JP7082972B2 - A method for manufacturing a gas barrier laminated body, a sealed body, a conductive laminated body, and a conductive laminated body. - Google Patents

Description

The present invention relates to a gas barrier laminate, a sealed body in which an electronic device is sealed with the gas barrier laminate, a conductive laminate using the gas barrier laminate, and a method for manufacturing the conductive laminate.

In recent years, in displays such as liquid crystal displays and electroluminescence (EL) displays, gas barrier films have been used instead of glass plates as substrates having electrodes in order to realize thinning, weight reduction, flexibility, and the like. ing.
In general, many gas barrier films have a structure in which a gas barrier layer is laminated on the surface of a resin film. Further, another layer is laminated on the surface of the gas barrier layer to develop a gas barrier laminated body having a new function.

For example, Patent Document 1 describes a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is formed on the surface of a gas barrier layer of a base material with a gas barrier layer. According to Patent Document 1, by using this adhesive sheet, an electronic device such as an organic EL element can be efficiently sealed.

International Publication No. 2012/032907

Like the pressure-sensitive adhesive sheet described in Patent Document 1, 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 laminated body having the function.
However, in general, the gas barrier layer of the gas barrier film has a low affinity with the organic layer containing an organic compound. Therefore, even if the organic layer is provided on the gas barrier layer, the layer between the gas barrier layer and the organic layer is formed. It has a problem that the adhesion is poor and delamination is likely to occur.
Further, when the interlayer adhesion between the gas barrier layer and the organic layer is inferior, gas such as water vapor or oxygen enters from the layers of the two layers, which causes deterioration of electronic devices such as organic EL elements.

In the present invention, a gas barrier laminate having excellent interlayer adhesion between a gas barrier layer and a functional layer provided to impart a specific function and having good gas barrier properties, and an electronic device are made of the gas barrier laminate. It is an object of the present invention to provide a sealed body formed by sealing, a conductive laminated body using the gas barrier laminated body, and a method for manufacturing the conductive laminated body.

By forming the functional layer from a composition containing an amine compound, the present inventors can obtain a gas barrier laminated body having improved interlayer adhesion between the functional layer and the gas barrier layer, which solves the above-mentioned problems. I found something that could be solved.

The present invention provides the following [1] to [15].
[1] It has a gas barrier layer and a functional layer directly laminated on one surface of the gas barrier layer.
A gas barrier laminate in which the functional layer is a layer formed from a composition containing an amine compound.
[2] 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.
[3] The gas barrier laminate according to the above [2], wherein the polymer compound is a polysilazane compound.
[4] The item according to any one of the above [1] to [3], wherein the functional layer is a layer formed from the composition (I) containing an amine-based silane coupling agent as the amine-based compound. The described gas barrier laminate.
[5] The gas barrier laminate according to the above [4], wherein the content of the amine-based silane coupling agent is 0.1 to 20% by mass with respect to the total amount of the active ingredient of the composition (I). ..
[6] The gas barrier laminate according to the above [4] or [5], wherein the composition (I) contains an energy ray curable resin.
[7] The above-mentioned [1] to [3], wherein the functional layer is a layer formed from the composition (II) containing a polyfunctional amine compound having two or more amino groups as the amine-based compound. The gas barrier laminate according to any one item.
[8] The gas barrier laminate according to the above [7], wherein the content of the polyfunctional amine compound is 25 to 80% by mass with respect to the total amount of the active ingredient of the composition (II).
[9] The gas barrier laminate according to the above [7] or [8], wherein the composition (II) contains a thermosetting resin.
[10] The gas barrier laminate according to the above [9], wherein the thermosetting resin contains a thermosetting epoxy resin.
[11] The gas barrier laminate according to any one of [1] to [10] above, wherein an organic layer is further laminated on the surface of the functional layer.
[12] The gas barrier laminate according to any one of [4] to [6] above, wherein the functional layer has a function as an electrode embedded layer in which an auxiliary electrode layer can be embedded.
[13] A method for producing a gas barrier laminate with an auxiliary electrode, which comprises 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 inside 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 surface of the cured functional layer.

The gas barrier laminate of the present invention has excellent interlayer adhesion with a functional layer provided to impart a specific function, and has good gas barrier properties.

It is sectional drawing which showed each process of the manufacturing method of the conductive laminated body of one aspect of this invention.

[Structure of gas barrier laminate]
The gas barrier laminated body of the present invention has a gas barrier layer and a functional layer directly laminated on one surface of the gas barrier layer, but layers other than these may be provided.
For example, from the viewpoint of forming a gas barrier laminate having excellent self-supporting property, the gas barrier laminate according to one aspect of the present invention further includes a base material layer on the surface side opposite to the side where the functional layer of the gas barrier layer is laminated. It is preferable to have.
In the above-mentioned gas barrier laminate with a base material, a new layer such as an adhesive layer, a primer layer, and a hard coat layer is further provided on the surface side of the base material layer opposite to the side on which the gas barrier layer is laminated. It may be provided as a configuration.
A primer layer may be provided between the base material layer and the gas barrier layer.

The gas barrier laminate of one aspect of the present invention may be configured by laminating another layer on the surface of the functional layer, and further an organic layer is laminated from the viewpoint of imparting excellent interlayer adhesion to the functional layer. It is preferable to have a configuration.
The organic layer may be a layer containing an organic compound such as a resin, and is preferably an adhesive layer.
By forming a gas barrier laminated body provided with an adhesive layer, it is possible to efficiently seal the electronic device and the like, and it is possible to effectively suppress the invasion of water vapor, oxygen, etc. into the electronic device. can.
Examples of the organic layer other than the adhesive layer include a pressure-sensitive adhesive layer and a quantum dot layer when the release sheet laminated on the functional layer has a pressure-sensitive adhesive layer.

Specific configuration examples of the gas barrier laminate according to one aspect of the present invention include the following aspects.
(I) Gas barrier layer / functional layer (ii) gas barrier layer / functional layer / adhesive layer (iii) base material layer / gas barrier layer / functional layer (iv) base material 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 layer / primer layer / gas barrier layer / functional layer / adhesive layer (xiii) hard coat layer / base material Layer / Gas barrier layer / Functional layer (xiv) Hard coat layer / Base material layer / Primer layer / Gas barrier layer / Functional layer (xv) Hard coat layer / Base material layer / Gas barrier layer / Functional layer / Adhesive layer (xvi) Hard Coat layer / Base material layer / Primer layer / Gas barrier layer / Functional layer / Adhesive layer (xvii) Gas barrier layer / Functional layer / Quantum dot layer

In the above aspect, when the functional layer, the adhesive layer, the gas barrier layer and the like are the outermost layers, the viewpoint of protecting the surface of these layers and the self-supporting property are improved, and the handling property is excellent. From the viewpoint of forming a gas barrier laminated body, a peelable sheet that can be peeled off at the time of use may be further laminated on the surface of these layers.
For example, in the embodiment (i) above, by providing a release sheet on the surface of at least one of the functional layer and the gas barrier layer, a gas barrier laminated body having excellent self-supporting property can be obtained. ..
Further, when the release sheet is provided on the surface of the gas barrier layer, it is preferable to provide a base layer between the gas barrier layer and the release sheet from the viewpoint of improving the release property of the release sheet.

Further, the adhesive layer may be provided on the functional layer side as in the above (v) or the like, or may be provided on the base material layer side as in the above (vii).
However, from the viewpoint of blocking gases such as water vapor and oxygen that have entered from the film thickness portion of the base material layer with the gas barrier layer and preventing these gases from reaching the electronic device that is the object to be sealed, the above (v). ), Etc., it is preferable to provide an adhesive layer on the surface on the functional layer side.

Further, in the configuration in which the functional layer such as (i) is the outermost layer, 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 according to one aspect of the present invention at the time of use is preferably 1 to 600 μm, more preferably 5 to 200 μm, and even more preferably 20 to 100 μm.
The above-mentioned "total thickness at the time of use" means the thickness of the gas barrier laminate after removing the release sheet provided for protecting the surface of the outermost layer of the gas barrier laminate.

The water vapor permeability of the gas barrier laminate of one aspect 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 0.005 g / (m ² · day) or less, and usually 1.0 × 10 It is ^-6 g / (m ² · day) or more.
In addition, in this specification, a water vapor transmittance means a value measured by the method described in an Example.

The gas barrier laminate according to one aspect of the present invention preferably has excellent transparency.
Specifically, the total light transmittance of the gas barrier laminate according to one aspect of the present invention is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more.
In this specification, the total light transmittance is a value measured according to JIS K 7631-1, and more specifically, it means a value measured by the method described in Examples.

Hereinafter, each layer of the gas barrier laminate of the present invention will be described.

[Gas barrier layer]
The gas barrier layer of the gas barrier laminated body of the present invention is a layer having a property of suppressing the permeation of a gas such as water vapor or oxygen (hereinafter referred to as “gas barrier property”).
The gas barrier layer included in the gas barrier laminated body of one aspect of the present invention may be a single layer or a plurality of layers in which two or more layers are laminated.

The water vapor permeability of the gas barrier layer of the gas barrier layer of one aspect 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. Is 0.5 g / (m ² · day) or less, more preferably 0.05 g / (m ² · day) or less, still more preferably 0.005 g / (m ² · day) or less, and usually 1 It is 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 the material for forming the gas barrier layer, but is preferably 1 nm to 50 μm, more preferably 3 nm to 2000 nm, still more preferably 5 to 1000 nm, and even more preferably 20. It is ~ 500 nm.
When the gas barrier layer is a multi-layer in which two or more layers are laminated, it is preferable that the thickness of the multi-layer is within the above range.

From the viewpoint of forming a gas barrier layer having improved interlayer adhesion with the functional layer more efficiently, the gas barrier layer preferably contains a compound having a nitrogen atom.
Examples of the gas barrier layer containing a compound having a nitrogen atom include an inorganic vapor deposition film formed by depositing an inorganic compound such as an inorganic nitride, an inorganic oxide nitride, and an inorganic carbide carbide, and a gas barrier resin film containing a gas barrier resin such as polyacrylonitrile. , And a modified polymer layer formed from a composition containing a polysilazane compound and having a modified region.

Examples of the gas barrier layer include the following three types of layers.
(1) An inorganic vapor-deposited film formed by depositing an inorganic compound.
(2) A gas barrier resin film containing a gas barrier resin.
(3) A modified polymer layer formed from a composition for forming a gas barrier layer containing a polymer compound and having a modified region.
Among these, from the viewpoint that thinning is possible and layer formation with excellent gas barrier properties is possible, the gas barrier layer is the inorganic vapor deposition film of (1) above or the modified height of (3) above. The molecular layer is preferable, and the modified polymer layer of (3) above is more preferable from the viewpoint of forming a gas-barrier laminated body having flexibility.
Hereinafter, aspects of the gas barrier layer will be described in detail in the above (1) to (3).

(1) Inorganic vapor-deposited film formed by vapor-filming an inorganic compound In the gas-barrier laminated body of one aspect of the present invention, an inorganic thin-film film formed by depositing an inorganic compound can be applied as a gas barrier layer. The inorganic vapor-filmed film may be a single layer composed of one layer or a plurality of layers in which two or more layers are laminated.

The thickness of the inorganic thin-film 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, still more preferably 40 to 200 nm from the viewpoint of gas barrier properties and handleability. be.
When the inorganic vapor-filmed film is a multi-layer formed by laminating two or more layers, the thickness of the multi-layer is preferably within the above range.

Examples of the inorganic compound that can form an inorganic vapor deposition film include inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, tin oxide, and tin oxide; silicon nitride, aluminum nitride, and titanium nitride. Inorganic nitrides such as; Inorganic carbides; Inorganic sulfides; Inorganic oxide nitrides such as silicon oxide; Inorganic oxide carbides; Inorganic nitride carbides; Inorganic oxide nitride carbides; Metals such as aluminum, magnesium, zinc, and tin; Can be mentioned.
These inorganic compounds may be used alone or in combination of two or more.
Among these, an inorganic vapor deposition film made from an inorganic oxide, an inorganic nitride or a metal is preferable from the viewpoint of gas barrier properties, and further, from the viewpoint of transparency, an inorganic vapor deposition made from an inorganic oxide or an inorganic nitride as a raw material is preferable. A membrane is preferred.

A known method can be applied to the method of forming the inorganic vapor deposition film, for example, PVD method such as vacuum vapor deposition method, sputtering method, ion plating method, thermal CVD method, plasma CVD method, optical CVD method and the like. The CVD method and the atomic layer deposition method (ALD method) can be mentioned.

(2) Gas Barrier Resin Film Containing Gas Barrier Resin In the gas barrier laminate according to one aspect 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 composed of one layer or a plurality of layers in which two or more layers are laminated.

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, still more preferably 40 to 200 nm, from the viewpoint of gas barrier properties.
When the gas barrier resin film is a multi-layer formed by laminating two or more layers, the thickness of the multi-layer is preferably within the above range.

The gas barrier resin is preferably a resin that does not easily permeate oxygen, water vapor, etc., and specifically, polyvinyl alcohol or a partially saponified product thereof, an ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, or polyvinyl chloride. Examples thereof include vinylidene and polychlorotrifluoroethylene.
These gas barrier resins may be used alone or in combination of two or more.

As a method for forming a gas barrier resin film, a solution containing a gas barrier resin is applied on the peeling surface of the release sheet or on a substrate to form a coating film, and the coating film is dried to form the coating film. Can be mentioned.
Examples of the coating method include a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method and the like.
Examples of the drying method include hot air drying, hot roll drying, infrared irradiation and the like.

(3) Modified Polymer Layer Formed from a Composition for Forming a Gas Barrier Layer Containing a Polymer Compound The modified polymer layer according to one aspect of the present invention contains a polymer compound as a gas barrier layer. 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 plurality of layers in which two or more layers are laminated.

The thickness of the modified polymer layer used as the gas barrier layer is preferably 20 nm to 50 μm, more preferably 30 nm to 1000 nm, still more preferably 40 nm to 500 nm, and even more preferably 70 to 450 nm.
When the modified polymer layer is a multi-layer formed by laminating two or more layers, the thickness of the multi-layer is preferably within the above range.

The composition for forming a gas barrier layer, which is a material for forming a modified polymer layer, contains a polymer compound, but as long as the effect of the present invention is not impaired, a curing agent, an antiaging agent, a light stabilizer, a flame retardant, etc. May contain a general purpose additive of.
However, the content of the polymer compound is preferably relative to the total amount of the modified high molecular weight (100% by mass) or the total amount of the active ingredient of the composition for forming the gas barrier layer (100% by mass). Is 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more.
In addition, in this specification, "the active ingredient of a composition" means a component which excludes a diluting solvent among the components contained in a target composition.

As used herein, 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.

Examples of the polymer compound include silicon-containing polymer compounds, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, and polyarylate. , Acrylic resin, alicyclic hydrocarbon resin, aromatic polymer and the like, and a silicon-containing polymer compound is preferable.
Examples of the silicon-containing polymer compound include polysilazane-based compounds, polycarbosilane-based compounds, polysilane-based compounds, polyorganosiloxane-based compounds, poly (disylanilenphenylene) -based compounds, and poly (disylanilen-ethynylene) -based compounds. Compounds and the like can be mentioned.
These polymer compounds may be used alone or in combination of two or more.

In one aspect of the present invention, the polysilazane compound is more preferable as the polymer compound from the viewpoint of further improving the gas barrier property and forming the gas barrier layer having excellent interlayer adhesion with the functional layer.
The polysilazane compound may be used alone or in combination of two or more.

The polysilazane compound is a polymer having a repeating unit containing a —Si—N— bond (silazane bond) in the molecule, and specifically, a polymer having a repeating unit represented by the following general formula (1). Is preferable.
The number average molecular weight (Mn) of the polysilazane compound is preferably 100 to 50,000, more preferably 1,000 to 50,000.

In the above general formula (1), n indicates the number of repeating units and represents an integer of 1 or more.
Rx, Ry and Rz are independently hydrogen atom, alkyl group having unsubstituted or substituent, cycloalkyl group having unsubstituted or substituent, alkenyl group having unsubstituted or substituent, unsubstituted or substituted. Represents an aryl group having a group or an alkylsilyl group.

Examples of the alkyl group 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. , N-hexyl group, n-heptyl group, n-octyl group and other alkyl groups having 1 to 10 carbon atoms can be mentioned.

Examples of the cycloalkyl group include cycloalkyl groups having 3 to 10 ring-forming carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.

Examples of the alkenyl group include an alkenyl group having 2 to 10 carbon atoms such as a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group and a 3-butenyl group.

Examples of the aryl group include an aryl group having 6 to 15 ring-forming carbon atoms such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group.

Examples of the alkylsilyl group 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, an ethylsilyl group and the like.

Examples of the substituent that the alkyl group, cycloalkyl group, and alkenyl group may have include 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; a glycidoxy. Group; (meth) acryloyloxy group; aryl group having an unsubstituted or substituent such as a phenyl group, 4-methylphenyl group, 4-chlorophenyl group; and the like.

Examples of the substituent that the aryl group may have include 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; and a methoxy group. , Ethoxy group and other alkoxy groups with 1 to 6 carbon atoms; nitro group; cyano group; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group; phenyl group, 4-methylphenyl group, 4- An aryl group having an unsubstituted or substituent such as a chlorophenyl group; and the like can be mentioned.

In one aspect of the present invention, as Rx, Ry, and Rz, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable, and a hydrogen atom is more preferable.
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. At least one of Ry and Rz may be an organic polysilazane which is an organic group other than a hydrogen atom.

Further, the polysilazane compound may be a modified polysilazane.
Examples of the polysilazane modified product include JP-A-62-195024, JP-A-2-844437, JP-A-63-81122, JP-A-1-138108, and JP-A No. 2-175726. , Japanese Patent Application Laid-Open No. 5-238827, Japanese Patent Application Laid-Open No. 5-238827, Japanese Patent Application Laid-Open No. 6-122852, Japanese Patent Application Laid-Open No. 6-306329, Japanese Patent Application Laid-Open No. 6-299118, Japanese Patent Application Laid-Open No. 9-313333, Examples thereof include those described in Kaihei 5-345926 and Japanese Patent Application Laid-Open No. 4-63833.
Further, as the polysilazane compound, a commercially available product commercially available 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 in the form of a solution.
Examples of the 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 and n-. An aliphatic hydrocarbon solvent such as hexane and n-heptane; an alicyclic hydrocarbon solvent such as cyclopentane and cyclohexane; and the like can be mentioned.
These organic solvents may be used alone or in combination of two or more.

As a method for forming a polymer layer from a composition for forming a gas barrier layer, a solution of the composition for forming a gas barrier layer is applied on the peeling surface of the release sheet, on the surface of the base layer provided on the release sheet, and as a base material. A method of forming a coating film by applying it on the surface of the above-mentioned material and drying the coating film to form the coating film can be mentioned.
Examples of the coating method include a bar coating method, a spin coating method, a dipping method, a roll coating method, a gravure coating method, a knife coating method, an air knife coating method, a roll knife coating method, a die coating method, a screen printing method, and a spray coating method. The gravure offset method and the like can be mentioned.
Examples of the method for drying the coating film include conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation. The heating temperature is usually 80 to 150 ° C., and the heating time is usually several tens of seconds to several tens of minutes.

A modified polymer layer can be obtained by subjecting the surface of the formed polymer layer to a modification treatment to form a modified region.
Examples of the reforming treatment include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, heat treatment and the like.
The ion implantation treatment is a method of injecting accelerated ions into the polymer layer to modify the polymer layer to form a modified region, and the details will be described later.
The plasma treatment is a method of exposing the polymer layer to plasma to modify the polymer layer to form a modified region, and can be performed, for example, according to the method described in JP-A-2012-106421. ..
The ultraviolet irradiation treatment is a method of irradiating the polymer layer with ultraviolet rays to modify the polymer layer to form a modified region, and can be performed, for example, according to the method described in JP2013-226757A. ..
Among these, ion implantation treatment is preferable as the modification treatment from the viewpoint that the surface of the modified polymer layer can be efficiently modified to the inside without roughening the surface and the gas barrier property can be further improved.

Examples of the ions to be injected into the polymer layer include rare gas ions such as argon, helium, neon, krypton, and xenone; ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; methane, Alcan gas ions such as ethane; Alken gas ions such as ethylene and propylene; Alkene gas ions such as pentadiene and butadiene; Alkin gas ions such as acetylene; Fragrances such as benzene and toluene Group hydrocarbon gas ions; cycloalkane gas ions such as cyclopropane; cycloalkene gas ions such as cyclopentene; metal ions; organic silicon compound ions; and the like.
These ions may be used alone or in combination of two or more.
Among these, rare gases such as argon, helium, neon, krypton, and xenon can be used from the viewpoint that ions can be injected 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 amount of ions injected can be appropriately determined according to the purpose of use (required gas barrier property, transparency, etc.) of the gas barrier laminated film.
Examples of the method for implanting ions include a method of irradiating ions (ion beam) accelerated by an electric field, a method of implanting plasma ions in plasma (plasma ion implantation method), and the like, but the plasma ion implantation method is preferable. ..

In the plasma ion injection method, for example, plasma is generated in an atmosphere containing a plasma-generating gas such as a rare gas, and a negative high-voltage pulse is applied to the polymer layer to generate ions (cations) in the plasma. , Can be performed by injecting into the surface portion of the polymer layer.
As a more specific method of the plasma ion implantation method, it can be carried out by the method described in WO2010 / 107018 or the like.

By ion implantation, the thickness of the region where ions are implanted can be controlled by the implantation conditions such as the type of ions, applied voltage, and processing time, depending on the thickness of the polymer layer and the purpose of use of the gas barrier laminated film. It may be determined accordingly, but it is usually 10 to 400 nm.
Further, the injection of ions can be confirmed by performing elemental analysis measurement in the vicinity of 10 nm from the surface of the polysilazane layer using X-ray photoelectron spectroscopy (XPS).

[Functional layer]
The functional layer of the gas barrier laminate of the present invention is a layer formed from a composition that is directly laminated on one surface of the gas barrier layer and contains an amine compound.
In one aspect of the present invention, the thickness of the functional layer is appropriately selected depending on the type of function carried out by the functional layer and the type of the composition which is the forming material, but is preferably 50 nm to 200 μm, more preferably 100 nm. It is ~ 150 μm, more preferably 150 nm ~ 100 μm.

By appropriately preparing the types of the main agent resin and the amine-based compound contained in the composition of the forming material, the functional layer can be imparted with a function according to the use of the gas barrier laminate.

The functional layer formed from the composition containing the amine compound can maintain good interlayer adhesion with the gas barrier layer.
Further, even when another layer such as an organic layer containing an organic compound (for example, an adhesive layer, an adhesive layer of a release sheet, etc.) or a conductive layer made of ITO or the like is provided on the surface of the functional layer. The interlayer adhesion between the functional layer and other layers can also 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. Therefore, the adhesiveness can be improved.
Therefore, the functional layer has a function as an "adhesion improving layer".

As the organic layer laminated on the functional layer, from the viewpoint of efficiency of the sealing work of the object to be sealed such as an electronic device, and from the viewpoint of efficiently suppressing the intrusion of water vapor, oxygen, etc. into the object to be sealed. Therefore, an adhesive layer is preferable on the surface of the functional layer.
In general, when the gas barrier layer and the adhesive layer are directly laminated, the interlayer adhesion between the two layers tends to be inferior. On the other hand, 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 embodiment can effectively suppress the intrusion of water vapor, oxygen, and the like from between the layers of the two layers, and has excellent gas barrier properties.

When the gas barrier layer is a modified polymer layer, it is preferable that the functional layer is laminated on the surface side of the gas barrier layer that has been modified. The modified surface of the modified polymer layer has a high density and a high elastic modulus, and tends to have poor adhesion to the organic layer. Therefore, the adhesion to the organic layer is also good through the functional layer. It becomes.
In addition, when the modified polymer layer is formed from a composition for forming a gas barrier layer containing a polysilazane compound, nitrogen atoms are unevenly distributed on the surface of the modified polymer layer that has been modified. There is. Therefore, the functional layer formed from the composition containing the amine compound is more likely to have the effect of improving the interlayer adhesion with the modified polymer layer.
In other words, when the modified polymer layer is formed from a composition for forming a gas barrier layer containing a polysilazane compound, the modified polymer layer is modified and the element abundance ratio of nitrogen atoms is increased. It is preferable that the functional layer is laminated on more surfaces.

When the modified polymer layer is formed by applying a solution of the composition for forming a gas barrier layer on the surface of the base layer or the base material, the solution permeates the unevenness of the surface of the base layer or the base material. .. Therefore, the interlayer adhesion between the modified polymer layer and the base layer or the base material is usually good and does not pose a big problem.

As the amine compound contained in the composition which is a material for forming the functional layer, an amine silane coupling agent or a polyfunctional amine compound having two or more amino groups is preferable.
That is, the composition as the material for forming the functional layer is preferably the composition (I) or (II) shown below depending on the type of the amine compound.
A composition (I) containing an amine-based silane coupling agent as the amine-based compound.
A composition (II) containing a polyfunctional amine compound having two or more amino groups as the amine 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 preferable, and the following general formula (b) is preferable. The compound represented by -1) or (b-2) is more preferable.

In the general formula (b), ^R1 to R3 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 is a group represented by-(CH ₂ ) _p -NH- (CH ₂ ) _q -NH ₂ (p, q are integers of 1 or more (preferably 2 to 10). It is preferably 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 any of a primary amine, a secondary amine, and a tertiary amine, but is preferably a primary amine.
Examples of the amine-based silane coupling agent which is a primary amine include N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, and N-2. -Aminoethyl-3-aminopropyltriethoxysilane, N-2-aminoethyl-8-aminooctyltrimethoxysilane, N-2-aminoethyl-8-aminooctyltriethoxysilane, 3-aminopropyltrimethoxysilane, Examples thereof include 3-aminopropyltriethoxysilane.

Examples of the amine-based silane coupling agent which is a secondary amine or a tertiary amine include N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, and [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-dipropylaminopropyltrimethoxysilane , N, N-dipropylaminopropyltriethoxysilane, N, N-dibutylaminopropyltrimethoxysilane, N, N-dibutylaminopropyltriethoxysilane, N-methyl-N-ethylaminopropyltrimethoxysilane, N- Examples thereof include methyl-N-phenylaminopropyltrimethoxysilane, piperidinopropyltrimethoxysilane, morpholinopropyltrimethoxysilane, (4-methylpiperazino) propyltrimethoxysilane, N, N-dimethylaminopropylmethyldimethoxysilane and the like. ..
These amine-based silane coupling agents may be used alone or in combination of two or more.

The content of the amine-based silane coupling agent contained in the composition (I) is preferably 0.1 to 20% by mass, more preferably 0.1 to 20% by mass, based on the total amount (100% by mass) of the active ingredient of the composition (I). Is 0.2 to 15% by mass, more preferably 0.3 to 12% by mass, and even more preferably 0.4 to 10% by mass.

Examples of the polyfunctional amine compound contained in the composition (II) include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylylenediamine, paraxylylenediamine, and 1,3-bis (aminomethyl) cyclohexane. , Diaminodiphenylmethane, metaphenylenediamine and the like.
These polyfunctional amine compounds may be used alone or in combination of two or more.

The content of the polyfunctional amine compound contained in the composition (II) is preferably 25 to 80% by mass, more preferably 35 to 75% with respect to the total amount (100% by mass) of the active ingredient of the composition (II). It is by mass, more preferably 40 to 70% by mass.

The functional layer is preferably curable from the viewpoint of facilitating film formation by coating or printing. Therefore, it is preferable that the composition which is a material for forming the functional layer contains an energy ray curable resin or a thermosetting resin together with the amine compound.

The composition (I) containing the above-mentioned amine-based silane coupling agent may further contain an energy ray-curable resin and may be an energy ray-curable composition, or may further contain a thermosetting resin. The thermosetting composition may be used, but it is preferable that the composition further contains an energy ray-curable resin to prepare an energy ray-curable composition.

Further, the composition (II) containing the above-mentioned polyfunctional amine compound may further contain an energy ray curable resin and may be an energy ray curable composition, or may further contain a thermosetting resin and is thermoset. The composition may be used, but it is preferable that the composition further contains a thermosetting resin to prepare a thermosetting composition.

Hereinafter, the embodiment of the energy ray-curable composition and the embodiment of the thermosetting composition will be described in detail.

<Aspects of energy ray-curable composition>
The functional layer formed from the energy ray-curable composition has a function as an electrode embedding layer in which an auxiliary electrode layer formed on a part of one surface of the transfer base material of the electrode transfer sheet can be embedded.
The functional layer formed from the energy ray-curable composition is preferably in an uncured state before the auxiliary electrode layer is embedded.
For example, as shown in FIG. 1A, an auxiliary formed on a part of one surface of the transfer base material 51 of the electrode transfer sheet 50 on the surface of the functional layer 12 formed from the energy ray-curable composition. Consider the case of embedding the electrode layer 52. At this time, the functional layer formed from the energy ray-curable composition can easily incorporate the auxiliary electrode layer into the functional layer, and is excellent in the embedding property of the auxiliary electrode layer.
After that, the auxiliary electrode layer 52 is embedded in the functional layer 12, and then, as shown in FIG. 1B, energy rays are irradiated to cure the functional layer 12.
After curing, as shown in FIG. 1C, the transfer substrate 51 of the electrode transfer sheet 50 is peeled off from the surface of the cured functional layer 12. Here, depending on the type of the material for forming the functional layer 12, the functional layer 12 and the transfer base material 51 may be in close contact with each other, and the transfer base material 51 may be difficult to peel off.
On the other hand, by using the functional layer formed from the energy ray-curable composition, there is an advantage that the functional layer after curing can be easily peeled off from the transfer base material 51. In addition, the final curing of the functional layer improves the interlayer adhesion between the gas barrier layer and the functional layer, improves the shape retention of the functional layer, and fixes the auxiliary electrode layer without misalignment. This makes it easy to provide a conductive layer on the functional layer.
That is, since the functional layer formed from the energy ray-curable composition has properties such as excellent embedding property of the auxiliary electrode layer before curing and excellent peelability from the transfer substrate after curing, the electrode is embedded. It has an excellent function as a layer.

The energy ray-curable composition contains an amine compound and an energy ray-curable resin, and preferably further contains a photopolymerization initiator.

In the present specification, the energy ray has an energy quantum in an electromagnetic wave or a charged particle beam, and refers to active light such as ultraviolet rays, an electron beam, or the like.
The functional layer formed from the energy ray-curable composition undergoes a curing reaction by irradiating with the above-mentioned energy rays and is cured, but it is preferably cured by irradiating with ultraviolet rays.

In addition to the above-mentioned components, the energy ray-curable composition 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, coloring pigments and the like. The content of these additives may be appropriately determined according to the purpose.

In one aspect of the present invention, 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 ingredient of the energy ray-curable composition. , More preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more.

Further, in one aspect of the present invention, the total content of the amine compound, the energy ray-curable resin and the photopolymerization initiator is preferably relative to the total amount (100% by mass) of the active ingredient of the energy ray-curable composition. Is 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and even 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 μm from the viewpoint of further improving the interlayer adhesion and imparting the function as an electrode embedded layer. It is preferably 5 to 150 μm, more preferably 10 to 100 μm, and even more preferably 15 to 70 μm.
The thickness of the functional layer is preferably within the above range both before and after curing.

(Energy ray curable resin)
The energy ray-curable resin may be any resin in which the energy ray-polymerizable group is introduced into the main chain and / or the side chain of the resin and has an energy ray-polymerizable group.
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 a resin having an energy ray-polymerizable group.
Examples of the resin into which the energy ray-polymerizable group is introduced include acrylic resin, urethane resin, polyester resin, rubber resin and the like.
The energy ray-curable resin may be used alone or in combination of two or more.

Among these, the energy ray-curable resin used in one aspect of the present invention preferably contains an energy ray-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, and further 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 further preferably 80 with respect to the total amount (100% by mass) of the energy ray-curable resin. It is ~ 100% by mass, more preferably 90-100% by mass.

In one aspect of the present invention, the content of the energy ray-curable resin is preferably 60 to 99.8% by mass, more preferably 60% by mass, based on the total amount (100% by mass) of the active ingredient of the energy ray-curable composition. It is 70 to 99.5% by mass, more preferably 75 to 99.0% by mass, and even more preferably 80 to 99.0% by mass.

As described above, it is preferable that the composition (I) is an energy ray-curable composition containing an amine-based silane coupling agent and an energy ray-curable resin.
The content of the amine-based silane coupling agent in this case is as described above.
However, in one aspect of the present invention, the composition (I), which is an energy ray-curable composition, contains a coupling agent that does not correspond to an amine-based silane coupling agent as long as the effects of the present invention are not impaired. You may.

However, from the viewpoint of improving the interlayer adhesion between the formed functional layer and the gas barrier layer, the content of the coupling agent other than the amine-based silane coupling agent is preferably smaller.
The content of the coupling agent other than the amine-based coupling agent is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass with respect to 100 parts by mass of the total amount of the amine-based coupling agent in the composition (I). It is by mass, more preferably 0 to 5 parts by mass, and even more preferably 0 to 1 part by mass.

(Photopolymerization initiator)
The energy ray-curable composition preferably further contains a photopolymerization initiator.
By containing the photopolymerization initiator, the polymerization curing time can be shortened when the functional layer to be formed is cured, and the curing reaction of the functional layer can be sufficiently proceeded even if the amount of light irradiation is small. Can be made to.

Examples of the photopolymerization initiator include aromatic ketone compounds, benzoin compounds, benzoin ether compounds, benzyl compounds, ester compounds, aclysine compounds, 2,4,5-triarylimidazole dimer, alkylphenone compounds, and α-. Examples thereof include hydroxyalkylphenone-based compounds and phosphine oxide-based compounds.

More specific photopolymerization initiators include, for example, 1-hydroxycyclohexylphenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthium monosulfide, and azobisisobutyronitrile. , Dibenzyl, diacetyl, β-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.

In one aspect of the present invention, 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. Parts, more preferably 0.1 to 10 parts by mass, still more preferably 0.2 to 5 parts by mass.

<Aspects of thermosetting composition>
The functional layer formed from the thermosetting composition is a layer in which the curing reaction proceeds and is cured by the 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, coloring pigments and the like. The content of these additives may be appropriately determined according to the purpose.

In one aspect of the present invention, 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 ingredient of the thermosetting composition. It is more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and even 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, still more preferably 150 nm or more, and a portable terminal, from the viewpoint of further improving the interlayer adhesion. From the viewpoint of making it applicable to articles requiring miniaturization such as, it is preferably 700 nm or less, more preferably 500 nm or less, still more preferably 450 nm or less.

(Thermosetting resin)
The thermosetting resin may be any resin that can be cured by heating, for example, 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 curable triazine resin and thermosetting melamine resin.
These thermosetting resins may be used alone or in combination of two or more.

Among these, in one aspect of the present invention, the thermosetting resin preferably contains a thermosetting epoxy resin.
The functional layer formed from the thermosetting composition containing a thermosetting epoxy resin can maintain good interlayer adhesion with the gas barrier layer even in a high temperature and high humidity environment.

From the above viewpoint, the content ratio of the thermosetting epoxy resin is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably, with respect 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.

Examples of the thermosetting epoxy resin include compounds having thermocurability and having a plurality of epoxy groups in the molecule, specifically, an epoxy resin having a glycidylamino group derived from metaxylylene diamine. Epoxy resins with glycidylamino groups derived from 1,3-bis (aminomethyl) cyclohexane, epoxy resins with glycidylamino groups derived from diaminodiphenylmethane, glycidylamino groups or glycidyloxy groups derived from paraaminophenol. Epoxy resin having, 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, derived from resorcinol. Examples thereof include epoxy resins having a glycidyloxy group.
These thermosetting epoxy resins may be used alone or in combination of two or more.
Among these, as the thermosetting epoxy resin, an epoxy resin containing an aromatic ring in the molecule is preferable.

In one aspect of the present invention, the content of the thermosetting resin is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, based on the total amount (100% by mass) of the active ingredient of the thermosetting composition. %, More preferably 25 to 45% by mass.

As described above, it is preferable that the composition (II) is a thermosetting composition containing a polyfunctional amine compound and a thermosetting resin.
In this thermosetting composition, the polyfunctional amine compound also has a function as a curing agent.
The content of the polyfunctional amine compound is preferably 20 to 800 parts by mass, more preferably 50 to 600 parts by mass with respect to 100 parts by mass of the total amount of the thermosetting resin in the composition (II) which is a thermosetting composition. Parts, more preferably 100 to 400 parts by mass, still more preferably 150 to 300 parts by mass.

<Method of forming a functional layer>
The method for forming the functional layer is not particularly limited, but the composition which is the material for forming the functional layer is applied on the surface of the already formed gas barrier layer to form a coating film, and the coating film is dried. It is preferable to form.

In one aspect of the present invention, the composition which is the material for forming the functional layer containing the above-mentioned compositions (I) and (II) may be in the form of a solution by adding a solvent.
Examples of 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-based solvent such as butyl acetate; Cellosolve-based solvent such as ethyl cellosolve; Ether-based solvent such as 1,3-dioxolane; and the like.
These solvents may be used alone or in combination of two or more.

As a method for applying the composition which is a material for forming the functional layer, a wet coating method can be used, for example, a dipping method, a roll coat, a gravure coat, a knife coat, an air knife coat, a roll knife coat, a die coat, and screen printing. Examples include the method, spray coating, and gravure offset method.

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.

When a functional layer is formed using an energy ray-curable composition, the functional layer is formed through a drying step, and then the functional layer is photo-cured by irradiating the functional layer with energy rays such as ultraviolet rays to cure the functional layer. May be. As described above, the functional layer formed from the energy ray-curable composition may be uncured, and the functional layer may be cured after the auxiliary electrode layer is embedded in the functional layer.
Further, when the functional layer is formed by using the thermosetting composition, the coating film may be thermally cured in the drying step of the coating film formed from the thermosetting composition to form a cured functional layer.

[Base layer]
The gas barrier laminate of one aspect of the present invention may further have a base material layer on the surface side opposite to the side on which the functional layer of the gas barrier layer is laminated.
By having the base material layer, it is possible to obtain a gas barrier laminated body having excellent self-supporting property, which is advantageous in terms of handleability.

The base material layer is preferably composed of a resin film.
Examples of 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, and acrylic resin. Examples thereof include cycloolefin polymers and aromatic polymers.

Among these, from the viewpoint of excellent transparency, the base material layer is preferably composed of a resin film containing a resin selected from polyester, polyamide, and cycloolefin-based polymer, and is preferably composed of polyester and cycloolefin-based polymer. It is more preferably composed of a resin film containing the selected resin.

Examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate and the like, and polyethylene terephthalate and polyethylene naphthalate are preferable.
Examples of the polyamide include all aromatic polyamides, nylon 6, nylon 66, nylon copolymers and the like.
Examples of the cycloolefin-based polymer include norbornene-based polymers, monocyclic cyclic olefin-based polymers, cyclic conjugated diene-based polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Specific examples thereof include Apel (ethylene-cycloolefin copolymer manufactured by Mitsui Kagaku Co., Ltd.), Arton (norbornene-based polymer manufactured by JSR Corporation), Zeonoa (norbornene-based polymer manufactured by Zeon Corporation), and the like. ..

The resin film constituting the base material layer may 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, colorants, pigments and the like. The content of these additives may be appropriately determined according to the purpose.

The thickness of the base material layer is preferably 0.4 to 400 μm, more preferably 1 to 300 μm, still more preferably 5 to 200 μm, still more preferably 10 to 150 μm.

[Primer layer]
The gas barrier laminate of one aspect of the present invention may form a primer layer on the surface of the base material layer from the viewpoint of improving the interlayer adhesion with other layers laminated on the surface of the base material layer. ..
For example, by providing a primer layer between the base material layer and the gas barrier layer, the interlayer adhesion can be improved.
The primer layer may be a single layer or a plurality of layers in which two or more layers are laminated.

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 ray curable component or a thermosetting component.
Examples of the energy ray-curable component include an acrylic monomer or an acrylic resin having an energy ray-curable group in the side chain, a urethane monomer or a urethane resin having an energy ray-curable group in the side chain, and the like. ..
Examples of the thermosetting component include epoxy-based resins, polyimide-based resins, and phenol-based resins.

Further, the curable composition which is a material for forming the primer layer includes an inorganic filler, a photopolymerization initiator, an ultraviolet absorber, an antioxidant, a light stabilizer, an antioxidant, a silane coupling agent, and a colorant. Various additives such as a surfactant, a plasticizer, and an antifoaming agent may be contained.

As the material for forming the primer layer, a commercially available curable composition in which a curable component and a filler are previously mixed may be used.
Examples of such commercially available curable compositions include Opstar Z7530, Opstar Z7524, Opstar TU4086, Opstar Z7537 (trade names, all manufactured by JSR Corporation) and the like.

The thickness of the primer layer is preferably 0.01 to 50 μm, more preferably 0.1 to 30 μm, still more preferably 0.3 to 20 μm, and even more preferably 0.5 to 10 μm.

[Release sheet]
The gas barrier laminate according to one aspect of the present invention is provided with a release sheet from the viewpoint of imparting self-supporting property particularly when it does not have a base material layer and from the viewpoint of protecting the surface of a layer such as a functional layer. It may be configured.

Examples of the release sheet include a resin film having a release agent layer formed from a release agent such as a silicone-based release agent provided on the surface of the resin film. Further, a pressure-sensitive adhesive layer having low adhesiveness for temporarily adhering to the gas barrier laminate may be provided on the resin film.

In the case of a gas barrier laminate having a release sheet, a gas barrier layer is formed on the release treatment surface of the release sheet by the above method, and then a functional layer is formed on the gas barrier layer to efficiently perform a gas barrier. A sex laminate can be produced.

[Underground layer]
From the viewpoint of facilitating the separation between the release sheet and the gas barrier layer and preventing damage to the gas barrier layer, in the gas barrier laminate of one aspect of the present invention, a base layer 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 mentioned above.
Further, the curable composition which is a material for forming the base layer further includes a thermoplastic resin, an inorganic filler, a photopolymerization initiator, an ultraviolet absorber, an antioxidant, a light stabilizer, an antioxidant, and a silane coupling agent. , Colorants, surfactants, plasticizers, defoaming agents and the like may be contained.

The thickness of the base layer is not particularly limited, but is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

[Organic layer]
The gas barrier laminate of one aspect of the present invention may further have an organic layer on the surface of the functional layer.
The gas barrier laminate according to one aspect of the present invention efficiently suppresses the intrusion of water vapor, oxygen, etc. into the sealed object from the viewpoint of efficiency of the sealing work of the sealed object such as an electronic device. From this point of view, it is preferable to have an adhesive layer laminated on the surface of the functional layer as an organic layer.

The adhesive constituting the adhesive layer is appropriately selected depending on the intended use, 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, epoxy adhesives and the like.
When 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, it is referred to as a gas barrier layer. The interlayer adhesion of the above tends to be inferior.
On the other hand, the functional layer of the gas barrier laminate of the present invention has good interlayer adhesion with the adhesive layer composed of the above adhesive, and is therefore suitable for using the above adhesive. There is.

Specific examples of the adhesive include rubber-based pressure-sensitive adhesives, for example, polyisobutylene-based 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-based light stabilizers. And an adhesive composition comprising a hindered phenolic antioxidant and containing 5 to 100 parts by mass of the polybutene resin with respect to 100 parts by mass of the polyisobutylene resin.
Further, an adhesive composition containing an isoprene-based rubber having a carboxylic acid-based functional group, an isobutylene-based polymer having no carboxylic acid-based functional group, and an epoxy-based cross-linking agent can also be used.
Examples of the olefin-based thermosetting adhesive include those composed of an adhesive composition containing a modified olefin-based resin, a polyfunctional epoxy compound, and an imidazole-based curing catalyst, and examples of the modified polyolefin-based resin include acid modification. Examples thereof include Unistor manufactured by Mitsui Kagaku Co., Ltd., which is a polyolefin resin.

The thickness of the adhesive layer is appropriately set depending on the intended use, but is preferably 0.5 to 100 μm, more preferably 1 to 60 μm, and even more preferably 3 to 40 μm.

In the gas barrier laminate of one aspect of the present invention, when the functional layer, the adhesive layer, the gas barrier layer and the like are the outermost layers, these layers are protected from the viewpoint of protecting the surface of these layers and from the viewpoint of handleability. The above-mentioned release sheet may be further laminated on the surface of the layer.

[Sealed body]
The sealed body of the present invention is formed by sealing the electronic device to be sealed with the above-mentioned gas barrier laminated body of the present invention.
Examples of the electronic device to be sealed include a liquid crystal display, an organic EL light emitter, an inorganic EL light emitter, electronic paper, a solar cell, and the like. The organic EL light emitter and the inorganic EL light emitter are generally used for applications such as displays and lighting.
The gas barrier laminate of the present invention serves as a sealing material for sealing the electronic device which is the object to be sealed.

Examples of the structure of the sealed body of the present invention include those in which an electronic device, which is an object to be sealed, formed on a transparent substrate is sealed with the gas barrier laminated body of the present invention, which is a sealing material. ..
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. Further, a material having high blocking performance to block moisture and gas from the outside of the element and having excellent solvent resistance and weather resistance is preferable.
Specifically, transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetylcellulose, brominated phenoxy, aramids, polyimides, polystyrene. Classes, polyarylates, polysulfones, transparent plastics such as polyolefins, and the above-mentioned gas barrier film;
The thickness of the transparent substrate is not particularly limited, and can be appropriately selected in consideration of the light transmittance and the performance of blocking the inside and outside of the element.

[Conductive laminate]
As shown in FIG. 1 (d), the conductive laminate 100 of the present invention has an auxiliary electrode layer 52 and a conductive layer 60 on the surface side of the functional layer 12 of the gas barrier laminate of the present invention described above.
The auxiliary electrode layer 52 is embedded in the surface and the inside of the functional layer 12, and has a structure in which the conductive layer 60 is laminated on the surface of the functional layer 12 and the surface of the auxiliary electrode layer 52.

In the conductive laminate of one aspect of the present invention, the functional layer is preferably cured.
By using the cured functional layer, 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 also becomes easy to provide a conductive layer on the functional layer.

The sheet resistance value ρ _s measured from the conductive layer side of the conductive laminate of one aspect of the present invention is preferably 10.0 Ω / □ or less, more preferably 5.0 Ω / □ or less, still more preferably 1.0 Ω. / □ or less.
In addition, in this specification, a sheet resistance value ρ _s means a value measured by the method described in an Example.

Further, the water vapor permeability measured in an environment of 40 ° C. and a relative humidity of 90% of the conductive laminate according to one aspect of the present invention is preferably 5.0 g / (m ² · day) or less, more preferably 0. It is .5 g / (m ² · day) or less, more preferably 0.05 g / (m ² · day) or less, even more preferably 0.005 g / (m ² · day) or less, and usually 1.0. × ^10-6 g / (m ² · day) or more.

(Auxiliary electrode layer)
The auxiliary electrode layer has a function of lowering the sheet resistance value of the conductive laminate. In particular, when the conductive layer is a transparent conductive layer, it may be difficult to obtain a highly conductive transparent conductive layer. By providing the auxiliary electrode layer from a highly conductive material, the auxiliary electrode layer becomes conductive as the transparent conductive layer. It can supplement the sex.
When the conductive layer is a transparent conductive layer, the auxiliary electrode layer is preferably configured to have a patterned opening from the viewpoint of suppressing a decrease in the light transmittance of the transparent conductive layer.

The material of the auxiliary electrode layer is not particularly limited, but when patterning is performed using a method such as photolithography, a single metal such as gold, silver, copper, aluminum, magnesium, nickel, platinum, or palladium, or silver-palladium. , Silver-copper, silver-magnesium, aluminum-silicon, aluminum-silver, aluminum-copper, aluminum-titanium-palladium and other binary or ternary alloys.

Further, as the material of the auxiliary electrode layer, a conductive paste containing a conductive material can be used.
As the conductive paste, for example, a material obtained by dispersing metal fine particles such as silver, copper and aluminum, conductive fine particles such as carbon and ruthenium oxide, and a conductive carbon material such as metal nanowires and carbon nanotubes in a solvent is used. It may further have a binder component, and two or more kinds of conductive pastes may be mixed and used. An auxiliary electrode layer can be formed by printing, firing or curing this conductive paste.

The auxiliary electrode layer may be a single layer or a multilayer structure. The multi-layer structure may be a multi-layer structure in which layers made of the same type of material are laminated, or may be a multi-layer structure in which layers made of at least two or more types of materials are laminated.

The auxiliary electrode layer is preferably patterned, but the pattern shape includes, for example, a grid shape, a honeycomb shape, a comb tooth shape, a strip shape (striped shape), a straight line shape, a curved line shape, a wavy line shape (sign curve, etc.). ), Polygonal mesh, circular mesh, elliptical mesh, irregular shape and the like.

The thickness of the auxiliary electrode layer is preferably 10 nm to 20 μm, more preferably 100 nm to 15 μm, and even more preferably 1 μm to 10 μm.
The line width of the auxiliary electrode layer is preferably 0.1 to 100 μm, more preferably 1 to 80 μm, and even more preferably 5 to 60 μm.

(Conductive layer)
The conductive layer is preferably a transparent conductive layer.
Examples of the material of the transparent conductive layer include indium-tin oxide (ITO), indium-zinc oxide (IZO), aluminum-zinc oxide (AZO), gallium-zinc oxide (GZO), and indium-gallium-. Examples thereof include zinc oxide (IGZO), niobium oxide, titanium oxide, tin oxide and the like.
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 even more preferably 20 to 50 nm.

[Manufacturing method of conductive laminate]
The method for producing the conductive laminate of the present invention is not particularly limited, but from the viewpoint of productivity, a production method having the following steps (1) to (3) is preferable.
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. The process of embedding.
-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 surface of the cured functional layer.

The electrode transfer sheet 50 in which the auxiliary electrode layer 52 is formed on the transfer base material 51 as shown in FIG. 1 may be prepared in advance.
The transfer base material 51 is preferably made 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. Be done.
The material for forming the auxiliary electrode layer 52 is as described above.

As a method for forming the auxiliary electrode layer, after providing an auxiliary electrode layer in which a pattern is not formed on the transfer substrate, a known physical treatment or chemical treatment mainly using a photolithography method, or a combination thereof is used. A pattern of the auxiliary electrode layer is directly formed by a method of processing into a predetermined pattern shape, a screen printing method, a rotary screen printing method, a screen offset printing method, an inkjet method, an offset printing method, a gravure offset printing method, or the like. How to do it, etc.
As a method for forming an auxiliary electrode layer in which a pattern is not formed, a PVD method (physical vapor deposition method) such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, a thermal CVD method, or an ALD method (atomic layer vapor deposition method) is used. ), Etc., dry process such as CVD method (chemical vapor deposition method), dip coating method, spin coating method, spray coating method, gravure coating method, die coating method, doctor blade method, etc. Wet process, silver salt method and the like can be mentioned, and the method is appropriately selected depending on the material of the auxiliary electrode layer.

Hereinafter, the above steps (1) to (3) of the method for manufacturing a conductive laminate of the present invention will be described with reference to FIG. 1 as appropriate.

<Process (1)>
In the 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 the process of embedding.
In FIG. 1A, the electrode transfer sheet 50 is used to bond 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 to form a functional layer. It shows a state in which the auxiliary electrode layer 52 is embedded in the inside of 12.

Here, the functional layer of the gas barrier laminate used in this step is a layer formed from the above-mentioned energy ray-curable composition, and particularly contains an amine-based silane coupling agent and an energy ray-curable resin. It is preferably a layer formed from the composition (I).
As described above, the functional layer formed from the composition (I) is in an uncured state and has excellent embedding property of the auxiliary electrode layer, and after the functional layer is cured by the step (2), in the step (3). , It has properties such as excellent peelability when peeling the transfer substrate. Further, the functional layer 12 has good interlayer adhesion with the gas barrier layer 11.

The surface of the electrode transfer sheet 50 on the side provided with the auxiliary electrode layer 52 in this step and the surface of the functional layer 12 of the gas barrier laminate 1 may be bonded using a laminator.

<Process (2)>
The step (2) is a step of irradiating the functional layer with energy rays to cure the functional layer.
As shown in FIG. 1 (b), it is preferable to irradiate the energy rays from the base material layer 13 side of the gas barrier laminate 1.
As a method of irradiating energy radiation, for example, when 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.
Further, when irradiating an electron beam, it is preferable to irradiate the electron beam at an irradiation amount of 150 to 350 kV using an electron beam accelerator or the like.

When the electrode transfer sheet is used, after the functional layer is cured, the transfer base material 51 of the electrode transfer sheet 50 is peeled off from the cured functional layer 12 as shown in FIG. 1 (c).
Here, since the functional layer 12 is a layer formed from the energy ray-curable composition, the transfer base material 51 can be easily peeled off from the surface of the cured functional layer.

<Process (3)>
As shown in FIG. 1 (d), the step (4) is a step of providing the conductive layer 60 on the surface of the functional layer 12 exposed by peeling off the transfer substrate in the step (3).
As a method for forming the conductive layer, for example, physical vapor deposition such as resistance heating vapor deposition method, electron beam vapor deposition method, molecular beam epitaxy method, ion beam method, ion plating method, and sputtering method is used by using the above-mentioned conductive layer forming material. It can be formed by a method such as a vapor deposition method (PVD), a chemical vapor deposition method (CVD) such as a thermal CVD method, a plasma CVD method, an optical CVD method, an epitaxial CVD method, and an atomic layer CVD method.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

Production Example 1-1 (Preparation of a laminate composed of a 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 Industry Co., Ltd., product name "A-DPH") is dissolved in 100 parts by mass of methylisobutylketone. 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 composition for forming a primer layer.
Then, as the base material layer, a polyethylene naphthalate (PEN) film having a thickness of 100 μm (manufactured by Teijin Film Solution Co., Ltd., product name “PENQ65HW”) was used.
A solution of the above-mentioned primer layer forming composition is applied on one surface of the PEN film, which is the base material layer, by a bar coating method to form a coating film, and the coating film is applied at 70 ° C. at 1 ° C. Heat dried for minutes. Then, using a UV light irradiation line (Fusion UV Systems JAPAN, high-pressure mercury lamp; integrated light amount 100 mJ / cm ² , peak intensity 1.466 W, line speed 20 m / min, number of passes 2 times), the coating film after drying. Was cured by UV irradiation to form a primer layer having a thickness of 1 μm.

(2) Formation of Gas Barrier Layer As the composition for forming the gas barrier layer, a perhydropolysilazane-containing solution (manufactured by AZ Electronic Materials Co., Ltd., product name "AZNL110A-20", Rx, Ry, Rz in the general formula (1) is used. A solution containing perhydropolysilazane having a repeating unit that is a hydrogen atom) was used.
The above-mentioned perhydropolysilazane-containing liquid is applied on the surface of the primer layer formed in (1) above by a spin coating method to form a coating film, and the coating film is heated and dried at 120 ° C. for 2 minutes to thicken it. A first polymer layer having a thickness of 200 nm was formed.
Then, under the conditions described later, argon (Ar) was implanted into the surface of the formed first polymer layer by plasma ions to form a modified region, and this was used as the first modified polymer layer.
Next, on the exposed surface of the first modified polymer layer, the same perhydropolysilazane-containing liquid as above was used to form a second polymer layer having a thickness of 150 nm in the same manner as above. Then, on the surface of the second polymer layer, argon (Ar) was implanted with plasma ions under the same conditions to form a modified region to form a second modified polymer layer.
As described above, the gas barrier layer composed of the first modified polymer layer and the second modified polymer layer having the modified regions was formed.

[Conditions for plasma ion implantation]
Plasma ion implantation was performed on the surfaces of the first polymer layer and the second polymer layer using the following devices under the following implantation conditions.
(Plasma ion implanter)
-RF power supply: product name "RF56000", manufactured by JEOL Ltd.-High voltage pulse power supply: product name "PV-3-HSHV-0835", manufactured by Kurita Seisakusho (plasma ion implantation conditions)
・ Plasma generated gas: Ar
・ Gas flow rate: 100 sccm
-Duty ratio: 0.5%
-Repeat frequency: 1000Hz
-Applied voltage: -10kV
-RF power supply: frequency = 13.56MHz, applied power = 1000W
・ Chamber internal pressure: 0.2Pa
・ Pulse width: 5 sec
-Processing time (ion implantation time): 200 sec
・ Transport speed: 0.2m / min

Production Example 1-2 (Preparation of electrode transfer sheet)
As the transfer substrate, a polyethylene terephthalate (PET) film having a thickness of 100 μm (manufactured by Toyobo Co., Ltd., product name “PET A4100”, PET film having an easy-adhesion treatment on one surface) was used.
Using a screen printing machine (manufactured by Microtech Co., Ltd., product name "MT-320TV") and a screen plate having a honeycomb structure with a line width of 30 μm and a pitch of 1200 μm (printing area: length 100 mm × width 100 mm), the above Silver paste (manufactured by Mitsuboshi Belt Co., Ltd., product name "Low temperature fired conductive paste MDot (registered trademark)") is printed as ink on a part of the surface of the transfer substrate that has not been easily adhered, and is uncured. An auxiliary electrode layer was formed.
Then, the uncured auxiliary electrode layer is temporarily dried at 70 ° C. for 1 minute, then put into a conveyor type hot air / IR firing furnace, fired at 150 ° C. for 10 minutes, and the auxiliary electrode layer is formed. Formed.
The line width of the formed auxiliary electrode layer was 40 μm, and the thickness was 8 μm.

Examples 1-1 to 1-7, Comparative Examples 1-1 to 1-6
(1) Preparation of energy ray-curable composition Each component of the type and blending amount (active ingredient ratio) shown in Table 1 is added and mixed to prepare the energy ray-curable composition (IA) to (I). -G) and (Ia) to (IF) were prepared, respectively.

The details of each component shown in Table 1 used for the preparation of the compositions (IA) to (IG) and (IA) to (IF) are as follows.
<Energy ray curable resin>
"UV curable urethane resin (A-1)": manufactured by Nippon Synthetic Chemical Industry Co., Ltd., product name "UT5746", urethane resin having an ultraviolet polymerizable group, ethyl acetate solution having a solid content of 80% by mass.
-"UV curable urethane resin (A-2)": manufactured by Asia Industries, Ltd., product name "RUA-048", urethane resin having an ultraviolet polymerizable group.
<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-based silane coupling agent (b'-1)": manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM403", 3-glycidoxypropyltrimethoxysilane.
-"Mercapt-based 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.
-"Ureid-based silane coupling agent (b'-4)": manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBE585", 3-ureidopropyltrialkoxysilane.
<Photopolymerization initiator>
-"Photopolymerization Initiator (C-1)": manufactured by BASF, product name "Irgacure819", bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

(2) Formation of functional layer Prepared in (1) above on the surface of the gas barrier layer of the laminated body in which the base material layer / primer layer / gas barrier layer prepared in Production Example 1-1 are laminated in this order. The energy ray-curable composition was applied with an applicator to form a coating film, and the coating film was dried at 90 ° C. for 2 minutes to form a functional layer.
By these steps, a gas barrier laminated body formed by laminating a base material layer / a primer layer / a gas barrier layer / a functional layer in this order was obtained.

(3) Preparation of Conductive Laminate A conductive laminate was prepared by the procedure shown in FIG.
First, as shown in FIG. 1 (a), the functional layer 12 of the gas barrier laminate 1 produced in (2) above and the surface of the electrode transfer sheet 50 produced in Production Example 1-2 on the auxiliary electrode layer 52 side. And were bonded together with a laminator, the auxiliary electrode layer 52 was embedded in the functional layer 12, and the layers were laminated as shown in FIG. 1 (b).
Then, in the state shown in FIG. 1 (b), a conveyor type UV irradiator (manufactured by Heraeus, product name "CV-110Q-G", high-pressure mercury lamp) was used from the base material layer side of the gas barrier laminate. Ultraviolet rays (UV) were irradiated with an integrated light amount of 250 mJ / cm ² , and the functional layer 12 was cured with the auxiliary electrode layer 52 embedded. The thickness of the functional layer after curing was 25 μm.
Then, as shown in FIG. 1 (c), the transfer base material 51 was peeled off at the interface between the cured functional layer 12 and the transfer base material 51.
Finally, as shown in FIG. 1 (d), a thickness of 50 nm made of ITO (indium tin oxide) is formed on the surface of the functional layer on the side where the auxiliary electrode layer 52 is embedded by a sputtering method under the following conditions. A conductive layer was formed to obtain a conductive laminate.
[Conditions for film formation of conductive layer]
-Target: ITO (manufactured by JX Nippon Mining & Metals Co., Ltd., SnO ₂ content = 10% by mass)
・ Method: DC magnetron sputtering ・ Application method: DC500W
・ Substrate heating: None ・ Carrier gas: Argon (Ar)
・ Film formation pressure: 0.6Pa

The following evaluations and physical property values were measured for the conductive laminates produced in Examples and Comparative Examples. These results are shown in Table 1.

[Evaluation of interlayer adhesion]
From the conductive layer side of the produced conductive laminate, cross-cutting was performed with a width of 1 mm in a grid pattern of 10 squares in length × 10 squares in width = 100 squares so that the cutting edge reaches the gas barrier layer.
Next, the adhesive surface of the adhesive tape (manufactured by Nichiban Co., Ltd., product name "Cellotape (registered trademark)") is attached to the surface of the conductive layer cross-cut in a grid pattern, and JIS K5600-5-6 (cloth) is attached. A cellophane tape (registered trademark) peeling test was performed in accordance with the grid tape method of the cutting method).
Then, the interlayer adhesion of the conductive layer, the functional layer after curing, and the adhesion layer was evaluated according to the following criteria.
-"A": The classification of the evaluation results in Table 1 of JIS K 5600-5-6 is 0 to 2.
-"F": The classification of the evaluation results in Table 1 of JIS K 5600-5-6 is 3-5.
The interlayer adhesion was first evaluated for the conductive laminate after being stored for 24 hours in an environment of 23 ° C. and a relative humidity of 50%.
Then, only when the evaluation is "A", after performing a moist heat test such that the conductive laminate is stored in an environment of 60 ° C. and a relative humidity of 95% for 1000 hours, the conductive laminate is stored at 23 ° C. and a relative humidity of 50%. The interlayer adhesion was also evaluated for the conductive laminate stored in the environment for 24 hours.

[Sheet resistance value ρ _s ]
Measurement was performed from the conductive layer side of the conductive laminate using a non-contact resistance measuring device (manufactured by Napson Corporation, product name "EC-80P").

[Water vapor permeability]
Using a water vapor permeability meter (manufactured by MOCON, product name "AQUATRAN"), measure the water vapor permeability (unit: g / ( ^m2 · day)) of the conductive laminate at 40 ° C. and 90% relative humidity. did. The gas flow rate was 20 sccm.

According to Table 1, the conductive laminates produced in Examples 1-1 to 1-7 had excellent interlayer adhesion, as well as good conductivity and gas barrier properties.
On the other hand, 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 functional layer and the gas barrier layer after curing. Therefore, the process was completed without measuring the sheet resistance value and the water vapor permeability.

Production Example 2-1 (Preparation of a laminate composed of a base material layer / primer layer / gas barrier layer)
(1) Formation of Primer Layer As the base material layer, a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name "PET50A4300") having a thickness of 50 μm 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 onto one surface of this base material, a PET film, using a Meyer bar to form a coating film. Then, the coating film was dried at 70 ° C. for 1 minute. Then, using an electrodeless UV lamp system (manufactured by Heraeus), the dried coating film was cured by UV irradiation with an illuminance of 250 mW / cm ² and a light intensity of 170 mJ / cm ² , and a primer layer having a thickness of 1000 nm was applied. Formed.

(2) Formation of gas barrier layer As a composition for forming a gas barrier layer, a coating agent containing perhydropolysilazane as a main component (manufactured by Merck Performance Materials, product name "Aquamica NL110-20", in the above general formula (1). A xylene solution containing perhydropolysilazane having a repeating unit in which Rx, Ry and Rz are hydrogen atoms) was used.
On the surface of the primer layer formed in (1) above, the above coating agent, which is a composition for forming a gas barrier layer, is applied at a rotation speed of 3000 rpm using a spin coater (manufactured by Mikasa, product name "MS-A200"). The coating film was applied at a rotation time of 30 seconds to form a coating film, and the coating film was heated and dried at 120 ° C. for 2 minutes to form a polymer layer having a thickness of 150 nm.
Next, plasma ions were implanted into the formed polymer layer using a plasma ion implantation device under the following conditions to form a modified region, and a gas barrier layer composed of the modified polymer layer was formed.

[Conditions for plasma ion implantation]
(Plasma ion implanter)
-RF power supply: product name "RF56000", manufactured by JEOL Ltd.-High voltage pulse power supply: product name "PV-3-HSHV-0835", manufactured by Kurita Seisakusho (plasma ion implantation conditions)
・ Chamber internal pressure: 0.2Pa
・ Plasma generated gas: Argon ・ Gas flow rate: 100 sccm
・ RF output: 1000W
・ RF frequency: 1000Hz
・ RF pulse width: 50 μsec ・ RF delay: 25 n sec ・ DC voltage: -6 kV
・ DC frequency: 1000Hz
・ DC pulse width: 5 μs ・ DC delay: 50 μs ・ Duty ratio: 0.5%
-Processing time: 200 seconds

Example 2-1
(1) Preparation of Thermocurable Composition (II-1) The components of the following types were added in the blending amounts (active ingredient ratio) shown below, 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 (manufactured by Mitsubishi Gas Chemical Company, Inc., product name "Maxive M-100", solid content 100% by mass): 100 parts by mass (converted to active ingredient)
-Polyfunctional amine resin (manufactured by Mitsubishi Gas Chemical Company, product name "Maxive C-93T", solid content: 65.2% by mass): 209 parts by mass (converted to active ingredient)

(2) Formation of functional layer Prepared in (1) above on the surface of the gas barrier layer of the laminated body in which the base material layer / primer layer / gas barrier layer prepared in Production Example 2-1 are laminated in this order. The thermosetting composition (II-1) was applied using a Meyer bar to form a coating film, and the coating film was heated at 100 ° C. for 2 minutes to be cured to form a functional layer having a thickness of 300 nm. Formed.
By these steps, a gas barrier laminated body formed by laminating a base material layer / a primer layer / a gas barrier layer / a functional layer in this order was obtained.

Example 2-2
(1) Preparation of Energy Ray Curable Composition (IB) The following components are added in the following blending amount (active ingredient ratio), mixed, and the energy ray curable composition (IB) is added. ) 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 having a solid content of 80% by mass): 100 parts by mass (converted to active ingredient) )
-Amine-based silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM6803", N-2-aminoethyl-8-aminooctyltrimethoxysilane): 1.0 part by mass (converted to active ingredient)
-Photopolymerization initiator (manufactured by BASF, product name "Irgacure819", bis (2,4,6-trimethylbenzoyl) -phenylphosphin oxide): 1.5 parts by mass (converted to active ingredient)

(2) Formation of functional layer Prepared in (1) above on the surface of the gas barrier layer of the laminated body in which the base material layer / primer layer / gas barrier layer prepared in Production Example 2-1 are laminated in this order. The energy ray-curable composition (IB) was applied using an applicator to form a coating film, and the coating film was dried at 90 ° C. for 2 minutes.
A peeling-treated surface of a peeling film (manufactured by Lintec Corporation, product name "SP-PET38131") is attached to the surface of the coated film after drying, and a conveyor-type UV irradiator (manufactured by Heleus Co., Ltd., product) is attached from the base material layer side. Using the name "CV-110Q-G" (high pressure mercury lamp), an ultraviolet (UV) was irradiated with an integrated light amount of 250 mJ / cm ² to form a cured functional layer having a thickness of 20 μm.
After that, the release film was removed, and a gas barrier laminate was obtained by laminating the base material layer / primer layer / gas barrier layer / functional layer in this order.

Comparative Example 2-1
(1) Preparation of Functional Layer Forming Composition (II-2) The following components were added in the following blending amounts (active ingredient 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"): 100 parts by mass (converted to active ingredient)
-2-Propanol: 15 parts by mass

(2) Formation of functional layer Prepared in (1) above on the surface of the gas barrier layer of the laminated body in which the base material layer / primer layer / gas barrier layer prepared in Production Example 2-1 are laminated in this order. The composition for forming a functional layer was applied using a Meyer bar to form a coating film, and the coating film was heated at 150 ° C. for 3 minutes and dried to form a functional layer having a thickness of 1000 nm.
By these steps, a gas barrier laminated body formed by laminating a base material layer / a primer layer / a gas barrier layer / a functional layer in this order was obtained.

Comparative Example 2-2
A UV curable acrylate resin (manufactured by JSR Corporation, product name) is placed on the surface of the gas barrier layer of the laminate formed by laminating the base material layer / primer layer / gas barrier layer in this order, which was produced in Production Example 2-1. "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.
Ultraviolet rays (UV) on the surface of the coating film after drying using an electrodeless UV lamp system (manufactured by Heleus, product name "CV-110Q-G") with an illuminance of 250 mW / cm ² and a light intensity of 170 mJ / cm ² . ) Was irradiated to cure the coating film to form a functional layer having a thickness of 150 nm.
By these steps, a gas barrier laminated body formed by laminating a base material layer / a primer layer / a gas barrier layer / a functional layer in this order was obtained.

Comparative Example 2-3
The following "energy ray-curable composition (Ia)" was prepared, and a 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 Industries, Ltd., product name "RUA-048", urethane resin having an ultraviolet polymerizable group): 100 parts by mass (converted to active ingredient)
-Epoxy-based silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM403", 3-glycidoxypropyltrimethoxysilane): 1.0 part by mass (converted to active ingredient)
-Photopolymerization initiator (manufactured by BASF, product name "Irgacure819", bis (2,4,6-trimethylbenzoyl) -phenylphosphin oxide): 1.5 parts by mass (converted to active ingredient)

The gas barrier laminates produced in Examples and Comparative Examples were evaluated and the physical property values were measured as follows. These results are shown in Table 2.

[Evaluation of interlayer adhesion]
(Evaluation 1)
Using the prepared gas barrier laminate as a test piece, a cross-cut test based on JIS K 5600-5-6 was performed, and depending on the number of peeled cells, the gas barrier layer and the functional layer were separated according to the following criteria. The interlayer adhesion was evaluated.
・ "A": The number of peeled squares is 0 out of 100 squares.
・ "B": Out of 100 squares, the number of peeled squares is 1 to 49.
・ "C": The number of peeled squares is 50 to 100 out of 100 squares.
(Evaluation 2)
The prepared gas barrier laminate was allowed to stand in an environment of 85 ° C. and a relative humidity of 85% for 1000 hours to perform a wet test, and then a cross-cut test was conducted in the same manner as in "Evaluation 1" described above, according to the above criteria. The interlayer adhesion between the gas barrier layer and the functional layer after the wet test was evaluated.

[Water vapor permeability]
Using a water vapor permeability measuring device (manufactured by mocon, product name "PERMATRAN"), measure the water vapor permeability (unit: g / ( ^m2 · day)) of the gas barrier laminate at 40 ° C and 90% relative humidity. did. The gas flow rate was 10 sccm.

[Total light transmittance]
The total light transmittance of the gas barrier laminate was measured according to JIS K 7631-1.

[HAZE]
The HAZE of the gas barrier laminate was measured according to JIS K 7136.

From Table 2, the gas barrier laminates produced in Examples 2-1 and 2-2 had excellent interlayer adhesion between the gas barrier layer and the functional layer, and also had good gas barrier properties and transparency.
On the other hand, when 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, and the result was that it was easily peeled off.
In addition, the gas barrier laminates of Comparative Examples 2-2 and 2-3 were inferior in interlayer adhesion both before and after being placed under high temperature and high humidity conditions.

1 Gas barrier laminated body 11 Gas barrier layer 12 Functional layer 13 Base material layer 50 Electrode transfer sheet 51 Transfer base material 52 Auxiliary electrode layer 60 Conductive layer 100 Conductive laminated body

Claims (8)

It has a gas barrier layer and a functional layer directly laminated on one surface of the gas barrier layer.
The functional layer is a layer formed from a composition containing a composition (I) containing an energy ray-curable resin and an amine- based silane coupling agent as an amine- based compound .
The gas barrier layer is a modified polymer layer formed of a composition for forming a gas barrier layer containing a polymer compound composed of a polysilazane compound and having a modified region.
A gas barrier laminate having a total content of the energy ray-curable resin and the amine-based silane coupling agent of 70% by mass or more with respect to the active ingredient obtained by removing the solvent from the composition (I) . The gas barrier laminate according to claim 1 , wherein the content of the amine-based silane coupling agent is 0.1 to 20% by mass with respect to the total amount of the active ingredient of the composition (I). It has a gas barrier layer and a functional layer directly laminated on one surface of the gas barrier layer.
The functional layer is a gas barrier laminate, which is a layer formed from a composition containing an amine compound.
An adhesive layer is laminated on the functional layer on the side opposite to the gas barrier layer side, and the adhesive layer is laminated.
The gas barrier layer is a modified polymer layer formed of a composition for forming a gas barrier layer containing a polymer compound composed of a polysilazane compound and having a modified region.
The functional layer was formed from a composition (II) containing a composition (II) containing a polyfunctional amine compound having two or more amino groups and a thermosetting epoxy resin as the amine-based compound. A gas barrier laminate that is a layer. The gas barrier according to claim 3, wherein the adhesive layer is an adhesive layer composed of at least one selected from the group consisting of an acrylic adhesive, a urethane adhesive, a rubber adhesive, and an olefin adhesive. Sexual laminate. The gas barrier laminate according to claim 3 or 4 , wherein the content of the polyfunctional amine compound is 25 to 80% by mass with respect to the total amount of the active ingredient of the composition (II). The gas barrier laminate according to claim 1 or 2 , wherein an organic layer is further laminated on the surface of the functional layer. The gas barrier laminate according to claim 1 or 2 , wherein the functional layer has a function as an electrode embedding layer in which an auxiliary electrode layer can be embedded. A method for producing a gas barrier laminate with an auxiliary electrode, which comprises 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 claim 1 or 2 and embedding the auxiliary electrode layer inside 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 surface of the cured functional layer.

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