JP7600525B2 - Laminate - Google Patents

Description

The present invention relates to laminates that can be used, for example, as packaging materials for foods and medicines that require high gas barrier properties, and as materials for electronic components such as solar cells, electronic paper, and organic electroluminescence (EL) displays.

Gas barrier films obtained by forming an inorganic layer of an inorganic substance (including an inorganic oxide) on the surface of a film substrate using 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 enhanced chemical vapor deposition, thermal chemical vapor deposition or photochemical vapor deposition, are used as packaging materials for foods, medicines and the like that require the blocking of various gases such as water vapor and oxygen, and as components for electronic devices such as electronic paper and solar cells, and these components are required to have high gas barrier properties with a water vapor transmission rate of 5.0 × 10 ^-2 g/m ² 24 hr atm or less.

As one method for achieving high gas barrier properties, a gas barrier film in which organic and inorganic layers are alternately laminated to form multiple layers, thereby preventing the occurrence of defects by a hole-filling effect (Patent Document 1), and a gas barrier film having a simple film structure in which a composite oxide film such as a ZnO- _SiO2 -based film is formed on a film substrate by sputtering using a target mainly composed of ZnO and _SiO2 (Patent Document 2) have been proposed.

JP 2005-324406 A JP 2013-147710 A

However, although it is possible to achieve high barrier properties by alternately laminating organic and inorganic layers in multiple layers as in Patent Document 1, there are problems with laminating multiple layers, such as reduced adhesion between the substrate and inorganic layers and between the organic and inorganic layers due to film stress, and increased costs due to the increased number of steps. In addition, although a laminate formed by sputtering a complex oxide as in Patent Document 2 can be manufactured at a lower cost than Patent Document 1, it is difficult to reduce costs due to limitations in increasing the film formation speed due to the nature of the manufacturing method.

In light of the background of the conventional technology, the present invention aims to provide a laminate that has high gas barrier properties and excellent adhesion even with a low-cost and simple structure.

In order to solve these problems, the present invention adopts the following means. That is, as follows:

A laminate having an A layer on at least one side of a substrate, the A layer containing silicon and/or metal elements, and oxygen, an average life measured from the A layer side by a positron beam method of 0.935 ns or less, and the number of delaminated masses in a cross-cut test (JIS K5600-5-6, 1999) is 10% or less of the total.

The present invention makes it possible to provide a laminate with high gas barrier properties against water vapor and excellent adhesion at low cost.

FIG. 1 is a cross-sectional view showing an example of a laminate of the present invention. FIG. 2 is a cross-sectional view showing another example of the laminate of the present invention. FIG. 2 is a cross-sectional view showing another example of the laminate of the present invention. FIG. 1 is a schematic diagram showing a take-up type deposition apparatus for producing a laminate of the present invention. FIG. 2 is a diagram showing the arrangement of deposition materials for producing a laminate of the present invention.

The details of the present invention are explained below.

[Laminate]
The laminate of the present invention has an A layer on at least one side of a substrate, the A layer containing silicon and/or a metal element, and oxygen, and has an average lifetime of 0.935 ns or less as measured from the A layer side by a positron beam method, and the number of peeled masses in a cross-cut test (JIS K5600-5-6, 1999) is 10% or less of the total.

Figure 1 shows a cross-sectional view of an example of the laminate of the present invention. In the laminate of the present invention, an A layer 2 is disposed on at least one surface of a substrate 1. The A layer contains silicon and/or metal elements, as well as oxygen, and has an average lifespan of 0.935 ns or less as measured from the A layer side by a positron beam method, resulting in flexibility and high gas barrier properties. Furthermore, the A layer has excellent adhesion even when handled or in harsh environments such as high temperature and high humidity, resulting in stable high gas barrier properties, as the number of peeled masses in the cross-cut test (JIS K5600-5-6, 1999) is 10% or less of the total.

As shown in Figure 2, another example of the laminate of the present invention has a layer B 3 between a substrate 1 and the layer A 2, and the layer B is a metal oxide layer, which can compensate for the weak adhesion of the layer A to the substrate, resulting in a laminate that exhibits higher adhesion and gas barrier properties.

Another example of the laminate of the present invention is one having an anchor coat layer 4 between the substrate 1 and layer B 2 on one side of the substrate 1, as shown in Figure 3. By having the anchor coat layer 4, even if there are protrusions or scratches on the surface of the substrate 1, it can be flattened, and layer A 2 grows uniformly without bias, resulting in a laminate that exhibits higher gas barrier properties.

The laminate of the present invention preferably has a water vapor permeability of less than 5.0×10 ⁻² g/m ² /day. From the viewpoint of use as a high-grade packaging material or for electronic device applications that require relatively high gas barrier properties, the laminate of the present invention more preferably has a water vapor permeability of less than 1.0×10 ⁻² g/m ² /day. [Substrate]
The substrate used in the present invention is preferably in the form of a film in order to ensure flexibility. The film may be a single-layer film or a film having two or more layers, for example, a film formed by a co-extrusion method. The type of film may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film.

The material of the substrate used in the present invention is not particularly limited, but it is preferable that the main component is an organic polymer. Examples of organic polymers 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, polystyrene, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymers, polyacrylonitrile, polyacetal, and various other polymers. Among these, it is preferable to use amorphous cyclic polyolefins or polyethylene terephthalate, which have excellent transparency, versatility, and mechanical properties. In addition, the organic polymer may be either a homopolymer or a copolymer, and only one type of organic polymer may be used, or multiple types may be blended.

The surface of the substrate on which the A layer is formed may be pretreated to improve adhesion and smoothness by corona treatment, plasma treatment, ultraviolet treatment, ion bombardment treatment, solvent treatment, or treatment to form an anchor coat layer composed of an organic or inorganic substance or a mixture of these. In addition, a coating layer of an organic or inorganic substance or a mixture of these may be laminated on the side opposite to the side on which the A layer is formed, in order to improve the slipperiness of the substrate when it is wound up and to improve the scratch resistance of the substrate.

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

[Layer A]
The laminate of the present invention has an A layer, and the A layer contains silicon and/or a metal element, and oxygen. Examples of the metal elements contained in the A layer include magnesium (Mg), aluminum (Al), titanium (Ti), chromium (Cr), manganese (Mn), zinc (Zn), gallium (Ga), germanium (Ge), zirconium (Zr), niobium (Nb), molybdenum (Mo), tin (Sn), and tantalum (Ta). The A layer contains silicon, a metal element, and oxygen, which allows the film hardness to be controlled, and the A layer is less likely to crack due to heat or external stress, and can stably exhibit high gas barrier properties. The metal element to be combined with silicon is not limited, but as a metal element that makes the entire film have an amorphous structure formed of fine particles and provides higher gas barrier properties, magnesium (Mg), aluminum (Al), zirconium (Zr), tin (Sn), and zinc (Zn) are more preferable, and magnesium (Mg) and zinc (Zn) are even more preferable.

As a preferred example, when layer A contains silicon, magnesium (Mg), and oxygen, the entire film has an amorphous structure formed of fine particles, and from the viewpoint of exhibiting high gas barrier properties, it is preferred that the magnesium (Mg) atomic concentration is 5 to 50 atom%, the silicon (Si) atomic concentration is 2 to 30 atom%, and the oxygen (O) atomic concentration is 45 to 70 atom%.

The A layer of the laminate of the present invention has an average lifetime of 0.935 ns or less measured from the A layer side by a positron beam method (thin film positron annihilation lifetime measurement method) (see Chapter I, Section 1, and Chapter V, Section 2 of "The Science of Positron Measurement" (Japan Radioisotope Association)). The positron beam method is one of the positron annihilation lifetime measurement methods, and is a method for measuring the time (on the order of several hundred ps to several tens of ns) from when a positron enters a sample until it annihilates, and for non-destructively evaluating information on the size, number concentration, and size distribution of vacancies of about 0.1 to ¹⁰ nm from the annihilation lifetime. The method is significantly different from the usual positron annihilation method in that a positron beam is used as a positron source instead of a radioisotope (22Na), and is a method that enables the measurement of thin films of about several hundred nm thick formed on silicon or quartz substrates. The average pore radius and number concentration of pores can be obtained from the obtained measured values by the nonlinear least squares program POSITRONFIT. The average lifetime of the third and fourth components can be obtained by analyzing the average lifetime of the third and fourth components. When an inorganic layer or a resin layer other than the A layer is formed on the surface of the A layer, the average lifetime of the A layer can be measured from the A layer side by the positron beam method after removing the inorganic layer or the resin layer by the thickness measured by the cross-sectional observation with a transmission electron microscope by ion etching.

Here, the third component refers to the average life obtained by selecting an analysis for three components as the measurement conditions for the average life by the positron beam method, and the fourth component refers to the average life obtained by selecting an analysis for four components as the measurement conditions for the average life by the positron beam method. When performing an analysis using POSITRONFIT, the number of components in POSITRONFIT is determined from the number of peaks obtained in the pore radius distribution curve calculated using the distribution analysis program CONTIN based on the inverse Laplace transform method. The validity of the analysis is determined by the agreement between the average pore radius calculated using POSITRONFIT and the peak position of the pore radius distribution curve of CONTIN. The average life in this invention refers to the average life of the third component.

If the average lifespan is greater than 0.935 ns, the density of layer A decreases, and gas barrier properties may not be exhibited. From the viewpoint of gas barrier properties, the average lifespan measured by the positron beam method is preferably 0.912 ns or less, and more preferably 0.863 ns or less. There is no particular limit to the lower limit of the average lifespan, but it is preferably 0.542 ns or more. If the average lifespan is less than 0.542 ns, flexibility may decrease.

In order to set the average lifetime of the A layer to 0.935 ns or less as measured by the positron beam method as specified in the present invention, this can be achieved, for example, by forming a dense composite oxide film with an appropriate composition ratio on a substrate with an Ra of 10.0 nm or less, or by adjusting the atomic concentrations of the metal elements and silicon contained in the A layer, which will be described later. "Densely formed" here refers to a state in which the oxides are mixed at the atomic level to form a dense network.

The layer A of the laminate of the present invention is preferably an amorphous film. Amorphous refers to an irregular structure in which atoms and molecules do not have a long-range regular order structure like crystals. A crystalline structure is preferable because grain boundaries form and become paths for water vapor permeation, which can lead to deterioration of gas barrier properties and cracking. Whether or not a film is amorphous can be confirmed by analytical methods such as cross-sectional TEM and X-ray diffraction (XRD). In the case of cross-sectional TEM, the contrast is uniform in an amorphous film and no grain boundaries are observed, while in a crystalline film, grain boundaries according to the crystal structure, such as a microcrystalline state or a columnar structure, are observed.

In order to stably exhibit high gas barrier properties, it is preferable that the number of delaminated masses in the cross-cut test (JIS K5600-5-6, 1999) of the A layer of the laminate of the present invention is 10% or less of the total. Furthermore, in order to maintain excellent adhesion for a long time even in a high-temperature and high-humidity environment of a temperature of 40°C or more and a humidity of 90% RH or more and to maintain high gas barrier properties, it is more preferable that the number of delaminated masses is 5% or less of the total.

In the A layer of the laminate of the present invention, when the atomic concentration of the metal element is Ma (atom%) and the atomic concentration of silicon is Sia (atom%), the ratio Ma/(Ma+Sia) of the atomic concentration of the metal element to the atomic concentration of silicon is preferably 0.45 to 0.85. From the viewpoint of denseness and gas barrier properties, Ma/(Ma+Sia) is more preferably in the range of 0.52 to 0.82, and even more preferably 0.55 to 0.79. When multiple metal elements are contained, the sum of the atomic concentrations of the multiple metal elements is Ma, excluding silicon. For example, when Zr 60 (atom%), Zn 10 (atom%), and Si 30 (atom%) are contained in the A layer, M(Zr+Zn) = 70 (atom%), Si = 30 (atom%), and Ma/(Ma+Si) = 0.7. If Ma/(Ma+Sia) is greater than 0.85, the film may become crystalline or may become less dense. If Ma/(Ma+Sia) is less than 0.45, the film quality may become non-uniform and the barrier properties may become unstable.

The A layer of the present invention preferably has a half-width of the oxygen atom (O1s) peak measured by X-ray photoelectron spectroscopy of 3.25 _eV or less. The half-width refers to the peak width when the peak intensity is _Fmax /2, where Fmax is the maximum value of the peak. The narrower the half-width of the O1s peak, the more uniform the bond network structure is formed, and the more likely it is to become a dense film. From the viewpoint of bond uniformity and barrier properties, it is more preferably 3.00 eV or less, and even more preferably 2.75 eV or less. The lower limit is not particularly limited, but is preferably 1.65 eV or more.

The thickness of the A layer is preferably 10 nm or more, and more preferably 20 nm or more. If the layer thickness is thinner than 10 nm, there may be some areas where the gas barrier property is not sufficiently ensured, resulting in variation in the gas barrier property. From the viewpoint of minimizing the thermal influence during the formation of the A layer on the substrate, the thickness of the A layer is preferably 500 nm or less, and more preferably 250 nm or less. If the A layer is thicker than 500 nm, residual stress within the layer may become large, and cracks or breakage may occur.

The thickness of layer A in the present invention can be obtained by cross-sectional observation using a transmission electron microscope (TEM). The composition of layer A can be obtained by X-ray photoelectron spectroscopy (XPS). When an inorganic layer or resin layer, which will be described later, is laminated on layer A, the thickness of the inorganic layer or resin layer measured by cross-sectional observation using a transmission electron microscope is removed by ion etching or chemical treatment, and then the analysis is performed using the method described above.

[B Layer]
The laminate of the present invention preferably has a layer B between the substrate and layer A, and the layer B is a metal oxide layer.

The laminate of the present invention has a layer B between the substrate and layer A, and the layer B is a metal oxide layer, which can compensate for the weak adhesion of layer A to the substrate, thereby achieving better adhesion and gas barrier properties. The metal oxide layer refers to a layer containing a metal oxide, and examples of metal elements contained in the metal oxide include magnesium (Mg), aluminum (Al), titanium (Ti), chromium (Cr), manganese (Mn), zinc (Zn), gallium (Ga), germanium (Ge), zirconium (Zr), niobium (Nb), molybdenum (Mo), tin (Sn), and tantalum (Ta).

The B layer preferably contains a metal element and silicon. By containing silicon, a metal element, and oxygen, the B layer can control the film hardness, and is less likely to crack due to heat or external stress, and can exhibit stable and excellent adhesion. There are no limitations on the metal element to be combined with silicon, but magnesium (Mg), aluminum (Al), zirconium (Zr), tin (Sn), and zinc (Zn) are preferred as metal elements that give the entire film an amorphous structure formed of fine particles and provide better adhesion and high gas barrier properties, with magnesium (Mg), aluminum (Al), and zinc (Zn) being more preferred.

In addition, the B layer in the present invention is preferably a silicon compound layer, and may contain silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, or a mixture thereof as the silicon compound. In particular, it is preferable that the B layer contains at least one silicon compound selected from the group consisting of silicon oxide, silicon carbide, silicon nitride, and silicon oxynitride.

By containing a metal oxide and a silicon compound, Layer B of the present invention tends to have an amorphous structure formed of fine particles throughout the film, resulting in a laminate with higher gas barrier properties. By containing a metal oxide and a silicon compound, it becomes possible to control the film hardness, so it is believed that Layer B can alleviate stress that occurs between the substrate and Layer A due to handling or impact, suppressing the occurrence of defects and cracks in Layer A, and consistently achieving high gas barrier properties.

The B layer of the laminate of the present invention contains a metal element and silicon, and when the atomic concentration of the metal element is Mb (atom%) and the atomic concentration of silicon is Sib (atom%), it is preferable that the ratio of the atomic concentrations of the metal element and silicon, Mb/(Mb+Sib), is Mb/(Mb+Sib)<0.6 or Mb/(Mb+Sib)>0.8. From the viewpoint of imparting flexibility and high adhesion to the B layer, it is more preferable that Mb/(Mb+Sib)<0.3 or Mb/(Mb+Sib)>0.9. When multiple metal elements are contained, the sum of the atomic concentrations of the multiple metal elements is Mb, excluding silicon. For example, if layer B contains 60 (atom%) Al, 10 (atom%) Zr, and 30 (atom%) Si, then Mb (Al + Zr) = 70 (atom%), Si = 30 (atom%), and Mb/(Mb + Sib) = 0.7.

The thickness of the B layer is preferably 1 nm or more, and more preferably 5 nm or more. If the thickness of the B layer is less than 1 nm, the adhesion between the substrate and the B layer may be insufficient. Furthermore, the B layer is preferably 300 nm or less, and more preferably 100 nm or less. If the thickness of the B layer is greater than 300 nm, the stress generated between the substrate and the B layer may reduce the adhesion of the B layer or cause defects in the A layer, and sufficient gas barrier properties may not be ensured. Therefore, the thickness of the B layer is preferably 1 nm or more and 300 nm or less, and more preferably 3 nm or more and 100 nm or less.

In order to achieve both adhesion and flexibility, the thickness of layer B is preferably 40% or less of the thickness of layer A, and from the viewpoint of being able to form it at low cost, it is preferably 25% or less, and from the viewpoint of achieving high adhesion by the sputtering method, it is more preferably greater than 0% and less than 15%.

The thickness of layer B in the present invention can be obtained by cross-sectional observation using a transmission electron microscope (TEM). The composition of layer B can be obtained by X-ray photoelectron spectroscopy (XPS). When layer A or a resin layer is laminated on layer B, the thickness of the inorganic layer or resin layer measured by cross-sectional observation using a transmission electron microscope is removed by ion etching or chemical treatment, and then analyzed by the method described above.

[Method of manufacturing A layer]
The method for forming the A layer is not particularly limited, and can be a vacuum deposition method, a sputtering method, a reactive sputtering method, a molecular beam epitaxy method, a cluster ion beam method, an ion plating method, an atomic layer deposition method, a plasma polymerization method, an atmospheric pressure plasma polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, etc. From the viewpoint of manufacturing cost, gas barrier property, etc., it is preferable to use a vacuum deposition method. When the A layer is a compound layer containing silicon and one or more metal elements or a compound layer containing two or more metal elements, it is preferable to use electron beam (EB) deposition or ion beam assisted deposition (IBAD) among the vacuum deposition methods.

An example of a method for forming the A layer using the winding type vapor deposition apparatus shown in FIG. 4 is shown. A compound thin film of materials C and D is provided as the A layer on the surface of the substrate 1 by electron beam vapor deposition. First, granular materials C and D having a size of about 2 to 5 mm are arranged as the vapor deposition materials as shown in FIG. 5. The vapor deposition material is not limited to granules, and may be in the shape of a molded body such as a square or tablet. In addition, the vapor deposition source materials are arranged in the width direction of the substrate in FIG. 5, but other arrangements such as mixing two materials in one hearth liner or arranging them in the longitudinal direction may be used. In addition, if the vapor deposition material absorbs moisture, the moisture in the material may be taken into the A layer, and the desired film composition and physical properties may not be obtained, so it is preferable to perform a dehydration treatment by heating before using the material. In the winding chamber 6, the unwinding roll 7 is set so that the surface of the substrate 1 on which the A layer is to be provided faces the hearth liner 12. Next, the inside of the vapor deposition apparatus 5 is depressurized to 5.0×10 ⁻³ Pa or less by a vacuum pump, and the temperature of the main drum 11 is cooled to 0° C. or less, for example. Next, the film is unwound and passed through guide rolls 8, 9, and 10 onto a main drum 11. At this time, an electron gun (hereinafter, EB gun) 14 is used as a heating source to heat the surfaces of materials C and D so that the desired film composition ratio is achieved. The EB gun adjusts the acceleration current, voltage, and film transport speed so that the layer A to be formed has a targeted thickness, forming layer A on the surface of the substrate 1. Thereafter, the film is taken up onto a take-up roll 19 via guide rolls 16, 17, and 18.

[Method of manufacturing layer B]
The method for forming the B layer is not particularly limited, and can be vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, atomic layer deposition, plasma polymerization, atmospheric plasma polymerization, plasma CVD, laser CVD, thermal CVD, coating, etc. When the B layer is a compound layer containing silicon and one or more metal elements or a compound layer containing two or more metal elements, it is preferable to form the B layer by vacuum deposition, sputtering, ion plating, etc. using a mixed sintering material adjusted to have the desired composition. Among these, sputtering is more preferable as a method for exhibiting excellent adhesion between the substrate and the B layer.

Next, an example of a method for forming a B layer using a winding type vapor deposition apparatus shown in FIG. 4 is shown. A compound thin film of materials E and F is provided as a B layer on the surface of a substrate 1 by a sputtering method. First, a sputtering target material 20 in which materials E and F are sintered in a desired composition ratio is attached to a sputtering electrode 21. In a winding chamber 6, the surface of the substrate 1 on which the B layer is to be provided is set on a winding roll 7 so that it faces the sputtering electrode 21. Next, the inside of the vapor deposition apparatus 5 is depressurized to 5.0×10 ⁻³ Pa or less by a vacuum pump, and the temperature of the main drum 11 is cooled to 0° C. or less, for example. Next, the film is unwound and passed through the main drum 11 via guide rolls 8, 9, and 10. At this time, argon gas and oxygen gas are introduced, and input power is applied from a power source to the sputtering electrode 21 to generate an argon-oxygen gas plasma, and the power of the sputtering electrode 21 and the film transport speed are adjusted so that the B layer has a desired thickness, and the B layer is formed on the surface of the substrate 1. Thereafter, the film is wound around a winding roll 19 via guide rolls 16, 17, and 18.

When forming layers B and A consecutively, it is possible to form layer B on the surface of substrate 1, then form layer A on layer B using the manufacturing method for layer A described above, and then wind it up on winding roll 19 via guide rolls 16, 17, and 18.

[Anchor coat layer]
The laminate of the present invention has an anchor coat layer, and it is preferable that one side of the anchor coat layer is in contact with the substrate, and the other side is in contact with the A layer or B layer. Furthermore, it is more preferable that the anchor coat layer contains a structure obtained by crosslinking a polyurethane compound having an aromatic ring structure. When defects such as protrusions or scratches exist on the substrate, pinholes or cracks may occur in the A layer and B layer laminated on the substrate starting from the defects, which may impair gas barrier properties and bending resistance, so it is preferable to provide an anchor coat layer. In addition, when the difference in thermal dimensional stability between the substrate and the A layer is large, the gas barrier properties and bending resistance may also decrease, so it is preferable to provide 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 more preferably contains an ethylenically unsaturated compound, a photopolymerization initiator, an organic silicon compound and/or an inorganic silicon compound.

The polyurethane compound having an aromatic ring structure used in the anchor coat layer of the laminate of the present invention has an aromatic ring and a urethane bond in the main chain or side chain, and can be obtained, for example, by polymerizing an epoxy (meth)acrylate, a diol compound, or a diisocyanate compound that has a hydroxyl group and an aromatic ring in the 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 glycol such as bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, hydrogenated bisphenol F type, resorcin, or hydroquinone with a (meth)acrylic acid derivative.

Examples of diol compounds 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-cyclohexa Examples of the compounds that can be used include diphenylmethanol, 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'-isopropylidenebisdiol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, and bisphenol A. These can be used alone or in combination of two or more.

Examples of diisocyanate compounds include aromatic diisocyanates such as 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, and 4,4-diphenylmethane diisocyanate, ethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. Examples of such compounds include aliphatic diisocyanate compounds such as 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; alicyclic isocyanate compounds such as isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, and methylcyclohexylene diisocyanate; and aromatic aliphatic isocyanate compounds such as xylylene diisocyanate and tetramethylxylylene diisocyanate. These compounds may be used alone or in combination of two or more.

The ratio of the components 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 it is within the range that results in the desired weight average molecular weight. The weight average molecular weight (Mw) of the polyurethane compound having an aromatic ring structure in the present invention is preferably 5,000 to 100,000. If the weight average molecular weight (Mw) is 5,000 to 100,000, the resulting cured film has excellent thermal dimensional stability and bending resistance, which is preferable. The weight average molecular weight (Mw) in the present invention is a value measured using gel permeation chromatography and converted into standard polystyrene.

Examples of ethylenically unsaturated compounds 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 tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, and 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 these, polyfunctional (meth)acrylates that have excellent thermal dimensional stability and surface protection performance are preferred. These may be used in a single composition or in a mixture of two or more components.

The amount 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, and more preferably in the range of 10 to 80% by mass, of the total amount including the polyurethane compound having an aromatic ring structure, which is 100% by mass.

There are no particular limitations on the material of the photopolymerization initiator as long as it can maintain the gas barrier properties and flex resistance of the laminate of the present invention. Examples of photopolymerization initiators that can be suitably used in the present invention include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl phenyl 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-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, phenyl glyoxylic acid methyl ester, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl). Examples of such photopolymerization initiators include alkylphenone-based photopolymerization initiators such as -butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, titanocene-based photopolymerization initiators such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-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-(O-benzoyloxime)], etc.

Among these, from the viewpoint of curability and surface protection performance, photopolymerization initiators selected from 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)-phenylphosphine oxide are preferred. These may be used in a single composition or in a mixture of two or more components.

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

Examples of organosilicon compounds 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-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-isocyanatopropyltriethoxysilane.

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

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

As the inorganic silicon compound, silica particles are preferred from the viewpoints of surface protection performance and transparency, and the primary particle size of the silica particles is preferably in the range of 1 to 300 nm, and more preferably in the range of 5 to 80 nm. Note that the primary particle size here refers to the particle diameter d calculated by applying the specific surface area s calculated by a gas adsorption method to the following formula (1):
d=6/ρs... (1)
ρ: density.

The thickness of the anchor coat layer is preferably 200 nm or more and 4,000 nm or less, more preferably 300 nm or more and 2,000 nm or less, and even more preferably 500 nm or more and 1,000 nm or less. If the thickness of the anchor coat layer is thinner than 200 nm, the adverse effects of defects such as protrusions and scratches present on the substrate may not be suppressed. If the thickness of the anchor coat layer is thicker than 4,000 nm, the smoothness of the anchor coat layer decreases and the uneven shape of the surface of the A layer laminated on the anchor coat layer also becomes large, making it difficult for the laminated vapor deposition film to become dense, and the effect of improving the gas barrier property may be difficult to obtain. Here, the thickness of the anchor coat layer can be measured from a cross-sectional observation image obtained by a transmission electron microscope (TEM).

The arithmetic mean roughness Ra of the anchor coat layer is preferably 10 nm or less. When the Ra is 10 nm or less, it is preferable because it is easy to form a homogeneous A layer on the anchor coat layer, and the repeatability and reproducibility of the gas barrier properties is improved. When the Ra of the surface of the anchor coat layer is greater than 10 nm, the uneven shape of the A layer surface on the anchor coat layer also becomes large, making it difficult for the vapor deposition film to become dense, and it may be difficult to obtain the effect of improving the gas barrier properties. In addition, cracks due to stress concentration are likely to occur in parts with many unevenness, which may cause a decrease in the repeatability and reproducibility of the gas barrier properties. Therefore, in the present invention, it is preferable to set the Ra of the anchor coat layer to 10 nm or less, and more preferably 5 nm or less. The Ra of the anchor coat layer in the present invention can be measured using an atomic force microscope (AFM) or the like.

When applying an anchor coat layer to the laminate of the present invention, the coating liquid containing the resin that forms the anchor coat layer is preferably applied by first adjusting the solids concentration of a coating material containing a polyurethane compound having an aromatic ring structure on a substrate so that the thickness after drying is the desired thickness, and then applying the coating material by, for example, 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. In addition, in the present invention, it is preferable to dilute the coating material containing a polyurethane compound having an aromatic ring structure with an organic solvent from the viewpoint of coating suitability.

Specifically, it is preferable to dilute the solids concentration 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, ethyl butyl ether, or tetrahydrofuran. These solvents may be used alone or in combination of two or more. In addition, various additives can be blended into the paint that forms the anchor coat layer as necessary. For example, catalysts, antioxidants, light stabilizers, stabilizers such as ultraviolet absorbers, surfactants, leveling agents, antistatic agents, etc. can be used.

Then, it is preferable to dry the coating film after application to remove the diluting solvent. Here, there is no particular restriction on the heat source used for drying, and any heat source such as a steam heater, an electric heater, or an infrared heater can be used. In order to improve gas barrier properties, it is preferable to perform the heating at a temperature of 50 to 150°C. In addition, it is preferable to perform the heating treatment for a period of several seconds to 1 hour. Furthermore, the temperature may be constant during the heating treatment, or the temperature may be gradually changed. In addition, the heating treatment may be performed while adjusting the humidity in the range of 20 to 90% RH in terms of relative humidity during the drying treatment. The heating treatment may be performed in the air or while an inert gas is enclosed.

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

The active energy rays to be applied in such a case are not particularly limited as long as they can cure the anchor coat layer, but from the viewpoint of versatility and efficiency, it is preferable to use ultraviolet treatment. As the ultraviolet ray generating source, known sources such as high pressure mercury lamps, metal halide lamps, microwave type electrodeless lamps, low pressure mercury lamps, xenon lamps, etc. can be used. In addition, from the viewpoint of curing efficiency, it is preferable to use active energy rays under an inert gas atmosphere such as nitrogen or argon. The ultraviolet treatment may be performed either under atmospheric pressure or under reduced pressure, but from the viewpoint of versatility and production efficiency, it is preferable to perform the ultraviolet treatment under atmospheric pressure in the present invention. Regarding the oxygen concentration during the ultraviolet treatment, from the viewpoint of controlling the degree of crosslinking of the anchor coat layer, the oxygen gas partial pressure is preferably 1.0% or less, more preferably 0.5% or less. The relative humidity may be arbitrary.

As a source of ultraviolet light, known sources such as high-pressure mercury lamps, metal halide lamps, microwave electrodeless lamps, low-pressure mercury lamps, xenon lamps, etc. can be used.

The cumulative light amount of the ultraviolet irradiation is preferably 0.1 to 1.0 J/ ^cm2 , and more preferably 0.2 to 0.6 J/ ^cm2 . If the cumulative light amount is 0.1 J/ ^cm2 or more, it is preferable because the desired degree of crosslinking of the anchor coat layer can be obtained. Also, if the cumulative light amount is 1.0 J/cm2 or ^less , it is preferable because damage to the substrate can be reduced.

[Other layers]
On the outermost surface of the laminate of the present invention, that is, on the A layer, an overcoat layer may be formed for the purpose of improving scratch resistance, chemical resistance, printability, etc., within a range in which the gas barrier property is not reduced, or a laminated structure may be formed in which an adhesive layer or film made of an organic polymer compound is laminated for bonding to an element, etc. Also, a low refractive index layer may be formed to improve optical properties. The outermost surface here refers to the surface of the A layer after the A layer is laminated on the substrate.

[Applications of the laminate]
The laminate of the present invention has high gas barrier properties and can be suitably used as a gas barrier film. The laminate of the present invention can also be used in various electronic devices. For example, the laminate can be suitably used in electronic devices such as solar cells, flexible circuit substrates, organic EL lighting, flexible organic EL displays, and scintillators. In addition, by taking advantage of the high barrier properties, the laminate can also be suitably used as an exterior material for lithium ion batteries, packaging materials for pharmaceuticals, and the like.

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

[Evaluation method]
(1) Thickness of each layer A sample for cross-sectional observation was prepared by the FIB method (specifically, based on the method described in "Polymer Surface Processing Science" (by Akira Iwamori), pp. 118-119) using a microsampling system (FB-2000A, Hitachi, Ltd.). The cross-section of the sample for observation was observed with a transmission electron microscope (H-9000UHRII, Hitachi, Ltd.) at an acceleration voltage of 300 kV, and the thicknesses of the A layer, B layer, and anchor coat layer of the laminate were measured.

(2) Composition of A layer, composition of B layer, and half-width of oxygen atom (O1s) peak The composition of A layer and B layer of the laminate was analyzed by X-ray photoelectron spectroscopy (XPS). The layers were removed by argon ion etching for 3 nm from the outermost surface of each layer, and the content ratio of each element was measured under the following conditions. When other layers were laminated on each layer, argon ion etching under the following conditions was repeated until the outermost surface of each layer. The measurement conditions for the XPS method were as follows.
Apparatus: PHI5000VersaProbe2II (ULVAC-PHI, Inc.)
・Excitation X-ray: monochromatic AlKα
Analysis range: φ100μm
Photoelectron escape angle: 45°
Ar ion etching: 2.0 kV, raster size 2 × 2, etching time 1 min.

The half-width of the oxygen atom (O1s) peak was calculated using the analysis software Multipak provided with the measurement device.

(3) Water vapor permeability (g/m ² /day)
The water vapor transmission rate of the laminate was measured under the conditions of a temperature of 40° C., a humidity of 90% RH, and a measurement area of 50 cm ² using a water vapor transmission rate measuring device (model name: DELTAPERM (registered trademark)) manufactured by Technolox, Ltd., UK. The measurements were performed using a water vapor pressure sensor. Two samples were taken per level. The data obtained by measuring the two samples was averaged and rounded off to the nearest tenth to obtain the average value for the level. The transmittance was expressed as g/m ² /day.

(4) Positron lifetime and pore radius distribution The positron lifetime and pore radius distribution were measured by the positron beam method (thin film positron annihilation lifetime measurement method). The sample to be measured was attached to a 15 mm x 15 mm square Si wafer and degassed in vacuum at room temperature, and then irradiated with a positron beam from the A layer side to perform the measurement. The measurement conditions were as follows.
Equipment: Fuji Invac small positron beam generator PALS200A
Positron source: ^22Na -based positron beam Gamma ray detector: _BaF2 scintillator + photomultiplier tube Instrument constant: 255-278ps, 24.55ps/ch
Beam intensity: 1 keV
Measurement depth: 0 to 100 nm (estimated)
Measurement temperature: room temperature Measurement atmosphere: vacuum Measurement count number: about 5,000,000 counts The measurement results were subjected to three-component or four-component analysis using the nonlinear least squares program POSITRONFIT.

(5) Adhesion According to the cross-cut test method (JIS K5600-5-6, 1999), 100 squares of cross-cuts were formed at 1 mm intervals from the A layer side of the laminate. Next, a 24 mm wide cellophane tape (manufactured by Nichiban) was attached to the surface of the A layer and peeled at a peel angle of 90°. The laminate was observed from the A layer side, the number of squares where the A layer or the B layer had peeled off was counted, and the ratio of the number of peeled squares out of 100 squares was calculated. The test was performed in an environment with a temperature of 23°C ± 2°C and a relative humidity of 50% ± 5%. Five cross-cut tests were performed for each sample, and the average value of the ratio of the number of peeled squares was calculated. When other layers were laminated on the A layer, the other layers were removed up to the outermost surface of the A layer by argon ion etching under the above-mentioned conditions, and then the adhesion was measured.

Example 1
(Synthesis of Polyurethane Compound Having Aromatic Ring Structure)
In a 5-liter four-neck flask, 300 parts by mass of bisphenol A diglycidyl ether acrylic acid adduct (manufactured by Kyoeisha Chemical Co., Ltd., product name: Epoxy Ester 3000A) and 710 parts by mass of ethyl acetate were placed and heated to an internal temperature of 60°C. 0.2 parts by mass of di-n-butyltin dilaurate was added as a synthesis catalyst, and 200 parts by mass of dicyclohexylmethane 4,4'-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise over 1 hour while stirring. After the end of the dropwise addition, the reaction was continued for 2 hours, and then 25 parts by mass of diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. After the dropwise addition, the reaction was continued for 5 hours to obtain a polyurethane compound having an aromatic ring structure with a weight average molecular weight of 20,000.

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

The coating liquid for forming the anchor coat layer was prepared by mixing 150 parts by weight of the polyurethane compound, 20 parts by weight of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate DPE-6A), 5 parts by weight of 1-hydroxy-cyclohexylphenyl ketone (manufactured by BASF Japan, product name: "IRGACURE" (registered trademark) 184), 3 parts by weight of 3-methacryloxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Silicones, product name: KBM-503), 170 parts by weight of ethyl acetate, 350 parts by weight of toluene, and 170 parts by weight of cyclohexanone. The coating liquid was then applied to the substrate using a microgravure coater (gravure line number 150UR, gravure rotation ratio 100%), dried at 100°C for 1 minute, and after drying, ultraviolet treatment was performed under the following conditions to provide an anchor coat layer with a thickness of 1 μm.

Ultraviolet treatment equipment: LH10-10Q-G (manufactured by Fusion UV Systems Japan)
Introduced gas: _N2 (nitrogen inert box)
UV source: Microwave electrodeless lamp Accumulated light quantity: 400 mJ/ ^cm2
Sample temperature control: room temperature.

(Formation of Layer B)
Using the winding type deposition apparatus shown in FIG. 4, a 50 nm thick MgO+SiO _bilayer was provided as a B layer on the surface of the anchor coat layer of the substrate by electron beam (EB) deposition.

The specific operation is as follows. First, as the deposition material, granular magnesium oxide MgO (purity 99.9%) having a size of 2 to 5 mm and silicon dioxide SiO ₂ (purity 99.99%) were each heated at 100° C. for 8 hours in advance. Then, each material was set in a carbon hearth liner 12 as shown in FIG. 5. In a winding chamber 6, the side of the substrate 1 on which the B layer was to be provided (the side on which the anchor coat layer was formed) was set to face the hearth liner 12 on the unwinding roll 7, and the substrate was unwound and passed through guide rolls 8, 9, and 10 to the main drum 11. At this time, the temperature of the main drum was controlled to −15° C. Next, the inside of the deposition device 5 was depressurized to 5.0×10 ⁻³ Pa or less by a vacuum pump. Next, one electron gun (hereinafter, EB gun) 14 was used as a heating source, and the heating ratio of MgO and SiO ₂ was controlled so that the composition ratio was about Mg:Si=1:2 (atom%). The accelerating current and the film transport speed were adjusted so that the thickness of the layer B formed would be 15 nm, and the layer B was formed on the surface of the anchor coat layer. Thereafter, the film was taken up on the take-up roll 18 via guide rolls 15, 16, and 17.

(Formation of Layer A)
Using the winding type deposition apparatus shown in FIG. 4, a 150 nm thick MgO+SiO _bilayer was formed as layer A on the surface of layer B by electron beam (EB) deposition.

The specific operation is as follows. First, as the deposition material, granular magnesium oxide MgO (purity 99.9%) having a size of 2 to 5 mm and silicon dioxide SiO ₂ (purity 99.99%) were each heated at 100° C. for 8 hours in advance. Then, each material was set in a carbon hearth liner 12 as shown in FIG. 5. In the winding chamber 6, the side of the substrate 1 on which the A layer was to be provided (the side on which the B layer was formed) was set on the unwinding roll 7 so that it faced the hearth liner 12. Next, the pressure inside the deposition device 5 was reduced to 5.0×10 ⁻³ Pa or less by a vacuum pump, and the temperature of the main drum was controlled to −15° C. Next, the material was unwound and passed through the main drum 11 via the guide rolls 8, 9, and 10. Next, one electron gun (hereinafter, EB gun) 14 was used as a heating source, and the heating ratio of MgO and SiO ₂ was controlled so that the composition ratio was about Mg:Si=2:1 (atom%). The accelerating current and the film transport speed were adjusted so that the thickness of the formed layer A was 150 nm, and the layer A was formed on the surface of the layer B. Thereafter, the film was taken up on a take-up roll 19 via guide rolls 16, 17, and 18.

Next, test pieces were cut out from the resulting laminate and various evaluations were carried out. The results are shown in Tables 1 to 3.

Example 2
A laminate was obtained in the same manner as in Example 1, except that a cyclic olefin resin film (ZF14-050 manufactured by Zeon Corporation) having a thickness of 50 μm was used as the substrate instead of a polyethylene terephthalate film having a thickness of 100 μm, and an anchor coat layer was not formed. The results are shown in Tables 1 to 3.

Example 3
A laminate was obtained in the same manner as in Example 1, except that in forming the MgO+SiO ₂ layer that was the B layer, the composition was controlled so that the composition ratio was about Mg:Si=1:1 (atom %). The results are shown in Tables 1 to 3.

Example 4
A laminate was obtained in the same manner as in Example 1, except that in forming the MgO+SiO ₂ layer that was the B layer, the composition was controlled so that the composition ratio was about Mg:Si=7:1 (atom %). The results are shown in Tables 1 to 3.

Example 5
A laminate was obtained in the same manner as in Example 1, except that layer B was formed by the method described below. The results are shown in Tables 1 to 3.

(Formation of Layer B)
Using the winding type deposition apparatus shown in FIG. 4, a 10 nm-thick Al ₂ O ₃ layer was provided as a B layer on the surface of the anchor coat layer of the substrate by a sputtering method.

The specific operation is as follows. First, a sputtering target material 20 of aluminum oxide Al ₂ O ₃ (purity 99.9%) was attached to a sputtering electrode 21. In a winding chamber 6, the surface of the substrate 1 on which the B layer was to be provided was set on the unwinding roll 7 so that it faced the sputtering electrode 21. Next, the inside of the deposition device 5 was depressurized to 5.0×10 ⁻³ Pa or less by a vacuum pump, and the temperature of the main drum 11 was controlled to 0° C. Next, the film was unwound and passed through the main drum 11 via guide rolls 8, 9, and 10. At this time, argon gas and oxygen gas were introduced, and an input power of 1000 W was applied to the sputtering electrode 21 using a high-frequency power source to generate argon-oxygen gas plasma, and the power of the sputtering electrode 21 and the film transport speed were adjusted so that the B layer had a thickness of 10 nm, and the B layer was formed on the surface of the anchor coat layer. Then, the film was wound around the winding roll 19 via guide rolls 16, 17, and 18.

Example 6
A laminate was obtained in the same manner as in Example 1, except that in forming the MgO+SiO ₂ layer that was the A layer, the composition was controlled so that the composition ratio was about Mg:Si=2.5:1 (atom %). The results are shown in Tables 1 to 3.

(Example 7)
A laminate was obtained in the same manner as in Example 1, except that in forming the MgO+SiO ₂ layer that was the A layer, the composition was controlled so that the composition ratio was about Mg:Si=3:1 (atom %). The results are shown in Tables 1 to 3.

(Example 8)
A laminate was obtained in the same manner as in Example 5, except that zirconium oxide ZrO ₂ (purity 99.9%) was used instead of aluminum oxide, which was the sputtering target material in Example 5. The results are shown in Tables 1 to 3.

(Example 9)
A laminate was obtained in the same manner as in Example 5, except that silicon dioxide SiO ₂ (purity 99.9%) was used instead of aluminum oxide, which was the sputtering target material in Example 5. The results are shown in Tables 1 to 3.

(Example 10)
A laminate was obtained in the same manner as in Example 5, except that magnesium oxide (MgO, purity 99.9%) was used instead of aluminum oxide, which was the sputtering target material in Example 5. The results are shown in Tables 1 to 3.

Example 11
A laminate was obtained in the same manner as in Example 5, except that a mixed sintered material of zinc oxide ZnO and silicon dioxide _SiO2 was used instead of aluminum oxide, which was the sputtering target material of Example 5. The composition ratio of Zn and Si contained in the mixed sintered material was Zn:Si=1:1 (atom%). The results are shown in Tables 1 to 3.

Example 12
A laminate was obtained in the same manner as in Example 7, except that zirconium oxide ZrO ₂ (purity 99.9%) was used instead of magnesium oxide, which was the deposition material for layer A. The results are shown in Tables 1 to 3.

Example 13
A laminate was obtained in the same manner as in Example 7, except that tin oxide (SnO) (purity 99.9%) was used instead of magnesium oxide, which was the deposition material for layer A. The results are shown in Tables 1 to 3.

(Example 14)
A laminate was obtained in the same manner as in Example 7, except that zinc oxide ZnO (purity 99.9%) was used instead of magnesium oxide, which was the deposition material for layer A. The results are shown in Tables 1 to 3.

(Example 15)
A laminate was obtained in the same manner as in Example 7, except that aluminum oxide Al ₂ O ₃ (purity 99.9%) was used instead of magnesium oxide, which was the deposition material for layer A. The results are shown in Tables 1 to 3.

(Comparative Example 1)
A laminate was obtained in the same manner as in Example 1, except that the B layer in Example 1 was not formed, and further, silicon dioxide, which is a deposition material used in forming the A layer, was not used, and only magnesium oxide was used to form an MgO layer having a thickness of 150 nm. The results are shown in Tables 1 to 3.

(Comparative Example 2)
A laminate was obtained in the same manner as in Example 1, except that the B layer in Example 1 was not formed, and further, magnesium oxide, which is a deposition material in forming the A layer, was not used, and only silicon dioxide was used to form a _SiO2 layer having a thickness of 150 nm. The results are shown in Tables 1 to 3.

(Comparative Example 3)
A laminate was obtained in the same manner as in Example 1, except that the magnesium oxide used as the deposition material in forming the B layer in Example 1 was replaced with aluminum oxide Al ₂ O ₃ (purity 99.9%), the composition was controlled to have a composition ratio of Al:Si=approximately 3:1 (atom %), and an Al ₂ O ₃ +SiO ₂ layer having a thickness of 50 nm was provided. The results are shown in Tables 1 to 3.

(Comparative Example 4)
A laminate was obtained in the same manner as in Example 1, except that the layer B in Example 1 was not formed, and further, the magnesium oxide used as the deposition material in forming the layer A was replaced with zirconium oxide ZrO ₂ (purity 99.9%), the composition was controlled to have a composition ratio of Zr:Si=approximately 7:1 (atom %), and a ZrO ₂ +SiO ₂ layer having a thickness of 150 nm was provided. The results are shown in Tables 1 to 3.

(Comparative Example 5)
In Example 1, the magnesium oxide used as the deposition material in forming the B layer was replaced with zirconium oxide ZrO ₂ (purity 99.9%), and a ZrO ₂ +SiO ₂ layer having a thickness of 50 nm was provided by controlling the composition to have a composition ratio of about Zr:Si=3:1 (atom %). Furthermore, in forming the MgO+SiO ₂ layer as the A layer, a laminate was obtained in the same manner as in Example 1, except that the composition was controlled to have a composition ratio of about Mg:Si=3:1 (atom %). The results are shown in Tables 1 to 3.

(Comparative Example 6)
A laminate was obtained in the same manner as in Example 1, except that the layer B in Example 1 was not formed, and further, in the formation of the MgO+SiO ₂ layer as the layer A, the composition was controlled so that the composition ratio was about Mg:Si=6:1 (atom %). The results are shown in Tables 1 to 3.

(Comparative Example 7)
A laminate was obtained in the same manner as in Example 1, except that the B layer in Example 1 was not formed, and further, in the formation of the MgO+SiO ₂ layer as the A layer, the composition was controlled so that the composition ratio was about Mg:Si=1:3 (atom %). The results are shown in Tables 1 to 3.

The laminate of the present invention has excellent gas barrier properties against oxygen gas, water vapor, etc., and can be usefully used, for example, as packaging materials for food, medicines, etc., and as components for electronic devices such as organic electroluminescence televisions and solar cells, but its uses are not limited to these.

Reference Signs List 1 Substrate 2 A layer 3 B layer 4 Anchor coat layer 5 Wind-up type electron beam (EB) deposition device 6 Wind-up chamber 7 Unwinding rolls 8, 9, 10 Unwinding side guide roll 11 Main drum 12 Hearth liner 13 Deposition material 14 Electron gun 15 Electron beam 16, 17, 18 Wind-up side guide roll 19 Wind-up roll 20 Sputtering target material 21 Sputtering electrode 22 Deposition material C
23 Evaporation material D

Claims (9)

A laminate having an A layer on at least one side of a substrate, the A layer containing silicon and/or metal elements, and oxygen, an average life measured from the A layer side by a positron beam method of 0.935 ns or less, the number of masses peeled off in a cross-cut test (JIS K5600-5-6, 1999) being 10% or less of the total, and having a B layer between the substrate and the A layer, the B layer being a metal oxide layer. A laminate having an A layer on at least one side of a substrate, the A layer containing magnesium, silicon, and oxygen, an average life measured from the A layer side by a positron beam method of 0.935 ns or less, the number of masses peeled off in a cross-cut test (JIS K5600-5-6, 1999) being 10% or less of the total, and the A layer having a magnesium atomic concentration of 5 to 50 atom%, a silicon atomic concentration of 2 to 30 atom%, and an oxygen atomic concentration of 45 to 70 atom%, measured by X-ray photoelectron spectroscopy. The laminate according to claim 1, wherein the thickness of the B layer is 15% or less of the thickness of the A layer. The laminate according to claim 1 or 3, wherein the layer B is a layer formed by a sputtering method. The laminate according to any one of claims 1, 3, and 4, wherein the B layer is a silicon compound layer. The laminate according to any one of claims 1, 3 to 5, wherein the B layer contains a metal element and silicon, and when the atomic concentration of the metal element is Mb (atom%) and the atomic concentration of silicon is Sib (atom%), the ratio of the atomic concentrations (atom%) of the metal element and silicon, Mb/(Mb+Sib), is Mb/(Mb+Sib)<0.6 or Mb/(Mb+Sib)>0.8. The laminate according to any one of claims 1, 3 to 6, wherein the ratio of the atomic concentration (atom%) of the metal element to the atomic concentration (atom%) of silicon in the A layer, Ma/(Ma+Sia), is 0.45 to 0.85, where Ma is the atomic concentration of the metal element and Sia is the atomic concentration of silicon. The laminate according to any one of claims 1 to 7, wherein the A layer has a half-width of the oxygen atom (O1s) peak measured by X-ray photoelectron spectroscopy of 3.25 eV or less. 8. The laminate according to claim 1, further comprising an anchor coat layer , one surface of the anchor coat layer being in contact with the substrate and the other surface being in contact with the layer B.

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