Laminate and method for manufacturing the same

Abstract

The present invention provides a laminate that can be manufactured quickly and stably without appearance defects due to variations in the thickness of the deposited film, even when using thick vapor deposition, and a method for manufacturing the laminate. [Solution] A laminate having a metal layer on one side of a substrate, a metal oxide layer on the surface side of the metal layer, where the ratio of the thickness T2 of the metal oxide layer to the total thickness (T1+T2) of the metal layer (T1 + T2) is 1.5% or more and 40% or less, and the (200) plane orientation coefficient measured by X-ray diffraction is 1% or more and 20% or less.

Description

Technical Field

[0001] The present invention relates to a laminate having excellent gas barrier properties and serving as an alternative to aluminum foil, and a method for producing the same.

Background Art

[0002] Packaging materials using aluminum foil have, in addition to the designability due to the metallic luster, light blocking properties and excellent gas barrier performance. Therefore, they are used as packaging materials such as for retort foods, outer packaging materials for vacuum insulation materials such as heat insulating materials for refrigerators and heat insulating panels for houses, and the like.

[0003] In order to solve the above problems of aluminum foil, an aluminum vapor-deposited film with a thick vapor-deposited film formed by a physical vapor deposition method such as a vacuum vapor deposition method on a thermoplastic film such as a polyester film is used as an alternative to aluminum foil.

[0004] As a gas barrier film for food applications, when the concentration of oxygen atoms contained in the vapor-deposited layer is below a predetermined amount, it is disclosed that the vapor-deposited film maintains excellent barrier properties and also has excellent adhesion after heat water treatment (Patent Document 1).

[0005] Further, a film having high gas barrier properties in which a vapor-deposited layer composed of an inorganic substance, an inorganic oxide or an inorganic nitride and a specific resin layer are laminated on at least one side of a plastic film is disclosed (Patent Document 2). On the other hand, a gas barrier film that can be firmly joined to a plastic film through an olefin resin layer, which is an adhesive resin, by extrusion lamination without performing an anchor coat treatment on the aluminum vapor-deposited film is disclosed (Patent Document 3).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

[0007] Packaging materials using aluminum foil had a problem of imposing a large load on the incinerator due to the residue after incineration. In addition, the handling of packaging materials using aluminum foil is difficult because pinholes are likely to occur due to bending of the aluminum foil, and it is difficult to manage the lamination process, bag-making process, and filling process.

[0008] In addition, when manufacturing an aluminum vapor-deposited film with a target vapor-deposited film thickness of 2.5 or more in optical density by induction heating method, there was a problem that the heat load was large and appearance defects occurred, and a beautiful appearance could not be obtained. Also, there was a problem that a high gas barrier property could not be obtained unless a resin layer was provided on the vapor-deposited layer.

[0009] The present invention aims to solve such problems of conventional aluminum foil replacement technologies, and provides a laminate that can be manufactured stably at high speed without appearance defects due to unevenness in the thickness of the vapor-deposited film even with thick vapor deposition, and a method for manufacturing the laminate. [Means for Solving the Problems]

[0010] In order to solve the above problems, the present invention has the following configuration. (1) A laminate having a metal layer on one surface of a base material, and having a metal oxide layer on the side of the metal layer opposite to the side where the base material is laminated, wherein the ratio {T2 / (T1 + T2)} of the thickness T2 of the metal oxide layer to the total thickness (T1 + T2) of the thickness T1 of the metal layer and the thickness T2 of the metal oxide layer is 1.5% or more and 40% or less, and the (200) plane orientation coefficient measured by X-ray diffraction method is 1% or more and 20% or less. (2) The laminate according to (1), wherein the thickness T1 of the metal layer is 30 nm or more and 200 nm or less. (3) The metal layer is on the side where the substrate is laminated, with a density of 30 ng / cm² 2 More than 200ng / cm 2 The laminate according to (1) or (2) above, having an anchor metal layer containing copper as follows: (4) The laminate according to any one of (1) to (3), wherein the thickness T2 of the metal oxide layer is 3 nm or more and 20 nm or less. (5) The laminate according to any one of (1) to (4) above, wherein the metal layer contains aluminum. (6) The laminate according to any one of (1) to (5), wherein the substrate contains 25 equivalents / ton or more and 55 equivalents / ton or less of carboxyl-terminated groups. (7) A laminate according to any one of (1) to (6) above, wherein the thermal shrinkage rate after heating in the longitudinal direction (MD) at 150°C for 30 minutes is 0.30% or more and 2.60% or less, and the thermal shrinkage rate after heating in the width direction (TD) at 150°C for 30 minutes is -0.70% or more and 1.20% or less. (8) A method for manufacturing a laminate, comprising the steps of unwinding a substrate in a vacuum chamber, depositing a metal to form a metal layer, and further introducing oxygen and depositing a metal to form a metal oxide layer, wherein the thickness T1 of the metal layer is 30 nm or more and 200 nm or less, the ratio of the thickness T2 of the metal oxide layer (T2 / (T1+T2)) to the thickness T2 of the metal oxide layer is 1.5% or more and 40% or less, and the (200) plane orientation coefficient of the manufactured laminate measured by X-ray diffraction is 1% or more and 20% or less. (9) In the process of forming the metal layer, after unwinding the substrate in a vacuum chamber, copper is deposited to form an anchor metal layer containing copper on the surface of the substrate, wherein the amount of copper in the anchor metal layer is 30 ng / cm³. 2 More than 200ng / cm 2 The method for manufacturing the laminate described in (8) above is as follows: (10) A method for manufacturing a laminate according to (8) or (9), wherein the thickness T2 of the metal oxide layer is 3 nm or more and 20 nm or less. (11) A composite laminate comprising a laminate described in any of (1) to (7) above, or a laminate obtained by a manufacturing method described in any of (8) to (10) above. (12) A packaging body using a laminate as described in any of (1) to (7) above, or a laminate obtained by a manufacturing method as described in any of (8) to (10) above, or a composite laminate as described in (11) above. [Effects of the Invention]

[0011] According to the present invention, even if the metal layer is thickened, there will be no unevenness in the thickness of the metal layer, and the laminate can be manufactured stably at high speed. [Brief explanation of the drawing]

[0012] [Figure 1] This is a schematic cross-sectional view showing one embodiment of the laminate of the present invention, namely, the configuration of a substrate / copper-containing anchor metal layer / metal layer / metal oxide layer. [Figure 2] This is a schematic diagram showing an example of a vacuum deposition apparatus for manufacturing the laminate of the present invention. [Modes for carrying out the invention]

[0013] The present invention will be described in detail below, along with its embodiments. The laminate according to the present invention has a metal layer on one side of a substrate, a metal oxide layer on the surface side of the metal layer, and the ratio of the thickness T2 of the metal oxide layer (T2 / (T1+T2)) which is the sum of the thickness T1 of the metal layer and the thickness T2 of the metal oxide layer is 1.5% or more and 40% or less, and the (200) plane orientation coefficient measured by X-ray diffraction is 1% or more and 20% or less.

[0014] In the present invention, the substrate is not particularly limited and includes films made of polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polypropylene terephthalate, and polybutylene terephthalate; polyolefin resins such as polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene, and polymethylpentene; cyclic polyolefin resins; polyamide resins; polyimide resins; polyether resins; polyesteramide resins; polyether ester resins; acrylic resins; polyurethane resins; polycarbonate resins; or polyvinyl chloride resins; and even biodegradable resins such as polylactic acid, polycaprolactone, polyglycolic acid, and polyvinyl alcohol.

[0015] The substrate in the present invention is preferably a film made of polyester resin, and preferably a film made of polyethylene terephthalate resin (hereinafter sometimes referred to as PET film) made from terephthalic acid and ethylene glycol.

[0016] The substrate in this invention may have an easy-adhesion layer formed on one side containing a polyester resin and a melamine compound. Methods for forming the easy-adhesion layer include applying the coating agent during film formation of the substrate (in-line pre-coating method) and applying it after film formation (post-coating method), and either method can be used. The in-line pre-coating method involves applying the coating agent to an unstretched or uniaxially oriented film, followed by stretching heat treatment. This allows for simultaneous film formation and drying of the coated layer, offering cost advantages in manufacturing. Furthermore, the high-temperature heat treatment enhances adhesion between the easy-adhesion layer and the substrate.

[0017] In this invention, recycled materials such as mechanically recycled or chemically recycled materials may be used as raw materials for the polyester film. Furthermore, the polyester film may be an unstretched film, but a stretched (uniaxial or biaxial) film is preferred because it has superior mechanical properties and thickness uniformity, and a biaxially stretched film is more preferred. Applicable stretching methods include roll stretching, rolling stretching, belt stretching, tenter stretching, tube stretching, and stretching methods that combine these.

[0018] There are no particular restrictions on the thickness of the polyester film, but a thickness of approximately 6 μm to 50 μm is practical.

[0019] [Metal layer] In the present invention, the metal constituting the metal layer is not particularly limited. Preferably, at least one metal selected from the group consisting of various light metals, silicon, tin, zinc, and indium is used. Preferred light metals include aluminum, magnesium, beryllium, titanium, alkali metals, and alkaline earth metals. Among these, the metal is preferably aluminum, titanium, silicon, or copper, and more preferably aluminum. In the present invention, metallic aluminum is evaporated by resistance heating, and the thickness of the metal layer is preferably 30 nm to 200 nm. Below 30 nm, the gas barrier performance may be insufficient, and the metallic appearance may also be unsatisfactory. More preferably, the thickness of the metal layer is 90 nm to 120 nm. Above 200 nm, the gas barrier performance may plateau, the cohesive energy during deposition of the metal layer may increase, and in the case of polyester film, it may deform with heat, resulting in an appearance that is not practical.

[0020] For metal layers, the proportion of (200) plane orientation coefficients measured by X-ray diffraction (hereinafter sometimes referred to as XRD) is between 1% and 20%. The proportion of (200) plane orientation coefficients measured by XRD refers to A as defined by the following formula (1), and is the ratio obtained by dividing the integrated intensity of the (200) plane measured by X-ray diffraction by the integrated intensity of the (111) plane measured by X-ray diffraction. A=[I200 / (I111+I200)]×100(%)...Equation (1) (I111: Integrated intensity of the (111) plane measured by X-ray diffraction; I200: Integrated intensity of the (200) plane measured by X-ray diffraction).

[0021] In other words, the proportion of (200) plane orientation coefficients measured by the XRD method refers to the proportion of molecules in a substrate, such as a polyester film, whose internal orientation within the metal layer is (200) plane relative to molecules whose internal orientation within the metal layer is (111) plane or (200) plane.

[0022] Regarding the metal layer mentioned above, if the proportion of (200) plane orientation coefficients measured by XRD is less than 1%, fewer molecules in the metal layer will be oriented in the (200) plane relative to the substrate, such as a polyester film. This can make it difficult for the adhesive to penetrate the metal layer, resulting in less integration between the metal layer and the adhesive, and potentially lowering the water-resistant adhesion of the composite laminate. Furthermore, if the proportion of (200) plane orientation coefficients measured by XRD exceeds 20%, more molecules in the metal layer will be oriented in the (200) plane relative to the substrate, such as a polyester film. This can reduce the strength of the metal layer itself in the horizontal direction relative to the polyester film, potentially lowering the water-resistant adhesion of the composite laminate. Additionally, it can lead to increased oxygen and water vapor permeability. A more preferable range for the (200) plane orientation coefficient is 2% to 19%.

[0023] [Definition of metal oxide layer] In the present invention, the metal oxide layer is formed on the surface of the metal layer, and its thickness is preferably 3 nm to 20 nm. In the present invention, the metal oxide layer is defined as the portion of the metal oxide surface layer with an oxygen atom concentration ratio of 30% or more. The portion of the metal oxide surface layer with a carbon atom concentration ratio of 35% or less is defined as a layer containing both the metal layer and the metal oxide layer. A characteristic of the laminate of the present invention is that the ratio of the thickness T2 of the metal oxide layer with an oxygen atom concentration ratio of 30% or more is 1.5% to 40% of the sum of the thickness T1 of the metal layer and the thickness T2 of the metal oxide layer. Preferably, it is 5.5% to 7.3%.

[0024] If the proportion of T2 {T2 / (T1+T2)} is less than 1.5%, moisture may enter between the metal layer and the metal oxide layer, resulting in insufficient water-resistant adhesion. If it exceeds 40%, there is a risk of a decrease in metallic luster. The metal oxide layer in this invention can be measured by the method described later.

[0025] In this invention, the concentration of oxygen atoms can be measured by X-ray photoelectron spectroscopy (XPS). Specifically, the concentration of oxygen atoms is measured by the following method: The sample is subjected to an etching treatment by sputtering for 15 seconds. Details of the etching treatment will be described later. After that, the atomic concentration is measured by X-ray photoelectron spectroscopy (XPS) (details of the measurement conditions are as follows). By repeating this process, the concentration of oxygen atoms (atomic %) in the thickness direction and the peak concentration of oxygen atoms in the thickness direction can be measured.

[0026] (Measurement conditions for X-ray photoelectron spectroscopy (XPS) depth profiling) ·Equipment: X-ray photoelectron spectrometer (XPS) • Manufacturer / Model: ULVAC-PHI, Inc. / PHI5000VersaProbe II • X-ray beam diameter (measurement range): φ100 μm Etching conditions (sputtering from the metal oxide layer side towards the substrate depth) • Ar ion gun acceleration voltage: 1kV • Etching area: 3mm x 3mm square interior ·Etching time: 15 seconds per time.

[0027] [Anchor metal layer containing copper] In the present invention, it is preferable that an anchor metal layer containing copper is formed on at least one side of the substrate. In the present invention, the "anchor metal layer containing copper" is formed in contact with the substrate.

[0028] Even if a metal layer is provided directly on the substrate, the waterproof adhesion between the metal layer and the substrate may be insufficient. The amount of copper in the anchor metal layer containing copper is 30 ng / cm 2 or more and 200 ng / cm 2 or less is preferable. Preferably, it is 70 ng / cm 2 or more and 100 ng / cm 2 or less. If the amount of copper in the anchor metal layer containing copper is less than 30 ng / cm 2 , the waterproof adhesion may be insufficient. If it exceeds 200 ng / cm 2 , wrinkles may occur and the appearance may be defective. The consumption of copper may be accelerated, the replacement frequency may increase, the productivity may deteriorate, and there may also be a problem that the cost increases.

[0029] The method for forming the anchor metal layer containing copper is not particularly limited, but a method for forming a copper vapor deposition layer by a sputtering method using copper as a target is preferable because a certain amount can be formed stably. Among them, the sputtering method of the planar magnetron type is more preferable from the viewpoint of easy input of large power and discharge stability. The anchor metal layer containing copper is preferably formed by an in-line (simultaneous) treatment immediately before vapor deposition in a normal roll-to-roll type vacuum vapor deposition machine, but it may also be formed in advance before vapor deposition.

[0030] In the present invention, after the above-mentioned anchor metal layer containing copper is formed on the substrate, it is preferable that a metal layer is subsequently laminated, and then a surface metal oxide layer is sequentially laminated.

[0031] [Manufacturing method of laminate] In the present invention, the method for manufacturing a laminate is preferably such that, after unwinding the substrate in a vacuum chamber, the metal is evaporated by resistance heating, and a metal layer is formed on the substrate surface such that the film thickness is 30 nm or more and 150 nm or less, and the (200) plane orientation coefficient of X-ray diffraction is 1% or more and 20% or less.

[0032] 30 ng / cm² on the substrate surface 2 More than 200ng / cm 2 The following copper-containing anchor metal layers can be formed by the method described above.

[0033] The method for forming a surface metal oxide layer with a thickness of 3 nm to 20 nm on a metal layer is described below.

[0034] In other words, the substrate is generally long and supplied in roll form. It is unwound from the roll in a vacuum chamber, vapor deposition is performed, and then it is wound back into a roll. In the initial stages of vapor deposition, a normal metal layer is formed. In the latter half of the deposition process, oxygen is introduced, and a metal oxide layer is formed by the reaction between the metal and oxygen. The oxygen introduced in the latter half of the deposition process diffuses from the winding side to the unwinding side of the substrate. Therefore, the metal layer and the surface metal oxide layer are not formed in a strictly separate manner. Rather, the reaction of oxygen proceeds continuously from the metal layer to the surface metal oxide layer according to the position of the vapor deposition zone through which the substrate passes, and the composition changes continuously in the direction of film thickness.

[0035] The laminate of the present invention described above has a configuration such as that shown in Figure 1. Specifically, an anchor metal layer 2 containing copper is formed on one surface of a base material 1, a metal layer 3 is laminated thereon, and a metal oxide layer 4 is laminated thereon.

[0036] Furthermore, the laminate of the present invention is manufactured using a vacuum deposition apparatus such as the one shown in Figure 2. Figure 2 shows a schematic configuration of the inside of the vacuum chamber 10 of the vacuum deposition apparatus. Corona discharge treatment is performed on the surface of the substrate 12 unwound onto the cooling roll 16 from a roll-shaped substrate mounted on the feed shaft 11, for example, by a discharge electrode 13, and metal from the metal evaporation source 15 is deposited. For example, in the metal deposition process, an anchor metal layer containing copper is formed, followed by the deposition of metal layers, and then metal oxide layers are sequentially deposited. The deposition of the anchor metal layer containing copper and the deposition of the metal layers and metal oxide layers may be performed in different processes, that is, the anchor metal layer containing copper may be deposited in the vacuum chamber 10, the equipment may be wound up, and then unwound again in the vacuum chamber 10 to deposit the metal layers and metal oxide layers. Regarding the deposition of the metal layers and metal oxide layers, as described above, the metal layer may be formed in the initial stage of deposition, and oxygen may be introduced from the oxygen introduction section 14 in the latter half of deposition, and the metal oxide layer may be formed by the reaction of the metal and oxygen. The substrate, after vapor deposition is complete, is wound into a roll on the winding shaft 17. The inside of the vacuum chamber 10 may be appropriately partitioned into unwinding and winding sections and a vapor deposition section, and each partitioned chamber may be controlled to have a different vacuum level as appropriate.

[0037] [Composite laminates, packaging] Using the laminate of the present invention, a composite laminated material (composite laminate) can be obtained by the manufacturing method described later. The composite laminated material may be a 2-layer, 3-layer, or 4-layer product, and can be formed in a manner suitable for the application. A packaging can be manufactured using the composite laminated material by the manufacturing method described later.

[0038] The substrate used in the composite laminate is not particularly limited, as long as properties such as chemical resistance, mechanical strength (film stiffness, abrasion resistance, puncture resistance), heat resistance, and weather resistance are taken into consideration depending on the application, but nylon film, polypropylene film, polyethylene film, etc. are preferably used.

[0039] [Method for manufacturing composite laminates and packaging materials] To 10 parts by weight of the main component of the adhesive (DIC Graphics Co., Ltd., product name: DIC Dry® LX500), 1 part by weight of the curing agent (DIC Graphics Co., Ltd., product name: DIC Dry® KW75), and 21 parts by weight of ethyl acetate as a solvent were mixed at room temperature while stirring. Using a bar coater, the mixture was applied to the corona-treated surface of the substrate (12 μm thick, manufactured by Futamura Chemical Co., Ltd., FE2001) to a dry thickness of 2.5 μm. After drying in a hot air oven, it was bonded to the metal oxide layer surface of a 12 μm laminate. Subsequently, the same adhesive used to bond the substrate was applied to the opposite side (non-deposited surface) of the bonded laminate to the same thickness. After drying in a hot air oven, it was bonded to a low-density polyethylene film (40 μm thick, manufactured by Mitsui Chemicals Tohcello Co., Ltd., FC-S). After bonding in this manner, the laminate material (composite laminate) was stored in a 40°C oven for 72 hours to produce a laminated material.

[0040] The laminated material described above was heat-sealed under the following heat-sealing conditions to produce a bag-shaped container (packaging): Heat-sealing temperature: 140°C, Heat-sealing pressure: 1 kg / cm² 2 The heat sealing time was set to 1 second.

[0041] [Gas barrier properties] The gas barrier properties of the laminate of the present invention are confirmed by checking the oxygen permeability and water vapor permeability. The oxygen permeability is 0.5 cc / (m³). 2 Preferably less than or equal to (day·atm), and more preferably 0.2cc / (m 2 The water vapor transmission rate is less than or equal to (day·atm). 2 Preferably less than or equal to 0.2 g / (m²) 2 It is less than or equal to (day).

[0042] Oxygen permeability is 0.5cc / (m 2 (day·atm), water vapor transmission rate is 0.5 g / (m 2 When a composite laminate is made using a laminate exceeding 1 day, and the contents are placed in a package and stored, the deterioration of the contents may be accelerated.

[0043] [Water-resistant adhesion] The water-resistant adhesion strength of the laminate of the present invention is preferably 0.9 N / 15 mm or more. More preferably 1.0 N / 15 mm or more. The water-resistant adhesion strength can be measured by the method described later. If it is less than 0.9 N / 15 mm, there is a risk of delamination occurring when the contents are filled in.

[0044] [Glossiness] In the laminate of the present invention, the glossiness of the metal layer side is preferably 700% or more and 900% or less. If it is less than 700%, the aesthetics, light-shielding properties, and gas barrier performance may be insufficient. If it exceeds 900%, the aesthetics, light-shielding properties, and gas barrier performance may be insufficient due to thermal damage to the substrate.

[0045] [exterior] The appearance of the laminate of the present invention may be dull in color and unsatisfactory if the thickness of the metal layer is less than 30 nm, and wrinkles may occur due to heat if the thickness of the metal layer exceeds 200 nm, resulting in an unsatisfactory appearance. Furthermore, if the amount of copper in the anchor metal layer containing copper is 200 ng / cm³ 2 If the value exceeds a certain limit, the color and appearance may yellow, resulting in a defect in appearance.

[0046] [Carboxyl-terminal group weight] The laminate of the present invention preferably has a carboxyl-terminal group content of 25 equivalents / ton or more and 55 equivalents / ton or less. More preferably, it has a content of 35 equivalents / ton or more and 53 equivalents / ton or less. If the carboxyl-terminal group content exceeds 55 equivalents / ton, the moisture and heat resistance of the laminate may deteriorate. If the carboxyl-terminal group content is less than 25 equivalents / ton, the water-resistant adhesion of the laminate may not be sufficiently exhibited.

[0047] The amount of carboxyl-terminated groups in this invention can be measured by the method described below. The amount of carboxyl-terminated groups was measured by potentiometric titration. 2 g of the sample (in the case of a layered structure, only the substrate separated) was dissolved in 50 mL of o-cresol / chloroform (weight ratio 7 / 3) at a temperature of 80°C. The sample was titrated with a 0.05 N KOH / methanol titrant while measuring the voltage with an electrode, and the carboxyl-terminated group concentration was measured and expressed as an equivalent / tonn of substrate (equivalent / ton). Phenol red was used as the indicator during titration, and the titration endpoint was defined as the point when the color changed from yellow-green to pale pink, or when the potential was neutralized. If the solution in which the sample was dissolved contained insoluble matter such as inorganic particles, the solution was filtered, the weight of the insoluble matter was measured, and the weight of the insoluble matter was subtracted from the weight of the sample to perform a correction.

[0048] [Thermal shrinkage rate] The laminate of the present invention preferably has a thermal shrinkage rate of 0.30% to 2.60% after heating at 150°C for 30 minutes in the longitudinal direction (MD), and a thermal shrinkage rate of -0.70% to 1.20% after heating at 150°C for 30 minutes in the width direction (TD). More preferably, the thermal shrinkage rate of 1.10% to 1.50% after heating at 150°C for 30 minutes in the longitudinal direction (MD), and a thermal shrinkage rate of -0.05% to 0.30% after heating at 150°C for 30 minutes in the width direction (TD). If the thermal shrinkage rate of less than 0.30% after heating at 150°C for 30 minutes in the longitudinal direction (MD) and more than 1.20% after heating at 150°C for 30 minutes in the width direction (TD), the substrate expands due to the heat of the metal evaporated during deposition, resulting in an uneven deposition film and a deterioration in water-resistant adhesion. If the thermal shrinkage rate after heating at 150°C for 30 minutes in the longitudinal direction (MD) exceeds 2.60% and the thermal shrinkage rate after heating at 150°C for 30 minutes in the width direction (TD) is less than -0.70%, the water-resistant adhesion of the laminate may not be fully achieved. The thermal shrinkage rate of the present invention can be measured by the method described later.

[0049] While there are no particular limitations on the method for achieving the aforementioned range of thermal shrinkage after heating at 150°C for 30 minutes in the longitudinal and width directions, examples include controlling the stretching temperature and stretching ratio in the longitudinal stretching process, the stretching temperature and stretching ratio in the transverse stretching process, and the temperature and time in the heat setting process, as well as performing tensioning or relaxation heat treatment in the heat setting process, and performing relaxation treatment at a low temperature (e.g., 150°C) after the heat setting process.

[0050] The film was cut into 150mm x 150mm sections in both the longitudinal (MD) and width (TD) directions to create samples. Markings were drawn on the samples at 50mm intervals from the edge in the width (TD) direction and at three points in the longitudinal (MD) direction. The distance between the three markings in the longitudinal (MD) direction was measured using a Mitutoyo PJ-H3000 projector. The same procedure was performed in the width (TD) direction. The samples were then placed in a hot air oven heated to a predetermined temperature (150°C) for 30 minutes for heat treatment. The distance between the markings after heat treatment was measured, and the thermal shrinkage rate was calculated from the change in the distance between the markings before and after heating using the following formula. The above measurement was performed on five randomly selected samples, and the number average was used as the thermal shrinkage rate. Thermal shrinkage rate (%) = {(gauge markings before heat treatment) - (gauge markings after heat treatment)} / (gauge markings before heat treatment) × 100 [Examples]

[0051] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Each characteristic value was measured by the following method.

[0052] (1) Oxygen permeability (cc / (m 2 ·day·atm)) The oxygen permeability of the laminate was measured under conditions of 23°C and 90% RH using an oxygen permeability meter (OXTRAN2 / 21) manufactured by MOCON, Inc., USA, based on the isobaric method described in JIS K7126-2. The oxygen permeability value was 1.0 cc / (m³). 2 The following was considered acceptable: oxygen permeability from the substrate surface (day·atm).

[0053] (2) Water vapor transmission rate (g / (m³) 2 ·day)) The water vapor transmission rate of the laminate was measured under conditions of 40°C and 90% RH using an oxygen permeability meter (PERMATRAN W3 / 31) manufactured by MOCON, Inc., USA, based on the infrared sensor method described in JIS K7129-B. The water vapor transmission rate was 0.5 g / (m³). 2 The following was considered acceptable: Water vapor transmission rate from the substrate surface.

[0054] (3) Glossiness (%) The glossiness of the metal layer side of the laminate was measured using a UGV-5D gloss meter manufactured by Suga Test Instruments Co., Ltd. Both the incident angle and the receiving angle were set to 60 degrees.

[0055] (4) Thickness of the metal layer and the thickness of the metal oxide layer (nm) Surface analysis was performed using a fully automated scanning X-ray photoelectron spectrometer (Quantera SXM, Physical Electronics) with an AlKα X-ray source, X-ray output of 25.1W, and a photoelectron extraction angle of 45°. Sputtering was performed from the metal layer side of the laminate using Ar ions at an Ar ion energy of 1 keV. Narrow-field photoelectron spectra were measured for carbon, oxygen, and aluminum at regular sputtering intervals. The composition ratio of each element was calculated from the narrow-field photoelectron peak area intensity ratio and relative sensitivity coefficient of C1s, O1s, and Al2p, and the depth-direction composition distribution was determined based on the following method.

[0056] First, we focused on the carbon concentration on the substrate side and considered the sputtering time corresponding to the intermediate (1 / 2) concentration of the peak carbon concentration as the sputtering time that reached the interface between the metal layer and the substrate. The signal originating from the copper-containing anchor metal layer at the interface was small and therefore ignored. We then correlated the thickness of the metal layer observed by TEM with the sputtering time corresponding to the interface and calculated the sputtering depth corresponding to the sputtering time.

[0057] Next, focusing on the oxygen concentration in the metal oxide layer, the sputtering depth calculated from the sputtering time corresponding to the intermediate (1 / 2) concentration of the peak oxygen concentration was considered as the interface between the metal oxide layer and the metal layer.

[0058] (5) Copper content of the anchor metal layer containing copper (ng / cm³) 2 ) Cut samples were prepared by cutting the laminate into 10 cm squares. After immersing the cut samples in 20 ml of nitric acid for 24 hours, the copper absorbance (wavelength 324.8 nm) of the resulting solution was measured using an atomic absorption spectrophotometer (Shimadzu AA-6300 type). Using a standard sample with a known copper concentration as a calibration curve, the amount of copper in the anchor metal layer was calculated. These calculations were performed using four different cut samples, and the average value of the obtained values ​​was used to determine the amount of copper in the anchor metal layer (ng / cm³). 2 )

[0059] (6) Calculation of the (200) plane orientation coefficient measured by X-ray diffraction (XRD) The proportion A of the (200) plane orientation coefficient measured by XRD was calculated using the following formula (1) by measuring the integrated intensities of the (111) plane and the (200) plane using a horizontal X-ray diffractometer (SMARTLAB 3FD, Rigaku Corporation) under the following conditions. Analysis was performed from the metal layer surface.

[0060] The integrated intensity was calculated from the X-ray diffraction pattern detected by irradiating an arbitrary location on one of the laminates with measurement X-rays (wavelength 0.15418 nm (CuKα)), with the horizontal axis representing the Bragg diffraction angle 2θ (deg) and the vertical axis representing the diffraction intensity (cps). Using the acquired Bragg diffraction angle 2θ (deg) and the numerical data obtained by subtracting the baseline component (cps) from the diffraction intensity (cps), the integrated intensity was calculated as the area of ​​each peak using numerical analysis software. In this process, the Bragg diffraction angle region where the peak intensity after subtracting the baseline component is 10% or more was calculated, and the obtained value was multiplied by (100 / 90) to obtain the integrated intensity (cps·deg). If other peaks overlapped the target peak in the diffraction pattern, the peaks were split using specialized software, and the numerical value of the target peak was used.

[0061] Here, diffraction of the (111) plane was observed at a Bragg angle of approximately 38.4°, and diffraction of the (200) plane was observed at a Bragg angle of approximately 44.3°. The integrated intensities of the observed (111) and (200) planes were denoted as I111 and I200, respectively. (200) Surface orientation coefficient ratio = [I200 / (I111+I200)] × 100 (%) ··(1).

[0062] (7) Method for manufacturing composite laminates and packaging To 10 parts by weight of the main component of the adhesive (DIC Graphics Co., Ltd., product name: DIC Dry® LX500), 1 part by weight of the curing agent (DIC Graphics Co., Ltd., product name: DIC Dry® KW75), and 21 parts by weight of ethyl acetate as a solvent were mixed at room temperature while stirring. Using a bar coater, the mixture was applied to the corona-treated surface of the substrate (12 μm thick, manufactured by Futamura Chemical Co., Ltd., FE2001) to a dry thickness of 2.5 μm. After drying in a hot air oven, it was bonded to the metal oxide layer surface of a 12 μm laminate. Subsequently, the same adhesive used to bond the substrate was applied to the opposite side (non-deposited surface) of the bonded laminate to the same thickness. After drying in a hot air oven, it was bonded to a low-density polyethylene film (40 μm thick, manufactured by Mitsui Chemicals Tohcello Co., Ltd., FC-S). After bonding in this manner, the laminate material (composite laminate) was stored in a 40°C oven for 72 hours to produce a laminated material.

[0063] The laminated material described above was heat-sealed under the following heat-sealing conditions to produce a bag-shaped container (packaging): Heat-sealing temperature: 140°C, Heat-sealing pressure: 1 kg / cm² 2 The heat sealing time was set to 1 second.

[0064] (8) Method for evaluating water-resistant adhesion After the adhesive curing of the composite laminate prepared in (7) above, cut samples were made by cutting them to a width of 15 mm and a length of 100 mm. Using Orientec Co., Ltd.'s "Tensilon" (PTM50 type), the laminate was placed on top of the "Tensilon" and the low-density polyethylene film side of the composite laminate was placed under the Tensilon in the chuck, and the laminate was peeled so that the peel surface was T-shaped. The peeling was carried out at a pulling speed of 50 mm / min while applying water to the peel interface with a cotton swab, and the water-resistant adhesion strength was confirmed by the average value of three samples for each level.

[0065] (9) Exterior The appearance of the laminate was categorized as "poor" if it had a dull color, wrinkles due to heat, or yellowing, and "good" if it did not exhibit these characteristics.

[0066] (Example 1) As the substrate, a biaxially oriented polyethylene terephthalate film (Toray Industries, Inc.'s "Lumirror" registered trademark P60) was used, which was fabricated to a thickness of 12 μm, a carboxyl-terminated group content of 52.3 equivalents / ton, a longitudinal (MD) thermal shrinkage rate of 1.21%, and a widthwise (TD) thermal shrinkage rate of 0.21%. After unwinding the polyester film in a vacuum chamber, a planar magnetron discharge electrode targeting copper was placed between the film unwinding section and the deposition section at a distance of 20 mm from the substrate running surface. By applying a voltage supplied by a high-frequency power supply (frequency 60 kHz) near the electrode, plasma was generated, and 84.5 ng / cm³ was deposited onto the substrate. 2 Oxygen gas and electricity were supplied to form an anchor metal layer containing copper. Subsequently, metallic aluminum was heated and evaporated by resistance heating so that the proportion of the (200) plane orientation coefficient of the metal layer was 11.2%, and oxygen was supplied so that the thickness of the metal layer was 195.0 nm and the thickness of the metal oxide layer was 3.1 nm, thereby fabricating a laminate.

[0067] (Example 2) In Example 1, the amount of copper in the anchor metal layer containing copper was 98.1 ng / cm³. 2A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 119.0 nm and the metal oxide layer to a thickness of 6.8 nm.

[0068] (Example 3) In Example 1, the amount of copper in the anchor metal layer containing copper was 98.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 118.0 nm and the metal oxide layer to a thickness of 6.8 nm.

[0069] (Example 4) In Example 1, the amount of copper in the anchor metal layer containing copper was 95.0 ng / cm³. 2、 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 86.0 nm, the metal oxide layer to a thickness of 6.0 nm, and the surface orientation coefficient ratio to 11.1%.

[0070] (Example 5) In Example 1, the amount of copper in the anchor metal layer containing copper was 98.2 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 103.0 nm and the metal oxide layer to a thickness of 8.0 nm.

[0071] (Example 6) In Example 1, the amount of copper in the anchor metal layer containing copper was 95.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 103.0 nm and the metal oxide layer to a thickness of 8.2 nm.

[0072] (Example 7) In Example 1, the amount of copper in the anchor metal layer containing copper was 101.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 31.0 nm, the metal oxide layer to a thickness of 19.5 nm, and the surface orientation coefficient ratio to 11.4%.

[0073] (Example 8) In Example 1, the amount of copper in the anchor metal layer containing copper was 87.0 ng / cm³.2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 84.0 nm and the surface orientation coefficient ratio was 11.0%.

[0074] (Example 9) In Example 1, the amount of copper in the anchor metal layer containing copper was 92.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 90.0 nm and the metal oxide layer to a thickness of 11.9 nm.

[0075] (Example 10) In Example 1, the amount of copper in the anchor metal layer containing copper was 95.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 99.5 nm, the metal oxide layer to a thickness of 14.0 nm, and the surface orientation coefficient ratio to 11.3%.

[0076] (Example 11) In Example 1, the amount of copper in the anchor metal layer containing copper was 72.3 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 50.0 nm, the metal oxide layer to a thickness of 19.8 nm, and the surface orientation coefficient ratio to 11.0%.

[0077] (Example 12) In Example 1, the amount of copper in the anchor metal layer containing copper was 33.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 32.5 nm, the metal oxide layer to a thickness of 3.5 nm, and the surface orientation coefficient ratio to 11.3%.

[0078] (Example 13) In Example 1, the amount of copper in the anchor metal layer containing copper was 68.5 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 120.6 nm and the metal oxide layer to a thickness of 9.3 nm.

[0079] (Example 14) In Example 1, the amount of copper in the anchor metal layer containing copper was 85.3 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the thickness of the metal layer was 68.2 nm and the thickness of the metal oxide layer was 6.5 nm.

[0080] (Example 15) In Example 1, the amount of copper in the anchor metal layer containing copper was 85.2 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 89.5 nm, the metal oxide layer to a thickness of 7.8 nm, and the surface orientation coefficient ratio to 11.1%.

[0081] (Example 16) In Example 1, the amount of copper in the anchor metal layer containing copper was 85.7 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 90.5 nm and the metal oxide layer to a thickness of 11.6 nm.

[0082] (Example 17) In Example 1, the amount of copper in the anchor metal layer containing copper was 85.2 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 105.0 nm, the metal oxide layer to a thickness of 13.1 nm, and the surface orientation coefficient ratio to 11.4%.

[0083] (Example 18) In Example 1, the amount of copper in the anchor metal layer containing copper was 85.3 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 84.0 nm, the metal oxide layer to a thickness of 9.0 nm, and the surface orientation coefficient ratio to 1.3%.

[0084] (Example 19) In Example 1, the amount of copper in the anchor metal layer containing copper was 85.4 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 84.1 nm, the metal oxide layer to a thickness of 9.2 nm, and the surface orientation coefficient ratio to 19.3%.

[0085] (Example 20) In Example 1, the amount of copper in the anchor metal layer containing copper was 33.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 84.3 nm, the metal oxide layer to a thickness of 9.3 nm, and the surface orientation coefficient ratio to 11.3%.

[0086] (Example 21) In Example 1, the amount of copper in the anchor metal layer containing copper was 194.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the metal layer was deposited to a thickness of 84.1 nm and the metal oxide layer to a thickness of 9.3 nm.

[0087] (Example 22) A laminate was prepared in the same manner as in Example 5, except that the amount of carboxyl-terminal groups in the substrate was changed to 35.6 equivalents / ton, the thermal shrinkage rate in the longitudinal direction (MD) was 1.40%, and the thermal shrinkage rate in the width direction (TD) was 0.00%.

[0088] (Example 23) A laminate was prepared in the same manner as in Example 5, except that the amount of carboxyl-terminal groups in the substrate was changed to 32.4 equivalents / ton, the thermal shrinkage rate in the longitudinal direction (MD) was 1.80%, and the thermal shrinkage rate in the width direction (TD) was -0.30%.

[0089] (Example 24) A laminate was prepared in the same manner as in Example 5, except that the amount of carboxyl-terminal groups in the substrate was changed to 30.8 equivalents / ton, the thermal shrinkage rate in the longitudinal direction (MD) was 1.70%, and the thermal shrinkage rate in the width direction (TD) was 0.00%.

[0090] (Example 25) A laminate was prepared in the same manner as in Example 5, except that the amount of carboxyl-terminal groups in the substrate was changed to 34.2 equivalents / ton, the thermal shrinkage rate in the longitudinal direction (MD) was 1.70%, and the thermal shrinkage rate in the width direction (TD) was -0.10%.

[0091] (Example 26) A laminate was prepared in the same manner as in Example 5, except that the amount of carboxyl-terminal groups in the substrate was changed to 54.0 equivalents / ton, the thermal shrinkage rate in the longitudinal direction (MD) was 1.30%, and the thermal shrinkage rate in the width direction (TD) was 0.10%.

[0092] (Example 27) A laminate was prepared in the same manner as in Example 5, except that the amount of carboxyl-terminal groups in the substrate was changed to 26.0 equivalents / ton, the thermal shrinkage rate in the longitudinal direction (MD) was 1.30%, and the thermal shrinkage rate in the width direction (TD) was 0.10%.

[0093] (Example 28) A laminate was prepared in the same manner as in Example 5, except that the amount of carboxyl-terminal groups in the substrate was changed to 56.0 equivalents / ton, the thermal shrinkage rate in the longitudinal direction (MD) was 1.30%, and the thermal shrinkage rate in the width direction (TD) was 0.10%.

[0094] (Example 29) A laminate was prepared in the same manner as in Example 5, except that the amount of carboxyl-terminal groups in the substrate was changed to 24.0 equivalents / ton, the thermal shrinkage rate in the longitudinal direction (MD) was 1.30%, and the thermal shrinkage rate in the width direction (TD) was 0.10%.

[0095] (Example 30) A laminate was prepared in the same manner as in Example 5, except that the amount of carboxyl-terminal groups in the substrate was changed to 43.0 equivalents / ton, the thermal shrinkage rate in the longitudinal direction (MD) was 2.50%, and the thermal shrinkage rate in the width direction (TD) was -0.69%.

[0096] (Example 31) A laminate was prepared in the same manner as in Example 5, except that the amount of carboxyl-terminal groups in the substrate was changed to 43.0 equivalents / ton, the thermal shrinkage rate in the longitudinal direction (MD) was 0.31%, and the thermal shrinkage rate in the width direction (TD) was 1.10%.

[0097] (Example 32) A laminate was prepared in the same manner as in Example 5, except that the amount of carboxyl-terminal groups in the substrate was changed to 43.0 equivalents / ton, the thermal shrinkage rate in the longitudinal direction (MD) was 2.70%, and the thermal shrinkage rate in the width direction (TD) was -0.69%.

[0098] (Example 33) A laminate was prepared in the same manner as in Example 5, except that the amount of carboxyl-terminal groups in the substrate was changed to 43.0 equivalents / ton, the thermal shrinkage rate in the longitudinal direction (MD) was 0.29%, and the thermal shrinkage rate in the width direction (TD) was 1.30%.

[0099] (Comparative Example 1) A 12 μm thick biaxially oriented polyethylene terephthalate film (Toray Industries, Inc.'s "Lumirror" (registered trademark) P60) was used as the substrate. Gas barrier performance was not achieved when the metal layer was less than 30.0 nm thick.

[0100] (Comparative Example 2) In Example 1, the surface orientation coefficient ratio was 0.5%, the metal layer was 205.0 nm, and the copper content of the copper-containing anchor metal layer was 83.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the deposition was carried out in the manner described above. When the metal layer exceeded 200 nm, the cohesive energy during deposition of the metal layer increased, and the polyester film was deformed by heat, resulting in wrinkles that made the appearance unsuitable for practical use.

[0101] (Comparative Example 3) In Example 1, the metal layer was 29.5 nm thick, the metal oxide layer was 20.0 nm thick, the surface orientation coefficient was 11.0%, and the copper content of the copper-containing anchor metal layer was 89.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the deposition was carried out in the manner described above. When the ratio of the thickness T2 of the metal oxide layer to the thickness T1 of the metal layer, T2 / (T1+T2), exceeded 40%, the metallic luster decreased, and the metallic color tone and appearance became dull.

[0102] (Comparative Example 4) In Example 1, the surface orientation coefficient ratio was 0.5%, the metal layer was 80.0 nm, the metal oxide layer was 7.0 nm, and the copper content of the copper-containing anchor metal layer was 85.0 ng / cm³. 2A laminate was fabricated in the same manner as in Example 1, except that the deposition was carried out in the manner described above. When the proportion of the (200) plane orientation coefficient measured by XRD method for the above metal layer was less than 1%, the number of molecules in the metal layer whose orientation is (200) plane relative to the polyester film decreased, making it difficult for the adhesive to penetrate the metal layer, and the water-resistant adhesion strength of the composite laminate material decreased.

[0103] (Comparative Example 5) In Example 1, the surface orientation coefficient ratio was 23.0%, the metal layer was 90.0 nm, the metal oxide layer was 12.0 nm, and the copper content of the copper-containing anchor metal layer was 87.0 ng / cm². 2 A laminate was fabricated in the same manner as in Example 1, except that the deposition was carried out in the manner described above. When the proportion of the (200) plane orientation coefficient measured by XRD exceeds 20% for the metal layer, the number of molecules in the metal layer that are oriented to the (200) plane relative to the polyester film increases, and the strength of the metal layer itself decreases in the direction horizontal to the polyester film, resulting in a decrease in the water-resistant adhesion of the composite laminate material.

[0104] (Comparative Example 6) In Example 1, the metal layer was 193.0 nm, the metal oxide layer was 2.8 nm, and the copper content of the copper-containing anchor metal layer was 89.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the deposition was carried out in the manner described above. When the ratio of the thickness T2 of the metal oxide layer with an oxygen atom concentration ratio of 30% or more was less than 2% of the sum of the thickness T1 of the metal layer and the thickness T2 of the metal oxide layer, moisture entered between the metal layer and the metal oxide layer, reducing the water-resistant adhesion.

[0105] (Comparative Example 7) In Example 1, the metal layer was 29.7 nm, the metal oxide layer was 21.0 nm, and the copper content of the copper-containing anchor metal layer was 91.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the deposition was carried out in the manner described above. When the oxygen atom concentration ratio exceeded 30%, the ratio of the metal oxide layer thickness T2 to the sum of the metal layer thickness T1 and the metal oxide layer thickness T2 exceeded 40%, and the metallic luster decreased, resulting in a dull metallic appearance.

[0106] (Comparative Example 8) In Example 1, the metal layer was 25.0 nm, the metal oxide layer was 20.1 nm, and the amount of copper in the copper-containing anchor metal layer was 93.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the deposition was carried out in the manner described above. When the metal layer was less than 30 nm, gas barrier performance was not achieved, and the metallic color appearance became dull.

[0107] (Comparative Example 9) In Example 1, the metal layer was 205 nm thick, the metal oxide layer was 3.0 nm thick, and the copper content of the copper-containing anchor metal layer was 91.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the deposition was carried out in the manner described above. When the metal layer exceeded 200 nm, the cohesive energy during deposition of the metal layer increased, and the polyester film was deformed by heat, resulting in wrinkles that made the appearance unsuitable for practical use.

[0108] (Comparative Example 10) In Example 1, the metal layer was 201.0 nm, the metal oxide layer was 2.8 nm, and the copper content of the copper-containing anchor metal layer was 27.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the deposition was carried out in such a manner. The amount of copper in the anchor metal layer containing copper was 30 ng / cm³. 2 Below a certain level, water-resistant adhesion decreased.

[0109] (Comparative Example 11) In Example 1, the metal layer was 196.0 nm, the metal oxide layer was 2.6 nm, and the amount of copper in the copper-containing anchor metal layer was 210.0 ng / cm³. 2 A laminate was fabricated in the same manner as in Example 1, except that the deposition was carried out in the manner described above. The amount of copper in the copper-containing anchor metal layer was 200 ng / cm³. 2 Beyond a certain point, wrinkles appeared, and the appearance became unsuitable for practical use.

[0110] (Comparative Example 12) A laminate was prepared in the same manner as in Comparative Example 2, except that the base material was changed to a biaxially oriented polyethylene terephthalate film (SHINPEX® M127, manufactured by Shinka Koden Co., Ltd.) with a thickness of 12 μm, a carboxyl-terminated group content of 35.6 equivalents / ton, a longitudinal (MD) thermal shrinkage rate of 1.40%, and a widthwise (TD) thermal shrinkage rate of 0.00%. When the metal layer exceeded 200 nm, the cohesive energy during the deposition of the metal layer increased, and the appearance became unsuitable for practical use due to wrinkles caused by thermal deformation of the polyester film.

[0111] Test specimens were cut from the laminates obtained in each example and comparative example, and various evaluations were performed. The results are shown in Tables 1 and 2.

[0112] [Table 1]

[0113] [Table 2]

[0114] Examples 1 to 33 showed excellent gas barrier performance, water-resistant adhesion performance, and appearance when the metal layer thickness T1 was 30 nm or more and 200 nm or less, the ratio of the metal oxide layer thickness T2 (T2 / (T1+T2)) to the metal oxide layer thickness T2 was 1.5% or more and 40% or less, and the (200) plane orientation coefficient measured by X-ray diffraction was 1% or more and 20% or less.

[0115] In Comparative Examples 1 and 8, the metal layer did not exhibit gas barrier performance when it was less than 30 nm, and the metallic appearance was also poor. In Comparative Examples 2, 9, and 12, when the metal layer exceeded 200 nm, the cohesive energy during deposition of the metal layer increased, resulting in poor appearance due to wrinkles caused by thermal deformation of the polyester film. On the other hand, Examples 1-10 and 14-33 showed high gas barrier performance and good appearance.

[0116] In Comparative Example 4, when the proportion of (200) plane orientation coefficients measured by XRD was less than 1%, there were fewer aluminum molecules with the (200) plane orientation relative to the polyester film, making it difficult for the adhesive to penetrate the metal layer, and thus the water-resistant adhesion performance of the composite laminate decreased. Conversely, in Comparative Example 5, where the proportion exceeded 20%, there were more molecules with the (200) plane orientation relative to the polyester film, and the strength of the metal layer itself decreased in the horizontal direction relative to the polyester film, resulting in a decrease in the water-resistant adhesion performance of the composite laminate, similar to Comparative Example 4. On the other hand, the water-resistant adhesion performance and gas barrier performance of Examples 1-10, 16-19, and 21-33 were good.

[0117] In Comparative Example 6, when the ratio of the thickness T2 of the metal oxide layer with an oxygen atom concentration ratio of 30% or more was less than 1.5% of the sum of the metal layer thickness T1 and the metal oxide layer thickness T2, moisture entered between the metal layer and the metal oxide layer, reducing the water-resistant adhesion performance. Conversely, in Comparative Examples 3, 7, and 8, where the ratio exceeded 40%, the metallic gloss decreased, resulting in a poor appearance. On the other hand, Examples 1-11, 14-19, and 21-33 had good appearance as well as good water-resistant adhesion performance.

[0118] The amount of copper in the anchor metal layer containing copper in Comparative Example 10 was 30 ng / cm³. 2 Below 200 ng / cm², the water-resistant adhesion performance decreases, while at 200 ng / cm², the water-resistant adhesion performance decreases. 2 Comparative Example 11, which exceeded the limit, developed wrinkles and had an inferior appearance. On the other hand, Examples 1-11, 14-19, and 21 had good water-resistant adhesion and appearance. [Industrial applicability]

[0119] The laminate of the present invention has a beautiful appearance and possesses oxygen barrier and water vapor barrier properties, making it useful as a replacement for applications currently using aluminum foil, and is an environmentally friendly packaging solution. [Explanation of Symbols]

[0120] 1 Base material 2. Anchor metal layer containing copper 3 metal layer 4. Metal oxide layer 10 Vacuum chamber 11. Retractable shaft 12 Base material 13 Discharge electrode 14. Oxygen introduction section 15 Metal Evaporation Sources 16 Cooling Rolls 17. Winding shaft

Claims

1. A laminate having a metal layer on one side of a substrate, and a metal oxide layer on the side of the metal layer opposite to the side on which the substrate is laminated, wherein the ratio of the thickness T2 of the metal oxide layer to the sum of the thickness T1 of the metal layer and the thickness T2 of the metal oxide layer (T1 + T2) {T2 / (T1 + T2)} is 1.5% or more and 40% or less, and the (200) plane orientation coefficient measured by X-ray diffraction is 1% or more and 20% or less.

2. The laminate according to claim 1, wherein the thickness T1 of the metal layer is 30 nm or more and 200 nm or less.

3. The metal layer is applied at a concentration of 30 ng / cm³ on the side where the substrate is laminated. ２ More than 200ng / cm ２ The laminate according to claim 1, having the following anchor metal layer containing copper.

4. The laminate according to claim 1, wherein the thickness T2 of the metal oxide layer is 3 nm or more and 20 nm or less.

5. The laminate according to claim 1, wherein the metal layer contains aluminum.

6. The laminate according to claim 1, wherein the substrate contains carboxyl-terminal groups in an amount of 25 equivalents / ton or more and 55 equivalents / ton or less.

7. The laminate according to claim 1, wherein the thermal shrinkage rate after heating in the longitudinal direction (MD) at 150°C for 30 minutes is 0.30% or more and 2.60% or less, and the thermal shrinkage rate after heating in the width direction (TD) at 150°C for 30 minutes is -0.70% or more and 1.20% or less.

8. A method for manufacturing a laminate, comprising the steps of unwinding a substrate in a vacuum chamber, depositing a metal to form a metal layer, and further introducing oxygen and depositing a metal to form a metal oxide layer, wherein the thickness T1 of the metal layer is 30 nm or more and 200 nm or less, the ratio of the thickness T2 of the metal oxide layer to the total thickness (T1 + T2) of the metal layer and the metal oxide layer {T2 / (T1 + T2)} is 1.5% or more and 40% or less, and the (200) plane orientation coefficient of the manufactured laminate measured by X-ray diffraction is 1% or more and 20% or less.

9. In the process of forming the metal layer, after unwinding the substrate in a vacuum chamber, copper is deposited to form a copper-containing anchor metal layer on the surface of the substrate, wherein the amount of copper in the anchor metal layer is 30 ng / cm³. ２ More than 200ng / cm ２ The method for manufacturing a laminate according to claim 8, which is as follows:

10. The method for manufacturing a laminate according to claim 8, wherein the thickness T2 of the metal oxide layer is 3 nm or more and 20 nm or less.

11. A composite laminate comprising the laminate described in claim 1, or a laminate obtained by the method for manufacturing the laminate described in claim 8.

12. A packaging body using the laminate described in claim 1, or a laminate obtained by the method for manufacturing the laminate described in claim 8.

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