Laminates and packaging

Abstract

The present invention provides a laminate with good barrier properties and a packaging material, comprising a polyolefin resin film on which a metal layer and / or an inorganic compound layer and a coating layer are laminated. [Solution] A laminate having a metal layer and / or an inorganic compound layer and a coating layer in that order on a polyolefin resin film, wherein the coating layer contains a polyvinyl alcohol resin backbone and a siloxane compound. A laminate that meets the following requirements 1 and 2. Requirement 1: A1 / (A1+A2) is between 0.50 and 0.85. Requirement 2: [B1 / (B1+B2)-A1 / (A1+A2)] is 0.10 or less. A1: Area of ​​Raman bands showing the network structure derived from siloxane compounds, obtained by laser Raman spectroscopy of the coating layer. A2: Area of ​​Raman bands showing linear polysiloxane structures and cyclic siloxanes with four or fewer members, obtained by measuring the coating layer using laser Raman spectroscopy. B1: Area of ​​Raman bands showing the network structure obtained by laser Raman spectroscopy after heat treatment at 121°C for 30 minutes. B2: After heat treatment at 121°C for 30 minutes, the area of ​​Raman bands showing the linear polysiloxane structure and cyclic siloxanes with 4 or fewer members was measured by laser Raman spectroscopy of the coating layer.

Description

[Technical Field]

[0001] The present invention relates to laminates and packaging materials with good barrier properties using polyolefin resin substrates. [Background technology]

[0002] Packaging materials for food, pharmaceuticals, and daily necessities require oxygen barrier and water vapor barrier properties to prevent deterioration of the contents. Barrier films, which consist of a resin film such as polyester laminated with a metal layer such as aluminum, a metal oxide layer, or a protective layer, have been used as such barrier packaging materials. In particular, films laminated with a metal oxide layer are widely used because they are transparent, offering good visibility, and are convenient for food packaging, such as allowing microwave heating.

[0003] On the other hand, plastic packaging materials are a cause for concern because they do not decompose in soil even when landfilled after use, and they generate a large amount of heat when incinerated. Furthermore, in recent years, marine pollution caused by leaked plastic waste has become a major problem, and there is a growing global movement to reduce the use of plastic materials and to reuse them. Therefore, from an environmental protection perspective, the collection and recycling of packaging materials is being advocated.

[0004] Conventional barrier films used in packaging materials have traditionally utilized polyester resins, such as polyethylene terephthalate, which offers high heat resistance and transparency, or polyamide resins, which provide excellent mechanical strength. These films lack the heat-sealing properties necessary for bag-making and other packaging processes, and are therefore laminated with heat-sealable polypropylene resins for use in packaging materials. However, lamination of dissimilar materials is difficult to separate during recycling. To improve recyclability, attempts have been made to create monomaterials, where the packaging material is composed of a single material; that is, to use olefin materials similar to heat-sealable polypropylene resins as the base material for barrier films. However, olefin materials have the drawback of having poorer oxygen barrier properties compared to polyester and polyamide resins. Therefore, methods have been investigated to improve barrier properties by forming a coating layer in order to enhance oxygen barrier properties and improve the preservation of contents in packaging materials (Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 4784039 [Patent Document 2] Patent No. 4972951 [Overview of the project] [Problems that the invention aims to solve]

[0006] Patent Document 1 discloses a gas barrier film having an inorganic oxide vapor-deposited film and a gas barrier coating film on a substrate. However, the processing conditions are high, at 150°C or higher, and when applied to polyolefin resin films, which have lower heat resistance than polyester resins, there was a problem of wrinkles and cracks occurring. Patent Document 2 discloses a vapor-deposited film that can be used as a packaging material by laminating a vapor-deposited layer and a composite coating on a polypropylene film. However, it is not sufficiently hardened to suppress the deterioration of the contents and is not adequate to obtain barrier properties, leaving room for improvement.

[0007] The object of the present invention is to provide a laminate with good barrier properties and a package, wherein a metal layer and / or an inorganic compound layer and a coating layer are laminated on a polyolefin resin film. [Means for solving the problem]

[0008] A preferred embodiment of the present invention is as follows: (1) A laminate having a metal layer and / or an inorganic compound layer and a coating layer in this order on at least one surface of a polyolefin resin film, The coating layer contains a polyvinyl alcohol-based resin backbone and a siloxane compound. A laminate that meets the following requirements 1 and 2. Requirement 1: A1 / (A1+A2) is between 0.50 and 0.85. Requirement 2: [B1 / (B1+B2)-A1 / (A1+A2)] is 0.10 or less. A1: Area of ​​Raman bands showing the network structure derived from siloxane compounds, obtained by laser Raman spectroscopy of the coating layer. A2: Area of ​​Raman bands showing linear polysiloxane structures and cyclic siloxanes with four or fewer members, obtained by measuring the coating layer using laser Raman spectroscopy. B1: Area of ​​Raman bands showing the network structure obtained by laser Raman spectroscopy after heat treatment at 121°C for 30 minutes. B2: After heat treatment at 121°C for 30 minutes, the area of ​​Raman bands showing the linear polysiloxane structure and cyclic siloxanes with 4 or fewer members was measured by laser Raman spectroscopy of the coating layer. (2) The stress at 121°C in the direction of the principal orientation axis, measured by thermomechanical analysis (TMA), is SF 121℃ , the stress at 145°C in the direction of the main orientation axis is SF 145℃ When that happens, SF 145℃ -SCIENCE FICTION 121℃ The laminate described in (1) has a pressure of ≤2.50 MPa. (3) The laminate according to (1) or (2), wherein the loss tangent tanδ at 145 °C in the main alignment axis direction is 0.25 or less. (4) Let the elongation at break in the main alignment axis direction be T0, and let the elongation at break in the main alignment axis direction measured after heat-treating the laminate at 130 °C for 10 minutes be T 130 When, T0 / T 130 The laminate according to any one of (1) to (3), wherein the value of is 1.20 or less. (5) The laminate according to any one of (1) to (4), wherein the value of the ratio P1 / P2 of the following peak intensities P1 and P2 detected by measuring the coating layer by the FT-IR-ATR method (total reflection Fourier transform infrared spectroscopy) is 3.5 or more and 8.0 or less. P1: The intensity of the maximum peak existing at 1,050 to 1,080 cm -1 P2: The intensity of the maximum peak existing at 920 to 970 cm -1 (6) The laminate according to any one of (1) to (5), wherein [B1 / (B1 + B2) - A1 / (A1 + A2)] is 0.08 or less. (7) The laminate according to any one of (1) to (6), wherein the water vapor transmission rate of the laminate is 1.0 g / m 2 / 24 hr or less, and the oxygen transmission rate is 1.0 cc / m 2 / 24 hr or less. (8) The laminate according to any one of (1) to (7), wherein the thickness of the coating layer is 200 nm or more and 600 nm or less. (9) The laminate according to any one of (1) to (8), wherein the metal layer or the inorganic compound layer contains aluminum. (10) A package having the laminate according to any one of (1) to (9).

Advantages of the Invention

[0009] According to the present invention, it is possible to provide a dense and good-barrier laminate and a package having a metal layer and / or an inorganic compound layer and a coating layer on a polyolefin resin film.

Brief Description of the Drawings

[0010] ​​[Figure 1] This is a schematic cross-sectional view showing an example of the structure of the laminate of the present invention. [Modes for carrying out the invention]

[0011] A preferred embodiment of the laminate, packaging, and method for manufacturing the laminate of the present invention will be described in more detail below.

[0012] The polyolefin resin film in the present invention is a film mainly composed of a resin whose main constituent unit is an olefin hydrocarbon. The main constituent unit refers to the monomer unit that has the highest content (number of units) among the monomer units contained in the resin, and the main component refers to the component that has the highest content (mass%) among all the constituent components. Examples of polyolefin resins include polymers and copolymers of α-olefins having alkyl groups in their side chains, such as ethylene, propylene, and 4-methyl-1-pentene, or copolymers obtained by copolymerizing α-olefins with acrylic acid, C=C bond-containing carboxylic acids, C=C bond-containing carboxylate salts, or C=C bond-containing alkyl carboxylate esters, polymers of norbornene and cyclodiene, and polymers of these, and may be a single layer or multiple layers. Among these, it is preferable to include polyethylene or polypropylene because they are relatively inexpensive, and it is more preferable to include polypropylene in terms of heat resistance, and even more preferable to have polypropylene as the main component from the same viewpoint. The film may be unstretched or stretched, but it is preferable to be biaxially stretched from the viewpoint of thermal dimensional stability. That is, it is preferable to have a biaxially stretched polyolefin resin film. The polyolefin resin film preferably has a melting point of 150°C or higher. A melting point of 150°C or higher prevents thermal damage during processes such as metal oxide formation or packaging material construction, and also improves heat resistance after processing, thereby suppressing deterioration of barrier properties. The melting point of the film shall be determined by the method described in the examples.

[0013] The glass transition temperature (Tg) of the polyolefin resin film is preferably 50°C or lower. This embodiment increases the flexibility of the film even at low temperatures, making it less likely to harden at low temperatures when used as packaging, and enabling stable use over a wide temperature range.

[0014] The thickness of the polyolefin resin film is preferably 3 μm to 100 μm, more preferably 5 μm to 50 μm, and even more preferably 8 μm to 30 μm. A film thickness of 3 μm or more maintains rigidity as a support, while a thickness of 100 μm or less maintains flexibility as a packaging material and improves conformability, which is preferable. The thickness of the polyolefin resin film shall be determined by the method described in the examples.

[0015] Furthermore, the polyolefin resin film is preferably smooth on the surface. Surface smoothness can be expressed by the arithmetic mean height Sa as defined in ISO 25178 (2012), where Sa is preferably 50 nm or less, and more preferably 30 nm or less. The arithmetic mean height Sa shall be determined by the method described in the examples. By smoothing the surface, the defects of the inorganic oxide layer laminated on the surface can be reduced, resulting in a good inorganic oxide layer and improved barrier properties.

[0016] The laminate of the present invention preferably has a metal layer and / or an inorganic compound layer on at least one surface of the polyolefin resin film.

[0017] The metal layer and / or the inorganic compound layer preferably contain at least one element from groups 2 to 14 of the periodic table (excluding carbon), and the inorganic compound layer preferably further contains at least one element, oxygen, or nitrogen. Among these, from the viewpoint of processing cost and gas barrier properties, the metal layer preferably contains aluminum, and more preferably has aluminum as its main component. Similarly, from the same viewpoint, the inorganic compound layer preferably contains at least one element from aluminum, magnesium, titanium, tin, indium, and silicon, and more preferably contains silicon or aluminum. Examples of preferred inorganic compound layers include silicon oxide, silicon oxynitride, and aluminum oxide. Furthermore, in the inorganic oxide layer, it is preferable that the proportion of aluminum in the total sum of elements from groups 2 to 14 of the periodic table (excluding carbon) is 50 atomic% or more.

[0018] If a metal layer is present, the thickness of the metal layer is preferably 5 nm to 500 nm, and more preferably 10 nm to 100 nm. A thickness of 5 nm or more improves barrier properties, while a thickness of 500 nm or less suppresses thermal damage to the substrate during film formation, which is preferable.

[0019] When an inorganic compound layer is present, the thickness of the inorganic compound layer is preferably 2 nm to 50 nm, more preferably 2 nm to 20 nm, and even more preferably 4 nm to 10 nm. A thickness of 1 nm or more can reduce defects such as pinholes in the inorganic compound layer, and a thickness of 50 nm or less can suppress cracks, which is preferable. The thickness of the metal layer and the inorganic compound layer shall be determined by the method described in the examples.

[0020] In the present invention, the coating layer refers to at least one outermost layer of the laminate, and is a layer laminated on the side of the metal layer and / or inorganic compound layer opposite to the polyolefin resin, and is a layer containing a polyvinyl alcohol resin skeleton and a siloxane compound. The polyvinyl alcohol resin skeleton is contained in polyvinyl alcohol resins and their derivatives. Examples of polyvinyl alcohol resins that form the basis of the skeleton include polyvinyl alcohol, ethylene-vinyl alcohol copolymers, modified polyvinyl alcohol, etc., and these resins may be used individually or as a mixture of two or more. The average molecular weight of the polyvinyl alcohol resin (according to JIS K 6726 (1994)) is preferably 500 to 3,000. If the molecular weight is small, the polymer may not be easily fixed in the layer, and the barrier properties may decrease.

[0021] Polyvinyl alcohol-based resins are generally obtained by saponifying polyvinyl acetate. This can be partial saponification, where some of the acetate groups are saponified, or complete saponification, but a higher degree of saponification is preferable. The degree of saponification (according to JIS K 6727 (1994)) is preferably 90 mol% or higher, and more preferably 95 mol% or higher. A higher degree of saponification is preferable because it reduces the number of sterically hindered acetate groups, decreases the free volume of the coating layer, and increases the crystallinity of the resin, which is advantageous for improving barrier properties.

[0022] Modified polyvinyl alcohol resins refer to resins obtained by chemically reacting polyvinyl alcohol with monomers of different chemical structures, or by copolymerizing monomers of different chemical structures. Examples of modified polyvinyl alcohol resins include vinyl esters such as propioninyl, carboxylic acid resins, methacrylic acid esters, vinyl ethers such as methyl vinyl ether, and glycol resins. The modified site of a polyvinyl alcohol resin may be located in the main chain, side chains, or crosslinking chains, but modification of the main chain is preferable. If the side chains have functional groups with high steric hindrance, the free volume of the coating layer increases, which may reduce barrier properties. However, if the modified structure is located in part of the main chain, steric hindrance can be reduced, and the free volume of the coating layer also decreases, which is advantageous for improving barrier properties and is therefore preferable.

[0023] The detailed structure of the polyvinyl alcohol-based resin skeleton contained in the coating layer can be analyzed by NMR (nuclear magnetic resonance spectroscopy). A film piece is immersed in deuterated isopropanol to dissolve the coating layer composition in the solvent, or the coating layer is physically scraped using a spatula or the like. Whether the coating layer has dissolved or been scraped off can be confirmed by measuring the thickness of the coating layer in the same way as the thickness evaluation method described later. Next, the sample dissolved in the solvent is analyzed by liquid NMR, or the scraped sample is analyzed by solid NMR. 13 By analyzing the carbon and protons and assigning the corresponding peaks, the structure can be confirmed. Furthermore, by combining this with FT-IR diffuse reflectance analysis of the coating layer obtained in the same manner, information about its structure can be obtained.

[0024] The siloxane compound contained in the coating layer is preferably made from at least one of the following: a silicon alkoxide represented by Si(OR)4, a hydrolysate of a silicon alkoxide, and a polycondensate of a hydrolysate of a silicon alkoxide. Here, R is an alkyl group, and a lower alkyl group having 1 to 4 carbon atoms is particularly preferred. In particular, from the viewpoint of reactivity, stability, and cost, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane can be suitably used, and these may be used individually or as a mixture of two or more. These silicon alkoxides may be hydrolyzed or polycondensed to form a network.

[0025] The hydrolysis and / or polycondensation of silicon alkoxides can proceed in the presence of water, a catalyst, and an organic solvent. The amount of water used in the reaction is preferably between 0.8 and 5 equivalents relative to the alkoxy groups of Si(OR)4. A water amount of 0.8 equivalents or more is preferable because it allows sufficient hydrolysis to proceed and a network to form. A water amount of 5 equivalents or less is preferable because it allows for adjustment of the degree of hydrolysis, suppressing random network formation, reducing the free volume of the film, and improving barrier properties.

[0026] The catalyst used in the reaction of silicon alkoxides is preferably an acid catalyst. Examples of acid catalysts include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, and tartaric acid. Typically, the hydrolysis and polycondensation reactions of silicon alkoxides can proceed with either an acid catalyst or a base catalyst. When an acid catalyst is used, the monomers in the system are easily hydrolyzed on average, and condensation proceeds easily in linear or network structures. On the other hand, when a base catalyst is used, the reaction mechanism is such that the hydrolysis and polycondensation reactions of alkoxides bonded to the same molecule proceed easily, so the reaction product tends to be granular with a large free volume and many voids. Since the voids in the film serve as pathways for water vapor and oxygen permeation, it is preferable to use an acid catalyst. The amount of catalyst used is preferably 0.01 mol% to 0.5 mol%, and more preferably 0.01 mol% to 0.3 mol%, relative to the total molar amount of silicon alkoxide.

[0027] The organic solvent used in the reaction of silicon alkoxides can be water and alcohols that are miscible with silicon alkoxides, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol.

[0028] Commercially available silicate oligomers or polysiloxanes can also be used as polycondensates of silicon alkoxides. Silicate oligomers and polysiloxanes may be used alone or mixed with low-molecular-weight silicon alkoxides, but it is preferable to use them mixed with low-molecular-weight silicon alkoxides to suppress crack formation due to excessive crosslinking. When using silicate oligomers or polysiloxanes, selecting linear or network structures is preferable as it reduces the free volume of the film and improves barrier properties.

[0029] The coating layer may also contain leveling agents, crosslinking agents, curing agents, adhesion promoters, stabilizers, UV absorbers, antistatic agents, etc., to the extent that they do not impair the gas barrier properties. Examples of crosslinking agents include metal alkoxides and complexes of aluminum, titanium, zirconium, etc., and examples of adhesion promoters include various silane coupling agents.

[0030] The coating layer of the present invention can be obtained by applying and drying a coating agent, which is obtained by mixing the polyvinyl alcohol-based resin and a siloxane compound, onto a metal layer and / or an inorganic compound layer. The ratio of resin to siloxane compound contained in the coating layer is the ratio of the mass of the resin to the mass of silicon in the siloxane compound when it is completely oxidized (equivalent mass of SiO2), where the equivalent mass of resin / silicon oxide is preferably in the range of 15 / 85 to 85 / 15, more preferably in the range of 20 / 80 to 65 / 35, even more preferably in the range of 20 / 80 to 40 / 60, and particularly preferably in the range of 20 / 80 to 50 / 50. A ratio of 15 / 85 or higher is preferable because it can suppress the weakening of the film and the occurrence of cracks due to an excess amount of siloxane compound. A ratio of 85 / 15 or lower is preferable because it can immobilize the resin with a network of siloxane compounds and suppress the decrease in water vapor barrier properties. The ratio of resin to silicon dioxide can be determined by the ratio c / s of the peak intensity c of carbon-derived fragment ions to the peak intensity s of fragment ions derived from segments with Si-O bonds, measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS) at the center of the coating layer thickness. A c / s of 0.015 to 0.650 is preferred. While no pretreatment is necessary if the coating layer is exposed to the outermost surface, if other layers are formed on the coating layer, each layer can be removed by etching with an argon ion beam or other ions, or by chemical treatment, before analysis. Measurement can be performed, for example, by the following method: Using a TOF-SIMS5 time-of-flight secondary ion mass spectrometer manufactured by ION TOF, measurement is performed under the following conditions. After analysis, the sample is examined using a stylus-type step meter (BRUKER Dektak XTL) to determine the actual crater depth. The average etching rate, obtained by dividing the depth by the etching time, is used to convert the value at the center. If TOF-SIMS measurement data for the portion that is exactly half the film thickness is unavailable, the TOF-SIMS measurement data from the measurement point closest to that portion will be used. If there is more than one measurement point closest to the portion that is half the film thickness, the average c / s value obtained from the measurement data of each measurement point will be used as the c / s value for the portion that is half the film thickness.The analysis will involve reading the raw data using SURFACE LAB 7.1 software included with the measurement device and reading the peaks attributed to various ions from the mass spectrum.

[0031] <Measurement conditions> Primary ion species: Bi + (2 pA, 50 μs) Acceleration voltage: 25kV Detected ion polarity: positive Measurement range: 100 μm × 100 μm Resolution: 128×128 Etching ion species: O 2+ (2 keV, 170 nA) Etching area: 300 μm × 300 μm Etching rate: 1 sec / cycle.

[0032] In the coating layer of the present invention, the ratio of the area of ​​the random network structure A1 / (A1+A2) to the sum of the area A1 of the Raman bands showing a random network structure derived from a siloxane compound and the area A2 of the Raman bands showing a linear polysiloxane structure and cyclic siloxanes with four or fewer members, obtained by measurement by laser Raman spectroscopy, is preferably 0.50 or more and 0.85 or less. Furthermore, in the ratio of the area of ​​the random network structure B1 / (B1+B2) to the sum of the area B1 of the Raman bands showing a random network structure derived from a siloxane compound and the area B2 of the Raman bands showing a linear polysiloxane structure and cyclic siloxanes with four or fewer members, the change before and after heat treatment [B1 / (B1+B2)-A1 / (A1+A2)] is preferably 0.10 or less, and more preferably 0.08 or less. Furthermore, A1 / (A1+A2) and B1 / (B1+B2) shall be determined by the method described in the examples. If a layer is formed on top of the coating layer, the coating layer shall be exposed by polishing, stripping, or etching before measurement.

[0033] The siloxane compounds contained in the coating layer can be obtained by hydrolysis and polycondensation of silicon alkoxides. Silicon alkoxides are represented by the general formula Si(OR)4, and through hydrolysis and polycondensation, they become compounds having Si-O-Si siloxane bonds via oxygen atoms bonded to silicon atoms. At this time, the four bonds of silicon do not all become siloxane bonds uniformly, but can take on various bonding states such as 3-membered rings, 4-membered rings, linear structures, and even network structures in which parts of the linear chain are cross-linked. As a result of diligent research, the inventors found that increasing the proportion of network structures among these siloxane structures suppresses the molecular motion of the polyvinyl alcohol-based resin backbone by forming a mesh-like structure, thereby improving barrier properties and achieving barrier stability before and after heat treatment. The bonding state of siloxanes can be analyzed by laser Raman spectroscopy, and the network structure can be analyzed at wavenumber 425 cm⁻¹. -1 Nearby, annular and linear structures with four or fewer members contribute little to the immobilization of polyvinyl alcohol-based resins, and are 485 cm². -1 It is detected in the vicinity. By waveform separation of these spectra, the ratio of the network structure to the peak area can be determined. The signal showing the network structure is at wavenumbers 415-430 cm⁻¹. -1 Ring-like structures and linear structures with four or fewer members that have a peak in the range of 480-500 cm² and contribute little to the network are found in the range of 480-500 cm². -1The peaks are located within this range. In the Raman spectrum of the coating layer, when these are separated by peak separation, and the area of ​​the Raman band showing the network structure derived from the siloxane compound is denoted as A1, and the area of ​​the Raman band showing the linear polysiloxane structure and cyclic siloxanes with four or fewer members is denoted as A2, the value of A1 / (A1+A2) indicates the proportion of the network structure among the main siloxane bonds. The value of A1 / (A1+A2) is preferably 0.50 to 0.85, and more preferably 0.60 to 0.80. When A1 / (A1+A2) is 0.50 or higher, there are many siloxanes in the network structure, and the coating layer can be fixed in a mesh-like structure, thus providing a stable barrier, which is preferable. When A1 / (A1+A2) is 0.85 or lower, it is preferable because it avoids embrittlement due to an excess of siloxane network structure and maintains flexibility.

[0034] Furthermore, in the Raman spectrum of the coating layer after heat treatment at 121°C for 30 minutes, these were separated into peaks. When the area of ​​the Raman band showing a random network structure derived from the siloxane compound is denoted as B1 and the area of ​​the Raman band showing linear polysiloxane structures and cyclic siloxanes with four or fewer members is denoted as B2, the value of B1 / (B1+B2) indicates the proportion of the network structure among the main siloxane bonds.

[0035] The value of [B1 / (B1+B2)-A1 / (A1+A2)] is preferably 0.10 or less, and more preferably 0.08 or less. When [B1 / (B1+B2)-A1 / (A1+A2)] is 0.10 or less, it indicates that the change in the siloxane bond network structure due to heat treatment can be minimized, and a dense network structure has been formed. This is preferable because the coating layer can be fixed in a mesh-like structure, allowing for stable barrier properties even after heat treatment. There is no particular lower limit, but from the viewpoint of avoiding embrittlement due to an excessive siloxane network structure and maintaining flexibility, a value of 0.02 or more is preferred.

[0036] One preferred embodiment for obtaining a siloxane compound with a dense network structure is the use of alkoxysilanes or siloxane compounds with short chain lengths of pentamers or less of alkoxysilanes. If a polymer that has undergone polycondensation beforehand is used as the siloxane compound, the amount of active silanol groups is limited, making it difficult for polycondensation between molecular chains to proceed, and thus preventing the formation of a sufficient network structure. It is preferable to use a low molecular weight component as a crosslinking agent to bond the molecular chains, as this allows for the formation of a dense network structure. Therefore, the inventors conducted diligent research and found that by proceeding with the hydrolysis reaction of the alkoxy group at a slow rate, the formation of coarse oligomers due to branched structures can be suppressed, and a siloxane compound that is easily crosslinked can be obtained. Coarse oligomers have difficulty in forming a dense network structure because the silanol groups do not come into close proximity due to their own steric hindrance, which is a factor that makes it difficult to obtain stable barrier properties. With low-molecular-weight or linear components, the silanol groups tend to come into closer proximity, which is thought to increase the density of the siloxane network structure. By bringing the raw materials that form the siloxane network structure into close proximity, these reactions proceed more easily, which reduces the thermal energy required for siloxane network formation and allows for the formation of a sufficient network structure even at low temperatures.

[0037] The coating layer of the present invention is preferably manufactured using a chain-like siloxane compound. Using a chain-like siloxane compound is preferable because it allows for the formation of a dense network structure with suppressed random structuring. The chain-like siloxane compound has an IR peak intensity (1,100-1,200 cm²) indicating the random structure of the siloxane compound. -1 ) and peak intensity (1,050~1,080 cm) showing a chain-like structure -1 This can be confirmed by the ratio of ) or by NMR.

[0038] The coating layer of the present invention preferably has a ratio of peak intensities P1 to P2 detected by the FT-IR-ATR method, P1 / P2, of 3.5 to 8.0, and more preferably 4.0 to 6.5 (where P1: 1,050 to 1,080 cm²). -1The intensity of the maximum peak present, P2: 920~970cm -1 This shows the intensity of the maximum peak present. Peak intensity refers to the absorbance (unitless) at the peak position. The FT-IR-ATR method allows for the capture of the characteristics of the surface coating layer; P1 represents the reaction product Si-O-Si, and P2 represents the amount of the reaction raw material Si-OH. Therefore, the ratio of peak intensities P1 to P2, P1 / P2, increases as the polycondensation of alkoxysilane progresses. As the polycondensation reaction of alkoxysilane progresses, the terminal OH groups decrease, forming a strong film with improved barrier properties and resistance to heat and humidity during retort processing as a packaging material. A P1 / P2 ratio of 3.5 or higher results in a strong film with reduced terminal OH groups, creating a layer with excellent barrier properties and heat and humidity resistance. A P1 / P2 ratio of 8.0 or lower is preferable as it suppresses cracking and embrittlement due to film shrinkage. P1 and P2 shall be determined by the method described in the examples. If a layer is formed on top of the coating layer, the coating layer shall be exposed by polishing, stripping, or etching before measurement.

[0039] To achieve a desirable peak intensity ratio P1 / P2 detected by FT-IR-ATR, the reaction of the alkoxysilane must proceed sufficiently. Since the polycondensation of alkoxysilane is a dehydration reaction, it can be advanced by heating. However, the polyolefin resin film constituting the laminate of the present invention has lower heat resistance compared to conventional polyester resins, making it difficult to ensure sufficient reaction progress. After diligent research, the inventors discovered that by using a polyvinyl alcohol resin having a hydrophobic modifying group, the hydrolysis of the alkoxysilane and the interaction between the polycondensate and the resin are reduced, while the hydrolysis of the alkoxysilane and the interaction between the polycondensates are enhanced. Furthermore, by using alkoxysilane or siloxane compounds with short chain lengths of pentamer or less of alkoxysilane, the hydrolysis reaction of the alkoxy group proceeds at a slow rate, facilitating the progress of these reactions and enabling the formation of a network at low temperatures. They also found that adjusting P1 / P2 to between 3.5 and 8.0 suppresses the deterioration of barrier properties in subsequent processes. When the laminate of the present invention is used as a packaging material, it is subjected to heating and pressure during printing and bag-making processes. In this case, a coating with a moderately structured network can also function as a protective film, which is preferable. On the other hand, if, for example, P1 / P2 is less than 3.5, there are many unreacted metal alkoxides, so the coating layer does not harden properly, making it susceptible to scratches and deterioration of barrier properties. Depending on the processing conditions, the unreacted metal alkoxides may harden and shrink, further degrading the barrier. On the other hand, if P1 / P2 exceeds 8.0, the coating layer becomes brittle, making it prone to cracking due to pressure during bonding and transport tension, which can degrade barrier properties.

[0040] The coating layer of the present invention preferably has a free volume radius of vacancies of 0.260 nm or less, as determined by the positron annihilation method. The positron beam method is one of the positron annihilation lifetime measurement methods, which measures the time (on the order of several hundred ps to several tens of ns) from the time a positron is incident on a sample until it annihilates, and is a non-destructive method for evaluating information regarding the size, number concentration, and size distribution of vacancies of approximately 0.1 to 10 nm from that annihilation lifetime. A radioactive isotope is used as the positron source. 22The use of a positron beam instead of Na) is a key difference from conventional positron annihilation methods, enabling the measurement of thin films with a thickness of several hundred nanometers deposited on silicon or quartz substrates. The free volume radius can be measured, for example, by the following procedure: The laminate is attached to a 15 mm × 15 mm silicon wafer, and the positron annihilation lifetime is measured under the following conditions using a sample that has been vacuum-degassed at 25°C.

[0041] Measurement device: Fuji Invac PALS-200A compact positron annihilation generator Positron source: 22 Na-based positron annihilation Gamma-ray detector: BaF2 scintillator and photomultiplier tube Beam intensity: 3 keV Measurement temperature: 25℃ Measurement atmosphere: Vacuum Total count: Approximately 5,000,000 counts.

[0042] The obtained positron annihilation lifetime curves were subjected to a three-component analysis using the nonlinear least-squares program POSITRONFIT, and the annihilation lifetimes were designated as τ1, τ2, and τ3 from shortest to longest. From the longest average annihilation lifetime τ3, the free volume radius R3 (nm) of the vacancy was calculated using the following formula.

[0043] τ3=(1 / 2)[1-{R3 / (R3+0.166)}+(1 / 2π)sin{2πR3 / (R3+0.166)}] -1 .

[0044] When the free volume radius of the coating layer is 0.260 nm or less, the pore size of the coating layer is small and the layer is dense, resulting in good barrier properties. There is no particular lower limit to the free volume radius, but from the viewpoint of brittleness, it is preferable to be 0.240 nm or more.

[0045] To reduce the free volume radius, it is preferable to control the bonding mode of the silicon alkoxide mentioned above or to increase the reaction rate. It is known that the structure of silicon alkoxide changes depending on the hydrolysis conditions during coating preparation, and using an acid as a hydrolysis catalyst is preferable because it reduces the cyclic structure and thus reduces the free volume radius. Also, if the reaction rate is low, there are unreacted hydroxyl groups with a high degree of freedom of movement, which increases the free volume, so it is preferable to fix them by polycondensation. Furthermore, reducing the branching of the modifying group of the polyvinyl alcohol resin is also effective in reducing the free volume. If the steric hindrance of the modifying group of the polyvinyl alcohol resin is large, or if the degree of saponification is low and steric hindrance is large, the free volume will also increase, which may worsen the barrier properties.

[0046] The coating layer of the present invention preferably has a thickness of 200 nm to 600 nm, and more preferably 200 nm to 400 nm. A thickness of 200 nm or more allows for coating of the metal layer and / or metal compound layer without defects and improves barrier properties. A thickness of 600 nm or less is preferable because it prevents cracks due to thermal shrinkage during curing and insufficient curing. The thickness of the coating layer shall be determined by the method described in the examples.

[0047] The laminate of the present invention has a stress in the principal orientation axis direction at 121°C measured by thermomechanical analysis (TMA) that is SF 121℃ , the stress at 145°C in the direction of the main orientation axis is SF 145℃ When that happens, SF 145℃ -SCIENCE FICTION 121℃ It is preferable that the value be ≤2.50 MPa. Each stress shall be determined by the method described in the examples. The main orientation axis of the laminate refers to the direction in which the stress of the maximum point strength is greatest when a rectangular sample of 50 mm (measurement direction) x 10 mm width is pulled in the measurement direction at room temperature at a tensile speed of 300 mm / min, and the stress is determined from the maximum load until fracture. Details of the method for determining this are described in the examples. SF 145℃ -SCIENCE FICTION 121℃By satisfying a pressure of ≤2.50 MPa, when the laminate of the present invention is subjected to post-processing including high-temperature treatment such as heat sealing, deformation of the laminate due to heat and the generation of defects such as pinholes and cracks in the inorganic oxide layer can be suppressed. As a result, the laminate can maintain excellent water vapor barrier properties.

[0048] science fiction 145℃ -SCIENCE FICTION 121℃ Satisfying ≤2.50MPa means that the shrinkage stress is small in the high-temperature range of 121°C or higher. When the shrinkage stress is small in the high-temperature range of 121°C or higher, the shrinkage stress becomes even smaller in the temperature range from below 121°C to room temperature, resulting in extremely small dimensional changes over time. Therefore, when making bags with the laminate of the present invention, dimensional stability is improved, which reduces the deterioration of quality due to deformation during printing, lamination, and bag making. This is particularly preferable when heat sealing during bag making, as it suppresses wrinkles and shrinkage in the heated area and increases the yield of the final product. Furthermore, when storing the laminate of the present invention on a roll for a long period of time, it is expected to suppress deformation of the roll, such as the occurrence of wrinkles (tightening).

[0049] From the above perspective, SF 145℃ -SCIENCE FICTION 121℃ The upper limit is preferably 2.00 MPa, more preferably 1.80 MPa, and even more preferably 1.50 MPa. 145℃ -SCIENCE FICTION 121℃ A smaller value is preferable, and while the lower limit is not particularly limited, it is practically around 0.05 MPa.

[0050] science fiction 145℃ or SF 121℃ This can be determined by performing thermomechanical analysis under the temperature and load conditions shown in the examples, and reading the resulting thermal shrinkage stress curve. The thermomechanical analyzer is not particularly limited as long as it is capable of measurement and can be appropriately selected; for example, the TMA / SS6000 manufactured by Seiko Instruments Inc. can be used.

[0051] Layered SF 145℃ -SCIENCE FICTION 121℃Methods for controlling the pressure to 2.50 MPa or less or within the above preferred range are not particularly limited, but include, for example, adjusting the conditions of the tenter apparatus when forming the polypropylene resin film constituting the laminate. More specifically, methods include setting the lower limit of the tenter heat treatment temperature to 140°C, more preferably 150°C, even more preferably 155°C, particularly preferably 161°C, and the upper limit to 167°C, more preferably 166°C, even more preferably 165°C; setting the lower limit of the relaxation rate to 2%, more preferably 5%, even more preferably 7%, particularly preferably 9%, and the upper limit to 20%, more preferably 18%, even more preferably 17%, particularly preferably 15%. If the tenter heat treatment temperature is set to 168°C or higher, the molecular chains that were strongly oriented in the direction of the main orientation axis will loosen, and SF 145℃ -SCIENCE FICTION 121℃ It may be difficult to control the pressure to 2.50 MPa or less. Furthermore, methods for controlling the polypropylene resin composition constituting the polypropylene resin film include setting the molecular weight distribution Mz / Mw to 1.5 or more and 4.5 or less, and setting the differential distribution value to 1.0% or more and 10% or less when the logarithmic molecular weight Log(M) is 6.5. Note that none of these methods are mandatory requirements, and they can be combined as appropriate. Mz is the Z-average molecular weight, and Mw is the weight-average molecular weight. The logarithmic molecular weight Log(M) is the common logarithm of the polymer molecular weight M.

[0052] The laminate of the present invention preferably has a loss tangent tanδ in the direction of the principal orientation axis at 145°C of 0.25 or less. The loss tangent tanδ correlates with the degree of mobility of the molecular chains of the resin constituting the laminate, and generally increases with increasing temperature in the region above 100°C. The tanδ in the direction of the principal orientation axis at 145°C is an index that correlates with the degree of mobility of the molecular chains in the film around 145°C. By reducing this value, in other words, by suppressing the movement of molecular chains at high temperatures, the thermal shrinkage stress of the laminate at high temperatures is suppressed, and the stress in the direction of the principal orientation axis at 121°C, as measured by thermomechanical analysis (TMA) of the laminate, is reduced to SF 121℃ , the stress at 145°C in the direction of the main orientation axis is SF 145℃ When that happens, SF 145℃-SCIENCE FICTION 121℃ This makes it easier to satisfy ≤2.50 MPa. From the above viewpoint, the tanδ in the direction of the main orientation axis at 145°C is preferably 0.23 or less, more preferably 0.21 or less, and even more preferably 0.19 or less. Note that a smaller tanδ in the direction of the main orientation axis at 145°C is preferable, and although there is no particular lower limit, it is substantially around 0.01. Tanδ can be determined from the viscoelastic-temperature curve obtained by cooling to -100°C and then raising the temperature from -100°C to 180°C, and the details of the measurement method are as described in the examples.

[0053] Methods for reducing the tanδ in the direction of the main orientation axis of a laminate to 0.25 or less at 145°C are not particularly limited, but include methods for reducing the molecular weight distribution Mz / Mw of the resin composition constituting the polypropylene film, methods for applying a heat relaxation treatment after uniaxial stretching in the film-forming process of the polypropylene resin film, methods for increasing the heat treatment temperature of the tenter, and methods for increasing the relaxation rate of the tenter. By using these methods individually or in appropriate combinations, the tanδ can be reduced.

[0054] In the present invention, the elongation at the break point in the principal orientation axis is defined as T0, and the elongation at the break point in the principal orientation axis direction, measured after heat treatment of the laminate at 130°C for 10 minutes, is defined as T 130 In that case, T0 / T 130 It is preferable that the value of is 1.20 or less. The elongation at the breaking point is the maximum elongation at the breaking point when a rectangular sample with a length of 150 mm and a width of 10 mm is prepared with the main orientation axis as the longer side, and pulled in the measurement direction at a tensile speed of 300 mm / min at room temperature, and is specifically determined by the method described in the examples. The elongation at the breaking point is determined by (l-l0) / l0 × 100, where l0 is the length of the sample before the test and l is the length at the breaking point. In the present invention, T0 / T 130A value of 1.20 or less indicates that the change from before heat treatment is small even after heat treatment at 130°C for 10 minutes, and that there is little thermal damage during manufacturing. Heat treatment at 130°C for 10 minutes refers to a process in which the product is placed in an oven (for example, the ESPEC Corporation's Safety Oven SPHH-201 with a safety door) that is stable at a set temperature of 130°C for 10 minutes or more under a laboratory environment of 23°C and 50% RH, and then removed after 10 minutes. --T0 / T 130 By setting the ratio to 1.20 or less, thermal damage during laminate manufacturing can be suppressed, and good barrier properties can be achieved. Furthermore, the tightening of the polyolefin resin film can be suppressed, thus preventing a decrease in barrier properties. T0 / T 130 The lower limit is effectively 0.5.

[0055] The ratio of the elongation at the break point in the principal orientation axis direction before and after heat treatment of the laminate of the present invention at 130°C for 10 minutes, T0 / T 130 To keep the elongation at break below 1.20, it is preferable to avoid exposing the product to high temperatures during the manufacturing process. When polyolefin resin, for example, is used as the base film, it is susceptible to heat, and exposure to high temperatures can cause the crystal structure to collapse or the orientation to relax, reducing the elongation at break. Once the polymer structure collapses after being exposed to high temperatures, exposure to high temperatures again will further reduce the elongation at break. In other words, in the case of a laminate manufactured without exposure to high temperatures, T 130 The decrease is small, T0 / T 130 While the value of becomes 1.20 or less, the laminate manufactured at high temperature is T 130 The decrease is significant, T0 / T 130The value will be greater than 1.20. Steps in the manufacturing of the laminate of the present invention that are exposed to high temperatures include the step of laminating a metal layer or a metal oxide layer, and the step of laminating a coating layer. As described later, known methods such as vapor deposition can be applied to the step of laminating a metal layer or a metal oxide layer. In this step, the main roll can be cooled to suppress damage to the substrate, and because the processing is done at a very high speed, the thermal effects can be relatively suppressed. On the other hand, in the steps of laminating a coating layer or allowing its reaction to proceed, it is impossible to avoid heating for drying the coating agent and for the reaction of the coating layer, so the effect on the substrate is significant. From the viewpoint of thermal damage, a preferred temperature range for the drying step of the coating layer is, for example, 120°C or less, more preferably 110°C or less. Even when further heat treatment is performed after drying to improve the barrier properties of the coating layer, the treatment temperature is preferably 80°C or less, and more preferably 60°C or less, in order to suppress thermal damage as much as possible. In addition, a treatment time of 14 days or less can suppress thermal damage and is also preferable from the viewpoint of production efficiency.

[0056] The laminate of the present invention has a water vapor transmission rate of 1.0 g / m². 2 Preferably, it should be less than 24 hours, and 0.5 g / m² 2 It is more preferable that the oxygen permeability is 1.0 cc / m³ or less. 2 Preferably, it is 0.3 cc / m³ or less, and 24 hours or less. 2 It is more preferable that the water vapor transmission rate is 0.01 g / m³ or less. The lower the water vapor transmission rate and oxygen transmission rate, the better. While there is no particular lower limit, the water vapor transmission rate is substantially 0.01 g / m³. 2 / 24hr, oxygen permeability is 0.01cc / m³ 2 The value is / 24hr. The water vapor transmission rate is 1.0 g / m³. 2 Less than 24 hours, oxygen permeability of 1.0 cc / m³ 2 Setting the humidity to 24 hours or less is preferable because it prevents deterioration of the contents due to moisture absorption and oxidation when packaged. The water vapor permeability and oxygen permeability shall be determined by the method described in the examples.

[0057] The laminate of the present invention has a water vapor transmission rate of 1.7 g / m² after retort treatment. 2Preferably, it should be 1.0 g / m² or less per 24 hours. 2 Preferably, it should be less than 24 hours, and 0.7 g / m² 2 It is more preferable that the oxygen permeability is 1.7 cc / m³ or less after retort processing. 2 Preferably, it is 1.0 cc / m³ or less, and 24 hours or less. 2 Preferably, it should be less than 24 hours, and 0.5 cc / m³ 2 It is more preferable that the water vapor transmission rate is 0.01 g / m³ or less per 24 hours. The lower limit is not particularly limited, but in practice, the water vapor transmission rate should be 0.01 g / m³. 2 / 24hr, oxygen permeability is 0.01cc / m³ 2 The rate is / 24hr. The water vapor transmission rate after retort processing is 1.0 g / m³. 2 Less than 24 hours, oxygen permeability after retort processing is 1.0 cc / m³. 2 A heat treatment time of 24 hours or less is preferable because it prevents deterioration of the contents due to moisture absorption and oxidation even after the packaging has been heat-treated. The water vapor and oxygen permeability after retort treatment shall be determined by the method described in the examples.

[0058] The laminate of the present invention has a water vapor transmission rate Δ of 0.7 g / m², which is the difference before and after retort treatment. 2 Preferably, it should be less than 24 hours, and 0.5 g / m² 2 It is more preferable that the oxygen permeability is less than 24 hours. Furthermore, the oxygen permeability Δ, which is the difference before and after retort processing, should be 0.7 cc / m³. 2 Preferably, it should be less than 24 hours, and 0.5 cc / m³ 2 It is more preferable that the water vapor transmission rate Δ is less than or equal to 24 hours. The lower limit is not particularly limited, but the water vapor transmission rate Δ is substantially 0.01 g / m³. 2 / 24hr, oxygen permeability Δ is 0.01 cc / m³ 2 The timeframe is / 24hr. The difference in water vapor transmission rate Δ before and after retort processing is 0.7g / m³. 2 / 24hr or less, oxygen permeability Δ 0.7cc / m 2Setting the time interval to 24 hours or less is preferable because it suppresses the deterioration of the barrier properties when heat treatment is applied to the packaging, thereby stabilizing its performance. The difference in water vapor permeability Δ and oxygen permeability Δ before and after retort treatment shall be determined by the method described in the examples.

[0059] The laminate of the present invention can be obtained by forming a metal layer and / or an inorganic compound layer on at least one surface of a polyolefin resin film, and then laminating a coating layer. The metal layer and / or inorganic compound layer can be formed using known methods such as vacuum deposition, sputtering, ion plating, and plasma vapor deposition, but the vapor deposition method is particularly suitable because it allows for high-speed film formation with good productivity. Vacuum deposition methods include, but are not limited to, electron beam (EB) deposition, resistance heating, and induction heating. When forming a metal layer and / or inorganic compound layer on a long pair of resin film rolls, the main roll for deposition is preferably cooled to prevent the film from being damaged by heat, and its temperature is preferably 20°C or lower, more preferably 0°C or lower. As a method for obtaining the metal layer, an example is to deposit the target metal as a raw material. As a method for obtaining the inorganic compound layer, in addition to depositing a compound of the target composition as a raw material, an example can be given of a method in which a metal is used as a raw material and a reaction gas is introduced into the deposited metal vapor to obtain an inorganic compound. For example, when obtaining an aluminum oxide layer, aluminum is used as the deposition raw material, and an oxygen-containing gas is introduced into the evaporated aluminum vapor to form an inorganic oxide layer on the film. The gas introduced only needs to contain a gas with a composition that reacts with the evaporated metal and is incorporated into the layer, and may also contain an inert gas for film quality control. The surface of the resin film forming the metal layer and / or inorganic compound layer may be subjected to surface modification treatment to improve interlayer adhesion. The surface modification treatment may be performed in-line or offline, and the modification treatment method is not particularly limited, but known methods include corona treatment, plasma treatment, ion beam treatment, flame treatment, etc. These surface modification treatments can be performed using air, as well as argon, nitrogen, oxygen, carbon dioxide, hydrogen, ammonia, hydrocarbons (C n H2n+2 The treatment may be carried out under an atmosphere of various gases (where n is an integer from 1 to 4) or a mixture thereof. The gas used for the surface modification treatment can be selected depending on the ease of discharge, the energy of the active species obtained, and the type of functional group to be introduced, but it is preferable to include carbon dioxide or oxygen gas, or argon or nitrogen which facilitate stable discharge in order to introduce functional groups. In addition, the surface of the resin film forming the metal layer and / or inorganic compound layer may be provided with a coating layer to improve interlayer adhesion.

[0060] The laminate of the present invention is preferably manufactured by a manufacturing method that includes the steps of applying a coating agent containing a polyvinyl alcohol resin and a siloxane compound to the inorganic layer surface of a laminate having a metal layer and / or an inorganic compound layer on at least one surface of a polyolefin resin film, and drying. This embodiment makes it possible to obtain a dense laminate with good barrier properties. Furthermore, it is possible to obtain a laminate with high water vapor barrier and oxygen barrier properties while suppressing the environmental burden during manufacturing. In particular, this embodiment is preferable because it can be sufficiently cured even at low temperatures, and even at high temperatures, it can be sufficiently cured in a particularly short time, thereby reducing the environmental burden during manufacturing.

[0061] Furthermore, from the viewpoint of water vapor barrier properties and oxygen barrier properties, the mass ratio of the polyvinyl alcohol-based resin in the coating agent to the SiO2 equivalent mass when the silicon of the siloxane compound is completely oxidized is preferably in the range of resin / SiO2 equivalent mass = 15 / 85 to 85 / 15, more preferably in the range of 20 / 80 to 65 / 35, even more preferably in the range of 20 / 80 to 40 / 60, and particularly preferably in the range of 20 / 80 to 50 / 50.

[0062] Furthermore, in the method for manufacturing the laminate, it is preferable that the film obtained through the steps of applying the coating agent and drying has an A1 / (A1+A2) ratio of 0.50 to 0.85 and a B1 / (B1+B2)-A1 / (A1+A2) ratio of 0.10 or less. This embodiment indicates that the siloxane compound has a network structure as its main structure, thereby immobilizing the polyvinyl alcohol-based resin and reducing its mobility, thereby improving barrier properties.

[0063] The coating method for the coating agent containing polyvinyl alcohol resin and siloxane compound is not particularly limited and any known method can be used, such as direct gravure, reverse gravure, microgravure, rod coat, bar coat, die coat, or spray coat. The drying temperature after coating is preferably 70°C to 120°C, and more preferably 80°C to 110°C. Note that the drying temperature refers to the highest temperature reached on the film surface. Setting it to 70°C or higher allows for the removal of the solvent and the formation of a layer, while setting it to 120°C or lower suppresses thermal shrinkage and deformation of the polyolefin resin film. After coating and drying, the laminate of the present invention may be further aged to promote the polycondensation reaction of silicon alkoxide and improve barrier properties. The ambient temperature for aging is preferably 30°C to 80°C, and more preferably 30°C to 60°C. The aging treatment time is preferably 1 day to 14 days, and more preferably 3 days to 7 days. By setting the aging temperature to 30°C or higher, crosslinking of the coating layer can be promoted, improving barrier properties. By setting it to 60°C or lower, curling and shrinkage of the film due to the aging process can be suppressed.

[0064] The packaging of the present invention has the laminate described above. The packaging may be laminated with a heat-seal layer for printing or other purposes, or with another resin film to improve rigidity. The heat-seal layer and the resin film for improving rigidity are preferably made of polyolefin resin to improve recyclability. Including the laminate in the packaging provides good and stable water vapor barrier and oxygen barrier properties, which suppresses deterioration of the contents and is therefore preferable. [Examples]

[0065] The present invention will be described below based on examples. However, the present invention is not limited to these examples, and these examples can be modified or altered in accordance with the spirit of the invention; such modifications do not exclude them from the scope of the invention. [Evaluation Method] (1) Thickness of the base film The thickness of 10 arbitrary points was measured using an Anritsu Corporation electronic micrometer (K-312A model) under an atmosphere of 23°C and 65% RH. The arithmetic mean of the obtained thicknesses of the 10 points was defined as the thickness of the substrate film (unit: μm).

[0066] (2) Method for measuring the melting point of the base film Using a differential scanning calorimeter (EXSTAR DSC6220, Seiko Instruments Inc.), a 3 mg sample was heated from 30°C to 260°C in a nitrogen atmosphere at a heating rate of 20°C / min. It was then held at 260°C for 5 minutes, and subsequently cooled to 30°C at a rate of 20°C / min. After holding at 30°C for another 5 minutes, the sample was reheated from 30°C to 260°C at a rate of 20°C / min. The peak temperature of the endothermic curve obtained during this reheating was defined as the melting point. If multiple peak temperatures were observed, the highest temperature was used as the melting point.

[0067] (3) Arithmetic mean height Sa The measurement can be performed using a non-contact surface observation device, such as a scanning white-light interference microscope manufactured by Hitachi High-Tech Science Corporation. The measurement was performed using a 10x objective lens, a 1x microscope tube, and a 1x zoom lens, with the wavelength filter set to 530nm·white, and the measurement mode set to wave, measuring an area of ​​0.561mm × 0.561mm. The measurement software used was VS-Measure Version 10.0.4.0, and the analysis software was VS-Viewer Version 10.0.3.0. In the analysis, the undulation component was removed from the captured image using polynomial quartic approximation surface correction, then processed with a median (3×3) filter, followed by interpolation (a process that compensates for pixels where height data could not be obtained by using height data calculated from surrounding pixels), and then Sa was calculated.

[0068] (4) Thickness of the metal layer and / or inorganic compound layer The thickness was measured by cross-sectional observation using a transmission electron microscope (TEM). Observation samples were prepared using the FIB method (specifically, based on the method described in "Polymer Surface Processing" (by Akira Iwamori), pp. 118-119) with a Hitachi FB-2000A microsampling system. Subsequently, the cross-section of the observation samples was observed using a Hitachi H-9000UHRII transmission electron microscope at an acceleration voltage of 300kV, and the thickness of the metal layer and / or inorganic compound layer was confirmed at 10 arbitrary locations. The arithmetic mean of these values ​​was defined as the thickness of the metal layer and / or inorganic compound layer (unit: nm).

[0069] (5) Thickness of the coating layer The laminate was cut perpendicular to the film surface using a microtome, and the cross-section of the laminate was observed and measured using a scanning electron microscope. Observation was performed using a Hitachi, Ltd. STEM (Scanning Transmission Electron Microscope / H-9000UHRII), with three points of imaging taken at 100,000x magnification. The thickness of the coating layer was measured from the three obtained images, and the average value was used as the thickness of the coating layer.

[0070] (6) Laser Raman spectroscopy The coating layer of the laminate was separated by cutting, and the Raman spectrum of the coating layer was obtained by measuring under the following conditions. Also, the laminate was placed in an oven (Safety Oven SPHH-201 with safety door, manufactured by Espec Corporation) that was stable at a set temperature of 121 °C for 10 minutes or more, taken out after 30 minutes, returned to room temperature, and then the coating layer of the laminate was separated by cutting to obtain the Raman spectrum of the coating layer after heat treatment. · Equipment: Laser Raman microscope RAMANtouch (manufactured by Nano Photon Co., Ltd.) · Measurement mode: Micro Raman, point mode · Objective lens: ×10 · Laser wavelength: 532 nm · Laser power: 100 mW · Diffraction grating: Single 600 gr / mm · Slit: 100 μm · Detector: CCD 400×1,340 The obtained spectrum was analyzed using the analysis software RAMAN Viewer manufactured by Nano Photon. After smoothing the spectrum by the moving average method and correcting the baseline with a spline curve, in the range of 600~250 cm -1 , the auto-fitting was performed with the setting of separating into two components with peak frequencies of 425 cm -1 , 485 cm -1 by Lorentz function approximation. From the areas A1 (peak position 425 cm -1 ) and area A2 (peak frequency 485 cm -1 ) of the two separated components, the area ratio A1 / (A1 + A2) was calculated. Similarly, from the areas B1 (peak position 425 cm -1 ) and area B2 (peak frequency 485 cm -1 ) of the two separated components from the Raman spectrum of the coating layer after heat treatment, the area ratio B1 / (B1 + B2) was calculated.

[0071] (7) SF 145℃ -SF 121℃ <Specification of the main orientation axis of the laminate> Cut out a rectangle measuring 50mm in length and 10mm in width from the laminate, with any direction as the longer side. <1> This was done. In this case, a rectangular sample <1> We defined the direction in which the longer side of the object points as 0°. Next, we created a sample of the same size such that the direction of the longer side is rotated 15° to the right from the 0° direction. <2> A sample was taken. Similarly, the rectangular sample was rotated by 15° along its longer side, and the sample was taken in the same manner. <3> ~ <12> Samples were collected. Next, each rectangular sample was set on a tensile testing machine (Orientec Co., Ltd. "Tensilon" (registered trademark) UCT-100) with an initial chuck distance of 20 mm so that the longer side was the tensile direction, and a tensile test was performed at room temperature with a tensile speed of 300 mm / min. At this time, the maximum load until the sample broke was read, and the value divided by the cross-sectional area of ​​the sample before the test (film thickness × width) was calculated as the stress at the maximum point strength. The same measurement was performed five times for each sample, and the average value of the stress at the maximum point strength was determined, and the longer side direction of the sample with the highest average value was taken as the main orientation axis of the laminate.

[0072] <Measurement of thermal shrinkage stress by thermomechanical analysis (TMA)> The laminate was cut into a rectangular sample with a width of 4 mm and a length of 50 mm, with the "main orientation axis direction" defined above as the longer side, and clamped in a metal chuck to a test length of 20 mm. It was then placed in the thermomechanical analyzer described below, and the thermal shrinkage stress curve in the main orientation axis direction of the laminate was determined under the following temperature and load conditions while maintaining a constant test length. • Equipment: TMA / SS6000 (manufactured by Seiko Instruments Inc.) Temperature range: 23~200℃ • Heating rate: 10°C / min ·Hold: 10 minutes • Sampling time: 10 seconds / sampling • Nitrogen cooling: None • Control Mode: L • Maximum displacement during standby: 0 μm • Starting displacement: 0 μm • Load rate: 0.1 μm / min ·Holding: 600 minutes • Measurement atmosphere: Under nitrogen · Measured thickness: The sum of the thickness of the base film, the thickness of the metal layer and / or inorganic compound layer, and the thickness of the coating layer.

[0073] <SF 145℃ -SF 121℃ Calculation> From the thermal shrinkage stress curve obtained by the above measurement method, after correcting the shrinkage stress value at the temperature closest to 25°C as the zero point, the following numerical values were read, and SF 145℃ -SF 121℃ was calculated. SF 145℃ : Thermal shrinkage stress (MPa) at 145°C in the main orientation axis direction of the laminate SF 121℃ : Thermal shrinkage stress (MPa) at 121°C in the main orientation axis direction of the laminate.

[0074] (8) Loss tangent tanδ at 145°C in the main orientation axis direction (7) Using the main orientation axis direction of the laminate determined in (7) as the measurement direction, a test piece (width 5 mm × length 20 mm) cut out with the measurement direction as the long side was attached to the device chuck part in a 23°C atmosphere, cooled to a low temperature of -100°C, and the tanδ from -100°C to 180°C after the start of temperature increase was measured. A viscoelastic-temperature curve was drawn by the dynamic viscoelastic method, and the tanδ at each temperature was calculated. The test was performed with n = 3, and the average value of the obtained values was taken as the tanδ in the measurement direction. The measurement device and conditions are as follows. · Device: Rheogel-E4000 (manufactured by UBM) · Geometry: Tensile <00004​​​​​​​​​​​​​​​​​​​​The measurement direction was defined as the main orientation axis of the laminate as specified in (7), and a rectangle measuring 150 mm in length and 10 mm in width was sampled with the main orientation axis of the laminate as the longer side. Using the Orientec Co., Ltd. "Tensilon" (registered trademark) universal testing machine RTG-1210, the sample was set with an initial chuck distance of 120 mm so that the longer side was the tensile direction, and the elongation at the breaking point was determined from the length at the breaking point when the sample was pulled in the measurement direction at a tensile speed of 300 mm / min at room temperature. The elongation at the breaking point is (l-l0) / l0 × 100, where l0 is the length of the sample before the test and l is the length at the breaking point. The elongation at the breaking point T0 was measured without prior heat treatment. 130 The measurements were taken after placing the samples in an oven (ESPEC Corporation's Safety Oven SPHH-201 with a safety door) that was stable at a set temperature of 130°C for more than 10 minutes under a laboratory environment of 23°C and 50% RH, removing them after 10 minutes, and allowing them to return to room temperature.

[0076] (12) Analysis using FT-IR-ATR method: P1 / P2 Spectral measurements were performed using a 30mm x 30mm sample of the laminate, and predetermined peaks P1 and P2 were detected using the peak detection mode of the analysis software. The P1 / P2 ratio was calculated from the obtained values ​​of P1 and P2.

[0077] P1 / P2 was calculated at three points in different locations, and the values ​​of the three points were averaged to obtain the P1 / P2 for that sample. • Equipment: Fourier transform infrared spectrophotometer FT / IR-6100 (manufactured by JASCO Corporation) • Light source: High-brightness ceramic light source • Detector: TGS • Beam splitter: Ge / KBr • Measurement mode: ATR method (Ge prism, incident angle 45°) • Measurement wavefrequency range: 4,000 cm -1 ~600cm -1 ·Resolution: 4cm -1 • Total number of times: 32 • Analysis: Peaks were detected using the Spectra Manager Version 2 spectral analysis program.

[0078] (13) Water vapor transmission In accordance with Method B of JIS K7129 (2008), water vapor transmission was measured using a MOCON / Modern Controls water vapor transmission rate analyzer ("PERMATRAN" (registered trademark) W3 / 31) under conditions of 40°C and 90% RH humidity. Measurements were performed twice on each of two test specimens, and the average of the four measured values ​​was calculated to determine the water vapor transmission rate.

[0079] (14) Oxygen permeability The oxygen permeability was measured using a MOCON / Modern Controls oxygen permeability measuring device ("OXTRAN"® 2 / 20) in accordance with the isobaric method of JIS K7126-2 (2006) at a temperature of 23°C and a humidity of 90% RH. Measurements were performed twice on each of two test specimens, and the average of the four obtained measurements was calculated as the oxygen permeability.

[0080] (15) Retort processing For retort processing samples, a polyester-based dry laminating adhesive (DIC Graphics Co., Ltd.'s "DIC Dry®" LX-500 / KO55) with a solid content of 3.0 g / m² was applied to the coating layer of the laminate. 2 The material was coated in this manner and laminated with a 70 μm thick unoriented polypropylene film (CPP) (Toray Film Processing Co., Ltd.'s "Trefan®" ZK-207). Afterward, it was aged at 40°C for 3 days to obtain laminate samples for retort processing.

[0081] Next, the laminated samples for retort processing were subjected to retort processing in a high-temperature hot water bath at 121°C for 30 minutes using a high-temperature pressurized vessel.

[0082] Subsequently, measurements were performed in the same manner as described above for measuring water vapor permeability and oxygen permeability, and the water vapor permeability and oxygen permeability after retort treatment were obtained. The difference between the water vapor permeability and oxygen permeability before and after retort treatment, Δ, was calculated as: water vapor permeability after retort treatment - water vapor permeability of the laminate, and oxygen permeability after retort treatment - oxygen permeability of the laminate.

[0083] [Example 1] (Formation of a metal layer or inorganic compound layer) A 7nm aluminum oxide layer was formed as an inorganic compound layer on one side of a 12μm thick biaxially oriented polypropylene film (Toray Industries, Inc. polypropylene film, melting point 170℃, Sa21nm). The aluminum oxide layer was deposited using a reaction vapor deposition method in which aluminum is evaporated and then oxidized by introducing oxygen into the deposition area.

[0084] (Formation of the coating layer 1) Modified polyvinyl alcohol (special modified polyvinyl alcohol resin "Exceval" (registered trademark) RS-1717, manufactured by Kuraray Co., Ltd.) was added to a solvent of water / isopropyl alcohol in a mass ratio of 97 / 3, and heated and stirred at 90°C to obtain a water-soluble polymer solution with a solid content of 10% by mass. Next, 10.6 g of 0.02 N hydrochloric acid aqueous solution was added dropwise to a solution of 6.7 g of tetraethoxysilane (TEOS) and 2.7 g of methanol, and stirred to obtain a TEOS hydrolysate. The water-soluble polymer solution and the TEOS hydrolysate were mixed so that the ratio of the modified polyvinyl alcohol solid content to the SiO2 equivalent mass of TEOS was 35 / 65. The mixture was diluted with water to a total solid content of 13% by mass to prepare a coating agent, which was applied to the above-mentioned aluminum oxide layer and dried at 100°C to obtain a laminate.

[0085] [Example 2] A laminate was obtained in the same manner as in Example 1, except that the coating agent was applied, dried, and then aged at 40°C for 3 days.

[0086] [Example 3] A laminate was obtained in the same manner as in Example 2, except that the formation of the coating layer was 2.

[0087] (Formation of the coating layer 2) Polyvinyl alcohol (hereinafter sometimes abbreviated as PVA, POVA 28-98 manufactured by Kuraray Co., Ltd.) was added to a solvent of water / isopropyl alcohol in a mass ratio of 97 / 3, and heated and stirred at 90°C to obtain a water-soluble polymer solution with a solid content of 10% by mass. Next, 5.3 g of 0.02 N hydrochloric acid aqueous solution was added dropwise to a solution of 6.7 g of TEOS and 8.0 g of methanol, and stirred to obtain a TEOS hydrolysate. The water-soluble polymer solution and the TEOS hydrolysate were mixed so that the ratio of the PVA solid content of the water-soluble polymer solution to the SiO2 equivalent mass of TEOS was PVA solid content / SiO2 equivalent mass = 35 / 65. The mixture was diluted with water to a total solid content of 13% by mass to prepare a coating agent, which was applied to the above-mentioned aluminum oxide layer and dried at 100°C to obtain a laminate.

[0088] [Example 4] A laminate was obtained in the same manner as in Example 2, except that the formation of the coating layer was 3.

[0089] (Formation of the coating layer 3) Polyvinyl alcohol (Poval 28-98, manufactured by Kuraray Co., Ltd.) was added to a solvent of water / isopropyl alcohol in a mass ratio of 97 / 3, and heated and stirred at 90°C to obtain a water-soluble polymer solution with a solid content of 10% by mass. Next, 2.1 g of 0.02 N hydrochloric acid aqueous solution was added dropwise to a solution of 6.7 g of TEOS and 11.2 g of methanol, and stirred to obtain a TEOS hydrolysate. The water-soluble polymer solution and the TEOS hydrolysate were mixed so that the ratio of the PVA solid content of the water-soluble polymer solution to the SiO2 equivalent mass of TEOS was PVA solid content / SiO2 equivalent mass = 35 / 65. The mixture was diluted with water to a total solid content of 13% by mass to prepare a coating agent, which was applied to the aforementioned aluminum oxide layer and dried at 100°C to obtain a laminate.

[0090] [Example 5] A laminate was obtained in the same manner as in Example 2, except that the formation of the coating layer was 4.

[0091] (Formation of the coating layer 4) Polyvinyl alcohol (Poval 28-98, manufactured by Kuraray Co., Ltd.) was added to a solvent of water / isopropyl alcohol in a mass ratio of 97 / 3, and heated and stirred at 90°C to obtain a water-soluble polymer solution with a solid content of 10% by mass. Next, 10.6 g of 0.01 N hydrochloric acid aqueous solution was added dropwise to a solution of 6.7 g of TEOS and 11.2 g of methanol, and stirred to obtain a TEOS hydrolysate. The water-soluble polymer solution and the TEOS hydrolysate were mixed so that the ratio of the PVA solid content of the water-soluble polymer solution to the SiO2 equivalent mass of TEOS was PVA solid content / SiO2 equivalent mass = 35 / 65. The mixture was diluted with water to obtain a coating agent with a total solid content of 13% by mass, applied to the aforementioned aluminum oxide layer, and dried at 100°C to obtain a laminate.

[0092] [Example 6] A laminate was obtained in the same manner as in Example 5, except that the coating agent was applied, dried, and then aged at 60°C for 3 days.

[0093] [Example 7] A laminate was obtained in the same manner as in Example 2, except that the formation of the coating layer was 5.

[0094] (Formation of the coating layer 5) Polyvinyl alcohol (Poval 28-98, manufactured by Kuraray Co., Ltd.) was added to a solvent of water / isopropyl alcohol in a mass ratio of 97 / 3, and heated and stirred at 90°C to obtain a water-soluble polymer solution with a solid content of 10% by mass. Next, 10.6 g of 0.004 N hydrochloric acid aqueous solution was added dropwise to a solution of 6.7 g of TEOS and 11.2 g of methanol, and stirred to obtain a TEOS hydrolysate. The water-soluble polymer solution and the TEOS hydrolysate were mixed so that the ratio of the PVA solid content of the water-soluble polymer solution to the SiO2 equivalent mass of TEOS was PVA solid content / SiO2 equivalent mass = 35 / 65. The mixture was diluted with water to a total solid content of 13% by mass to prepare a coating agent, which was applied to the aforementioned aluminum oxide layer and dried at 100°C to obtain a laminate.

[0095] [Example 8] A laminate was obtained in the same manner as in Example 2, except that the formation of the coating layer was 6.

[0096] (Formation of the coating layer 6) Polyvinyl alcohol (Poval 28-98, manufactured by Kuraray Co., Ltd.) was added to a solvent of water / isopropyl alcohol in a mass ratio of 97 / 3, and heated and stirred at 90°C to obtain a water-soluble polymer solution with a solid content of 10% by mass. Next, 10.6 g of 0.02 N hydrochloric acid aqueous solution was added dropwise to a solution of 6.7 g of TEOS and 2.7 g of methanol, and the mixture was cooled and stirred to a temperature of 20°C to obtain a TEOS hydrolysate. The water-soluble polymer solution and the TEOS hydrolysate were mixed so that the ratio of the PVA solid content of the water-soluble polymer solution to the SiO2 equivalent mass of TEOS was PVA solid content / SiO2 equivalent mass = 35 / 65. The mixture was diluted with water to a total solid content of 13% by mass to prepare a coating agent, which was applied to the aforementioned aluminum oxide layer and dried at 100°C to obtain a laminate.

[0097] [Example 9] A laminate was obtained in the same manner as in Example 5, except that the polyvinyl alcohol in the coating layer was replaced with a special modified polyvinyl alcohol resin "Exceval" (registered trademark) RS-1717 manufactured by Kuraray Co., Ltd.

[0098] [Example 10] A laminate was obtained in the same manner as in Example 7, except that the polyvinyl alcohol in the coating layer was replaced with a special modified polyvinyl alcohol resin "Exceval" (registered trademark) RS-1717 manufactured by Kuraray Co., Ltd.

[0099] [Examples 11 and 12] Laminates were obtained in the same manner as in Example 3, except that the ratio of PVA solids to the SiO2 equivalent mass of TEOS hydrolysate was changed in the preparation of the coating for the coating layer as shown in the table.

[0100] [Examples 13 and 14] Laminates were obtained in the same manner as in Example 3, except that the drying temperature of the coating layer was changed as shown in the table.

[0101] [Examples 15 and 16] Laminates were obtained in the same manner as in Example 3, except that the coating thickness of the coating layer was changed as shown in the table.

[0102] [Example 17] A laminate was obtained in the same manner as in Example 3, except that the biaxially oriented polypropylene film was changed to a biaxially oriented polypropylene film with a melting point of 168°C and a Sa of 14 nm.

[0103] [Example 18] A laminate was obtained in the same manner as in Example 3, except that an undercoat layer was formed on one side of a biaxially oriented polypropylene film before forming an inorganic compound layer. The undercoat layer was formed by the following procedure: 100 parts by mass of "Hydran" (registered trademark) AP-201 (manufactured by DIC Corporation, solid content concentration 23% by mass), a polyester urethane-based water-dispersible resin, was mixed with 6 parts by mass of the melamine compound "Amidia" (registered trademark) APM (manufactured by DIC Corporation) as a crosslinking agent, and 1 part by mass of "Catalyst" PTS (manufactured by DIC Corporation), a water-soluble acidic compound, as a crosslinking catalyst. Then, pure water was added to adjust the overall solid content concentration to 10% by mass to obtain a mixed coating. This mixed coating was applied to one side of a biaxially oriented polypropylene film and dried at 100°C to form an undercoat layer with a thickness of 700 nm.

[0104] [Comparative Example 1] A laminate was obtained in the same manner as in Example 2, except that no metal layer or inorganic compound layer was formed.

[0105] [Comparative Example 2] A laminate was obtained in the same manner as in Example 1, except that the polyvinyl alcohol-based resin of the coating layer was polyvinyl alcohol (Poval 28-98, manufactured by Kuraray Co., Ltd.).

[0106] [Comparative Example 3] A laminate was obtained in the same manner as in Example 2, except that the polyvinyl alcohol-based resin of the coating layer was polyvinyl alcohol (Poval 28-98 manufactured by Kuraray Co., Ltd.).

[0107] [Comparative Examples 4 and 5] Laminates were obtained in the same manner as in Comparative Example 3, except that the aging treatment conditions after coating and drying were changed as shown in the table.

[0108] [Comparative Example 6] A laminate was obtained in the same manner as in Comparative Example 3, except that the drying temperature of the coating agent during the formation of the coating layer was 160°C.

[0109] [Comparative Example 7] A laminate was obtained in the same manner as in Comparative Example 3, except that the formation of the coating layer was 7.

[0110] (Formation of the coating layer 7) Polyvinyl alcohol (Poval 28-98, manufactured by Kuraray Co., Ltd.) was added to a solvent of water / isopropyl alcohol in a mass ratio of 97 / 3, and heated and stirred at 90°C to obtain a water-soluble polymer solution with a solid content of 10% by mass. Next, 10.6 g of 0.06 N hydrochloric acid aqueous solution was added dropwise to a solution of 6.7 g of TEOS and 2.7 g of methanol, and stirred to obtain a TEOS hydrolysate. The water-soluble polymer solution and the TEOS hydrolysate were mixed so that the ratio of the PVA solid content of the water-soluble polymer solution to the SiO2 equivalent mass of TEOS was PVA solid content / SiO2 equivalent mass = 35 / 65. The mixture was diluted with water to obtain a coating agent with a total solid content of 13% by mass, applied to the aforementioned aluminum oxide layer, and dried at 100°C to obtain a laminate.

[0111] [Table 1]

[0112] [Table 2]

[0113] [Table 3] [Explanation of symbols]

[0114] 1. Resin film 2. Metal layer and / or inorganic oxide layer 3 Covering layer

Claims

1. A laminate having a metal layer and / or an inorganic compound layer and a coating layer in this order on at least one surface of a polyolefin resin film, The coating layer contains a polyvinyl alcohol-based resin backbone and a siloxane compound. A laminate that satisfies requirements 1 and 2 below. Requirement 1: A1 / (A1+A2) is between 0.50 and 0.

85. Requirement 2: [B1 / (B1+B2)-A1 / (A1+A2)] is 0.10 or less. A1: Area of ​​Raman bands showing the network structure derived from siloxane compounds, obtained by measuring the coating layer using laser Raman spectroscopy. A2: Area of ​​Raman bands showing linear polysiloxane structures and cyclic siloxanes with four or fewer members, obtained by measuring the coating layer using laser Raman spectroscopy. B1: Area of ​​Raman bands showing the network structure obtained by measuring the coating layer by laser Raman spectroscopy after heat treatment at 121°C for 30 minutes. B2: After heat treatment at 121°C for 30 minutes, the area of ​​Raman bands indicating the linear polysiloxane structure and cyclic siloxanes with four or fewer members was measured by laser Raman spectroscopy of the coating layer.

2. The stress in the principal orientation axis direction at 121°C, measured by thermomechanical analysis (TMA), is defined as SF. １２１℃ The stress at 145° in the direction of the main orientation axis is SF １４５℃ When that happens, SF １４５℃ -SF １２１℃ The laminate according to claim 1, wherein the pressure is ≤ 2.50 MPa.

3. The laminate according to claim 1 or 2, wherein the loss tangent tanδ at 145°C in the direction of the principal orientation axis is 0.25 or less.

4. The elongation at the fracture point in the direction of the principal orientation axis is T. ０ The elongation at the break point in the principal orientation axis direction, measured after heat-treating the laminate at 130°C for 10 minutes, is defined as T. １３０ In that case, T ０ / T １３０ The laminate according to claim 1 or 2, wherein the value of is 1.20 or less.

5. The laminate according to claim 1 or 2, wherein the ratio P1 / P2 of the following peak intensities P1 and P2 detected by measuring the coating layer using the FT-IR-ATR method (total reflection Fourier transform infrared spectroscopy) is 3.5 or more and 8.0 or less. P1: 1,050 to 1,080 cm －１ The intensity of the maximum peak present P2: 920-970cm －１ The intensity of the maximum peak present

6. The laminate according to claim 1 or 2, wherein B1 / (B1+B2)-A1 / (A1+A2) is 0.08 or less.

7. The water vapor permeability of the laminate is 1.0 g / m². ２ Less than 24hr and with an oxygen permeability of 1.0 cc / m³ ２ The laminate according to claim 1 or 2, wherein the ferrous film is 24hr or less.

8. The laminate according to claim 1 or 2, wherein the thickness of the coating layer is 200 nm or more and 600 nm or less.

9. The laminate according to claim 1 or 2, wherein the metal layer or inorganic compound layer comprises aluminum.

10. A packaging body having the laminate according to claim 1 or 2.

Images