WO2018180963A1 - Stratifié barrière contre les gaz, corps d'étanchéité, stratifié conducteur, et procédé de production d'un stratifié conducteur - Google Patents

Stratifié barrière contre les gaz, corps d'étanchéité, stratifié conducteur, et procédé de production d'un stratifié conducteur Download PDF

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WO2018180963A1
WO2018180963A1 PCT/JP2018/011634 JP2018011634W WO2018180963A1 WO 2018180963 A1 WO2018180963 A1 WO 2018180963A1 JP 2018011634 W JP2018011634 W JP 2018011634W WO 2018180963 A1 WO2018180963 A1 WO 2018180963A1
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layer
gas barrier
functional layer
composition
barrier laminate
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PCT/JP2018/011634
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English (en)
Japanese (ja)
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務 原
達矢 泉
健太 西嶋
健寛 大橋
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リンテック株式会社
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Priority to JP2019509698A priority Critical patent/JP7082972B2/ja
Publication of WO2018180963A1 publication Critical patent/WO2018180963A1/fr

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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a gas barrier laminate, a sealed body obtained by sealing an electronic device with the gas barrier laminate, a conductive laminate using the gas barrier laminate, and a method for producing the conductive laminate.
  • gas barrier films have been used in displays such as liquid crystal displays and electroluminescence (EL) displays in place of glass plates as substrates having electrodes in order to achieve thickness reduction, weight reduction, and flexibility.
  • EL electroluminescence
  • many gas barrier films have a structure in which a gas barrier layer is laminated on the surface of a resin film. On the surface of the gas barrier layer, another layer is further laminated to develop a gas barrier laminate having a new function.
  • Patent Document 1 describes an adhesive sheet in which an adhesive layer is formed on the surface of a gas barrier layer of a substrate with a gas barrier layer. According to Patent Document 1, electronic devices such as organic EL elements can be efficiently sealed by using this adhesive sheet.
  • a new layer having a specific function can be laminated on the surface of the gas barrier layer of the gas barrier film to obtain a gas barrier laminate having the function.
  • the gas barrier layer of the gas barrier film has a low affinity with the organic layer containing an organic compound, so even if an organic layer is provided on the gas barrier layer, an interlayer between the gas barrier layer and the organic layer is used. Adhesion is inferior and delamination is likely to occur.
  • a gas such as water vapor or oxygen enters from the two layers, which may cause deterioration of an electronic device such as an organic EL element.
  • the present invention provides a gas barrier laminate and an electronic device having excellent gas barrier properties and an excellent interlayer adhesion between a gas barrier layer and a functional layer provided for imparting a specific function. It aims at providing the manufacturing method of the sealing body formed by sealing, the electroconductive laminated body using the said gas-barrier laminated body, and an electroconductive laminated body.
  • the inventors of the present invention can form a gas barrier laminate having improved interlayer adhesion between the functional layer and the gas barrier layer by forming the functional layer from a composition containing an amine compound. I found out that it could be solved.
  • the present invention provides the following [1] to [15].
  • [1] having a gas barrier layer and a functional layer directly laminated on one surface of the gas barrier layer; A gas barrier laminate, wherein the functional layer is a layer formed from a composition containing an amine compound.
  • the gas barrier laminate according to the above [1] wherein the gas barrier layer is a modified polymer layer formed from a composition for forming a gas barrier layer containing a polymer compound and having a modified region.
  • the polymer compound is a polysilazane compound.
  • the functional layer is a layer formed from a composition (II) containing a polyfunctional amine compound having two or more amino groups as the amine compound.
  • the gas barrier laminate according to any one of the above.
  • the composition (II) contains a thermosetting resin.
  • the thermosetting resin includes a thermosetting epoxy resin.
  • a method for producing a gas barrier laminate with an auxiliary electrode comprising the following steps (1) to (3).
  • Step (1) A step of bonding the auxiliary electrode layer and the surface of the functional layer of the gas barrier laminate according to the above [6], and embedding the auxiliary electrode layer in the functional layer.
  • Step (2) A step of irradiating the functional layer with energy rays to cure the functional layer.
  • Step (3) A step of providing a conductive layer on the surface of the auxiliary electrode layer and the cured functional layer.
  • the gas barrier laminate of the present invention is excellent in interlayer adhesion with a functional layer provided for imparting a specific function, and has a good gas barrier property.
  • the gas barrier laminate of the present invention has a gas barrier layer and a functional layer directly laminated on one surface of the gas barrier layer, but other layers may be provided.
  • the gas barrier laminate of one embodiment of the present invention may further include a base material layer on the surface side opposite to the side on which the functional layers of the gas barrier layer are laminated. It is preferable to have.
  • new layers such as an adhesive layer, a primer layer, and a hard coat layer are further provided on the surface side of the base material layer opposite to the side on which the gas barrier layer is laminated. It is good also as a provided structure.
  • a primer layer may be provided between the base material layer and the gas barrier layer.
  • the gas barrier laminate of one embodiment of the present invention may have a configuration in which another layer is laminated on the surface of the functional layer, and further laminated with an organic layer from the viewpoint of imparting better interlayer adhesion to the functional layer.
  • a configuration is preferable.
  • the organic layer may be a layer containing an organic compound such as a resin, and is preferably an adhesive layer.
  • gas barrier layer / functional layer (ii) gas barrier layer / functional layer / adhesive layer (iii) substrate layer / gas barrier layer / functional layer (iv) substrate layer / primer layer / gas barrier layer / functional layer (v) Base material layer / gas barrier layer / functional layer / adhesive layer (vi) base material layer / primer layer / gas barrier layer / functional layer / adhesive layer (vii) adhesive layer / base material layer / gas barrier layer / functional layer (viii) ) Adhesive layer / base material layer / primer layer / gas barrier layer / functional layer (ix) primer layer / base material layer / gas barrier layer / functional layer (x) primer layer / base material layer / primer layer / gas barrier layer / functional layer (Xi) Primer layer / base material layer / gas barrier layer / functional layer / adhesive layer (xii) primer layer / base material
  • a release sheet that can be peeled off at the time of use may be further laminated on the surface of these layers.
  • a gas barrier laminate excellent in self-supporting property can be obtained by providing a release sheet on the surface of at least one of the functional layer and the gas barrier layer. .
  • the adhesive layer may be provided on the functional layer side as in (v) above, or may be provided on the base material layer side as in (vii) above.
  • the adhesive layer is provided on the surface on the functional layer side.
  • a conductive layer made of ITO or the like may be further provided on the surface of the functional layer to form a conductive laminate.
  • the total thickness of the gas barrier laminate of one embodiment of the present invention when used is preferably 1 to 600 ⁇ m, more preferably 5 to 200 ⁇ m, and still more preferably 20 to 100 ⁇ m.
  • said "total thickness at the time of use” means the thickness of the gas barrier laminate after removing the release sheet provided to protect the outermost surface of the gas barrier laminate.
  • the water vapor transmission rate of the gas barrier laminate of one embodiment of the present invention measured in an environment of 40 ° C. and a relative humidity of 90% is preferably 5.0 g / (m 2 ⁇ day) or less, more preferably 0.5 g. / (m 2 ⁇ day) or less, more preferably 0.05 g / (m 2 ⁇ day) or less, even more preferably at 0.005 g / (m 2 ⁇ day) or less, and usually 1.0 ⁇ 10 -6 g / (m 2 ⁇ day) or more.
  • water vapor permeability means a value measured by the method described in the examples.
  • the gas barrier laminate of one embodiment of the present invention is preferably excellent in transparency.
  • the total light transmittance of the gas barrier laminate of one embodiment of the present invention is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
  • the total light transmittance is a value measured according to JIS K 7361-1, and more specifically means a value measured by the method described in the examples.
  • the gas barrier layer included in the gas barrier laminate of the present invention is a layer having a property of suppressing the permeation of gas such as water vapor and oxygen (hereinafter referred to as “gas barrier property”).
  • gas barrier property a property of suppressing the permeation of gas such as water vapor and oxygen
  • the gas barrier layer included in the gas barrier laminate of one embodiment of the present invention may be a single layer or a multilayer formed by stacking two or more layers.
  • the water vapor permeability measured in an environment of 40 ° C. and 90% relative humidity of the gas barrier layer of the gas barrier laminate of one embodiment of the present invention is preferably 5.0 g / (m 2 ⁇ day) or less, more preferably It is 0.5g / (m 2 ⁇ day) or less, more preferably 0.05g / (m 2 ⁇ day) or less, even more preferably at 0.005g / (m 2 ⁇ day) or less, and usually 1 0.0 ⁇ 10 ⁇ 6 g / (m 2 ⁇ day) or more.
  • the thickness of the gas barrier layer is appropriately set as described later depending on the type of material for forming the gas barrier layer, but is preferably 1 nm to 50 ⁇ m, more preferably 3 nm to 2000 nm, still more preferably 5 to 1000 nm, and still more preferably 20 ⁇ 500 nm.
  • the thickness of the multilayer is preferably within the above range.
  • the gas barrier layer preferably contains a compound having a nitrogen atom.
  • the gas barrier layer containing a compound having a nitrogen atom include an inorganic vapor-deposited film formed by vapor-depositing an inorganic compound such as inorganic nitride, inorganic oxynitride, and inorganic oxynitride carbide, and a gas barrier resin film containing a gas barrier resin such as polyacrylonitrile.
  • a modified polymer layer formed from a composition containing a polysilazane compound and having a modified region.
  • the gas barrier layer examples include the following three layers.
  • the gas barrier layer may be the inorganic vapor-deposited film of (1) or the modified layer of (3). It is preferably a molecular layer, and more preferably the modified polymer layer of (3) above from the viewpoint of providing a gas barrier laminate having flexibility.
  • embodiments of the gas barrier layer in the above (1) to (3) will be described in detail.
  • inorganic vapor-deposited film formed by vapor-depositing inorganic compound in the gas barrier laminate of one embodiment of the present invention, an inorganic vapor-deposited film formed by vapor-depositing an inorganic compound can be applied as the gas barrier layer.
  • the inorganic vapor deposition film may be a single layer composed of one layer or a multilayer formed by laminating two or more layers.
  • the thickness of the inorganic vapor deposition film used as the gas barrier layer is preferably 1 to 2000 nm, more preferably 3 to 1000 nm, still more preferably 5 to 500 nm, and still more preferably 40 to 200 nm, from the viewpoints of gas barrier properties and handling properties. is there.
  • the thickness of the multilayer is preferably within the above range.
  • inorganic vapor deposition films using inorganic oxides, inorganic nitrides or metals as raw materials are preferable from the viewpoint of gas barrier properties, and inorganic vapor deposition using inorganic oxides or inorganic nitrides as raw materials from the viewpoint of transparency.
  • a membrane is preferred.
  • a known method can be applied, for example, a PVD method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method, a photo CVD method, etc.
  • CVD method and atomic layer deposition method ALD method.
  • gas barrier resin film containing gas barrier resin in the gas barrier laminate of one embodiment of the present invention, a gas barrier resin film containing a gas barrier resin can be applied as the gas barrier layer.
  • the resin film may be a single layer formed of one layer or a multilayer formed by stacking two or more layers.
  • the thickness of the gas barrier resin film used as the gas barrier layer is preferably 1 to 2000 nm, more preferably 3 to 1000 nm, still more preferably 5 to 500 nm, and still more preferably 40 to 200 nm from the viewpoint of gas barrier properties.
  • the thickness of the multilayer is preferably within the above range.
  • the gas barrier resin is preferably a resin that hardly permeates oxygen, water vapor, and the like.
  • polyvinyl alcohol or a partially saponified product thereof ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, polyvinyl chloride, and the like. Examples thereof include vinylidene and polychlorotrifluoroethylene.
  • These gas barrier resins may be used alone or in combination of two or more.
  • a solution containing a gas barrier resin is applied on a release treatment surface of a release sheet or a substrate to form a coating film, and then the coating film is dried to form.
  • the coating method include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
  • the drying method include hot air drying, hot roll drying, and infrared irradiation.
  • Modified polymer layer formed from a gas barrier layer-forming composition containing a polymer compound and having a modified region In the gas barrier laminate of one embodiment of the present invention, the gas barrier layer contains a polymer compound.
  • a modified polymer layer formed from a composition for forming a gas barrier layer and having a modified region can be applied.
  • the modified polymer layer may be a single layer composed of one layer or a multilayer formed by laminating two or more layers.
  • the thickness of the modified polymer layer used as the gas barrier layer is preferably 20 nm to 50 ⁇ m, more preferably 30 nm to 1000 nm, still more preferably 40 nm to 500 nm, and still more preferably 70 to 450 nm.
  • the thickness of the multilayer is preferably within the above range.
  • the composition for forming a gas barrier layer which is a material for forming the modified polymer layer, contains a polymer compound, but does not impair the effects of the present invention, and the curing agent, anti-aging agent, light stabilizer, flame retardant, etc.
  • General-purpose additives may be contained.
  • the content of the polymer compound is preferably based on the total amount (100% by mass) of the modified high molecular weight or the total amount (100% by mass) of the active ingredients of the gas barrier layer forming composition. Is 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more.
  • the “active ingredient of the composition” refers to a component excluding the dilution solvent among the components contained in the target composition.
  • the polymer compound means a compound having a predetermined repeating unit and having a number average molecular weight (Mn) of 100 or more.
  • the number average molecular weight (Mn) of the polymer compound is preferably 100 to 50,000, more preferably 1,000 to 50,000.
  • polymer compound examples include silicon-containing polymer compounds, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, and polyarylate.
  • Acrylic resins, alicyclic hydrocarbon resins, aromatic polymers and the like, and silicon-containing polymer compounds are preferred.
  • silicon-containing polymer compounds include polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, poly (disilanylene phenylene) compounds, and poly (disilanylene ethynylene) compounds. Compounds and the like. These high molecular compounds may be used independently and may use 2 or more types together.
  • a polysilazane compound is more preferable as the polymer compound from the viewpoint of further improving gas barrier properties and providing a gas barrier layer excellent in interlayer adhesion with a functional layer.
  • a polysilazane compound may be used independently and may use 2 or more types together.
  • the polysilazane compound is a polymer having a repeating unit containing —Si—N— bond (silazane bond) in the molecule, specifically, a polymer having a repeating unit represented by the following general formula (1) It is preferable that The number average molecular weight (Mn) of the polysilazane compound is preferably 100 to 50,000, more preferably 1,000 to 50,000.
  • n represents the number of repeating units and represents an integer of 1 or more.
  • Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, unsubstituted or substituted
  • An aryl group having a group or an alkylsilyl group is represented.
  • alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group.
  • alkyl groups having 1 to 10 carbon atoms such as n-hexyl group, n-heptyl group and n-octyl group.
  • cycloalkyl group examples include cycloalkyl groups having 3 to 10 ring carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • alkenyl group examples include alkenyl groups having 2 to 10 carbon atoms such as vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group and 3-butenyl group.
  • aryl group examples include aryl groups having 6 to 15 ring carbon atoms such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • alkylsilyl group examples include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tri-t-butylsilyl group, a methyldiethylsilyl group, a dimethylsilyl group, a diethylsilyl group, a methylsilyl group, and an ethylsilyl group.
  • alkyl group, cycloalkyl group, and alkenyl group may have include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; a thiol group; an epoxy group; Groups; (meth) acryloyloxy groups; unsubstituted or substituted aryl groups such as phenyl, 4-methylphenyl, 4-chlorophenyl; and the like.
  • Examples of the substituent which the aryl group may have include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; a methoxy group , Ethoxy group, etc .; nitro group; cyano group; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group; phenyl group, 4-methylphenyl group, 4- An unsubstituted or substituted aryl group such as a chlorophenyl group;
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom
  • an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group
  • Rx, Ry, and Rz are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and more preferably a hydrogen atom.
  • the polysilazane compound contained in the modified polymer layer may be an inorganic polysilazane (perhydropolysilazane) in which Rx, Ry, and Rz in the general formula (1) are all hydrogen atoms, Rx, Organic polysilazane in which at least one of Ry and Rz is an organic group that is not a hydrogen atom may be used.
  • the polysilazane compound may be a polysilazane modified product.
  • modified polysilazane include, for example, JP-A-62-195024, JP-A-2-84437, JP-A-63-81122, JP-A-1-138108, and JP-A-2-175726.
  • JP-A-5-238827, JP-A-5-238827, JP-A-6-122852, JP-A-6-306329, JP-A-6-299118, JP-A-9-31333 Examples thereof include those described in Kaihei 5-345826 and JP-A-4-63833.
  • a polysilazane compound a commercially available product as a glass coating material or the like can be used as it is.
  • the composition for forming a gas barrier layer may further contain an organic solvent to form a solution.
  • organic solvent include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; n-pentane, n- And aliphatic hydrocarbon solvents such as hexane and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; and the like. These organic solvents may be used alone or in combination of two or more.
  • a solution of the gas barrier layer forming composition is applied to the release treatment surface of the release sheet, the surface of the underlayer provided on the release sheet, and the substrate.
  • coating and forming a coating film on the surface of this, and drying and forming the said coating film is mentioned.
  • the coating method for example, bar coating method, spin coating method, dipping method, roll coating method, gravure coating method, knife coating method, air knife coating method, roll knife coating method, die coating method, screen printing method, spray coating method, Examples include a gravure offset method.
  • drying method of a coating film conventionally well-known drying methods, such as hot air drying, hot roll drying, and infrared irradiation, are mentioned.
  • the heating temperature is usually 80 to 150 ° C.
  • the heating time is usually several tens of seconds to several tens of minutes.
  • the surface of the formed polymer layer is subjected to a modification treatment to form a modified region, whereby a modified polymer layer can be obtained.
  • modification treatment include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment.
  • the ion implantation process is a method in which accelerated ions are implanted into the polymer layer, and the polymer layer is modified to form a modified region, and the details are as described later.
  • the plasma treatment is a method in which the polymer layer is exposed to plasma and the polymer layer is modified to form a modified region, and can be performed, for example, according to the method described in JP 2012-106421 A .
  • the ultraviolet irradiation treatment is a method of forming a modified region by irradiating the polymer layer with ultraviolet rays, and can be performed, for example, according to the method described in JP2013-226757A .
  • the ion implantation treatment is preferable as the modification treatment from the viewpoint that the modified polymer layer can be efficiently modified to the inside without roughening the surface and the gas barrier property can be further improved.
  • ions implanted into the polymer layer include rare gas ions such as argon, helium, neon, krypton, and xenon; ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; methane, Ion of alkane gas such as ethane; Ion of alkene gas such as ethylene and propylene; Ion of alkadiene gas such as pentadiene and butadiene; Ion of alkyne gas such as acetylene; Aroma such as benzene and toluene Ions of group hydrocarbon hydrocarbons; ions of cycloalkanes such as cyclopropane; ions of cycloalkenes such as cyclopentene; ions of metals; ions of organosilicon compounds; These ions may be used alone or in combination of two or more.
  • rare gas ions such as argon, helium, neon, krypton, and xen
  • noble gases such as argon, helium, neon, krypton, and xenon are used from the viewpoint that ions can be implanted more easily and a modified polymer layer having better gas barrier properties can be formed. Ions are preferred, and argon ions are more preferred.
  • the ion implantation amount can be appropriately determined according to the purpose of use of the gas barrier laminate film (necessary gas barrier properties, transparency, etc.).
  • Examples of a method for implanting ions include a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting plasma ions in plasma (plasma ion implantation method), and the like, but the plasma ion implantation method is preferable. .
  • plasma is generated in an atmosphere containing a plasma generation gas such as a rare gas, and a negative high voltage pulse is applied to the polymer layer to thereby remove ions (positive ions) in the plasma. It can be performed by injecting into the surface portion of the polymer layer.
  • a plasma generation gas such as a rare gas
  • a negative high voltage pulse is applied to the polymer layer to thereby remove ions (positive ions) in the plasma. It can be performed by injecting into the surface portion of the polymer layer.
  • the thickness of the region into which ions are implanted can be controlled by implantation conditions such as ion type, applied voltage, and processing time. Although it may be determined accordingly, it is usually 10 to 400 nm. Further, the ion implantation can be confirmed by performing an elemental analysis measurement in the vicinity of 10 nm from the surface of the polysilazane layer using X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the functional layer included in the gas barrier laminate of the present invention is a layer that is directly laminated on one surface of the gas barrier layer and formed from a composition containing an amine compound.
  • the thickness of the functional layer is appropriately selected depending on the type of function of the functional layer and the type of composition as a forming material, but is preferably 50 nm to 200 ⁇ m, more preferably 100 nm. To 150 ⁇ m, more preferably 150 nm to 100 ⁇ m.
  • the functional layer can be provided with a function according to the use of the gas barrier laminate by appropriately preparing the types of the main resin and the amine compound contained in the composition of the forming material.
  • a functional layer formed from a composition containing an amine compound can satisfactorily maintain interlayer adhesion with the gas barrier layer.
  • other layers such as an organic layer containing an organic compound (for example, an adhesive layer, an adhesive layer of a release sheet) or a conductive layer made of ITO or the like are provided on the surface of the functional layer.
  • interlayer adhesion between the functional layer and other layers can be improved. Therefore, since the formed functional layer has excellent interlayer adhesion with the gas barrier layer and other layers (adhesive layer, conductive layer, etc.), the functional layer is interposed between the two layers having poor interlayer adhesion. Thereby, adhesiveness can be made favorable. Therefore, the functional layer has a function as an “adhesion improving layer”.
  • an adhesive layer is preferable on the surface of the functional layer.
  • the functional layer used in the present invention is excellent in interlayer adhesion with the gas barrier layer and also in interlayer adhesion with the adhesive layer. Therefore, the gas barrier laminate of this aspect can effectively suppress the entry of water vapor, oxygen, and the like from between the two layers, and has excellent gas barrier properties.
  • the functional layer is preferably laminated on the surface side subjected to the modification treatment in the gas barrier layer.
  • the modified surface of the modified polymer layer has a high density and a high elastic modulus, and tends to be inferior in adhesion to the organic layer. Therefore, the adhesion to the organic layer is also good through the functional layer. It becomes.
  • the modified polymer layer is formed from a gas barrier layer forming composition containing a polysilazane compound, nitrogen atoms are unevenly distributed on the surface of the modified polymer layer that has been subjected to the modification treatment. Yes.
  • a functional layer formed from a composition containing an amine compound is more likely to have an effect of improving interlayer adhesion with the modified polymer layer.
  • the modified polymer layer is formed from a composition for forming a gas barrier layer containing a polysilazane compound
  • the modified polymer layer is subjected to a modification treatment, and an element abundance ratio of nitrogen atoms is increased. It is preferable that the functional layer is laminated on more surfaces.
  • the modified polymer layer is formed by applying a solution of the gas barrier layer forming composition on the surface of the underlayer or substrate, the solution penetrates into the irregularities on the surface of the underlayer or substrate. . For this reason, the interlayer adhesion between the modified polymer layer and the underlying layer or the base material is usually good and does not cause a big problem.
  • an amine silane coupling agent or a polyfunctional amine compound having two or more amino groups is preferable.
  • the composition that is a material for forming the functional layer is preferably a composition (I) or (II) shown below depending on the type of the amine compound.
  • -Composition (I) containing an amine-based silane coupling agent as the amine-based compound.
  • Examples of the amine-based silane coupling agent contained in the composition (I) include silane compounds having one or more amino groups, but compounds represented by the following general formula (b) are preferred, and the following general formula (b The compound represented by -1) or (b-2) is more preferable.
  • R 1 to R 3 are alkyl groups having 1 to 4 carbon atoms (preferably 1 to 2 carbon atoms).
  • X is an organic group having an amino group, and a group represented by — (CH 2 ) p —NH— (CH 2 ) q —NH 2 (p, q is an integer of 1 or more (preferably 2 to 10). An integer)) or a group represented by — (CH 2 ) r —NH 2 (r is an integer of 1 or more (preferably an integer of 2 to 10)).
  • the amine-based silane coupling agent may be a primary amine, a secondary amine, or a tertiary amine, but is preferably a primary amine.
  • Examples of amine-based silane coupling agents that are primary amines include N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, and N-2.
  • Examples of amine-based silane coupling agents that are secondary amines or tertiary amines include N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, [3- ( 2,4-dinitrophenylamino) propyl] triethoxysilane, N, N-dimethylaminopropyltrimethoxysilane, N, N-dimethylaminopropyltriethoxysilane, N, N-dimethylaminopropyltripropoxysilane, N, N -Dimethylaminopropyltributoxysilane, N, N-dimethylaminoethyltrimethoxysilane, N, N-diethylaminopropyltrimethoxysilane, N, N-diethylaminopropyltriethoxysilane, N, N-dipropylamin
  • the content of the amine-based silane coupling agent contained in the composition (I) is preferably 0.1 to 20% by mass, more preferably based on the total amount (100% by mass) of the active ingredients in the composition (I). Is 0.2 to 15% by mass, more preferably 0.3 to 12% by mass, and still more preferably 0.4 to 10% by mass.
  • polyfunctional amine compound contained in the composition (II) examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane. , Diaminodiphenylmethane, metaphenylenediamine and the like. These polyfunctional amine compounds may be used independently and may use 2 or more types together.
  • the content of the polyfunctional amine compound contained in the composition (II) is preferably 25 to 80% by mass, more preferably 35 to 75%, based on the total amount (100% by mass) of the active ingredients of the composition (II).
  • the mass is more preferably 40 to 70 mass%.
  • the functional layer preferably has curability from the viewpoint of facilitating film formation by coating or printing. Therefore, it is preferable that the composition which is a formation material of a functional layer contains an energy beam curable resin or a thermosetting resin with an amine compound.
  • composition (I) containing the above-described amine-based silane coupling agent further contains an energy ray curable resin
  • composition (II) containing the polyfunctional amine compound described above further contains an energy ray curable resin, and may be an energy ray curable composition, or further contains a thermosetting resin, and is thermoset. Although it is good also as a curable composition, it is preferable to contain a thermosetting resin and to set it as a thermosetting composition.
  • the functional layer formed from the energy beam curable composition has a function as an electrode embedding layer capable of embedding the auxiliary electrode layer formed on a part of one surface of the transfer substrate of the electrode transfer sheet.
  • the functional layer formed from the energy beam curable composition is preferably in an uncured state before the auxiliary electrode layer is embedded.
  • the electrode layer 52 is embedded.
  • the functional layer formed from the energy-beam curable composition is easy to take in an auxiliary electrode layer in the inside, and is excellent in the embedding property of an auxiliary electrode layer.
  • the auxiliary electrode layer 52 is embedded in the functional layer 12, as shown in FIG. 1B
  • the functional layer 12 is cured by irradiation with energy rays.
  • the transfer substrate 51 of the electrode transfer sheet 50 is peeled off from the surface of the functional layer 12 after the curing.
  • the functional layer 12 and the transfer substrate 51 may be in close contact with each other, and the transfer substrate 51 may be difficult to peel off.
  • the functional layer formed from the energy beam curable composition has an advantage that peeling from the transfer substrate 51 becomes easy.
  • the functional layer is finally cured, the adhesion between the gas barrier layer and the functional layer is improved, the shape retention of the functional layer is improved, and the auxiliary electrode layer is fixed without misalignment. It is easy to provide a conductive layer in the functional layer.
  • the functional layer formed from the energy ray-curable composition has properties such as excellent embedding of the auxiliary electrode layer before curing and excellent releasability from the transfer substrate after curing. It has an excellent function as a layer.
  • the energy ray curable composition contains an amine compound and an energy ray curable resin, but preferably further contains a photopolymerization initiator.
  • an energy ray has an energy quantum in electromagnetic waves or a charged particle beam, and refers to active light, such as ultraviolet rays, or an electron beam.
  • the functional layer formed from the energy ray-curable composition is one that cures by being irradiated with the above-mentioned energy rays, and is preferably cured by irradiation with ultraviolet rays.
  • the energy beam curable composition may further contain various additives as long as the effects of the present invention are not impaired in addition to the above-described components.
  • various additives include ultraviolet absorbers, antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, and coloring pigments. What is necessary is just to determine suitably content of these additives according to the objective.
  • the total content of the amine compound and the energy ray curable resin is preferably 70% by mass or more with respect to the total amount (100% by mass) of the active ingredients of the energy ray curable composition. More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more.
  • the total content of the amine compound, the energy beam curable resin, and the photopolymerization initiator is preferably based on the total amount (100% by mass) of the active ingredients of the energy beam curable composition. Is 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
  • the thickness of the functional layer formed from the energy ray-curable composition is preferably 1 to 200 ⁇ m from the viewpoint of further improving the interlayer adhesion and imparting a function as an electrode embedding layer.
  • the thickness is preferably 5 to 150 ⁇ m, more preferably 10 to 100 ⁇ m, and still more preferably 15 to 70 ⁇ m.
  • the thickness of the functional layer is preferably within the above range both before and after curing.
  • the energy ray curable resin may be a resin having an energy ray polymerizable group introduced into the main chain and / or side chain of the resin.
  • the energy ray polymerizable group may be any group having an energy ray polymerizable carbon-carbon double bond, and examples thereof include a (meth) acryloyl group and a vinyl group.
  • the energy ray curable resin may be a low molecular weight compound having an energy ray polymerizable group such as a polyfunctional (meth) acrylate compound, or may be a resin having an energy ray polymerizable group.
  • the resin into which the energy beam polymerizable group is introduced include acrylic resins, urethane resins, polyester resins, rubber resins, and the like.
  • energy beam curable resin may be used independently and may use 2 or more types together.
  • the energy beam curable resin used in one embodiment of the present invention preferably includes an energy beam curable urethane resin.
  • the weight average molecular weight (Mw) of the energy ray curable urethane resin is preferably 1,000 to 100,000, more preferably 3,000 to 80,000, still more preferably 5,000 to 50,000. .
  • the content ratio of the energy ray curable urethane resin is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 80% with respect to the total amount (100% by mass) of the energy ray curable resin. To 100% by mass, and more preferably 90 to 100% by mass.
  • the content of the energy beam curable resin is preferably 60 to 99.8% by mass, more preferably based on the total amount (100% by mass) of the active ingredients of the energy beam curable composition. It is 70 to 99.5% by mass, more preferably 75 to 99.0% by mass, and still more preferably 80 to 99.0% by mass.
  • composition (I) is an energy-beam curable composition containing an amine-type silane coupling agent and energy-beam curable resin.
  • the content of the amine silane coupling agent in this case is as described above.
  • the composition (I) that is an energy ray-curable composition contains a coupling agent that does not fall under the amine-based silane coupling agent as long as the effects of the present invention are not impaired. May be.
  • the content of the coupling agent other than the amine-based silane coupling agent is preferably as small as possible.
  • the content of the coupling agent other than the amine coupling agent is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts per 100 parts by mass of the total amount of the amine coupling agent in the composition (I). Part by mass, more preferably 0 to 5 parts by mass, and still more preferably 0 to 1 part by mass.
  • the energy beam curable composition preferably further contains a photopolymerization initiator.
  • a photopolymerization initiator By containing a photopolymerization initiator, when curing the functional layer to be formed, the polymerization curing time can be shortened, and the curing reaction of the functional layer proceeds sufficiently even with a small amount of light irradiation. Can be made.
  • photopolymerization initiator examples include aromatic ketone compounds, benzoin compounds, benzoin ether compounds, benzyl compounds, ester compounds, acridine compounds, 2,4,5-triarylimidazole dimers, alkylphenone compounds, ⁇ - Examples include hydroxyalkylphenone compounds and phosphine oxide compounds.
  • photopolymerization initiators include, for example, 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile. , Dibenzyl, diacetyl, ⁇ -chloranthraquinone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. These photopolymerization initiators may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 12 parts by mass with respect to 100 parts by mass of the total amount of the energy ray curable resin. Part, more preferably 0.1 to 10 parts by weight, and still more preferably 0.2 to 5 parts by weight.
  • thermosetting composition The functional layer formed from the thermosetting composition is a layer that cures as the curing reaction proceeds by heat treatment.
  • the thermosetting composition contains an amine compound and a thermosetting resin, but may further contain various additives as long as the effects of the present invention are not impaired. Examples of various additives include ultraviolet absorbers, antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, and coloring pigments. What is necessary is just to determine suitably content of these additives according to the objective.
  • the total content of the amine compound and the thermosetting resin is preferably 70 to 100% by mass with respect to the total amount (100% by mass) of the active ingredients of the thermosetting composition, More preferably, it is 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
  • the thickness of the functional layer formed from the thermosetting composition is preferably 50 nm or more, more preferably 100 n or more, and further preferably 150 nm or more, from the viewpoint of further improving interlayer adhesion. From the viewpoint of being applicable to articles that require miniaturization, such as 700 nm or less, more preferably 500 nm or less, and still more preferably 450 nm or less.
  • thermosetting resin may be any resin that can be cured by heating.
  • a thermosetting epoxy resin a thermosetting phenol resin, a thermosetting unsaturated imide resin, a thermosetting cyanate resin, and a thermosetting isocyanate.
  • Resin thermosetting benzoxazine resin, thermosetting oxetane resin, thermosetting amino resin, thermosetting unsaturated polyester resin, thermosetting allyl resin, thermosetting dicyclopentadiene resin, thermosetting silicone resin, heat Examples thereof include a curable triazine resin and a thermosetting melamine resin. These thermosetting resins may be used alone or in combination of two or more.
  • thermosetting resin includes a thermosetting epoxy resin.
  • a functional layer formed from a thermosetting composition containing a thermosetting epoxy resin can maintain good interlayer adhesion with a gas barrier layer even in a high temperature and high humidity environment.
  • the content of the thermosetting epoxy resin is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably relative to the total amount (100% by mass) of the thermosetting resin. It is 80 to 100% by mass, more preferably 90 to 100% by mass.
  • thermosetting epoxy resin examples include thermosetting and compounds having a plurality of epoxy groups in the molecule, specifically, an epoxy resin having a glycidylamino group derived from metaxylylenediamine, Epoxy resin having glycidylamino group derived from 1,3-bis (aminomethyl) cyclohexane, epoxy resin having glycidylamino group derived from diaminodiphenylmethane, glycidylamino group or glycidyloxy group derived from paraaminophenol Epoxy resin having glycidyloxy group derived from bisphenol A, epoxy resin having glycidyloxy group derived from bisphenol F, epoxy resin having glycidyloxy group derived from phenol novolac Epoxy resins having a glycidyloxy group derived from resorcinol and the like. These thermosetting epoxy resins may be used independently and may use 2 or more types together. Among these, as the thermosetting epoxy resin,
  • the content of the thermosetting resin is preferably 10 to 60% by mass, more preferably 20 to 50% by mass with respect to the total amount (100% by mass) of the active ingredients of the thermosetting composition. %, More preferably 25 to 45% by mass.
  • composition (II) is a thermosetting composition containing a polyfunctional amine compound and a thermosetting resin.
  • the polyfunctional amine compound also functions as a curing agent.
  • the content of the polyfunctional amine compound with respect to 100 parts by mass of the total amount of the thermosetting resin in the composition (II) which is a thermosetting composition is preferably 20 to 800 parts by mass, more preferably 50 to 600 parts by mass. Part, more preferably 100 to 400 parts by weight, and still more preferably 150 to 300 parts by weight.
  • the method for forming the functional layer is not particularly limited, but a coating film is formed by applying a composition that is a functional layer forming material on the surface of the already formed gas barrier layer, and then the coating film is dried. It is preferable to form.
  • the composition that is a material for forming the functional layer may be in the form of a solution by adding a solvent.
  • the solvent include aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2- Halogenated hydrocarbon solvents such as dichloroethane and monochlorobenzene; alcohol solvents such as methanol, ethanol, propanol, butanol and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone; ethyl acetate Ester solvent such as butyl acetate; cellosolv solvent such as ethyl acetate; cellosolv solvent such as ethyl acetate, cellosolv solvent
  • a wet coating method can be used as a method for applying the composition that is a material for forming the functional layer. For example, dipping, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, and screen printing. Method, spray coating, gravure offset method and the like.
  • the drying temperature of the formed coating film is preferably 70 to 180 ° C., more preferably 80 to 150 ° C., and the drying time is preferably 30 seconds to 10 minutes, more preferably 1 to 7 minutes.
  • the functional layer is irradiated with energy rays such as ultraviolet rays, photocured, and cured. It is good.
  • the functional layer formed from the energy beam curable composition may be uncured, and the functional layer may be cured after the auxiliary electrode layer is embedded in the functional layer.
  • the functional layer formed from the thermosetting composition in the drying process of the coating film formed from the thermosetting composition, it is good also as a functional layer which hardened
  • the gas barrier laminate of one embodiment of the present invention may further include a base material layer on the surface side opposite to the side on which the functional layers of the gas barrier layer are laminated.
  • a base material layer By having a base material layer, it can be set as the gas-barrier laminated body excellent in self-supporting property, and there exists an advantage in terms of handleability.
  • the base material layer is preferably composed of a resin film.
  • the resin contained in the resin film include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, acrylic resin, A cycloolefin type polymer, an aromatic polymer, etc. are mentioned.
  • the base material layer is preferably composed of a resin film containing a resin selected from polyester, polyamide, and cycloolefin-based polymer. More preferably, it is composed of a resin film containing a selected resin.
  • polyester examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate, and polyethylene terephthalate and polyethylene naphthalate are preferable.
  • polyamide examples include wholly aromatic polyamide, nylon 6, nylon 66, nylon copolymer, and the like.
  • cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof.
  • Apel an ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals
  • Arton a norbornene polymer manufactured by JSR
  • Zeonoa a norbornene polymer manufactured by Nippon Zeon
  • the resin film which comprises a base material layer may contain various additives in the range which does not impair the effect of this invention.
  • the various additives include ultraviolet absorbers, antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, colorants, pigments, and the like. What is necessary is just to determine suitably content of these additives according to the objective.
  • the thickness of the base material layer is preferably 0.4 to 400 ⁇ m, more preferably 1 to 300 ⁇ m, still more preferably 5 to 200 ⁇ m, and still more preferably 10 to 150 ⁇ m.
  • a primer layer may be formed on the surface of the base material layer from the viewpoint of improving interlayer adhesion with other layers laminated on the surface of the base material layer.
  • interlayer adhesion can be improved by providing a primer layer between the base material layer and the gas barrier layer.
  • the primer layer may be a single layer or a multilayer formed by laminating two or more layers.
  • the primer layer can be formed by curing a layer made of a curable composition containing a curable component.
  • the curable component may be an energy beam curable component or a thermosetting component.
  • the energy ray curable component include an acrylic monomer or an acrylic resin having an energy ray curable group in a side chain, a urethane monomer or a urethane resin having an energy ray curable group in a side chain, and the like.
  • the thermosetting component include an epoxy resin, a polyimide resin, and a phenol resin.
  • the curable composition that is a material for forming the primer layer further includes an inorganic filler, a photopolymerization initiator, an ultraviolet absorber, an antioxidant, a light stabilizer, an antistatic agent, a silane coupling agent, a colorant, You may contain various additives, such as surfactant, a plasticizer, and an antifoamer.
  • a commercially available curable composition in which a curable component and a filler are blended in advance may be used.
  • examples of such commercially available curable compositions include OPSTAR Z7530, OPSTAR Z7524, OPSTAR TU4086, OPSTAR Z7537 (all trade names, manufactured by JSR Corporation), and the like.
  • the thickness of the primer layer is preferably 0.01 to 50 ⁇ m, more preferably 0.1 to 30 ⁇ m, still more preferably 0.3 to 20 ⁇ m, still more preferably 0.5 to 10 ⁇ m.
  • the gas barrier laminate of one embodiment of the present invention is provided with a release sheet from the viewpoint of imparting self-supporting properties particularly when the base material layer is not provided and from the viewpoint of protecting the surface of a layer such as a functional layer. It is good also as a structure.
  • the release sheet examples include those in which a release agent layer formed from a release agent such as a silicone release agent is provided on the surface of the resin film. Moreover, what provided the adhesive layer with low adhesiveness for temporarily adhering with a gas-barrier laminated body on the resin film may be used.
  • a gas barrier layer is formed on the release treatment surface of the release sheet by the above-described method, and then a functional layer is formed on the gas barrier layer, whereby the gas barrier is efficiently formed. Can be manufactured.
  • an underlayer is provided between the release sheet and the gas barrier layer. It is preferable to provide it.
  • the underlayer is preferably a cured product of a layer formed from a curable composition containing an energy curable resin. Examples of the energy curable resin include those described above.
  • the curable composition that is a material for forming the underlayer further includes a thermoplastic resin, an inorganic filler, a photopolymerization initiator, an ultraviolet absorber, an antioxidant, a light stabilizer, an antistatic agent, and a silane coupling agent.
  • Various additives such as a colorant, a surfactant, a plasticizer, and an antifoaming agent may be contained.
  • the thickness of the underlayer is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
  • the gas barrier laminate of one embodiment of the present invention may further have an organic layer on the surface of the functional layer. Note that the gas barrier laminate of one embodiment of the present invention efficiently suppresses the entry of water vapor, oxygen, or the like into the sealing target from the viewpoint of the efficiency of sealing the sealing target such as an electronic device. In view of the above, it is preferable that an adhesive layer is further laminated as an organic layer on the surface of the functional layer.
  • the adhesive constituting the adhesive layer is appropriately selected depending on the application, and may be a pressure-sensitive adhesive or a thermosetting adhesive.
  • Specific examples of the adhesive include acrylic adhesives, urethane adhesives, silicone adhesives, rubber adhesives, olefin adhesives, and epoxy adhesives.
  • an adhesive layer composed of an adhesive selected from the group consisting of acrylic adhesives, urethane adhesives, rubber adhesives, and olefin adhesives is provided directly on the gas barrier layer, the gas barrier layer and There is a tendency that the interlaminar adhesion is poor.
  • the functional layer of the gas barrier laminate of the present invention has good interlayer adhesion with the adhesive layer composed of the above-mentioned adhesive, and is therefore suitable for the case where the above-described adhesive is used. Yes.
  • the adhesive include rubber-based pressure-sensitive adhesives such as polyisobutylene resins having a weight average molecular weight of 300,000 to 500,000, polybutene resins having a weight average molecular weight of 1,000 to 250,000, and hindered amine light stabilizers. And a hindered phenol-based antioxidant, and the polybutene resin is made of an adhesive composition containing 5 to 100 parts by mass with respect to 100 parts by mass of the polyisobutylene-based resin.
  • An adhesive composition containing an isoprene rubber having a carboxylic acid functional group, an isobutylene polymer having no carboxylic acid functional group, and an epoxy crosslinking agent can also be used.
  • olefin-based thermosetting adhesive examples include those composed of an adhesive composition containing a modified olefin resin, a polyfunctional epoxy compound, and an imidazole-based curing catalyst.
  • modified polyolefin resin examples include acid-modified resins. Examples thereof include unistole manufactured by Mitsui Chemicals, which is a polyolefin resin.
  • the thickness of the adhesive layer is appropriately set depending on the application, but is preferably 0.5 to 100 ⁇ m, more preferably 1 to 60 ⁇ m, and further preferably 3 to 40 ⁇ m.
  • the functional layer, the adhesive layer, the gas barrier layer, and the like are the outermost layers, from the viewpoint of protecting the surface of these layers and from the viewpoint of handling properties,
  • the above-described release sheet may be further laminated on the surface of the layer.
  • the sealing body of the present invention is obtained by sealing an electronic device that is an object to be sealed with the above-described gas barrier laminate of the present invention.
  • electronic devices that are objects to be sealed include liquid crystal displays, organic EL light emitters, inorganic EL light emitters, electronic paper, and solar cells.
  • the organic EL light-emitting body and the inorganic EL light-emitting body are used for applications such as a display and illumination.
  • the gas barrier laminate of the present invention plays a role as a sealing material for sealing the electronic device that is the object to be sealed.
  • the thing formed by sealing the electronic device which is a to-be-sealed object formed on the transparent substrate with the gas barrier laminated body of this invention which is a sealing material is mentioned.
  • the transparent substrate is not particularly limited, and various substrate materials can be used. In particular, it is preferable to use a substrate material having a high visible light transmittance. In addition, a material having a high blocking performance for blocking moisture and gas to enter from the outside of the element and having excellent solvent resistance and weather resistance is preferable.
  • transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetyl cellulose, brominated phenoxy, aramids, polyimides, polystyrene , Transparent plastics such as polyarylates, polysulfones, and polyolefins, and the gas barrier film described above.
  • the thickness of the transparent substrate is not particularly limited, and can be appropriately selected in consideration of light transmittance and performance for blocking the inside and outside of the element.
  • the electroconductive laminated body 100 of this invention has the auxiliary electrode layer 52 and the conductive layer 60 on the surface side of the functional layer 12 of the above-mentioned gas barrier laminated body of this invention.
  • the auxiliary electrode layer 52 is embedded in the surface and inside of the functional layer 12, and the conductive layer 60 is laminated on the surface of the functional layer 12 and the surface of the auxiliary electrode layer 52.
  • the functional layer is preferably cured.
  • the interlayer adhesion between the gas barrier layer and the functional layer is improved, the shape retention of the functional layer is improved, and the auxiliary electrode layer can be fixed without misalignment, It is also easy to provide a conductive layer in the functional layer.
  • the sheet resistance value ⁇ s measured from the conductive layer side of the conductive laminate of one embodiment of the present invention is preferably 10.0 ⁇ / ⁇ or less, more preferably 5.0 ⁇ / ⁇ or less, and still more preferably 1.0 ⁇ . / ⁇ or less.
  • the sheet resistance value ⁇ s means a value measured by the method described in the examples.
  • the water vapor permeability of the conductive laminate of one embodiment of the present invention measured in an environment of 40 ° C. and 90% relative humidity is preferably 5.0 g / (m 2 ⁇ day) or less, more preferably 0. .5g / (m 2 ⁇ day) or less, more preferably 0.05g / (m 2 ⁇ day) or less, even more preferably at 0.005g / (m 2 ⁇ day) or less, and usually 1.0 ⁇ 10 ⁇ 6 g / (m 2 ⁇ day) or more.
  • the auxiliary electrode layer has a function of reducing the sheet resistance value of the conductive laminate.
  • the conductive layer is a transparent conductive layer
  • the auxiliary electrode layer is electrically conductive with the transparent conductive layer.
  • an auxiliary electrode layer is the structure which patterned and provided the opening part from a viewpoint of suppressing the fall of the light transmittance of the said transparent conductive layer.
  • the material of the auxiliary electrode layer is not particularly limited. However, when patterning is performed using a method such as photolithography, a single metal such as gold, silver, copper, aluminum, magnesium, nickel, platinum, or palladium, silver-palladium Binary or ternary alloys such as silver-copper, silver-magnesium, aluminum-silicon, aluminum-silver, aluminum-copper, aluminum-titanium-palladium, and the like.
  • a single metal such as gold, silver, copper, aluminum, magnesium, nickel, platinum, or palladium
  • silver-palladium Binary or ternary alloys such as silver-copper, silver-magnesium, aluminum-silicon, aluminum-silver, aluminum-copper, aluminum-titanium-palladium, and the like.
  • a conductive paste containing a conductive material can be used as a material for the auxiliary electrode layer.
  • a metal fine particle such as silver, copper, or aluminum
  • a conductive fine particle such as carbon or ruthenium oxide
  • a conductive carbon material such as metal nanowire or carbon nanotube
  • the auxiliary electrode layer can be formed by printing and baking or curing this conductive paste.
  • the auxiliary electrode layer may be a single layer or a multilayer structure.
  • the multilayer structure may be a multilayer structure in which layers made of the same kind of material are laminated, or a multilayer structure in which layers made of at least two kinds of materials are laminated.
  • the auxiliary electrode layer is preferably patterned, but the pattern shape may be, for example, a lattice shape, a honeycomb shape, a comb shape, a strip shape (stripe shape), a straight shape, a curved shape, a wavy shape (sine curve, etc.) ), A polygonal mesh, a circular mesh, an elliptical mesh, and an indeterminate shape.
  • the thickness of the auxiliary electrode layer is preferably 10 nm to 20 ⁇ m, more preferably 100 nm to 15 ⁇ m, still more preferably 1 ⁇ m to 10 ⁇ m.
  • the line width of the auxiliary electrode layer is preferably from 0.1 to 100 ⁇ m, more preferably from 1 to 80 ⁇ m, still more preferably from 5 to 60 ⁇ m.
  • the conductive layer is preferably a transparent conductive layer.
  • the material for the transparent conductive layer include indium-tin oxide (ITO), indium-zinc oxide (IZO), aluminum-zinc oxide (AZO), gallium-zinc oxide (GZO), and indium-gallium- Zinc oxide (IGZO), niobium oxide, titanium oxide, tin oxide, and the like can be given. These may be used alone or in combination of two or more.
  • the thickness of the conductive layer is preferably 5 to 200 nm, more preferably 10 to 100 nm, and still more preferably 20 to 50 nm.
  • the method for producing the conductive laminate of the present invention is not particularly limited, but is preferably a production method having the following steps (1) to (3) from the viewpoint of productivity.
  • Step (1) The auxiliary electrode layer is bonded to the surface of the functional layer of the gas barrier laminate having the functional layer formed from the energy ray curable composition, and the auxiliary electrode layer is placed inside the functional layer. Embedding process.
  • Step (2) A step of irradiating the functional layer with energy rays to cure the functional layer.
  • an electrode transfer sheet 50 in which an auxiliary electrode layer 52 is formed on a transfer substrate 51 as shown in FIG. 1 may be prepared in advance.
  • the transfer substrate 51 is preferably composed of a resin film, and examples thereof include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polypropylene and polymethylpentene, polycarbonate films, and polyvinyl acetate films. It is done.
  • the material for forming the auxiliary electrode layer 52 is as described above.
  • a method of forming the auxiliary electrode layer after providing an auxiliary electrode layer on which a pattern is not formed on a transfer substrate, a known physical treatment or chemical treatment mainly using a photolithography method, or a combination thereof.
  • the pattern of the auxiliary electrode layer is formed directly by a method of processing into a predetermined pattern shape, or by a screen printing method, a rotary screen printing method, a screen offset printing method, an ink jet method, an offset printing method, a gravure offset printing method, etc. And the like.
  • a PVD method physical vapor deposition method
  • a vacuum deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, an ALD method (atomic layer deposition method).
  • CVD chemical vapor deposition
  • various coatings such as dip coating, spin coating, spray coating, gravure coating, die coating, and doctor blade, and electrodeposition.
  • a wet process, a silver salt method, etc. are mentioned, and it is suitably selected according to the material of the auxiliary electrode layer.
  • Step (1) the auxiliary electrode layer and the surface of the functional layer of the gas barrier laminate having the functional layer formed from the energy ray curable composition are bonded together, and the auxiliary electrode layer is placed inside the functional layer.
  • This is an embedding process.
  • FIG. 1A using the electrode transfer sheet 50, the surface of the electrode transfer sheet 50 on the side provided with the auxiliary electrode layer 52 and the surface of the functional layer 12 of the gas barrier laminate 1 are bonded to each other. 12 shows a state in which the auxiliary electrode layer 52 is embedded in the inside of the body 12.
  • the functional layer of the gas barrier laminate used in this step is a layer formed from the above-mentioned energy beam curable composition, and particularly includes an amine-based silane coupling agent and an energy beam curable resin.
  • a layer formed from the composition (I) is preferred.
  • the functional layer formed from the composition (I) is in an uncured state and excellent in embedding of the auxiliary electrode layer, and after the functional layer is cured in the step (2), in the step (3) And having excellent properties such as excellent releasability when the transfer substrate is peeled off.
  • the functional layer 12 also has good interlayer adhesion with the gas barrier layer 11.
  • the laminator may be used to bond the surface of the electrode transfer sheet 50 provided with the auxiliary electrode layer 52 and the surface of the functional layer 12 of the gas barrier laminate 1 in this step.
  • Step (2) is a step of curing the functional layer by irradiating the functional layer with energy rays.
  • the energy ray irradiation is preferably performed from the base material layer 13 side of the gas barrier laminate 1.
  • a method of irradiating energy radiation for example, in the case of irradiating ultraviolet rays, it is preferable to irradiate with a light amount of 100 to 500 mJ / cm 2 using a high pressure mercury lamp, a fusion H lamp, a xenon lamp or the like.
  • an electron beam accelerator or the like at an irradiation dose of 150 to 350 kV.
  • the transfer substrate 51 of the electrode transfer sheet 50 is peeled from the cured functional layer 12 as shown in FIG.
  • the functional layer 12 is a layer formed from the energy beam curable composition, the transfer substrate 51 can be easily peeled off from the surface of the functional layer after curing.
  • a process (4) is a process of providing the conductive layer 60 on the surface of the said functional layer 12 which peeled and exposed the transfer base material in the process (3).
  • the above-described conductive layer forming material is used, for example, physical heating such as resistance heating vapor deposition, electron beam vapor deposition, molecular beam epitaxy, ion beam, ion plating, and sputtering. It can be formed by a method such as chemical vapor deposition (CVD) such as vapor deposition (PVD), thermal CVD, plasma CVD, photo CVD, epitaxial CVD, atomic layer CVD, or the like.
  • Production Example 1-1 (Preparation of laminate comprising base material layer / primer layer / gas barrier layer) (1) Formation of primer layer A solution in which 20 parts by mass (active ingredient ratio) of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name “A-DPH”) is dissolved in 100 parts by mass of methyl isobutyl ketone 0.62 parts by mass (active ingredient ratio) of a photopolymerization initiator (manufactured by BASF, product name “Irgacure 127”) was added and mixed to prepare a solution of a primer layer forming composition.
  • A-DPH dipentaerythritol hexaacrylate
  • a photopolymerization initiator manufactured by BASF, product name “Irgacure 127”
  • PEN polyethylene naphthalate
  • product name “PENQ65HW” manufactured by Teijin Film Solutions Co., Ltd.” was used as the base material layer.
  • the primer layer-forming composition solution is applied by a bar coating method to form a coating film. Heat drying for a minute.
  • the primer layer was cured by UV irradiation to form a primer layer having a thickness of 1 ⁇ m.
  • a perhydropolysilazane-containing liquid manufactured by AZ Electronic Materials, product name “AZNL110A-20”, Rx, Ry, Rz in the general formula (1) is A solution containing perhydropolysilazane having a repeating unit which is a hydrogen atom) was used.
  • the above-mentioned perhydropolysilazane-containing liquid is applied by spin coating to form a coating film, and the coating film is dried by heating at 120 ° C. for 2 minutes, A first polymer layer having a thickness of 200 nm was formed.
  • argon (Ar) was ion-implanted into the surface of the formed first polymer layer under the conditions described later to form a modified region, thereby forming a first modified polymer layer.
  • a 150 nm thick second polymer layer was formed on the exposed surface of the first modified polymer layer using the same perhydropolysilazane-containing liquid as described above.
  • argon (Ar) was plasma ion-implanted under the same conditions to form a modified region to form a second modified polymer layer.
  • a gas barrier layer composed of a first modified polymer layer and a second modified polymer layer each having a modified region was formed.
  • Plasma ion implantation for the surfaces of the first polymer layer and the second polymer layer was performed using the following apparatus under the following implantation conditions.
  • PET film having a thickness of 100 ⁇ m product name “PET A4100” manufactured by Toyobo Co., Ltd., PET film with one surface subjected to easy adhesion treatment) was used.
  • a silver paste (manufactured by Mitsuboshi Belting Co., Ltd., product name “low-temperature fired conductive paste MDot (registered trademark)”) is printed as an ink on a part of the surface of the transfer substrate that has not been subjected to easy adhesion treatment, and is uncured.
  • An auxiliary electrode layer was formed. Then, the uncured auxiliary electrode layer was temporarily dried at 70 ° C. for 1 minute, and then placed in a conveyor-type hot air / IR baking furnace and baked at 150 ° C. for 10 minutes. Formed.
  • the formed auxiliary electrode layer had a line width of 40 ⁇ m and a thickness of 8 ⁇ m.
  • Examples 1-1 to 1-7, Comparative Examples 1-1 to 1-6 (1) Preparation of energy beam curable composition The components of the types and blending amounts (active ingredient ratio) shown in Table 1 were added and mixed to obtain energy beam curable compositions (IA) to (I -G) and (Ia) to (If) were prepared, respectively.
  • ⁇ Silane coupling agent> “Amine-based silane coupling agent (B-1)” manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM6803”, N-2-aminoethyl-8-aminooctyltrimethoxysilane. “Amine-based silane coupling agent (B-2)” manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM603”, N-2-aminoethyl-3-aminopropyltrimethoxysilane. “Amine-based silane coupling agent (B-3)” manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM903”, 3-aminopropyltrimethoxysilane.
  • Epoxy silane coupling agent (b′-1) manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM403”, 3-glycidoxypropyltrimethoxysilane.
  • Mercapto silane coupling agent (b'-2) manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM803”, 3-mercaptopropyltrimethoxysilane.
  • Acrylic silane coupling agent (b′-3) manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM5103”, 3-acryloxypropyltrimethoxysilane.
  • Photopolymerization initiator “Photopolymerization initiator (C-1)”: manufactured by BASF, product name “Irgacure 819”, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • the surface of the functional layer on the side where the auxiliary electrode layer 52 is embedded has a thickness of 50 nm made of ITO (indium tin oxide) by sputtering under the following conditions.
  • the conductive layer was formed to obtain a conductive laminate.
  • [Conductive layer deposition conditions] Target: ITO (manufactured by JX Nippon Mining & Metals, SnO 2 content 10% by mass) ⁇ Method: DC magnetron sputtering ⁇ Application method: DC500W ⁇ Substrate heating: None ⁇ Carrier gas: Argon (Ar) ⁇ Film pressure: 0.6Pa
  • the interlayer adhesion of the conductive layer, the functional layer after curing, and the adhesion layer was evaluated according to the following criteria.
  • ⁇ "A” Classification of evaluation results in Table 1 of JIS K 5600-5-6 is 0-2
  • ⁇ "F” Classification of evaluation results in Table 1 of JIS K 5600-5-6 is 3-5
  • evaluation of interlayer adhesiveness was first performed on the conductive laminate after being stored for 24 hours in an environment of 23 ° C. and 50% relative humidity. Then, only when the evaluation was “A”, after conducting a wet heat test in which the conductive laminate was stored for 1000 hours in an environment of 60 ° C. and 95% relative humidity, 23 ° C. and 50% relative humidity. Interlayer adhesion was also evaluated for conductive laminates stored in the environment for 24 hours.
  • Water vapor transmission rate Using a water vapor transmission meter (manufactured by MOCON, product name “AQUATRAN”), the water vapor transmission rate (unit: g / (m 2 ⁇ day)) of the conductive laminate at 40 ° C. and relative humidity of 90% is measured. did. The gas flow rate was 20 sccm.
  • the conductive laminates produced in Examples 1-1 to 1-7 were excellent in interlayer adhesion, as well as in conductivity and gas barrier properties.
  • the conductive laminates produced in Comparative Examples 1-1 to 1-6 were inferior in interlayer adhesion, and in particular, peeling was observed between the cured functional layer and the gas barrier layer. Therefore, the measurement was terminated without measuring the sheet resistance value and the water vapor transmission rate.
  • Production Example 2-1 (Preparation of laminate comprising base material layer / primer layer / gas barrier layer) (1) Formation of primer layer As a base material layer, a polyethylene terephthalate (PET) film (product name “PET50A4300” manufactured by Toyobo Co., Ltd.) having a thickness of 50 ⁇ m and subjected to double-sided easy adhesion treatment was used. A UV curable acrylate resin composition (manufactured by JSR Corporation, product name “OPSTAR Z7530”) is applied on one surface of the PET film, which is the base material layer, using a Mayer bar to form a coating film. The coating film was dried at 70 ° C. for 1 minute.
  • PET polyethylene terephthalate
  • the coating film after drying was cured by UV irradiation at an illuminance of 250 mW / cm 2 and a light amount of 170 mJ / cm 2 , and a primer layer having a thickness of 1000 nm Formed.
  • a coating agent mainly composed of perhydropolysilazane manufactured by Merck Performance Materials, product name “Aquamica NL110-20”, in the general formula (1)
  • a xylene solution containing perhydropolysilazane having a repeating unit in which Rx, Ry and Rz are hydrogen atoms was used.
  • the above coating agent which is a composition for forming a gas barrier layer, is rotated at 3000 rpm using a spin coater (manufactured by Mikasa, product name “MS-A200”).
  • the coating film was formed by coating at a rotation time of 30 seconds, and the coating film was dried by heating at 120 ° C. for 2 minutes to form a polymer layer having a thickness of 150 nm.
  • plasma ion implantation was performed on the formed polymer layer using a plasma ion implantation apparatus under the following conditions to form a modified region, thereby forming a gas barrier layer composed of the modified polymer layer.
  • thermosetting composition (II-1) The following types of ingredients were added in the following amounts (effective ingredient ratios) and diluted with 5166 parts by mass of methanol and 586 parts by mass of ethyl acetate.
  • a thermosetting composition (II-1) was prepared.
  • -Thermosetting epoxy resin Mitsubishi Gas Chemical Co., Ltd., product name “Maxibe M-100”, solid content 100% by mass
  • Polyfunctional amine resin Mitsubishi Gas Chemical Co., Ltd., product name “MAXIVE C-93T”, solid content: 65.2% by mass
  • Example 2-2 Preparation of energy beam curable composition (IB) The following components were added in the following blending amount (active ingredient ratio) and mixed to obtain an energy beam curable composition (IB). ) was prepared.
  • the composition (IB) is the same as the energy ray curable composition (IB) used in Example 1-2.
  • -UV curable urethane resin manufactured by Nippon Synthetic Chemical Industry Co., Ltd., product name “UT5746", urethane resin having an ultraviolet polymerizable group, ethyl acetate solution with a solid content of 80% by mass
  • Amine-based silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM6803”, N-2-aminoethyl-8-aminooctyltrimethoxysilane
  • Photopolymerization initiator manufactured by BASF, product name “Irgacure 819”, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
  • the surface of the coating film after drying is bonded to the release-treated surface of a release film (manufactured by Lintec Corporation, product name “SP-PET381031”), and from the substrate layer side, a conveyor-type UV irradiator (manufactured by Heraeus, product) Using a name “CV-110Q-G” (high pressure mercury lamp), a functional layer having a thickness of 20 ⁇ m was formed by irradiating with ultraviolet rays (UV) with an integrated light amount of 250 mJ / cm 2 and curing. Thereafter, the release film was removed, and a gas barrier laminate obtained by laminating the base material layer / primer layer / gas barrier layer / functional layer in this order was obtained.
  • a release film manufactured by Lintec Corporation, product name “SP-PET381031”
  • a conveyor-type UV irradiator manufactured by Heraeus, product
  • UV ultraviolet rays
  • Comparative Example 2-1 Preparation of functional layer forming composition (II-2) The following components were added in the following blending amounts (effective component ratio) and mixed to prepare a functional layer forming composition.
  • ⁇ Polyester resin manufactured by Nippon Synthetic Chemical Industry Co., Ltd., product name “Polyester HR-521”
  • ⁇ 2-propanol 15 parts by mass
  • Comparative Example 2-2 A UV curable acrylate resin (manufactured by JSR Corporation, product name) is formed on the surface of the gas barrier layer of the laminate obtained by laminating the base material layer / primer layer / gas barrier layer in this order. “Opster Z7530”) was applied using a Meyer bar to form a coating film, and the coating film was dried at 70 ° C. for 1 minute. Using an electrodeless UV lamp system (manufactured by Heraeus, product name “CV-110Q-G”), ultraviolet rays (UV) with an illuminance of 250 mW / cm 2 and a light amount of 170 mJ / cm 2 are applied to the surface of the coated film after drying. ) To cure the coating film to form a functional layer having a thickness of 150 nm. By these steps, a gas barrier laminate obtained by laminating a base layer / primer layer / gas barrier layer / functional layer in this order was obtained.
  • Comparative Example 2-3 The following “energy ray curable composition (Ia)” was prepared, and the base layer was formed in the same manner as in Example 2-2, except that the functional layer was formed using the composition (Ia). A gas barrier laminate obtained by laminating a material layer / primer layer / gas barrier layer / functional layer in this order was obtained.
  • the composition (Ia) is the same as the composition (Ia) used in Comparative Example 1-1.
  • UV curable urethane resin manufactured by Asia Kogyo Co., Ltd., product name “RUA-048”, urethane resin having an ultraviolet polymerizable group
  • Epoxy silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM403”, 3-glycidoxypropyltrimethoxysilane
  • Photopolymerization initiator manufactured by BASF, product name “Irgacure 819”, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
  • Total light transmittance Based on JIS K 7361-1, the total light transmittance of the gas barrier laminate was measured.
  • the gas barrier laminates produced in Examples 2-1 and 2-2 were excellent in interlayer adhesion between the gas barrier layer and the functional layer, and also had good gas barrier properties and transparency.
  • the gas barrier laminate of Comparative Example 2-1 was placed under high-temperature and high-humidity conditions, the interlayer adhesion between the gas barrier layer and the functional layer was inferior, resulting in easy peeling.
  • the gas barrier laminates of Comparative Examples 2-2 and 2-3 had poor interlayer adhesion before and after being placed under a high temperature and high humidity condition.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un stratifié barrière contre les gaz qui présente une couche barrière contre les gaz et une couche fonctionnelle qui est directement stratifiée sur une surface de la couche barrière contre les gaz, la couche fonctionnelle étant formée à partir d'une composition qui contient un composé à base d'amine. Ledit stratifié barrière contre les gaz fait preuve d'une excellente adhérence interlaminaire entre la couche barrière contre les gaz et la couche fonctionnelle destinée à conférer une fonction spécifique, et présente des propriétés de barrière contre les gaz satisfaisantes.
PCT/JP2018/011634 2017-03-30 2018-03-23 Stratifié barrière contre les gaz, corps d'étanchéité, stratifié conducteur, et procédé de production d'un stratifié conducteur WO2018180963A1 (fr)

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