阅读说明：本技术 叠层体 (Laminate ) 是由 德永幸大 佐藤诚 上林浩行 于 2019-10-04 设计创作，主要内容包括：一种叠层体,其在基材的至少一侧具有A层,上述A层包含选自周期表的第IIA、IIIB、IVB、VB、IIB、IIIA和IVA族的元素中的至少2种元素、以及氧,上述A层表面的通过原子力显微镜(AFM)算出的算术平均粗糙度Ra为5.0nm以下。提供低成本并且即使为简单的构成也具有高度的阻气性的叠层体。(A laminate comprising a substrate and, formed on at least one side thereof, an A layer containing at least 2 elements selected from the group consisting of elements belonging to groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic table and oxygen, wherein the surface of the A layer has an arithmetic average roughness Ra of 5.0nm or less as calculated by an Atomic Force Microscope (AFM). Provided is a laminate which has high gas barrier properties at low cost and even with a simple configuration.)

1. A laminate having an A layer on at least one side of a substrate,

the A layer contains at least 2 elements selected from elements of groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic Table, and oxygen,

the surface of the A layer has an arithmetic average roughness Ra of 5.0nm or less as calculated by an Atomic Force Microscope (AFM).

2. A laminate having an A layer on at least one side of a substrate,

the A layer contains at least 2 elements selected from elements of groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic Table, and oxygen,

the average lifetime of the A layer is 0.935ns or less as measured by a positron beam method.

3. Laminate according to claim 1 or 2, the a layer comprising:

1 kind selected from magnesium, calcium, titanium, zirconium, zinc and aluminum, and

silicon or tin or germanium.

4. The laminate according to any one of claims 1 to 3, wherein the layer A is an amorphous film.

5. The laminate according to any one of claims 1 to 4, wherein the half width of the peak of O1s, which is an oxygen atom, of the A layer as measured by X-ray photoelectron spectroscopy is 3.25eV or less.

6. Laminate according to any one of claims 1 to 5, having a water vapor transmission rate of less than 5.0 x 10^-2g/m²The day is.

7. Laminate according to any one of claims 1-6, the A layer comprising magnesium and silicon, or zinc and silicon as at least 2 of the elements selected from groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic Table.

8. Laminate according to any one of claims 1 to 7, the A layer having silicate bonds.

9. Laminate according to any one of claims 1 to 8, having a bonding layer, the bonding layer having one side in contact with the substrate and the other side in contact with the A layer.

10. The laminate according to any one of claims 1 to 9, wherein the a layer contains magnesium and silicon as at least 2 elements of the elements selected from groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic table, and has a magnesium Mg 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%, as measured by X-ray photoelectron spectroscopy.

11. The laminate according to claim 10, wherein a ratio of atomic concentration of magnesium Mg atoms to silicon Si atoms Mg/Si of the a layer is 0.30 to 11.00, and the atomic concentration is in atm%.

12. The laminate according to any one of claims 1 to 11, wherein the layer A is a layer formed by a vacuum evaporation method.

Technical Field

The present invention relates to a laminate used as a packaging material for foods and medicines, a material for electronic parts such as solar cells, electronic paper, and organic Electroluminescence (EL) displays, which require high gas barrier properties.

Background

A gas barrier film in which an inorganic layer of an inorganic substance (including an inorganic oxide) is formed on the surface of a film base by a physical vapor deposition method (PVD method) such as vacuum deposition, sputtering, or ion plating, or a chemical vapor deposition method (CVD method) such as plasma chemical vapor deposition, thermal chemical vapor deposition, or photochemical vapor deposition, is used as a packaging material for foods, medicines, and the like, which require blocking of various gases such as water vapor and oxygen, and electronic device members such as electronic paper, solar cell, and the like, and these members are required to have a water vapor transmission rate of 5.0 × 10^-2g/m²High gas barrier properties of 24hr atm or less.

As one of the methods for satisfying the high gas barrier property, a gas barrier film in which an organic layer and an inorganic layer are alternately laminated in multiple layers to prevent the occurrence of defects by a hole filling effect has been proposed (patent document 1), and ZnO and SiO are used₂Sputtering a target as a main component to thereby form ZnO-SiO₂Such a complex oxide film is formed as a gas barrier film composed of a simple film on a film base (patent document 2).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2005-324406

Patent document 2: japanese patent laid-open publication No. 2013-147710

Disclosure of Invention

Problems to be solved by the invention

However, as in patent document 1, high barrier properties can be achieved by alternately stacking organic layers and inorganic layers in a multilayer manner, but stacking the layers increases the number of steps and increases the cost. In addition, although a laminate in which a complex oxide is formed by sputtering as in patent document 2 can be produced at a lower cost than that of patent document 1, it is difficult to reduce the cost because of limitations in the nature of the production method, such as a limitation in increasing the film formation rate.

In view of the background of the prior art, the present invention provides a laminate having high gas barrier properties at low cost and with a simple configuration.

Means for solving the problems

In order to solve the above problems, the present invention adopts the following means. Namely, the following.

(1) A laminate comprising a substrate and, formed on at least one side thereof, an A layer containing at least 2 elements selected from the group consisting of elements belonging to groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic table and oxygen, wherein the surface of the A layer has an arithmetic average roughness Ra of 5.0nm or less as calculated by an Atomic Force Microscope (AFM).

(2) A laminate comprising a substrate and, formed on at least one side thereof, an A layer containing at least 2 elements selected from the group consisting of elements belonging to groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic Table and oxygen, wherein the average lifetime of the A layer as measured by an positron beam method is 0.935ns or less.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a laminate having a high gas barrier property against water vapor can be provided at low cost.

Drawings

FIG. 1 is a sectional view showing an example of a laminate of the present invention.

FIG. 2 is a sectional view showing another example of the laminate of the present invention.

Fig. 3 is a schematic view schematically showing a roll-to-roll electron beam deposition apparatus for producing a laminate of the present invention.

Fig. 4 is a view schematically showing, from the upper side, the material arrangement for producing the laminated body of the present invention.

Fig. 5 is a diagram schematically showing the arrangement of materials for producing the laminated body of the present invention from the side.

Detailed Description

The details of the present invention will be described below.

In addition, when it is referred to as the present invention 1, it refers to the present invention of the following embodiment.

A laminate comprising a substrate and, formed on at least one side thereof, an A layer containing at least 2 elements selected from the group consisting of elements belonging to groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic table and oxygen, wherein the surface of the A layer has an arithmetic average roughness Ra of 5.0nm or less as calculated by an atomic force microscope (hereinafter, AFM).

Note that, when it is referred to as the present invention 2, it refers to the present invention of the following embodiment.

A laminate comprising a substrate and, formed on at least one side thereof, an A layer containing at least 2 elements selected from the group consisting of elements belonging to groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic Table and oxygen, wherein the average lifetime of the A layer as measured by an positron beam method is 0.935ns or less.

Further, when only the present invention is described, it is a general term of 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 a substrate, the a layer containing at least 2 elements selected from elements of groups IIA, IIIB, IVB, VB, IIB, IIIA, and IVA of the periodic table and oxygen, and the surface of the a layer having an arithmetic average roughness Ra calculated by an Atomic Force Microscope (AFM) of 5.0nm or less. The laminate of the present invention 2 has an a layer on at least one side of the substrate, the a layer containing at least 2 elements selected from the elements of groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic table and oxygen, and the a layer having an average lifetime as measured by a positron beam method of 0.935ns or less.

Examples of the elements of groups IIA, IIIB, IVB, VB, IIB, IIIA, and IVA of the periodic table included in the a layer include magnesium, calcium, strontium, scandium, titanium, zirconium, tantalum, zinc, aluminum, gallium, indium, silicon, germanium, tin, and the like. The combination of at least 2 elements selected from the elements of groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic table is not limited, but from the viewpoints of gas barrier properties, formation of an amorphous film, and the like, magnesium and silicon, zinc and silicon, tin and zinc, calcium and silicon, zirconium and silicon, aluminum and silicon are preferable as the at least 2 elements. From the viewpoint of gas barrier properties and having a silicate bond, a combination of magnesium and silicon or a combination of zinc and silicon is more preferable as at least 2 elements selected from elements of groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic table.

The form of at least 2 elements selected from the elements of groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic table included in the a layer is not particularly limited, and may be an oxide, nitride oxide, carbide, or the like, but is preferably present as an oxide, nitride oxide, or the like, from the viewpoint of gas barrier properties, optical characteristics, or the like. From the viewpoint of forming an amorphous film and gas barrier properties, it is more preferable to contain at least 1 compound selected from the group consisting of oxides, nitrides, oxynitrides, and carbides.

The layer a of the laminate of the present invention may contain other inorganic compounds as long as it contains at least 2 elements selected from the elements of groups IIA, IIIB, IVB, VB, IIB, IIIA, and IVA of the periodic table, and oxygen.

The laminate of the present invention 1 has an arithmetic average roughness Ra of the surface of the layer A of 5.0nm or less as calculated by AFM. If Ra is more than 5.0nm, the A layer becomes less dense, and thus there is a possibility that the gas barrier properties are no longer exhibited. From the viewpoint of gas barrier properties, Ra is preferably 3.0nm or less, more preferably 2.0nm or less. The lower limit of Ra is not particularly limited, but is preferably 0.1nm or more. When Ra is less than 0.1nm, the adhesiveness may be deteriorated. The analysis range of the AFM for calculating the arithmetic average roughness Ra was set to 1 μm × 1 μm.

In order to make the arithmetic average roughness Ra of the surface of the a layer, which is defined in the present invention 1 and calculated by an Atomic Force Microscope (AFM), 5.0nm or less, it is realized by forming a composite oxide film on a substrate having Ra of 5.0nm or less at an appropriate composition ratio, for example. By forming the composite oxide film as the a layer, a smooth film can be formed as compared with the case where an oxide film of a single metal is formed as the a layer.

The average lifetime of the a layer of the laminate of the present invention 2 measured by a positive electron beam method (positron annihilation lifetime measurement method) (see "yang particle ) (participating in japan アイソトープ) section I1 and section V2) is 0.935ns or less. The positron beam method is one of positron annihilation lifetime measurement methods, and is a method of measuring the time (on the order of hundreds of ps to tens of ns) from when a positron is incident on a sample to annihilation, and nondestructively evaluating the size, number concentration, and size distribution of pores of about 0.1 to 10nm from the annihilation lifetime. In place of the radioisotope (²²Na) is a method capable of measuring a thin film having a thickness of about several hundred nm formed on a silicon or quartz substrate, in contrast to a normal positron annihilation method, in which a positron beam is used as a positron source. From the obtained measurement values, the average pore radius and the number concentration of pores can be determined by the nonlinear least square program positronsit. The values corresponding to the sub-nm pores and the basic skeleton were obtained by analyzing the average lifetimes of the 3 rd component and the 4 th component.

Here, the 3 rd component is an average lifetime obtained by selecting an analysis of the 3 rd component as a measurement condition of the average lifetime by the positron beam method, and the 4 th component is an average lifetime obtained by selecting an analysis of the 4 th component as a measurement condition of the average lifetime by the positron beam method. When the analysis is performed by positronit, the fraction of positronit is determined from the number of peaks obtained from the pore radius distribution curve calculated by using the distribution analysis program CONTIN based on the inverse laplace method. The average pore radius calculated from positronnit was matched with the peak position of the pore radius distribution curve of CONTIN, and it was judged that the analysis was proper. The average lifetime in the present invention 2 means the average lifetime of the component 3.

If the average lifetime is more than 0.935ns, the A layer is not densified any more, and thus there is a possibility that the gas barrier properties are not exhibited any more. From the viewpoint of gas barrier properties, the average lifetime measured by the positron beam method is preferably 0.912ns or less, more preferably 0.863ns or less. The lower limit of the average lifetime is not particularly limited, but is preferably 0.542ns or more. If the average lifetime is less than 0.542ns, the flexibility may be reduced.

In order to make the average lifetime of the a layer defined in the present invention 2, as measured by the positron beam method, 0.935ns or less, it is achieved by densely forming a composite oxide film on a substrate having Ra of 3.0nm or less at an appropriate composition ratio, for example. The dense formation here means a state in which the oxides are mixed at an atomic level to form a dense network.

The layer a of the laminate of the present invention is preferably an amorphous film. Amorphous means that atoms and molecules do not form a regular, correct ordered structure over a long distance like crystals, but an irregular structure. The crystal structure is preferably amorphous because crystal grain boundaries are generated, and thus the crystal grain boundaries serve as water vapor transmission paths to deteriorate gas barrier properties or are prone to cracking. Whether or not the amorphous form is present can be confirmed by analysis methods such as cross-sectional TEM and X-ray diffraction (XRD). In the case of the cross-sectional TEM, the contrast becomes uniform for the amorphous film, and crystal grain boundaries are not observed, while crystal grain boundaries corresponding to the crystal structure, such as a microcrystalline state and a columnar structure, are observed for the crystalline film.

The half width of the peak of the oxygen atom (O1s) in the a layer of the present invention measured by X-ray photoelectron spectroscopy is preferably 3.25eV or less. The maximum value of the peak is set as F_maxIn the case of (2), the half-width indicates that the intensity of the peak is F_maxPeak width at/2. When the half-value width of the peak of O1s is narrow, a network structure with uniform bonding is formed, and therefore a dense film is easily formed. From the viewpoint of uniformity of bonding and barrier properties, it is more preferably 3.00eV or less, and still more preferably 2.75eV or less. The lower limit is not particularly limited, but is preferably 1.65eV or more.

The laminate of the present invention preferably has a water vapor permeability of less than 5.0X 10^-2g/m²The day is. The laminate of the present invention has a water vapor permeability of less than 1 more preferably from the viewpoint of use in high-grade packaging materials and electronic device applications requiring high gas barrier properties.0×10^-2g/m²The day is. The lower limit of the water vapor permeability is not particularly limited, but if the film is excessively dense, cracks are likely to occur, and therefore the water vapor permeability of the laminate of the present invention is preferably 1.0 × 10^-4g/m²More than one day.

The layer a preferably has a silicate bond. The silicate bond is a bond between silicon (Si) and a metal (M) via oxygen (O), and may be referred to as Si — O — M. Examples thereof include a zinc silicate bond (Si-O-Zn), a magnesium silicate bond (Si-O-Mg), an aluminum silicate bond (Si-O-Al), etc. The layer a has a silicate bond, and thus has a dense structure, thereby achieving high gas barrier properties. Examples of the method of analyzing the presence or absence of silicate bonds (confirmation method) include X-ray photoelectron spectroscopy, X-ray absorption microstructure (XAFS), and the like.

In order to provide the a layer with a silicate bond, as described above, the a layer preferably includes a combination of magnesium and silicon or a combination of zinc and silicon as at least 2 elements selected from elements of groups IIA, IIIB, IVB, VB, IIB, IIIA, and IVA of the periodic table, and further includes oxygen. The presence or absence of the silicate bond can be confirmed by X-ray photoelectron spectroscopy, and the detailed method thereof is described in the examples.

The film density of the A layer is preferably 2.0 to 7.0g/cm from the viewpoint of gas barrier properties and denseness³. If it is less than 2.0g/cm³In some cases, the obtained a layer is not dense and sufficient gas barrier properties cannot be obtained. On the other hand, if the film density of the A layer is more than 7.0g/cm³Sometimes the a layer tends to harden, to introduce cracks or to crack. The film density of the layer A is more preferably 2.5 to 6.0g/cm from the viewpoint of gas barrier properties and cracking easiness³。

In the present invention, the film density of the a layer is a value measured by an X-ray reflectance method (XRR method) ("X-line reflectance" is entered in the section "cori" (cherry-well key edition) p.51 to 78). Specifically, first, X-rays are generated from an X-ray source, and after parallel beams are formed by a multilayer film mirror, the X-rays are incident on a measurement sample while the angle of the X-rays is restricted by an incident slit. Incident light is made at a shallow angle substantially parallel to the sample surface for measuring the incident angle of the X-ray to the sample, thereby generating a reflected beam of the X-ray that is reflected and interfered at each layer of the sample and the interface of the substrate. The generated reflected beam is limited to a necessary X-ray angle by passing through a light receiving slit, and then incident on a detector to measure the X-ray intensity. By using the method, the incident angle of the X-ray is continuously changed, so that the total reflection X-ray intensity spectrum under each incident angle can be obtained.

As a method for analyzing the film density of each layer, the obtained measured data of the total reflection X-ray intensity map with respect to the incident angle of the X-ray is fitted to the theoretical equation of parrat by the nonlinear least square method (see "X-shaped reflectivity section" (edited by primi of cherry) p.81 to 141).

The method for forming the a layer is not particularly limited, and a sputtering method, a vacuum deposition method, an ion plating method, a CVD method, an Atomic Layer Deposition (ALD), or the like is used. Among these methods, vacuum vapor deposition is preferred as a method which is inexpensive, simple, and capable of obtaining desired properties. That is, the a layer is preferably formed by a vacuum evaporation method. Among the vacuum vapor deposition methods, the Electron Beam (EB) vapor deposition method is more preferable from the viewpoint of vapor deposition of a compound to control the film composition. Further, reactive vapor deposition may be performed by introducing oxygen, nitrogen, water vapor, or the like as a reactive gas or by using ion assist or the like. The vacuum deposition method may be any of film formation patterns such as a sheet type and a winding type. Fig. 3 shows an example of a roll-to-roll apparatus.

[ example of method for producing layer A ]

An example of a method of forming the layer a in fig. 3 using a roll-to-roll deposition apparatus is shown. A thin film of the compounds of materials B and C was formed as a layer a on the surface of the substrate 1 by electron beam evaporation. First, as a vapor deposition material, a granular material B and a granular material C having a size of about 2 to 5mm are alternately arranged as shown in fig. 4 and 5. The area ratio in the case of alternating arrangement is arranged according to the target film composition of the a layer, the EB irradiation method, and the like. The width of each unit material arranged at this time is preferably 10 to 100 mm. If the thickness is larger than 100mm, the composition ratio in the width direction of the materials B and C and the variation in film quality tend to be large. If less than 10mm, it is possible to configure the materialThe workability in the case of time is lowered. From the viewpoint of the composition ratio in the width direction, the variation in film quality, the workability, etc., it is more preferably 10 to 80 mm. The vapor deposition material is not limited to particles, and a vapor deposition material having a shape such as a square or a molded body of a sheet (tablet) may be used. Further, if the vapor deposition material absorbs moisture, moisture in the material may be taken into the a layer, and a desired film composition and physical properties may not be obtained, so that it is preferable to subject the material to dehydration treatment by heating before use. In the winding chamber 5, the surface of the base material 1 on which the layer a is provided is placed on an unwinding roll 6 so as to face a hearth lining (hearth liner)11, unwound, and passed through a main drum 10 via guide rollers 7, 8, and 9. Then, the pressure in the deposition apparatus 4 was reduced by a vacuum pump to obtain 5.0 × 10^-3Pa or less. The degree of vacuum (degree of vacuum reached by the evaporation apparatus, Japanese text: degree of vacuum) is preferably 5.0X 10^-3Pa or less. If reaching the vacuum degree of more than 5.0 multiplied by 10^-3Pa, residual gas may be introduced into the a layer, and desired film composition and physical properties may not be obtained. The temperature of the main drum 10 is set to-15 ℃ as an example. From the viewpoint of preventing thermal damage to the base material, it is preferably 20 ℃ or lower, and more preferably 0 ℃ or lower. Next, as a heat source, one electron gun (hereinafter, EB gun) 13 was used to uniformly heat the surface of the material B, C. An EB gun was set to an accelerating voltage of 6kV, an applied current of 50-200 mA, and a deposition rate of 1nm/sec, and an A layer was formed on the surface of the substrate 1 by EB deposition. Further, the thickness of the a layer formed is adjusted according to the film conveying speed. Then, the yarn is wound around a winding roller 18 via guide rollers 15, 16, and 17.

The composition ratio of the a layer can be measured by X-ray photoelectron spectroscopy (XPS method) and fluorescent X-ray (XRF) analysis. In the case of using X-ray photoelectron spectroscopy, since hydrocarbons and water contained in the air are adsorbed on the outermost surface and the exact composition of the a layer is not reflected, the layer from the outermost surface to a distance of about 5nm from the outermost surface is removed by argon ion etching to measure the content ratio of each element. In the case of using fluorescent X-ray spectroscopy, the content ratio of the constituent elements was measured by a basic parameter method (FP method).

The A layer preferably contains magnesium and silicon as at least 2 elements selected from elements of groups IIA, IIIB, IVB, VB, IIB, IIIA and IVA of the periodic table, and has a magnesium (Mg) 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%, as measured by X-ray photoelectron spectroscopy. From the viewpoint of film quality and gas barrier properties, it is more preferable that the atomic concentration of magnesium (Mg) is 8 to 35 atm%, the atomic concentration of silicon (Si) is 6 to 25 atm%, and the atomic concentration of oxygen (O) is 50 to 65 atm%. If the magnesium atom concentration is more than 50 atm% or the silicon atom concentration is less than 2 atm%, the proportion of silicon atoms becomes small and the a layer is liable to form a crystal layer and to introduce cracks in some cases. If the magnesium atom concentration is less than 5 atm% or the silicon atom concentration is more than 30 atm%, the ratio of silicate bonds in the a layer is reduced, and therefore, the denseness may be reduced without exhibiting the gas barrier property. If the oxygen atom concentration is less than 45 atm%, magnesium and silicon may be insufficiently oxidized, resulting in a decrease in light transmittance. Further, if the oxygen atom concentration is more than 70 atm%, oxygen may be excessively introduced, so that voids and defects increase, and the gas barrier property decreases.

The A layer preferably has a ratio Mg/Si of 0.30 to 11.00 in terms of atomic concentration (atm%) of magnesium (Mg) atoms to silicon (Si) atoms. When the ratio of the atomic concentration (atm%) Mg/Si is less than 0.30, the ratio of silicate bonds in the a layer is reduced, and therefore, the gas barrier property may not be exhibited because the denseness is reduced. When the ratio of the atomic concentration (atm%) Mg/Si is > 11.00, the A layer is likely to become a crystalline layer and cracks are likely to be introduced. From the viewpoint of gas barrier properties, the ratio Mg/Si of the atomic concentration (atm%) is more preferably 0.50 to 4.60, and still more preferably 0.80 to 2.70.

The thickness of the a layer in the present invention can be obtained by evaluation using a Transmission Electron Microscope (TEM) and an X-ray reflectance method (XRR method). The thickness of the A layer is preferably 5nm or more, more preferably 10nm or more. If the thickness is less than 5nm, a region not formed as a layer may be formed, and sufficient gas barrier properties may not be secured. The thickness of the a layer is preferably 500nm or less, and more preferably 300nm or less. If the thickness of the a layer is more than 500nm, cracks may be easily introduced, and the bending resistance and the stretchability may be reduced.

[ base Material ]

The substrate used in the present invention preferably has a film form in view of ensuring flexibility. The film may be a single-layer film or a film having 2 or more layers and produced by, for example, coextrusion. As the kind of the film, unstretched, uniaxially stretched, biaxially stretched film or the like can be used.

The material of the substrate used in the present invention is not particularly limited, but an organic polymer is preferably used 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, polycarbonates, polystyrenes, polyvinyl alcohols, saponified products of ethylene-vinyl acetate copolymers, various polymers such as polyacrylonitrile and polyacetal. Among them, amorphous cyclic polyolefin or polyethylene terephthalate excellent in transparency, versatility and mechanical properties is preferably used. The organic polymer may be a homopolymer or a copolymer, and only 1 type of the organic polymer may be used, or a plurality of types may be used in combination.

In order to improve the adhesion and smoothness, the surface of the substrate on the side on which the layer a is formed may be subjected to a pretreatment such as corona treatment, plasma treatment, ultraviolet treatment, ion bombardment treatment, solvent treatment, or formation treatment of a bonding layer made of an organic substance, an inorganic substance, or a mixture thereof. On the side opposite to the side on which the layer a 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 sliding property when the substrate is wound and the scratch resistance of the substrate.

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

[ bonding layer ]

The laminate of the present invention preferably has a tie layer (anchor coat layer) having one side in contact with the substrate and the other side in contact with the a layer. Further, the anchor layer more preferably contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure. When the substrate has defects such as projections and scratches, the a layer laminated on the substrate may have pinholes or cracks, which may impair the gas barrier properties and the bending resistance, from the above-mentioned defects. Further, when the difference in thermal dimensional stability between the substrate and the a layer is large, the gas barrier property and the flexibility may be lowered, and therefore, it is preferable to provide a bonding layer. In addition, the tie layer used in the present invention preferably contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure, and more preferably contains an ethylenically unsaturated compound, a photopolymerization initiator, an organosilicon compound and/or an inorganic silicon compound, from the viewpoint of thermal dimensional stability and bending resistance.

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

Epoxy (meth) acrylates having a hydroxyl group and an aromatic ring in the molecule can be obtained by reacting a diepoxy compound of an aromatic diol such as bisphenol a, hydrogenated bisphenol a, bisphenol F, hydrogenated bisphenol F, resorcinol, or hydroquinone with a (meth) acrylic acid derivative.

Examples of the diol compound that can be used 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, 2,4, 4-tetramethyl-1, 3-cyclobutanediol, and the like, 4,4 ' -thiodiphenol, bisphenol A, 4 ' -methylenediphenol, 4 ' - (2-norbornylene) diphenol, 4 ' -dihydroxybiphenol, o-dihydroxybenzene, m-dihydroxybenzene, and p-dihydroxybenzene, 4 ' -isopropylidenephenol, 4 ' -isopropylidenebis (4, 4 ' - イソプロピリデンビンジオール), cyclopentane-1, 2-diol, cyclohexane-1, 4-diol, bisphenol A, and the like. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

Examples of the diisocyanate compound include aromatic diisocyanates such as 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2, 4-diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate, aliphatic diisocyanate compounds such as ethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate, alicyclic isocyanate compounds such as isophorone diisocyanate, dicyclohexylmethane-4, 4-diisocyanate and methylcyclohexylene diisocyanate, alicyclic isocyanate compounds such as compounds having a high affinity for water, water and oil, and mixtures thereof, Aromatic and aliphatic isocyanate compounds such as xylylenediisocyanate and tetramethylxylylene diisocyanate. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The ratio of the epoxy (meth) acrylate having a hydroxyl group and an aromatic ring in the molecule, the diol compound, and the diisocyanate compound is not particularly limited as long as the ratio is within a desired weight average molecular weight range. 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. It is preferable that the weight average molecular weight (Mw) is 5,000 to 100,000 because the resulting cured film has excellent thermal dimensional stability and bending resistance. The weight average molecular weight (Mw) in the present invention is a value in terms of standard polystyrene, which is measured by gel permeation chromatography.

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, polyfunctional (meth) acrylates such as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, epoxy acrylates such as bisphenol a type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate and bisphenol S type epoxy di (meth) acrylate. Among them, preferred is a polyfunctional (meth) acrylate excellent in thermal dimensional stability and surface protection properties. In addition, they may be used in a single composition, or two or more components may be used in combination.

The content of the ethylenically unsaturated compound is not particularly limited, but is preferably in the range of 5 to 90% by mass, more preferably 10 to 80% by mass, based on 100% by mass of the total amount of the ethylenically unsaturated compound and the polyurethane compound having an aromatic ring structure, from the viewpoint of thermal dimensional stability and surface protection performance.

The photopolymerization initiator is not particularly limited as long as it can maintain the gas barrier properties and the bending resistance of the laminate of the present invention. Examples of the photopolymerization initiator which can be suitably used in the present invention include 2, 2-dimethoxy-1, 2-diphenylethan-1-one, 1-hydroxy-cyclohexylphenylketone, 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, methyl benzoylformate, and mixtures thereof, An alkylphenone-based photopolymerization initiator such as 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone, an acylphosphine oxide-based photopolymerization initiator such as 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide or bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (. eta.5-2, 4-cyclopentadien-1-yl) -bis (2), titanocene-based photopolymerization initiators such as 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, and photopolymerization initiators having an oxime ester structure such as 1, 2-octanedione, 1- [4- (phenylthio) -,2- (0-benzoyloxime) ].

Among them, from the viewpoint of curability and surface protection performance, a photopolymerization initiator selected from the group consisting of 1-hydroxy-cyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4, 6-trimethylbenzoyl) -phenyl phosphine oxide is preferable. In addition, they may be used in a single composition, or two or more components may be used in combination.

The content of the photopolymerization initiator is not particularly limited, but is preferably in the range of 0.01 to 10% by mass, and more preferably in the range of 0.1 to 5% by mass, in the total amount of the polymerizable components, from the viewpoint of curability and surface protection performance.

Examples of the organosilicon compound include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-tert-butylaminopropylmethyldimethoxysilane, N-propylmethyldimethoxysilane, N-propyl, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.

Among them, from the viewpoint of curability and polymerization activity by irradiation with active energy rays, at least 1 organic silicon compound selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane is preferable. In addition, they may be used in a single composition, or two or more components may be used in combination.

The content of the organosilicon compound is not particularly limited, but is preferably in the range of 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, in the total amount of the polymerizable components, from the viewpoint of curability and surface protection performance.

The inorganic silicon compound is preferably silica particles 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 300nm, more preferably in the range of 5 to 80 nm. Here, the primary particle diameter refers to a particle diameter d obtained by applying a specific surface area s obtained by a gas adsorption method to the following formula (1).

d＝6/ρs (1)

ρ: density.

The thickness of the bonding layer is preferably 200nm or more and 4,000nm or less, more preferably 300nm or more and 2,000nm or less, and still more preferably 500nm or more and 1,000nm or less. If the thickness of the bonding layer is less than 200nm, the adverse effect of the defects such as projections and scratches on the substrate may not be suppressed. If the thickness of the anchor coat is more than 4,000nm, the smoothness of the anchor coat is lowered, and the surface of the a layer laminated on the anchor coat has a large uneven shape, and the vapor deposited film to be laminated is less likely to be dense, and the effect of improving the gas barrier property is less likely to be obtained. Here, the thickness of the binding layer can be measured from a cross-sectional observation image of a Transmission Electron Microscope (TEM).

The bonding layer preferably has an arithmetic average roughness Ra of 10nm or less. When Ra is 10nm or less, a homogeneous a layer is easily formed on the bonding layer, and the reproducibility of the gas barrier property is improved, which is preferable. If the Ra of the surface of the anchor coat is more than 10nm, the surface of the a layer on the anchor coat may have large irregularities, the vapor deposited film may not be easily densified, and the gas barrier property may not be easily improved. Therefore, in the present invention, the Ra of the bonding layer is preferably 10nm or less, more preferably 5nm or less. The Ra of the bonding layer in the present invention can be measured using an Atomic Force Microscope (AFM) or the like.

When the anchor coat is applied to the laminate of the present invention, as a means for applying a coating solution containing a resin forming the anchor coat, it is preferable to first apply a coating solution containing a urethane compound having an aromatic ring structure on a base material by, for example, a reverse coating method, a gravure coating method, a bar coating method, a die coating method, a spray coating method, a spin coating method, or the like by adjusting the solid content concentration so that the thickness after drying becomes a desired thickness. In the present invention, it is preferable that the coating material containing the polyurethane compound having an aromatic ring structure is diluted with an organic solvent from the viewpoint of coating suitability.

Specifically, it is preferable to use a hydrocarbon solvent such as xylene, toluene, methylcyclohexane, pentane, or hexane, an ether solvent such as dibutyl ether, ethylbutyl ether, or tetrahydrofuran, or the like, and dilute the solid content to 10 mass% or less. These solvents may be used alone or in combination of 2 or more. In addition, various additives may be blended as necessary in the coating material forming the anchor coat layer. For example, a catalyst, an antioxidant, a light stabilizer, a stabilizer such as an ultraviolet absorber, a surfactant, a leveling agent, an antistatic agent, and the like can be used.

Next, the coated film is preferably dried to remove the diluting solvent. Here, the heat source used for drying is not particularly limited, and any heat source such as a steam heater, an electric heater, an infrared heater, or the like can be used. In addition, in order to improve the gas barrier property, the heating temperature is preferably 50 to 150 ℃. The heat treatment time is preferably several seconds to 1 hour. Further, the temperature may be constant during the heating treatment or may be gradually changed. In addition, in the drying treatment, the heat treatment can be performed while adjusting the relative humidity in the range of 20 to 90% RH. The heating treatment may be performed in the atmosphere or while enclosing an inert gas.

Next, it is preferable to perform an active energy ray irradiation treatment on the dried coating film containing the polyurethane compound having an aromatic ring structure to crosslink the coating film, thereby forming the anchor layer.

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

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

The cumulative amount of light of the ultraviolet irradiation is preferably 0.1 to 1.0J/cm²More preferably 0.2 to 0.6J/cm². If the above-mentioned integrated light quantity is 0.1J/cm²The above is preferable because a desired degree of crosslinking of the bonding layer is obtained. Further, if the above-mentioned integrated light quantity is 1.0J/cm²The following is preferable because damage to the substrate can be reduced.

[ other layers ]

The top layer of the laminate of the present invention, i.e., the layer a, may be a laminate in which an adhesive layer or a film made of an organic polymer compound for bonding to a device or the like is laminated, and a top coat layer for the purpose of improving scratch resistance, chemical resistance, printability, and the like may be formed on the top surface of the laminate without lowering the gas barrier property. In addition, a low refractive index layer for improving optical characteristics may be formed. Here, the outermost surface refers to a surface of the a layer after the a layer is laminated on the substrate.

[ use of the laminate ]

The laminate of the present invention has high gas barrier properties, and therefore can be suitably used as a gas barrier film. Further, the laminate of the present invention can be used for various electronic devices. The resin composition can be suitably used for electronic devices such as solar cells, flexible circuit substrates, organic EL lighting, flexible organic EL displays, and scintillators. Further, the film can exhibit high barrier properties, and is also suitable for use as a packaging material for lithium ion batteries, a packaging material for pharmaceuticals, and the like.

Examples

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

[ evaluation method ]

(1) Thickness of each layer

A sample for cross-section observation was prepared by the FIB method (specifically, the method described in "Polymer surface engineering" (Nissan Seisakusho) p.118 to 119) using a microsampling system (FB-2000A, Hitachi, Ltd.). The thickness of the A layer and the bonding layer of the laminate was measured by observing the cross section of the observation sample with a transmission electron microscope (H-9000 UHRII, manufactured by Hitachi Ltd.) at an acceleration voltage of 300 kV.

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

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

An apparatus: PHI5000Versa Probe2 (manufactured by アルバックファイ Co., Ltd.)

Excitation X-ray: monochromatic AlK alpha

Analysis range: phi 100 mu m

Photoelectron take-off angle: 45 degree

Ar ion etching: 2.0kV, grating size 2X 2, etching time 1 min.

The half-width of the oxygen atom (O1s) peak was calculated by the analytic software Multipak attached to the measurement apparatus.

In addition, the presence or absence of the silicate bond is analyzed by XPS method under the above conditions, and after the peak top of O1s is corrected to 531.0eV, the peak top position of Si2p is confirmed, and if it falls within the range of 101.0 to 103.0eV, the silicate bond (Y) is present, if it is out of the range, the silicate bond (N) is absent, and if it does not contain Si, the Si peak (-) is absent.

(3) Water vapor transmission rate (g/m)²Day)

The laminate has a water vapor permeability of 50cm at a temperature of 40 deg.C and a humidity of 90% RH²Under the conditions (D) described above, the measurement was carried out using a water vapor transmittance measuring apparatus (model name: DELTAPERM (registered trademark)) manufactured by テクノロックス (Technolox) of UK. With respect to the number of samples, 2 samples were taken per level. The data obtained by measuring 2 samples were averaged, and the 2 nd position after the decimal point was rounded off to obtain an average value at that level, and the value was defined as the water vapor transmission rate (g/m)²Day).

(4) Determination of surface roughness

The arithmetic average roughness Ra was measured using an Atomic Force Microscope (AFM). The laminate was cut out to an arbitrary size, and the field of view of 1 μm × 1 μm on the surface of the a layer was measured under the following conditions. The measurement was performed such that n-2 was used as an average value of Ra. In the case where another layer such as a hard coat layer is present on the a layer, the other layer is removed, and then measurement is performed on the surface of the a layer.

The measurement device: de-mension icon manufactured by Bruker

Measurement range: 1 μm × 1 μm

Scan rate (scan rate): 1Hz

Scan line (scan line): 512

Analysis software: nanoscope Analysis.

(5) Positron lifetime and pore radius distribution

The positron lifetime and pore radius distribution were measured by a positron beam method (thin film positron annihilation lifetime measurement method). The sample to be measured was attached to a 15mm × 15mm square Si wafer, vacuum degassed at room temperature, and then measured. The measurement conditions are as follows.

An apparatus: フジ - インバック small positive electron beam generator PALS200A

Positron emission source: based on²²Positron beam of Na

Gamma ray detector: BaF₂Scintillator and photomultiplier tube

Device constants: 255-278 ps, 24.55ps/ch

Beam intensity: 1keV

Measurement depth: 0 to 100nm (estimated)

Measurement temperature: at room temperature

Measurement atmosphere: vacuum

Assay count: about 5,000,000 counts

The measurement results were analyzed for 3-component or 4-component by nonlinear least squares program positronsit.

(example 1)

(Synthesis of polyurethane Compound having aromatic Ring Structure)

A5-liter 4-neck flask was charged with 300 parts by mass of a bisphenol A diglycidyl ether acrylic acid adduct (product of Kyoeisha chemical Co., Ltd., trade name: エポキシエステル 3000A) and 710 parts by mass of ethyl acetate, and heated to an internal temperature of 60 ℃. 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) was added dropwise over 1 hour while stirring. After completion of the dropwise addition, the reaction was continued for 2 hours, and then 25 parts by mass of diethylene glycol (Wako pure chemical industries, Ltd.) was added dropwise over 1 hour. The reaction was continued for 5 hours after the dropwise addition, and a polyurethane compound having an aromatic ring structure and a weight-average molecular weight of 20,000 was obtained.

(formation of bonding layer)

As the substrate, a polyethylene terephthalate film having a thickness of 100 μm (manufactured by imperial レ, Inc. "ルミラー" (registered trademark) U48) was used.

As a coating liquid for forming a bonding layer, 150 parts by mass of the above polyurethane compound, 20 parts by mass of dipentaerythritol hexaacrylate (product name: ライトアクリレート DPE-6A, product of Kyoeisha chemical Co., Ltd.), 5 parts by mass of 1-hydroxy-cyclohexylphenyl ketone (product name: IRGACURE (registered trademark) 184, product of BASF ジャパン Co., Ltd.), 3 parts by mass of 3-methacryloxypropylmethyldiethoxysilane (product name: KBM-503, product of shin シリコーン Co., Ltd.), 170 parts by mass of ethyl acetate, 350 parts by mass of toluene and 170 parts by mass of cyclohexanone were blended to prepare a coating liquid. Subsequently, the coating liquid was applied to a substrate by a micro gravure coater (gravure line number 150UR, gravure spin ratio 100%), dried at 100 ℃ for 1 minute, and after drying, subjected to ultraviolet treatment under the following conditions to provide a bonding layer having a thickness of 1 μm.

An ultraviolet treatment device: LH10-10Q-G (フュージョン UV システムズ & ジャパン Co., Ltd.)

Introducing gas: n is a radical of₂(Nitrogen inert box)

An ultraviolet ray generating source: microwave electrodeless lamp

Cumulative light quantity: 400mJ/cm²

Sample temperature adjustment: and (4) room temperature.

(formation of layer A)

Using a winding type vapor deposition apparatus shown in FIG. 3, MgO + SiO was provided on the surface of the bonding layer of the substrate in a thickness of 150nm by an Electron Beam (EB) vapor deposition method₂The layer serves as the A layer.

The specific operation is as follows. First, as vapor deposition materials, granular magnesium oxide MgO (purity: 99.9%) having a size of about 2 to 5mm and silicon dioxide SiO₂(purity 99.99%) was heated at 100 ℃ for 8 hours. Next, each material was placed on the carbon hearth lining 11 as shown in fig. 4. Making MgO and SiO₂The material area ratio of (a) is MgO: SiO 2₂4: 1. in the winding chamber 5, the surface of the base material 1 on the side where the layer a is provided (the side where the bonding layer is formed) is placed on the unwinding roll 6 so as to face the hearth liner 11, unwound, and passed through the main drum 10 via the guide rollers 7, 8, and 9. At this time, the temperature of the main drum is controlledThe temperature was set at-15 ℃. Then, the pressure in the deposition apparatus 4 was reduced by a vacuum pump to obtain 5.0 × 10^-3Pa or less. Next, MgO and SiO were mixed using an electron gun (hereinafter, EB gun) 13 as a heat source₂Uniform heating was performed. The EB gun has an accelerating voltage of 6kV, an applied current of 50-200 mA, and a deposition rate of 1 nm/sec. An a layer was formed on the surface of the bonding layer of the substrate by EB evaporation. Further, the thickness of the a layer formed is adjusted by the film conveying speed. Then, the yarn is wound around a winding roller 18 via guide rollers 15, 16, and 17.

Next, test pieces were cut out from the obtained laminate, and various evaluations were performed. The results are shown in table 1.

(example 2)

In the layer of MgO + SiO₂In the formation of the layer, MgO and SiO are used₂The material area ratio of (a) is MgO: SiO 2₂3: a laminate was obtained in the same manner as in example 1, except that the composition was controlled in accordance with 1. The results are shown in table 1.

(example 3)

In the layer of MgO + SiO₂In the formation of the layer, MgO and SiO are used₂The material area ratio of (a) is MgO: SiO 2₂7: a laminate was obtained in the same manner as in example 1, except that the composition was controlled as described in example 3. The results are shown in table 1.

(example 4)

In the layer of MgO + SiO₂In the formation of the layer, MgO and SiO are used₂The material area ratio of (a) is MgO: SiO 2₂2: a laminate was obtained in the same manner as in example 1, except that the composition was controlled in accordance with 1. The results are shown in table 1.

(example 5)

In the layer of MgO + SiO₂In the formation of the layer, MgO and SiO are used₂The material area ratio of (a) is MgO: SiO 2₂6.5: a laminate was obtained in the same manner as in example 1, except that the composition was controlled to 3.5. The results are shown in table 1.

(example 6)

In the presence of Mg as layer AO+SiO₂In the formation of the layer, MgO and SiO are used₂The material area ratio of (a) is MgO: SiO 2₂5.5: a laminate was obtained in the same manner as in example 1, except that the composition was controlled to 4.5. The results are shown in table 1.

(example 7)

As the deposition material, granular zinc oxide ZnO (purity 99.9%) having a size of about 1 to 3mm and granular silicon oxide SiO (purity 99.9%) having a size of about 2 to 5mm were used, and in the formation of the ZnO + SiO layer as the a layer, the material area ratio of ZnO to SiO was set to ZnO: SiO 3: a laminate was obtained in the same manner as in example 1, except that the composition was controlled in accordance with 1. The results are shown in table 1.

(example 8)

In the formation of the ZnO + SiO layer as the a layer, the material area ratio of ZnO to SiO was made to be ZnO: SiO 2: a laminate was obtained in the same manner as in example 7, except that the composition was controlled in accordance with 1. The results are shown in table 1.

(example 9)

In the formation of the ZnO + SiO layer as the a layer, the material area ratio of ZnO to SiO was made to be ZnO: SiO 1: a laminate was obtained in the same manner as in example 7, except that the composition was controlled in accordance with 1. The results are shown in table 1.

(example 10)

As the vapor deposition material, particulate zinc oxide ZnO (purity 99.9%) having a size of about 1 to 3mm and particulate tin oxide SnO (purity 99.9%) having a size of about 2 to 5mm were used, and in the formation of the ZnO + SnO layer as the a layer, the material area ratio of ZnO to SnO was set to ZnO: SnO 3: a laminate was obtained in the same manner as in example 1, except that the composition was controlled in accordance with 1. The results are shown in table 1.

(example 11)

A laminate was obtained in the same manner as in example 1, except that a polyethylene terephthalate film having a thickness of 12 μm ("ルミラー" (registered trademark) P60, manufactured by imperial レ corporation) was used as the substrate, and the a layer was directly formed without forming a tie layer. The results are shown in table 1.

(example 12)

A laminate was obtained in the same manner as in example 5, except that a polyethylene terephthalate film having a thickness of 12 μm ("ルミラー" (registered trademark) P60, manufactured by imperial レ corporation) was used as the substrate, and the a layer was directly formed without forming a tie layer. The results are shown in table 1.

(example 13)

As the deposition material, granular calcium oxide CaO (purity: 99.9%) having a size of about 2 to 5mm and granular silicon dioxide SiO having a size of about 2 to 5mm were used₂(purity: 99.9%) in CaO + SiO layer as layer A₂In the formation of the layer, CaO and SiO are used₂The material area ratio of (b) is CaO: SiO 2₂When the ratio is 8: a laminate was obtained in the same manner as in example 1, except that the composition was controlled in accordance with 1. The results are shown in table 1.

(example 14)

As a deposition material, a granular zirconia ZrO having a size of about 2 to 5mm is used₂(purity: 99.9%) and a granular silica SiO having a size of about 2 to 5mm₂(purity: 99.9%) in ZrO as layer A₂+SiO₂In the formation of the layer, ZrO is caused₂Material area ratio to SiO ZrO₂：SiO₂When the ratio is 8: a laminate was obtained in the same manner as in example 1, except that the composition was controlled in accordance with 1. The results are shown in table 1.

Comparative example 1

A laminate was obtained in the same manner as in example 1, except that granular magnesium oxide MgO (purity 99.9%) having a size of about 2 to 5mm was used as the vapor deposition material, the material was placed on the carbon hearth liner 11 without the interlayer, and the vapor deposition material was heated by an EB gun at an acceleration voltage of 6kV, an applied current of 50 to 200mA, and a vapor deposition rate of 1 nm/sec. The results are shown in table 1.

Comparative example 2

As the deposition material, granular silicon dioxide SiO with the size of about 2-5 mm is used₂(purity 99.99%) otherwise, and comparisonA laminate was obtained in the same manner as in example 1. The results are shown in table 1.

Comparative example 3

A laminate was obtained in the same manner as in comparative example 1, except that particulate zinc oxide ZnO (purity 99.99%) having a size of about 1 to 3mm was used as a vapor deposition material. The results are shown in table 1.

Comparative example 4

A laminate was obtained in the same manner as in example 1, except that the layer a was formed directly on the base material without forming the anchor layer. The results are shown in table 1.

Comparative example 5

A laminate was obtained in the same manner as in example 5, except that the layer a was formed directly on the base material without forming the anchor layer. The results are shown in table 1.

Comparative example 6

As the deposition material, flake magnesium Mg (purity 99.9%) having a size of about 2 to 5mm and granular silicon Si (purity 99.9%) having a size of about 2 to 5mm were used, and in the formation of the Mg + Si layer as the a layer, the material area ratio of Mg to Si was set to Mg: si-5: a laminate was obtained in the same manner as in example 1, except that the composition was controlled in accordance with 1. The results are 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%) having a size of about 2 to 5mm was used as a vapor deposition material. The results are 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 99.99%) having a size of about 2 to 5mm was used as a vapor deposition material. The results are shown in table 1.

Comparative example 9

As the deposition material, a granular zirconia ZrO having a size of about 2 to 5mm is used₂A laminate was obtained in the same manner as in comparative example 1, except that the purity was changed to 99.99%. Will be provided withThe results are shown in Table 1.

TABLE 2

In the table, (1)/(2) in the case where (1) is Mg and (2) is Si means the ratio Mg/Si of the atomic concentration (atm%) of magnesium (Mg) atoms to silicon (Si) atoms.

In examples 1 to 6, a composite oxide film of magnesium oxide and silicon dioxide having Ra of 2.0nm or less was formed on the surface of A layer, and the water vapor permeability was less than 5.0X 10-²(g/m²Day), is good. In examples 2 to 5, the mean lifetime of the component No. 3 in the electropositive electron beam method was 0.860ns or less (mean pore radius was 0.138nm or less), and the water vapor permeability was less than 5.0X 10-³(g/m²Day), is further preferable.

As in examples 7 to 10, 13 and 14, the water vapor permeability was less than 5.0X 10-²(g/m²Day), is good.

Further, as in examples 11 and 12, even when no bonding layer was present, the Ra of the surface of the a layer was 5.0nm or less, and the water vapor permeability was less than 1.0 × 10^-1(g/m²Day).

On the other hand, comparative examples 1,2, 8, and 9 are made of a single material, and have inferior gas barrier properties compared to examples in which 2 types of vapor deposition materials are mixed. In comparative examples 3 and 7, the adhesion was poor, and the gas barrier properties were not exhibited. In comparative examples 4 and 5, the surface roughness of the a layer surface was large, so that a dense film was not formed and the gas barrier property was not exhibited. In comparative example 6, although a composite metal film was formed, the gas barrier properties were not exhibited.

Industrial applicability

The laminate of the present invention is excellent in gas barrier properties against oxygen, water vapor, and the like, and therefore can be usefully used as a packaging material for foods, medicines, and the like, and a member for electronic devices such as organic EL televisions, solar cells, and the like, for example, but the application is not limited thereto.

Description of the symbols

1 base material

2A layer

3 bonding layer

4-winding Electron Beam (EB) evaporation device

5 winding chamber

6 uncoiling roller

7. 8, 9 uncoiling side guide roller

10 main rotary drum

11 hearth lining

12 vapor deposition material

13 electron gun

14 electron beam

15. 16, 17 winding side guide roller

18 winding roller

19 vapor deposition Material B

20 vapor-depositing a material C.