JP2018138381A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have a high gas barrier property even with a low cost and a simple configuration, further to be excellent in scratch resistance, to be hard to be scratched during film transfer and a post-process, and to be excellent in chemical resistance, when manufacturing an organic EL element. Providing a laminate that is resistant to the etching solution used. SOLUTION: This is a laminate having a first layer 2 containing zinc and silicon and a second layer 3 containing silicon and a metal element other than silicon on at least one surface of the base material 1 in this order from the base material side. A laminated body having a film density of the second layer 3 of 2.5 to 7.0 g / cm3. [Selection diagram] Fig. 1

Description

  The present invention relates to a laminate used for a food or pharmaceutical packaging material that requires a high gas barrier property, or a material for an electronic component such as a solar cell, electronic paper, or an organic electroluminescence (EL) display.

On the surface of the film substrate, physical vapor deposition (PVD) such as vacuum deposition, sputtering, ion plating, or plasma chemical vapor deposition, thermal chemical vapor deposition, photochemical vapor deposition Gas barrier films formed by depositing vapor deposition layers of inorganic substances (including inorganic oxides) using chemical vapor deposition methods (CVD methods), etc., require blocking of various gases such as water vapor and oxygen It is used as packaging materials for foods and pharmaceuticals, and electronic device members such as electronic paper and solar cells. In these members, the water vapor transmission rate is 1.0 × 10 ⁻⁴ g / m ² · 24 hr · atm. The following high gas barrier properties are required.

As one of the methods for satisfying high gas barrier properties, a gas barrier film (Patent Document 1) in which defects are prevented from being generated due to a hole filling effect by alternately laminating organic layers and inorganic layers, mainly ZnO and SiO ₂ are used. A gas barrier film (Patent Document 2) in which a ZnO—SiO ₂ film is formed on a film substrate by sputtering using a component target has been proposed.

Japanese Patent Laying-Open No. 2005-324406 (Claims) JP2013-147710A (Claims)

However, although it is possible to express a high barrier property by alternately laminating an organic layer and an inorganic layer as in Patent Document 1, there is a problem in that the number of steps increases because of the lamination, resulting in a high cost. was there. In addition, a laminate that forms a gas barrier layer mainly composed of ZnO and SiO ₂ as in Patent Document 2 has poor scratch resistance when the thickness of the gas barrier layer is reduced, and is scratched during film transport and post-processing. There was a problem that made it easier.

  In view of the background of such prior art, the present invention has high gas barrier properties even with a low-cost and simple configuration, and further has excellent scratch resistance, is hardly scratched during film transportation and subsequent processes, and is resistant to chemicals. It is an object of the present invention to provide a laminate having excellent properties and having resistance to an etching solution used when producing an organic EL device.

The present invention employs the following means in order to solve such problems. That is,
(1) A laminated body having a first layer containing zinc and silicon and a second layer containing a metal element other than silicon and silicon in this order on at least one surface of the base material in this order, the second layer The laminated body whose film density is 2.5-7.0 g / cm < ³ >.
(2) The laminate according to (1), wherein the metal element other than silicon is at least one metal element selected from the group consisting of tin, zirconium, titanium, aluminum, tantalum, gallium, germanium, and indium.
(3) The laminate according to (1) or (2), wherein the first layer includes at least one selected from the group consisting of zinc oxide, silicon oxide, and aluminum oxide.
(4) The laminate according to any one of (1) to (3), wherein the second layer includes tin oxide and silicon oxide.
(5) The laminate according to any one of (1) to (4), which has an anchor coat layer between the base material and the first layer.
(6) The first layer has a zinc (Zn) atom concentration of 3 to 37 atm%, a silicon (Si) atom concentration of 5 to 20 atm%, and an aluminum (Al) atom concentration of 1 to 1 as measured by X-ray photoelectron spectroscopy. The laminated body according to any one of (1) to (5), which has 7 atm% and an oxygen (O) atom concentration of 50 to 70 atm%.
(7) The second layer contains tin, and the tin (Sn) atom concentration measured by X-ray photoelectron spectroscopy is 10 to 30 atm%, the silicon (Si) atom concentration is 10 to 30 atm%, and the oxygen (O) atom. The laminated body in any one of (1)-(6) whose density | concentration is 50-75 atm%.
(8) An organic electroluminescence device having a positive electrode layer, a light emitting unit, and a negative electrode layer in this order from the laminate side on the laminate according to any one of (1) to (7).

A laminate having a high gas barrier property against water vapor and scratch resistance can be provided.

It is sectional drawing which showed an example of the laminated body of this invention. It is sectional drawing which showed an example of the laminated body of this invention. It is the schematic which shows typically the winding-type sputtering apparatus for manufacturing the laminated body of this invention. It is sectional drawing which showed an example of the organic electroluminescent element of this invention.

[Laminate]
The laminate of the present invention is a laminate having, in this order from the substrate side, a first layer containing zinc and silicon and a second layer containing a metal element other than silicon and silicon on at least one surface of the substrate, The second layer is a laminate having a film density of 2.5 to 7.0 g / cm ³ .

  As the zinc contained in the first layer, zinc oxide, zinc sulfide, zinc nitride, a mixture thereof or the like is preferably used, and zinc oxide and / or zinc sulfide is more preferable from the viewpoint of gas barrier properties. From the viewpoint of optical properties, zinc oxide is more preferable.

  By providing the first layer, a dense film can be formed even with an extremely thin film (several tens of nanometers) and high gas barrier properties can be expressed. Therefore, even in the structure of the laminate, high gas barrier properties can be expressed.

By providing the second layer, the gas barrier property is complemented by filling the defects of the first layer, and the dense film is formed by the film density of the second layer being 2.5 to 7.0 g / cm ^3. Therefore, scratch resistance and chemical resistance can be imparted.

  The form of silicon contained in the first layer is not limited to oxides, nitrides, oxynitrides, carbides, etc., but is preferably present as oxides, nitrides, oxynitrides from the viewpoint of gas barrier properties and the like. . From the viewpoint of forming an amorphous film and gas barrier properties, it is more preferable that it is contained as at least one silicon compound selected from the group consisting of oxides, nitrides, oxynitrides and carbides.

  The form of silicon contained in the second layer is not limited to oxides, nitrides, oxynitrides, carbides, etc., but is preferably present as oxides, nitrides, oxynitrides from the viewpoint of gas barrier properties. . From the viewpoint of forming an amorphous film and gas barrier properties, it is more preferable that it is contained as at least one silicon compound selected from the group consisting of oxides, nitrides, oxynitrides and carbides.

  The metal element other than silicon contained in the second layer is preferably at least one metal element selected from the group consisting of tin, zirconium, titanium, aluminum, tantalum, gallium, germanium, and indium. The form of metal elements other than silicon contained in the second layer is not limited to oxides, nitrides, oxynitrides, carbides, etc., but exists as oxides, nitrides, oxynitrides from the viewpoint of gas barrier properties, etc. It is preferable to do. As described above, the second layer may contain an inorganic compound other than the above as long as it contains silicon and a metal element other than silicon.

In this invention, it is preferable to have a 1st layer and a 2nd layer in this order from the base material side. Since the first layer contains zinc and silicon, a dense film can be formed even with an extremely thin film (several tens of nanometers), so that a high gas barrier property can be exhibited. No particular limitation is imposed on the form of zinc and silicon is preferably present in the form of composite oxide from the viewpoint of forming a dense film (Zn 2 _{SiO 4).} By forming the second layer on the first layer and filling the defects of the first layer, the gas barrier property can be supplemented, and further, scratch resistance and chemical resistance can be imparted. When the first layer and the second layer are interchanged, desired gas barrier properties, scratch resistance, and chemical resistance may not be obtained.

The film density of the second layer is preferably in the range of 2.5 to 7.0 g / cm ³ . When the film density of the second layer is less than 2.5 g / cm ³ , the denseness of the second layer is lowered, and sufficient gas barrier properties may not be obtained, or the scratch resistance may be insufficient. When the film density is higher than 7.0 g / cm ^3, cracks may be easily formed because the film becomes excessively dense. Therefore it is preferable that the film density of the second layer is in the range of 2.5~7.0g / cm ^3, and more preferably in the range of 3.0~6.0g / cm ^3.

  In the present invention, the film density of the second layer is a value measured by an X-ray reflectivity method (XRR method) ("Introduction to X-ray reflectivity" (edited by Kenji Sakurai) p. 51-78). Specifically, first, X-rays are generated from an X-ray source, converted into a parallel beam by a multilayer mirror, and then the X-ray angle is limited through an entrance slit to be incident on a measurement sample. By making the incident angle of the X-rays to the sample enter at a shallow angle substantially parallel to the sample surface to be measured, a reflected beam of X-rays reflected and interfered with each layer and substrate interface of the sample is generated. The generated reflected beam is passed through the light receiving slit and limited to the required X-ray angle, and then incident on the detector to measure the X-ray intensity. Using this method, the total reflection X-ray intensity profile at each incident angle can be obtained by continuously changing the incident angle of X-rays.

  The analysis method of the film density of each layer is obtained by fitting the measured data of the total reflection X-ray intensity profile with respect to the incident angle of the obtained X-ray to the theoretical formula of Parratt by the nonlinear least square method (“X-ray reflection “Introduction to rate” (edited by Kenji Sakurai) p. 81-141). A specific analysis method will be described in the example section.

  The method for forming the first layer and the second layer is not particularly limited, and the first layer and the second layer can be formed by sputtering, vacuum evaporation, ion plating, CVD, atomic layer deposition (ALD), or the like. Among these methods, the sputtering method is preferable as a method that is inexpensive, simple, and obtains desired properties. Further, the sputtering method may be any of single wafer type and roll-to-roll. FIG. 3 shows an example of a roll-to-roll apparatus. The composition ratio of the first layer can be measured by X-ray photoelectron spectroscopy (XPS method). After removing the second layer by sputter etching, the content ratio of each element is measured. The layer is removed from the surface layer side by argon ion etching until the thickness of the first layer becomes 1/2, and the content ratio of each element is measured. The composition ratio of the first layer is such that the zinc (Zn) atom concentration is 3 to 37 atm%, the silicon (Si) atom concentration is 5 to 20 atm%, the aluminum (Al) atom concentration is 1 to 7 atm%, and the oxygen (O) atom concentration Is preferably in the range of 50 to 70 atm%. If the zinc atom concentration is less than 3 atm% or the silicon atom concentration is more than 20 atm%, the proportion of zinc atoms that make the first layer highly flexible decreases, so the flexibility of the gas barrier film decreases. There is a case. If the zinc atom concentration is higher than 37 atm% or the silicon atom concentration is lower than 5 atm%, the ratio of silicon atoms decreases, so that the first layer is likely to be a crystal layer and cracks are likely to occur. If the aluminum atom concentration is less than 1 atm%, the affinity between zinc oxide and silicon dioxide is impaired, and voids and defects may easily occur in the first layer. On the other hand, if the aluminum atom concentration is higher than 7 atm%, the affinity between zinc oxide and silicon dioxide becomes excessively high, so that cracks are likely to occur against heat and external stress. When the oxygen atom concentration is less than 50 atm%, zinc, silicon, and aluminum are insufficiently oxidized, and the light transmittance may decrease. On the other hand, when the oxygen atom concentration is higher than 70 atm%, oxygen is taken in excessively, so that voids and defects increase, and the gas barrier property may deteriorate.

  The thickness of the first layer in the present invention can be obtained by cross-sectional observation with a transmission electron microscope (TEM). The thickness of the first layer is preferably 5 nm or more, and more preferably 10 nm or more. If the thickness is less than 5 nm, a region that is not formed as a layer is generated, and gas barrier properties may not be sufficiently secured. Further, the thickness of the first layer is preferably 300 nm or less, and more preferably 200 nm or less. If the thickness of the first layer is greater than 300 nm, cracks may easily occur or the bending resistance may decrease.

  The composition ratio of the second layer can be measured by the XPS method as in the first layer. The layer is removed from the surface layer by argon ion etching until the thickness of the layer becomes 1/2, and the content ratio of each element is measured.

  The second layer contains tin, and the tin (Sn) atom concentration measured by the XPS method is 10 to 30 atm%, the silicon (Si) atom concentration is 10 to 30 atm%, and the oxygen (O) atom concentration is 50 to 75 atm%. It is preferable that it is the range of these. If the tin atom concentration is less than 10 atm% or the silicon atom concentration is more than 30 atm%, the desired scratch resistance may not be obtained. On the other hand, if the tin atom concentration is higher than 30 atm% or the silicon atom concentration is lower than 10 atm%, problems such as a desired gas barrier property not being exhibited and optical characteristics may be deteriorated.

  The thickness of the second layer in the present invention can be obtained by cross-sectional observation with a transmission electron microscope (TEM) as in the first layer. The thickness of the second layer is preferably 10 nm or more, and more preferably 20 nm or more. When the thickness is less than 10 nm, a region that is not formed as a layer is generated, and gas barrier properties may not be sufficiently secured, or scratch resistance and chemical resistance may not be obtained. The thickness of the second layer is preferably 200 nm or less, and more preferably 100 nm or less. If the thickness of the second layer is greater than 200 nm, cracks may easily occur or bending resistance may be reduced.

[Base material]
It is preferable that the base material used for this invention has a film form from a viewpoint of ensuring a softness | flexibility. The structure of the film may be a single-layer film or a film having two or more layers, for example, a film formed by a coextrusion method. As the type of film, a film stretched in a uniaxial direction or a biaxial direction may be used.

  The material of the base material used in the present invention is not particularly limited, but it is preferable that the main component is an organic polymer. Examples of the organic polymer that can be suitably used in the present invention include crystalline polyolefins such as polyethylene and polypropylene, amorphous cyclic polyolefins having a cyclic structure, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, Examples include polystyrene, polyvinyl alcohol, saponified ethylene vinyl acetate copolymer, various polymers such as polyacrylonitrile and polyacetal. Among these, it is preferable to include amorphous cyclic polyolefin or polyethylene terephthalate having excellent transparency, versatility, and mechanical properties. Further, the organic polymer may be either a homopolymer or a copolymer, and only one type may be used as the organic polymer, or a plurality of types may be blended.

  The surface on the side of forming the first layer of the base material is composed of corona treatment, plasma treatment, ultraviolet treatment, ion bombardment treatment, solvent treatment, organic or inorganic matter, or a mixture thereof in order to improve adhesion and smoothness. A pretreatment such as an anchor coat layer forming treatment may be performed. Further, on the side opposite to the side on which the first layer is formed, a coating layer of an organic material, an inorganic material, or a mixture thereof may be laminated for the purpose of improving the slipping property when winding the substrate.

  The thickness of the substrate used in the present invention is not particularly limited, but is preferably 500 μm or less from the viewpoint of ensuring flexibility, and preferably 5 μm or more from the viewpoint of ensuring strength against tension or impact. Furthermore, the thickness of the substrate is more preferably 10 μm or more and 200 μm or less because of the ease of film processing and handling.

[Anchor coat layer]
In the laminate of the present invention, an anchor coat layer is preferably provided between the base material and the first layer. Furthermore, it is more preferable to provide an anchor coat layer including a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure between the base material and the first layer. If there are defects such as protrusions or scratches on the substrate, pinholes and cracks may occur in the first layer laminated on the substrate starting from the defects, and the gas barrier property and bending resistance may be impaired. For this reason, it is preferable to provide an anchor coat layer. In addition, even when there is a large difference in thermal dimensional stability between the base material and the first layer, the gas barrier property and the bending resistance may be lowered. Therefore, it is preferable to provide an anchor coat layer. In addition, the anchor coat layer used in the present invention preferably contains a polyurethane compound having an aromatic ring structure from the viewpoint of thermal dimensional stability and flex resistance, and further includes an ethylenically unsaturated compound and a photopolymerization initiator. It is more preferable to contain an organosilicon compound and / or an inorganic silicon compound.

  The polyurethane compound having an aromatic ring structure used in the present invention has an aromatic ring and a urethane bond in the main chain or side chain. For example, an epoxy (meth) having a hydroxyl group and an aromatic ring in the molecule. It can be obtained by polymerizing acrylate, diol compound and diisocyanate compound.

  As epoxy (meth) acrylate having a hydroxyl group and an aromatic ring in the molecule, diepoxy compounds of aromatic glycols such as bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, hydrogenated bisphenol F type, resorcin, hydroquinone, etc. And a (meth) acrylic acid derivative.

  Examples of the diol compound include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, neopentyl Glycol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4, 4-tetramethyl-1,3-cyclobutanediol, 4,4′-thiodiph Diol, bisphenol A, 4,4′-methylenediphenol, 4,4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4 '-Isopropylidenephenol, 4,4'-isopropylidenebindiol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, bisphenol A, and the like can be used. These can be used alone or in combination of two or more.

  Examples of the diisocyanate compound include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, and 4,4-diphenylmethane diisocyanate. Aromatic diisocyanate compounds such as aromatic diisocyanate, ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, etc. Aliphores such as isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, methylcyclohexylene diisocyanate Systems isocyanate compound, diisocyanate, aromatic aliphatic isocyanate compounds such as tetramethyl xylylene diisocyanate. These can be used alone or in combination of two or more.

  The component ratio of the epoxy (meth) acrylate having a hydroxyl group and an aromatic ring in the molecule, a diol compound, and a diisocyanate compound is not particularly limited as long as it has a desired weight average molecular weight. The weight average molecular weight (Mw) of the polyurethane compound having an aromatic ring structure in the present invention is preferably 5,000 to 100,000. A weight average molecular weight (Mw) of 5,000 to 100,000 is preferable because the resulting cured film has excellent thermal dimensional stability and flex resistance. In addition, the weight average molecular weight (Mw) in this invention is the value measured using the gel permeation chromatography method and converted with standard polystyrene.

  Examples of the ethylenically unsaturated compound include di (meth) acrylates such as 1,4-butanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and penta Multifunctional (meth) acrylates such as erythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A type epoxy di (meth) acrylate And epoxy acrylates such as bisphenol F type epoxy di (meth) acrylate and bisphenol S type epoxy di (meth) acrylate. Among these, polyfunctional (meth) acrylates excellent in thermal dimensional stability and surface protection performance are preferable. Moreover, these may be used by a single composition, and may mix and use two or more components.

  The content of the ethylenically unsaturated compound is not particularly limited, but from the viewpoint of thermal dimensional stability and surface protection performance, the total amount with the polyurethane compound having an aromatic ring structure is in the range of 5 to 90% by mass. It is preferable that it is in the range of 10 to 80% by mass.

  The material for the photopolymerization initiator is not particularly limited as long as the gas barrier property and the bending resistance of the laminate of the present invention can be maintained. Examples of the photopolymerization initiator that can be suitably used in the present invention include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexylphenyl-ketone, and 2-hydroxy-2- Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- { 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- (4-methylthio Phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 Alkylphenone photopolymerization initiators such as 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6 -Acylphosphine oxide photopolymerization initiators such as trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η5-2,4-cyclopentadien-1-yl) -Titanocene photopolymerization initiators such as bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1,2-octanedione, 1- [4- (phenylthio)-, And 2- (0-benzoyloxime)] and the like photopolymerization initiators having an oxime ester structure.

  Among these, from the viewpoint of curability and surface protection performance, 1-hydroxy-cyclohexylphenyl-ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4,6 A photopolymerization initiator selected from trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferable. Moreover, these may be used by a single composition, and may mix and use two or more components.

  Although content of a photoinitiator is not specifically limited, From a viewpoint of sclerosis | hardenability and surface protection performance, it is preferable that it is the range of 0.01-10 mass% in the total amount of 100 mass% of a polymeric component, 0 More preferably, it is in the range of 1 to 5% by mass.

  Examples of the organosilicon compound include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3 Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanate propyl triethoxysilane, and the like.

  Among these, from the viewpoint of curability and polymerization activity by irradiation with active energy rays, selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. At least one organosilicon compound is preferred. Moreover, these may be used by a single composition, and may mix and use two or more components.

  The content of the organosilicon compound is not particularly limited, but from the viewpoint of curability and surface protection performance, it is preferably in the range of 0.01 to 10% by mass in 100% by mass of the total amount of polymerizable components. A range of 1 to 5% by mass is more preferable.

As the inorganic silicon compound, silica particles are preferable from the viewpoint of surface protection performance and transparency, and the primary particle diameter of the silica particles is preferably in the range of 1 to 300 nm, and more preferably in the range of 5 to 80 nm. . In addition, the primary particle diameter here refers to the particle diameter d calculated | required by applying the specific surface area s calculated | required by the gas adsorption method to following formula (1).
d = 6 / ρs (1)
ρ: Density.

  The thickness of the anchor coat layer is preferably 200 nm or more and 4,000 nm or less, more preferably 300 nm or more and 2,000 nm or less, and further preferably 500 nm or more and 1,000 nm or less. When the thickness of the anchor coat layer is less than 200 nm, the adverse effects of defects such as protrusions and scratches present on the substrate may not be suppressed. When the thickness of the anchor coat layer is larger than 4,000 nm, the smoothness of the anchor coat layer is lowered, and the uneven shape on the surface of the first layer laminated on the anchor coat layer is increased, so that there is a gap between the sputtered particles to be laminated. Therefore, the film quality is less likely to be dense, and the effect of improving gas barrier properties may be difficult to obtain. Here, the thickness of the anchor coat layer can be measured from a cross-sectional observation image by a transmission electron microscope (TEM).

  The center coat average roughness SRa of the anchor coat layer is preferably 10 nm or less. When SRa is 10 nm or less, it is easy to form a homogeneous first layer on the anchor coat layer, and it is preferable because repeated reproducibility of gas barrier properties is improved. When the SRa on the surface of the anchor coat layer is larger than 10 nm, the uneven shape on the surface of the first layer on the anchor coat layer also increases, and a gap is formed between the sputtered particles to be laminated. In some cases, it is difficult to obtain an improvement effect, and cracks due to stress concentration are likely to occur in portions where there are many irregularities, which may reduce the reproducibility of gas barrier properties. Therefore, in the present invention, the SRa of the anchor coat layer is preferably 10 nm or less, more preferably 7 nm or less.

  SRa of the anchor coat layer in the present invention can be measured using a three-dimensional surface roughness measuring machine.

  When applying an anchor coat layer to the laminate of the present invention, as a means for applying a coating liquid containing a resin forming the anchor coat layer, first, after drying a paint containing a polyurethane compound having an aromatic ring structure on a substrate The solid content concentration is adjusted so that the thickness of the film becomes a desired thickness, and it is preferably applied by, for example, reverse coating method, gravure coating method, rod coating method, bar coating method, die coating method, spray coating method, spin coating method, etc. . Moreover, in this invention, it is preferable to dilute the coating material containing the polyurethane compound which has an aromatic ring structure using an organic solvent from a viewpoint of coating suitability.

  Specifically, using a hydrocarbon solvent such as xylene, toluene, methylcyclohexane, pentane or hexane, or an ether solvent such as dibutyl ether, ethyl butyl ether or tetrahydrofuran, the solid content concentration is diluted to 10% by mass or less. Are preferably used. These solvents may be used alone or in combination of two or more. Moreover, various additives can be mix | blended with the coating material which forms an anchor coat layer as needed. For example, a catalyst, an antioxidant, a light stabilizer, a stabilizer such as an ultraviolet absorber, a surfactant, a leveling agent, an antistatic agent, or the like can be used.

  Subsequently, it is preferable to dry the coating film after application | coating and to remove a dilution solvent. Here, there is no restriction | limiting in particular as a heat source used for drying, Arbitrary heat sources, such as a steam heater, an electric heater, and an infrared heater, can be used. In order to improve gas barrier properties, the heating temperature is preferably 50 to 150 ° C. The heat treatment time is preferably several seconds to 1 hour. Furthermore, the temperature may be constant during the heat treatment, or the temperature may be gradually changed. Moreover, you may heat-process, adjusting humidity in the range of 20 to 90% RH by relative humidity during a drying process. The heat treatment may be performed in the air or while enclosing an inert gas.

  Next, it is preferable to form an anchor coat layer by subjecting the coating film containing a polyurethane compound having an aromatic ring structure after drying to an active energy ray irradiation treatment to crosslink the coating film.

  The active energy ray applied in such a case is not particularly limited as long as the anchor coat layer can be cured, but it is preferable to use ultraviolet treatment from the viewpoint of versatility and efficiency. As the ultraviolet ray generation source, a known source such as a high pressure mercury lamp metal halide lamp, a microwave type electrodeless lamp, a low pressure mercury lamp, a xenon lamp or the like can be used. Moreover, it is preferable to use an active energy ray in inert gas atmosphere, such as nitrogen and argon, from a viewpoint of hardening efficiency. The ultraviolet treatment may be performed under atmospheric pressure or reduced pressure, but in the present invention, the ultraviolet treatment is preferably performed under atmospheric pressure from the viewpoint of versatility and production efficiency. The oxygen concentration during the ultraviolet treatment is preferably 1.0% or less, more preferably 0.5% or less, from the viewpoint of controlling the degree of crosslinking of the anchor coat layer. The relative humidity may be arbitrary.

  As the ultraviolet ray generation source, a known source such as a high pressure mercury lamp metal halide lamp, a microwave type electrodeless lamp, a low pressure mercury lamp, a xenon lamp or the like can be used.

Preferably the integrated light quantity of ultraviolet irradiation is ^{0.1~1.0J / cm 2, 0.2~0.6J / cm} 2 is more preferable. It is preferable that the integrated light amount is 0.1 J / cm ² or more because a desired degree of crosslinking of the anchor coat layer can be obtained. Moreover, it is preferable if the integrated light quantity is 1.0 J / cm ² or less because damage to the substrate can be reduced.

[Other layers]
On the outermost surface of the laminate of the present invention, a hard coat layer for the purpose of further improving the scratch resistance may be formed as long as the gas barrier property does not deteriorate, or a film made of an organic polymer compound is laminated. It is good also as a laminated structure. Moreover, you may form the layer aiming at the further improvement of chemical resistance. In addition, the outermost surface here means the surface of the second layer on the side not in contact with the first layer after the first layer and the second layer are laminated in this order on the substrate.

[Use of laminate]
Since the laminate of the present invention has high gas barrier properties, scratch resistance, and chemical resistance, it can be suitably used as a gas barrier film. In addition, the laminate of the present invention can be used for various electronic devices. For example, it can be suitably used for an electronic device such as a solar cell backsheet, flexible circuit substrate, organic EL illumination, and flexible organic EL display. Furthermore, taking advantage of its high gas barrier properties, it can be suitably used as a packaging film for foods and electronic parts, in addition to electronic devices.

[Organic electroluminescence (EL) element]
The organic EL element of the present invention has a positive electrode layer, a light emitting unit, and a negative electrode layer in this order from the laminate side on the laminate. In view of the nature of the organic EL element, at least one of the positive electrode layer and the negative electrode layer is preferably transparent.

(Positive electrode layer)
The positive electrode layer used in the organic EL element is not particularly limited in its shape, structure, size and the like, and can be appropriately selected from known electrode materials according to the use and purpose of the light emitting unit. The positive electrode layer is usually provided as a transparent electrode.

  For the positive electrode layer, a metal, an alloy, a metal oxide, a conductive compound, or a mixture thereof is preferably used. Specifically, metals such as gold and silver and alloys based on those metals, conductive metal oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO) Materials, organic conductive materials such as polyaniline and polythiophene, and mixtures and laminates of metals and conductive metal oxides. From the viewpoint of high conductivity and transparency, ITO, silver, and an alloy containing silver as a main component are preferable.

  The positive electrode layer is made of a suitable material such as a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method or an ion plating method, or a chemical method such as a CVD or plasma CVD method. Can be formed on the laminate by a suitable method. The positive electrode layer may be formed on the entire surface of the laminate, or a pattern may be formed. The positive electrode layer may be patterned by any method as long as it can form a pattern, but can be performed by wet etching using a mask, vapor deposition, sputtering, etc., chemical etching by photolithography, physical etching by laser, etc. It can be carried out.

  The film thickness of the positive electrode layer can be appropriately selected depending on the material, but is usually about 10 nm to 5 μm, preferably 10 to 500 nm.

(Light emitting unit)
As the structure of the light emitting unit, hole transport layer / electron injection layer / light emitting layer, hole transport layer / light emitting layer / electron transport layer, hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer , Hole injection layer / hole transport layer / light emitting layer / hole block layer / electron transport layer / electron injection layer, and the like can be considered, but any configuration may be used as long as it is a known configuration. Details of each configuration will be described below.

(1) Hole injection layer The hole injection layer is a layer provided between the positive electrode layer and the light emitting layer in order to lower the driving voltage and improve the light emission luminance. Injection from the positive electrode layer to the light emitting layer It serves to lower the barrier.

  Hole injection layer is triazole derivative, oxadiazole derivative, imidazole derivative, polyarylalkane derivative, pyrazoline derivative and pyrazolone derivative, phenylenediamine derivative, arylamine derivative, amino-substituted chalcone derivative, oxazole derivative, styrylanthracene derivative, fluorenone derivative , A hydrazone derivative, a stilbene derivative, a silazane derivative, an aniline copolymer, a conductive polymer oligomer, particularly a thiophene oligomer, and the like.

  The thickness of the hole injection layer is preferably 500 nm or less from the viewpoint of lowering the driving voltage. Furthermore, it is preferable that it is 0.1 nm-200 nm, and it is more preferable that it is 0.5 nm-100 nm. The hole injection layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.

  The hole injection layer can be formed by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, or an LB method.

(2) Hole transport layer The hole transport layer is made of a hole transport material having a function of transporting holes, and the hole injection layer and the electron blocking layer can also function as a hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers. The hole transport layer may have a single layer structure composed of one or more of the following materials.

  The material used for the hole transport layer has either hole injection or transport or electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, particularly thiophene oligomers. In particular, it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  The thickness of the hole transport layer is preferably 500 nm or less from the viewpoint of lowering the driving voltage. It is more preferably 0.1 nm to 200 nm, and further preferably 0.5 nm to 100 nm. The hole injection layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.

  The hole transport layer can be formed by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, or an LB method.

(3) Electron transport layer The electron transport layer is made of an electron transport material having a function of transporting electrons, and the electron injection layer and the hole blocking layer can also function as an electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers. The hole transport layer may have a single layer structure composed of one or more of the following materials.

  Materials used for the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluoreni For metal complexes of redenemethane derivatives, distyrylpyrazine derivatives, aromatic ring tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, 8-quinolinol derivatives and metal complexes with metal phthalocyanine, benzoxazole and benzothiazole ligands Various representative metal complexes, organosilane derivatives, and the like can be used.

  The thickness of the electron transport layer is preferably 500 nm or less from the viewpoint of lowering the driving voltage. It is more preferably 0.1 nm to 200 nm, and further preferably 0.5 nm to 100 nm. The electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

(4) Electron injection layer The electron injection layer is a layer provided between the negative electrode layer and the light emitting layer for the purpose of lowering the driving voltage and improving the light emission luminance, and an injection barrier from the negative electrode layer to the light emitting layer. It plays the role of lowering.

  Materials used for the electron injection layer are triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives And a layer containing a fluorenone derivative, a hydrazone derivative, a stilbene derivative, a silazane derivative, an aniline copolymer, a conductive polymer oligomer, particularly a thiophene oligomer.

  The thickness of the electron injection layer is preferably 500 nm or less from the viewpoint of lowering the driving voltage. It is more preferably 0.1 nm to 200 nm, and further preferably 0.5 nm to 100 nm. The electron injection layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.

  The electron injection layer can be formed by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, or an LB method.

(5) Light emitting layer The light emitting layer is a layer that emits light by recombination of electrons injected from the negative electrode or the electron transport layer and holes injected from the hole transport layer, and the light emitting portion is the light emitting layer. The interface between the light emitting layer and the adjacent layer may be used. There is no particular limitation on the structure of the light emitting layer as long as the light emitting material contained satisfies the light emission requirements.

  The light emitting layer may be composed of only the light emitting material, or may be a mixed layer of the host material and the light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one type or two or more types. The host material is preferably an electron transport material. The host material may be one type or two or more types, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  The light emitting layer can be formed of a light emitting material or a host compound by a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method.

  The thickness of the light emitting layer is preferably in the range of 1 to 200 nm, and more preferably in the range of 1 to 50 nm because a lower driving voltage can be obtained.

  As the host material contained in the light emitting layer, a known host material may be used alone, or a plurality of types may be used. By using a plurality of types of host materials, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. Moreover, arbitrary luminescent colors can be obtained by using multiple types of luminescent materials.

  Host materials include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, those having an arylsilane skeleton, a hole injection layer, a positive Examples thereof include materials exemplified in the terms of the hole transport layer, the electron injection layer, and the electron transport layer.

  Fluorescent materials include benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed aromatic compounds, perinone derivatives, Oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, diketopyrrolopyrrole derivatives, Various metals represented by aromatic dimethylidin compounds, metal complexes of 8-quinolinol derivatives and metal complexes of pyromethene derivatives Body like, polythiophene, polyphenylene, polymeric compounds such as polyphenylene vinylene, include compounds such as organic silane derivatives.

  Examples of the phosphorescent material include a complex containing a transition metal atom or a lanthanoid atom.

Although it does not specifically limit as a transition metal atom, Preferably, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum are mentioned, More preferably, they are rhenium, iridium, and platinum.
Examples of lanthanoid atoms include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

  Complex ligands include halogen ligands (eg, chlorine ligands), nitrogen-containing heterocyclic ligands (eg, phenylpyridine, benzoquinoline, quinolinol, bipyridyl, phenanthroline, etc.), diketone ligands ( For example, acetylacetone etc.), carboxylic acid ligand (eg acetic acid ligand etc.), carbon monoxide ligand, isonitrile ligand, cyano ligand, more preferably nitrogen-containing heterocyclic coordination A child. The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Further, different metal atoms may be contained simultaneously.

  The phosphorescent material is preferably contained in the light emitting layer in an amount of 0.1 to 40% by mass, and more preferably 0.5 to 20% by mass. The concentration ratio of the phosphorescent light emitting material may be changed in the thickness direction of the light emitting layer.

(Negative electrode layer)
For the negative electrode layer, a metal, an alloy, a metal oxide, a conductive compound, or a mixture thereof is preferably used. Specific examples include alkali metals and alkaline earth metals, gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium-silver alloys, rare earth metals such as indium and ytterbium. Two or more kinds can be mixed and used from the viewpoints of electron injection and durability. Moreover, the material which has aluminum as a main component from a viewpoint of electroinjection property and storage stability is preferable. The material containing aluminum as a main component refers to an aluminum simple substance or an alloy or mixture containing 70 mass% or more of aluminum.

  The negative electrode layer is composed of a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method or an ion plating method, or a chemical method such as a CVD or plasma CVD method. In consideration of the suitability, it can be formed using a suitable method. The negative electrode layer may be formed on the entire surface of the laminate, or a pattern may be formed. The negative electrode layer can be patterned by any method as long as a pattern can be formed, but can be performed by wet etching using a mask, vapor deposition, sputtering, etc., chemical etching by photolithography, physical etching by laser, etc. It can be carried out.

  The thickness of the negative electrode layer can be appropriately selected depending on the material, but is usually about 10 nm to 5 μm, preferably 10 to 500 nm.

[Sealing material]
Since the organic EL element is very sensitive to oxygen and moisture in the atmosphere and the element is deteriorated, high sealing performance is required. Therefore, the organic EL element needs to be sealed with an appropriate sealing member. .

  The sealing member is a plate-like (film-like) member that covers the upper surface of the organic EL element, and is fixed to the laminated body side by an adhesive portion. The sealing member may be a sealing film. Such a sealing member is provided in a state in which the electrode terminal portion of the organic EL element is exposed and at least the light emitting unit is covered. Moreover, the structure which provides an electrode in a sealing member and makes the electrode terminal part of an organic EL element and the electrode of a sealing member electrically connect may be sufficient.

  Examples of the plate-like (film-like) sealing member include a glass substrate, a polymer resin substrate, a metal substrate, and the like, and these are preferably used in the form of a thin film from the viewpoint that the element can be thinned.

  Examples of the glass substrate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Polymer resin substrates include crystalline polyolefins such as polyethylene and polypropylene, amorphous cyclic polyolefins having a cyclic structure, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamide, polycarbonate, polystyrene, polyvinyl alcohol, and ethylene vinyl acetate. Examples thereof include saponified copolymers, various polymers such as polyacrylonitrile and polyacetal. Examples of the metal substrate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum. Although it depends on the light emitting side of the organic EL element, the sealing member is preferably transparent. Further, the total light transmittance is more preferably 90% or more.

Furthermore, the polymer resin substrate in the form of a film has a water vapor transmission rate (temperature: 40 ° C., relative humidity: 90% RH) measured by a method according to JIS K 7126-1-2006 of 1.0 × 10 ⁻³ g. / (M ² · 24 hr · atm) or less is preferable. As a means for satisfying the water vapor transmission rate, it is preferable to form a gas barrier film on the polymer resin substrate. The gas barrier film is configured using an inorganic material or an organic material. As the inorganic material, metal oxides such as Si, Al, Zn, Mg, Sn, Zr, Ti, and Nb, nitrides, oxynitrides, carbides, fluorides, and the like are used. These may be a single material or a mixture. Moreover, you may laminate | stack the layer formed with the inorganic material and the organic material from a gas-barrier viewpoint.

  The method for forming the gas barrier film is not particularly limited, and includes a vacuum deposition method, a sputtering method, a reactive sputtering method, a molecular beam epitaxy method, a cluster ion beam method, an ion plating method, an atomic layer deposition (ALD) method, a plasma weighting method. A combination method, atmospheric pressure plasma polymerization method, plasma CVD method, laser CVD method, thermal CVD method, coating method, or the like can be used. From the viewpoint of gas barrier properties, it is preferable to use a sputtering method, a reactive sputtering method, a plasma CVD method, or an ALD method.

  Moreover, the adhesion part which fixes a sealing member to the laminated body side is used as a sealing agent for sealing an organic EL element with a sealing member and a laminated body. Adhesives include photo-curing and thermosetting adhesives with reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, moisture-curing types such as 2-cyanoacrylate, and epoxy-based heat and chemical curing. Examples include molds (two-component mixing), hot-melt types such as polyamide, polyester, and polyolefin, and ultraviolet effect types such as epoxy resin.

  In addition, the organic material which comprises an organic EL element may deteriorate with heat processing. For this reason, the adhesive part is preferably one that can be adhesively cured from room temperature (25 ° C.) to 80 ° C. Moreover, you may disperse | distribute a desiccant in an adhesion part. Further, when a gap is formed between the plate-shaped sealing member and the laminate, in the gap and in the gas phase and the liquid phase, an inert gas such as nitrogen and argon, fluorinated hydrocarbon, and silicon oil are used. It is preferable to inject such an inert liquid. Moreover, it can also be set as a vacuum or a hygroscopic compound can be enclosed inside.

  Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide), sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.). Metal halides (e.g., calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide, etc.), perchloric acids (e.g., barium perchlorate, In particular, anhydrous salts are preferably used in sulfates, metal halides and perchloric acids.

  On the other hand, when a sealing film is used as the sealing member, the sealing film is provided on the laminate in a state where the light emitting unit in the organic EL element is completely covered and the electrode terminal portion of the organic EL element is exposed. Such a sealing film is configured using an inorganic material or an organic material. As the inorganic material, metal oxides such as Si, Al, Zn, Mg, Sn, Zr, Ti, and Nb, nitrides, oxynitrides, carbides, fluorides, and the like are used. These may be a single material or a mixture. Moreover, you may laminate | stack the layer formed with the inorganic material and the organic material from a gas-barrier viewpoint.

  The method for forming the sealing film is not particularly limited, and includes a vacuum deposition method, a sputtering method, a reactive sputtering method, a molecular beam epitaxy method, a cluster ion beam method, an ion plating method, an atomic layer deposition method, a plasma polymerization method, An atmospheric pressure plasma polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used. From the viewpoint of gas barrier properties and step following capability with a light emitting unit or the like, it is preferable to use a sputtering method, a reactive sputtering method, a plasma CVD method, or an ALD method.

[Applications of organic EL elements]
The organic EL device of the present invention can be used as various light sources such as a lighting device and a backlight. Although it can be used for a display device (display) of a type that visually recognizes a still image or a moving image, a projection device of a type that projects an image, etc., the application is not limited to the above.

  Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the following examples.

[Evaluation method]
(1) Layer thickness Samples for cross-sectional observation were obtained by the FIB method using a micro-sampling system (FB-2000A manufactured by Hitachi, Ltd.) (specifically, “Polymer Surface Processing” (by Atsushi Iwamori) p) .118-119)). Using a transmission electron microscope (H-9000UHRII, manufactured by Hitachi, Ltd.), the cross section of the observation sample was observed at an acceleration voltage of 300 kV, and the thicknesses of the first layer, the second layer, and the anchor coat layer of the laminate were measured. .

(2) Film density of layer The film density of each layer of the laminate was evaluated using an X-ray reflectivity method (XRR method). That is, the laminate formed on the base material is irradiated with X-rays from the oblique direction, and the dependence of the total reflection X-ray intensity on the laminate surface with respect to the incident X-ray intensity is measured. A total reflection X-ray intensity profile of the reflected wave was obtained. Thereafter, simulation fitting of the total reflection X-ray intensity profile was performed to determine the thickness and film density of each layer. The fitting method is shown below.

  In the fitting, initial values are set for the parameters of the number of layers, the thickness of each layer, and the film density of each layer, so that the standard deviation of the residual of the X-ray intensity profile and measured data obtained from the set configuration is minimized. Determine final parameters. Other analyzes were performed in advance to determine the initial values in the fitting. The number of layers and the thickness of each layer were measured with a transmission electron microscope (TEM), and composition analysis was performed with X-ray photoelectron spectroscopy (XPS) to determine initial values. A reliability factor (R factor) is generally used as an index indicating the reliability of fitting. In the present invention, fitting was performed until the number of layers was the minimum and the R factor was 1.0% or less, and the parameters of the number of layers, the thickness of each layer, and the film density of each layer were determined.

  In the examples, fitting was performed using Rigaku Global Fit, which is analysis software of an apparatus used for X-ray reflection measurement (SmartLab, Rigaku). When the analysis is performed, fitting is performed with the minimum possible number of layers, and when the R factor is not 1.0% or less, fitting is performed with a configuration in which one new layer is added. Then, this is continued until the R factor is 1.0% or less, and the final structural model is obtained after confirming the validity against other analysis results. In addition, when adding a new layer, if the residual sum of squares after optimization is reduced by 10% or more, it is considered that the addition of the layer is the most likely configuration. Perform fitting.

The measurement conditions were as follows.
・ Apparatus: SmartLab manufactured by Rigaku
-Analysis software: Rigaku Global Fit ver. 2.0.8.0
・ Sample size: 30mm x 40mm
-Incident X-ray wavelength: 0.1541 nm (CuKα1 ray)
・ Output: 45kV, 30mA
-Entrance slit size: 0.05mm x 5.0mm
・ Reception slit size: 0.05mm × 20.0mm
Measurement range (θ): 0 to 3.0 °
Step (θ): 0.002 °.

(3) Composition of layer The composition analysis of each layer of the laminate was performed by X-ray photoelectron spectroscopy (XPS method). The layer was removed from the surface layer by argon ion etching until the thickness of the layer became 1/2, and the content ratio of each element was measured under the following conditions. The measurement conditions of the XPS method were as follows.
・ Equipment: ESCA 5800 (manufactured by ULVAC-PHI)
Excitation X-ray: monochromic AlKα
・ X-ray output: 300W
-X-ray diameter: 800 μm
-Photoelectron escape angle: 45 °
Ar ion etching: 2.0 kV, 10 mPa.

(4) Water vapor transmission rate (g / (m ² · 24 hr · atm))
The water vapor transmission rate of the laminate is a water vapor transmission rate measuring device (model name: DELTAPERRM (registered trademark)) manufactured by Technolox, UK, under conditions of a temperature of 40 ° C., a humidity of 90% RH, and a measurement area of 50 cm ^2. Was measured using. The number of samples was 2 samples per level. Data obtained by measuring two samples were averaged, and the first decimal place was rounded off to obtain an average value at that level, which was taken as the water vapor permeability (g / (m ² · 24 hr · atm)).

(5) Scratch resistance test The scratch resistance of the surface of the laminate was evaluated using a flat abrasion tester. After testing with a flat surface wear tester, the presence or absence of scratches was observed by visual inspection. The evaluation conditions were as follows.
・ Equipment: Plane abrasion tester PA-300A manufactured by Daiei Scientific Instruments
・ Wear: Steel wool ・ Test load: 200g
・ Wear reciprocating speed: 40 times / min ・ Sample size: 100 mm × 50 mm
Evaluation was performed according to the following evaluation criteria.
1: No scratch 2: No more than 10 scratches 3: No more than 11 scratches

(6) Evaluation of organic EL element When direct current was applied to the obtained organic EL element using a source measure unit type 2400 manufactured by Tektronix, all the organic EL elements emitted light well.

  Next, after the above evaluation, the sample was allowed to stand at 85 ° C. and 85% relative humidity for 24 hours, and then the same evaluation was performed to examine the presence or absence of light emission. 70% or more with respect to the initial light emitting area was marked with ◯, and less than 70% with x.

Example 1
(Synthesis of polyurethane compounds having an aromatic ring structure)
In a 5-liter four-necked flask, 300 parts by mass of bisphenol A diglycidyl ether acrylic acid adduct (Kyoeisha Chemical Co., Ltd., trade name: epoxy ester 3000A) and 710 parts by mass of ethyl acetate are added, and the internal temperature becomes 60 ° C. So warmed. As a synthesis catalyst, 0.2 part by mass of di-n-butyltin dilaurate was added, and 200 parts by mass of dicyclohexylmethane 4,4′-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour with stirring. Reaction was continued for 2 hours after completion | finish of dripping, and 25 mass parts of diethylene glycol (made by Wako Pure Chemical Industries Ltd.) was dripped over 1 hour continuously. The reaction was continued for 5 hours after the dropwise addition to obtain a polyurethane compound having an aromatic ring structure with a weight average molecular weight of 20,000.

(Formation of anchor coat layer)
As the substrate, a polyethylene terephthalate film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 100 μm was used.

  As a coating solution for forming an anchor coat layer, 150 parts by mass of the polyurethane compound, 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DPE-6A), 1-hydroxy-cyclohexylphenyl- 5 parts by weight of ketone (manufactured by BASF Japan, trade name: IRGACURE 184), 3 parts by weight of 3-methacryloxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Silicone, trade name: KBM-503), and 170 parts by weight of ethyl acetate Parts, 350 parts by mass of toluene, and 170 parts by mass of cyclohexanone were added to prepare a coating solution. Next, the coating liquid was applied on a substrate with a micro gravure coater (gravure wire number 150UR, gravure rotation ratio 100%), dried at 100 ° C. for 1 minute, dried, and then subjected to UV treatment under the following conditions to obtain a thickness of 1, An anchor coat layer of 000 nm was provided.

Ultraviolet ray processing apparatus: LH10-10Q-G (manufactured by Fusion UV Systems Japan)
Introduced gas: N ₂ (nitrogen inert BOX)
Ultraviolet light source: Microwave type electrodeless lamp Integrated light quantity: 400 mJ / cm ²
Sample temperature control: room temperature.

(Formation of the first layer)
Using a winding-type sputtering apparatus (hereinafter referred to as a sputtering apparatus) 5 shown in FIG. 3, a sputtering target, which is a mixed sintered material formed of zinc oxide, silicon dioxide, and aluminum oxide, is placed on the sputtering electrode 12, and argon is added. Sputtering with gas and oxygen gas was performed, and a ZnO—SiO ₂ —Al ₂ O ₃ layer having a thickness of 10 nm was provided on the anchor coat surface of the substrate 1 as a first layer.

The specific operation is as follows. First, in the winding chamber 6 of the sputtering apparatus 5 in which a sputtering target sintered with a composition ratio of zinc oxide / silicon dioxide / aluminum oxide of 77/20/3 (unit: mass%) is installed on the sputtering electrode 12. Then, the unwinding roll 7 is set so that the surface on which the first layer of the base material 1 is provided (the side on which the anchor coat is formed) faces the sputter electrode 12, unwinding, and guide rolls 8, 9, 10 was passed through the main drum 11 controlled to a temperature of 100 ° C. Next, the inside of the sputtering apparatus 5 was depressurized with a vacuum pump to obtain 2.0 × 10 ⁻³ Pa or less. Next, argon gas and oxygen gas are introduced at a partial pressure of oxygen gas of 10% so that the degree of vacuum is 1.5 × 10 ⁻¹ Pa, and an input power of 3,000 W is applied to the sputtering electrode 12 by a DC pulse power source. Then, an argon / oxygen gas plasma was generated, and a ZnO—SiO ₂ —Al ₂ O ₃ layer was formed on the anchor coat surface of the substrate 1 by sputtering. The thickness of the _ZnO-SiO 2 _-Al 2 _{O 3} layer formed were adjusted by the film transport speed. Then, it wound up on the winding roll 17 via the guide rolls 14, 15, and 16.

(Formation of the second layer)
Subsequent to the formation of the first layer, a second layer was provided on the first layer of the substrate 1 using a sputtering apparatus having the structure shown in FIG. A sputter target, which is a mixed sintered material formed of tin and silicon, is placed on the sputter electrode 13 and sputtered with argon gas and oxygen gas. On the first layer of the substrate 1, SnO is formed as a second layer. _{A 2-} SiO ₂ layer was provided with a thickness of 30 nm.

The specific operation is as follows. First, in the winding chamber 6 of the sputtering apparatus 5 in which a sputtering target sintered with a tin / silicon atomic concentration of 50/50 atm% is installed on the sputtering electrode 13, the first roll of the substrate 1 is placed on the unwinding roll 7. The surface on which the two layers are provided (the side on which the first layer is formed) is set so as to face the sputter electrode 13, unwinds, and is controlled to a temperature of 100 ° C. via the guide rolls 8, 9, 10. Passed through the main drum 11. Next, the inside of the sputtering apparatus 5 was depressurized with a vacuum pump to obtain 2.0 × 10 ⁻³ Pa or less. Subsequently, argon gas and oxygen gas are introduced at an oxygen gas partial pressure of 50% so that the degree of vacuum is 5.0 × 10 ⁻¹ Pa, and an input power of 1,500 W is applied to the sputtering electrode 13 by a DC pulse power source. Then, an argon / oxygen gas plasma was generated, and a SnO ₂ —SiO ₂ layer was formed on the surface of the first layer of the substrate 1 by sputtering. Moreover, the thickness of the SnO ₂ —SiO ₂ layer to be formed was adjusted by the film conveyance speed. Then, the winding laminated body was obtained by the winding roll 17 via the guide rolls 14, 15, and 16.

  Then, the test piece was cut out from the obtained laminated body, and various evaluation was implemented. The results are shown in Table 1.

(Production of organic EL element)
A positive electrode layer of indium tin oxide (ITO, indium / tin = 95/5 molar ratio) was formed on the laminate cut out to 25 mm × 25 mm by a sputtering method using a DC power source (thickness 0.2 μm). A mask pattern was placed on the surface of the positive electrode layer of the obtained laminate with a positive electrode layer, and a resist pattern was formed by printing using a resist ink. The obtained resist pattern was dried at 100 ° C. for 10 minutes. Next, the portion where the resist pattern was formed was immersed in an etching solution (iron chloride II: 27 mass%, hydrochloric acid: 10 mass%), and ITO in the portion where the resist pattern was not formed was dissolved and removed.

On this positive electrode layer, copper phthalocyanine (CuPc) was provided as a hole injection layer in a thickness of 20 nm by vacuum deposition, and N, N′-dinaphthyl-N, N′-diphenylbenzidine was provided thereon as a hole transport layer. Was provided with a thickness of 40 nm by a vacuum deposition method. On top of this, 4,4′-N, N′-dicarbazol-biphenyl as a host material, and tris (2-phenylpyridine) iridium complex (Ir (ppy) ₃ ) as a dopant material so as to have a mass ratio of 100/4. A light emitting layer having a thickness of 40 nm was obtained.

  Further, tris (8-quinolinolato) aluminum as an electron transport material was provided thereon with an electron transport layer having a thickness of 50 nm by a vacuum deposition method.

  A patterned mask (a mask with a light emission area of 5 mm × 5 mm) is placed on the organic compound layer, lithium fluoride is deposited to a thickness of 1 nm in a deposition apparatus, and aluminum is further deposited to a thickness of 100 nm to form a negative electrode. A layer was provided. An aluminum EL lead wire was drawn out from each of the positive electrode layer and the negative electrode layer to prepare an organic EL device. The device was placed in a glove box substituted with nitrogen gas, and sealed with a glass cap and an ultraviolet curable adhesive (XNR 5493, manufactured by Nagase Ciba). Evaluation was implemented regarding the obtained organic EL element. The results are shown in Table 1.

(Example 2)
In the formation of the SnO ₂ —SiO ₂ layer as the _second layer, the laminate and organic layer were formed in the same manner as in Example 1, except that a sputter target sintered at an atomic concentration of tin / silicon of 62/38 atm% was used. An EL element was obtained. The results are shown in Table 1.

(Example 3)
In the formation of the SnO ₂ —SiO ₂ layer as the _second layer, the laminate and organic layer were formed in the same manner as in Example 1, except that a sputter target sintered at an atomic concentration of tin / silicon of 32/68 atm% was used. An EL element was obtained. The results are shown in Table 1.

(Example 4)
In the formation of the SnO ₂ —SiO ₂ layer as the _second layer, a laminate and an organic EL device were obtained in the same manner as in Example 1 except that the film conveyance speed was adjusted with the aim of a film thickness of 50 nm. The results are shown in Table 1.

(Example 5)
In the formation of the ZnO—SiO ₂ —Al ₂ O ₃ layer, which is the first layer, a laminate and an organic EL element were formed in the same manner as in Example 1 except that the film transport speed was adjusted with the aim of a film thickness of 30 nm. . The results are shown in Table 1.

(Example 6)
In the formation of the second layer, a laminate and an organic EL device were obtained in the same manner as in Example 1 except that a sputter target sintered at an atomic concentration of zirconium / silicon of 33/67 atm% was used. The results are shown in Table 1.

(Example 7)
In the formation of the ZnO—SiO ₂ —Al ₂ O ₃ layer, which is the first layer, the film transport speed is adjusted aiming at a film thickness of 50 nm, and in the formation of the SnO ₂ —SiO ₂ layer, which is the second layer, the film thickness is 30 nm. A laminated body and an organic EL element were obtained in the same manner as in Example 1 except that the film conveyance speed was adjusted with the aim. The results are shown in Table 1.

(Example 8)
In the formation of the ZnO—SiO ₂ —Al ₂ O ₃ layer as the first layer, the film conveyance speed is adjusted with the aim of the film thickness of 150 nm, and in the formation of the SnO ₂ —SiO ₂ layer as the _second layer, the film thickness is 50 nm. A laminated body and an organic EL element were obtained in the same manner as in Example 1 except that the film conveyance speed was adjusted with the aim. The results are shown in Table 1.

(Comparative Example 1)
In the formation of the first layer, the ZnO—SiO ₂ —Al ₂ O ₃ layer, the laminate was prepared in the same manner as in Example 1 except that the film transport speed was adjusted with the aim of film thickness of 40 nm and the second layer was not formed. And the organic EL element was formed. The results are shown in Table 1.

(Comparative Example 2)
In the formation of the second layer, a laminate and an organic EL device were formed in the same manner as in Example 1 except that a silicon sputtering target was used and the film conveyance speed was adjusted with a target of a film thickness of 50 nm. The results are shown in Table 1.

(Comparative Example 3)
In the formation of the second layer, a laminate and an organic EL element were formed in the same manner as in Example 1 except that a sputter target of tin was used. The results are shown in Table 1.

(Comparative Example 4)
In the formation of the SnO ₂ —SiO ₂ layer as the _second layer, the laminate and organic layer were formed in the same manner as in Example 1 except that a sputter target sintered at an atomic concentration of tin / silicon of 3/97 atm% was used. An EL element was obtained. The results are shown in Table 1.

(Comparative Example 5)
The SnO ₂ —SiO ₂ layer, which is the second layer of Example 1, was formed as the first layer, and then the ZnO—SiO ₂ —Al ₂ O ₃ layer, which was the first layer of Example 1, was formed as the second layer. Except for the above, a laminate and an organic EL element were obtained in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 6)
The SnO ₂ —SiO ₂ layer, which is the second layer of Example 1, was used as the first layer, the film thickness was adjusted to 40 nm by adjusting the transport speed, and the second layer was not formed. The body and the organic EL element were obtained. The results are shown in Table 1.

(Comparative Example 7)
In the formation of the ZnO—SiO ₂ —Al ₂ O ₃ layer as the first layer, a laminate and an organic EL device were obtained in the same manner as in Comparative Example 1 except that the film conveyance speed was adjusted with a target of a film thickness of 150 nm. . The results are shown in Table 1.

  Examples 1 to 8 have good gas barrier properties and good scratch resistance. On the other hand, Comparative Examples 1 to 5 and 7 have good gas barrier properties but are inferior in scratch resistance. In Comparative Example 6, the scratch resistance is good, but the gas barrier property is poor. That is, by using the configuration of the present invention, it is possible to obtain a laminate having a high gas barrier property even with a simple configuration and having excellent scratch resistance.

Moreover, the organic EL elements produced using the laminates of Examples 1 to 8 and Comparative Examples 2 to 4 emit light well even after being left for 24 hours at 85 ° C. and 85% relative humidity. On the other hand, the organic EL elements produced using the laminates of Comparative Examples 1 and 5 to 7 had the same result that no light emission was observed or almost no light emission after standing. This is because in Comparative Examples 1 and 7, the first layer (ZnO—SiO ₂ —Al ₂ O ₃ ) has no resistance to the etching solution, and is dissolved during the positive electrode layer etching, so that it does not exhibit gas barrier properties. It depends. As a result, the light emitting unit deteriorated due to the infiltrated moisture. Similarly, Comparative Example 5 has no resistance to the etching solution of the second layer (ZnO—SiO ₂ —Al ₂ O ₃ ), and since it was dissolved during the positive electrode layer etching, gas barrier properties were not exhibited. Although the comparative example 6 did not melt | dissolve the 1st layer at the time of an etching, the light emission unit deteriorated as a result by low gas barrier property.

  Since the laminate of the present invention is excellent in gas barrier properties against oxygen gas, water vapor and the like, it can be usefully used, for example, as a packaging material for foods, pharmaceuticals, etc., and as a member for electronic devices such as thin televisions and solar cells. The application is not limited to these.

DESCRIPTION OF SYMBOLS 1 Base material 2 1st layer 3 2nd layer 4 Anchor coat layer 5 Winding-type sputtering apparatus 6 Winding chamber 7 Unwinding roll 8, 9, 10 Unwinding side guide roll 11 Main drum 12, 13 Sputtering electrodes 14, 15 , 16 Winding side guide roll 17 Winding roll 18 Positive electrode layer 19 Hole injection layer 20 Hole transport layer 21 Light emitting layer 22 Electron transport layer 23 Negative electrode layer 24 Sealing member 25 Adhesive part 26 Laminate 27 Light emitting unit

Claims (8)

A laminated body having a first layer containing zinc and silicon and a second layer containing a metal element other than silicon and silicon in this order from at least one side of the substrate in this order, and the film density of the second layer Is a laminate having a thickness of 2.5 to 7.0 g / cm ³ . The laminate according to claim 1, wherein the metal element other than silicon is at least one metal element selected from the group consisting of tin, zirconium, titanium, aluminum, tantalum, gallium, germanium, and indium. The laminate according to claim 1 or 2, wherein the first layer includes at least one selected from the group consisting of zinc oxide, silicon oxide, and aluminum oxide. The laminate according to any one of claims 1 to 3, wherein the second layer contains tin oxide and silicon oxide. The laminated body in any one of Claims 1-4 which has an anchor-coat layer between the said base material and the said 1st layer. The first layer has a zinc (Zn) atom concentration of 3 to 37 atm%, a silicon (Si) atom concentration of 5 to 20 atm%, and an aluminum (Al) atom concentration of 1 to 7 atm%, as measured by X-ray photoelectron spectroscopy. The laminate according to any one of claims 1 to 5, wherein the oxygen (O) atom concentration is 50 to 70 atm%. The second layer contains tin, and has a tin (Sn) atom concentration of 10 to 30 atm%, a silicon (Si) atom concentration of 10 to 30 atm%, and an oxygen (O) atom concentration of 50 as measured by X-ray photoelectron spectroscopy. It is -75atm%, The laminated body in any one of Claims 1-6. The organic electroluminescent element which has a positive electrode layer, a light emitting unit, and a negative electrode layer in this order from the laminated body side on the laminated body in any one of Claims 1-7.

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