Laminate and packaging using same

Abstract

To provide a laminate with good high-speed filling suitability even if it contains paper, and packages using the laminate.SOLUTION: A laminate 10 is a laminate comprising a paper base material layer 11, a barrier adhesive layer 14, a metal or inorganic oxide deposition layer 13, and a sealant layer 12, in this order. The basis weight of the paper base material layer 11 is 25 g / m2 or more and 150 g / m2 or less, and the innermost layer of the sealant layer 12 contains mainly propylene-based resin, and when the surface of the innermost layer of the sealant layer 12 is measured by the reflectance infrared absorption spectroscopy, a maximum value p1 of the absorption peak at 2945 cm-1 or more and 2960 cm-1 or less and a maximum value p2 of the absorption peak at 2910 cm-1 or more and 2920 cm-1 or less are found, and an absorption intensity ratio P, defined as an absorption intensity ratio of P=p2 / p1, is 1.5 or more and 5.0 or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a laminate and a package using the same. [Background technology]

[0002] In order to design packaging for food products, daily necessities, and the like with consideration for the environment, it has been proposed to use paper, which is a renewable material (see, for example, Patent Document 1). Furthermore, from the viewpoint of reducing the environmental impact, there is a demand to increase the proportion of paper used in packaging, and as a result, there is a trend toward thicker paper in laminates containing paper. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-130470 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when laminating a laminate using paper, heat sealing cannot be performed at low temperatures and high speeds compared to lamination using only plastic films, and high-speed filling suitability is poor. In particular, as the thickness of the paper increases, the heat insulation properties of the paper increase, preventing the heat from heat sealing from reaching the sealant layer sufficiently. This results in processing defects and requires a long processing time to sufficiently transfer the heat to the sealant layer.

[0005] An object of the present disclosure is to provide a laminate that has good suitability for high-speed filling even when it contains paper, and a package using the same. [Means for solving the problem]

[0006] The present disclosure solves the above-mentioned problems by the following means: For ease of understanding, the following description will be given with reference numerals corresponding to the embodiments of the present disclosure, but the present disclosure is not limited to these.

[0007] The first disclosure is a laminate (10) comprising a paper substrate layer (11), a barrier adhesive layer (14), a vapor-deposited layer of a metal or inorganic oxide (13), and a sealant layer (12) in this order, and the basis weight of the paper substrate layer (11) is 25 g / m 2 More than 150g / m 2 The innermost layer of the sealant layer (12) mainly contains a propylene-based resin, and when the surface of the innermost layer of the sealant layer (12) is measured by reflection infrared absorption spectroscopy, the -1 More than 2960cm -1 The maximum absorption peak p1 at 2910 cm -1 More than 2920cm -1 and a maximum value p2 of the absorption peak in the following range, and the absorption intensity ratio P defined by the following formula (1) is 1.5 or more and 5.0 or less. Absorption intensity ratio P = p2 / p1 Equation (1)

[0008] A second disclosure is the laminate (10) according to the first disclosure, in which the absorption intensity ratio P is 3.0 or more and 4.0 or less.

[0009] A third disclosure is the laminate (10) according to the first or second disclosure, wherein the innermost layer of the sealant layer (12) has a first melting point peak of 100°C or higher and 130°C or lower and a second melting point peak of 140°C or higher and 170°C or lower when measured by differential thermal analysis (DSC).

[0010] The fourth disclosure states that the oxygen permeability measured at 23°C and 90% RH in accordance with JIS K 7126-2 is 3.0 cc / m 2 The laminate (10) according to any one of the first to third disclosures, wherein the thermal conductivity is 1 / day / atm or less.

[0011] The fifth disclosure is a method for manufacturing a paper substrate layer (11) of 1 m 2 The mass per unit area of ​​the sealant layer (12) including the vapor deposition layer (13) is t1. 2 The laminate (10) according to any one of the first to fourth disclosures satisfies 1.0≦t1 / t2≦3.0, where t2 is the mass per unit area.

[0012] The sixth disclosure is that the basis weight of the paper base layer (11) is 35 g / m 2 More than 100g / m 2 The laminate (10) is described in any one of the first to fifth disclosures below.

[0013] A seventh disclosure is the laminate (10) according to any one of the first to sixth disclosures, wherein the barrier adhesive layer (14) is a cured product of a resin composition containing a resin having two or more hydroxyl groups per molecule and an isocyanate compound having two or more isocyanate groups per molecule, the main skeleton of the resin being polyester or polyester polyurethane, and containing an ortho-oriented aromatic dicarboxylic acid or an anhydride thereof as a polyester-constituting monomer component.

[0014] An eighth disclosure is a packaging body (1) formed using the laminate (10) according to any one of the first to seventh disclosures.

[0015] The ninth disclosure is the packaging body (1) according to the eighth disclosure, in which the weight ratio of paper in the entire packaging body (1) is the largest among the materials constituting the packaging body (1). [Effects of the Invention]

[0016] According to the present disclosure, it is possible to provide a laminate that has good suitability for high-speed filling even when it contains paper, and a package using the same. [Brief explanation of the drawings]

[0017] [Figure 1] 1A and 1B show examples of cross-sectional views of a first stack and a second stack according to the present disclosure. [Figure 2] 1 is a diagram showing a package using the laminate of the present embodiment. FIG. [Figure 3] 10A and 10B are diagrams showing another example of a package using the laminate of the present embodiment. [Figure 4] 10A and 10B are diagrams showing another example of a package using the laminate of the present embodiment. [Figure 5] 10A and 10B are diagrams showing another example of a package using the laminate of the present embodiment. [Figure 6] 10A and 10B are diagrams showing another example of a package using the laminate of the present embodiment. [Figure 7] FIG. 1 is a diagram summarizing the results of evaluation of barrier properties, hand tearability, and dead hold properties for laminate examples and reference examples. [Figure 8] FIG. 1 is a diagram showing the results of measuring the water vapor permeability (water vapor barrier) under the same conditions as in Test Example 1. [Figure 9] 1 is a chart showing the results of measuring the absorption peak in a reflection ATR method from the sealant layer surface side (sealing surface side) opposite the deposition layer of aluminum-deposited CPP film 1. [Figure 10] 1 is a temperature rise chart showing a DSC curve of a sample taken from the sealant layer surface side of aluminum vapor-deposited CPP film 1. [Figure 11] 1 is a chart showing the results of measuring the absorption peak in a reflection ATR method from the sealant layer surface side (sealing surface side) opposite the deposition layer of aluminum-deposited CPP film 2. [Figure 12] 1 is a temperature rise chart showing a DSC curve of a sample taken from the sealant layer surface side of aluminum-deposited CPP film 2. [Figure 13] 1 is a chart showing the results of measuring the absorption peak in a reflection ATR method from the sealant layer surface side (sealing surface side) opposite the deposition layer of aluminum-deposited CPP film 3. [Figure 14] 1 is a temperature rise chart showing a DSC curve of a sample taken from the sealant layer surface side of aluminum-deposited CPP film 3. [Figure 15] 1 is a diagram summarizing the measurement results of the seal strength in Example 1, Comparative Example 1, and Comparative Example 2. [Figure 16] 16 is a chart showing the seal strength curves of Example 1, Comparative Example 1, and Comparative Example 2. The horizontal axis of Fig. 16 is the seal temperature (unit: °C), and the vertical axis is the seal strength (unit: N / 15 mm). [Figure 17] FIG. 1 is a diagram showing the results of evaluation of the processability of thermal lamination for Examples and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION

[0018] The laminate according to the present invention will be described with reference to the drawings, in which an example of a cross-sectional view of the laminate according to the present invention is shown in FIG. <Laminate of the embodiment> The laminate 10 is a packaging material used, for example, to package food products, etc. As shown in Fig. 1 , the laminate 10 according to an embodiment of the present invention has a paper substrate layer 11, a sealant layer 12 having a vapor deposition layer 13 provided on one side of the paper substrate layer 11, and a barrier adhesive layer 14 having barrier properties that bonds the vapor deposition layer 13 to the paper substrate layer 11. That is, the laminate 10 has the paper substrate layer 11, the barrier adhesive layer 14, the vapor deposition layer 13, and the sealant layer 12 laminated in this order. Each layer constituting the laminate 10 will be described below.

[0019] (Paper base layer) The paper substrate layer 11 is a substrate layer that supports the sealant layer 12 having the vapor deposition layer 13, and the basis weight of the paper substrate layer 11 is 25 g / m 2 More than 150g / m 2 The paper base layer 11 preferably has a basis weight of 100 g / m or less. 2 Unlike base paper for cups of paper cups larger than 100 mm or base paper for milk cartons for paper containers, it is more preferable that the base paper be a flexible paper substrate that constitutes so-called soft paper packaging. Specifically, the paper substrate layer has a basis weight of 35 g / m 2 More than 100g / m 2 Preferably, it is 40 g / m or less. 2 More than 70g / m 2 It is more preferable that the basis weight of the paper base layer is 35 g / m or less. 2 More than 100g / m2 When the thickness is below this, the paper substrate layer 11 has high mechanical strength, excellent hand tearability and deadholdability, and flexibility suitable for use as a packaging body such as a packaging bag. Examples of the paper substrate layer 11 include kraft paper, fine paper, coated paper, and paper with barrier properties (barrier coated paper).

[0020] Here, on the surface of the paper substrate layer 11 opposite to the barrier adhesive layer 14, a pattern layer and a surface layer may be provided in this order as required. (Picture layer) The picture layer is a printed layer on which a picture is printed, and is provided on the surface of the paper base layer 11 opposite to the barrier adhesive layer 14. Here, the picture refers to a recording object in various forms that can be recorded or printed on the paper base layer 11, and is not particularly limited and broadly includes figures, letters, designs, patterns, symbols, patterns, marks, etc. In particular, when the laminate 10 is used for packaging such as packaging bags intended to contain food, a picture of the contents or letters indicating information such as the product name, expiration date, production date, and production number of the contents are used as the picture.

[0021] (Surface layer) The surface layer is a layer provided on the pattern layer, and is the layer located furthest outward from the container when the laminate 10 is used in a package such as a packaging bag. The surface layer is formed, for example, from overprint varnish (OP varnish), and can prevent the pattern layer from being lost due to rubbing or the like, and can prevent the pattern from being tampered with. In the above description, an example has been described in which a design layer and a surface layer are sequentially provided on the paper base layer 11, but the design layer and the surface layer may be omitted as appropriate, if necessary.

[0022] (sealant layer) The sealant layer 12 is a layer that appears on the surface of the laminate 10 opposite the paper base layer 11. When the laminate 10 is used to form a package such as a packaging bag, the sealant layer 12 is the innermost layer and has heat-sealing properties that allow it to adhere when heated. In addition, a vapor deposition layer 13 is provided on the sealant layer 12 on the paper base layer 11 side. Details of the vapor deposition layer 13 will be described later.

[0023] The sealant layer 12 may be a single layer. Alternatively, the sealant layer 12 may include multiple layers. For example, the sealant layer 12 may include, in order from the vapor deposition layer 13 side, a first layer, a second layer, and a third layer. In this case, the innermost layer is the entire sealant layer in the case of a single layer, the second layer in the case of two layers, and the third layer in the case of three layers.

[0024] The total thickness of the sealant layer 12 is preferably 20 μm or more, more preferably 25 μm or more, and is preferably 60 μm or less, more preferably 40 μm or less.

[0025] If the thickness of sealant layer 12 is 20 μm or more, heat seal strength can be maintained particularly in areas where three or more laminates overlap (for example, areas where the spine seal overlaps with the top or bottom seal) when, for example, a packaging bag 1A (see FIG. 2) described below is produced using laminate 10. Furthermore, by setting the thickness of sealant layer 12 to 60 μm or less, excellent hand-tearability and dead-holdability can be maintained.

[0026] The innermost layer of the sealant layer 12 mainly contains a propylene-based resin. It may further contain an ethylene-based resin. Here, "mainly" means that the proportion of the propylene-based resin in the innermost layer is 51% by mass or more. The proportion of the propylene-based resin in the innermost layer may be 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more. When a propylene-based resin and an ethylene-based resin are mixed, the ratio thereof may be 100:1-49, 100:1-40, 100:1-30, 100:1-20, or 100:1-10, in parts by mass.

[0027] The propylene-based resin constituting the innermost layer may be any of homopolypropylene, random copolymer polypropylene, and block copolymer polypropylene, but random copolymer propylene is preferred from the viewpoints of low-temperature sealing property and transparency. Random copolymer propylene is a random copolymer containing propylene and an α-olefin other than propylene. For example, the random copolymer contains, in addition to propylene, ethylene, butene-1, 4-methyl-1-pentene, etc. For example, the random copolymer propylene includes an ethylene-propylene random copolymer. The random copolymer propylene may also include a terpolymer.

[0028] The propylene-based resin may contain biomass-derived polypropylene or may contain mechanically recycled or chemically recycled polypropylene.

[0029] When a polyethylene-based resin is contained in the innermost layer, the polyethylene-based resin may be an ethylene homopolymer or a copolymer of ethylene and an α-olefin (hereinafter also referred to as an ethylene-α-olefin copolymer). The content of the α-olefin in the ethylene-α-olefin copolymer is preferably 5 mol % or less.

[0030] The mass ratio of polyethylene in the innermost layer may be 1% or more, 5% or more, or 10% or more, and may be 30% or less, 25% or less, or 20% or less.

[0031] Ethylene homopolymers include, for example, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), etc. High density polyethylene has a density of 0.942 g / cm 3 Medium density polyethylene is polyethylene with a density of 0.930 g / cm or more. 3 More than 0.942g / cm 3 Low density polyethylene is polyethylene having a density of less than 0.910 g / cm3 More than 0.930g / cm 3 It is a polyethylene having a density of less than 1000 kJ / cm2. The density is measured in accordance with Method B (pycnometer method) or Method D (density gradient tube method) of JIS K7112:1999. The choice between Method B and Method D is made depending on the shape and mass of the test piece to be measured. When Method D is selected, the measurement temperature (liquid temperature) is 23°C.

[0032] An example of an ethylene-α-olefin copolymer is linear polyethylene. Linear polyethylene is a copolymer of ethylene and an α-olefin polymerized using a multi-site catalyst, such as a Ziegler-Natta catalyst, or a single-site catalyst, such as a metallocene catalyst. Linear polyethylene is distinguished from ethylene homopolymers. The α-olefins that serve as monomers for linear polyethylene have three or more carbon atoms. Examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 4-methylpentene, 3,3-dimethylbutene, and mixtures thereof.

[0033] [Absorption peaks in reflection ATR method] When the surface of the innermost layer of the sealant layer 12 was measured by reflection infrared absorption spectroscopy, -1 More than 2960cm -1 The maximum absorption peak p1 at 2910 cm -1 More than 2920cm -1 and the absorption intensity ratio P defined by the following formula (1) is 1.5 or more and 5.0 or less, preferably 3.0 or more and 4.0 or less. Absorption intensity ratio P = p2 / p1 Equation (1)

[0034] Here, the absorption peak including the maximum value p1 is a vibration peak attributed to the antisymmetric stretching of CH3- (methyl group) in the side chain of the propylene-based resin. Typically, it is 2945 cm -1 Over 2955cm -1The absorption peak p2, including the maximum value p2, is a vibration peak attributed to the CH antisymmetric stretching of -CH2- (methylene group) in the main chain of ethylene-based resins and propylene-based resins. Typically, it is at 2915 cm -1 The absorption peak is around

[0035] Therefore, the absorption intensity ratio P defined by p2 / p1 reflects the ratio of methylene groups derived from propylene-based resins and ethylene-based resins to methyl groups derived from propylene-based resins, and the larger the absorption intensity ratio P, the higher the proportion of methylene groups derived from ethylene units. If the lower limit is less than 1.5, the low-temperature sealability will be poor due to the small number of ethylene units. If the upper limit is more than 5.0, the high number of ethylene units will result in poor oil resistance, making it necessary to carefully select the contents. The reflection infrared absorption spectroscopy (ATR) was measured using, for example, a Nicolet iS5 device manufactured by Thermo Fisher Scientific, with eight accumulations. In the reflection ATR, the measurement target is a depth of several microns from the surface.

[0036] [DSC curve] When the innermost layer of the sealant layer 12 is measured by differential scanning calorimetry (DSC), it has a first melting point peak of 100°C to 130°C and a second melting point peak of 140°C to 170°C. The first melting point peak is derived from the ethylene units in the propylene-based resin and the ethylene-based resin and is at 100°C to 130°C, preferably 120°C to 130°C. The second melting point peak is derived from the propylene-based resin and is at 140°C to 170°C, preferably 140°C to 160°C, more preferably 140°C to 150°C. The second melting point peak is, for example, a melting point peak specific to random copolymerized propylene.

[0037] The melting point peak can be determined by analyzing the innermost layer of the sealant layer using a differential scanning calorimeter in accordance with JIS K7121:2012. For example, in a nitrogen atmosphere, a sample is heated from 20°C to a holding temperature at a heating rate of 10°C / min. The holding temperature is a temperature sufficiently higher than the melting point, e.g., 200°C. The sample is then heated at the holding temperature for 10 minutes. Thereafter, the sample is cooled from the holding temperature to 20°C at a heating rate of 10°C / min. This heating, holding, and cooling process is repeated once more. The differential scanning calorimeter can be, for example, a thermal analyzer from Hitachi High-Tech Science Corporation's TA7000 series.

[0038] The sealant layer 12 may contain additives, such as antioxidants, antiblocking agents, and neutralizing agents.

[0039] Examples of antioxidants include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, vitamin E-based antioxidants, and amine-based antioxidants.

[0040] Examples of phenolic antioxidants include 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxy)benzene, n-octadecyl-β-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis-3-(3-t-butyl-4-hydroxyphenyl)propionate, -5-methylphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1,1-dimethyl-2-[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]-undecane, bis-[3,3-bis-(4'-hydroxy-3'-t-butylphenyl)-butanoic acid)-glycol ester, butylhydroxytoluene (BHT), and the like can be mentioned. Examples of phosphorus-based antioxidants include tris(2,4-di-t-butylphenyl)phosphite, distearyl pentaerythritol diphosphite, cyclic neopentanetetraylbis(2,6-di-t-butyl-4-methylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, and triphenyl phosphite (TPP). Examples of sulfur-based antioxidants include dioctadecyl disulfide and distearyl thiodipropionate (DSTDP). Examples of vitamin E antioxidants include 2,5,7,8-tetramethyl-2(4',8',12'-trimethyltridecyl)chroman-6-ol. An example of the amine-based antioxidant is phenyl-β-naphthylamine (PBN).

[0041] The antiblocking agent, for example, forms irregularities on the surface of the sealant layer 12, thereby preventing adhesion of the laminate 10 to itself when the laminate 10 including the sealant layer 12 is wound into a roll. Examples of the antiblocking agent include calcium carbonate, silicon dioxide, and synthetic zeolite.

[0042] The neutralizing agent has the effect of suppressing the reaction between the polyethylene or the copolymer of ethylene and an α-olefin and the additives. Examples of the neutralizing agent include calcium stearate.

[0043] A primer layer may be formed on the side of the sealant layer 12 on which the vapor deposition layer 13 is to be disposed. The primer layer can improve adhesion of the vapor deposition layer 13 to the sealant layer 12. The primer layer may contain, for example, a urethane-based resin, a cellulose-based resin, etc. The primer layer may be formed, for example, by applying a solution containing materials constituting the primer layer and drying it. The thickness of the primer layer is, for example, 0.1 μm or more, or may be 0.5 μm or more, or may be 1.0 μm or more. The thickness of the primer layer is, for example, 5.0 μm or less, or may be 4.0 μm or less, or may be 3.0 μm or less.

[0044] (deposited layer) The vapor-deposited layer 13 is a barrier layer provided to suppress the transmission of oxygen and water vapor through the laminate 10. As described above, the vapor-deposited layer 13 of this embodiment is provided on the surface of the sealant layer 12 facing the paper substrate layer 11, and is formed of a metal or an inorganic oxide. In the present invention, the vapor-deposited layer refers to a film formed by a vapor deposition method in a broad sense, and includes not only films formed by vacuum deposition but also films formed by sputtering or the like.

[0045] Here, examples of metals that can be used for the vapor-deposited layer 13 include aluminum (Al), magnesium (Mg), tin (Sn), sodium (Na), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), gold (Au), and chromium (Cr). In particular, for packaging, it is preferable to have an aluminum vapor-deposited film.

[0046] Examples of inorganic oxides used for the vapor-deposited layer 13 include metal oxides of the above metals such as aluminum oxide and titanium oxide, as well as silica, which is an oxide of silicon (Si). In particular, for packaging, it is preferable to provide a vapor-deposited film of aluminum oxide.

[0047] The thickness of the vapor-deposited layer 13 varies depending on the type of metal used, but is desirably selected from the range of, for example, 50 to 2000 Å, preferably 100 to 1000 Å. More specifically, in the case of an aluminum vapor-deposited film, the thickness is desirably 50 to 600 Å, more preferably 100 to 450 Å.

[0048] Examples of methods for forming the deposition layer 13 include physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, and ion plating, and chemical vapor deposition (CVD) methods such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition.

[0049] The vapor deposition layer 13 can be formed, for example, by applying the above-mentioned metal or inorganic oxide directly to the sealant layer 12 by the above-mentioned vacuum vapor deposition method or the like. When the vapor-deposited layer 13 is provided directly on the sealant layer 12 as described above, the surface of the sealant layer 12 can be pretreated as needed. Specifically, the surface can be pretreated by physical treatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, or glow discharge treatment, or chemical treatments such as oxidation treatment using chemicals. When the vapor-deposited layer 13 is provided directly on the sealant layer 12, a commercially available product, such as ML-TUX F manufactured by Mitsui Chemicals Tohcello, Inc., can be used as the sealant layer 12 having the vapor-deposited layer 13. The thickness of the sealant layer 12 on which the vapor-deposited layer 13 is directly formed is desirably 20 μm to 40 μm in total. The sealant layer 12 having the vapor deposition layer 13 is not limited to the above-described form, and for example, an intermediate layer serving as an anchor layer that strengthens the adhesion between the sealant layer 12 and the vapor deposition layer 13 may be further provided between the sealant layer 12 and the vapor deposition layer 13.

[0050] The oxygen permeability of the sealant layer 12 including the vapor-deposited layer 13, measured at 23°C and 90% RH in accordance with JIS K 7126-2, is, for example, 15 cc / m when an aluminum-deposited polyethylene film (ML-TUX F, manufactured by Mitsui Chemicals Tocello, Inc., thickness 30 μm) is used. 2 / day / atm or more, 25cc / m 2 / day / atm or less, and the oxygen barrier property is insufficient. Therefore, it is necessary to improve the oxygen barrier property by combining it with a barrier adhesive layer, which will be described later.

[0051] (Barrier adhesive layer) The barrier adhesive layer 14 is a layer made of an adhesive with barrier properties that suppress the transmission of oxygen and water vapor, and is provided between the paper base layer 11 and the vapor-deposited layer 13 to bond the paper base layer 11 and the vapor-deposited layer 13. The barrier adhesive layer 14 is provided to further suppress the oxygen and water vapor that permeates the laminate that cannot be suppressed by the vapor-deposited layer 13. Specifically, a fine uneven shape is formed on the surface of the vapor-deposited layer 13, and at the fine level, the thickness of the vapor-deposited layer 13 is not uniform, and the barrier property is low in relatively thin parts, resulting in non-uniform barrier property overall. However, when the barrier adhesive layer 14 comes into contact with the vapor-deposited layer 13, the uneven shape is filled in and flattened, making the barrier property uniform and further enhancing the effect of suppressing the transmission of oxygen and water vapor.

[0052] The barrier adhesive layer 14 is preferably a urethane-based adhesive having urethane bonds, which is a cured product of a resin composition containing a resin (polyol) having two or more hydroxyl groups per molecule and an isocyanate compound (polyisocyanate) having two or more isocyanate groups per molecule. The urethane-based adhesive is preferably a two-component curing type. Examples of methods for imparting barrier properties to the resin composition include a method of introducing a skeleton having barrier properties into the resin constituting the resin composition (barrier organic adhesive), a method of incorporating a phosphate-modified compound into the resin composition, and a method of incorporating a plate-like inorganic compound into the resin composition (barrier inorganic adhesive), and one or more of these methods can be combined.

[0053] As a method for introducing a skeleton having barrier properties into the resin constituting the above-mentioned resin composition, it is preferable that the main skeleton of the resin (polyol) is polyester or polyester polyurethane, and that the polyester-constituting monomer component contains an ortho-oriented aromatic dicarboxylic acid or its anhydride.

[0054] The resin has two or more hydroxyl groups in one molecule and a main skeleton of a polyester structure or a polyester polyurethane structure. The polyester portion of the main skeleton structure is obtained by polycondensation reaction of a polycarboxylic acid and a polyhydric alcohol by a known, commonly used method. Examples of polycarboxylic acids include aliphatic polycarboxylic acids and aromatic polycarboxylic acids. Specific examples of the aliphatic polycarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

[0055] Specific examples of aromatic polycarboxylic acids include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, and anhydrides of these dicarboxylic acids; polybasic acids such as p-hydroxybenzoic acid and p-(2-hydroxyethoxy)benzoic acid. These polycarboxylic acids can be used alone or in combination of two or more.

[0056] In the present invention, as a component having barrier properties, it is preferable that the polycarboxylic acid contains an ortho-oriented aromatic dicarboxylic acid or an anhydride thereof.The content of the ortho-oriented aromatic dicarboxylic acid or an anhydride thereof is preferably 70 to 100 mass% relative to the total polycarboxylic acid components of the polyester-constituting monomer components.

[0057] Specific examples of the ortho-oriented aromatic dicarboxylic acid include orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and anhydrides of these dicarboxylic acids.

[0058] Examples of the polyhydric alcohol include aliphatic polyhydric alcohols and aromatic polyhydric phenols. Specific examples of the aliphatic polyhydric alcohol include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol.

[0059] Specific examples of aromatic polyhydric phenols include hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, bisphenol F, tetramethylbiphenol, and ethylene oxide-extended products and hydrogenated alicyclic phenols thereof.

[0060] The isocyanate compound (polyisocyanate) has two or more isocyanate groups in the molecule, and may be either aromatic or aliphatic, and may be either a low-molecular-weight compound or a high-molecular-weight compound, and known compounds such as diisocyanate compounds with two isocyanate groups or polyisocyanate compounds with three or more isocyanate groups can be used. The isocyanate compound may be a blocked isocyanate compound obtained by addition reaction using a known isocyanate blocking agent by an appropriate known and commonly used method.

[0061] Among these, polyisocyanate compounds are preferred from the viewpoint of adhesiveness and retort resistance, and those having an aromatic ring are preferred from the viewpoint of imparting oxygen barrier properties, and isocyanate compounds containing a metaxylene skeleton are particularly preferred.

[0062] Specific examples of the isocyanate compound include adducts, biuret compounds, and allophanate compounds obtained by reacting an excess amount of these isocyanate compounds with low-molecular-weight active hydrogen compounds such as ethylene glycol, propylene glycol, meta-xylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, and meta-xylylenediamine, and alkylene oxide adducts thereof, various polyester resins, polyether polyols, and high-molecular-weight active hydrogen compounds such as polyamides.

[0063] (Phosphate-modified compounds) The resin composition may contain, in addition to the above resins, a phosphate-modified compound, which has the effect of improving adhesive strength to inorganic members, and any known or commonly used phosphate-modified compound can be used.

[0064] Specific examples include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphate, and the like, and one or more of these can be used.

[0065] (plate-like inorganic compound) In addition to the above resins, the resin composition may contain a plate-like inorganic compound. The plate-like inorganic compound has the effect of improving the lamination strength and oxygen barrier properties of the laminate via the barrier adhesive layer 14. Specific examples of the plate-like inorganic compound (M) include kaolinite-serpentine group clay minerals (halloysite, kaolinite, endelite, dickite, nacrite, etc., antigorite, chrysotile, etc.), pyrophyllite-talc group (pyrophyllite, talc, kerola, etc.), etc., and one or more of these can be used.

[0066] The thickness of the barrier adhesive layer 14 is 0.5 to 8.0 μm, preferably 1.0 to 5.0 μm, and more preferably 2.0 to 4.5 μm. If it is thinner than this range, the gas barrier properties are likely to be insufficient, and if it is thicker than this range, the bending resistance is likely to be poor, which is likely to lead to a decrease in the gas barrier properties after bending.

[0067] The barrier adhesive layer 14 may be composed of a solvent-based adhesive or a solventless (non-solvent) adhesive. When a solvent-based adhesive is used for the barrier adhesive layer 14, for example, PASLIM VM001 / 108CP, a barrier organic adhesive manufactured by DIC Corporation, can be used, and the paper base layer 11 and the sealant layer 12 including the vapor-deposited layer 13 can be joined by a dry lamination method. When a solventless adhesive is used for the barrier adhesive layer 14, for example, PASLIM NSRD011 / NSRD006, a barrier organic adhesive manufactured by DIC Corporation, can be used, and the paper base layer 11 and the sealant layer 12 including the vapor-deposited layer 13 can be joined by a non-solvent lamination method. Another example of an organic barrier adhesive that can be used is "Maxieve (registered trademark)," which is disclosed in Japanese Patent Application Laid-Open Nos. 2003-300271 and 2010-012769, and is an adhesive that uses a non-bisphenol A polyepoxy resin as a base component and a polyamine as a curing agent, and is marketed by Mitsubishi Gas Chemical Company, Inc. as a gas barrier adhesive.

[0068] (Laminate) The laminate 10 of this embodiment has the barrier adhesive layer 14 having the above-mentioned barrier properties and the sealant layer 12 including the vapor deposition layer 13, and therefore can significantly suppress the permeation of oxygen and water vapor through the laminate 10. From the viewpoint of more effectively ensuring the oxygen barrier property, the laminate 10 has an oxygen permeability of 3.0 cc / m as a whole measured at 23°C and 90% RH in accordance with JIS K 7126-2. 2 / day / atm or less is desirable, and 2.0cc / m 2 / day / atm or less is more preferable, and 1.0cc / m 2 It is even more desirable that it be / day / atm or less. In addition, from the viewpoint of more effectively ensuring the water vapor barrier property, the laminate 10 has a water vapor permeability of 2.5 g / m as a whole measured in accordance with JIS K 7129 B method under the measurement conditions of 40°C and 90% RH. 2 / day or less is desirable, and 2.0 g / m 2 It is even more desirable that it be less than / day.

[0069] In the laminate 10 of this embodiment, from the viewpoint of ensuring excellent hand tearability and dead holdability of the entire laminate, the laminate 10 is 2 The mass (grammage) per unit area of ​​the sealant layer 12 having the vapor deposition layer 13 is t1. 2 When the mass (basis weight) per unit area is t2, it is desirable to satisfy the relationship of the following formula (2): Here, t2 indicates the basis weight of the sealant layer 12 and the vapor-deposited layer 13 when the vapor-deposited layer 13 is provided directly on the sealant layer 12, and indicates the total basis weight of the sealant layer 12, the vapor-deposited layer 13, and the intermediate layer when an intermediate layer such as an anchor layer is present between the sealant layer 12 and the vapor-deposited layer 13.

[0070] 1.0≦t1 / t2≦3.0...Equation (2)

[0071] If t1 / t2 is less than 1.0, the ratio of the sealant layer 12 with the vapor-deposited layer 13 to the paper base layer 11 in the laminate 10 becomes too large, which is undesirable, reducing the deadhold ability of the laminate 10. If t1 / t2 is greater than 3.0, the ratio of the sealant layer 12 with the vapor-deposited layer 13 to the paper base layer 11 in the laminate 10 becomes too small, which reduces the hand-tearability of the laminate 10 and makes the sealant layer 12 too thin, making it impossible to obtain sufficient heat-sealing performance, which is undesirable. As described above, if the thickness of the sealant layer 12 is 20 μm or more, sufficient heat sealability can be obtained.

[0072] In order to ensure better hand tearability and deadholdability, the paper base layer 11 of the laminate 10 has a basis weight of 35 g / m as described above. 2 More than 100g / m 2 and preferably 40 g / m 2 More than 70g / m 2 It is desirable that the following: Suppose the basis weight of the paper base layer 11 is 100 g / m 2 If the basis weight of the paper base layer 11 is larger than 35 g / m, the paper base layer 11 becomes too thick, which is undesirable as it reduces the hand tearability of the laminate. 2 If it is less than this, the paper substrate layer becomes too thin, which is undesirable as it reduces the deadhold properties of the laminate.

[0073] (Packaging using laminate) Fig. 2 is a diagram showing a package using the laminate of this embodiment. Fig. 2(A) is a diagram showing a packaging bag 1A which is an example of a package using the laminate 10 of this embodiment, and Fig. 2(B) is a diagram showing a packaging bag 1B which is another example of a package using the laminate 10 of this embodiment. Fig. 3 is a diagram showing another example of a package using the laminate of this embodiment. Fig. 3(A) is a plan view showing a packaging bag 1C, which is an example of a package using the laminate 10 of this embodiment, and Fig. 3(B) is a cross-sectional view of part B of Fig. 3(A). Fig. 4 shows another example of a package using the laminate of this embodiment. Fig. 4(A) is a plan view showing a packaging bag 1D, which is an example of a package using the laminate 10 of this embodiment, and Fig. 4(B) is a cross-sectional view of part B in Fig. 4(A). Fig. 5 is a diagram showing another example of a package using the laminate of this embodiment. Fig. 5(A) is a diagram showing a packaging bag 1E, which is an example of a package using the laminate 10 of this embodiment, Fig. 5(B) is a cross-sectional view of part B of Fig. 5(A), and Fig. 5(C) is a diagram explaining how to use the packaging bag 1E. Fig. 6 is a diagram showing another example of a package using the laminate of this embodiment. Fig. 6(A) is a diagram showing a box-shaped package 1F, which is an example of a package using the laminate 10 of this embodiment, and Fig. 6(B) is a diagram showing a box-shaped package 1G, which is another example of a package using the laminate 10 of this embodiment.

[0074] The laminate 10 of this embodiment can be applied to, for example, a pillow-shaped packaging bag 1A shown in Fig. 2(A) or a flat pouch-shaped packaging bag 1B shown in Fig. 2(B). The pillow-shaped packaging bag 1A shown in Fig. 2(A) is produced by heat-sealing the sealant layers 12 on a pair of opposing sides of a single rectangular laminate 10 to form a spine seal portion 2, thereby forming a cylindrical shape, and then heat-sealing the top and bottom openings of the cylindrical shape to form an upper seal portion 3 and a lower seal portion 4, respectively. In addition, the packaging bag 1B shown in Figure 2 (B) is produced by folding a single rectangular laminate 10 in half with the sealant layers 12 facing each other, and heat-sealing the three sides other than the fold line 5 to form the seal portion 6.

[0075] Furthermore, the packaging bag 1C shown in Fig. 3 is a packaging bag in which a zipper-operated opening / closing portion is provided at the opening portion of the flat pouch-type packaging bag shown in Fig. 2(B). Specifically, as shown in Fig. 3(A), a zipper portion 24 is provided on the inside of the vicinity of the top seal portion 21 of the packaging bag 1C so as to follow the top seal portion 21. As shown in Fig. 3(B), the zipper portion 24 is made up of, for example, a male member 24A and a female member 24B that can fit together, with the male member 24A being disposed on the inner surface of the laminate on the front side of the packaging bag 1C and the female member 24B being disposed on the inner surface of the laminate on the opposing back side, and the zipper portion 24 is in a closed state when they fit together. Furthermore, notch portions 25 for opening are provided by cutting out portions of the side seal portions 22, 23 at both ends of the packaging bag 1C between the top seal portion 21 and the zipper portion 24. With this configuration, the packaging bag 1C can be opened and closed freely by the zipper portion 24 after the top seal portion 21 is separated from the main body of the packaging bag 1C by the notch portions 25 and opened.

[0076] The laminate of this embodiment can also be used for a stand-up pouch-type packaging bag 1D, as shown in Fig. 4. The packaging bag 1D shown in Fig. 4 is formed by stacking two rectangular laminates 10A and 10B with their sealant layers 12 facing each other, and heat-sealing the top and both sides. The bottom side is formed by sandwiching a laminate 10C folded in half between the two laminates 10A and 10B with their sealant layers 12 facing each other, and then heat-sealing the outer edge of the laminate 10C to the laminates 10A and 10B. This configuration allows the packaging bag 1D filled with contents to become a self-standing pouch, with the laminate 10C serving as the bottom. As with the packaging bag 1C shown in Figure 3 above, a zipper portion 24 may be provided along the upper seal portion 21, and a notch portion 25 may be provided in part of the side seal portions 22, 23 between the zipper portion 24 and the upper seal portion 21, so that the opening can be opened and closed after the packaging bag is opened.

[0077] The laminate 10 of this embodiment can also be applied to a packaging bag 1E having an intermediate seal portion 31, as shown in Fig. 5. As shown in Figs. 5(A) and 5(B), the packaging bag 1E is formed by folding a long laminate 10A in half so that the front and back sides have different lengths, and joining the upper edge of the shorter side (front side) to the lower edge of a rectangular laminate 10B by heat sealing to form an intermediate seal portion 31. The upper edge of the longer side (rear side) to the upper edge of the rectangular laminate 10B is also joined by heat sealing to form an upper seal portion 32, and then joining both side edges of the joined laminates 10A and 10B by heat sealing to form side seal portions 33 and 34.

[0078] The packaging bag 1E has a notch 35 for opening formed in a portion of the side seals 33, 34 between the top seal 32 and the intermediate seal 31, and the packaging bag 1E can be opened by separating the top seal 32 from the main body of the packaging bag using this notch 35 as a trigger. The opening portion of the opened packaging bag 1E can be closed by folding the portion of the packaging bag 1E above the intermediate seal 31 so that it overlaps the portion below, with the intermediate seal 31 positioned at the top, as shown in Figure 5(C). As described above, the laminate used in the packaging bag 1E has a paper base layer, which provides excellent deadhold properties and allows the folded state to be properly maintained, minimizing leakage of the contents of the packaging bag from the opening or exposure to the outside air. The packaging bag 1E may be formed into a self-standing type by providing a laminated body that forms the bottom, as in the above-mentioned packaging bag 1D (see FIG. 4), if necessary.

[0079] The laminate 10 of this embodiment can also be applied to a box-shaped packaging 1F, as shown in Fig. 6. The packaging 1F shown in Fig. 6(A) is a box-shaped packaging made up of five laminates 10, and is formed from laminate 10A forming the bottom, laminates 10B and 10C forming the front and back portions, respectively, and laminates 10D and 10E forming the sides. The box-shaped packaging 1F is formed by joining the edges of adjacent laminates by heat sealing, with the sealant layer 12 facing inside the packaging 1F. In addition, the packaging body 1F shown in Figure 6(A) has its top and upper side edges directly heat-sealed to the laminate 10B that forms the front portion and the laminate 10C that forms the back portion, forming an upper seal portion 41 and side seal portions 42, 43, and is formed in a shape that is tapered at the top side compared to the bottom side. The package 1F is provided with an openable zipper 44 along the top seal 41, and a notch 45 for opening the package 1F, which is provided in part of the side seals 42, 43 between the zipper 44 and the top seal 41. As a result, after the top seal 41 is separated from the main body of the package 1F by the notch 45 and opened, the package 1F can be opened and closed freely by the zipper 44. The box-shaped packaging body 1F is not limited to the example shown in FIG. 6(A), but may be formed into a three-dimensional shape such as a rectangular parallelepiped or a cube, as shown in FIG. 6(B).

[0080] In addition, in any of the above-mentioned exemplary packaging forms, it is desirable that the weight ratio of paper in the entire packaging be the largest among the materials constituting the packaging. This increases the proportion of recyclable materials in the packaging, thereby reducing the environmental impact. In the packaging of this embodiment, the materials constituting the packaging include "paper," "resin," and "metal." The laminate 10 of this embodiment has superior hand-tearability and dead-holdability compared to conventional packaging materials, and therefore, when used in such packaging bags, the opening of the packaging bag can be easily opened by hand. In addition, the opened opening can be folded back to close and remain closed. The shape of the packaging bag is not limited to the above-mentioned shape, and may be a gusset-type packaging bag or the like. Furthermore, the laminate 10 of this embodiment can be used as a lid member for closing the opening of a container as another example of a packaging material, and further, not only the lid member but also the three-dimensional container itself may be formed from the laminate. As described above, the laminate 10 of this embodiment has excellent deadhold properties, and therefore can maintain the three-dimensional shape of the container, etc. In the present invention, the term "packaging" is a general term for the case where the laminate of the present invention is used as a packaging material, and includes not only packaging bags but also container-shaped objects, and even components that constitute part of a packaging container, such as lid materials, are included in the scope of the term "packaging."

[0081] Next, a preferred layer structure of the laminate 10 will be described together with test results. FIG. 7 is a diagram summarizing the results of evaluation of the barrier properties, hand tearability, and dead hold properties of the laminate examples and the reference example. <Test Example 1> [Laminated body example 1] The laminate of Laminate Example 1 has a paper base layer of unglazed kraft paper 50 g / m 2 Tokai Kraft C (manufactured by Tokai Tokushu Paper Co., Ltd.) was used, and gravure printing was performed on this coated paper using gravure ink, Sias HR (manufactured by DIC Graphics), to a dry thickness of 1 μm to form a design layer. Next, Sias HR (manufactured by DIC Graphics) was applied as an OP (overprint) varnish on the gravure print (design layer) to a dry thickness of 1 μm to form a surface layer. Next, a three-layer resin layer was formed by inflation film formation to form a sealant layer. The first layer, which was the deposition layer side of the resin layer (sealant layer), was made by mixing 90 parts by mass of fossil fuel-derived linear low-density polyethylene (LLDPE, manufactured by Prime Polymer Co., Ltd., SP2520), 10 parts by mass of fossil fuel-derived low-density polyethylene (LDPE, manufactured by Ube Maruzen Polyethylene Co., Ltd., F224N), and 0.04 parts by mass of an antioxidant (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GP), to a thickness of 8 μm (density 0.924 g / cm). 3 The second layer adjacent to the first layer was made by mixing 60 parts by mass of fossil fuel-derived high-density polyethylene (HDPE, manufactured by Prime Polymer Co., Ltd., HZ5000SF), 25 parts by mass of fossil fuel-derived linear low-density polyethylene (LLDPE, manufactured by Prime Polymer Co., Ltd., SP4020), 15 parts by mass of fossil fuel-derived low-density polyethylene (LDPE, manufactured by Ube Maruzen Polyethylene Co., Ltd., F224N), and 0.04 parts by mass of an antioxidant (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GP), and had a thickness of 24 μm (density 0.946 g / cm). 3 The third layer, which was provided on the opposite side of the second layer from the first layer, was made by mixing 95 parts by mass of fossil fuel-derived linear low-density polyethylene (LLDPE, manufactured by Prime Polymer Co., Ltd., SP2020), 0.04 parts by mass of an antioxidant (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GP), and 5 parts by mass of an antiblocking agent (manufactured by Sumitomo Chemical Co., Ltd., EMB-21), and had a thickness of 8 μm (density 0.918 g / cm). 3 The third layer is the layer of the sealant layer 12 that is the farthest from the vapor deposition layer, and when the above-mentioned package is formed from the laminate, it is the layer that forms the inner surface of the package and is joined to the opposing laminate by heat sealing. A vapor-deposited aluminum layer was formed on the first layer side of the resin film (sealant layer) by a conventionally known vacuum deposition method to a thickness of 45 nm to obtain a vapor-deposited sealant film. The vapor-deposited sealant film (sealant layer having a vapor-deposited layer) produced here had a layer thickness of 40 μm and a density of 0.94 g / cm. 3 , basis weight 37.5g / m 2 It was. A solvent-based barrier adhesive (PASLIM VM001 / 108CP manufactured by DIC Corporation) was applied to the vapor-deposited layer of the vapor-deposited sealant film to a dry thickness of 3 μm to form a barrier adhesive layer, which was then bonded to the surface of the paper base material opposite the printed layer and aged at 40°C for 3 days to obtain Laminate Example 1.

[0082] [Laminated body example 2] The laminate of Laminate Example 2 has a paper base layer of unglazed kraft paper 40 g / m 2 This laminate was the same as Laminate Example 1 except that the thickness was changed to Tokai Kraft C (manufactured by Tokai Tokushu Paper Co., Ltd.).

[0083] [Laminated body example 3] The laminate of Laminate Example 3 has a paper base layer of unglazed kraft paper 100 g / m 2 This laminate was the same as Laminate Example 1 except that the thickness was changed to Tokai Kraft C (manufactured by Tokai Tokushu Paper Co., Ltd.).

[0084] [Laminated body example 4] The laminate of Laminate Example 4 is the same as the laminate of Laminate Example 1, except that the sealant layer and the vapor deposition layer were changed to ML-TUX F 30 μm (manufactured by Mitsui Chemicals Tohcello Co., Ltd.), a film made of a fossil fuel-derived polyethylene resin vapor-deposited with aluminum. The vapor-deposited sealant film (sealant layer having a vapor-deposited layer) produced here had a layer thickness of 30 μm and a density of 0.934 g / cm 3 , basis weight 28.0g / m 2 It was.

[0085] [Laminated body example 5] The laminate of Laminate Example 5 is the same as the laminate of Laminate Example 1, except that the sealant layer is formed by an inflation film-forming method on a three-layer resin layer described below, and is changed to a vapor-deposited sealant film on which aluminum is vapor-deposited. The first layer, which is the deposition layer side of the resin layer (sealant layer), is made by mixing 100 parts by mass of fossil fuel-derived linear low-density polyethylene (LLDPE, manufactured by Prime Polymer Co., Ltd., SP2020) and 0.04 parts by mass of an antioxidant (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GP), and has a thickness of 6 μm (density 0.916 g / cm 3 The second layer adjacent to the first layer was made by mixing 100 parts by mass of fossil fuel-derived high density polyethylene (HDPE, manufactured by Prime Polymer Co., Ltd., HZ5000HF) and 0.04 parts by mass of an antioxidant (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GP), and had a thickness of 18 μm (density 0.956 g / cm). 3 Furthermore, the third layer, which was provided on the opposite side of the second layer from the first layer, was made by mixing 85 parts by mass of fossil fuel-derived linear low-density polyethylene (LLDPE, manufactured by Prime Polymer Co., Ltd., SP2520), 10 parts by mass of fossil fuel-derived low-density polyethylene (LDPE, manufactured by Ube Maruzen Polyethylene Co., Ltd., F224N), 0.04 parts by mass of an antioxidant (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GP), and 5 parts by mass of an anti-blocking agent (manufactured by Sumitomo Chemical Co., Ltd., EMB-21), to a thickness of 6 μm (density 0.928 g / cm). 3 ) was formed. The vapor-deposited sealant film (sealant layer having a vapor-deposited layer) produced here had a layer thickness of 30 μm and a density of 0.94 g / cm 3 , basis weight 28.3g / m 2 This becomes:

[0086] [Laminated body example 6] The laminate of Laminate Example 6 is the same as the laminate of Laminate Example 1, except that the sealant layer is formed by an inflation film-forming method on a three-layer resin layer described below, and is changed to a vapor-deposited sealant film in which aluminum is vapor-deposited. The first layer, which is the deposition layer side of the resin layer (sealant layer), is made by mixing 90 parts by mass of fossil fuel-derived linear low-density polyethylene (LLDPE, manufactured by Prime Polymer, SP2020), 10 parts by mass of biomass low-density polyethylene (LDPE, manufactured by BRASKEM, STN7006, minimum biomass content 95%), and 0.04 parts by mass of an antioxidant (manufactured by Sumitomo Chemical, Sumilizer GP), to a thickness of 8 μm (density 0.917 g / cm). 3The second layer adjacent to the first layer was formed by mixing 60 parts by mass of biomass high-density polyethylene (HDPE, manufactured by BRASKEM, SHE150, minimum biomass content 94%), 25 parts by mass of fossil fuel-derived linear low-density polyethylene LLDPE (C6: carbon number of the comonomer α-olefin) (manufactured by Prime Polymer, SP4020), 15 parts by mass of fossil fuel-derived low-density polyethylene (LDPE, manufactured by Ube Maruzen Polyethylene, F224N), and 0.04 parts by mass of an antioxidant (manufactured by Sumitomo Chemical, Sumilizer GP), to a thickness of 24 μm (density 0.942 g / cm). 3 Furthermore, the third layer, which was provided on the opposite side of the second layer from the first layer, was made by mixing 95 parts by mass of biomass linear low-density polyethylene (LLDPE, manufactured by BRASKEM, SLH118, minimum biomass content 84%), 5 parts by mass of antiblocking agent masterbatch (manufactured by Sumitomo Chemical Co., Ltd., EMB-21), and 0.04 parts by mass of antioxidant (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GP), to a thickness of 8 μm (density 0.918 g / cm). 3 The biomass content of the resulting sealant layer was 52.0%. The vapor-deposited sealant film (sealant layer having a vapor-deposited layer) produced here had a layer thickness of 40 μm and a density of 0.93 g / cm 3 , basis weight 37.3g / m 2 This becomes:

[0087] [Laminated body example 7] The laminate of Laminate Example 7 is the same as the laminate of Laminate Example 1, except that the sealant layer is formed by an inflation film-forming method on a three-layer resin layer described below, and is changed to a vapor-deposited sealant film with aluminum vapor-deposited on it. The first layer, which is the deposition layer side of the resin layer (sealant layer), is made by mixing 100 parts by mass of fossil fuel-derived linear low-density polyethylene (LLDPE, manufactured by Prime Polymer Co., Ltd., SP2020) and 0.04 parts by mass of an antioxidant (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GP), and has a thickness of 8 μm (density 0.916 g / cm 3The second layer adjacent to the first layer was formed by mixing 60 parts by mass of biomass high-density polyethylene (HDPE, manufactured by BRASKEM, SHE150, minimum biomass content 94%), 25 parts by mass of fossil fuel-derived linear low-density polyethylene LLDPE (C6: carbon number of the comonomer α-olefin) (manufactured by Prime Polymer, SP4020), 15 parts by mass of fossil fuel-derived low-density polyethylene (LDPE, manufactured by Ube Maruzen Polyethylene, F224N), and 0.04 parts by mass of an antioxidant (manufactured by Sumitomo Chemical, Sumilizer GP), to a thickness of 24 μm (density 0.942 g / cm). 3 Furthermore, the third layer, which was provided on the opposite side of the second layer from the first layer, was made by mixing 85 parts by mass of fossil fuel-derived linear low-density polyethylene (LLDPE, manufactured by Prime Polymer Co., Ltd., SP2520), 10 parts by mass of fossil fuel-derived low-density polyethylene (LDPE, manufactured by Ube Maruzen Polyethylene Co., Ltd., F224N), 0.04 parts by mass of an antioxidant (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GP), and 5 parts by mass of an anti-blocking agent (manufactured by Sumitomo Chemical Co., Ltd., EMB-21), to a thickness of 8 μm (density 0.928 g / cm). 3 The biomass content of the resulting sealant layer was 34.3%. The vapor-deposited sealant film (sealant layer having a vapor-deposited layer) produced here had a layer thickness of 40 μm and a density of 0.93 g / cm 3 , basis weight 37.3g / m 2 This becomes:

[0088] [Laminated body example 8] The laminate of Laminate Example 8 is the same as the laminate of Laminate Example 1, except that the barrier adhesive was changed to a non-solvent barrier adhesive (PASLIM NSRD011 / NSRD006 manufactured by DIC Corporation) and applied to the paper substrate side.

[0089] [Laminated body example 9] The laminate of Laminate Example 9 has a paper base layer made of barrier coated paper (Nippon Paper Shield Plus) 66 g / m 2 The laminate was the same as the laminate example 1 except for the change.

[0090] [Reference example 1] The laminate of Reference Example 1 is similar to the laminate of Laminate Example 1, except that the barrier adhesive was changed to a general-purpose solvent-based ester adhesive (A-315 / A-50 manufactured by Mitsui Chemicals, Inc.).

[0091] [Reference example 2] The laminate of Reference Example 2 has a paper base layer of pure white paper 30 g / m 2 The laminate was the same as Laminate Example 1 except that the adhesive was changed to Kinshachi (manufactured by Daio Paper Co., Ltd.).

[0092] [Reference example 3] The laminate of Reference Example 3 has a paper base layer of unglazed kraft paper 120 g / m 2 The laminate was the same as the laminate example 1 except that the polyester resin was changed to Tokai Kraft C (manufactured by Tokai Tokushu Paper Co., Ltd.).

[0093] [Reference example 4] The laminate of Reference Example 4 is similar to the laminate of Laminate Example 4, except that the barrier adhesive was changed to a general-purpose solvent-based ester adhesive (A-315 / A-50 manufactured by Mitsui Chemicals, Inc.).

[0094] FIG. 7 is a table summarizing the evaluation results of the laminate examples and the reference examples. [Barrier property evaluation] The oxygen permeability of the produced laminate examples and reference examples was measured at 23°C and 90% RH in accordance with JIS K 7126-2, and it was confirmed that, as shown in Figure 7, the laminates of Reference Examples 1 and 4, which used a general-purpose ester adhesive that is not a barrier adhesive, had significantly higher oxygen permeation amounts than the other laminate examples and the laminates of Reference Examples 2 and 3. This confirmed that the oxygen permeability of the laminates of each laminate example was significantly improved by the barrier adhesive layer. An oxygen permeability measuring device (manufactured by Mocon, product name "OXTRAN") was used.

[0095] Furthermore, the water vapor permeability of the laminate examples and reference examples was measured at 40°C and 90% RH in accordance with JIS K 7129 Method B, and it was confirmed that, as with oxygen, the laminates of Reference Examples 1 and 4, which do not have a barrier adhesive layer, had a significantly higher water vapor permeation amount than the other laminate examples and the laminates of Reference Examples 2 and 3. This confirmed that the water vapor permeability of the laminates of each laminate example was significantly improved by the barrier adhesive layer. A water vapor permeability measuring device (manufactured by Mocon, product name "Permatran") was used.

[0096] [Evaluation of hand tearability] The evaluation of hand tearability was a sensory evaluation in which an experimenter judged whether or not each of the created laminate examples and reference example laminates could be properly cut by hand. In FIG. 7, a case in which the laminate was properly cut along the intended line was marked with "◎", a case in which the laminate was cut to some extent along the intended line was marked with "◯", and a case in which the laminate could not be cut or was cut in an unexpected direction was marked with "×".

[0097] As shown in Figure 7, the laminate of Reference Example 3 had a ratio (t1 / t2) of the basis weight t1 of the paper base layer to the basis weight t2 of the sealant layer with a vapor deposition layer of 3.2, and the basis weight t1 of the paper base layer was too large compared to the basis weight t2 of the sealant layer with a vapor deposition layer, so the evaluation of hand tearability was "X". In contrast, the laminates of each laminate example were evaluated as "good" or "great" for hand tearability, and it was confirmed that the t1 / t2 of each example was within the preferred range (1.0 or more and 3.0 or less). Furthermore, the laminates of each laminate example were confirmed to have a basis weight of the paper base layer within the preferred range (35 g / m 2 More than 100g / m 2 It was also confirmed that the following conditions were met.

[0098] [Deadhold evaluation] The evaluation of dead holdability was a sensory evaluation in which each laminate example and each reference example created was folded in half, left to stand for 5 minutes, and then the experimenter judged whether the folded shape was maintained. In Figure 7, if the folded shape was maintained even after being folded in half and left to stand, it was marked with "◎", if the folded shape returned slightly to its original shape after being left to stand but the folded shape was mostly maintained, it was marked with "◯", and if the folded shape returned to its original shape after being folded, or if some creases remained but the folded shape was mostly restored, it was marked with "X".

[0099] As shown in Figure 7, the laminate of Reference Example 2 had a ratio (t1 / t2) of the basis weight t1 of the paper base layer to the basis weight t2 of the sealant layer with a vapor deposition layer of 0.8, and it is thought that the dead hold ability was evaluated as "×" because the basis weight t1 of the paper base layer was too small compared to the basis weight t2 of the sealant layer with a vapor deposition layer. In contrast, the laminates of each laminate example were evaluated as "good" or "great" for dead hold property, and it was confirmed that each t1 / t2 fell within the preferred range (1.0 or more and 3.0 or less).

[0100] <Test Example 2> [Laminated body example 10] In Laminate Example 4, the paper base layer is 50 g / m 2 A laminate of Laminate Example 10 was obtained in the same manner as in Laminate Example 4, except that the adhesive was changed to Star Pack A (manufactured by Marusumi Paper Co., Ltd.).

[0101] [Reference example 5] In Laminate Example 10, the paper base layer is 80 g / m 2 This laminate was the same as Laminate Example 10, except that the film thickness was changed to Star Pack A (manufactured by Marusumi Paper Co., Ltd.), and the sealant layer and vapor deposition layer were changed to ML-TUX F 25 μm (manufactured by Mitsui Chemicals Tohcello Co., Ltd.), a film made of a fossil fuel-derived polyethylene resin vapor-deposited with aluminum. The vapor-deposited sealant film (sealant layer having a vapor-deposited layer) produced here had a layer thickness of 25 μm and a density of 0.934 g / cm 3 , basis weight 23.5g / m2 It was.

[0102] [Reference example 6] In Laminate Example 10, the paper base layer is 40 g / m 2 This laminate was the same as Laminate Example 10, except that the coating was changed to Star White (manufactured by Marusumi Paper Co., Ltd.), and the sealant layer and vapor deposition layer were changed to ML-TUX F 50 μm (manufactured by Mitsui Chemicals Tohcello Co., Ltd.), a film made of a fossil fuel-derived polyethylene resin vapor-deposited with aluminum. The vapor-deposited sealant film (sealant layer having a vapor-deposited layer) produced here had a layer thickness of 50 μm and a density of 0.934 g / cm 3 , basis weight 46.7g / m 2 It was.

[0103] The laminates of Laminate Example 10 and Reference Examples 5 and 6 were cut into 10 cm x 10 cm test pieces. The samples used as test pieces were designated "unfolded." On the other hand, the test pieces were folded in half along one diagonal line with the paper facing outward, then unfolded, and then similarly cut in half along the other diagonal line. The fold was then unfolded to create a cross-shaped crease. These samples were designated "after folding." The water vapor permeability (water vapor barrier) of each test piece was measured under the same conditions as in Test Example 1. The average value for n=2 is shown in Figure 8.

[0104] FIG. 8 is a diagram showing the results of measuring the water vapor permeability (water vapor barrier) under the same conditions as in Test Example 1. From the results in FIG. 8, Laminate Example 10, which is within the range of t1 / t2 of the present disclosure, has a difference in water vapor transmission rate before and after bending, i.e., "without bending" - "after bending", of 0.2 g / m 2 In contrast, Reference Example 5, which is outside the range of t1 / t2 of the present disclosure, has a difference of 0.3 g / m 2 / day, and the difference in Reference Example 6 is 0.7 g / m 2 / day, and compared to Laminate Example 10, the deterioration of water vapor permeability due to bending is greater.

[0105] In Reference Example 5, the paper base layer had a larger basis weight, i.e., a larger thickness, resulting in higher paper rigidity, and therefore the paper did not bend evenly when folded, which is presumably why excessive force was applied locally to the vapor-deposited layer and why the water vapor permeability deteriorated.On the other hand, in Reference Example 6, the sealant layer was thicker, and the curvature of the sealant layer at the folding point was larger than in Laminate Example 10, which resulted in a larger curvature of the vapor-deposited layer, which in turn stretched the aluminum vapor-deposited layer significantly, causing vapor deposition cracks and resulting in a deterioration in water vapor permeability.

[0106] 7 and 8 show examples of sealant layers formed from polyethylene-based resins. Even in sealant layers containing polyethylene-based resins and polypropylene-based resins, the hand-tearability and dead holdability can be achieved as long as the ratio of t1 to t2 is satisfied, and the type of resin in the sealant layer has little effect, resulting in results equivalent to those in the above examples. Similarly, in sealant layers containing polyethylene-based resins and polypropylene-based resins, the oxygen barrier property is dominated by the vapor deposition layer and the barrier adhesive layer, so the type of resin in the sealant layer has little effect, resulting in results equivalent to those in the above examples. [Example]

[0107] Next, focusing on the processability of thermal lamination, examples and comparative examples will be described. [Example 1] The laminate of Example 1 used unglazed kraft paper 50 g / m2 (Tokai Kraft C, manufactured by Tokai Tokushu Paper Co., Ltd.) as the paper base layer, and a design layer was formed by gravure printing this coated paper with gravure ink, Sias HR (manufactured by DIC Graphics), to a dry thickness of 1 μm. Next, Sias HR (manufactured by DIC Graphics) was applied as an OP (overprint) varnish on the gravure print (design layer) to a dry thickness of 1 μm to form a surface layer. A solvent-based barrier adhesive (PASLIM VM001 / 108CP manufactured by DIC Corporation) was then applied to the vapor-deposited layer of the sealant layer described below to a dry thickness of 3 μm to form a barrier adhesive layer, which was then bonded to the surface of the paper base material opposite the printed layer and aged at 40°C for 3 days to obtain the laminate of Example 1.

[0108] [Sealant layer of Example 1] As the sealant layer and the vapor deposition layer, a CPP film containing mainly propylene-based resin and having aluminum vapor deposition (hereinafter referred to as aluminum vapor deposition CPP film 1), 2803EZ 25 μm (manufactured by Toray Film Processing Co., Ltd.) was used.

[0109] Figure 9 is a chart showing the results of measuring the absorption peaks by reflection ATR from the sealant layer surface (sealing surface) opposite the deposition layer of aluminum-deposited CPP film 1. The film had absorption peaks with maximum values ​​p1 and p2, and the absorption intensity ratio P was p2 / p1 = 0.313 / 0.111 = 2.82.

[0110] Figure 10 is a temperature rise chart showing the DSC curve of a sample taken from the sealant layer surface side of aluminum-deposited CPP film 1. A Hitachi High-Tech Science TA7000 series thermal analyzer was used, and the sample weight was 5.0 mg, with a heating rate of 10°C / min from 20 to 200°C. As a result of the measurement, in the second run (second heating), a first melting point peak was observed as a sub-peak at 127.7°C, and a main peak was observed at 146.2°C.

[0111] [Comparative Example 1] In Comparative Example 1, a laminate was prepared in the same form as in Example 1, except that a sealant layer, which will be described later, was used. [Sealant layer of Comparative Example 1] As the sealant layer and the vapor deposition layer, a CPP film containing mainly propylene-based resin and having aluminum vapor deposition (hereinafter referred to as aluminum vapor deposition CPP film 2), 2703 30 μm (manufactured by Toray Film Processing Co., Ltd.) was used.

[0112] Figure 11 is a chart showing the results of measuring the absorption peaks by reflection ATR from the sealant layer surface side (sealing surface side) opposite the deposition layer of aluminum-deposited CPP film 2. The film had absorption peaks with maximum values ​​p1 and p2, and the absorption intensity ratio P was p2 / p1 = 0.136 / 0.099 = 1.37.

[0113] Figure 12 is a temperature rise chart showing the DSC curve of a sample taken from the sealant layer surface side of aluminum-deposited CPP film 2. A Hitachi High-Tech Science TA7000 series thermal analyzer was used, and the sample weight was 4.8 mg, with a heating rate of 10°C / min from 20 to 200°C. As a result of the measurement, in the second run (second heating), a first melting point peak was observed as a sub-peak at 128.6°C, and a main peak was observed at 146.3°C.

[0114] Comparative Example 2 In Comparative Example 2, a laminate having the same configuration as that of Example 1 was prepared, except that a sealant layer, which will be described later, was used. [Sealant layer of Comparative Example 2] As the sealant layer and the vapor deposition layer, a CPP film containing mainly propylene-based resin and having aluminum vapor deposition (hereinafter referred to as aluminum vapor deposition CPP film 3), Sunmirror CP-VR 30 μm (manufactured by Reiko Co., Ltd.), was used.

[0115] Figure 13 is a chart showing the results of measuring the absorption peaks by reflection ATR from the sealant layer surface side (sealing surface side) opposite the deposition layer of aluminum-deposited CPP film 3. The film had absorption peaks with maximum values ​​p1 and p2, and the absorption intensity ratio P was p2 / p1 = 0.268 / 0.199 = 1.35.

[0116] Figure 14 is a temperature rise chart showing the DSC curve of a sample taken from the sealant layer surface side of aluminum-deposited CPP film 3. A Hitachi High-Tech Science TA7000 series thermal analyzer was used, and the sample weight was 5.0 mg, with a heating rate of 10°C / min from 20 to 200°C. As a result of the measurement, in the second run (second heating), a first melting point peak was observed as a sub-peak at 128.4°C, and a main peak was observed at 135.7°C.

[0117] [Seal strength measurement] FIG. 15 is a diagram summarizing the measurement results of the seal strength in Example 1, Comparative Example 1, and Comparative Example 2. Fig. 16 is a chart showing the seal strength curves of Example 1, Comparative Example 1, and Comparative Example 2. The horizontal axis of Fig. 16 is the seal temperature (unit: ° C.), and the vertical axis is the seal strength (unit: N / 15 mm).

[0118] The test specimens were prepared by stacking two 15 mm wide, 50 mm long laminates with the sealant layers facing each other, and heat sealing one end of the laminate to form a seal width of 10 mm at a pressure of 0.1 MPa for a heat sealing time of 1 second. The seal strength was measured at sealing temperatures of 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 150°C, or 160°C.

[0119] The seal strength of the sealed portion of the test pieces prepared at each sealing temperature was measured using a Tensilon STA-1150 manufactured by A&D Co., Ltd. The measurement was performed in an environment of 25°C and 50% relative humidity.

[0120] 15 and 16, it can be seen that the Examples exhibit excellent low-temperature sealing properties, with seal strengths of 1 N or more at 120°C, 2 N or more at 125°C, 4 N or more at 130°C, and 8 N or more at 135°C, all of which were obtained in a nearly linear fashion.

[0121] [Suitability for thermal lamination] Packages were produced using each of the above Example 1, Comparative Example 1, and Comparative Example 2, and the processability of thermal lamination was evaluated. FIG. 17 is a diagram showing the results of evaluation of the thermal lamination processability of the examples and comparative examples. Pillow bags (see Figure 2(A)) were made for each of Example 1, Comparative Example 1, and Comparative Example 2. Two types of bag making machines were used for evaluation: a vertical pillow packaging machine and a horizontal pillow packaging machine. The vertical pillow packaging machine is a pillow packaging machine in which the contents are dropped to fill the bag, while the horizontal pillow packaging machine is a pillow packaging machine in which the contents are filled by flowing them horizontally on a belt conveyor. In addition, a permeation test was conducted using each pillow bag after the bags were made to check for the presence or absence of leakage. In the permeation test, the pillow bag was cut into two parallel to the end seal, and an Ageless Checker was placed on the inside, and the permeation after one hour at room temperature was checked. If the Ageless Checker leaked and the bag was discolored, it was judged that there was leakage; if there was no leakage, it was judged that there was no leakage.

[0122] The above comparative test was conducted to confirm the suitability for high-speed filling. In Comparative Examples 1 and 2, sealing was not possible even when the sealing temperature was increased and the speed was reduced. In contrast, sealing was possible at a low temperature and high speed in Example 1. Therefore, it was confirmed that, in order to improve the suitability for thermal lamination, it is desirable for the absorption intensity ratio P to be 1.5 or more and 5.0 or less, as in Example 1.

[0123] As described above, the laminate and package of the present embodiment have an absorption intensity ratio P of the laminate of 1.5 or more and 5.0 or less, so that heat sealing can be performed at low temperature and high speed, and high-speed filling suitability can be improved. The present disclosure is not limited to the above-described embodiments, and various modifications and variations are possible, and these are also within the scope of the present disclosure. [Explanation of symbols]

[0124] 1(1A, 1B, 1C, 1D, 1E, 1F, 1G) Packaging bag (packaging body) 10 Laminate 11 Paper base layer 12 Sealant Layer 13 Deposited layer 14 Barrier adhesive layer

Claims

1. A laminate comprising, in this order, a paper substrate layer, a barrier adhesive layer, a vapor-deposited layer of a metal or inorganic oxide, and a sealant layer, The basis weight of the paper base layer is 25 g / m ２ 150g / m or more ２ is as follows: the innermost layer of the sealant layer mainly contains a propylene-based resin and may optionally contain an ethylene-based resin; the propylene-based resin is at least one selected from the group consisting of homopolypropylene, random copolymer polypropylene containing an ethylene unit, and block copolymer polypropylene containing an ethylene unit; When the innermost layer of the sealant layer is measured by differential thermal analysis (DSC), it has a first melting point peak of 100°C or higher and 130°C or lower and a second melting point peak of 140°C or higher and 170°C or lower, the first melting point peak is derived from the ethylene unit in the propylene-based resin and / or the ethylene component in the ethylene-based resin, the second melting point peak is a melting point peak specific to propylene in the propylene-based resin, When the surface of the innermost layer of the sealant layer was measured by reflection infrared absorption spectroscopy, The 2945 cm －１ More than 2960cm －１ The maximum value p1 of the absorption peak below, 2910 cm derived from the ethylene unit in the propylene-based resin and / or the ethylene component in the ethylene-based resin －１ 2920cm or more －１ and a maximum value p2 of the absorption peak at The absorption intensity ratio P defined by the following formula (1) is 2.82 or more and 5.0 or less. Laminate. Absorption intensity ratio P=p2 / p1 Equation (1)

2. The absorption intensity ratio P is 3.0 or more and 4.0 or less. The laminate according to claim 1 .

3. Oxygen permeability measured at 23°C and 90% RH in accordance with JIS K 7126-2 is 3.0 cc / m ２ / day / atm or less, The laminate according to claim 1 or 2.

4. 1 m of the paper base layer ２ The mass per unit is t1, 1 m of the sealant layer including the vapor deposition layer ２ When the mass per unit is t2, 1.0≦t1 / t2≦3.0 is satisfied, The laminate according to any one of claims 1 to 3.

5. The basis weight of the paper base layer is 35 g / m ２ More than 100g / m ２ is The laminate according to any one of claims 1 to 4.

6. the barrier adhesive layer is a cured product of a resin composition containing a resin having two or more hydroxyl groups per molecule and an isocyanate compound having two or more isocyanate groups per molecule, The main skeleton of the resin is polyester or polyester polyurethane, and contains an ortho-oriented aromatic dicarboxylic acid or its anhydride as a polyester-constituting monomer component. The laminate according to any one of claims 1 to 5.

7. A package formed using the laminate according to any one of claims 1 to 6.

8. 8. The packaging body according to claim 7, wherein the weight ratio of paper in the entire packaging body is the largest among the materials constituting the packaging body.

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