can have a well-known structure. For example, the organic EL element can have a substrate, a negative electrode, an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer, a positive electrode, and the like.
上述のガスバリア性フィルムは、基材、封止用材料等に使用されうる。基材として、例えば、太陽電池に使用される場合には、ガスバリア性フィルム上にITO等の透明導電性薄膜を透明電極として設けた樹脂支持体として適用することができる。この場合、ガスバリア性フィルムは、電子デバイス本体に組み込まれている。また、封止用材料として使用される場合には、例えば、液晶表示素子を封止した電子デバイスが得られうる。本発明に係るガスバリア性フィルムは、封止用材料として、電子デバイス本体の封止に用いられることが好ましい。 [Gas barrier film]
The gas barrier film described above can be used as a substrate, a sealing material, and the like. As a base material, when used for a solar cell, for example, it can be applied as a resin support in which a transparent conductive thin film such as ITO is provided as a transparent electrode on a gas barrier film. In this case, the gas barrier film is incorporated in the electronic device body. When used as a sealing material, for example, an electronic device in which a liquid crystal display element is sealed can be obtained. The gas barrier film according to the present invention is preferably used for sealing an electronic device body as a sealing material.
[実施例1]
(1)基材
10cm×10cmのサイズで厚み50μmのUPILEX-50SGA(ポリイミドフィルム、宇部興産株式会社製)を基材として使用した。以下の実施例では、基材は同様のサイズのものを用いた。 <Manufacture of gas barrier film>
[Example 1]
(1) Substrate UPILEX-50SGA (polyimide film, manufactured by Ube Industries, Ltd.) having a size of 10 cm × 10 cm and a thickness of 50 μm was used as a substrate. In the following examples, substrates having the same size were used.
以下のようにしてポリシラザンを含む塗布液を調製した。 (2) Formation of gas barrier layer (first layer) A coating liquid containing polysilazane was prepared as follows.
真空紫外線照射装置:ステージ可動型キセノンエキシマ照射装置
(MDエキシマ社製、MECL-M-1-200)
照度:140mW/cm2(172nm)
ステージ温度:100℃
処理環境:ドライ窒素ガス雰囲気下
処理環境の酸素濃度:0.1体積%
ステージ可動速度と搬送回数:10mm/秒で15回搬送
エキシマ光露光積算量:6500mJ/cm2。 (Vacuum ultraviolet (VUV light) irradiation treatment conditions)
Vacuum ultraviolet irradiation device: Stage movable xenon excimer irradiation device (MD excimer, MECL-M-1-200)
Illuminance: 140 mW / cm 2 (172 nm)
Stage temperature: 100 ° C
Processing environment: Under dry nitrogen gas atmosphere Oxygen concentration in processing environment: 0.1% by volume
Stage movable speed and number of times of conveyance: 15 times of conveyance at 10 mm / second Excimer light exposure integrated amount: 6500 mJ / cm 2 .
上記(2)と同様の方法で、上記ガスバリア層(1層目)上に膜厚40nmのガスバリア層(2層目)を形成した。さらに、250℃で60分間熱処理し、ポリイミド基材(オゾン処理)-ガスバリア層-ガスバリア層がこの順に積層されたガスバリア性フィルムを製造した。 (3) Formation of gas barrier layer (second layer) A gas barrier layer (second layer) having a thickness of 40 nm was formed on the gas barrier layer (first layer) by the same method as in (2) above. Further, heat treatment was performed at 250 ° C. for 60 minutes to produce a gas barrier film in which a polyimide substrate (ozone treatment) -gas barrier layer-gas barrier layer was laminated in this order.
(a)シーリングマスキングテープNo.2541(粘着力:1.3N/cm、ニチバン株式会社製)
(b)セロテープ(登録商標)No.5511(粘着力:2.7N/cm、ニチバン株式会社製)
(c)セロテープ(登録商標)No.405AP-24(粘着力:4N/cm、ニチバン株式会社製)
(d)ポリエスパーテープ(5.9N/m、積水化学工業株式会社製)。 In addition, the used adhesive tape is as follows;
(A) Sealing masking tape No. 2541 (Adhesive strength: 1.3 N / cm, manufactured by Nichiban Co., Ltd.)
(B) Cellotape (registered trademark) No. 5511 (Adhesive strength: 2.7 N / cm, manufactured by Nichiban Co., Ltd.)
(C) Cellotape (registered trademark) No. 405AP-24 (Adhesive strength: 4 N / cm, manufactured by Nichiban Co., Ltd.)
(D) Polysper tape (5.9 N / m, manufactured by Sekisui Chemical Co., Ltd.).
基材
厚み40μmのネオプリム(ポリイミドフィルム、シクロヘキサンテトラカルボン酸またはシクロヘキサンテトラカルボン酸二無水物と、ピロメリット酸またはピロメリット酸二無水物とからなるポリイミド、三菱ガス化学株式会社製)を基材として使用した。 [Example 2]
Base material: 40μm thick neoprim (polyimide film, polyimide consisting of cyclohexanetetracarboxylic acid or cyclohexanetetracarboxylic dianhydride and pyromellitic acid or pyromellitic dianhydride, manufactured by Mitsubishi Gas Chemical Co., Ltd.) used.
真空紫外線照射装置:ステージ可動型キセノンエキシマ照射装置
(MDエキシマ社製、MECL-M-1-200)
照度:140mW/cm2(172nm)
ステージ温度:100℃
処理環境:ドライ窒素ガス雰囲気下
処理環境の酸素濃度:0.1体積%
ステージ可動速度と搬送回数:20mm/秒で2回搬送
エキシマ光露光積算量:500mJ/cm2。 (Vacuum ultraviolet (VUV light) irradiation treatment conditions)
Vacuum ultraviolet irradiation device: Stage movable xenon excimer irradiation device (MD excimer, MECL-M-1-200)
Illuminance: 140 mW / cm 2 (172 nm)
Stage temperature: 100 ° C
Processing environment: Under dry nitrogen gas atmosphere Oxygen concentration in processing environment: 0.1% by volume
Stage movable speed and number of times of conveyance: 2 times of conveyance at 20 mm / sec. Excimer light exposure integrated amount: 500 mJ / cm 2 .
基材の表面処理直後に、実施例1と同様の方法で、ポリイミド基材上にガスバリア層を2層形成した。 Formation of Gas Barrier Layer Two gas barrier layers were formed on a polyimide base material by the same method as in Example 1 immediately after the surface treatment of the base material.
厚み50μmのカプトン(モノマー成分として、ピロメリット酸二無水物および4,4’-ジアミノジフェニルエーテルを有するポリイミドフィルム、東レ・デュポン株式会社製)を基材として使用した。得られたガスバリア性フィルムは、ポリイミド基材(エキシマ処理)-ガスバリア層-ガスバリア層がこの順に積層された構成を有する。 [Example 3]
Kapton having a thickness of 50 μm (polyimide film having pyromellitic dianhydride and 4,4′-diaminodiphenyl ether as monomer components, manufactured by Toray DuPont Co., Ltd.) was used as a substrate. The obtained gas barrier film has a structure in which a polyimide base material (excimer treatment), a gas barrier layer, and a gas barrier layer are laminated in this order.
基材
厚み40μmのUPILEX25-50S(ポリイミドフィルム、宇部興産株式会社製)を基材として使用した。 [Example 4]
Base material UPILEX 25-50S (polyimide film, manufactured by Ube Industries, Ltd.) having a thickness of 40 μm was used as the base material.
基材の表面処理直後に、実施例1と同様の方法で、ポリイミド基材上にガスバリア層を2層形成した。 Formation of Gas Barrier Layer Two gas barrier layers were formed on a polyimide base material by the same method as in Example 1 immediately after the surface treatment of the base material.
厚み50μmのカプトン(モノマー成分として、ピロメリット酸二無水物および4,4’-ジアミノジフェニルエーテルを有するポリイミドフィルム、東レ・デュポン株式会社製)を基材として使用した。 [Example 5]
Kapton having a thickness of 50 μm (polyimide film having pyromellitic dianhydride and 4,4′-diaminodiphenyl ether as monomer components, manufactured by Toray DuPont Co., Ltd.) was used as a substrate.
基材
厚み40μmのUPILEX-505SGA(ポリイミドフィルム、宇部興産株式会社製)を基材して使用した。 [Example 6]
Base material: UPILEX-505SGA (polyimide film, manufactured by Ube Industries, Ltd.) having a thickness of 40 μm was used as a base material.
基材の表面処理直後に、実施例1と同様の方法で、ポリイミド基材上にガスバリア層を2層形成した。 Formation of Gas Barrier Layer Two gas barrier layers were formed on a polyimide base material by the same method as in Example 1 immediately after the surface treatment of the base material.
(1)基材
厚み50μmのUPILEX-50SGA(ポリイミドフィルム、宇部興産株式会社製)を基材として使用した。 [Example 7]
(1) Substrate UPILEX-50SGA (polyimide film, manufactured by Ube Industries, Ltd.) having a thickness of 50 μm was used as a substrate.
基材の表面処理直後に、プラズマCVD装置を用いて、酸化チタン(TiO2)膜を30nm成膜した。 (2) Formation of adhesion layer Immediately after the surface treatment of the base material, a titanium oxide (TiO 2 ) film was formed to a thickness of 30 nm using a plasma CVD apparatus.
実施例1と同様の方法で、接着層上にガスバリア層を2層形成した。 (3) Formation of gas barrier layer In the same manner as in Example 1, two gas barrier layers were formed on the adhesive layer.
接着層として、Al2O3膜(厚さ30nm)を成膜したことを除いては、実施例7と同様の方法でガスバリア性フィルムを製造した。 [Example 8]
A gas barrier film was produced in the same manner as in Example 7 except that an Al 2 O 3 film (thickness 30 nm) was formed as an adhesive layer.
(1)基材
厚み50μmのUPILEX-50SGA(ポリイミドフィルム、宇部興産株式会社製)を基材として使用した。 [Example 9]
(1) Substrate UPILEX-50SGA (polyimide film, manufactured by Ube Industries, Ltd.) having a thickness of 50 μm was used as a substrate.
実施例1と同様の方法で、ポリイミド基材上に膜厚150nmのガスバリア層を1層形成した。 (2) Formation of gas barrier layer (first layer)
One gas barrier layer having a thickness of 150 nm was formed on the polyimide base material in the same manner as in Example 1.
上記(2)で得られたフィルムを、図1に示されるような製造装置31にセットして、搬送させた。次いで、成膜ローラー39と成膜ローラー40との間に磁場を印加すると共に、成膜ローラー39と成膜ローラー40にそれぞれ電力を供給して、成膜ローラー39と成膜ローラー40との間に放電してプラズマを発生させた。次いで、形成された放電領域に、成膜ガス(原料ガスとしてヘキサメチルジシロキサン(HMDSO)と反応ガスとして酸素ガス(放電ガスとしても機能する)との混合ガスを供給し、ガスバリア層(1層目)上に、プラズマCVD法にてその他のガスバリア層(2層目)を形成した。その他のガスバリア層の膜厚は40nmであった。成膜条件は、以下の通りとした。 (3) Formation of other gas barrier layers (second layer)
The film obtained in the above (2) was set in a
原料ガスの供給量:50sccm(Standard Cubic Centimeter per Minute、0℃、1気圧基準)
酸素ガスの供給量:500sccm(0℃、1気圧基準)
真空チャンバ内の真空度:3Pa
プラズマ発生用電源からの印加電力:0.8kW
プラズマ発生用電源の周波数:70kHz
フィルムの搬送速度:1.0m/min。 (Deposition conditions)
Source gas supply: 50 sccm (Standard Cubic Centimeter per Minute, 0 ° C, 1 atm standard)
Oxygen gas supply amount: 500 sccm (0 ° C., 1 atm standard)
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film conveyance speed: 1.0 m / min.
(1)基材
厚み50μmのカプトン(モノマー成分として、ピロメリット酸二無水物および4,4’-ジアミノジフェニルエーテルを有するポリイミドフィルム、東レ・デュポン株式会社製)を基材として使用した。 [Comparative Example 1]
(1) Base material Kapton having a thickness of 50 μm (a polyimide film having pyromellitic dianhydride and 4,4′-diaminodiphenyl ether as monomer components, manufactured by Toray DuPont Co., Ltd.) was used as the base material.
実施例1と同様の方法で、ポリイミド基材上にガスバリア層を1層形成した。 (2) Formation of Gas Barrier Layer One gas barrier layer was formed on the polyimide base material by the same method as in Example 1.
厚み50μmのUPILE-50S(ポリイミドフィルム、宇部興産株式会社製)を基材として使用した。 [Comparative Example 2]
UPILE-50S (polyimide film, manufactured by Ube Industries, Ltd.) having a thickness of 50 μm was used as a base material.
実施例1と同様の方法で、ポリイミド基材上にガスバリア層を1層形成した。 (2) Formation of Gas Barrier Layer One gas barrier layer was formed on the polyimide base material by the same method as in Example 1.
実施例1~9並びに比較例1および2で製造したガスバリア性フィルムを用いて、ガスバリア性フィルムの性能を評価した。 <Evaluation of gas barrier film>
Using the gas barrier films produced in Examples 1 to 9 and Comparative Examples 1 and 2, the performance of the gas barrier films was evaluated.
各ガスバリア性フィルムを、250℃1時間の高温処理したサンプルに対して、JIS K5400の方法に基づいたクロスカット法による密着性評価を実施した。250℃1時間の高温処理は、得られたガスバリア層を、大気雰囲気下、250℃の恒温槽で1時間保管することで行い、得られたサンプルを室温(25℃)に冷却して評価に用いた。密着性の評価において、マスの1/3面積が接着していない状態を剥離と判断した(×および△における剥離)。 (Adhesion)
Each gas barrier film was subjected to a high temperature treatment at 250 ° C. for 1 hour, and an adhesion evaluation by a cross-cut method based on the method of JIS K5400 was performed. The high temperature treatment at 250 ° C. for 1 hour is carried out by storing the obtained gas barrier layer in a constant temperature bath at 250 ° C. for 1 hour in the atmosphere, and the obtained sample is cooled to room temperature (25 ° C.) for evaluation. Using. In the evaluation of adhesion, a state where 1/3 area of the mass was not adhered was judged as peeling (peeling at x and Δ).
△:1~99/100マスが、ガスバリア層とPI基材との間で剥離
○:100/100マスが、剥離なし(各マスの50面積%~90面積%未満が接着)
◎:100/100マスが、剥離なし(各マスの90面積%以上が接着)。 ×: 100/100 square peeled between gas barrier layer and PI substrate Δ: 1 to 99/100 square peeled between gas barrier layer and PI substrate ○: 100/100 square peeled off (50 area% to less than 90 area% of each mass is bonded)
(Double-circle): 100/100 mass does not peel (90 area% or more of each mass adhere | attaches).
Claims (7)
- ポリイミド基材と、ポリシラザン改質物を含むガスバリア層と、を有し、
前記ポリイミド基材および前記ガスバリア層の接着強度が、1.3N/cm以上である、ガスバリア性フィルム。 A polyimide base material, and a gas barrier layer containing a polysilazane modified product,
A gas barrier film, wherein an adhesive strength between the polyimide base material and the gas barrier layer is 1.3 N / cm or more. - 前記ポリイミド基材および前記ガスバリア層の接着強度が、4N/cm以上である、請求項1に記載のガスバリア性フィルム。 The gas barrier film according to claim 1, wherein the adhesive strength between the polyimide base material and the gas barrier layer is 4 N / cm or more.
- 前記ポリイミドが、ビフェニルテトラカルボン酸二無水物およびp-フェニレンジアミンをモノマーとして含む重合体である、請求項1または2に記載のガスバリア性フィルム。 The gas barrier film according to claim 1 or 2, wherein the polyimide is a polymer containing biphenyltetracarboxylic dianhydride and p-phenylenediamine as monomers.
- 前記ポリイミド基材および前記ガスバリア層の間に、接着層を有する、請求項1~3のいずれか1項に記載のガスバリア性フィルム。 The gas barrier film according to any one of claims 1 to 3, further comprising an adhesive layer between the polyimide base material and the gas barrier layer.
- 前記ポリイミド基材の表面が、プラズマ処理、UVオゾン処理、またはエキシマ処理されてなる、請求項1~4のいずれか1項に記載のガスバリア性フィルム。 The gas barrier film according to any one of claims 1 to 4, wherein the surface of the polyimide substrate is subjected to plasma treatment, UV ozone treatment, or excimer treatment.
- 前記ポリシラザン改質物が、真空紫外光で改質処理されたものである、請求項1~5のいずれか1項に記載のガスバリア性フィルム。 The gas barrier film according to any one of claims 1 to 5, wherein the polysilazane modified product is modified with vacuum ultraviolet light.
- 電子デバイス本体と、請求項1~6のいずれか1項に記載のガスバリア性フィルムとを含む、電子デバイス。 An electronic device comprising an electronic device main body and the gas barrier film according to any one of claims 1 to 6.
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WO2018047208A1 (en) * | 2016-09-06 | 2018-03-15 | 株式会社麗光 | Transparent high-barrier film and high-barrier layered body using same |
JP6983039B2 (en) * | 2016-11-29 | 2021-12-17 | 住友化学株式会社 | Gas barrier film and flexible electronic device |
CN109622344A (en) * | 2018-12-28 | 2019-04-16 | 东南大学苏州医疗器械研究院 | The coating process of medical function coating and application |
CN114685833B (en) * | 2022-04-07 | 2023-09-19 | 杭州泽同新材料科技有限公司 | Degradable packaging material with high barrier property |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008133082A1 (en) * | 2007-04-13 | 2008-11-06 | Ube Industries, Ltd. | Polyimide film having smoothness on one surface |
JP2011044466A (en) * | 2009-08-19 | 2011-03-03 | Hitachi Chem Co Ltd | Coating material for solar cell module, and method of manufacturing the same |
JP2011161891A (en) * | 2010-02-15 | 2011-08-25 | Hitachi Chemical Techno Service Co Ltd | Heat-resistant gas barrier sheet |
WO2012090644A1 (en) * | 2010-12-27 | 2012-07-05 | コニカミノルタホールディングス株式会社 | Gas-barrier film and electronic device |
JP2013208867A (en) * | 2012-03-30 | 2013-10-10 | Konica Minolta Inc | Gas barrier film, and electronic device |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005074987A (en) * | 2003-09-04 | 2005-03-24 | Toppan Printing Co Ltd | Transparent gas-barrier film and method for producing the same |
JP2011222334A (en) * | 2010-04-09 | 2011-11-04 | Dainippon Printing Co Ltd | Heat conductive sealing member and device |
JP2012086436A (en) | 2010-10-19 | 2012-05-10 | Hitachi Chemical Techno Service Co Ltd | Gas barrier molding |
JP5895689B2 (en) * | 2012-04-27 | 2016-03-30 | コニカミノルタ株式会社 | Electronic device and manufacturing method thereof |
-
2015
- 2015-01-09 CN CN201580003895.7A patent/CN105899361A/en active Pending
- 2015-01-09 KR KR1020167017968A patent/KR20160096230A/en not_active Application Discontinuation
- 2015-01-09 WO PCT/JP2015/050535 patent/WO2015105188A1/en active Application Filing
- 2015-01-09 JP JP2015556851A patent/JPWO2015105188A1/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008133082A1 (en) * | 2007-04-13 | 2008-11-06 | Ube Industries, Ltd. | Polyimide film having smoothness on one surface |
JP2011044466A (en) * | 2009-08-19 | 2011-03-03 | Hitachi Chem Co Ltd | Coating material for solar cell module, and method of manufacturing the same |
JP2011161891A (en) * | 2010-02-15 | 2011-08-25 | Hitachi Chemical Techno Service Co Ltd | Heat-resistant gas barrier sheet |
WO2012090644A1 (en) * | 2010-12-27 | 2012-07-05 | コニカミノルタホールディングス株式会社 | Gas-barrier film and electronic device |
JP2013208867A (en) * | 2012-03-30 | 2013-10-10 | Konica Minolta Inc | Gas barrier film, and electronic device |
Also Published As
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KR20160096230A (en) | 2016-08-12 |
JPWO2015105188A1 (en) | 2017-03-23 |
CN105899361A (en) | 2016-08-24 |
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