KR20210078443A - laminate - Google Patents

Abstract

An A layer is provided on at least one side of a substrate, wherein the A layer contains at least two elements selected from the group consisting of elements of groups 2 to 5 and groups 12 to 14 of the periodic table, and oxygen; A laminate having an arithmetic mean roughness (Ra) of 5.0 nm or less as calculated by an atomic force microscope (AFM) on the surface of the layer. A laminate having high gas barrier properties even with a low cost and simple configuration is provided.

Description

laminate

The present invention relates to a laminate used for packaging materials for foods and pharmaceuticals requiring high gas barrier properties, and materials for electronic components such as solar cells, electronic papers, and organic electroluminescence (EL) displays.

Physical vapor deposition method (PVD method) such as vacuum deposition method, sputtering method, ion plating method, etc., or chemical vapor deposition method (CVD method) such as plasma chemical vapor deposition method, thermochemical vapor deposition method, and photochemical vapor deposition method on the surface of the film substrate ), etc. to form an inorganic layer of inorganic substances (including inorganic oxides), gas barrier films that require blocking of various gases such as water vapor and oxygen, packaging materials for food and pharmaceutical products, electronic paper, and solar cells It is used as electronic device members, such as these, and these members ^{WHEREIN: High gas-barrier property of 5.0x10 -2} g/m<2>*24hr*atm or less is calculated|required by water vapor transmission rate.

As one of the methods for satisfying the high gas barrier properties, a gas barrier film (Patent Document 1) that prevents the occurrence of defects due to the pore filling effect by alternately laminating an organic layer and an inorganic layer in multiple layers, or ZnO and SiO ₂ A gas barrier film (patent document 2) having a simple film structure in which a composite oxide film such as a _{ZnO-SiO 2} system is formed on a film substrate by sputtering using a target as a main component has been proposed.

Japanese Patent Laid-Open No. 2005-324406 Japanese Patent Laid-Open No. 2013-147710

However, although it is possible to express high barrier properties by alternately laminating an organic layer and an inorganic layer in multiple layers as in Patent Document 1, there is a problem in that the number of steps increases and the cost becomes high at the point of lamination. In addition, as in Patent Document 2, a laminate in which a complex oxide is formed by sputtering can be manufactured at a lower cost compared to Patent Document 1, but due to the nature of the manufacturing method, there is a limitation in increasing the film formation speed. It was difficult.

An object of the present invention is to provide a laminate having high gas barrier properties even with a low cost and simple configuration in view of the background of the prior art.

In order to solve this problem, the present invention employs the following means. That is, below.

(1) having an A layer on at least one side of the substrate, wherein the A layer contains at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table, and oxygen; , The laminate having an arithmetic mean roughness (Ra) of 5.0 nm or less calculated by atomic force microscopy (AFM) of the surface of the layer A.

(2) having an A layer on at least one side of the substrate, wherein the A layer contains at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table, and oxygen; , The layer A has an average lifetime measured by a positron beam method of 0.935 ns or less.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body which has high gas-barrier property with respect to water vapor|steam can be provided at low cost.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which showed an example of the laminated body of this invention.
2 is a cross-sectional view showing another example of the laminate of the present invention.
3 is a schematic diagram schematically showing a winding-up electron beam vapor deposition apparatus for manufacturing a laminate of the present invention.
It is a figure which shows typically the material arrangement|positioning for manufacturing the laminated body of this invention from the top.
It is a figure which shows typically the material arrangement|positioning for manufacturing the laminated body of this invention from the side.

The details of the present invention will be described below.

In addition, when it describes as this invention 1, it means this invention of the following aspects.

An A layer is provided on at least one side of a substrate, wherein the A layer contains at least two elements selected from the group consisting of elements of groups 2 to 5 and groups 12 to 14 of the periodic table, and oxygen; A laminate having an arithmetic mean roughness (Ra) of 5.0 nm or less as calculated by an atomic force microscope (hereinafter, AFM) on the surface of the layer.

In addition, when it describes as this invention 2, it means this invention of the following aspects.

An A layer is provided on at least one side of a substrate, wherein the A layer contains at least two elements selected from the group consisting of elements of groups 2 to 5 and groups 12 to 14 of the periodic table, and oxygen; The layer is a laminate having an average lifetime of 0.935 ns or less as measured by a positron beam method.

Incidentally, in the case where only the present invention is described, it is a generic term for the present invention 1 and the present invention 2.

[Laminate]

The laminate of the present invention 1 has an A layer on at least one side of the substrate, wherein the A layer includes at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table; It is a laminated body which contains oxygen and whose arithmetic mean roughness (Ra) computed by the atomic force microscope (AFM) of the said A-layer surface is 5.0 nm or less. In addition, the laminate of the present invention 2 has an A layer on at least one side of the substrate, wherein the A layer is at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table; and , oxygen, and the layer A is a laminate having an average lifetime measured by a positron beam method of 0.935 ns or less.

Elements of groups 2 to 5 and 12 to 14 of the periodic table included in layer A include magnesium, calcium, strontium, scandium, titanium, zirconium, tantalum, zinc, aluminum, gallium, indium, silicon, germanium, tin, etc. can be heard The combination of at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table is not limited, but from the viewpoint of gas barrier properties and formation of an amorphous film, at least two kinds of elements Preferred elements are magnesium and silicon, zinc and silicon, tin and zinc, calcium and silicon, zirconium and silicon, aluminum and silicon. At least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table from the viewpoint of gas barrier properties and silicate bonding are a combination of magnesium and silicon, or a combination of zinc and silicon more preferably.

The form of at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table included in layer A includes oxides, nitrides, oxynitrides, carbides, and the like, and is particularly limited However, it is preferable to exist in the form of oxides, nitrides, and oxynitrides from the viewpoints of gas barrier properties, optical properties, and the like. It is more preferable to contain as at least one compound selected from the group consisting of oxides, nitrides, oxynitrides and carbides from the viewpoint of forming an amorphous film and gas barrier properties.

When layer A of the laminate of the present invention contains oxygen and at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table, other inorganic compounds are included. it doesn't matter if

The arithmetic mean roughness (Ra) calculated by AFM of the surface of A-layer of the laminated body of this invention 1 is 5.0 nm or less. When Ra becomes larger than 5.0 nm, since A-layer will not become dense, gas barrier property may not be expressed. It is preferable that it is 3.0 nm or less from a viewpoint of gas barrier property, and, as for Ra, it is more preferable that it is 2.0 nm or less. In addition, although the lower limit of Ra is not specifically limited, It is preferable that it is 0.1 nm or more. When Ra is smaller than 0.1 nm, adhesiveness may worsen. In addition, the analysis range of AFM at the time of calculating arithmetic mean roughness Ra shall be 1 micrometer x 1 micrometer.

In order to make the arithmetic mean roughness (Ra) calculated by atomic force microscopy (AFM) of the surface of the layer A defined in the present invention 1 to 5.0 nm or less, for example, a composition suitable for a composite oxide film on a substrate having an Ra of 5.0 nm or less. This is achieved by forming in proportions. By forming the composite oxide film as the A layer, it is possible to form a smoother film than when a single metal oxide film is formed as the A layer.

Layer A of the laminate of the present invention 2 has an average lifetime measured by the positron beam method (a thin-film-corresponding positron annihilation lifetime measurement method) (see "Science of Positron Measurement" (Japan Isotope Association) Section I Section 1, Section V Section 2) 0.935ns or less. The positron beam method is one of the positron annihilation lifetime measurement methods, measures the time (in the order of several hundred ps to several tens of ns) from when a positron is incident on a sample until it disappears, and the size and number of pores of about 0.1 to 10 nm from the extinction lifetime It is a method of non-destructively evaluating information about the distribution of concentrations and sizes. ^{The use of a positron beam instead of a radioisotope (22} Na) as a positron source is significantly different from the conventional positron annihilation method, and it is a method that enables measurement of thin films with a thickness of several hundred nm formed on a silicon or quartz substrate. From the obtained measured value, an average pore radius and the number density of pores can be calculated|required by the nonlinear least square program POSITRONFIT. Corresponding to sub-nm order pores and basic skeletons are obtained by analyzing the average lifetimes of the third and fourth components.

Here, the third component refers to the average lifetime obtained by selecting the analysis for three components as the measurement conditions for the average lifetime by the positron beam method, and the fourth component refers to the analysis for the four components as the measurement conditions for the average lifetime by the positron beam method refers to the average lifespan obtained by selecting When analyzing with POSITRONFIT, the number of components of POSITRONFIT is determined from the number of peaks obtained from the pore radius distribution curve calculated using the distribution analysis program CONTIN based on the inverse Laplace transform method. When the average pore radius calculated from POSITRONFIT and the peak position of the pore radius distribution curve of CONTIN coincide, it is judged that the analysis is reasonable. The average lifespan as used in the present invention 2 refers to the average lifespan of the third component.

If the average lifetime is greater than 0.935 ns, the A layer will not be dense, so there is a possibility that the gas barrier properties will not be expressed. From the viewpoint of gas barrier properties, the average lifetime measured by the positron beam method is preferably 0.912 ns or less, and more preferably 0.863 ns or less. In addition, although the lower limit of an average lifetime is not specifically limited, It is preferable that it is 0.542 ns or more. When the average lifetime is less than 0.542 ns, the flexibility may decrease.

In order to make the average lifetime of the layer A measured by the positron beam method defined in the second aspect of the present invention 0.935 ns or less, for example, it is achieved by densely forming a composite oxide film at a suitable composition ratio on a substrate having an Ra of 3.0 nm or less. The dense formation as used herein refers to a state in which each oxide is mixed with each other at the atomic level to form a dense network.

It is preferable that layer A of the laminated body of this invention is an amorphous film. Amorphous means that atoms or molecules do not have an ordered structure over long distances like crystals, but have an irregular structure. If it is a crystal structure, it becomes a water vapor|steam permeation path|route from the point which a crystal grain boundary arises, and it is preferable that it is an amorphous thing from the point which gas barrier property worsens or becomes brittle. Whether or not it is amorphous can be confirmed by an analysis method such as cross-sectional TEM or X-ray diffraction (XRD). In the case of cross-sectional TEM, the contrast becomes uniform in the amorphous film, and grain boundaries are not observed, whereas in the crystalline film, grain boundaries depending on the crystal structure such as a microcrystalline state or a columnar structure are observed.

In the layer A of the present invention, the half width of the peak of the oxygen atom (O1s) measured by X-ray photoelectron spectroscopy is preferably 3.25 eV or less. Half band width refers to the peak width at the time when the maximum value of the peak to F _max, the intensity of the peak F _max / 2 days. The narrower the half width of the O1s peak tends to form a dense film because a network structure of uniform bonds is formed. From the viewpoints of bonding uniformity and barrier properties, 3.00 eV or less is more preferable, and 2.75 eV or less is still more preferable. Moreover, although a lower limit is not specifically limited, It is preferable that it is 1.65 eV or more.

The laminate of the present invention preferably has a water vapor transmission rate of ^{less than 5.0×10 −2} g/m 2 /day. ^{It is more preferable that the water vapor permeability of the laminate of the present invention is less than 1.0×10 −2} g/m 2 /day from the viewpoint of being used for high-quality packaging materials or electronic devices requiring relatively high gas barrier properties. In addition, the lower limit of the water vapor permeability is not particularly limited, but the water vapor permeability of the laminate of the present invention ^{is preferably 1.0×10 −4} g/m 2 /day or more, since cracks are likely to occur when the film becomes denser than necessary.

The layer A preferably has a silicate bond. The silicate bond is a bond between silicon (Si) and metal (M) through oxygen (O), and may be described as Si-O-M. For example, a zinc silicate bond (Si-O-Zn), a magnesium silicate bond (Si-O-Mg), an aluminum silicate bond (Si-O-Al), etc. are mentioned. By having a silicate bond in A-layer, it becomes a dense structure and high gas-barrier property is acquired. Methods, such as X-ray photoelectron spectroscopy and X-ray absorption microstructure (XAFS), are mentioned as an analysis method (confirmation method) of the presence or absence of a silicate bond.

In order for the A layer to have a silicate bond, as described above, the A layer is a combination of magnesium and silicon, or zinc as at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table. and a combination of silicon, and preferably further contains oxygen. In addition, the presence or absence of a silicate bond can be confirmed by X-ray photoelectron spectroscopy, and the detailed method is described in the section of Examples.

It is preferable that the film density of A-layer is 2.0-7.0 g/cm<3> from a viewpoint of gas barrier property and compactness. When it is smaller than 2.0 g/cm<3>, the obtained layer A is not dense and sufficient gas-barrier property may not be acquired. On the other hand, when the film density of A-layer is larger than 7.0 g/cm<3>, A-layer will become hard easily, and a crack may become easy to form or it may become easy to crack. It is more preferable that the film density of A-layer is 2.5-6.0 g/cm<3> from a viewpoint of gas barrier property and brittleness.

In the present invention, the film density of the layer A is a value measured by the X-ray reflectance method (XRR method) (“Introduction to X-ray reflectance” (Edited by Kenji Sakurai) p.51 to 78). Specifically, first, X-rays are generated from an X-ray source, and the beams are collimated by a multilayer mirror, then passed through an incident slit to limit the X-ray angle, and are incident on a measurement sample. By making the X-rays incident at a shallow angle substantially parallel to the surface of the sample for measuring the incident angle of the X-rays, a reflected beam of X-rays reflected and interfered with each layer of the sample and the interface of the substrate is generated. The X-ray intensity is measured by passing the generated reflected beam through a light-receiving slit, restricting it to a required X-ray angle, and entering it on a detector. By continuously changing the angle of incidence of X-rays using this method, a total reflection X-ray intensity profile at each angle of incidence can be obtained.

As an analysis method of the film density of each layer, it is obtained by fitting the obtained actual measurement data of the total reflection X-ray intensity profile with respect to the incident angle of X-rays to Parratt's theoretical equation by the nonlinear least square method (“Introduction to X-ray reflectance” (Edited by Kenji Sakurai) See p.81-141).

The formation method of the A layer is not particularly limited, and a formation method such as a sputtering method, a vacuum deposition method, an ion plating method, a CVD method, or an atomic layer deposition (ALD) is used. Among these methods, the vacuum vapor deposition method is preferable as a method for obtaining a desired property because it is inexpensive and simple. That is, it is preferable that layer A is a layer formed by the vacuum deposition method. Among the vacuum deposition methods, the electron beam (EB) deposition method is more preferable from the viewpoint of controlling the film composition by depositing a compound. Moreover, it is good also as reactive vapor deposition using oxygen, nitrogen, water vapor|steam etc. as a reactive gas, or using ion assist etc. In addition, the vacuum deposition method may be any of film-forming modes, such as a single-wafer type and a winding type. Fig. 3 shows an example of a winding-up device.

[Example of manufacturing method of layer A]

Wind-up vapor deposition apparatus An example of the formation method of A-layer by FIG. 3 is shown. A thin film of the compound of materials B and C is formed as an A layer on the surface of the base material 1 by the electron beam vapor deposition method. First, as deposition materials, granular material B and material C having a size of about 2 to 5 mm are alternately arranged as shown in FIGS. 4 and 5 . The area ratio at the time of alternate arrangement is arranged according to the target film composition of the A layer, the EB irradiation method, and the like. It is preferable that the width|variety for every material to arrange|position in that case is 10-100 mm. When it is larger than 100 mm, the composition ratio in the width direction of the materials B and C and the nonuniformity of a film|membrane quality become large easily. If it is less than 10 mm, the workability at the time of arranging a material may fall. It is more preferable that it is 10-80 mm from a viewpoint of the composition ratio of the width direction, the nonuniformity of film|membrane quality, workability, etc. In addition, the vapor deposition material is not limited to granules, You may use the thing of shapes, such as a molded object, such as a square shape and a tablet shape. In addition, if the vapor deposition material absorbs moisture, moisture in the material is introduced into the layer A, and there is a possibility that the desired film composition or physical properties may not be obtained. Therefore, it is preferable to dehydrate the material by heating before use. In the winding chamber 5, on the unwinding roll 6, the surface of the base material 1 on the side forming the layer A is set to face the hearth liner 11, is unwound, and the guide rolls 7, 8, 9 is passed through the main drum (10). Next, the inside of the vapor deposition apparatus 4 is pressure-reduced with a vacuum pump, and 5.0x10 ^-3 Pa or less is obtained. The achieved vacuum degree is ^{preferably 5.0×10 -3} Pa or less. When the achieved vacuum degree is ^{larger than 5.0 x 10 -3} Pa, residual gas is introduced into the A layer, and there is a possibility that the desired film composition and physical properties cannot be obtained. The temperature of the main drum 10 is set to -15°C as an example. From a viewpoint of preventing the heat loss of a base material, 20 degrees C or less is preferable, More preferably, it is 0 degrees C or less. Next, one electron gun (hereinafter, EB gun) 13 was used as a heating source, and the surfaces of the materials B and C were uniformly heated. The EB gun was set to have an accelerating voltage of 6 kV, an applied current of 50 to 200 mA, and a deposition rate of 1 nm/sec, to form a layer A on the surface of the substrate 1 by EB deposition. In addition, the thickness of A-layer to form was adjusted with the film conveyance speed. Thereafter, it is wound on the winding roll 18 via the guide rolls 15 , 16 , and 17 .

The composition ratio of the layer A can be measured by X-ray photoelectron spectroscopy (XPS method) or fluorescence X-ray (XRF) analysis. When using X-ray photoelectron spectroscopy, hydrocarbons and water contained in the air are adsorbed on the outermost surface, and since the correct composition of the A layer is not reflected, the layer is removed by argon ion etching about 5 nm from the outermost surface to contain each element. measure the ratio. When fluorescence X-ray spectroscopy is used, the content ratio of the constituent elements is measured by the fundamental parameter method (FP method).

Layer A contains magnesium and silicon as at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table, and magnesium (Mg) atoms measured by X-ray photoelectron spectroscopy. It is preferable that the concentration is 5 to 50 atm%, the silicon (Si) atom concentration is 2 to 30 atm%, and the oxygen (O) atom concentration is 45 to 70 atm%. From the viewpoints of film quality and gas barrier properties, it is more preferable that the magnesium (Mg) atom concentration is 8 to 35 atm%, the silicon (Si) atom concentration is 6 to 25 atm%, and the oxygen (O) atom concentration is 50 to 65 atm%. When the magnesium atom concentration is more than 50 atm% or the silicon atom concentration is less than 2 atm%, since the ratio of silicon atoms decreases, the A layer tends to become a crystalline layer, and cracks are likely to be formed in some cases. When the magnesium atom concentration is less than 5 atm% or the silicon atom concentration is more than 30 atm%, the proportion of silicate bonds in the A layer decreases. When the oxygen atom concentration is less than 45 atm%, magnesium and silicon become insufficiently oxidized, and the light transmittance may decrease. In addition, when the oxygen atom concentration is more than 70 atm%, oxygen is introduced excessively, so that voids and defects increase and the gas barrier property may decrease.

In the layer A, the ratio (Mg/Si) of the atomic concentration (atm%) of magnesium (Mg) atoms to silicon (Si) atoms is preferably 0.30 to 11.00. When the ratio of the atomic concentration (atm%) (Mg/Si) < 0.30, the ratio of silicate bonds in the A-layer decreases, so that the compactness is lowered and the gas barrier property is not expressed in some cases. When the ratio (Mg/Si) of the atomic concentration (atm%)>11.00, the A layer tends to become a crystalline layer, and cracks are likely to be formed in some cases. From a viewpoint of gas barrier property, 0.50-4.60 are more preferable, and, as for the ratio (Mg/Si) of atomic concentration (atm%), 0.80-2.70 are still more preferable.

The thickness of the layer A in the present invention can be obtained by evaluation by a transmission electron microscope (TEM) and an X-ray reflectance method (XRR method). 5 nm or more is preferable and, as for the thickness of A-layer, 10 nm or more is more preferable. When the thickness is thinner than 5 nm, a region not formed as a layer occurs, and sufficient gas barrier properties cannot be ensured in some cases. Moreover, 500 nm or less is preferable and, as for the thickness of A-layer, 300 nm or less is more preferable. When the thickness of A-layer is thicker than 500 nm, a crack may be easy to form, or bending resistance and ductility may fall.

[materials]

The substrate used in the present invention preferably has a film form from the viewpoint of securing flexibility. As a structure of a film, a single-layer film or the film formed into a film by the coextrusion method of two or more layers, for example may be sufficient. As the kind of the film, a non-stretched, uniaxially stretched, or biaxially stretched film may be used.

Although the raw material of the base material used for this invention is not specifically limited, It is preferable to use organic polymer as a main component. 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, and poly Various polymers, such as carbonate, polystyrene, polyvinyl alcohol, the saponified material of ethylene vinyl acetate copolymer, polyacrylonitrile, polyacetal, etc. are mentioned. Among these, it is preferable to use an amorphous cyclic polyolefin or polyethylene terephthalate excellent in transparency, versatility, and mechanical properties. In addition, any of a homopolymer and a copolymer may be sufficient as the said organic polymer, and only one type may be used as an organic polymer, and multiple types may be blended and used for it.

On the surface of the substrate on the side on which the layer A is to be formed, corona treatment, plasma treatment, ultraviolet treatment, ion bombardment treatment, solvent treatment, an anchor coat layer composed of an organic material or an inorganic material or a mixture thereof is formed in order to improve adhesion and smoothness. Pre-processing, such as a process, may be performed. Further, on the opposite side of the side on which the layer A is formed, a coating layer of an organic substance, an inorganic substance, or a mixture thereof may be laminated for the purpose of improving the activity during winding of the substrate and scratch resistance of the substrate.

Although the thickness of the base material used in this invention is not specifically limited, From a viewpoint of ensuring flexibility, 500 micrometers or less are preferable, and 5 micrometers or more are preferable from a viewpoint of ensuring strength with respect to tension or an impact. Moreover, as for the thickness of a base material, 10 micrometers or more and 200 micrometers or less are more preferable from the easiness of processing and handling of a film.

[Anchor Court Floor]

It is preferable that the laminate of the present invention has an anchor coat layer, and one side of the anchor coat layer is in contact with the substrate and the other side is in contact with the layer A. Moreover, it is more preferable that the anchor-coat layer contains the structure obtained by bridge|crosslinking the polyurethane compound which has an aromatic ring structure. When defects such as protrusions and scratches exist on the substrate, pinholes or cracks may occur in the A layer laminated on the substrate with the above defects as a starting point, and gas barrier properties and bending resistance may be impaired, so an anchor coat layer is formed It is preferable to do Moreover, since gas barrier property and flexibility may fall also when the thermal dimensional stability difference between a base material and A-layer is large, it is preferable to form an anchor-coat layer. In addition, the anchor coat layer used in the present invention preferably contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure from the viewpoint of thermal dimensional stability and bending resistance, and further, an ethylenically unsaturated compound, 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 layer A of the laminate of the present invention is one having an aromatic ring and a urethane bond in a main chain or a side chain, for example, an epoxy (meth)acrylic having a hydroxyl group and an aromatic ring in the molecule. It can be obtained by superposing|polymerizing a rate, a diol compound, and a diisocyanate compound.

Examples of the epoxy (meth)acrylate having a hydroxyl group and an aromatic ring in the molecule include diepoxy compounds of aromatic glycols such as bisphenol A, hydrogenated bisphenol A, bisphenol F, hydrogenated bisphenol F, resorcin, and hydroquinone, and (meth) ) by reacting an 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'-thiodiphenol, 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 individually by 1 type or in combination of 2 or more types.

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, Aromatic diisocyanate such as 4,4-diphenylmethane diisocyanate, ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine Aliphatic diisocyanate compounds, such as syndiisocyanate and lysine triisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, alicyclic isocyanate compounds, such as methylcyclohexylene diisocyanate, xylene diisocyanate, tetramethyl Aroaliphatic isocyanate compounds, such as xylylene diisocyanate, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

The component ratio of the epoxy (meth)acrylate which has a hydroxyl group and an aromatic ring in the said molecule|numerator, a diol compound, and a diisocyanate compound will not be specifically limited if it becomes a range used as a desired weight average molecular weight. It is preferable that the weight average molecular weights (Mw) of the polyurethane compound which has an aromatic ring structure in this invention are 5,000-100,000. Since it is excellent in the thermal dimensional stability of the cured film obtained as a weight average molecular weight (Mw) is 5,000-100,000, and bending resistance, it is preferable. In addition, the weight average molecular weight (Mw) in this invention is the value converted into standard polystyrene measured using the gel permeation chromatography method.

Examples of the ethylenically unsaturated compound include di(meth)acrylates such as 1,4-butanediol di(meth)acrylate and 1,6-hexanedioldi(meth)acrylate, pentaerythritol tri(meth)acrylate , pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyfunctional (meth) acrylate, such as dipentaerythritol hexa (meth) acrylate, bisphenol Epoxy acrylates, such as A-type epoxy di(meth)acrylate, a bisphenol F-type epoxy di(meth)acrylate, and a bisphenol S-type epoxy di(meth)acrylate, etc. are mentioned. Among these, polyfunctional (meth)acrylate excellent in thermal dimensional stability and surface protection performance is preferable. In addition, 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, it is preferably in the range of 5 to 90% by mass among 100% by mass of the total amount with the polyurethane compound having an aromatic ring structure, It is more preferable that it is the range of 10-80 mass %.

As a photoinitiator, if the gas barrier property and bending resistance of the laminated body of this invention can be maintained, a raw material will not be specifically limited. As a photoinitiator which can be used suitably for this invention, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy Roxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl -1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-( Alkylphenone-based photopolymerization initiators such as dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyl -Acyl phosphine oxide-based photopolymerization initiator such as diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(η5-2,4-cyclopentadien-1-yl) -Bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl) titanocene-based photopolymerization initiator such as titanium, 1,2-octanedione, 1-[4-(phenylthio)- , 2-(0-benzoyloxime)] and the like, and a photopolymerization initiator having an oxime ester structure.

Among these, 1-hydroxy-cyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4, A photoinitiator selected from 6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is preferable. In addition, 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, It is preferable that it is the range of 0.01-10 mass % in the total amount of a polymerizable component from a viewpoint of sclerosis|hardenability and surface protection performance, It is more preferable that it is a range of 0.1-5 mass %.

Examples of the organosilicon compound include vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethyl Toxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldime oxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. are mentioned. can

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

Although content of an organosilicon compound is not specifically limited, It is preferable that it is the range of 0.01-10 mass % in the total amount of a polymerizable component from a viewpoint of sclerosis|hardenability and surface protection performance, It is more preferable that it is a range of 0.1-5 mass %.

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, 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 a gas adsorption method to following formula (1).

d=6/ρs ... ( 1)

ρ: density.

200 nm or more and 4,000 nm or less are preferable, as for the thickness of an anchor-coat layer, 300 nm or more and 2,000 nm or less are more preferable, 500 nm or more and 1,000 nm or less are still more preferable. When the thickness of the anchor coat layer is thinner than 200 nm, the adverse effect of defects such as protrusions and scratches on the substrate cannot be suppressed in some cases. When the thickness of the anchor coat layer is thicker than 4,000 nm, the smoothness of the anchor coat layer is lowered, the uneven shape of the surface of the layer A laminated on the anchor coat layer is increased, and the deposited film to be laminated is difficult to be dense, and the gas barrier property is improved. may be difficult to obtain. Here, the thickness of the anchor coat layer can be measured from a cross-sectional observation image with a transmission electron microscope (TEM).

It is preferable that the arithmetic mean roughness (Ra) of an anchor-coat layer is 10 nm or less. When Ra is 10 nm or less, it is preferable to form a homogeneous layer A on the anchor coat layer and to improve the repeatability of gas barrier properties. When the Ra of the surface of the anchor coat layer is greater than 10 nm, the uneven shape of the surface of the A layer on the anchor coat layer is also large, and the vapor deposition film is difficult to be dense, and the effect of improving the gas barrier properties may be difficult to obtain. Since cracks are likely to occur in the portion due to stress concentration, it may cause a decrease in the repeatability of gas barrier properties. Therefore, in the present invention, Ra of the anchor coat layer is preferably 10 nm or less, and more preferably 5 nm or less. Ra of the anchor coat layer in the present invention can be measured using an atomic force microscope (AFM) or the like.

When the anchor coat layer is applied to the laminate of the present invention, as a means for applying the coating liquid containing the resin forming the anchor coat layer, first, the thickness after drying the paint containing the polyurethane compound having an aromatic ring structure on the substrate. It is preferable to adjust the solid content concentration so as to have a desired thickness, and apply, for example, by a reverse coating method, a gravure coating method, a rod coating method, a bar coating method, a die coating method, a spray coating method, a spin coating method, or the like. 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, the solid content concentration is diluted to 10% by mass or less using a hydrocarbon solvent such as xylene, toluene, methylcyclohexane, pentane or hexane, or an ether solvent such as dibutyl ether, ethylbutyl ether or tetrahydrofuran. It is preferable to use These solvents may be used individually or in mixture of 2 or more types. Moreover, various additives can be mix|blended with the coating material which forms an anchor-coat layer as needed. For example, stabilizers, such as a catalyst, antioxidant, a light stabilizer, and a ultraviolet absorber, surfactant, a leveling agent, an antistatic agent, etc. can be used.

Next, 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, an infrared heater, can be used. Moreover, in order to improve gas barrier property, it is preferable to perform heating temperature at 50-150 degreeC. In addition, it is preferable to perform heat processing time for several seconds - 1 hour. In addition, the temperature may be constant during heat processing, and you may change the temperature gradually. In addition, you may heat-process, adjusting humidity to the range of 20-90 %RH with a relative humidity during a drying process. The heat treatment may be performed in the air or while sealing an inert gas.

Next, it is preferable to crosslink the said coating film by giving an active energy ray irradiation process to the coating film containing the polyurethane compound which has an aromatic ring structure after drying, and to form an anchor-coat layer.

Although there will be no restriction|limiting in particular as an active energy ray applied in such a case as long as an anchor-coat layer can be hardened, It is preferable to use ultraviolet treatment from a viewpoint of versatility and efficiency. As the ultraviolet generating source, known ones such as a high-pressure mercury lamp, a metal halide lamp, a microwave type electrodeless lamp, a low-pressure mercury lamp, and a xenon lamp 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 either under atmospheric pressure or under reduced pressure, but in the present invention, from the viewpoint of versatility and production efficiency, it is preferable to perform ultraviolet treatment under atmospheric pressure. From the viewpoint of controlling the degree of crosslinking of the anchor coat layer, the oxygen concentration during the ultraviolet treatment is preferably 1.0% or less, and more preferably 0.5% or less, as for the partial pressure of oxygen gas. The relative humidity may be arbitrary.

As the ultraviolet generating source, known ones such as a high-pressure mercury lamp, a metal halide lamp, a microwave type electrodeless lamp, a low-pressure mercury lamp, and a xenon lamp can be used.

It is preferable that it is 0.1-1.0 J/cm<2>, and, as for the accumulated light quantity of ultraviolet irradiation, 0.2-0.6 J/cm<2> is more preferable. Since the desired degree of crosslinking of the anchor coat layer can be obtained, it is preferable that the said integrated light amount is 0.1 J/cm<2> or more. Moreover, since the damage to a base material can be decreased that the said integrated light amount is 1.0 J/cm<2> or less, it is preferable.

[Other floors]

On the outermost surface of the laminate of the present invention, that is, on the layer A, an overcoat layer for the purpose of improving scratch resistance, chemical resistance, printability, etc. may be formed in the range in which gas barrier properties do not decrease, and for bonding to elements, etc. It is good also as a laminated structure which laminated the adhesive layer which consists of an organic high molecular compound, or a film. Moreover, you may form the low-refractive-index layer for improving an optical characteristic. In addition, the outermost surface here means the surface of A-layer after A-layer is laminated|stacked on a base material.

[Use of laminate]

Since the laminate of the present invention has high gas barrier properties, it can be suitably used as a gas barrier film. Moreover, the laminated body of this invention can be used for various electronic devices. For example, it can use suitably for electronic devices, such as a solar cell, a flexible circuit base material, organic electroluminescent illumination, a flexible organic electroluminescent display, and a scintillator. Moreover, it can be used suitably also as a packaging material of a lithium ion battery, a packaging material of a pharmaceutical, etc. taking advantage of high barrier property.

Example

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

[Assessment Methods]

(1) Thickness of each layer

The cross-sectional observation sample was subjected to the FIB method using a microsampling system (FB-2000A manufactured by Hitachi, Ltd.) (specifically, based on the method described in "Polymer surface processing" (Iwamori Akatsuki) p.118 to 119). so) was made. With 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 thickness of the layer A and the anchor coat layer of the laminate was measured.

(2) Composition of layer A, half width of oxygen atom (O1s) peak, presence or absence of silicate bond (atomic concentration of atoms in layer A, ratio of atomic concentration (Mg/Si))

The composition analysis of the layer A of the laminate was performed by X-ray photoelectron spectroscopy (XPS method). The layer was removed by argon ion etching about 5 nm from the outermost surface, and the content ratio of each element was measured under the following conditions. The measurement conditions of the XPS method were as follows.

・Device: PHI5000VersaProbe2 (manufactured by ALBAEKPA)

Excitation X-ray: monochromatic AlKα

・Analysis range: φ100㎛

·Photoelectron escape angle: 45°

· Ar ion etching: 2.0 kV, raster size 2 x 2, etching time 1 min.

The half width of the oxygen atom (O1s) peak was taken as the value calculated by the analysis software Multipak of the band with a measuring device.

In addition, as for the presence or absence of silicate bonding, after analysis by XPS method under the above conditions, the peak top of O1s is corrected to 531.0 eV, the position of the peak top of Si2p is confirmed, and if it is in the range of 101.0 to 103.0 eV, silicate bonding If it was present (Y), outside the range, there was no silicate bond (N), and when Si was not contained, it was set as no Si peak (-).

(3) Water vapor permeability (g/m2/day)

The water vapor transmission rate of the laminate was measured using a water vapor transmission rate measuring device (model name: DELTAPERM (registered trademark)) manufactured by Technolox, UK, under the conditions of a temperature of 40° C., a humidity of 90% RH, and a measurement area of 50 cm2. . The number of samples was 2 samples per level. The data obtained by measuring two samples were averaged, the second decimal place was rounded off, the average value in the said level was calculated|required, and the value was made into water vapor transmission rate (g/m<2>/day).

(4) Measurement of surface roughness

Arithmetic mean roughness (Ra) was measured using an atomic force microscope (AFM). The laminate was cut out to an arbitrary size, and measurement was performed under the following conditions with respect to a field of view of 1 µm × 1 µm on the surface of the A layer. Measurement was performed with n=2, and the average value of n=2 was used for the value of Ra. In addition, when other layers, such as a hard-coat layer, exist on A-layer, after removing said other layer, it shall measure in A-layer surface.

・Measuring device: Demens icon made by Bruker

・Measurement range: 1 μm × 1 μm

Scan rate: 1Hz

・scan line:512

· Analysis software: Nanoscope Analysis.

(5) Positron lifetime and pore radius distribution

Positron lifetime and pore radius distribution were measured by the positron beam method (a thin-film-corresponding positron annihilation lifetime measurement method). The measurement was performed after the sample to be measured was pasted on a 15 mm x 15 mm Si wafer and vacuum degassed at room temperature. Measurement conditions are as follows.

・Apparatus: PALS200A, a compact positron beam generator made by Fuji Inbaek

Positron source: ²² Na-based positron beam

・γ-ray detector: BaF ₂ scintillator + photomultiplier tube

Device constant: 255 to 278 ps, 24.55 ps/ch

·Beam intensity: 1keV

・Measurement depth: around 0 to 100 nm (estimated)

・Measurement temperature: room temperature

・Measurement atmosphere: vacuum

・Measured counts: Approx. 5,000,000 counts

About the measurement result, 3-component or 4-component analysis was performed by the nonlinear least square program POSITRONFIT.

(Example 1)

(Synthesis of a polyurethane compound having an aromatic ring structure)

In a 5-liter 4-neck flask, 300 parts by mass of bisphenol A diglycidyl ether acrylic acid adduct (manufactured by Kyoeisha Chemical Co., Ltd., trade name: epoxy ester 3000A) and 710 parts by mass of ethyl acetate were placed, and the temperature was set to 60°C. warmed up 0.2 mass parts of di-n-butyltin dilaurate was added as a synthesis catalyst, and 200 mass parts of dicyclohexylmethane 4,4'- diisocyanate (made by Tokyo Kasei Kogyo Co., Ltd.) was dripped over 1 hour, stirring. The reaction was continued for 2 hours after completion|finish of dripping, and then, 25 mass parts of diethylene glycol (made by Wako Pure Chemical Industries, Ltd.) was dripped over 1 hour. The reaction was continued for 5 hours after dripping, and the polyurethane compound which has an aromatic ring structure with a weight average molecular weight of 20,000 was obtained.

(Formation of Anchor Coat Layer)

A polyethylene terephthalate film ("Lumiror" (registered trademark) U48, manufactured by Toray Corporation) having a thickness of 100 mu m was used as the substrate.

As a coating liquid 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- 5 parts by mass of hydroxycyclohexylphenyl ketone (manufactured by BASF Japan, trade name: "IRGACURE" (registered trademark) 184), 3-methacryloxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Silicone, trade name: KBM-503) 3 mass parts, 170 mass parts of ethyl acetate, 350 mass parts of toluene, and 170 mass parts of cyclohexanone were mix|blended, and the coating liquid was adjusted. Next, the coating solution is applied on the substrate with a micro gravure coater (gravure turn 150UR, gravure rotation ratio 100%), dried at 100° C. for 1 minute, dried, UV-treated under the following conditions, and an anchor coat layer with a thickness of 1 μm has formed

Ultraviolet rays processing device: LH10-10Q-G (product made in fusion UV systems Japan company)

Introduced gas: N ₂ (nitrogen inert BOX)

Ultraviolet light source: Microwave method electrodeless lamp

Integrated light intensity: 400mJ/cm2

Sample temperature control: room temperature.

(Formation of layer A)

_{A MgO+SiO 2} layer having a thickness of 150 nm was formed as an A layer on the surface of the anchor coat layer of the substrate by electron beam (EB) vapor deposition using the winding-up vapor deposition apparatus shown in FIG. 3 .

Specific operation is as follows. First, as vapor deposition materials, granular magnesium oxide MgO (purity 99.9%) and silicon dioxide SiO ₂ (purity 99.99%) having a size of about 2 to 5 mm were previously heated at 100° C. for 8 hours, respectively. Then, each material was set to the hearth liner 11 made of carbon as shown in FIG. The material area ratio of MgO and SiO _{2 was MgO:SiO 2} =4:1. In the winding chamber 5, on the unwinding roll 6, the surface of the substrate 1 on the side where the A layer is formed (the side on which the anchor coat is formed) is set to face the hearth liner 11, unwinded, and a guide roll (7, 8, 9) passed through the main drum (10). At this time, the main drum was controlled to the temperature of -15 degreeC. Then, the inside of the vapor deposition apparatus 4 was pressure-reduced with the vacuum pump, and 5.0x10 ^-3 Pa or less was obtained. _{Next, MgO and SiO 2} were uniformly heated using one electron gun (hereinafter, EB gun) 13 as a heating source. The EB gun was set to have an acceleration voltage of 6 kV, an applied current of 50 to 200 mA, and a deposition rate of 1 nm/sec. A layer was formed on the surface of the anchor coat layer of the substrate by EB deposition. In addition, the thickness of A-layer to form was adjusted with the film conveyance speed. Then, it wound on the take-up roll 18 via the guide rolls 15, 16, and 17.

Then, the test piece was cut out from the obtained laminated body, and various evaluation was performed. A result is shown in Table 1.

(Example 2)

A laminate was obtained in the same manner as in Example 1 except that in the formation of the MgO+SiO ₂ layer as the A layer, the material area ratio of _{MgO and SiO 2 was MgO:SiO 2 =3:1 to control the composition.} A result is shown in Table 1.

(Example 3)

A laminate was obtained in the same manner as in Example 1 except that the composition was controlled by making the material area ratio of _{MgO and SiO 2 to be MgO:SiO 2} =7:3 in the formation of the MgO+SiO _{2 layer as the A layer.} A result is shown in Table 1.

(Example 4)

A laminate was obtained in the same manner as in Example 1 except that the composition was controlled by making the material area ratio of _{MgO and SiO 2 to MgO:SiO 2} =2:1 in the formation of the MgO+SiO _{2 layer as the A layer.} A result is shown in Table 1.

(Example 5)

A laminate was obtained in the same manner as in Example 1 except that the composition was controlled so that the material area ratio of _{MgO and SiO 2 was MgO:SiO 2} =6.5:3.5 in the formation of the MgO+SiO _{2 layer as the A layer.} A result is shown in Table 1.

(Example 6)

A laminate was obtained in the same manner as in Example 1, except that the composition was controlled so that the material area ratio of _{MgO and SiO 2 was MgO:SiO 2} =5.5:4.5 in the formation of the MgO+SiO _{2 layer as the A layer.} A result is shown in Table 1.

(Example 7)

As the deposition material, granular zinc oxide ZnO (purity 99.9%) with a size of about 1 to 3 mm and granular silicon oxide SiO (purity 99.9%) with a size of about 2 to 5 mm are used, and the ZnO+SiO layer, which is layer A, is formed. A laminate was obtained in the same manner as in Example 1 except that the composition was controlled so that the material area ratio of ZnO and SiO was ZnO:SiO=3:1. A result is shown in Table 1.

(Example 8)

A laminate was obtained in the same manner as in Example 7 except that in the formation of the ZnO+SiO layer, which is the A layer, the composition was controlled by making the material area ratio of ZnO and SiO to ZnO:SiO=2:1. A result is shown in Table 1.

(Example 9)

A laminate was obtained in the same manner as in Example 7, except that in the formation of the ZnO+SiO layer, which is the A layer, the composition was controlled such that the material area ratio of ZnO and SiO was ZnO:SiO=1:1. A result is shown in Table 1.

(Example 10)

As the deposition material, granular zinc oxide ZnO (purity 99.9%) with a size of about 1 to 3 mm and granular tin oxide SnO (purity 99.9%) with a size of about 2 to 5 mm are used, and the A-layer ZnO+SnO layer is formed. A laminate was obtained in the same manner as in Example 1 except that the composition was controlled so that the material area ratio of ZnO and SnO was ZnO:SnO=3:1. A result is shown in Table 1.

(Example 11)

As in Example 1, except that a 12 µm-thick polyethylene terephthalate film (“Lumiror” (registered trademark) P60 manufactured by Toray Corporation) was used as the base material, and the A layer was directly formed without forming an anchor coat layer. Thus, a laminate was obtained. A result is shown in Table 1.

(Example 12)

As in Example 5, except that a 12 µm-thick polyethylene terephthalate film (“Lumiror” (registered trademark) P60 manufactured by Toray Corporation) was used as the base material, and the A layer was directly formed without forming an anchor coat layer. Thus, a laminate was obtained. A result is shown in Table 1.

(Example 13)

As the deposition material, granular calcium oxide CaO (purity 99.9%) with a size of about 2-5 mm and granular silicon dioxide SiO ₂ (purity 99.9%) with a size of about 2-5 mm are used, and CaO+SiO ₂ layer, which is layer A In the formation of , a laminate was obtained in the same manner as in Example 1 except that the _{material area ratio of CaO and SiO 2} was set to CaO:SiO _{2 =8:1 and the composition was controlled.} A result is shown in Table 1.

(Example 14)

As a deposition material, a granular zirconium oxide ZrO ₂ (purity 99.9%) of a size of about 2-5 mm and a granular silicon dioxide SiO ₂ (purity of 99.9%) of a size of about 2-5 mm are used, and the A-layer ZrO ₂ +SiO in the formation of the _second layer, the material area ratio of ZrO ₂ and _{SiO ZrO 2: SiO 2 = 8} : 1 except that the composition controls to ensure that this is likewise to obtain a layered product in example 1. A result is shown in Table 1.

(Comparative Example 1)

Granular magnesium oxide MgO (purity 99.9%) of about 2 to 5 mm is used as a vapor deposition material, and it is set in a carbon hearth liner 11 without partitions, and the EB gun has an acceleration voltage of 6 kV and an applied current of 50 to 200 mA. , A laminate was obtained in the same manner as in Example 1 except that the deposition material was heated at a deposition rate of 1 nm/sec. A result is shown in Table 1.

(Comparative Example 2)

A laminate was obtained in the same manner as in Comparative Example 1 except that _{granular silicon dioxide SiO 2} (purity of 99.99%) having a size of about 2 to 5 mm was used as the vapor deposition material. A result is shown in Table 1.

(Comparative Example 3)

A laminate was obtained in the same manner as in Comparative Example 1 except that granular zinc oxide ZnO (purity of 99.99%) having a size of about 1 to 3 mm was used as the vapor deposition material. A result is shown in Table 1.

(Comparative Example 4)

A laminate was obtained in the same manner as in Example 1 except that the A layer was directly formed without forming an anchor coat layer on the substrate. A result is shown in Table 1.

(Comparative Example 5)

A laminate was obtained in the same manner as in Example 5 except that the A layer was directly formed without forming the anchor coat layer on the substrate. A result is shown in Table 1.

(Comparative Example 6)

Flake-like magnesium Mg (purity 99.9%) with a size of 2-5 mm and granular silicon Si (purity 99.9%) of a size of 2-5 mm are used as deposition materials, and in the formation of the Mg+Si layer, which is the A layer, , A laminate was obtained in the same manner as in Example 1 except that the composition was controlled by making the material area ratio of Mg and Si to Mg:Si=5:1. A result is shown in Table 1.

(Comparative Example 7)

A laminate was obtained in the same manner as in Comparative Example 1 except that granular tin oxide SnO (purity 99.99%) of a size of about 2 to 5 mm was used as the vapor deposition material. A result is shown in Table 1.

(Comparative Example 8)

A laminate was obtained in the same manner as in Comparative Example 1 except that granular calcium oxide CaO (purity of 99.99%) having a size of about 2 to 5 mm was used as the vapor deposition material. A result is shown in Table 1.

(Comparative Example 9)

A laminate was obtained in the same manner as in Comparative Example 1 except that _{granular zirconium oxide ZrO 2} (purity 99.99%) of about 2 to 5 mm was used as the vapor deposition material. A result is shown in Table 1.

In the table, (1)/(2) when (1) is Mg and (2) is Si is the ratio (Mg) of the atomic concentration (atm%) of magnesium (Mg) atoms and silicon (Si) atoms. /Si).

Examples 1 to 6 form a composite oxide film of magnesium oxide and silicon dioxide having an Ra of 2.0 nm or less on the surface of the layer A, and have a good water vapor transmission rate of ^{less than 5.0 × 10 -2} (g/m 2 /day). Further, in Examples 2 to 5, the average lifetime of the third component in the positron beam method is 0.860 ns or less (average pore radius is 0.138 nm or less), and the water vapor transmission rate is 5.0 × 10 ^-3 (g/m 2 /day) less is better.

As in Examples 7 to 10, 13 and 14, also in other composite oxides (zinc oxide and silicon oxide, zinc oxide and tin oxide, calcium oxide and silicon dioxide, zirconium oxide and silicon dioxide), the water vapor permeability was 5.0 × 10 ^{Less than -2} (g/m 2 /day) is good.

Moreover, as in Examples 11 and 12, even without an anchor coat layer, when Ra of the surface of A layer is 5.0 nm or less, water vapor transmission rate expresses less than 1.0x10 ^-1 (g/m<2>/day).

On the other hand, Comparative Examples 1, 2, 8, and 9 were a single material, and the gas barrier properties were inferior to those of Examples in which two types of vapor deposition materials were mixed. Moreover, the comparative examples 3 and 7 have poor adhesiveness and do not express gas barrier property either. Moreover, in Comparative Examples 4 and 5, since the surface roughness of the A-layer surface is large, a dense film|membrane is not formed and gas-barrier property is not expressed. Comparative Example 6 formed a composite metal film, but gas barrier properties were not expressed.

(Industrial Applicability)

Since the laminate of the present invention has excellent gas barrier properties against oxygen gas, water vapor, etc., it can be usefully used, for example, as a packaging material for food and pharmaceutical products, and as a member for electronic devices such as organic EL televisions and solar cells. is not limited to these.

1 description
2A floor
3 Anchor coat layer
4 Winding Electron Beam (EB) Deposition Apparatus
5 winding thread
6 Unwind Roll
7, 8, 9 Unwind side guide roll
10 main drum
11 hearth liner
12 deposition material
13 electron gun
14 electron beam
15, 16, 17 Winding-side guide roll
18 winding roll
19 Deposition material B
20 deposition material C

Claims (12)

having an A layer on at least one side of the substrate,
The A layer contains at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table, and oxygen;
The laminated body whose arithmetic mean roughness (Ra) computed by atomic force microscope (AFM) of the said A-layer surface is 5.0 nm or less. having an A layer on at least one side of the substrate,
The A layer contains at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table, and oxygen;
The layer A has an average lifetime measured by a positron beam method of 0.935 ns or less. 3. The method according to claim 1 or 2,
The layer A is a laminate including one selected from the group consisting of magnesium, calcium, titanium, zirconium, zinc, and aluminum, and any one of silicon, tin, or germanium. 4. The method according to any one of claims 1 to 3,
The layer A is a laminate of an amorphous film. 5. The method according to any one of claims 1 to 4,
The layer A is a laminate having a half width of the peak of oxygen atoms (O1s) measured by X-ray photoelectron spectroscopy of 3.25 eV or less. 6. The method according to any one of claims 1 to 5,
A laminate having a water vapor permeability of ^{less than 5.0×10 -2} g/m 2 /day. 7. The method according to any one of claims 1 to 6,
The layer A is a laminate comprising magnesium and silicon, or zinc and silicon as at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table. 8. The method according to any one of claims 1 to 7,
The layer A is a laminate having a silicate bond. 9. The method according to any one of claims 1 to 8,
A laminate comprising an anchor coat layer, wherein one side of the anchor coat layer is in contact with the substrate and the other side is in contact with the layer A. 10. The method according to any one of claims 1 to 9,
The layer A contains magnesium and silicon as at least two elements selected from the group consisting of elements of groups 2 to 5 and 12 to 14 of the periodic table, and magnesium (Mg) measured by X-ray photoelectron spectroscopy. ) A laminate having an atomic concentration of 5 to 50 atm%, a silicon (Si) atomic concentration of 2 to 30 atm%, and an oxygen (O) atomic concentration of 45 to 70 atm%. 11. The method of claim 10,
In the layer A, a ratio (Mg/Si) of an atomic concentration (atm%) of magnesium (Mg) atoms to silicon (Si) atoms is 0.30 to 11.00. 12. The method according to any one of claims 1 to 11,
A laminate in which the layer A is a layer formed by vacuum deposition.

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