TW201902715A - Gas barrier laminate, sealing body, conductive laminate, and method for producing conductive laminate - Google Patents

Abstract

Provided is a gas barrier laminate that has a gas barrier layer and a functional layer which is directly laminated on one surface of the gas barrier layer, wherein the functional layer is formed from a composition that contains an amine-based compound. Said gas barrier laminate exhibits excellent inter-laminar adhesion between the gas barrier layer and the functional layer provided for imparting a specific function and has good gas barrier properties.

Description

Gas barrier laminated body, sealing body, conductive laminated body, and manufacturing method of conductive laminated body

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

In recent years, in order to reduce the thickness, weight, and flexibility of displays such as liquid crystal displays and electroluminescence (EL) displays, gas-repellent films have been used as substrates with electrodes instead of glass plates. Gas-barrier films are generally composed of a gas-barrier layer laminated on the surface of a resin film. In addition, a gas-barrier layered body is also developed on the surface of the gas-barrier layer, and other layers are laminated to give new functions.

For example, Patent Document 1 describes an adhesive sheet formed by forming an adhesive layer on the surface of a gas barrier layer of a substrate with a gas barrier layer. According to Patent Document 1, by using this adhesive sheet, electronic devices such as organic EL elements can be efficiently packaged. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2012/032907

[Problems to be Solved by the Invention]

As in the adhesive sheet described in Patent Document 1, a new layer having a specific function is laminated on the surface of the gas barrier layer of the gas barrier film, and a gas barrier laminate having the function can be obtained. Generally speaking, the gas barrier layer of a gas barrier film has a low affinity with an organic layer containing an organic compound. Therefore, even if an organic layer is provided on the gas barrier layer, the interlayer density between the gas barrier layer and the organic layer is low. Since the adhesion is poor, there is a problem that peeling between layers is liable to occur. In addition, when the interlayer adhesion between the gas barrier layer and the organic layer is poor, gas such as water vapor or oxygen can enter from between the two layers, and it becomes an important cause of deterioration of electronic devices such as organic EL elements.

An object of the present invention is to provide a gas barrier laminate having excellent interlayer adhesion between a gas barrier layer and a functional layer imparting a specific function and having good gas barrier properties, and an electronic device sealed with the gas barrier laminate. The resulting sealed body, a conductive laminated body using the gas-barrier laminated body, and a method for producing a conductive laminated body. [Means to solve the problem]

The present inventors have formed a functional layer from a composition containing an amine compound, and found that the gas barrier layered body can be used as a gas barrier laminate that can improve the adhesion between the functional layer and the gas barrier layer, and can solve the above-mentioned problems.

The present invention provides the following [1] to [15]. [1] A gas-barrier laminated body, which has a gas-barrier layer and a functional layer laminated directly on one surface of the gas-barrier layer; The aforementioned functional layer is a layer formed of a composition containing an amine compound. [2] The gas-barrier laminated body according to the above [1], wherein the gas-barrier layer is formed of a composition for forming a gas-barrier layer containing a polymer compound, and has a modified polymer having a modified region. Floor. [3] The gas-barrier laminated body according to [2] above, wherein the polymer compound is a polysilazane-based compound. [4] The gas barrier laminate according to any one of the above [1] to [3], wherein the functional layer is formed from a composition (I) containing an amine-based silane coupling agent as the amine-based compound Floor. [5] The gas-barrier laminate according to [4] above, wherein the content of the amine-based silane coupling agent is 0.1 to 20% by mass based on the total amount of the active ingredients of the composition (I). [6] The gas-barrier laminated body of the above-mentioned [4] or [5], wherein the composition (I) is an energy ray-curable resin. [7] The gas-barrier laminate according to any one of the above [1] to [3], wherein the functional layer is composed of a polyfunctional amine compound having two or more amine groups as the amine compound (II). [8] The gas-barrier laminate according to [7] above, wherein the content of the polyfunctional amine compound is 25 to 80% by mass based on the total amount of the active ingredients of the composition (II). [9] The gas-barrier laminated body 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 laminated body according to any one of the above [1] to [10], wherein an organic layer is further laminated on the surface of the functional layer. [12] The gas-barrier laminated body according to any one of the above [4] to [6], wherein the functional layer has a function as an electrode embedding layer capable of embedding an auxiliary electrode layer. [13] A method for manufacturing a gas-barrier laminated body with an auxiliary electrode, which has the following steps (1) to (3): (1) Step (1): bonding the auxiliary electrode layer with the gas-barrier as described in [6] above A step of burying the auxiliary electrode layer in the functional layer on the surface of the functional layer of the laminated body. Step (2): a step of irradiating the functional layer with energy rays to harden 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 functional layer after hardening. [Inventive effect]

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

[Configuration of Gas Barrier Layer] The gas barrier layer system 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 a gas barrier laminate having excellent self-supporting properties, a gas barrier laminate system according to one aspect of the present invention has a surface side opposite to a side of a functional layer having a gas barrier layer, and further has a substrate. The layers are better. The above-mentioned gas barrier laminated body with a base material may be provided on the surface side opposite to the side of the gas barrier layer laminated with a base material layer, further provided with an adhesive layer, a primer layer, and a hard layer. Composition of new layers such as coatings. Furthermore, an undercoat layer may be provided between the base material layer and the gas barrier layer.

The gas-barrier laminated body according to one aspect of the present invention may have a structure in which other layers are laminated on the surface of the functional layer. From the viewpoint of providing excellent interlayer adhesion from the functional layer, the structure of the further laminated organic layer is good. The organic layer may be a layer containing an organic compound such as a resin, and an adhesive layer is preferred.作为 As a gas-barrier laminated body provided with an adhesive layer, electronic devices and the like can be efficiently packaged, and at the same time, intrusion of water vapor or oxygen into electronic devices can be effectively suppressed. The organic layer other than the adhesive layer includes, for example, an adhesive layer and a quantum dot layer when the release sheet laminated on the functional layer is an adhesive layer.

A specific configuration example of the gas-barrier laminated body according to one aspect of the present invention includes the following aspects. (i) gas barrier layer / functional layer (ii) gas barrier layer / functional layer / adhesive layer (iii) substrate layer / gas barrier layer / functional layer (iv) substrate layer / undercoat layer / gas barrier layer / Functional layer (v) substrate layer / gas barrier layer / functional layer / adhesive layer (vi) substrate layer / undercoat layer / gas barrier layer / functional layer / adhesive layer (vii) adhesive layer / substrate layer / Gas barrier layer / Functional layer (viii) Adhesive layer / Substrate layer / Under coating layer / Gas barrier layer / Functional layer (ix) Primer layer / Substrate layer / Gas barrier layer / Functional layer (x) Primer Layer / substrate layer / primer layer / gas barrier layer / functional layer (xi) primer layer / substrate layer / gas barrier layer / functional layer / adhesive layer (xii) primer layer / substrate layer / primer layer Layer / gas barrier layer / functional layer / adhesive layer (xiii) hard coating / substrate layer / gas barrier layer / functional layer (xiv) hard coating / substrate layer / primer coating / gas barrier layer / functional layer (xv) Hard Coating / Substrate Layer / Gas Barrier Layer / Functional Layer / Adhesive Layer (xvi) Hard Coating / Substrate Layer / Bottom Coating / Gas Barrier Layer / Functional Layer / Adhesive Layer (xvii) Gas layer / function layer / quantum dot layer

In addition, in the above aspect, when the functional layer, the adhesive layer, and the gas barrier layer are the outermost layers, from the viewpoint of protecting the surface of these layers and improving self-supportability, it is excellent in usability. From the viewpoint of the gas-barrier laminated body, a peelable sheet that can be peeled off during use can be laminated on the surface of these layers. For example, the aspect (i) described above can be used as a gas barrier laminate having excellent self-supporting properties by providing a release sheet on the surface of at least one of the functional layer and the gas barrier layer. In addition, when a release sheet is provided on the surface of the gas barrier layer, the peeling property of the release sheet is good, and a configuration in which a base layer is provided between the gas barrier layer and the release sheet is preferred.

The adhesive layer may be provided on the functional layer side as described in (v) above, or may be provided on the substrate layer side as described in (vii) above. However, from the viewpoint of blocking gas such as water vapor or oxygen that has penetrated from the thick part of the base material layer with the gas barrier layer and preventing these gases from reaching the electronic device to be sealed, the function is as described in (v) above. A structure in which an adhesive layer is provided on the surface of the layer is preferable.

In addition, in the configuration in which the functional layer such as (i) above becomes the outermost layer, a conductive layer made of ITO or the like may be further provided on the surface of the functional layer as a conductive laminate.

Regarding the gas-barrier laminated body according to one aspect of the present invention, the total thickness at the time of use is preferably 1 to 600 μm, more preferably 5 to 200 μm, and still more preferably 20 to 100 μm. In addition, the "total thickness at the time of use" means the thickness of the gas-barrier laminate after removing a sheet provided to protect the outermost surface of the gas-barrier laminate.

The moisture vapor transmission rate of the gas-barrier laminate of one aspect of the present invention measured under an environment of 40 ° C and a relative humidity of 90% is preferably 5.0 g / (m ² ･ day) or less, and more preferably 0.5 g / (m ² ･ day) or less, more preferably 0.05 g / (m ² ･ day) or less, more preferably 0.005 g / (m ² ･ day) or less, and usually 1.0 × 10 ^-6 g / ( m ² ･ day) or more. In addition, in this specification, a water vapor transmission rate means the value measured by the method as described in an Example.

In one aspect of the present invention, the gas barrier laminated system is preferably one having excellent transparency. Specifically, the total light transmittance of the gas-barrier laminate of one aspect of the present invention is preferably 80% or more, more preferably 85% or more, and still more than 90%. In addition, in this specification, the total light transmittance is a value measured in accordance with JIS K 7361-1, and more specifically, a value measured by a method described in Examples.

Hereinafter, each layer of the gas-barrier laminated body of the present invention will be described.

[Gas-barrier layer] The gas-barrier layer of the gas-barrier laminate of the present invention is a layer having a property (hereinafter referred to as "gas-barrier") that suppresses the permeation of gas such as water vapor or oxygen.气 The gas barrier layer of the gas barrier laminated body according to one aspect of the present invention may be a single layer or a multilayer formed by stacking two or more layers.

The gas barrier layer of the gas barrier laminated body of one aspect of the present invention has a water vapor transmission rate measured under an environment of 40 ° C and a relative humidity of 90%, preferably 5.0 g / (m ² ･ day) or less. , More preferably 0.5 g / (m ² ･ day) or less, still more preferably 0.05 g / (m ² ･ day) or less, still more preferably 0.005 g / (m ² ･ day) or less, usually 1.0 × 10 ^-6 g / (m ² ･ day) or more.

The thickness of the gas barrier layer depends on the type of the material forming the gas barrier layer. It is appropriately set as described later, but it is preferably 1 nm to 50 μm, more preferably 3 nm to 2000 nm, still more preferably 5 to 1000 nm, and still more preferably 20 to 500nm. In addition, when the gas barrier layer is a multilayer formed by stacking two or more layers, the thickness of the multilayer is preferably within the above range.

From the viewpoint of more effectively improving the interlayer adhesion with the functional layer as the gas barrier layer, 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-deposited film formed by vapor-depositing an inorganic compound such as an inorganic nitride, an inorganic oxide nitride, or an inorganic oxide nitride carbide, and a gas barrier property including polyacrylonitrile. A gas barrier resin film of a resin, and a modified polymer layer formed of a composition containing a polysilazane compound and having a modified region.

Examples of the gas barrier layer include the following three aspects. (1) An inorganic vapor-deposited film obtained by vapor-depositing an inorganic compound. (2) A gas barrier resin film containing a gas barrier resin. (3) A modified polymer layer formed of a composition for forming a gas barrier layer containing a polymer compound and having a modified region. Among these, a thin film can be formed and a layer having excellent gas barrier properties can be formed. The gas barrier layer is preferably the inorganic vapor-deposited film of the above (1) or the modified polymer layer of the above (3). In addition, from the viewpoint of being a flexible gas-barrier laminated body, the modified polymer layer of the above (3) is more preferable. The following aspects (1) to (3) of the gas barrier layer are described in detail below.

(1) Inorganic vapor-deposited film formed by vapor-depositing an inorganic compound 中 In the gas-barrier laminated body according to one aspect of the present invention, an inorganic vapor-deposited film formed by vapor-depositing an inorganic compound can be applied. In addition, the inorganic vapor-deposited film may be a single layer formed by one layer, or a multilayer formed by stacking two or more layers.

The thickness of the inorganic vapor-deposited film used as the gas barrier layer is preferably from 1 to 2000 nm, more preferably from 3 to 1000 nm, still more preferably from 5 to 500 nm, and even more preferably from 40 to 500 in terms of gas barrier properties and operability. 200nm. In addition, when the inorganic vapor-deposited film is a multilayer composed of two or more layers, the thickness of the multilayer is preferably within the above range.

Inorganic compounds capable of forming an inorganic vapor-deposited film include, for example, inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, stannous oxide, and zinc tin oxide; silicon nitride, aluminum nitride, and nitride Inorganic nitrides such as titanium; inorganic carbides; inorganic sulfides; inorganic oxide nitrides such as silicon oxide nitride; inorganic oxide carbides; inorganic nitride carbides; inorganic oxide nitride carbides; aluminum, magnesium, zinc, And metals such as tin. These inorganic compounds may be used alone or in combination of two or more. Among these, an inorganic vapor-deposited film using an inorganic oxide, an inorganic nitride, or a metal as a raw material is preferable from the viewpoint of gas barrier properties, and an inorganic oxide or an inorganic nitride is used as a raw material from the viewpoint of transparency. An inorganic vapor-deposited film is preferable.

As a method for forming an inorganic vapor deposition film, a conventional method may be used, and examples thereof include a PVD method such as a vacuum evaporation method, a sputtering method, an ion coating method, or a CVD method such as a thermal CVD method, a plasma CVD method, and a photo CVD method. Method, atomic layer deposition method (ALD method).

(2) Gas-barrier resin film containing a gas-barrier resin 中 In the gas-barrier laminated body according to one aspect of the present invention, a gas-barrier resin film containing a gas-barrier resin can be used as the gas-barrier layer. The resin film may be a single layer formed of one layer or a multilayer formed of two or more layers.

From the viewpoint of gas barrier properties, the thickness of the gas barrier resin film used as the gas barrier layer is preferably 1 to 2000 nm, more preferably 3 to 1000 nm, still more preferably 5 to 500 nm, and still more preferably 40 to 200 nm. When the gas barrier resin film is a multilayer formed by stacking two or more layers, the thickness of the multilayer is preferably within the above range.

The gas-barrier resin is preferably a resin that does not penetrate easily, such as oxygen or water vapor. Specific examples include polyvinyl alcohol or a part of saponification thereof, ethylene-vinyl alcohol copolymer, polyacrylonitrile, and polyvinyl chloride. , Polyvinylidene chloride, polyvinyl chloride trifluoroethylene, etc. These gas barrier resins can be used alone or in combination of two or more.

The method of forming a gas barrier resin film includes a method of applying a solution containing a gas barrier resin on the release-treated surface of a release sheet or a substrate, forming a coating film, and drying the coating film. The coating method includes, for example, a spin coating method, a spray coating method, a bar coating method, a blade coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method. The drying method includes, for example, hot air drying, hot roll drying, and infrared irradiation.

(3) A modified polymer layer formed of a composition for forming a gas barrier layer containing a polymer compound and having a modified region. The gas barrier layered body of one aspect of the present invention can be used as a gas barrier layer. A modified polymer layer formed of a composition for forming a gas barrier layer containing a polymer compound and having a modified region is used.

In addition, the modified polymer layer may be a single layer formed by one layer or a multilayer formed by stacking two or more layers.

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 still more preferably 70 to 450 nm. In addition, when the modified polymer layer is a multilayer formed by stacking two or more layers, the thickness of the multilayer is preferably within the above range.

The composition for forming the gas barrier layer of the modified polymer layer forming material includes a polymer compound, but may also contain a hardener, an anti-aging agent, a light stabilizer, and a flame retardant as long as the effect of the present invention is not impaired. Additives for general use. However, the content of the polymer compound is preferably 50% by mass relative to the entire amount (100% by mass) of the modified high molecular weight or the total amount (100% by mass) of the active ingredient of the composition for forming the gas barrier layer. Above, more preferably 70% by mass or more, still more preferably 80% by mass or more, and even more preferably 90% by mass or more. In addition, in this specification, "active ingredient of a composition" means the component contained in the component of a target composition, and removing a solvent for dilution.

In this specification, a polymer compound means a compound having a specific 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, and more preferably 1,000 to 50,000.

Examples of the polymer compound include a silicon-containing polymer compound, polyimide, polyimide, polyimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, and polycarbonate. Ester, polyfluorene, polyetherfluorene, polyphenylene sulfide, polyaromatic ester, acrylic resin, alicyclic hydrocarbon resin, aromatic polymer, etc., are preferably silicon-containing polymer compounds. Examples of the silicon-containing polymer compound include a polysilazane-based compound, a polycarbosilane-based compound, a polysilane-based compound, a polyorganosiloxane compound, and a poly (disilanylenephenylene) -based compound. , And poly (spanylacetylene) compounds. These polymer compounds may be used alone or in combination of two or more kinds.

In one aspect of the present invention, a polysilazane-based compound is more preferred as the high-molecular compound based on the viewpoint that the gas-barrier layer further improves the gas-barrier property and has excellent interlayer adhesion with the functional layer. Polysilazane compounds can be used alone or in combination of two or more.

The polysilazane-based compound is a polymer having a repeating unit including -Si-N-bond (silazane bond) in the molecule, and specifically, has a repeating unit represented by the following general formula (1) Polymers are preferred. The number average molecular weight (Mn) of the polysilazane-based compound is preferably 100 to 50,000, and more preferably 1,000 to 50,000.

In the general formula (1), n represents the number of repeating units, and represents an integer of 1 or more. Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aromatic group Or alkylsilyl.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, An alkyl group having 1 to 10 carbon atoms such as neopentyl, n-hexyl, n-heptyl, and n-octyl.

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

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

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

Examples of the alkylsilyl group include trimethylsilyl, triethylsilyl, triisopropylsilyl, tri-t-butylsilyl, methyldiethylsilyl, and dimethyl Methylsilyl, diethylsilyl, methylsilyl, ethylsilyl 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 mercapto group; an epoxy group; an epoxy group; (Meth) acrylfluorenyloxy; unsubstituted or substituted aryl groups such as phenyl, 4-methylphenyl, and 4-chlorophenyl.

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; a methoxy group and an ethoxy group Alkoxy groups having 1 to 6 carbon atoms; nitro; cyano; hydroxy; mercapto; epoxy; glycidyloxy; (meth) acryloxy; phenyl; 4-methylbenzene And unsubstituted or substituted aryl groups such as 4-chlorophenyl and the like.

In one aspect of the present invention, Rx, Ry, and Rz are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and more preferably a hydrogen atom. The polysilazane-based compound contained in the modified polymer layer may be an inorganic polysilazane (perhydropolysilazane) in which all of Rx, Ry, and Rz in the general formula (1) are hydrogen atoms. ) May be an organic polysilazane in which at least one of Rx, Ry, and Rz is an organic group other than a hydrogen atom.

The polysilazane-based compound may be a modified polysilazane. Examples of the modified polysilazane include, for example, Japanese Patent Laid-Open No. 62-195024, Japanese Patent Laid-Open No. 2-84437, Japanese Patent Laid-Open No. 63-81122, Japanese Patent Laid-Open No. 1-138108, and Japanese Patent Laid-Open No. 2-38108. Gazette No. 175726, Gazette No. 5-238827, Gazette No. 5-238827, Gazette No. 6-122852, Gazette No. 6-306329, Gazette No. 6-299118, Gazette No. 9-31333 Those described in the Gazette, Japanese Patent Application Laid-Open No. 5-345826, Japanese Patent Application Laid-Open No. 4-63833, and the like. The polysilazane-based compound can also be used as a commercially available product such as a glass coating material.

The composition for forming a gas barrier layer may be in the form of a solution further containing an organic solvent. Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; and ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. ; Aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane; and alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane. These organic solvents can be used alone or in combination of two or more.

A method for forming a polymer layer from a composition for forming a gas barrier layer includes applying a solution of the composition for forming a gas barrier layer on a release-treated surface of a release sheet, and placing the solution on a surface of a base layer of the release sheet, And a method of forming a coating film on the surface of a substrate and drying the coating film. 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 doctor blade coating method, an air doctor blade coating method, a knife roller coating method, a die coating method, and a screen. Offset printing method, spray coating method, gravure transfer method, and the like. The method of drying the coating film includes hot air drying, hot roll drying, infrared irradiation, and the like, and conventionally known drying methods. The heating temperature is usually 80 to 150 ° C, and the heating time is usually tens of seconds to tens of minutes.

The modified polymer layer can be formed by applying a modification treatment to the surface of the formed polymer layer. (I) The modification treatment includes, for example, ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment. The technetium ion implantation process is a method of implanting accelerated ions into a polymer layer to modify the polymer layer to form a modified region, which will be described in detail later. (2) Plasma treatment is a method in which a polymer layer is placed in a plasma, and the polymer layer is modified to form a modified region. For example, the method can be performed according to the method described in Japanese Patent Application Laid-Open No. 2012-106421. (2) 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. For example, the method can be performed according to a method described in Japanese Patent Application Laid-Open No. 2013-226757. In these cases, the surface of the modified polymer layer is not roughened, and the modification to the inside thereof is efficiently performed, so that the gas barrier property can be further improved. The modification treatment is preferably an ion implantation treatment.

Ions implanted into the polymer layer include, for example, ions of rare gases such as argon, helium, neon, krypton, and xenon; fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur, and other ions; methane Ions of alkane-based gases such as ethane and ethane; ions of olefin-based gases such as ethylene and propylene; alkadienes of pentadiene and butadiene; acetylene-based gases such as acetylene Ionic ions; Ions of aromatic hydrocarbons such as benzene and toluene; Ions of cycloalkanes such as cyclopropane; Ions of cycloolefins such as cyclopentene; Ions of metals; Organic silicon compounds The ion and so on. These ions can be used alone or in combination of two or more. Among these, ions can be implanted more easily and a modified polymer layer having better gas barrier properties can be formed, and ions of rare gases such as argon, helium, neon, krypton, and xenon are preferred, and more Preferred is argon ion.

The amount of ion implantation can be appropriately determined in accordance with the purpose of use of the gas barrier laminated film (necessary gas barrier properties, transparency, etc.). The method of ion implantation includes a method of irradiating ions (ion beams) accelerated by an electric field, a method of implanting plasma ions in a plasma (plasma ion implantation method), and the like, but a plasma ion implantation method is preferred.

Plasma ion implantation, for example, can generate a plasma in an environment containing a plasma-generating gas such as a rare gas, and apply a negative high voltage pulse to a polymer layer to generate ions (cations) in the plasma. ) Injection is performed on the surface portion of the polymer layer. A more specific method of the plasma ion implantation method can be implemented by a method described in WO2010 / 107018 and the like.

By ion implantation, the thickness of the area where the ions are implanted can be controlled by the type of ions or the implantation conditions such as the applied voltage and processing time. It can be determined by the thickness of the polymer layer or the purpose of the gas barrier laminate film. , Usually 10 to 400 nm. In addition, ion implantation can be confirmed by X-ray photoelectron spectroscopy (XPS) and elemental analysis measurement of the surface of the polysilazane layer at about 10 nm.

[Functional layer] 气 The functional layer of the gas barrier laminated body of the present invention is a layer formed directly on one surface of the gas barrier layer and composed of a composition containing an amine compound. In one aspect of the present invention, the thickness of the functional layer may be appropriately selected according to the type of the function performed by the functional layer or the type of the material forming composition, and is preferably 50 nm to 200 μm, and more preferably 100 nm to 150 μm. , And more preferably 150 nm to 100 μm.

This functional layer is capable of imparting the function of using the gas-barrier laminated body by appropriately adjusting the types of the main resin and the amine compound contained in the composition forming the material.

The functional layer formed of a composition containing an amine compound can maintain good interlayer adhesion with the gas barrier layer. In addition, even when an organic layer containing an organic compound (for example, an adhesive layer, an adhesive layer for a release sheet, etc.) or a conductive layer made of ITO or the like is provided on the surface of the functional layer, the function is functional. The adhesion between the layers and other layers is also good. Therefore, the formed functional layer has excellent interlayer adhesion with the gas barrier layer and other layers (adhesive layer, conductive layer, etc.). Therefore, by interposing the functional layer between the two layers with poor interlayer adhesion, At the same time, the adhesion can be made good. Therefore, this function layer has a function as an "adhesion improvement layer".

The organic layer laminated on the functional layer is laminated on the surface of the functional layer from the viewpoint of the efficiency of the packaging operation of the packaging object such as an electronic device and the viewpoint of efficiently suppressing the intrusion of water vapor or oxygen into the packaging object. The adhesive layer is preferred. In general, when the gas barrier layer and the adhesive layer are directly laminated, the adhesion between the two layers tends to be poor. In contrast, the functional layer system and the gas barrier layer used in the present invention have excellent interlayer adhesion, and also have excellent interlayer adhesion with the adhesive layer. Therefore, the gas-barrier laminate of this aspect can effectively inhibit water vapor or oxygen from entering between 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 modified gas barrier layer after the modification treatment. The modified surface of the modified polymer layer has a high density, a high elastic modulus, and a tendency of poor adhesion to the organic layer. By intervening the functional layer, the adhesion to the organic layer also becomes good. . In addition, when the modified polymer layer is formed of a composition for forming a gas barrier layer containing a polysilazane compound, nitrogen atoms are unevenly distributed on the modified surface of the modified polymer layer. Therefore, the functional layer formed of the composition containing the amine compound can more easily obtain the effect of improving the adhesion between the layers and the modified polymer layer. In other words, when the modified polymer layer is formed of a composition for forming a gas barrier layer containing a polysilazane compound, the modified polymer layer is subjected to the modification treatment, and the element atomic ratio of nitrogen is greater. On the surface, the laminated functional layer is better.

In addition, when a solution of the composition for forming a gas barrier layer is applied on the surface of the base layer or the substrate to form a modified polymer layer, the solution penetrates into the unevenness on the surface of the base layer or the substrate. Therefore, the interlayer adhesion between the modified polymer layer and the base layer or the base material is usually good without major problems.

The amine compound contained in the composition of the functional layer forming material is preferably an amine silane coupling agent or a polyfunctional amine compound having two or more amine groups. In other words, the composition of the functional layer forming material is preferably the composition (I) or (II) shown below depending on the type of the amine compound. (Ii) 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 amine groups as the amine-based compound.

Examples of the amine-based silane coupling agent contained in the composition (I) include a silane compound having one or more amine groups, but a compound represented by the following general formula (b) is preferable, and the following general formula (b) is more preferable -1) or a compound represented by (b-2).

In the aforementioned general formula (b), R ¹ to R ³ are alkyl groups having 1 to 4 carbon atoms (preferably 1 to 2 carbon atoms). X is an organic group having an amine group, and a group represented by-(CH ₂ ) _p -NH- (CH ₂ ) _q -NH ₂ (p and q are integers of 1 or more (preferably integers of 2 to 10)) Alternatively, a base represented by-(CH ₂ ) _r -NH ₂ (r is an integer of 1 or more (preferably an integer of 2 to 10)) is preferred.

The amine-based silane coupling agent may be any of a primary amine, a secondary amine, and a tertiary amine, and is preferably a primary amine. Examples of the amine-based silane coupling agent of the primary amine include N-2-aminoethyl-3-aminopropylmethyldimethoxysilane and N-2-aminoethyl-3-aminopropyl Trimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, N-2-aminoethyl-8-aminooctyltrimethoxysilane, N-2- Aminoethyl-8-aminooctyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and the like.

Examples of amine-based silane coupling agents for secondary or tertiary amines include N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, [3- (2,4-dinitrophenylamino) propyl] triethoxysilane, N, N-dimethylaminopropyltrimethoxysilane, N, N-dimethylamino Propyltriethoxysilane, N, N-dimethylaminopropyltripropoxysilane, N, N-dimethylaminopropyltributoxysilane, N, N-dimethylamine Ethyl trimethoxysilane, N, N-diethylaminopropyltrimethoxysilane, N, N-diethylaminopropyltriethoxysilane, N, N-dipropylamino Propyltrimethoxysilane, N, N-dipropylaminopropyltriethoxysilane, N, N-dibutylaminopropyltrimethoxysilane, N, N-dibutylaminopropyl Triethoxysilane, N-methyl-N-ethylaminopropyltrimethoxysilane, N-methyl-N-phenylaminopropyltrimethoxysilane, piperidinylpropyltrimethoxy Silane, morpholinylpropyltrimethoxysilane, (4-methylpiperazino) propyltrimethoxysilane, N, N-dimethylaminopropylmethyldimethoxysilane WaitThese amine-based silane coupling agents may be used alone or in combination of two or more kinds.

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

Examples of the polyfunctional amine compound contained in the composition (II) include ethylenediamine, ethylenediamine, triethylenetetramine, tetraethyleneethylenepentamine, m-xylylenediamine, p-xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, diaminodiphenylmethane, m-phenylenediamine, and the like. These polyfunctional amine compounds may be used singly or in combination of two or more kinds.

The content of the polyfunctional amine compound contained in the composition (II) is relative to the total amount (100% by mass) of the effective ingredients of the composition (II), preferably 25 to 80% by mass, and more preferably 35 to 75% by mass And more preferably 40 to 70% by mass.

In addition, the functional layer is preferably one having hardenability from the viewpoint of easy film formation by coating or printing. Therefore, it is preferable that the composition of the material forming the functional layer includes an amine compound and an energy ray-curable resin or a thermosetting resin.

In addition, the composition (I) containing the amine-based silane coupling agent may further contain an energy ray-curable resin as an energy ray-curable composition, or may further contain a thermosetting resin as a thermosetting composition. It contains an energy ray-curable resin and is preferably used as an energy ray-curable composition.

In addition, the composition (II) containing the polyfunctional amine compound may further contain an energy ray-curable resin as an energy ray-curable composition, or may further contain a thermosetting resin as a thermosetting composition. Containing a thermosetting resin is preferred as a thermosetting composition.

Hereinafter, the aspect as an energy ray-curable composition and the aspect as a thermosetting composition will be described in detail.

<The appearance of the energy ray-curable composition> The functional layer formed of the energy ray-curable composition has an auxiliary electrode layer that can be embedded in a part of a surface of a transfer substrate formed on the electrode transfer sheet. Function of electrode buried layer. In addition, it is preferable that the functional layer formed of the energy ray-curable composition is uncured before being buried in the auxiliary electrode layer. For example, as shown in FIG. 1 (a), it is considered that a supplementary electrode formed on a surface of the functional layer 12 formed of the energy ray-curable composition and being part of one surface of the transfer substrate 51 of the electrode transfer sheet 50 is embedded. Case of layer 52. In this case, the functional layer formed of the energy ray-curable composition is easily incorporated into the auxiliary electrode layer, and the auxiliary electrode layer has excellent embedding properties. Then, after the auxiliary electrode layer 52 is buried in the functional layer 12, as shown in FIG. 1 (b), the energy layer is irradiated to harden the functional layer 12. After hardening, as shown in FIG. 1 (c), the transfer substrate 51 of the electrode transfer sheet 50 is peeled from the surface of the hardened functional layer 12. Here, depending on the type of the material forming the functional layer 12, the functional layer 12 and the transfer substrate 51 are in close contact, and the transfer substrate 51 may not be easily peeled. In contrast, as a functional layer formed of an energy ray-curable composition, the cured functional layer has an advantage that peeling from the transfer substrate 51 becomes easy. In addition, the functional layer is finally hardened, which can improve the adhesion between the gas barrier layer and the functional layer, improve the shape retention of the functional layer, and fix the auxiliary electrode layer without shifting the position, and set the conductive layer on the functional layer. Layers also become easy. In other words, the functional layer formed from the energy ray-curable composition has the characteristics of being excellent in embedding of the auxiliary electrode layer before curing, and having excellent peelability from the transfer substrate after curing. Excellent performance.

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

In this specification, the energy ray refers to those having an energy quantum among electromagnetic waves or charged particle beams, such as active light such as ultraviolet rays or electron beams.者 A functional layer formed of an energy ray-curable composition is preferably cured by irradiating the energy ray and performing a curing reaction, but it is preferably cured by irradiation of ultraviolet rays.

In addition, the energy ray-curable composition may further contain various additives in addition to the above components, as long as the effects of the present invention are not impaired. 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-based compound and the energy ray-curable resin is preferably 70% by mass or more with respect to the total amount (100% by mass) of the active ingredients of the energy-ray-curable composition. It is more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass or more.

Moreover, in one aspect of the present invention, the total content of the amine-based compound, the energy-ray-curable resin, and the photopolymerization initiator is preferably based on the total amount (100% by mass) of the active ingredients of the energy-ray-curable composition. It is 70 to 100 mass%, more preferably 80 to 100 mass%, still more preferably 90 to 100 mass%, and still more preferably 95 to 100 mass%.

In addition, the thickness of the functional layer formed from the energy ray-curable composition is more preferably 1 to 200 μm, and more preferably 5 to more preferably a viewpoint of improving the interlayer adhesion and a viewpoint of providing a function as an electrode embedding layer. 150 μm, more preferably 10 to 100 μm, and still more preferably 15 to 70 μm.厚度 The thickness of the functional layer, whether before or after hardening, is preferably within the above range.

(Energy-ray-curable resin) Energy-ray-curable resin is any resin as long as the energy-ray polymerizable group is introduced into the main chain and / or side chain of the resin and has an energy-ray polymerizable group. The fluorene energy ray polymerizable group may be any group having a carbon-carbon double bond that is energy ray polymerizable, and examples thereof include (meth) acrylic fluorene groups and vinyl groups. 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.树脂 Resins into which the energy ray polymerizable group is introduced include, for example, acrylic resins, urethane resins, polyester resins, and rubber resins. In addition, the energy ray-curable resin can be used alone or in combination of two or more kinds.

Among these, the energy ray-curable resin used in one aspect of the present invention preferably contains an energy ray-curable urethane-based 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 still more preferably 5,000 to 50,000.

The content ratio of the energy ray curable urethane resin is based on the total amount (100% by mass) of the energy ray curable resin, preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and more It is preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.

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

As described above, the composition (I) is preferably 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 at this time is as described above. However, in one aspect of the present invention, the composition (I) of the energy ray-curable composition may contain a coupling agent not corresponding to an amine-based silane coupling agent within a range that does not impair the effects of the present invention.

However, from the viewpoint of improving the adhesion between the formed functional layer and the gas barrier layer, the smaller the content of the coupling agent other than the amine-based silane coupling agent, the better. The content of the coupling agent other than the amine coupling agent is 100 parts by mass with respect to the entire amount of the amine coupling agent in the composition (I), preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass, and more It is 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 contains a photopolymerization initiator.含有 When the formed functional layer is hardened by containing a photopolymerization initiator, the polymerization hardening time can be shortened, and the hardening reaction of the functional layer can proceed sufficiently even if the amount of light irradiation is small.

Examples of the photopolymerization initiator include aromatic ketone compounds, benzoin compounds, benzoin ether compounds, benzyl compounds, ester compounds, acridine compounds, and 2,4,5-triarylthiouracil dimers. , Alkyl phenone-based compounds, α-hydroxyalkyl phenone-based compounds, phosphine oxide-based compounds, and the like.

More specific photopolymerization initiators include, for example, 1-hydroxycyclohexylphenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl diphenyl sulfide. , Tetramethylthiuram monosulfide, azobisisobutyronitrile, bibenzyl, diethylfluorenyl, β-chloroanthraquinone, bis (2,4,6-trimethylbenzyl) -benzene Based phosphine oxides and the like. These photopolymerization initiators can be used alone or in combination of two or more.

In one aspect of the present invention, the content of the photopolymerization initiator is 100 parts by mass relative to the entire amount of the energy ray-curable resin, preferably 0.01 to 15 parts by mass, more preferably 0.05 to 12 parts by mass, and even more preferably It is 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass.

<The aspect of a thermosetting composition> 之 The functional layer formed from a thermosetting composition is a layer which is hardened by performing a hardening reaction by heat treatment. The thermosetting composition contains an amine-based compound and a thermosetting resin, but may further contain various additives as long as the effect of the present invention is not impaired. 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.

Moreover, in one aspect of the present invention, the total content of the amine-based compound and the thermosetting resin is based on the total amount (100% by mass) of the active ingredients of the thermosetting composition, and is preferably 70 to 100% by mass. It is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass.

The thickness of the functional layer formed of the thermosetting composition further improves the adhesion between layers, and is preferably 50 nm or more, more preferably 100 n or more, and more preferably 150 nm or more. It is also applicable to From the viewpoint of articles requiring miniaturization, such as a mobile terminal, it is preferably 700 nm or less, more preferably 500 nm or less, and still more preferably 450 nm or less.

(Thermosetting resin) The thermosetting resin may be any resin that can be cured by heating. Examples of the thermosetting resin include thermosetting epoxy resin, thermosetting phenol resin, thermosetting unsaturated fluorene resin, and Curable cyanate resin, thermosetting isocyanate resin, thermosetting benzoxazine resin, thermosetting oxetane resin, thermosetting amine resin, thermosetting unsaturated polyester resin, thermosetting Allyl resin, thermosetting dicyclopentadiene resin, thermosetting silicone resin, thermosetting triazine resin, thermosetting melamine resin, and the like. These thermosetting resins can 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.的 The functional layer formed of a 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 point of view, the content ratio of the thermosetting epoxy resin is 50 to 100% by mass, more preferably 70 to 100% by mass, and more preferably 100% by mass relative to the total amount of the thermosetting resin. 80 to 100% by mass, and more preferably 90 to 100% by mass.

Examples of the thermosetting epoxy resin include compounds having thermosetting properties and a plurality of epoxy groups in a molecule, and specifically, a ring having an epoxypropylamine group derived from m-xylylenediamine. Epoxy resin, epoxy resin with epoxypropylamine derived from 1,3-bis (aminomethyl) cyclohexane, epoxypropylamine with diaminodiphenylmethane Epoxy resin based on p-aminophenol, epoxy resin with glycidylamino or propyleneoxy group derived from p-aminophenol, epoxy resin with glycidoxy group derived from bisphenol A, Epoxy resin with propylene oxide derived from bisphenol F, epoxy resin with propylene oxide derived from phenol novolac, epoxy resin with propylene oxide derived from resorcinol Epoxy. These thermosetting epoxy resins can be used alone or in combination of two or more. Among these, the thermosetting epoxy resin is preferably an epoxy resin containing an aromatic ring in the molecule.

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

As described above, the composition (II) is preferably a thermosetting composition containing a polyfunctional amine compound and a thermosetting resin. In addition, in this thermosetting composition, the polyfunctional amine compound also has a function as a hardener. The content of the polyfunctional amine compound is preferably 20 to 800 parts by mass, and 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) of the thermosetting composition. It is more preferably 100 to 400 parts by mass, and still more preferably 150 to 300 parts by mass.

<Method for forming functional layer> 方法 The method for forming the functional layer is not particularly limited, but the composition of the material for forming the functional layer is coated on the surface of the formed gas barrier layer to form a coating film, and the coating film is dried The formation is better.

In one aspect of the present invention, a composition containing a material for forming a functional layer of the above-mentioned compositions (I) and (II) may be added with a solvent as a solution form. Examples of the solvent include aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, Halogenated hydrocarbon solvents such as 1,2-dichloroethane and monochlorobenzene; alcohol solvents such as methanol, ethanol, propanol, butanol, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, 2-pentyl Ketone solvents such as ketones, isophorone, and cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; cellulose solvents such as ethyl cellosolve; 1,3-dioxane Ether solvents such as pentane. These solvents can be used alone or in combination of two or more.

The coating method for the composition of the functional layer forming material can be a wet coating method, and examples thereof include dipping, roll coating, gravure coating, doctor blade coating, air doctor blade coating, roller doctor blade coating, and die coating. Coating, screen printing, spray coating, gravure transfer, etc.

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, and more preferably 1 to 7 minutes.

When forming a functional layer using an energy ray-curable composition, the functional layer is irradiated with energy rays such as ultraviolet rays after the drying step to form the functional layer, so that the light is hardened and can be used as a hardened functional layer. As described above, the functional layer formed of the energy ray-curable composition is not hardened, and the functional layer may be hardened after the auxiliary electrode layer is buried in the functional layer. In addition, when the functional layer is formed using a thermosetting composition, the coating film may be thermally cured in the drying step of the coating film formed from the thermosetting composition as a hardened functional layer.

[Substrate layer] 气 The gas-barrier laminated body according to one aspect of the present invention may further include a substrate layer on the surface side opposite to the side where the functional layer having the gas-barrier layer is laminated.具有 By having a base material layer, it can be used as a gas barrier laminate having excellent self-supporting properties, and has advantages in terms of usability.

The substrate layer is preferably composed of a resin film. Examples of the resin contained in the resin film include polyimide, polyimide, polyimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, Polyfluorene, polyetherfluorene, polyphenylene sulfide, acrylic resins, cycloolefin-based polymers, aromatic polymers, and the like.

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 a cycloolefin-based polymer, and more preferably a resin film containing Resin film of polyester and cycloolefin-based polymer resin.

Examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyaromatic ester, and the like, and polyethylene terephthalate and polyethylene terephthalate are preferred. Polyethylene naphthalate. As the polyfluorene, a fully aromatic polyamine, nylon 6, nylon 66, nylon copolymer, etc. are mentioned. Cycloolefin-based polymers 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 made by Mitsui Chemicals), ARTON (norbornene polymer made by JSR Corporation), ZEONOR (norbornene polymer made by Japan Zeon Corporation), and the like .

The resin film constituting the base material layer may contain various additives as long as the effect of the present invention is not impaired. Various additives include, for example, 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 substrate layer is preferably 0.4 to 400 μm, more preferably 1 to 300 μm, still more preferably 5 to 200 μm, and still more preferably 10 to 150 μm.

[Undercoating layer] 气 The gas-barrier laminated body according to one aspect of the present invention may be applied to the surface of the base material layer from the viewpoint of good adhesion between layers and other layers laminated on the surface of the base material layer. An undercoat is formed. For example, by providing an undercoat layer between the substrate layer and the gas barrier layer, the adhesion between layers can be improved. In addition, the undercoat layer may be a single layer or a multilayer formed by laminating more than two layers.

The undercoat layer can be formed by hardening a layer made of a hardenable composition containing a hardenable component. The hardenable component may be an energy ray-curable component or a thermosetting component. The energy ray-curable component includes, for example, an acrylic monomer or an acrylic resin having an energy ray-curable group in a side chain, or a urethane-based monomer or an amine group having an energy-ray-curable group in a side chain. Formate resin and the like. The thermosetting component includes epoxy resin, polyimide resin, phenol resin, and the like.

The curable composition of the material for forming the undercoat layer may further contain an inorganic filler, a photopolymerization initiator, an ultraviolet absorber, an antioxidant, a light stabilizer, an antistatic agent, a silane coupling agent, a colorant, Various additives such as surfactants, plasticizers, and defoamers.

As the material for forming the undercoat layer, a commercially available curable composition prepared in advance with a curable component and a filler may be used. Such commercially available hardening compositions include, for example, OPSTAR Z7530, OPSTAR Z7524, OPSTAR TU4086, OPSTAR Z7537 (both are trade names, manufactured by JSR Corporation), and the like.

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

[Peeling sheet] 气 The gas-barrier laminated body according to one aspect of the present invention may be provided with peeling from the viewpoint of providing self-supporting properties and the viewpoint of protecting the surface of layers such as a functional layer when the base layer is not provided. Composition of flakes.

The release sheet may include a release agent layer formed of a release agent such as a silicone-based release agent on the surface of the resin film. In addition, a resin film may be provided with a low-adhesive adhesive layer to be temporarily adhered to the gas-barrier laminated body.

In the case of a gas barrier laminate having a release sheet, a gas barrier layer is formed by the above method on the peeling treatment surface of the release sheet, and then a functional layer is formed on the gas barrier layer, so that a gas barrier laminate can be efficiently manufactured. .

[Base layer] From the viewpoint of easy peeling of the release sheet and the gas barrier layer, the prevention of damage to the gas barrier layer, and the like, the gas barrier laminate of one aspect of the present invention is provided between the release sheet and the gas barrier layer. The base layer is preferred. The base layer is preferably a cured product of a layer formed of a curable composition containing an energy curable resin. Examples of the energy curable resin include the above. In addition, the hardening composition of the base layer forming material may further contain a thermoplastic resin, an inorganic filler, a photopolymerization initiator, an ultraviolet absorber, an antioxidant, a light stabilizer, an antistatic agent, a silane coupling agent, and a colorant. , Surfactants, plasticizers, defoamers and other additives.

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] 气 The gas barrier laminated body according to one aspect of the present invention may further have an organic layer on the surface of the functional layer. In addition, the gas-barrier laminated body according to one aspect of the present invention is based on the viewpoint of the efficiency of the packaging operation of the packaging object such as an electronic device, and the viewpoint of efficiently suppressing the intrusion of water vapor or oxygen into the packaging object. A structure in which an adhesive layer as an organic layer is further laminated on the surface of the functional layer is preferable.

The adhesive constituting the adhesive layer may be appropriately selected depending on the application, and may be a pressure-sensitive adhesive or a thermosetting adhesive. Specific adhesives include, for example, acrylic adhesives, urethane adhesives, silicone adhesives, rubber adhesives, olefin adhesives, and epoxy adhesives. When an adhesive layer composed of an adhesive selected from the group consisting of an acrylic adhesive, a urethane adhesive, a rubber adhesive, and an olefin adhesive is directly provided on the gas barrier layer, Poor adhesion to the gas barrier layer. In contrast, the functional layers of the gas-barrier laminate of the present invention and the adhesive layer composed of the above-mentioned adhesive also have good interlayer adhesion, and thus are suitable for the case where the above-mentioned adhesive is used.

Specific examples of the adhesive agent include rubber-based pressure-sensitive adhesives, for example, a polyisobutylene resin containing a weight average molecular weight of 300,000 to 500,000, a polybutene resin having a weight average molecular weight of 1,000 to 250,000, A hindered amine-based light stabilizer and a hindered phenol-based antioxidant are each composed of an adhesive composition characterized by containing 5 to 100 parts by mass of the aforementioned polybutene resin relative to 100 parts by mass of the aforementioned polyisobutylene resin. In addition, an adhesive composition containing an isoprene-based rubber having a carboxylic acid functional group, an isobutylene-based polymer not having a carboxylic acid functional group, and an epoxy crosslinking agent may be used. Examples of olefin-based thermosetting adhesives include those formed from an adhesive composition containing a modified olefin-based resin, a polyfunctional epoxy compound, and a thiouracil-based curing catalyst, and modified polyolefin-based resins. For example, acid modified polyolefin resin, such as unistole manufactured by Mitsui Chemicals.

The thickness of the adhesive layer is appropriately set according to the application, and is preferably 0.5 to 100 μm, more preferably 1 to 60 μm, and still more preferably 3 to 40 μm.

When the functional barrier layer, the adhesive layer, and the gas barrier layer and the like are the outermost layers of the gas barrier multilayer system according to one aspect of the present invention, the viewpoint of protecting the surface of these layers and the viewpoint of usability may be here. The surface of the equal layer is further laminated with the above-mentioned release sheet.

[Sealing body] 密封 The sealing system of the present invention is obtained by encapsulating an electronic device of a package with the gas barrier laminate of the present invention. The electronic device to be encapsulated includes, for example, a liquid crystal display, an organic EL light emitter, an inorganic EL light emitter, an electronic paper, and a solar cell. It is generally used for applications such as organic EL light emitters, inorganic EL light emitters, displays, and lighting.气 The gas-barrier multilayer system of the present invention serves as a function of a packaging material for an electronic device that encapsulates the packaged object.

The structure of the sealing body of the present invention includes an electronic device in which a packaged material of the gas-barrier laminated body of the present invention is used to package an electronic device to be packaged on a transparent substrate. The transparent substrate is not particularly limited, and various substrate materials can be used. In particular, a substrate material having a high transmittance of visible light is used. In addition, a material having a high blocking performance against moisture or gas to be infiltrated from the outside of the device and excellent in solvent resistance and weather resistance is preferred. Specific examples include transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, and polyphenylene sulfide , Polyvinylidene fluoride, ethyl cellulose, brominated phenoxy, aromatic polyamines, polyimines, polystyrenes, polyaromatic esters, polyfluorenes, polyolefins, etc. Transparent plastic, the aforementioned gas barrier film. The thickness of the transparent substrate is not particularly limited. It can be appropriately selected in consideration of the light transmittance or 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 is provided on the surface side of the functional layer 12 of the gas barrier laminate of the present invention, and has an auxiliary electrode layer 52 and a conductive layer. 60. In addition, the auxiliary electrode layer 52 is embedded in the surface and the inside of the functional layer 12, and a conductive layer 60 is laminated on the surface of the functional layer 12 and the surface of the auxiliary electrode layer 52.

In one aspect of the present invention, it is preferable that the functional layer is hardened. As a hardened functional layer, the adhesion between the gas barrier layer and the functional layer is good, and at the same time, the shape retention of the functional layer is improved, and the auxiliary electrode layer can be fixed without displacement, and it can also be easily applied to the functional layer. Provide a conductive layer.

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

In addition, in one aspect of the present invention, the water vapor transmission rate measured under the 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, 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 reducing the sheet resistance of the conductive laminate. In particular, when the conductive layer is a transparent conductive layer, it is sometimes difficult to obtain a transparent conductive layer having high conductivity. Providing a supplementary electrode layer with a highly conductive material may supplement the conductivity of the transparent electrode layer as the supplementary electrode layer. In addition, when the conductive layer is a transparent conductive layer, from the viewpoint of suppressing a decrease in light transmittance of the transparent conductive layer, it is preferable that the auxiliary electrode layer be patterned and provided with an opening.

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, palladium, silver-palladium, Silver-copper, silver-magnesium, aluminum-silicon, aluminum-silver, aluminum-copper, aluminum-titanium-palladium, etc. 2- to 3-element alloys.

As the material of the auxiliary electrode layer, a conductive paste containing a conductive material can be used. As the conductive paste, for example, metal fine particles of silver, copper, aluminum, etc., conductive fine particles of carbon, ruthenium oxide, or conductive carbon materials such as metal nanowires, carbon nanotubes, etc. may be used. It also has a binder component, and it is also possible to mix and use two or more types of conductive paste. By printing this conductive paste, the auxiliary electrode layer can be formed by firing or hardening.

The auxiliary electrode layer may be a single layer or a multilayer structure. The multilayer structure may be a multilayer structure in which layers made of the same material are laminated, or a multilayer structure in which layers are formed of at least two kinds of materials.

The auxiliary electrode layer is preferably patterned, but the pattern shape includes, for example, a lattice shape, a honeycomb shape, a comb-tooth shape, a strip shape (stripe: Stripe), a straight shape, a curved shape, and a wave shape (sine). Sine curves, etc.), polygonal meshes, circular meshes, oval meshes, irregular shapes, etc.

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 still 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-zinc. Oxide (IGZO), niobium oxide, titanium oxide, stannous oxide, etc. These can be used alone or in combination of two or more.

The thickness of the conductive layer is preferably 5 to 200 nm, more preferably 10 to 100 nm, and still more preferably 20 to 50 nm.

[Manufacturing method of conductive laminated body] 方法 The manufacturing method of the conductive laminated body of the present invention is not particularly limited, but from the viewpoint of productivity, a manufacturing method having the following steps (1) to (3) is preferred. ･ Step (1): bonding the auxiliary electrode layer and the surface of the functional layer of the gas barrier laminate having a functional layer formed of an energy ray-curable composition, and burying the auxiliary electrode layer in the functional layer Internal steps. ･ Step (2): a step of irradiating the functional layer with energy rays to harden 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 functional layer after hardening.

Further, as shown in FIG. 1, an electrode transfer sheet 50 having an auxiliary electrode layer 52 formed on a transfer substrate 51 is prepared in advance. The transfer substrate 51 is preferably a resin film, and examples thereof include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polypropylene, and polymethylpentene. Polyolefin film, polycarbonate film, polyvinyl acetate film, etc. The material for forming the auxiliary electrode layer 52 is as described above.

The method for forming the auxiliary electrode layer may include providing a patterned auxiliary electrode layer on a transfer substrate, and then performing a known physical treatment or chemical treatment with a photolithography method as the main body, or a combination of them. A method of processing into a specific pattern shape, or by a screen printing method, a rotary screen printing method, a screen offset printing method, an inkjet method, a lithographic method, a gravure method A method such as a lithography method in which a pattern of an auxiliary electrode layer is directly formed. Examples of the method for forming the auxiliary electrode layer without a pattern include a PVD method (physical vapor growth method) such as a vacuum evaporation method, a sputtering method, and an ion coating method; a thermal CVD method; and an ALD method (atomic layer vapor deposition). Method), dry process such as CVD method (chemical vapor growth method), or dip-coating method, spin coating method, spray coating method, gravure coating method, die coating method, doctor blade coating method Wet processes such as various coating or electrodeposition (electrodeposition) methods, silver salt methods, and the like are suitable for the material of the auxiliary electrode layer.

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

<Step (1)> (1) Step (1) is to attach the auxiliary electrode layer and the surface of the functional layer of a gas barrier laminate having a functional layer formed of an energy ray-curable composition, and bury the auxiliary electrode layer. Steps inside the aforementioned functional layer. FIG. 1 (a) shows an electrode transfer sheet 50 bonded together, a surface on the side of the auxiliary electrode layer 52 provided with the electrode transfer sheet 50, and a surface of the functional layer 12 of the gas barrier laminate 1, and the auxiliary electrode layer is shown. 52 is a state buried in the functional layer 12.

Here, the functional layer of the gas-barrier laminated body used in this step is a layer formed of the above-mentioned energy ray-curable composition, and particularly a composition (I) containing an amine-based silane coupling agent and an energy-ray-curable resin. The layer formed is preferred. As described above, the functional layer formed from the composition (I) is in an unhardened state, and the auxiliary electrode layer has excellent embedding properties. At the same time, after the functional layer of the step (2) is hardened, the functional layer is formed in the step (3). It has properties such as excellent peelability when peeling off the transfer substrate. The interlayer adhesion between the functional layer 12 and the gas barrier layer 11 is also good.

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

<Step (2)> Step (2) is a step of irradiating the functional layer with energy rays to harden the functional layer. The energy ray irradiation is preferably performed from the base material layer 13 side of the gas barrier laminate 1 as shown in FIG. 1 (b). As a method of irradiating energy radiation, for example, when irradiating ultraviolet rays, a high-pressure mercury lamp, a Fusion H lamp, a xenon lamp, or the like is used, and the light amount is preferably 100 to 500 mJ / cm ² . When irradiating an electron beam, an electron beam accelerator or the like is used, and the irradiation amount is preferably 150 to 350 kV.

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

<Step (3)> As shown in FIG. 1 (d), step (4) is a step of peeling off the transfer substrate in step (3), and providing a conductive layer 60 on the exposed surface of the functional layer 12. The conductive layer is formed using the above-mentioned conductive layer forming material. For example, the conductive layer can be formed by resistance heating evaporation method, electron beam evaporation method, molecular beam epitaxy method, ion beam method, ion coating method, sputtering, etc. Physical vapor growth (PVD) methods such as plating or chemical vapor growth (CVD) methods such as thermal CVD, plasma CVD, photoCVD, epitaxial CVD, and atomic layer CVD And other methods to form. [Example]

The following examples illustrate the present invention in more detail. However, the present invention is not limited to the following examples.

Manufacturing Example 1-1 (Fabrication of Laminated Body Made of Substrate Layer, Undercoat Layer, and Gas Barrier Layer) (1) The undercoat layer was formed by dipentaerythritol hexaacrylate (produced by Shin Nakamura Chemical Industry Co., Ltd. (Named "A-DPH") 20 parts by mass (active ingredient ratio) dissolved in 100 parts by mass of methyl isobutyl ketone, and 0.62 parts by mass of a photopolymerization initiator (manufactured by BASF, product name "Irgacure127") was added. (Effective ingredient ratio), a solution of the composition for forming an undercoat layer is prepared by mixing. The substrate layer was made of a polyethylene naphthalate (PEN) film (manufactured by Teijin Film Solutions Co., Ltd. under the product name "PENQ65HW") with a thickness of 100 μm. On one surface of the PEN film of this base material layer, a solution of the above-mentioned composition for forming an undercoat layer was applied by a bar coating method to form a coating film, and the coating film was dried by heating at 70 ° C for 1 minute. Then, UV light was used to irradiate the line (high-pressure mercury lamp manufactured by Fusion UV Systems Japan; integrated light amount of 100 mJ / cm ² , peak intensity of 1.466 W, line speed of 20 m / min, and number of irradiations twice), and the dried coating film was applied. UV irradiation hardens to form an undercoat layer with a thickness of 1 μm.

(2) Formation of the gas barrier layer The composition for forming the gas barrier layer is formed by using a perhydropolysilazane liquid (manufactured by AZ ELECTRONIC MATERIALS, product name "AZNL110A-20", and having the aforementioned general formula (1) Where Rx, Ry, and Rz are repeating units of a hydrogen atom, a solution containing perhydropolysilazane). On the surface of the undercoat layer formed in (1) above, the above-mentioned polyhydrogen-containing polysilazane solution was applied by spin coating to form a coating film, and the coating film was dried by heating at 120 ° C for 2 minutes to form a thickness. 200nm first polymer layer. Then, on the surface of the first polymer layer to be formed, argon (Ar) was plasma ion-implanted under conditions described later to form a modified region as the first modified polymer layer. Next, on the exposed surface of the first modified polymer layer, a second polymer layer having a thickness of 150 nm was formed in the same manner as described above using a perhydrogen-containing polysilazane solution as described above. Then, on the surface of the second polymer layer, plasma ion implantation of argon (Ar) was performed under the same conditions to form a modified region as a second modified polymer layer. As described above, a gas barrier layer formed of the first modified polymer layer and the second modified polymer layer each having a modified region is formed.

[Conditions of Plasma Ion Implantation] (1) Plasma ion implantation on the surfaces of the first polymer layer and the second polymer layer was performed using the following apparatus and the following implantation conditions. (Plasma ion implantation device) ･ RF power supply: Product name "RF56000", manufactured by Japan Electronics Co., Ltd. ･ High-voltage pulse power supply: Product name "PV-3-HSHV-0835", manufactured by Kurita Manufacturing Co., Ltd. (plasma ion implantation conditions) ･ Plasma generated gas: Ar ･ Gas flow rate: 100 sccm ･ Duty ratio: 0.5% ･ Repetition frequency: 1000Hz 加 Applied voltage: -10kV ･ RF power: Frequency = 13.56MHz, external power = 1000W ･ Cavity internal pressure: 0.2Pa ･ Pulse width: 5sec ･ Processing time (ion implantation time): 200sec ･ Transport speed: 0.2m / min

Manufacturing Example 1-2 (Production of electrode transfer sheet) The transfer substrate was a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd. under the product name "PET A4100") with a thickness of 100 μm. One surface is coated with a PET film that is easy to handle). A screen printing machine (manufactured by MicroTec, product name "MT-320TV") and a screen plate (printing area: 100 mm in width x 100 mm in width) having a honeycomb structure with a line width of 30 μm and a pitch of 1200 μm were used. A part of the surface of the printing substrate which has not been easily treated is printed with a silver paste (made by Mitsuboshi Belting Co., Ltd., product name "Low-temperature firing conductive paste MDot (registered trademark)") as an ink to form an unhardened subsidy Electrode layer. In addition, the uncured auxiliary electrode layer is temporarily dried at 70 ° C for 1 minute, and then put into a Conveyor type hot air / IR firing furnace, and fired at 150 ° C for 10 minutes to form an auxiliary electrode layer. . In addition, the line width of the auxiliary electrode layer to be formed is 40 μm and the thickness is 8 μm.

Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-6 (1) Preparation of energy ray-curable composition Each component of the type and blending amount (effective component ratio) shown in Table 1 was added. The energy ray-curable compositions (IA) to (IG) and (Ia) to (If) are prepared by mixing.

The details of each component described in Table 1 used in the preparation of the compositions (I-A) to (I-G) and (I-a) to (I-f) are as follows. <Energy ray curable resin> ･ "UV-curable urethane resin (A-1)": Japan Synthetic Chemical Industry Co., Ltd., product name "UT5746", urethane having a UV-polymerizable group Ester-based resin, 80% by mass solid solution in ethyl acetate. ･ "UV-curable urethane resin (A-2)": A product made by Asia Industrial Co., Ltd. under the product name "RUA-048", a urethane resin having an ultraviolet polymerizable group. <Silane coupling agent> ･ "Amine-based silane coupling agent (B-1)": manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name "KBM6803", N-2-aminoethyl-8-aminooctyltrimethoxy Silane. ･ "Amine-based silane coupling agent (B-2)": manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name "KBM603", N-2-aminoethyl-3-aminopropyltrimethoxysilane. ･ "Amine-based silane coupling agent (B-3)": manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name "KBM903", 3-aminopropyltrimethoxysilane. ･ "Epoxy-based silane coupling agent (b'-1)": manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name "KBM403", 3-glycidoxypropyltrimethoxysilane. ･ "Mercaptosilane coupling agent (b'-2)": manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name "KBM803", 3-mercaptopropyltrimethoxysilane. ･ "Acrylic Silane Coupling Agent (b'-3)": manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name "KBM5103", 3-propenyloxypropyltrimethoxysilane. ･ "Urea-based silane coupling agent (b'-4)": manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name "KBE585", 3-ureidopropyltrialkoxysilane. <Photopolymerization initiator> ･ "Photopolymerization initiator (C-1)": manufactured by BASF, product name "Irgacure819", bis (2,4,6-trimethylbenzyl) -phenyl Phosphine oxide.

(2) Formation of the functional layer on the surface of the gas barrier layer of the laminated body produced in the order of the base material layer, the undercoat layer, and the gas barrier layer produced in the manufacturing example 1-1, and coated with a coater. The energy-ray-curable composition prepared in the above (1) was applied to form a coating film, and the coating film was dried at 90 ° C. for 2 minutes to form a functional layer.由此 Through these steps, a gas-barrier laminated body obtained by laminating in the order of the substrate layer, the undercoat layer, the gas barrier layer, and the functional layer is obtained.

(3) Production of Conductive Laminated Body A conductive laminate is produced by the steps shown in FIG. 1. First, as shown in FIG. 1 (a), a laminating machine is used to bond the functional layer 12 of the gas barrier laminated body 1 produced in the above (2) and the auxiliary electrode layer of the electrode transfer sheet 50 produced in the manufacturing example 1-2. On the surface on the side of 52, the auxiliary electrode layer 52 is buried in the functional layer 12, and laminated as shown in FIG. 1 (b). In addition, in the state shown in Fig. 1 (b), a conveyance UV irradiator (product name "CV-110Q-G", high-pressure mercury lamp, manufactured by Heraeus Co., Ltd.) was used from the base material layer side of the gas barrier laminate. The functional layer 12 is hardened while being irradiated with ultraviolet rays (UV) at a cumulative light amount of 250 mJ / cm ² and buried in the auxiliary electrode layer 52. The thickness of the functional layer after curing was 25 μm. Next, as shown in FIG. 1 (c), the transfer substrate 51 is peeled off at the interface between the cured functional layer 12 and the transfer substrate 51. Finally, as shown in FIG. 1 (d), a conductive layer having a thickness of 50 nm made of ITO (indium tin oxide) was formed on the surface of the functional layer on the side where the auxiliary electrode layer 52 was embedded by sputtering under the following conditions. Layer to obtain a conductive laminate. [Film forming conditions of conductive layer] ･ Target: ITO (manufactured by JX Nippon Nissei Metal Co., Ltd., SnO ₂ content = 10% by mass) ･ Method: DC magnetron sputtering ･ Application method: DC500W ･ Substrate heating: no Carrier gas: Argon (Ar) Krypton film formation pressure: 0.6Pa

The conductive laminates produced in the examples and comparative examples were subjected to the following evaluations and physical property value measurements. These results are shown in Table 1.

[Evaluation of Interlayer Adhesiveness] From the conductive layer side of the produced conductive laminate, cut crosswise to a gas barrier layer with a width of 1 mm to form a checkerboard of 10 squares × 10 horizontals = 100 squares. Grid. Next, the surface of the cross-cut checkerboard-shaped conductive layer was adhered with an adhesive tape (manufactured by Nichiban Co., Ltd., product name "Transparent Tape (registered trademark)") in accordance with JIS K5600-5-6 (Cross-cut method) ) Using a checkerboard tape method to perform a scotch tape (registered trademark) peel test. In addition, the interlayer adhesion of the conductive layer, the functional layer after hardening, and the adhesion layer was evaluated by the following criteria. ･ "A": The classification of the evaluation results in Table 1 of JIS K 5600-5-6 is 0 to 2. F "F": The classification of the evaluation results in Table 1 of JIS K 5600-5-6 is 3 to 5. In addition, the evaluation of the interlayer adhesion was first performed on the conductive laminate after storage for 24 hours in an environment of 23 ° C. and a relative humidity of 50%. In addition, only in the case where the evaluation was "A", the conductive laminate was stored at 60 ° C and a relative humidity of 95% for 1,000 hours, and then subjected to a moist heat test, and also at an environment of 23 ° C and a relative humidity of 50%. The conductive laminate was stored for 24 hours, and the interlayer adhesion was evaluated.

[Sheet resistance value ρ _s ] The non-contact resistance measuring device (manufactured by Napson, product name "EC-80P") was used to measure from the conductive layer side of the conductive laminate.

[Water vapor transmission rate] Using a water vapor transmission rate meter (manufactured by MOCON, product name "AQUATRAN"), measure the water vapor transmission rate of the conductive laminate at 40 ° C and 90% relative humidity (unit: g / (m ² ･ day)). The gas flow rate was 20 sccm.

As can be seen from Table 1, the conductive laminate system produced in Examples 1-1 to 1-7 has excellent interlayer adhesion, and also has good conductivity and gas barrier properties. In addition, the conductive laminate system produced in Comparative Examples 1-1 to 1-6 had poor interlayer adhesion. In particular, peeling was observed between the functional layer and the gas barrier layer after curing. Therefore, the measurement is not completed and the sheet resistance value and the water vapor transmission rate are not measured.

Manufacturing Example 2-1 (Fabrication of Laminated Body Made of Base Material Layer, Undercoat Layer, and Gas Barrier Layer) (1) Formation of Undercoat Layer The base material layer is a polymer pair with two sides that are easy to be treated with a thickness of 50 μm. Ethylene phthalate (PET) film (manufactured by Toyobo Co., Ltd., product name "PET50A4300"). On one surface of the PET film of this substrate layer, a UV-curable acrylate resin composition (manufactured by JSR Corporation, product name "OPSTARZ7530") was coated with a wire rod to form a coating film, and the coating film was allowed to stand at 70 ° C. Dry for 1 minute. Then, using an electrodeless UV lamp system (Heraeus Co., Ltd.) at an intensity of 250mW / cm ^2, light quantity of 170mJ / cm dried coating film irradiated with ultraviolet rays after ^two pairs (UV) hardened to form a 1000 nm-thick undercoat layer.

(2) Formation of the gas barrier layer The composition for forming the gas barrier layer is a coating agent containing a perhydropolysilazane as a main component (manufactured by Merck-performance-materials, product name "AquamicaNL110-20", having The xylene solution containing perhydropolysilazane in which Rx, Ry, and Rz in the aforementioned general formula (1) are repeating units of a hydrogen atom). On the surface of the undercoat layer formed in the above (1), a spin coater (manufactured by Mikasa, product name "MS-A200") was used to apply a composition for forming a gas barrier layer at a rotation speed of 3000 rpm and a rotation time of 30 seconds. The above coating agent is used to form a coating film, and the coating film is heated and dried at 120 ° C. for 2 minutes to form a polymer layer having a thickness of 150 nm. Then, using the plasma ion implantation device for the formed polymer layer, plasma ion implantation is performed under the following conditions to form a modified region as a gas barrier layer formed by the modified polymer layer.

[Conditions of Plasma Ion Implantation] (Plasma Ion Implantation Device) ･ RF power supply: product name "RF56000", manufactured by Japan Electronics Co., Ltd. ･ high voltage pulse power supply: product name "PV-3-HSHV-0835", Kurita Manufacturing Co., Ltd. (Plasma ion implantation conditions) 内 Internal pressure in the cavity: 0.2Pa ･ Plasma generation gas: Argon ･ Gas flow rate: 100 sccm ･ RF output: 1000W ･ RF frequency: 1000Hz ･ RF pulse width: 50μs ･ RF delay: 25n seconds ･ DC voltage: -6kV ･ 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 thermosetting composition (II-1) A component of the type shown below was added at a blending amount (active ingredient ratio) shown below, and 5166 parts by mass of methanol and ethyl acetate were used. 586 parts by mass of the ester was diluted to prepare a thermosetting composition (II-1). ･ Thermosetting epoxy resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name "maxive M-100", solid content 100% by mass): 100 parts by mass (effective component conversion) ･ Polyfunctional amine resin (Mitsubishi Gas Chemical Co., Ltd. System, product name "maxive C-93T", solid content: 65.2% by mass): 209 parts by mass (effective component conversion)

(2) Formation of the functional layer on the surface of the gas barrier layer of the laminated body formed by laminating the substrate layer, the undercoat layer, and the gas barrier layer in the order of Manufacturing Example 2-1, and coating with a wire rod The thermosetting composition (II-1) prepared in the above (1) forms a coating film, and the coating film is heated at 100 ° C. for 2 minutes to harden to form a functional layer having a thickness of 300 nm.由此 Through these steps, a gas-barrier laminated body obtained by laminating in the order of the substrate layer, the undercoat layer, the gas barrier layer, and the functional layer is obtained.

Example 2-2 (1) Preparation of energy ray-curable composition (I-B) The components shown below were added at the following formulation amount (effective ingredient ratio), and the energy ray-curable composition (I-B) was prepared by mixing. This composition (I-B) is the same as the energy ray-curable composition (I-B) used in Example 1-2. ･ UV-curable urethane-based resin (manufactured by Japan Synthetic Chemical Industry Co., Ltd., product name "UT5746", urethane-based resin with ultraviolet polymerizable group, 80% by mass ethyl acetate solution ): 100 parts by mass (equivalent to active ingredient conversion) fluorene-based silane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name "KBM6803", N-2-aminoethyl-8-aminooctyltrimethoxysilane) : 1.0 part by mass (effective component conversion) 成分 Photopolymerization initiator (manufactured by BASF, product name "Irgacure819", bis (2,4,6-trimethylbenzyl) -phenylphosphine oxide): 1.5 parts by mass (equivalent to active ingredient)

(2) Formation of the functional layer on the surface of the gas barrier layer of the multilayer body formed by laminating the base material layer, the undercoat layer, and the gas barrier layer in the order of Manufacturing Example 2-1, using a coater The energy ray-curable composition (IB) prepared in the above (1) was applied to form a coating film, and the coating film was dried at 90 ° C for 2 minutes. The peeled surface of a release film (manufactured by Lintec Co., Ltd., product name "SP-PET381031") was attached to the dried coating film surface, and a transfer UV irradiation machine (manufactured by Heraeus company, product name " CV-110Q-G ", high-pressure mercury lamp), irradiate ultraviolet rays (UV) with a cumulative light amount of 250 mJ / cm ² , and harden to form a functional layer with a thickness of 20 μm. Thereafter, the release film was removed to obtain a gas-barrier laminated body in the order of the substrate layer, the undercoat layer, the gas barrier layer, and the functional layer.

Comparative Example 2-1 (1) Preparation of composition (II-2) for functional layer formation The components shown below were added at the following formulation amount (effective component ratio), and the composition for formation of the functional layer was mixed. ･ Polyester resin (manufactured by Japan Synthetic Chemical Industry Co., Ltd., product name "POLYESTER HR-521"): 100 parts by mass (effective component conversion)) 2-propanol: 15 parts by mass

(2) Formation of the functional layer on the surface of the gas barrier layer of the laminated body formed by laminating the substrate layer, the undercoat layer, and the gas barrier layer in the order of the manufacturing example 2-1, and coating with a wire rod The composition for forming a functional layer prepared in the above (1) forms a coating film, and the coating film is heated at 150 ° C. for 3 minutes, and dried to form a functional layer having a thickness of 1000 nm.由此 Through these steps, a gas barrier laminate is obtained in which the substrate layer, the undercoat layer, the gas barrier layer, and the functional layer are laminated in this order.

Comparative Example 2-2 On the surface of the gas barrier layer of the laminated body formed by laminating the base material layer, the undercoat layer, and the gas barrier layer in the order of Manufacturing Example 2-1, UV curing was applied using a wire rod. A acrylate resin (manufactured by JSR Corporation, product name "OPSTARZ7530") was used to form a coating film, and the coating film was dried at 70 ° C for 1 minute. For the coating surface after drying, using an electrodeless UV lamp system (Heraeus Corporation, product name "CV-110Q-G"), at an intensity of 250mW / cm ^2, light quantity of 170mJ / cm ² irradiated with ultraviolet (UV), so that the The coating film is hardened to form a functional layer with a thickness of 150 nm. Through these steps, a gas-barrier laminated body obtained by laminating in the order of the substrate layer, the undercoat layer, the gas barrier layer, and the functional layer is obtained.

Comparative Example 2-3 Preparation of the "energy ray curable composition (Ia)" below, using this composition (Ia) to form the outside of the functional layer, and in the same manner as in Example 2-2, a base layer / primer coating was obtained. Layer / gas barrier layer / functional layer in the order of lamination. The composition (I-a) is the same as the composition (I-a) used in Comparative Example 1-1. ･ UV-curable urethane resin (product made by Asia Industrial Corporation, product name "RUA-048", urethane resin with ultraviolet polymerizable group): 100 parts by mass (effective component conversion) ･ Epoxy-based silane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name "KBM403", 3-glycidoxypropyltrimethoxysilane): 1.0 part by mass (effective component conversion) ･ Photopolymerization initiator ( Made by BASF, product name "Irgacure819", bis (2,4,6-trimethylbenzyl) -phenylphosphine oxide): 1.5 parts by mass (equivalent to active ingredient conversion)

The following evaluations and measurement of physical property values were performed for the gas-barrier laminates produced in the examples and comparative examples. These results are shown in Table 2.

[Evaluation of Interlayer Adhesiveness] (Evaluation 1) Use the gas-barrier laminate as a test piece, and perform a grid test in accordance with JIS K 5600-5-6. The number of grids peeled off is based on the following criteria: , Evaluate the adhesion between the gas barrier layer and the functional layer. ･ "A": The number of peeled squares is 0 out of 100 squares ･ "B": The number of peeled squares is 100 to 100 in 100 squares ･ "C": The stripped squares in 100 squares The number is 50 to 100 (Evaluation 2) The produced gas-barrier laminated body was left to stand for 1000 hours under an environment of 85 ° C and a relative humidity of 85%, and then subjected to a humidity test. Then, a grid test was performed in the same manner as in "Evaluation 1" above. Based on the above criteria, the adhesion between the gas barrier layer and the functional layer after the wetting test was evaluated.

[Water vapor transmission rate] Using a water vapor transmission rate measuring device (manufactured by Mocon, product name "PERMATRAN"), the water vapor transmission rate of the gas-barrier laminate at 40 ° C and a relative humidity of 90% (unit: g) / (m ² ･ day)). The gas flow rate was 10 sccm.

[Total light transmittance] 测量 Measure the total light transmittance of gas-barrier laminates in accordance with JIS K 7361-1.

[HAZE Haze] 测量 According to JIS K 7136, measure HAZE of gas-barrier laminates.

As can be seen from Table 2, the interlayer adhesion between the gas barrier layer and the functional layer of the gas barrier laminated system produced in Examples 2-1 and 2-2 was excellent, and gas barrier properties and transparency were also good. In contrast, 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 poor, resulting in easy peeling. In addition, the gas barrier laminates of Comparative Examples 2-2 and 2-3 were inferior in adhesion between layers before and after being placed under high temperature and high humidity conditions.

1‧‧‧Gas barrier layer

11‧‧‧Gas barrier

12‧‧‧Functional layer

13‧‧‧ substrate layer

50‧‧‧electrode transfer sheet

51‧‧‧ transfer substrate

52‧‧‧Auxiliary electrode layer

60‧‧‧ conductive layer

100‧‧‧ conductive laminate

[Fig. 1] A schematic cross-sectional view showing each step of a method for producing a conductive laminated body according to an aspect of the present invention.

Claims (13)

A gas barrier layered body has a gas barrier layer and a functional layer laminated directly on one surface of the gas barrier layer. The aforementioned functional layer is a layer formed of a composition containing an amine compound. For example, the gas-barrier laminate according to claim 1, wherein the gas-barrier layer is a modified polymer layer formed of a composition for forming a gas-barrier layer containing a polymer compound and having a modified region. The gas-barrier laminate according to claim 2, wherein the polymer compound is a polysilazane-based compound. The gas-barrier laminate according to any one of claims 1 to 3, wherein the functional layer is a layer formed from a composition (I) containing an amine-based silane coupling agent as the amine-based compound. The gas-barrier laminate according to claim 4, wherein the content of the aforementioned amine-based silane coupling agent is 0.1 to 20% by mass based on the total amount of the active ingredients of the composition (I). The gas-barrier laminated body according to claim 4 or 5, wherein the composition (I) is an energy ray-curable resin. The gas barrier laminate according to any one of claims 1 to 3, wherein the functional layer is formed from a composition (II) containing a polyfunctional amine compound having two or more amine groups as the amine compound. Layers. According to the gas-barrier laminate of claim 7, wherein the content of the aforementioned polyfunctional amine compound is 25 to 80% by mass based on the total amount of the active ingredients of the composition (II). The gas barrier laminated body according to claim 7 or 8, wherein the composition (II) contains a thermosetting resin. The gas-barrier laminated body according to claim 9, wherein the thermosetting resin includes a thermosetting epoxy resin. The gas barrier laminated body according to any one of claims 1 to 10, wherein an organic layer is further laminated on the surface of the aforementioned functional layer. The gas-barrier laminated body according to any one of claims 4 to 6, wherein the functional layer has a function as an electrode embedding layer capable of embedding an auxiliary electrode layer. A method for manufacturing a gas-barrier laminated body with an auxiliary electrode, which comprises the following steps (1) to (3): (1) Step (1): bonding the gas-barrier laminated body with the auxiliary electrode layer as in claim 6 A step of burying the auxiliary electrode layer inside the functional layer on the surface of the functional layer; step (2): irradiating the functional layer with energy rays to harden the functional layer; step (3): in the foregoing A step of providing a conductive layer on the surface of the auxiliary electrode layer and the surface of the aforementioned functional layer after hardening;