JP2023075177A - Laminate, and pouch for retort or boil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate capable of being favorably used as a mono-material packaging container, capable of prominently improving adhesion of the interlayer between a substrate and a vapor-deposited film, capable of achieving favorable gas barrier property, and having heat resistance.

SOLUTION: A laminate 10A includes at least a first substrate 11A, a vapor-deposited film 12A, a barrier coat layer 16A, and a sealant layer 13A, where the first substrate is a biaxially-stretched resin film including a polypropylene resin layer 14A, a surface resin layer 15A disposed on one surface of the polypropylene resin layer, and an adhesive resin layer 17A between the polypropylene resin layer and the surface resin layer, the surface resin layer includes a resin material having a melting point of 180°C or higher where the resin material is a vinyl resin, nylon 6, nylon 6,6, MXD nylon, or polyester, the vapor-deposited film is composed of an inorganic oxide, and the sealant layer includes a polyolefin having a melting point of 110°C or higher.

SELECTED DRAWING: Figure 4

COPYRIGHT: (C)2023,JPO&INPIT

Description

The present invention relates to laminates, retort or boiling pouches.

Conventionally, a film made of polyester such as polyethylene terephthalate (hereinafter also referred to as a polyester film) has excellent mechanical properties, chemical stability, heat resistance and transparency, and is inexpensive. It is used as a base material that constitutes a laminate used in the production of packaging containers such as.

A polyester film is usually laminated with a sealant layer to form a laminate, and then formed into a packaging container. The sealant layer is a polyolefin film such as polypropylene film.

It is difficult to separate the respective resin films in a packaging container obtained by forming a laminate obtained by bonding different types of resin films, that is, a polyester film and a polypropylene film. Therefore, packaging containers collected after use are not suitable for recycling and are not actively recycled at present.

In view of this situation, in order to improve the recyclability of packaging containers, instead of polyester film, stretched polypropylene film (stretched polypropylene film) is applied to the base material, and is composed of the same material. Preparation of a packaging container using a laminate (mono-material packaging container) has been studied.

Recently, the present inventors formed a vapor-deposited film on the surface of the stretched polypropylene film in order to compensate for the gas barrier properties that were lowered by changing the polyester film to the stretched polypropylene film. However, the adhesion between the oriented polypropylene film and the deposited film was not sufficient, and the desired gas barrier property was not achieved. Accordingly, the present inventors have found such a new problem.

The present inventors provided a surface resin layer containing a resin material having a melting point of 180 ° C. or higher on the surface of the stretched polypropylene film instead of forming a vapor deposition film on the surface of the stretched polypropylene film, and vapor deposited on the surface resin layer. The present inventors have found that the formation of a film improves the adhesion as well as the gas barrier property.

In addition, the present inventors provided a surface coat layer containing a resin material having a polar group on the surface of the stretched polypropylene film instead of forming a vapor deposition film on the surface of the stretched polypropylene film, and deposited a vapor deposition film on the surface coat layer. The inventors have found that the formation of is improved in adhesion and gas barrier properties.

Furthermore, packaging containers are sometimes required to have heat resistance. The present inventors have found that a laminate comprising a sealant layer containing a polyolefin having a melting point of 110° C. or higher provides a packaging container with heat resistance.

The present invention has been made based on such findings, and the problem to be solved is that it can be suitably used for a monomaterial packaging container, and can significantly improve the interlayer adhesion between the substrate and the vapor deposition film, which is preferable. Disclosed is a laminate that can achieve gas barrier properties and has heat resistance.

Moreover, the problem to be solved by the present invention is to provide a pouch for retort or boiling which is composed of the laminate.

In a first aspect, the present invention is a laminate comprising:
At least, comprising a first base material, a deposited film, a barrier coat layer and a sealant layer,
The first base material includes a polypropylene resin layer, a surface resin layer provided on one surface of the polypropylene resin layer, and an adhesive resin layer between the polypropylene resin layer and the surface resin layer. An axially stretched resin film,
The adhesive resin layer is provided on the polypropylene resin layer,
The surface resin layer is provided on the adhesive resin layer,
The deposited film is provided on the surface resin layer of the first base material,
The surface resin layer contains a resin material having a melting point of 180° C. or higher,
the resin material is vinyl resin, nylon 6, nylon 6,6, MXD nylon or polyester;
The deposited film is composed of an inorganic oxide,
The laminate is such that the sealant layer contains polyolefin having a melting point of 110° C. or higher.

In one embodiment, the surface resin layer contains a resin material having a melting point of 180° C. or higher and 265° C. or lower.

In one embodiment, the resin material of the surface resin layer has a melting point TA,
The polypropylene of the polypropylene resin layer has a melting point TB,
The difference between the melting point TA and the melting point TB is 20° C. or more and 80° C. or less.

In one embodiment, the resin material of the surface resin layer is made of a polymer having a polar group.

In one embodiment, the ratio of the thickness of the surface resin layer to the total thickness of the first base material is 1% or more and 10% or less.

In one embodiment, the sealant layer comprises a sealant material having a melting point of 150°C or higher.

In one embodiment, the sealant layer comprises polypropylene having a melting point of 150°C or higher.

In one embodiment, the laminate further comprises a second substrate.

In one embodiment, the second substrate comprises polypropylene.

In one embodiment, the first substrate and the deposited film are located between the second substrate and the sealant layer.

In one embodiment, the laminate comprises an intermediate layer between the deposited film and the sealant layer,
The intermediate layer is the second base material.

In one embodiment, the intermediate layer is made of a stretched polypropylene resin film.

In one embodiment, the barrier coat layer is provided between the deposited film and the sealant layer.

In one embodiment, the barrier coat layer is a gas barrier coating film of a mixture of a metal alkoxide and a water-soluble polymer, or a gas barrier coating of a mixture of a metal alkoxide, a water-soluble polymer and a silane coupling agent. membrane.

In one embodiment, the laminate is used for packaging containers.

The present invention is a pouch for retort packaging or boiling, comprising the laminate.

In one embodiment, the retort or boil pouch is provided with a notch.

In one embodiment, the retort or boil pouch is provided with a half cut line.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a laminate that can be suitably used for a monomaterial packaging container, can remarkably improve the interlayer adhesion between the base material and the deposited film, can achieve preferable gas barrier properties, and has heat resistance. .
Further, according to the present invention, it is possible to provide a retort or boiling pouch comprising the laminate.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows one Embodiment of the laminated body of this invention. FIG. 4 is a plan view showing an example of a loop stiffness measuring device; FIG. 9 is a cross-sectional view of the loop stiffness measuring device of FIG. 8 along line V-V; FIG. 4 is a diagram for explaining a process of attaching a test piece to the loop stiffness measuring instrument; It is a figure for demonstrating the process of forming a loop part in a test piece. It is a figure for demonstrating the process of applying a load to the loop part of a test piece. It is a figure for demonstrating the process of applying a load to the loop part of a test piece. It is a figure for demonstrating the process of applying a load to the loop part of a test piece. It is a schematic sectional drawing which shows one Embodiment of a vapor deposition apparatus. It is a schematic sectional drawing which shows one Embodiment of a vapor deposition apparatus. It is a schematic sectional drawing which shows another one Embodiment of a vapor deposition apparatus. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows one Embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows one Embodiment of the laminated body of this invention. 1 is a front view showing an embodiment of a pouch for retort or boiling of the present invention; FIG. 1 is a perspective view showing an embodiment of a pouch for retort or boiling of the present invention. FIG. It is a schematic diagram showing an example of a method of measuring lamination strength. It is a schematic diagram showing an example of a method of measuring lamination strength. FIG. 4 is a diagram showing changes in tensile stress with respect to the distance between a pair of grippers that pull on the substrate side and the sealant layer side to measure laminate strength. It is a figure which shows an example of the measuring method of a puncture strength.

[Laminate in the first aspect]
As shown in FIG. 1, the laminate 10A of the present invention includes a first substrate 11A, a deposited film 12A, and a sealant layer 13A. The first substrate 11A includes a polypropylene resin layer 14A and a surface resin layer. 15A.
In one embodiment of the present invention, the laminate 10A may further include a barrier coat layer 16A between the deposited film 12A and the sealant layer 13A, as shown in FIG.
In one embodiment of the present invention, the first base material 11A may include an adhesive resin layer 17A between the polypropylene resin layer 14A and the surface resin layer 15A, as shown in FIG.
In one embodiment of the present invention, as shown in FIG. 4, the laminate 10A includes a first substrate 11A, a vapor deposition film 12A, a barrier coat layer 16A provided on the vapor deposition film 12A, and a sealant layer 13A. may be provided. The first base material 11A includes a polypropylene resin layer 14A, an adhesive resin layer 17A, and a surface resin layer 15A. The adhesive resin layer 17A is provided between the polypropylene resin layer 14A and the surface resin layer 15A. may
In one embodiment of the invention, the laminate may further comprise a second substrate. When the laminate includes the second substrate, the laminate 10A includes, as shown in FIG. 5, the second substrate 18A, the deposited film 12A, the first substrate 11A, and the sealant layer 13A in this order. Alternatively, as shown in FIG. 6, a second substrate 18A, a first substrate 11A, a deposited film 12A, and a sealant layer 13A may be provided in this order, and as shown in FIG. The material 11A, the deposited film 12A, the second base material 18A, and the sealant layer 13A may be provided in this order. The second substrate 18A in the laminate 10A of FIGS. 5 and 6 and the first substrate 11A in the laminate 10A of FIG. 7 may be positioned in the outermost layers of the laminate 10A.
In one embodiment of the present invention, the laminate 10A may include an adhesive layer (not shown) between any of the deposited film, the sealant layer, the first substrate and the second substrate. In another embodiment, the laminate of the present invention may comprise an intermediate layer between the deposited film and the sealant layer, and the intermediate layer may be the second substrate.

The haze value of the laminate is preferably 20% or less, more preferably 5% or less. Thereby, the transparency of the laminate can be improved.
In this specification, the haze value of the laminate is measured by a haze meter (Murakami Color Research Laboratory) in accordance with JIS K 7105:1981.

In the laminate in the first aspect, the lamination strength between the first substrate and the deposited film is preferably 3N or more, more preferably 4N or more, and even more preferably 5.5N or more in a width of 15 mm. The upper limit of the laminate strength of the laminate may be 20N or less.
A method for measuring the lamination strength of the laminate will be described in the examples below.

The tensile strength in one direction of the laminate may be 30 MPa or more, or 35 MPa or more. The tensile strength in one direction of the laminate may be 70 MPa or less, or 50 MPa or less. One direction of the laminate may be the longitudinal direction (MD direction).
The tensile strength of the laminate in a direction perpendicular to the one direction may be 40 MPa or more, or 60 MPa or more. The tensile strength of the laminate in a direction perpendicular to the one direction may be 150 MPa or less, or 100 MPa or less. The direction perpendicular to the one direction may be the lateral direction (TD direction) of the laminate.
In this specification, the tensile strength of the laminate is measured according to JIS K7127:1999. As a measuring instrument, a tensile tester STA-1150 manufactured by Orientec Co., Ltd. can be used.
A rectangular laminate having a width of 10 mm and a length of 150 mm can be used as the test piece. The distance between the pair of chucks holding the test piece is 50 mm at the start of the measurement, and the pulling speed is 300 mm/min. In this specification, unless otherwise specified, the environment during the measurement of tensile strength is a temperature of 23° C. and a relative humidity of 50%.

The loop stiffness in one direction of the laminate may be 30 mN or more, 50 mN or more, or 70 mN or more. The loop stiffness in one direction of the laminate may be 200 mN or less, 150 mN or less, or 120 mN or less. One direction of the laminate may be the longitudinal direction (MD direction).
The loop stiffness of the laminate in a direction perpendicular to the one direction may be 30 mN or more, 50 mN or more, or 70 mN or more. The loop stiffness of the laminate in a direction perpendicular to the one direction may be 200 mN or less, 150 mN or less, or 130 mN or less. The direction perpendicular to the one direction may be the lateral direction (TD direction) of the laminate.

Loop stiffness is a parameter representing stiffness of a laminate. A method of measuring loop stiffness will be described below with reference to FIGS. 8 to 14. FIG.

8 is a plan view showing the test piece 20 and the loop stiffness measuring device 25, and FIG. 9 is a cross-sectional view of the test piece 20 and the loop stiffness measuring device 25 of FIG. 8 taken along line VV. The test piece 20 is a rectangular laminate having long sides and short sides. In this specification, the length X1 of the long side of the test piece 20 was set to 150 mm, and the length X2 of the short side was set to 15 mm. As the loop stiffness measuring device 25, No. 1 manufactured by Toyo Seiki Co., Ltd. is used. A 581 Loop Stiffness Tester® LOOP STIFFNESS TESTER Model DA can be used. The length X1 of the long side of the test piece 20 can be adjusted as long as the test piece 20 can be gripped by a pair of chuck portions 26, which will be described later.

The loop stiffness measuring instrument 25 has a pair of chuck portions 26 for gripping a pair of longitudinal ends of the test piece 20 and a support member 27 supporting the chuck portions 26 . The chuck section 26 includes a first chuck 26A and a second chuck 26B. 8 and 9, the test strip 20 is placed on the pair of first chucks 26A, and the second chuck 26B has not yet gripped the test strip 20 between itself and the first chucks 26A. . As will be described later, the test piece 20 is gripped between the first chuck 26A and the second chuck 26B of the chuck portion 26 during measurement. The second chuck 26B may be connected to the first chuck 26A via a hinge mechanism.

A method of measuring the loop stiffness of the test piece 20 using the loop stiffness measuring device 25 will be described. First, as shown in FIGS. 8 and 9, the test piece 20 is placed on the first chuck 26A of the pair of chuck portions 26 arranged with the interval X3 therebetween. In this specification, the interval X3 is set so that the length of the loop portion 21 described later (hereinafter also referred to as loop length) is 60 mm. The test piece 20 includes an inner surface 20x located on the side of the first chuck 26A and an outer surface 20y located on the opposite side of the inner surface 20x. When the loop portion 21 to be described later is formed in the test piece 20 , the inner surface 20 x is positioned inside the loop portion 21 and the outer surface 20 y is positioned outside the loop portion 21 . Subsequently, as shown in FIG. 10, the second chuck 26B is placed on the test piece 20 so as to grip the ends of the test piece 20 in the longitudinal direction between the first chuck 26A.

Subsequently, as shown in FIG. 11, at least one of the pair of chuck portions 26 is slid on the support member 27 in the direction in which the distance between the pair of chuck portions 26 is reduced. Thereby, the loop portion 21 can be formed in the test piece 20 . A test piece 20 shown in FIG. 11 has a loop portion 21 , a pair of intermediate portions 22 and a pair of fixing portions 23 . The pair of fixing portions 23 are portions of the test strip 20 that are gripped by the pair of chuck portions 26 . The pair of intermediate portions 22 are portions of the test strip 20 located between the loop portion 21 and the pair of intermediate portions 22 . As shown in FIG. 11, the chuck portion 26 is slid on the support member 27 until the inner surfaces 20x of the pair of intermediate portions 22 come into contact with each other. Thereby, the loop portion 21 having a loop length of 60 mm can be formed. The loop length of the loop portion 21 is defined by the position P1 where the surface of the second chuck 26B on the loop portion 21 side and the test piece 20 intersect, and the surface of the other second chuck 26B on the loop portion 21 side and the test piece 20. is the length of the test piece 20 between the crossing position P2. When ignoring the thickness of the test piece 20, the above-mentioned interval X3 is a value obtained by adding 2×t to the length of the loop portion 21. As shown in FIG. t is the thickness of the second chuck 26B of the chuck portion 26;

Subsequently, as shown in FIG. 12, the attitude of the chuck portion 26 is adjusted so that the projection direction Y of the loop portion 21 with respect to the chuck portion 26 is horizontal. For example, the posture of the chuck portion 26 supported by the support member 27 is adjusted by moving the support member 27 so that the normal direction of the support member 27 faces the horizontal direction. In the example shown in FIG. 12, the projecting direction Y of the loop portion 21 coincides with the thickness direction of the chuck portion. In addition, the load cell 28 is prepared at a position separated by a distance Z1 from the second chuck 26B in the projecting direction Y of the loop portion 21 .

Subsequently, as shown in FIG. 13 , the load cell 28 is moved toward the loop portion 21 to bring the load cell 28 into contact with the loop portion 12 . A distance Z1 is the distance between the load cell 28 and the second chuck 26B of the chuck portion 26 .

Thereafter, as shown in FIG. 14, the load cell 28 pushes the loop portion 21 toward the chuck portion 26 by a distance Z2. In this specification, the distance Z2 is set to 15 mm.
Next, as shown in FIG. 14, the load cell 28 is moved toward the chuck portion 26 by a distance Z2, and in a state in which the load cell 28 is pushing the loop portion 21 of the test piece 20, the load applied from the loop portion 21 to the load cell 28 is reduced. After the value has stabilized, record the value of the load. The value of the load thus obtained is defined as the loop stiffness of the laminate constituting the test piece 20 . In this specification, unless otherwise specified, the environment during the loop stiffness measurement is a temperature of 23° C. and a relative humidity of 50%.

The laminate may have a piercing strength of 10 N or more, or 15 N or more.
The puncture strength of the laminate is measured according to JIS Z1707 7.4. A specific measuring method will be described in Examples described later.

Conventionally, a laminate in which a substrate and a sealant layer are made of different resin materials has been used for packaging containers. On the other hand, since it is difficult to separate the base material and the sealant layer after collecting the used packaging container, there is a current situation that recycling is not actively carried out.
In the present invention, a stretched polypropylene resin film is used as the first base material, the sealant layer is a layer containing polypropylene having a melting point of 110 ° C. or higher, and both are made of the same material to form a laminate. The recyclability can be improved when used as a packaging container.

From the viewpoint of recyclability, it can be said that the higher the percentage of polypropylene contained in the sealant layer, the better. This point will be described later.
When the sealant layer is made of polypropylene, the content of polypropylene with respect to the total amount of the resin material contained in the laminate of the present invention is preferably 80% by mass or more, and more preferably 95% by mass or more. Thereby, the recyclability of the packaging container produced using the laminate of the present invention can be further improved.

Each layer included in the laminate of the present invention will be described below.

(First base material)
The first substrate includes at least a polypropylene resin layer and a surface resin layer, and if desired, an adhesive resin layer may be provided between the polypropylene resin layer and the surface resin layer.

(Polypropylene resin layer)
The polypropylene resin layer is made of polypropylene. The polypropylene resin layer may have a single layer structure or a multilayer structure.
By providing the polypropylene resin layer to the first base material, the heat resistance and oil resistance of the packaging container produced using the first base material can be improved.

The polypropylene resin layer is a stretched film. The stretching treatment may be uniaxial stretching or biaxial stretching.
The draw ratio of the polypropylene resin layer in the machine direction (MD direction) and the transverse direction (TD direction) is preferably 2 times or more and 15 times or less, and preferably 5 times or more and 13 times or less.
By setting the draw ratio to 2 times or more, the strength and heat resistance of the polypropylene resin layer can be further improved. Moreover, the printability to a polypropylene resin layer can be improved.
From the viewpoint of breaking limit of the polypropylene resin layer, the draw ratio is preferably 15 times or less.

The polypropylene contained in the polypropylene resin layer may be homopolymer, random copolymer or block copolymer.
A polypropylene homopolymer is a polymer of propylene only, and a polypropylene random copolymer is a polymer of propylene and other α-olefins other than propylene (eg, ethylene, butene-1, 4-methyl-1-pentene, etc.). A polypropylene block copolymer, which is a random copolymer, is a copolymer having a polymer block composed of propylene and a polymer block composed of an α-olefin other than the above-mentioned propylene.
Among these polypropylenes, homopolymers or random copolymers are preferably used from the viewpoint of transparency. It is preferable to use a homopolymer when emphasizing the rigidity and heat resistance of the packaging bag, and to use a random copolymer when emphasizing impact resistance and the like.
In addition, biomass-derived polypropylene and mechanically recycled or chemically recycled polypropylene can also be used.

The content of polypropylene in the polypropylene resin layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

The polypropylene resin layer may contain a heat seal modifier. Thereby, the heat-sealing property of the polypropylene resin layer can be improved, and the packaging container can be more easily produced by sticking an envelope.
The heat seal modifier is not particularly limited as long as it is highly compatible with the polypropylene constituting the heat seal layer, and examples thereof include olefin copolymers.
Also, a conventionally known heat sealing agent may be applied to the surface of the polypropylene resin layer and dried.

The polypropylene resin layer may contain a resin material other than polypropylene as long as the characteristics of the present invention are not impaired. Examples of resin materials other than polypropylene include polyolefins such as polyethylene, (meth)acrylic resins, vinyl resins, cellulose resins, polyamide resins, polyesters and ionomer resins.
The polypropylene resin layer may contain additives within a range that does not impair the properties of the present invention. Additives include, for example, cross-linking agents, antioxidants, anti-blocking agents, slip agents, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments and modifying resins. mentioned.

The thickness of the polypropylene resin layer is preferably 10 μm or more, more preferably 10 μm or more. The thickness of the polypropylene resin layer is preferably 50 μm or less, more preferably 40 μm or less.
By setting the thickness of the polypropylene resin layer to 10 μm or more, the strength and heat resistance of the first base material can be further improved.
By setting the thickness of the polypropylene resin layer to 50 μm or less, the film formability and workability of the first base material can be further improved.

The polypropylene resin layer may have a printed layer on its surface. The image formed on the printed layer is not particularly limited, and may be characters, patterns, symbols, combinations thereof, or the like.
Printing layer formation on the first substrate can be performed using a biomass-derived ink. As a result, the environmental load can be further reduced.
The method for forming the printed layer is not particularly limited, and conventionally known printing methods such as gravure printing, offset printing, and flexographic printing can be used.

The polypropylene resin layer may be surface-treated. Thereby, the adhesion with the surface coat layer can be improved.
The method of surface treatment is not particularly limited, and examples include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas and/or nitrogen gas, physical treatment such as glow discharge treatment, and oxidation using chemicals. Chemical treatments such as treatments are included.

(Surface resin layer)
The first base material has a surface resin layer containing a resin material having a melting point of 180° C. or higher (hereinafter also referred to as a high melting point resin material). Thereby, a deposited film having high adhesiveness can be formed on the surface resin layer, and the gas barrier property can be improved.
Moreover, as will be described later, a packaging container produced using a laminate having the surface resin layer has high lamination strength.
In one embodiment, the surface resin layer may be provided on the polypropylene resin layer. That is, the surface resin layer may be adjacent to the polypropylene resin layer.
In one embodiment, when the first substrate is provided with an adhesive resin layer between the polypropylene resin layer and the surface resin layer, the adhesive resin layer is provided on the polypropylene resin layer, and the surface resin layer is adhesive It may be provided on the resin layer. That is, the adhesive resin layer may be adjacent to the polypropylene resin layer, and the surface resin layer may be adjacent to the adhesive resin layer.

The melting point of the high melting point resin material is preferably 185° C. or higher, more preferably 190° C. or higher, and particularly preferably 205° C. or higher.
By setting the melting point of the high-melting-point resin material to 185° C. or higher, the adhesion of the deposited film can be further improved, and the gas barrier properties can be further improved. Moreover, the lamination strength of the packaging container can be further improved.
From the viewpoint of the film formability of the first substrate, the melting point of the high melting point resin material is preferably 265° C. or lower, more preferably 260° C. or lower, and even more preferably 250° C. or lower.
As used herein, the melting point can be measured according to JIS K7121:2012 (method for measuring transition temperature of plastics). Specifically, using a differential scanning calorimeter (DSC) apparatus, the DSC curve can be measured at a heating rate of 10° C./min to determine the melting point.

The high melting point resin material contained in the surface resin layer has a melting point TA, the polypropylene contained in the polypropylene resin layer has a melting point TB, and the difference between the melting points TA and TB is preferably 20° C. or more. The difference between melting point TA and melting point TB is preferably 80° C. or less, and more preferably 60° C. or less.
When the difference between the melting point TA and the melting point TB is 20° C. or more, the adhesion of the deposited film can be further improved, and the gas barrier properties can be further improved. Moreover, the lamination strength of the packaging container can be further improved.
Further, when the difference between the melting point TA and the melting point TB is 80° C. or less, the film formability of the first substrate can be further improved.

The high melting point resin material preferably has a polar group. In the present invention, a polar group refers to a group containing one or more heteroatoms. Polar groups include, for example, ester groups, epoxy groups, hydroxyl groups, amino groups, amide groups, carboxyl groups, carbonyl groups, carboxylic acid anhydride groups, sulfone groups, thiol groups and halogen groups. Among these, hydroxyl group, ester group, amino group, amide group, carboxyl group and carbonyl group are preferable, and amide group is more preferable, from the viewpoint of lamination strength of the packaging container.

The high-melting-point resin material can be used without particular limitation as long as it has a melting point of 180° C. or higher. Examples of high-melting resin materials include vinyl resins, polyamides, polyimides, polyesters, (meth)acrylic resins, cellulose resins, polyolefins, and ionomer resins.

The high-melting-point resin material has a melting point of 180° C. or higher and is particularly preferably a resin material having a polar group, and is preferably polyester or polyamide such as nylon 6, nylon 6,6, MXD nylon, and amorphous nylon.
By using such a resin material, the adhesiveness of the deposited film formed on the surface resin layer can be significantly improved, and the gas barrier property can be effectively improved.

In one embodiment, the high melting point resin material is preferably polyamide. By using polyamide as the high-melting-point resin material, it is possible to suppress deterioration of the gas barrier property even after bending the laminate, and to improve the heat resistance of the laminate. In addition, deterioration of gas barrier properties can be suppressed even after the laminate is subjected to retort treatment and boiling treatment, which will be described later. Nylon 6 is more preferable as the high melting point resin material.

The content of the high melting point resin material in the surface resin layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

The surface resin layer may contain a resin material other than the high-melting-point resin material as long as the characteristics of the present invention are not impaired.
The surface resin layer may contain additives within a range that does not impair the properties of the present invention. Additives include, for example, cross-linking agents, antioxidants, anti-blocking agents, slip agents, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments and modifying resins. mentioned.

The ratio of the thickness of the surface resin layer to the total thickness of the first substrate is preferably 1% or more. The ratio of the thickness of the surface resin layer to the total thickness of the first substrate is preferably 10% or less, more preferably 5% or less.
By setting the ratio of the thickness of the surface resin layer to the total thickness of the first base material to be 1% or more, the adhesion of the deposited film can be further improved, and the gas barrier properties can be further improved. Moreover, the lamination strength of the packaging container can be further improved.
By setting the ratio of the thickness of the surface resin layer to 10% or less with respect to the total thickness of the first base material, the film formability and workability of the first base material can be further improved. Moreover, as will be described later, it is possible to improve the recyclability of the packaging container produced using the laminate of the laminate of the present invention and a sealant layer made of polypropylene.

The thickness of the surface resin layer is preferably 0.1 μm or more. The thickness of the surface resin layer is preferably 5 μm or less, more preferably 4 μm or less.
By setting the thickness of the surface resin layer to 0.1 μm or more, the adhesion of the deposited film can be further improved, and the gas barrier properties can be further improved. Moreover, the lamination strength of the packaging container can be further improved.
Further, by setting the thickness of the surface resin layer to 5 μm or less, the film formability and workability of the first base material can be further improved. Moreover, as will be described later, it is possible to improve the recyclability of the packaging container produced using the laminate of the laminate of the present invention and a sealant layer made of polypropylene.

(Adhesive resin layer)
In one embodiment of the present invention, the first substrate may have an adhesive resin layer between the polypropylene resin layer and the surface resin layer. This can improve the interlayer adhesion between the polypropylene resin layer and the surface resin layer.

The adhesive resin layer can be formed from adhesive resins such as polyethers, polyesters, silicone resins, epoxy resins, polyurethanes, vinyl resins, phenolic resins, polyolefins, and acid-modified polyolefins. Among these, from the viewpoint of recyclability, polyolefin and acid-modified products thereof are preferred, and polypropylene and acid-modified products thereof are particularly preferred. As the adhesive polypropylene, a commercially available one can be used, for example, Admer series manufactured by Mitsui Chemicals, Inc. can be used.

Although the thickness of the adhesive resin layer is not particularly limited, it can be, for example, 1 μm or more and 15 μm or less. By setting the thickness of the adhesive resin layer to 1 μm or more, the adhesion between the polypropylene resin layer and the surface resin layer can be further improved. By setting the thickness of the adhesive resin layer to 15 μm or less, the workability of the first base material can be improved.

A stretching treatment is applied to the first base material composed of the respective layers described above. The mechanical strength is improved by applying the stretching treatment. The stretching treatment may be uniaxial stretching or biaxial stretching.

In one embodiment, the first substrate is a co-extruded film. A co-extruded film can be produced by forming a film using a T-die method, an inflation method, or the like, forming a laminated film, and then stretching the film. The inflation method is preferable from the viewpoint of productivity because film formation and stretching treatment can be continuously performed in one step.

The draw ratio of the first substrate in the machine direction (MD direction) and the transverse direction (TD direction) is preferably 2 times or more, more preferably 5 times or more. The draw ratio of the first substrate in the machine direction (MD direction) and the transverse direction (TD direction) is preferably 15 times or less, more preferably 13 times or less. By setting the draw ratio to 2 times or more, the strength of the first base material can be further improved. Moreover, the printability to the 1st base material can be improved. On the other hand, from the viewpoint of breaking limit of the first substrate, the draw ratio is preferably 15 times or less. When the polypropylene resin layer included in the first base material is given heat-sealing properties and a packaging container (for example, a tube) is produced by pasting an envelope, the draw ratio is more preferably 2 times or more and 10 times or less. , particularly preferably 2.5 times or more and 7 times or less.

In one embodiment, the stretching treatment is preferably performed so that the tensile strength in the machine direction (MD direction) of the first base material is greater than the tensile strength in the transverse direction (TD direction). With such a configuration, the packaging container produced from the laminate of the present invention can be imparted with high easiness of tearing in one direction.
The tensile strength in the longitudinal direction (MD direction) of the first base material is preferably 1.05 times or more, more preferably 1.10 times or more, relative to the tensile strength in the transverse direction (TD direction). Preferably, it is more preferably 1.2 times or more.
The tensile strength in the machine direction (MD direction) can be, for example, 200 MPa or more and 300 MPa or less.
As used herein, the tensile strength of the first substrate is measured according to JIS K7127:1999. As a measuring instrument, a tensile tester STA-1150 manufactured by Orientec Co., Ltd. can be used.
A rectangular film having a width of 15 mm and a length of 150 mm cut out from the first base material can be used as the test piece. The distance between the pair of chucks holding the specimen at the start of the measurement is 100 mm, and the pulling speed is 300 mm/min. In this specification, unless otherwise specified, the environment during the measurement of tensile strength is a temperature of 23° C. and a relative humidity of 50%.

A surface treatment may be applied to the surface resin layer that constitutes the first base material. This can improve adhesion with the adjacent layer (vapor-deposited film).
The method of surface treatment is not particularly limited, and examples include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas and/or nitrogen gas, physical treatment such as glow discharge treatment, and oxidation using chemicals. Chemical treatments such as treatments are included.

(evaporation film)
The laminate of the present invention has a deposited film made of an inorganic oxide on the surface resin layer. That is, the deposited film is adjacent to the surface resin layer. Thereby, gas barrier properties, specifically, oxygen barrier properties and water vapor barrier properties can be imparted to the laminate. Moreover, it is possible to suppress the decrease in the mass of the contents filled in the packaging container produced using the laminate of the present invention.

Examples of inorganic oxides include aluminum oxide (alumina), silicon oxide (silica), magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, and silicon oxide carbide (carbon-containing silicon oxide). etc. Among these, silica, silicon carbide oxide and alumina are preferable, and silica is particularly preferable from the viewpoint that aging treatment after vapor deposition film formation is unnecessary.

In one embodiment, the inorganic oxide is more preferably carbon-containing silicon oxide from the viewpoint of suppressing deterioration of the gas barrier property even after bending the laminate.

The thickness of the deposited film is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more. The thickness of the deposited film is preferably 150 nm or less, more preferably 60 nm or less, and even more preferably 40 nm or less. By setting the thickness of the deposited film to 1 nm or more, the oxygen barrier property and water vapor barrier property of the laminate can be further improved. On the other hand, by setting the thickness of the vapor deposition film to 150 nm or less, the generation of cracks in the vapor deposition film can be prevented. Moreover, if the thickness of the deposited film is within the above range, the suitability for recycling when the laminate is used as a packaging container is not impaired.

A vapor deposition film can be formed using a conventionally known method. Examples of methods for forming a deposited film include physical vapor deposition methods (physical vapor deposition methods, PVD methods) such as vacuum deposition methods, sputtering methods, and ion plating methods, as well as plasma chemical vapor deposition methods and thermal chemical vapor deposition methods. A chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a growth method and a photochemical vapor deposition method can be used.

The vapor deposited film may be a single layer formed by one vapor deposition process, or a multi-layer formed by multiple vapor deposition processes. If multiple layers, each layer may be of the same or different material. Further, each layer may be formed by the same method or by different methods.

A plasma-assisted vacuum film forming apparatus can be used as the apparatus used in the method of forming a deposited film by the PVD method.
An embodiment of a vapor deposition film forming method using a plasma-assisted vacuum film forming apparatus will be described below.

In one embodiment of the present invention, as shown in FIGS. 15 and 16, the vacuum film forming apparatus includes a vacuum container A, an unwinding section B, a film forming drum C, a winding section D, a transport roll E, and an evaporation source F. , a reaction gas supply unit G, a deposition protection box H, a vapor deposition material I, and a plasma gun J.
15 is a schematic cross-sectional view of the vacuum film forming apparatus in the XZ plane direction, and FIG. 16 is a schematic cross-sectional view of the vacuum film forming apparatus in the XY plane direction.

As shown in FIG. 15, a first base material 11A to be wound around a film forming drum C is arranged in the upper part of the vacuum container A with its surface resin layer facing downward. Below C, an electrically grounded anti-adhesion box H is arranged. An evaporation source F is arranged on the bottom surface of the anti-adhesion box H. A film-forming material is placed in the vacuum vessel A so that the surface resin layer surface of the first base material 11A wound around the film-forming drum C is located at a position facing the upper surface of the evaporation source F with a certain gap. A drum C is placed.

Between the unwinding section B and the film-forming drum C, and between the film-forming drum C and the winding section D, a transport roll E is arranged.
The vacuum vessel is connected with a vacuum pump (not shown).
The evaporation source F is for holding the vapor deposition material I, and is provided with a heating device (not shown).
The reaction gas supply part G is a part for supplying a reaction gas (oxygen, nitrogen, helium, argon, a mixed gas thereof, etc.) that reacts with the evaporated vapor deposition material.

The vapor deposition material I that is heated and evaporated from the evaporation source F is irradiated onto the surface resin layer of the first substrate 11A, and at the same time, plasma is also irradiated from the plasma gun J toward the surface resin layer. , a vapor deposition film is formed. Details of this forming method are disclosed in Japanese Patent Application Laid-Open No. 2011-214089.

As a plasma generator used in the plasma chemical vapor deposition method, a generator for high-frequency plasma, pulse wave plasma, microwave plasma, or the like can be used. Also, an apparatus having two or more film formation chambers may be used. The apparatus preferably has a vacuum pump so that each film forming chamber can be kept in vacuum.
The degree of vacuum in each film forming chamber is preferably 1×10 Pa or more and 1×10 ⁻⁶ Pa or less.
An embodiment of a deposition film forming method using a plasma generator will be described below.

First, the first substrate is delivered to the film formation chamber and conveyed onto the cooling/electrode drum at a predetermined speed via the auxiliary rolls.
Next, from the gas supply device, a mixed gas composition containing a film-forming monomer gas containing an inorganic oxide, an oxygen gas, an inert gas, and the like is supplied into the film-forming chamber, and a plasma is formed on the surface resin layer by glow discharge. is generated and irradiated to form a deposited film containing an inorganic oxide on the surface resin layer. Details of this forming method are disclosed in Japanese Patent Application Laid-Open No. 2012-076292.

FIG. 17 is a schematic configuration diagram showing a plasma chemical vapor deposition apparatus used for the CVD method.

In one embodiment, as shown in FIG. 17, the plasma enhanced chemical vapor deposition apparatus unwinds the first base material 11A from the unwinding part B1 arranged in the vacuum vessel A1, and then the first base material 11A. , and conveying rolls E1 onto the peripheral surface of the cooling/electrode drum C1 at a predetermined speed. Oxygen, nitrogen, helium, argon, and mixed gases thereof are supplied from G1 to the reactive gas supply, and a monomer gas for film formation is supplied from the source gas supply unit I1, and a mixed gas composition for vapor deposition consisting of them is prepared. While introducing the mixed gas composition for vapor deposition into the vacuum vessel A1 through the raw material supply nozzle H1, and the surface resin layer of the first substrate 11A conveyed onto the peripheral surface of the cooling/electrode drum C1. Plasma is generated on the top by glow discharge plasma F1 and irradiated to form a deposited film. At this time, the cooling/electrode drum C1 is supplied with a predetermined power from a power source K1 arranged outside the vacuum vessel A1, and a magnet J1 is arranged near the cooling/electrode drum C1 to generate plasma. Promotes development. Next, the first base material 11A is wound by the winding section D1 via the transport roll E1 at a predetermined winding speed after forming the deposited film. In the figure, L1 represents a vacuum pump.

A continuous vapor deposition film forming apparatus having a plasma pretreatment chamber and a film forming chamber can be used as an apparatus used in the vapor deposition film forming method.

An embodiment of a vapor deposition film forming method using the apparatus will be described below.
First, in the plasma pretreatment chamber, the surface resin layer of the first substrate is irradiated with plasma from the plasma supply nozzle. Next, in the film forming chamber, a vapor deposition film is formed on the surface resin layer that has been subjected to the plasma treatment. Details of this forming method are disclosed in International Publication WO2019/087960.

The surface of the deposited film is preferably subjected to the surface treatment described above. This can improve adhesion with adjacent layers.

In the laminate of the present invention, the deposited film is preferably a deposited film formed by a CVD method, more preferably a carbon-containing silicon oxide deposited film formed by a CVD method. As a result, deterioration of the gas barrier properties can be suppressed even after the laminate is bent.

The carbon-containing silicon oxide deposited film contains silicon, oxygen, and carbon. In the carbon-containing silicon oxide deposited film, the carbon ratio C is preferably 3% or more, more preferably 5% or more, with respect to the total 100% of the three elements of silicon, oxygen, and carbon. It is more preferably 10% or more. In the carbon-containing silicon oxide deposited film, the carbon ratio C is preferably 50% or less, more preferably 40% or less, with respect to the total 100% of the three elements of silicon, oxygen, and carbon. It is more preferably 35% or less.
By setting the carbon ratio C in the carbon-containing silicon oxide deposition film within the above range, it is possible to suppress deterioration of the gas barrier property even after bending the laminate.
In addition, in this specification, the ratio of each element is based on mol.

In one embodiment of the deposited film of carbon-containing silicon oxide, the ratio Si of silicon is preferably 1% or more, preferably 3% or more, with respect to the total 100% of the three elements of silicon, oxygen, and carbon. is more preferable, and 8% or more is even more preferable. The ratio Si of silicon is preferably 45% or less, more preferably 38% or less, and further preferably 33% or less with respect to the total 100% of the three elements of silicon, oxygen, and carbon. preferable.
In one embodiment of the deposited film of carbon-containing silicon oxide, the oxygen ratio O is preferably 10% or more, preferably 20% or more, with respect to the total 100% of the three elements of silicon, oxygen, and carbon. is more preferable, and 25% or more is even more preferable. It is preferably 70% or less, more preferably 65% or less, even more preferably 60% or less.
By setting the ratio Si of silicon and the ratio O of oxygen in the above ranges in the carbon-containing silicon oxide deposition film, it is possible to further suppress deterioration of gas barrier properties even after bending the laminate.

In one embodiment of the carbon-containing silicon oxide deposited film, the oxygen proportion O is preferably higher than the carbon proportion C, and the silicon proportion Si is preferably lower than the carbon proportion C. The proportion O of oxygen is preferably higher than the proportion Si of silicon, ie the respective proportions preferably decrease in the order of proportion O, proportion C and proportion Si. This makes it possible to further suppress deterioration of gas barrier properties even after bending the laminate.

The ratio C, ratio Si and ratio O in the carbon-containing silicon oxide deposited film can be measured by X-ray photoelectron spectroscopy (XPS) by narrow scan analysis under the following measurement conditions.
(Measurement condition)
Equipment used: “ESCA-3400” (manufactured by Kratos)
[1] Spectrum collection conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV)
X-ray output: 150W (10kV/15mA)
X-ray scanning area (measurement area): about 6mmφ
Photoelectron capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar ⁺
Acceleration voltage: 0.2 (kV)
Emission current: 20 (mA)
Etching range: 10mmφ
Ion sputtering time: 30 seconds, spectrum collected

(Barrier coat layer)
In one embodiment of the present invention, a barrier coat layer may be provided on the deposited film. By forming a barrier coat layer on the vapor deposition film surface, the oxygen barrier property and water vapor barrier property of the laminate are further improved.

In one embodiment, the barrier coat layer is a polyamide such as ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyacrylonitrile, nylon 6, nylon 6,6 and polymetaxylylene adipamide (MXD6). , polyesters, polyurethanes, and gas barrier resins such as (meth)acrylic resins. Among these, polyvinyl alcohol is preferable from the viewpoint of oxygen barrier properties and water vapor barrier properties.
Moreover, by including polyvinyl alcohol in the barrier coat layer, it is possible to effectively prevent the occurrence of cracks in the deposited film.

The content of the gas barrier resin in the barrier coat layer is preferably 50% by mass or more, more preferably 75% by mass or more. By setting the content of the gas barrier resin in the barrier coat layer to 50% by mass or more, the oxygen barrier properties and water vapor barrier properties can be further improved. The content of the gas barrier resin in the barrier coat layer is preferably 95% by mass or less, more preferably 90% by mass or less.

The barrier coat layer may contain additives such as those exemplified in the description of the first base material within a range that does not impair the properties of the present invention.

The thickness of the barrier coat layer is preferably 0.01 μm or more, more preferably 0.1 μm or more. The thickness of the barrier coat layer is preferably 10 μm or less, more preferably 5 μm or less. By setting the thickness of the barrier coat layer to 0.01 μm or more, the oxygen barrier property and water vapor barrier property of the laminate can be further improved. On the other hand, by setting the thickness of the barrier coat layer to 10 μm or less, the workability of the laminate can be improved. Further, if the thickness of the barrier coat layer is within the above range, even a different material different from polypropylene does not impair recyclability.

The barrier coat layer can be formed by dissolving or dispersing the above gas barrier resin in water or a suitable solvent, coating and drying. The barrier coat layer can also be formed by coating and drying a commercially available barrier coat agent.

In another embodiment, the barrier coat layer is obtained by polycondensing a mixture of a metal alkoxide and a water-soluble polymer by a sol-gel method in the presence of a sol-gel catalyst, water, an organic solvent, and the like. The gas barrier coating film contains at least one resin composition such as a decomposition product or a hydrolytic condensate of metal alkoxide. In one embodiment, the gas-barrier coating film is a gas-barrier coating film of a mixture of a metal alkoxide and a water-soluble polymer, or a gas-barrier coating film of a mixture of a metal alkoxide, a water-soluble polymer and a silane coupling agent. is.
By providing such a barrier coat layer on the vapor deposition film, the generation of cracks in the vapor deposition film can be effectively prevented.

In one embodiment, the metal alkoxide is represented by the following general formula.
R ¹ _n M (OR ² ) _m
(In the formula, R ¹ and R ² each represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents an integer of 1 or more. , n+m represents the valence of M.)

As the metal atom M, for example, silicon, zirconium, titanium and aluminum can be used.
Examples of organic groups represented by R ¹ and R ² include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group.

Metal alkoxides satisfying the general formula include, for example, tetramethoxysilane (Si( _OCH3 ) ₄ ), tetraethoxysilane ₍ Si _{( OC2H5} ) ₄ ), tetrapropoxysilane (Si( _OC3H7 ) ₄ ), tetrabutoxysilane (Si(OC ₄ H ₉ ) ₄ ), and the like.

A silane coupling agent is preferably used with the metal alkoxide.
As the silane coupling agent, known organic reactive group-containing organoalkoxysilanes can be used, but organoalkoxysilanes having an epoxy group are particularly preferred. Examples of organoalkoxysilanes having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. be done.

Two or more of the above silane coupling agents may be used, and the silane coupling agent is used in an amount of about 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the metal alkoxide. preferably.

As the water-soluble polymer, polyvinyl alcohol and ethylene-vinyl alcohol copolymer are preferable, and from the viewpoint of oxygen barrier properties, water vapor barrier properties, water resistance and weather resistance, it is preferable to use these together.

The content of the water-soluble polymer in the gas barrier coating film is preferably 5 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the metal alkoxide.
By setting the content of the water-soluble polymer in the gas barrier coating film to 5 parts by mass or more with respect to 100 parts by mass of the metal alkoxide, the oxygen barrier properties and water vapor barrier properties of the laminate can be further improved. Also, by setting the content of the water-soluble polymer in the gas barrier coating film to 500 parts by mass or less per 100 parts by mass of the metal alkoxide, the film formability of the gas barrier coating film can be improved.

In the gas barrier coating film, the ratio of metal alkoxide to water-soluble polymer (metal alkoxide/water-soluble polymer) is preferably 4.5 or less, more preferably 3.5 or less, on a mass basis. . The ratio of metal alkoxide to water-soluble polymer (metal alkoxide/water-soluble polymer) is preferably 1.0 or more, more preferably 1.7 or more, on a mass basis.
By setting the ratio of the metal alkoxide to the water-soluble polymer to 4.5 or less, deterioration of the gas barrier properties can be suppressed even after bending the laminate.
By setting the ratio of the metal alkoxide to the water-soluble polymer to 1.0 or more, the heat resistance of the laminate can be improved. In addition, deterioration of gas barrier properties can be suppressed even after the laminate is subjected to retort treatment and boiling treatment.
In addition, the said ratio is a solid content ratio.

On the surface of the gas barrier coating film, the ratio of silicon atoms to carbon atoms (Si/C) measured by X-ray photoelectron spectroscopy (XPS) is preferably 1.60 or less, and 1.35 or less. is more preferable. The ratio of silicon atoms to carbon atoms (Si/C) measured by X-ray photoelectron spectroscopy (XPS) is preferably 0.50 or more, more preferably 0.90 or more.
By setting the ratio of silicon atoms to carbon atoms at 1.60 or less, it is possible to suppress deterioration of gas barrier properties even after bending the laminate.
By setting the ratio of silicon atoms to carbon atoms to 0.50 or more, the heat resistance of the laminate can be improved. In addition, deterioration of gas barrier properties can be suppressed even after the laminate is subjected to retort treatment and boiling treatment.
The above range of the silicon atom to carbon atom ratio can be achieved by appropriately adjusting the ratio of the metal alkoxide to the water-soluble polymer.
In this specification, the ratio of silicon atoms to carbon atoms is on a molar basis.

The ratio of silicon atoms to carbon atoms by X-ray photoelectron spectroscopy (XPS) can be measured by narrow scan analysis under the following measurement conditions.
(Measurement condition)
Equipment used: “ESCA-3400” (manufactured by Kratos)
[1] Spectrum collection conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV)
X-ray output: 150W (10kV/15mA)
X-ray scanning area (measurement area): about 6mmφ
Photoelectron capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar ⁺
Acceleration voltage: 0.2 (kV)
Emission current: 20 (mA)
Etching range: 10mmφ
Ion sputtering time: 30 seconds + 30 seconds + 60 seconds (total 120 seconds) to collect spectra

The thickness of the gas barrier coating film is preferably 0.01 μm or more, more preferably 0.1 μm or more. The thickness of the gas barrier coating film is preferably 100 μm or less, more preferably 50 μm or less. Thereby, the oxygen barrier property and the water vapor barrier property can be further improved while maintaining the recyclability.
By setting the thickness of the gas barrier coating film to 0.01 μm or more, the oxygen barrier property and water vapor barrier property of the laminate can be improved. Also, cracks can be prevented from occurring in the deposited film.
By setting the thickness of the gas-barrier coating film to 100 μm or less, it is possible to improve the recyclability of the packaging container produced using the laminate of the laminate of the present invention and a sealant layer made of polypropylene.

The gas barrier coating film is formed by applying a composition containing the above materials by conventionally known means such as roll coating such as gravure roll coater, spray coating, spin coating, dipping, brush, bar code, and applicator. It can be formed by polycondensing the material by the sol-gel method.
As the sol-gel process catalyst, an acid or amine compound is suitable. As the amine-based compound, tertiary amines that are substantially insoluble in water and soluble in organic solvents are suitable. amines and the like. Among these, N,N-dimethylbenzylamine is preferred.
The sol-gel catalyst is preferably used in the range of 0.01 parts by mass or more and 1.0 parts by mass or less, and is used in the range of 0.03 parts by mass or more and 0.3 parts by mass or less per 100 parts by mass of the metal alkoxide. is more preferable.
By setting the amount of the sol-gel catalyst to be used to 0.01 parts by mass or more per 100 parts by mass of the metal alkoxide, the catalytic effect can be improved. Further, by setting the amount of the sol-gel process catalyst used to 1.0 parts by mass or less per 100 parts by mass of the metal alkoxide, the thickness of the gas barrier coating film formed can be made uniform.

The composition may further contain an acid. Acids are used as catalysts for sol-gel processes, mainly for hydrolysis of metal alkoxides and silane coupling agents.
Examples of acids that can be used include mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid. The amount of the acid used is preferably 0.001 mol or more and 0.05 mol or less with respect to the total molar amount of the metal alkoxide and the alkoxide portion (for example, silicate portion) of the silane coupling agent.
By setting the amount of the acid used to be 0.001 mol or more with respect to the total molar amount of the metal alkoxide and the alkoxide portion (for example, silicate portion) of the silane coupling agent, the catalytic effect can be improved. In addition, the amount of acid used is 0.05 mol or less with respect to the total molar amount of the metal alkoxide and the alkoxide portion (for example, the silicate portion) of the silane coupling agent. can be made uniform.

The composition preferably contains water in a proportion of preferably 0.1 mol or more and 100 mol or less, more preferably 0.8 mol or more and 2 mol or less, per 1 mol of the total molar amount of the metal alkoxide. .
By setting the water content to 0.1 mol or more per 1 mol of the total molar amount of the metal alkoxide, the laminate of the present invention can have improved oxygen barrier properties and water vapor barrier properties. Further, by setting the content of water to 100 mol or more per 1 mol of the total molar amount of the alkoxide, the hydrolysis reaction can be carried out quickly.

The composition may contain an organic solvent. Examples of organic solvents that can be used include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butanol.

An embodiment of a method for forming a gas barrier coating film will be described below.

First, a composition is prepared by mixing a metal alkoxide, a water-soluble polymer, a sol-gel process catalyst, water, an organic solvent, and optionally a silane coupling agent. A polycondensation reaction proceeds gradually in the composition.
Then, the composition is applied onto the deposited film by the above-described conventionally known method and dried. By this drying, the polycondensation reaction of the metal alkoxide and the water-soluble polymer (and the silane coupling agent when the composition contains a silane coupling agent) further proceeds to form a composite polymer layer.
Finally, the composition is heated at a temperature of 20° C. to 250° C., preferably 50° C. to 220° C. for 1 second to 10 minutes to form a gas barrier coating film.

A printed layer may be formed on the surface of the barrier coat layer. The method for forming the printed layer and the like are as described above.

(sealant layer)
The sealant layer comprises a polyolefin having a melting point of 110°C or higher. Thereby, the heat resistance of the laminate can be improved. Moreover, the packaging container produced using this laminated body has heat resistance. The polyolefin is not particularly limited as long as it has a melting point of 110° C. or higher, and examples thereof include polyethylene and polypropylene.
In this specification, "polyolefin having a melting point of 110°C or higher" means polyolefin having a maximum peak temperature of 110°C or higher in DSC.

The sealant layer preferably comprises a sealant material having a melting point of 150°C or higher.
Packaging containers such as retort or boiling pouches are subjected to retort treatment or boiling treatment after being filled with contents, which may lead to deterioration of gas barrier properties and heat sealing properties. Since the sealant layer contains a sealant material having a melting point of 150° C. or higher, the packaging container produced by using the laminate having the sealant layer has gas barrier properties and heat sealing properties even in heat treatment such as retort treatment or boiling treatment. (Retort processing suitability, boiling processing suitability).
Retort processing is processing in which a retort pouch is filled with contents and sealed, and then the retort pouch is heated under pressure using steam or heated hot water. The retort treatment is performed at 121° C. for 3 minutes, for example. The boiling treatment is performed at 90° C. for 3 minutes, for example.

BACKGROUND ART Conventionally, a laminate in which a base material and a sealant layer are made of different resin materials has been used to produce packaging containers. On the other hand, since it is difficult to separate the base material and the sealant layer after collecting the used packaging container, there is a current situation that recycling is not actively carried out.
By forming the first base material and the sealant layer from the same material, there is no need to separate the first base material and the sealant layer, and the suitability for recycling can be improved. That is, the sealant layer preferably contains polypropylene having a melting point of 150° C. or higher from the viewpoint of recyclability of the packaging container produced using the laminate.
In addition, by including the polypropylene in the sealant layer, the oil resistance of the packaging container produced using the laminate can be improved.
Polypropylene can be homopolymers, random copolymers and block copolymers. Among these, block copolymers are preferred from the viewpoint of suitability for retort processing and boiling processing.
Moreover, by using a block copolymer, the impact resistance of packaging containers such as retort pouches or boiling pouches produced using the laminate of the present invention can be improved. That is, it is possible to suppress the breakage of packaging containers such as retort pouches or boiling pouches produced using the laminate of the present invention due to impact when dropped.
As block copolymers, for example, propylene-ethylene block copolymers and the like can be used.

"Propylene-ethylene block copolymer" means a polymer having the structural formula shown below in formula (1). In formula (1), m1, m2 and m3 represent integers of 1 or more.

"Propylene-ethylene random copolymer" means a polymer having the structural formula shown below in Formula (2). In formula (2), m and n represent integers of 1 or more.

The sealant layer can contain sealant materials other than polypropylene, for example, polyethylene, as long as the properties of the present invention are not compromised. Thereby, a sea-island structure can be formed in the sealant layer. The term "sea-island structure" as used herein means a structure in which polyethylene is discontinuously dispersed within a region in which polypropylene is continuous.
When the sealant layer contains a sealant material other than polypropylene, the sealant layer is not limited to having a sea-island structure, and may be in a state in which two materials are compatible with each other.

The sealant layer can contain the heat seal modifiers and additives as long as the characteristics of the present invention are not impaired.

The sealant layer may have a single layer structure or a multilayer structure.

The thickness of the sealant layer is preferably 15 μm or more, more preferably 20 μm or more. The thickness of the sealant layer is preferably 100 μm or less, more preferably 70 μm or less.
By setting the thickness of the sealant layer to 15 μm or more, the lamination strength, suitability for retort treatment, and suitability for boiling of the packaging container comprising the laminate of the present invention can be further improved.
Further, by setting the thickness of the sealant layer to 100 μm or less, the workability of the laminate of the present invention can be further improved.

The sealant layer may be formed by laminating stretched or unstretched films having heat-sealing properties via a conventionally known adhesive, or may be formed by coating and drying a heat-sealing agent. The term "unstretched film" is a concept that includes not only a film that is not stretched at all but also a film that is slightly stretched due to the tension applied during film formation.

(adhesion layer)
The adhesive layer contains at least one kind of adhesive, and may be either a one-component curing type, a two-component curing type, or a non-curing type adhesive. The adhesive may be a non-solvent type adhesive or a solvent type adhesive, but the non-solvent type adhesive can be preferably used from the viewpoint of environmental load.
Examples of solventless adhesives include polyether adhesives, polyester adhesives, silicone adhesives, epoxy adhesives and urethane adhesives. system adhesives can be preferably used.
Examples of solvent-based adhesives include rubber-based adhesives, vinyl-based adhesives, silicone-based adhesives, epoxy-based adhesives, phenol-based adhesives, and olefin-based adhesives.

The thickness of the adhesive layer is not particularly limited, and can be, for example, 0.1 μm or more and 10 μm or less.

(Second base material)
The second base material fulfills the function of holding each layer. The second base material includes a resin material such as polyolefin, vinyl resin, polyester, (meth)acrylic resin, and cellulose resin. Among these, polypropylene is particularly preferable from the viewpoint of recyclability of the laminate.

The second base material may contain additives similar to those described above as long as the properties of the present invention are not impaired.

The second base material may be provided with the vapor deposition film or the barrier coat layer on its surface.

The second base material is preferably composed of a resin film composed of the above resin material, and the resin film is preferably stretched. The stretching treatment may be uniaxial stretching or biaxial stretching.

In the embodiment provided with the second substrate, it is particularly preferable to form the second substrate from a stretched polypropylene resin film from the viewpoint of recyclability.

The thickness of the second base material is preferably 10 μm or more. The thickness of the second base material is preferably 50 μm or less, more preferably 40 μm or less.
By setting the thickness of the second base material to 10 μm or more, the strength of the laminate can be further improved.
Further, by setting the thickness of the second base material to 50 μm or less, the workability of the laminate can be further improved.

A 2nd base material can be provided through an above-described contact bonding layer.

A printed layer may be formed on the surface of the second base material. The method for forming the printed layer and the like are as described above.

(middle layer)
In one embodiment, the laminate may be provided with an intermediate layer between the deposited film and the sealant layer (when the barrier coat layer is provided, between the barrier coat layer and the sealant layer). . The intermediate layer includes a resin material such as polyolefin, vinyl resin, polyester, (meth)acrylic resin, and cellulose resin. Among these, polypropylene is particularly preferable from the viewpoint of recyclability of the laminate.

The intermediate layer may contain additives similar to those described above as long as the properties of the present invention are not impaired.

The intermediate layer may have the vapor-deposited film or barrier coat layer on its surface.

The intermediate layer is preferably composed of a resin film composed of the above resin material, and the resin film is preferably stretched.

In embodiments with an intermediate layer, it is particularly preferred to use a oriented polypropylene resin film as the intermediate layer.
When a stretched polypropylene resin film is used for the intermediate layer, the ease of tearing can be further improved as compared with the case where the stretched polypropylene resin film is not used. This is because when a stretched film is not used for the intermediate layer, the film that constitutes the heat seal layer is unstretched, so it is flexible and stretchable, so it is difficult to open the film or leave a film when unsealing. This is because it is considered that the tear easiness related to the is inferior.
In addition, wrinkles that may occur due to heat shrinkage due to retort treatment, boiling treatment, or heating during heat sealing can be reduced, and the appearance is improved. Furthermore, when the laminate is used as a cover material, it is possible to prevent the occurrence of wrinkles after heat-sealing, and the appearance is improved.

The thickness of the intermediate layer is preferably 10 μm or more. The thickness of the intermediate layer is preferably 50 μm or less, more preferably 40 μm or less.
By setting the thickness of the intermediate layer to 10 μm or more, the strength of the laminate can be further improved.
Further, by setting the thickness of the intermediate layer to 50 μm or less, the workability of the laminate can be further improved.

The intermediate layer can be provided via the adhesive layer described above.

A printed layer may be formed on the surface of the intermediate layer. The method for forming the printed layer and the like are as described above.

In one embodiment, the intermediate layer may be the second substrate.

[Laminate in Second Aspect]
As shown in FIG. 18, the laminate 10B of the present invention includes a first base material 11, a deposited film 12, and a sealant layer 13. The first base material 11 includes a polypropylene resin layer 14 and a surface coating layer. 15.
In one embodiment of the present invention, the laminate 10 may further include a barrier coat layer 16 between the deposited film 12 and the sealant layer 13, as shown in FIG.
In one embodiment of the invention, the laminate may further comprise a second substrate. When the laminate includes the second base material, the laminate 10 includes the second base material 17, the deposited film 12, the first base material 11, and the sealant layer 13 in this order, as shown in FIG. Alternatively, as shown in FIG. 21, a second base material 17, a first base material 11, a deposited film 12, and a sealant layer 13 may be provided in order, and as shown in FIG. The material 11, the deposited film 12, the second substrate 17, and the sealant layer 13 may be provided in this order. The second base material 17 in the laminate 10 of FIGS. 20 and 21 and the first base material 11 in the laminate 10 of FIG.
In one embodiment of the present invention, laminate 10 may include an adhesive layer (not shown) between any of the deposited film, sealant layer, first substrate, and second substrate. In another embodiment, the laminate of the present invention may comprise an intermediate layer between the deposited film and the sealant layer, and the intermediate layer may be the second substrate.

The haze value of the laminate is preferably 20% or less, more preferably 5% or less. Thereby, the transparency of the laminate can be improved.

In the laminate in the second aspect, the lamination strength between the first base material and the deposited film is preferably 3N or more, more preferably 4N or more, and still more preferably 5.5N or more in a width of 15 mm. The upper limit of the laminate strength of the laminate in the second aspect may be 20 N or less.
A method for measuring the lamination strength of the laminate will be described in the examples below.

The tensile strength in one direction of the laminate may be 30 MPa or more, or 35 MPa or more. The tensile strength in one direction of the laminate may be 70 MPa or less, or 50 MPa or less. One direction of the laminate may be the longitudinal direction (MD direction).
The tensile strength of the laminate in a direction perpendicular to the one direction may be 40 MPa or more, or 60 MPa or more. The tensile strength of the laminate in a direction perpendicular to the one direction may be 150 MPa or less, or 100 MPa or less. The direction perpendicular to the one direction may be the lateral direction (TD direction) of the laminate.
In this specification, the tensile strength of the laminate is measured according to JIS K7127:1999. As a measuring instrument, a tensile tester STA-1150 manufactured by Orientec Co., Ltd. can be used.
A rectangular laminate having a width of 10 mm and a length of 150 mm can be used as the test piece. The distance between the pair of chucks holding the test piece is 50 mm at the start of the measurement, and the pulling speed is 300 mm/min. In this specification, unless otherwise specified, the environment during the measurement of tensile strength is a temperature of 23° C. and a relative humidity of 50%.

The loop stiffness in one direction of the laminate may be 30 mN or more, 50 mN or more, or 70 mN or more. The loop stiffness in one direction of the laminate may be 200 mN or less, 150 mN or less, or 120 mN or less. One direction of the laminate may be the longitudinal direction (MD direction).
The loop stiffness of the laminate in a direction perpendicular to the one direction may be 30 mN or more, 50 mN or more, or 70 mN or more. The loop stiffness of the laminate in a direction perpendicular to the one direction may be 200 mN or less, 150 mN or less, or 130 mN or less. The direction perpendicular to the one direction may be the lateral direction (TD direction) of the laminate.
The loop stiffness measuring method is as described in the first aspect.

The laminate may have a piercing strength of 10 N or more, or 15 N or more.
The puncture strength of the laminate is measured according to JIS Z1707 7.4. A specific measuring method will be described in Examples described later.

As in the first aspect, it is preferable that the sealant layer is made of the same material as the polypropylene resin layer of the first substrate, that is, polypropylene. Thereby, the recyclability of the packaging container produced using the laminate of the present invention can be improved.

When the sealant layer is made of polypropylene, the content of polypropylene with respect to the total amount of the resin material contained in the laminate of the present invention is preferably 80% by mass or more, and more preferably 95% by mass or more. Thereby, the recyclability of the packaging container produced using the laminate of the present invention can be further improved.

Hereinafter, the laminate in the second aspect of the present invention will be described, but the layers other than the surface coat layer constituting the first base material are the same as the laminate in the first aspect described above, so here Description is omitted.

(Surface coat layer)
A 1st base material equips a surface coat layer containing the resin material which has a polar group on a polypropylene resin layer. Thereby, a deposited film having high adhesion can be formed on the surface coat layer, and the gas barrier property can be improved.
Moreover, as will be described later, a packaging container produced using a laminate having the surface coat layer has high lamination strength.
In one embodiment, the surface coat layer may be provided on the polypropylene resin layer. That is, the surface coat layer may be adjacent to the polypropylene resin layer.

The surface coat layer contains a resin material having a polar group. In the present invention, a polar group refers to a group containing one or more heteroatoms. Polar groups include, for example, ester groups, epoxy groups, hydroxyl groups, amino groups, amide groups, carboxyl groups, carbonyl groups, carboxylic acid anhydride groups, sulfone groups, thiol groups and halogen groups. Among these, carboxyl group, carbonyl group, ester group, hydroxyl group and amino group are preferable, and carboxyl group and hydroxyl group are more preferable, from the viewpoint of laminating property of the packaging container.

As the resin material having a polar group, polyester, polyethyleneimine, hydroxyl group-containing (meth)acrylic resin, polyamide such as nylon 6, nylon 6,6, MXD nylon, amorphous nylon, polyurethane, and the like are preferable.
By using such a resin material, the adhesiveness of the deposited film formed on the surface coat layer can be significantly improved, and the gas barrier property can be effectively improved.

In one embodiment, the resin material having a polar group is preferably a hydroxyl group-containing (meth)acrylic resin. Thereby, the heat resistance of the laminate can be improved. In addition, deterioration of gas barrier properties can be suppressed even after the laminate is subjected to retort treatment and boiling treatment.

In one embodiment of the present invention, the hydroxyl group-containing (meth)acrylic resin used for forming the surface coat layer is a polymer of a neutral monomer and a hydroxyl group-containing (meth)acrylic monomer.
Examples of neutral monomers include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( meth)lauryl acrylate, styrene, vinyl toluene, vinyl acetate and the like.
Examples of hydroxyl group-containing (meth)acrylic monomers include 2-hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

The glass transition temperature (Tg) of the hydroxyl group-containing (meth)acrylic resin is preferably 50°C or higher, more preferably 70°C or higher. The glass transition temperature (Tg) of the hydroxyl group-containing (meth)acrylic resin is preferably 200° C. or lower, more preferably 150° C. or lower.
By setting the glass transition temperature (Tg) of the hydroxyl group-containing (meth)acrylic resin to 50° C. or higher, the blocking resistance can be improved.
By setting the glass transition temperature (Tg) of the hydroxyl group-containing (meth)acrylic resin to 200° C. or less, the reactivity of these when using an isocyanate compound together with the hydroxyl group-containing (meth)acrylic resin for forming the surface coat layer can be improved.
In this specification, Tg can be measured according to JIS K7121:2012 (method for measuring transition temperature of plastics). Specifically, using a differential scanning calorimeter (DSC) device, the DSC curve can be measured at a heating rate of 10° C./min to determine the Tg.

The number average molecular weight of the hydroxyl group-containing (meth)acrylic resin is preferably 10,000 or more. The number average molecular weight of the hydroxyl group-containing (meth)acrylic resin is preferably 100,000 or less.
By setting the number average molecular weight of the hydroxyl group-containing (meth)acrylic resin to 10,000 or more, the blocking resistance can be improved.
By setting the number average molecular weight of the hydroxyl group-containing (meth)acrylic resin to 100,000 or more, the easiness of forming the surface coat layer can be improved.
In addition, in this specification, a number average molecular weight can be measured by a gel permeation chromatography (GPC). In GPC measurement, the number average molecular weight of a polymer is generally measured in terms of standard polystyrene.

The hydroxyl value of the hydroxyl-containing (meth)acrylic resin is preferably 20 mgKOHL/g or more, more preferably 30 mgKOHL/g or more. The hydroxyl value of the hydroxyl-containing (meth)acrylic resin is preferably 200 mgKOHL/g or less, more preferably 150 mgKOHL/g or less.
By setting the hydroxyl value of the hydroxyl group-containing (meth)acrylic resin to 20 mgKOHL/g or more, the reactivity of these when using an isocyanate compound together with the hydroxyl group-containing (meth)acrylic resin for forming the surface coat layer can be improved.
By setting the hydroxyl value of the hydroxyl group-containing (meth)acrylic resin to 200 mgKOHL/g or less, the amount of isocyanate compound used can be suppressed, and the production cost can be reduced.
In the present specification, hydroxylation can be measured according to JIS K0070:1992 (testing methods for oxidation, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products).

In the present invention, the surface coat layer can be formed using an aqueous emulsion or a solvent emulsion. Specific examples of water-based emulsions include polyamide-based emulsions, polyethylene-based emulsions, and polyurethane-based emulsions. Specific examples of solvent-based emulsions include polyester-based emulsions.

The content of the resin material having a polar group in the surface coat layer is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

The surface coat layer may contain a resin material other than the resin material having a polar group, as long as the characteristics of the present invention are not impaired.
In one embodiment of the present invention, the surface coat layer may contain an isocyanate compound.
The surface coat layer may contain additives as long as the properties of the present invention are not impaired. Additives include, for example, cross-linking agents, antioxidants, anti-blocking agents, slip agents, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments and modifying resins. mentioned.

The ratio of the thickness of the surface coat layer to the total thickness of the first substrate is preferably 0.08% or more, more preferably 0.2% or more, and 1% or more. More preferably, it is still more preferably 3% or more. The ratio of the thickness of the surface coat layer to the total thickness of the first substrate is preferably 20% or less, more preferably 10% or less.
By setting the ratio of the thickness of the surface coat layer to the total thickness of the first base material to be 0.08% or more, the adhesion of the deposited film can be further improved, and the gas barrier properties can be further improved. Moreover, the lamination strength of the packaging container can be further improved.
By setting the ratio of the thickness of the surface coat layer to 20% or less with respect to the total thickness of the first base material, the film formability and workability of the first base material can be further improved. Moreover, as will be described later, it is possible to improve the recyclability of the packaging container produced using the laminate of the laminate of the present invention and a sealant layer made of polypropylene.

The thickness of the surface coat layer is preferably 0.02 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and even more preferably 0.2 μm or more. preferable. The thickness of the surface coat layer is preferably 10 μm or less, more preferably 5 μm or less.
By setting the thickness of the surface coat layer to 0.02 μm or more, the adhesion of the deposited film can be further improved, and the gas barrier properties can be further improved. Moreover, the lamination strength of the packaging container can be further improved.
By setting the thickness of the surface coat layer to 10 μm or less, the film formability and workability of the first base material can be further improved. Moreover, as will be described later, it is possible to improve the recyclability of the packaging container produced using the laminate of the laminate of the present invention and a sealant layer made of polypropylene.

The first base material can be manufactured off-line, specifically, a resin composition containing polypropylene is formed into a film using a T-die method or an inflation method, etc., and then stretched to form a resin film. It can be prepared by applying a coating liquid for forming a coat thereon and drying it.
In addition, the first base material can be manufactured in-line. Specifically, a resin composition containing polypropylene is formed into a film by using a T-die method or an inflation method, and after making a resin film, the lengthwise direction (MD direction ), apply a coat-forming coating solution on the resin film, dry it, and then stretch it in the transverse direction (TD direction). In addition, you may perform extending|stretching to a horizontal direction first. In addition, the film may be stretched in both the longitudinal direction and the transverse direction before or after the coat-forming coating liquid is applied.

[Packaging container]
A packaging container of the present invention is characterized by comprising the laminate described above. Examples of packaging containers include packaging products (packaging bags), lids, laminate tubes, and the like.
In the present invention, the laminate is particularly excellent in retort treatment suitability and boiling treatment suitability, so that the packaging container is preferably a retort pouch or a boiling pouch among packaging bags.

As a packaging bag, for example, standing pouch type, side seal type, two side seal type, three side seal type, four side seal type, envelope pasted seal type, palm pasted seal type (pillow seal type), pleated seal type, flat bottom seal type , square bottom seal type, and gusset type packaging bags.

Hereinafter, a preferred embodiment of the present invention, a pouch for retort or boiling, will be described.

As shown in FIG. 23, the retort or boiling pouch 30 of the present invention is obtained by bonding two laminates together (hatched portions are heat-sealed portions). After the content is filled from one side of the retort or boiling pouch 30 that is not heat-sealed, this side is also heat-sealed.
When the tensile strength in the longitudinal direction (MD direction) of the first base material is greater than the tensile strength in the transverse direction (TD direction), the longitudinal direction (MD direction) of the first base material is a pouch for retort or boiling It is preferable to manufacture the packaging bag so that the lateral direction of the first substrate (TD direction) corresponds to the longitudinal direction of the retort pouch or boiling pouch 30 . Such a configuration makes it extremely easy to tear the packaging container in the lateral direction. The same applies to packaging containers exemplified below.

The pouch for retort or boiling shown in FIG. 24 is a standing type pouch 40 for retort or boiling.
As shown in FIG. 24, a standing-type retort or boiling pouch 40 is composed of a body (side sheet) 41 and a bottom (bottom sheet) 42 .
At least one of the side sheet 41 and the bottom sheet 42 of the standing-type retort or boiling pouch 40 is composed of the laminate of the present invention.

In one embodiment, the body portion 41 of the standing-type retort or boiling pouch 40 can be formed by making a bag so that the sealant layer of the laminate of the present invention is the innermost layer.
In another embodiment, for the side sheets 41, two laminates of the present invention are prepared, these are superimposed so that the sealant layers face each other, and the sealant layer is on the outside from both ends of the superimposed laminate. It can be formed by inserting and heat-sealing two laminated bodies folded in a V shape as shown in FIG. According to such a manufacturing method, a stand-type retort or boiling pouch having a body with side gussets can be obtained.

In one embodiment, the bottom sheet 42 of the standing-type retort or boiling pouch 40 is formed by inserting the laminate of the present invention between the bag-made side sheets and heat-sealing them. can be done. More specifically, the laminate can be formed by folding the laminate into a V shape with the sealant layer on the outside, inserting it between the bag-made side sheets, and heat-sealing.

Moreover, the packaging container may be provided with an easy opening means 51 as shown in FIGS. 23 and 24 .
Examples of the easy-to-open means 51 include a notch 52 as a starting point of tearing, and a half-cut line 53 formed by laser processing or a cutter as a tearing path, as shown in FIG.

As the heat sealing method, known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, and ultrasonic sealing can be used.

The content filled in the packaging container is not particularly limited, and may be liquid, powder, or gel. Moreover, the content may be food or non-food.

<Other aspects>
In another aspect, the invention is a laminate comprising:
At least, comprising a first substrate, a deposited film and a sealant layer,
The first base material comprises a polypropylene resin layer and a surface resin layer provided on one surface of the polypropylene resin layer,
The deposited film is provided on the surface resin layer of the first base material,
The first base material is stretched,
The surface resin layer contains a resin material having a melting point of 180° C. or higher,
The deposited film is composed of an inorganic oxide,
The laminate is such that the sealant layer contains polyolefin having a melting point of 110° C. or higher.
In one embodiment, the surface resin layer is provided on the polypropylene resin layer.
In one embodiment, the first substrate comprises an adhesive resin layer between the polypropylene resin layer and the surface resin layer,
The adhesive resin layer is provided on the polypropylene resin layer,
The surface resin layer is provided on the adhesive resin layer.
In one embodiment, the surface resin layer contains a resin material having a melting point of 180° C. or higher and 265° C. or lower.
In one embodiment, the resin material of the surface resin layer has a melting point TA,
The polypropylene of the polypropylene resin layer has a melting point TB,
The difference between the melting point TA and the melting point TB is 20° C. or more and 80° C. or less.
In one embodiment, the resin material of the surface resin layer is made of a polymer having a polar group.
In one embodiment, the resin material of the surface resin layer is one or more resin materials selected from nylon 6, nylon 6,6, MXD nylon and amorphous nylon.
In one embodiment, the ratio of the thickness of the surface resin layer to the total thickness of the first base material is 1% or more and 10% or less.
In one embodiment, the first substrate is a co-extruded film.
In another aspect, the invention is a laminate comprising:
At least, comprising a first substrate, a deposited film and a sealant layer,
The first base material comprises a polypropylene resin layer and a surface coat layer provided on one surface of the polypropylene resin layer,
The deposited film is provided on the surface coat layer of the first base material,
The first base material is stretched,
The surface coat layer contains a resin material having a polar group,
The deposited film is composed of an inorganic oxide,
The laminate is such that the sealant layer contains polyolefin having a melting point of 110° C. or higher.
In one embodiment, the resin material of the surface coat layer is one or more resin materials selected from polyester, polyethyleneimine, hydroxyl group-containing (meth)acrylic resin, nylon 6, nylon 6,6, MXD nylon, amorphous nylon and polyurethane. is.
In one embodiment, the surface coat layer is a layer formed using an aqueous emulsion or a solvent emulsion.
In one embodiment, the ratio of the thickness of the surface coat layer to the total thickness of the first base material is 0.08% or more and 20% or less.
In one embodiment, the surface coat layer has a thickness of 0.02 μm or more and 10 μm or less.
In one embodiment, the sealant layer comprises a sealant material having a melting point of 150°C or higher.
In one embodiment, the sealant layer comprises polypropylene having a melting point of 150°C or higher.
In one embodiment, the laminate further comprises a second substrate.
In one embodiment, the second substrate comprises polypropylene.
In one embodiment, the first substrate and the deposited film are located between the second substrate and the sealant layer.
In one embodiment, the laminate comprises an intermediate layer between the deposited film and the sealant layer,
The intermediate layer is the second base material.
In one embodiment, the intermediate layer is made of a stretched polypropylene resin film.
In one embodiment, a barrier coat layer is further provided between the deposited film and the sealant layer.
In one embodiment, the barrier coat layer is a gas barrier coating film of a mixture of a metal alkoxide and a water-soluble polymer, or a gas barrier coating of a mixture of a metal alkoxide, a water-soluble polymer and a silane coupling agent. membrane.
In one embodiment, the laminate is used for packaging containers.
In another aspect, the present invention is a pouch for retorting or boiling, comprising the laminate.
In one embodiment, the retort or boil pouch is provided with a notch.
In one embodiment, the retort or boil pouch is provided with a half cut line.

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

Example 1
Polyamide (manufactured by Ube Industries, Ltd., polyamide 6, melting point: 220 ° C.), adhesive resin (manufactured by Mitsui Chemicals, Admer QF500, maleic anhydride-modified polypropylene), and polypropylene (manufactured by Japan Polypropylene Corporation, Novatec FL203D, melting point: 160°C), and then stretched 5 times in the machine direction (MD direction) and 10 times in the transverse direction (TD direction) by a sequential biaxial stretching device to obtain a surface resin made of polyamide. A substrate having a thickness of 21 μm was prepared, comprising a layer (0.4 μm), an adhesive resin layer (1 μm) made of an adhesive resin, and a polypropylene resin layer (19.6 μm) made of polypropylene. The ratio of the thickness of the surface resin layer made of polyamide to the layer thickness of the substrate was 2%.

On the surface resin layer of the base material produced as described above, using a low-temperature plasma chemical vapor deposition apparatus, which is an actual machine, by Roll to Roll while applying tension to the base material, carbon-containing oxidation with a thickness of 12 nm is performed. A silicon deposition film was formed (CVD method). In addition, vapor deposition film forming conditions were as follows.
(Formation conditions)
・ Hexamethyldisiloxane: oxygen gas: helium = 1:10:10 (unit: slm)
・Power supplied to cooling/electrode drum: 22 kw
・Line speed: 100m/min

In the carbon-containing silicon oxide vapor deposition film, the ratio C of carbon, the ratio Si of silicon, and the ratio O of oxygen are 32.7% and 29%, respectively, with respect to the total 100% of the three elements of silicon, oxygen, and carbon. .8% and 37.5%. The proportion of each element was measured by X-ray photoelectron spectroscopy (XPS) by narrow scan analysis under the following measurement conditions.
(Measurement condition)
Equipment used: “ESCA-3400” (manufactured by Kratos)
[1] Spectrum collection conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV)
X-ray output: 150W (10kV/15mA)
X-ray scanning area (measurement area): about 6mmφ
Photoelectron capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar ⁺
Acceleration voltage: 0.2 (kV)
Emission current: 20 (mA)
Etching range: 10mmφ
Ion sputtering time: 30 seconds, spectrum collected

385 g of water, 67 g of isopropyl alcohol and 9.1 g of 0.5N hydrochloric acid were mixed to obtain a prepared pH 2.2 solution. To this solution, 175 g of tetraethoxysilane as a metal alkoxide and 9.2 g of glycidoxypropyltrimethoxysilane as a silane coupling agent were mixed while cooling to 10° C. to obtain a solution A.
A solution B was obtained by mixing 14.7 g of polyvinyl alcohol having a saponification degree of 99% or more and a degree of polymerization of 2400 as a water-soluble polymer, 324 g of water and 17 g of isopropyl alcohol.
Solution A and solution B were mixed at a ratio of 6.5:3.5 on a mass basis to obtain a barrier coating agent.

A barrier coating agent was applied onto the deposited film formed on the substrate by spin coating, and heat-treated in an oven at 80° C. for 60 seconds to form a barrier coating layer having a thickness of 300 nm.

On the barrier coat layer formed as described above, a 70 μm thick unstretched polypropylene film (ZK207, melting point 163° C., containing a propylene-ethylene block copolymer, manufactured by Toray Advanced Film Co., Ltd.) is adhered as a sealant layer with polyurethane. Dry lamination is carried out through an agent (Mitsui Chemicals Co., Ltd., Takelac A-969V/Takenate A-5 (blending ratio: 3/1)) and allowed to stand at 40°C for 24 hours to obtain the laminate of the present invention. rice field. The thickness of the adhesive layer formed by the polyurethane adhesive was 1 μm.
The content of polypropylene in the laminate was 92% by mass.

Example 2
A solution for forming a surface coat layer having the following composition was applied to the corona-treated surface of a 20 μm-thick biaxially oriented polypropylene film (manufactured by Mitsui Chemicals Tohcello Co., Ltd., ME-1) and dried on one side. Then, a surface coat layer having a thickness of 0.5 μm was formed to prepare a base material.
(Preparation of surface coat layer forming solution)
A hydroxyl group-containing (meth) acrylic resin (number average molecular weight 25000, glass transition temperature 99 ° C., hydroxyl value 80 mg KOHL / g) was mixed with a mixed solvent of methyl ketone and ethyl acetate (mixing ratio 1: 1), and the solid content concentration was It was diluted to 10% by mass to prepare a main agent.
An ethyl acetate solution (solid content: 75% by mass) containing tolylene diisocyanate was added as a curing agent to the main component to obtain a solution for forming a surface coat layer. The amount of curing agent used was 10 parts by mass with respect to 100 parts by mass of the main agent.

On the surface coating layer of the base material produced as described above, a carbon-containing oxide having a thickness of 12 nm is applied to the base material by Roll to Roll using a low-temperature plasma chemical vapor deposition apparatus, which is an actual machine, while applying tension to the base material. A silicon deposition film was formed (CVD method). In addition, vapor deposition film forming conditions were as follows.
(Formation conditions)
・ Hexamethyldisiloxane: oxygen gas: helium = 1:10:10 (unit: slm)
・Power supplied to cooling/electrode drum: 22 kw
・Line speed: 100m/min

In the same manner as in Example 1, the ratio C of carbon, the ratio Si of silicon, and the ratio O of oxygen in the carbon-containing silicon oxide deposited film were measured. The ratio C of carbon, the ratio Si of silicon, and the ratio O of oxygen are 32.7%, 29.8%, and 37.5%, respectively, with respect to the total 100% of the three elements of silicon, oxygen, and carbon. %Met.

385 g of water, 67 g of isopropyl alcohol and 9.1 g of 0.5N hydrochloric acid were mixed to obtain a prepared pH 2.2 solution. To this solution, 175 g of tetraethoxysilane as a metal alkoxide and 9.2 g of glycidoxypropyltrimethoxysilane as a silane coupling agent were mixed while cooling to 10° C. to obtain a solution A.
A solution B was obtained by mixing 14.7 g of polyvinyl alcohol having a saponification degree of 99% or more and a degree of polymerization of 2400 as a water-soluble polymer, 324 g of water and 17 g of isopropyl alcohol.
Solution A and solution B were mixed at a ratio of 6.5:3.5 on a mass basis to obtain a barrier coating agent.

A barrier coating agent was applied onto the deposited film formed on the substrate by spin coating, and heat-treated in an oven at 80° C. for 60 seconds to form a barrier coating layer having a thickness of 300 nm.

On the barrier coat layer formed as described above, a 70 μm thick unstretched polypropylene film (ZK207, manufactured by Toray Advanced Film Co., Ltd.) is applied as a sealant layer with a polyurethane adhesive (Takelac A, manufactured by Mitsui Chemicals, Inc.). -969V/Takenate A-5 (blending ratio: 3/1)), and allowed to stand at 40°C for 24 hours to obtain a laminate of the present invention. The thickness of the adhesive layer formed by the polyurethane adhesive was 1 μm.
The content of polypropylene in the laminate was 92% by mass.

Comparative example 1
After extruding the above polypropylene (manufactured by Japan Polypropylene Corporation, Novatec FL203D, melting point: 160° C.), it is stretched 5 times in the machine direction (MD direction) and 10 times in the transverse direction (TD direction) with a sequential biaxial stretching device. Then, a propylene film having a thickness of 20 μm was produced.
A laminate was produced in the same manner as in Example 1, except that the base material in Example 1 was changed to the polypropylene film produced as described above.

<<Gas barrier property evaluation>>
Test pieces were obtained by cutting out the laminates obtained in the above examples and comparative examples. Using this test piece, oxygen permeability (cc/m ² ·day·atm) and water vapor permeability (g/m ² ·day) were measured by the following method, and the results are summarized in Table 1.

[Oxygen permeability]
Using an oxygen permeability measuring device (OX-TRAN2/20, manufactured by MOCON), the substrate side of the test piece is set so that the oxygen supply side is set, and the temperature is measured at 23°C and a relative humidity of 90 according to JIS K 7126. Oxygen permeability was measured under %RH environment.
[Water vapor permeability]
Using a water vapor transmission rate measuring device (manufactured by MOCON, PERMATRAN-w 3/33), the substrate side of the test piece is set so that it is on the water vapor supply side, and is measured at 40 ° C. relative to JIS K 7129 The water vapor transmission rate was measured under a humidity of 90% RH environment.

<< Laminate strength test >>
Samples obtained by cutting the laminates obtained in the above examples and comparative examples into strips with a width of 15 mm are subjected to JIS K6854-2 using a tensile tester (manufactured by Orientec Co., Ltd., Tensilon Universal Material Testing Machine). Laminate strength (N/15 mm) was measured using 90° peel (T-peel method) at a peel speed of 50 mm/min.
Specifically, first, a strip-shaped test piece 70 was prepared by cutting out the laminate and separating the substrate side 71 and the sealant layer side 72 by 15 mm in the long side direction, as shown in FIG. 25 . After that, as shown in FIG. 26, the already peeled portions of the base material side 71 and the sealant layer side 72 were respectively gripped by grips 73 of the measuring instrument. Each of the grips 73 is pulled at a speed of 50 mm/min in directions perpendicular to the surface direction of the portion where the base material side 71 and the sealant layer side 72 are still laminated, and the stable area (Fig. 27) was measured. The interval S between the grips 73 at the start of pulling was set to 30 mm, and the interval S between the grips 73 at the end of pulling was set at 60 mm. FIG. 27 is a diagram showing changes in tensile stress with respect to the distance S between the grips 73. As shown in FIG. As shown in FIG. 27, the change in tensile stress with respect to the interval S passes through the first region and enters the second region (stable region) where the rate of change is smaller than that of the first region.
The average value of the tensile stress in the stable region was measured for five test pieces 70, and the average value was taken as the laminate strength. The environment during the measurement was a temperature of 23° C. and a relative humidity of 50%. Table 1 summarizes the measurement results.

<<Evaluation of gas barrier properties after retort processing>>
[Oxygen permeability]
Two sheets each of the laminates obtained in the above Examples and Comparative Examples were prepared, and these were placed face to face, and three sides were heat-sealed to produce a retort pouch shown in FIG. 23 .
This retort pouch was filled with 100 mL of tap water, and the remaining one side was heat-sealed to form a content-filled retort pouch.

The contents-filled retort pouch was subjected to retort treatment at 121° C. for 30 minutes at 2 atm.
Subsequently, after retorting, the content-filled retort pouch was cut out to obtain a test piece.

Using an oxygen transmission rate measuring device (OX-TRAN10/50A, manufactured by MOCON), the substrate side of the test piece is set so that the oxygen supply side is set, and JIS K 7126 compliant, 30 ° C., relative humidity 70 Oxygen permeability was measured under %RH environment. Table 1 summarizes the measurement results.

[Water vapor permeability]
The water vapor transmission rate of the test piece after the retort treatment was measured using a water vapor transmission rate measuring device (PERMATRAN-w 3/33, manufactured by MOCON), and the base side of the test piece was set to the water vapor supply side. , in accordance with JIS K 7129 at 40° C. and a relative humidity of 90% RH. Table 1 summarizes the measurement results.

<<Laminate strength after retort treatment>>
After the retort treatment, the contents-filled retort pouch was cut out to obtain a sample cut into strips with a width of 15 mm. In the same manner as above, using a tensile tester (manufactured by Orientec Co., Ltd., Tensilon Universal Material Testing Machine), the laminate strength (N / 15 mm) of this sample was measured according to JIS K6854-2 at a peel speed of 50 mm. /min using a 90° peel (T-peel method). Table 1 summarizes the measurement results.

Example 3-1
A substrate was prepared in the same manner as in Example 1, and a vapor deposition film was formed on the substrate.

A barrier coat layer was formed on the deposited film so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 5.1 on a mass basis.

The ratio of Si element and C element present on the surface of the barrier coat layer was measured. The measurement was performed by narrow scan analysis under the following measurement conditions by X-ray photoelectron spectroscopy (XPS). Also in the following examples, the ratio of Si element and C element present on the surface of the barrier coat layer was similarly measured.
(Measurement condition)
Equipment used: “ESCA-3400” (manufactured by Kratos)
[1] Spectrum collection conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV)
X-ray output: 150W (10kV/15mA)
X-ray scanning area (measurement area): about 6mmφ
Photoelectron capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar ⁺
Acceleration voltage: 0.2 (kV)
Emission current: 20 (mA)
Etching range: 10mmφ
Ion sputtering time: 30 seconds + 30 seconds + 60 seconds (total 120 seconds) and collect the spectrum

Next, on the barrier coat layer, a 70 μm thick unstretched polypropylene film (ZK207 manufactured by Toray Advanced Film Co., Ltd.) is dry-laminated with a two-liquid curable polyurethane adhesive to form a sealant layer. A laminate in the mode was obtained.

Example 3-2
Same as Example 3-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 4.1 on a mass basis. Thus, a laminate in the first mode was produced.

Example 3-3
Same as Example 3-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 3.3 on a mass basis. Thus, a laminate in the first mode was produced.

Example 3-4
Same as Example 3-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 2.7 on a mass basis. Thus, a laminate in the first mode was produced.

Example 3-5
Same as Example 3-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 1.9 on a mass basis. Thus, a laminate in the first mode was produced.

Examples 3-6
Same as Example 3-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 1.5 on a mass basis. Then, a laminate according to the first aspect was produced.

Example 4-1
A laminate in the first mode was produced in the same manner as in Example 3-1, except that the deposition film formation was changed as follows.
On the surface resin layer, using a continuous vapor deposition film deposition device that separates a pretreatment section in which an oxygen plasma pretreatment device is arranged and a film formation section, which is an actual machine, in the pretreatment section, Roll to Roll While applying tension to the multilayer substrate, plasma is introduced from the plasma supply nozzle under the following conditions, oxygen plasma pretreatment is performed, and the film is continuously transported. A reactive resistance heating system was used as a heating means for vapor deposition, and an aluminum oxide (alumina) vapor deposition film having a thickness of 12 nm was formed (PVD method).
(Formation conditions)
(Oxygen plasma pretreatment conditions)
・Plasma intensity: 200 W·sec/m ²
・Plasma forming gas ratio: oxygen: argon = 2: 1
・Applied voltage between pretreatment drum and plasma supply nozzle: 340V
(Deposition conditions)
・Conveyance speed: 400m/min
・Oxygen gas supply amount: 20000sccm

Example 4-2
Same as Example 4-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 4.1 on a mass basis. Thus, a laminate in the first mode was produced.

Example 4-3
Same as Example 4-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 3.3 on a mass basis. Thus, a laminate in the first mode was produced.

Example 4-4
Same as Example 4-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 2.7 on a mass basis. Thus, a laminate in the first mode was produced.

Example 4-5
Same as Example 4-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 1.9 on a mass basis. Thus, a laminate in the first mode was produced.

Example 4-6
Same as Example 4-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 1.5 on a mass basis. Thus, a laminate in the first mode was produced.

Example 5-1
A substrate was prepared in the same manner as in Example 2, and a vapor deposition film was formed on the substrate.

Next, a barrier coat layer was formed on the deposited film so that the solid content ratio of metal alkoxide to water-soluble polymer (metal alkoxide/water-soluble polymer) was 5.1 on a mass basis.

Next, on the barrier coat layer, a 70 μm thick unstretched polypropylene film (ZK207 manufactured by Toray Advanced Film Co., Ltd.) is dry-laminated with a two-liquid curable polyurethane adhesive to form a sealant layer. A laminate in the mode was obtained.

Example 5-2
Same as Example 5-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 4.1 on a mass basis. Thus, a laminate in the second mode was produced.

Example 5-3
Same as Example 5-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 3.3 on a mass basis. Thus, a laminate in the second mode was produced.

Example 5-4
Same as Example 5-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 2.7 on a mass basis. Thus, a laminate in the second mode was produced.

Example 5-5
Same as Example 5-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 1.9 on a mass basis. Thus, a laminate in the second mode was produced.

Example 5-6
Same as Example 5-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 1.5 on a mass basis. Thus, a laminate in the second mode was produced.

Example 6-1
A laminate in the second embodiment was produced in the same manner as in Example 5-1, except that the deposition film formation was changed as follows.
On the surface coat layer, a silicon oxide (silica) deposition film with a thickness of 20 nm is formed by roll-to-roll using an induction heating vacuum film-forming apparatus equipped with a plasma gun, which is an actual machine, while applying tension to the substrate. formed (PVD method). In addition, vapor deposition film forming conditions were as follows.
(Formation conditions)
(Plasma irradiation conditions)
・Line speed: 30 m/min ・Degree of vacuum: 1.7×10 ⁻² Pa
・Output: 5.7kw
・Acceleration voltage: 151V
・Ar gas flow rate: 7.5 sccm
(Deposition conditions)
・Vapor deposition material: SiO
・Reactive gas: _O2
・Reaction gas flow rate: 100 sccm

Example 6-2
Same as Example 6-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 4.1 on a mass basis. Thus, a laminate in the second mode was produced.

Example 6-3
Same as Example 6-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 3.3 on a mass basis. Thus, a laminate in the second mode was produced.

Example 6-4
Same as Example 6-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 2.7 on a mass basis. Thus, a laminate in the second mode was produced.

Example 6-5
Same as Example 6-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 1.9 on a mass basis. Thus, a laminate in the second mode was produced.

Example 6-6
Same as Example 6-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 1.5 on a mass basis. Thus, a laminate in the second mode was produced.

Example 7-1
A laminate in the second embodiment was produced in the same manner as in Example 5-1, except that the deposition film formation was changed as follows.

On the surface coat layer, using a continuous vapor deposition film forming apparatus that separates a pretreatment section in which an actual oxygen plasma pretreatment apparatus is arranged and a film formation section, Roll to Roll is performed in the pretreatment section. While applying tension to the multilayer substrate, plasma is introduced from the plasma supply nozzle under the following conditions, oxygen plasma pretreatment is performed, and the film is continuously transported. A reactive resistance heating system was used as a heating means for vapor deposition, and an aluminum oxide (alumina) vapor deposition film having a thickness of 12 nm was formed (PVD method).
(Formation conditions)
(Oxygen plasma pretreatment conditions)
・Plasma intensity: 200 W·sec/m ²
・Plasma forming gas ratio: oxygen: argon = 2: 1
・Applied voltage between pretreatment drum and plasma supply nozzle: 340V
(Deposition conditions)
・Conveyance speed: 400m/min
・Oxygen gas supply amount: 20000sccm

Example 7-2
Same as Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 4.1 on a mass basis. Thus, a laminate in the second mode was produced.

Example 7-3
Same as Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 3.3 on a mass basis. Thus, a laminate in the second mode was produced.

Example 7-4
Same as Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 2.7 on a mass basis. Thus, a laminate in the second mode was produced.

Example 7-5
Same as Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 1.9 on a mass basis. Thus, a laminate in the second mode was produced.

Example 7-6
Same as Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide/water-soluble polymer) was 1.5 on a mass basis. Thus, a laminate in the second mode was produced.

<<Evaluation of gas barrier property after lamination>>
The laminates obtained in Examples 3 to 7 were cut out to obtain test pieces. Using this test piece, the oxygen permeability (cc/m ² ·day·atm) and water vapor permeability (g/m ² ·day) were measured in the same manner as described above. The results are summarized in Tables 2-6. In addition, in Tables 2 to 6, the units of oxygen permeability and water vapor permeability are omitted.

<<Evaluation of gas barrier property after boiling treatment>>
Two sheets of each of the laminates obtained in Examples 3 to 7 were prepared, and these sheets were placed face to face and three sides were heat-sealed to prepare a boiling pouch shown in FIG.
This pouch for boiling was filled with 100 mL of tap water, and the remaining one side was heat-sealed to form a pouch for filling boiling.
The filled boiling pouch was boiled at 95°C for 30 minutes. Subsequently, a laminate was cut out from the content-filled boiling pouch after boiling to obtain a test piece. Using this test piece, the oxygen permeability (cc/m ² ·day·atm) and water vapor permeability (g/m ² ·day) were measured in the same manner as described above. The results are summarized in Tables 2-6. In addition, in Tables 2 to 6, the units of oxygen permeability and water vapor permeability are omitted.

<<Evaluation of gas barrier properties after retort processing>>
Two sheets of each of the laminates obtained in Examples 3 to 7 were prepared, and these sheets were placed face to face and three sides were heat-sealed to prepare a retort pouch shown in FIG.
This retort pouch was filled with 100 mL of tap water, and the remaining one side was heat-sealed to form a content-filled retort pouch.
The contents-filled boiling pouch was subjected to retort treatment at 121° C. for 30 minutes at 2 atm. Subsequently, a laminate was cut out from the content-filled retort pouch after retorting to obtain a test piece. Using this test piece, the oxygen permeability (cc/m ² ·day·atm) and water vapor permeability (g/m ² ·day) were measured in the same manner as described above. The results are summarized in Tables 2-6. In addition, in Tables 2 to 6, the units of oxygen permeability and water vapor permeability are omitted.

<<Evaluation of gas barrier property after gelboflex test>>
Cylindrical bags were produced using the laminates obtained in Examples 3-7. Using this bag, the gelboflex test according to ASTM F392 was repeated 10 times.
After that, a laminate was cut out from the bag to obtain a test piece. Using this test piece, the oxygen permeability (cc/m ² ·day·atm) and water vapor permeability (g/m ² ·day) were measured in the same manner as described above. The results are summarized in Tables 2-6. In addition, in Tables 2 to 6, the units of oxygen permeability and water vapor permeability are omitted.

Example 8-1
A substrate was prepared in the same manner as in Example 1, a vapor deposition film was formed on the surface resin layer, and a barrier coat layer was formed on the vapor deposition film.

Next, a printed layer was formed on the barrier coat layer. The thickness of the printed layer was 1 μm.

Next, as a sealant layer, a 60 μm-thick unstretched polypropylene film (manufactured by Toray Advanced Film Co., Ltd., ZK500, melting point 164° C., containing propylene-ethylene block copolymer, polyethylene, and thermoplastic elastomer) is placed on the printed layer as a polyurethane layer. Dry lamination is performed via an adhesive (Mitsui Chemicals Co., Ltd., Takelac A-969V / Takenate A-5 (blending ratio 3/1)), left at 40 ° C. for 24 hours, and lamination in the first embodiment. got a body The thickness of the adhesive layer was 4 μm. The laminate thus obtained comprises a substrate, a deposited film, a barrier coat layer, a printed layer, an adhesive layer, and a sealant layer in this order.
The thickness of the entire laminate was 85 μm. The content of polypropylene in the laminate was 91% by mass.

Example 8-2
A substrate was prepared in the same manner as in Example 1, a vapor deposition film was formed on the surface resin layer, and a barrier coat layer was formed on the vapor deposition film.

Separately, a biaxially oriented polypropylene resin film having a thickness of 20 μm was prepared. A printed layer was formed on a biaxially oriented polypropylene resin film. The thickness of the printed layer was 1 μm.
Next, on the printed layer, the barrier coat layer of the base material is dry-laminated via a polyurethane adhesive (Mitsui Chemicals Co., Ltd., Takelac A-969V/Takenate A-5 (blending ratio: 3/1)), It was allowed to stand at 40° C. for 24 hours to obtain a pre-laminate.

Next, on the biaxially stretched polypropylene resin film of the pre-laminate, a 60 μm thick unstretched polypropylene film (manufactured by Toray Advanced Film Co., Ltd., ZK500) is applied with a polyurethane adhesive (manufactured by Mitsui Chemicals, Inc., Takelac A-969V). /Takenate A-5 (blending ratio 3/1)) and allowed to stand at 40°C for 24 hours to obtain a laminate in the first embodiment. The thickness of the adhesive layer was 4 μm. The laminate thus obtained comprises, in this order, a first base material, a deposited film, a barrier coat layer, an adhesive layer, a printed layer, a second base material, an adhesive layer, and a sealant layer.
The thickness of the entire laminate was 109 μm. The content of polypropylene in the laminate was 89% by mass.

Example 9-1
A substrate was prepared in the same manner as in Example 2, a vapor deposition film was formed on the surface coat layer, and a barrier coat layer was formed on the vapor deposition film.

Next, a printed layer was formed on the barrier coat layer. The thickness of the printed layer was 1 μm.

Next, as a sealant layer, a 60 μm thick unstretched polypropylene film (ZK500, manufactured by Toray Advanced Film Co., Ltd.) is applied to the printed layer with a polyurethane adhesive (Takelac A-969V/Takenate A-, manufactured by Mitsui Chemicals, Inc.). 5 (blending ratio 3/1)) and left at rest at 40° C. for 24 hours to obtain a laminate in the second embodiment. The thickness of the adhesive layer was 4 μm. The laminate thus obtained comprises a substrate, a deposited film, a barrier coat layer, a printed layer, an adhesive layer, and a sealant layer in this order.
The thickness of the entire laminate was 85 μm. The content of polypropylene in the laminate was 91% by mass.

Example 9-2
A substrate was prepared in the same manner as in Example 2, a vapor deposition film was formed on the surface coat layer, and a barrier coat layer was formed on the vapor deposition film.

Separately, a biaxially oriented polypropylene resin film having a thickness of 20 μm was prepared. A printed layer was formed on a biaxially oriented polypropylene resin film. The thickness of the printed layer was 1 μm.
Next, on the printed layer, the barrier coat layer of the base material is dry-laminated via a polyurethane adhesive (Mitsui Chemicals Co., Ltd., Takelac A-969V/Takenate A-5 (blending ratio: 3/1)), It was allowed to stand at 40° C. for 24 hours to obtain a pre-laminate.

Next, on the biaxially stretched polypropylene resin film of the pre-laminate, a 60 μm thick unstretched polypropylene film (manufactured by Toray Advanced Film Co., Ltd., ZK500) is applied with a polyurethane adhesive (manufactured by Mitsui Chemicals, Inc., Takelac A-969V). /Takenate A-5 (blending ratio: 3/1)) and allowed to stand at 40°C for 24 hours to obtain a laminate in the second embodiment. The thickness of the adhesive layer was 4 μm. The laminate thus obtained comprises, in this order, a first base material, a deposited film, a barrier coat layer, an adhesive layer, a printed layer, a second base material, an adhesive layer, and a sealant layer.
The thickness of the entire laminate was 109 μm. The content of polypropylene in the laminate was 89% by mass.

<<Measurement of tensile strength>>
The tensile strength in the machine direction (MD) and transverse direction (TD) of the laminates produced in Examples 8 and 9 were measured. The tensile strength of the laminate was measured according to JIS K7127:1999. As a tensile tester, a tensile tester STA-1150 manufactured by Orientec was used. As a test piece, a rectangular film having a width of 10 mm and a length of 150 mm cut out from the laminate can be used. The distance between the pair of chucks holding the specimen at the start of the measurement is 50 mm, and the pulling speed is 300 mm/min. The environment during the measurement was a temperature of 23° C. and a relative humidity of 50%. Table 7 summarizes the measurement results.

<<Measurement of loop stiffness>>
The loop stiffness of the laminates of Examples 8 and 9 was measured. The specific measuring method is as described with reference to FIGS. 8 to 14. FIG. Table 7 summarizes the measurement results.

<<Measurement of puncture strength>>
The puncture strength of the laminates of Examples 8 and 9 was measured according to JIS Z1707 7.4. As a measuring instrument, a Tensilon universal material testing machine RTC-1310 manufactured by A&D was used. Specifically, as shown in FIG. 28, a semicircular needle 111 with a diameter of 1.0 mm and a tip shape radius of 0.5 mm is applied to a fixed test piece 110 at 50 mm/min (1 min. The needle 111 was pierced at a speed of 50 mm per inch), and the maximum value of the stress until the needle 111 penetrated the test piece 110 was measured. The maximum value of stress was measured for five or more test pieces 111, and the average value was taken as the puncture strength of the laminate. The environment during the measurement was a temperature of 23° C. and a relative humidity of 50%. Table 7 summarizes the measurement results.

10A: Laminate, 11A: First substrate, 12A: Deposited film, 13A: Sealant layer, 14A: Polypropylene resin layer, 15A: Surface resin layer, 16A: Barrier coat layer, 17A: Adhesive resin layer, 10B: Lamination Body, 11B: first substrate, 12B: deposited film, 13B: sealant layer, 14B: polypropylene resin layer, 15B: surface coat layer, 16B: barrier coat layer, 17B: second substrate, 20: test piece, 20x: inner surface, 20y: outer surface, 21: loop portion, 22: intermediate portion, 23: fixed portion, 25: loop stiffness measuring instrument, 26: chuck portion, 26A: first chuck, 26B: second chuck, 27: support Member, 28: Load cell, 30: Retort or boiling pouch, 40: Standing type retorting or boiling pouch, 41: Body (side sheet), 42: Bottom (bottom sheet), 51: Easy opening means, 52: Notch portion, 53: Half-cut line, 70: Test piece, 71: Base material side, 72: Sealant layer side, 73: Grip, 110: Test piece, 111: Needle, A: Vacuum container, B: Winding Delivery unit, C: film forming drum, D: winding unit, E: transport roll, F: evaporation source, G: reaction gas supply unit, H: deposition prevention box, I: vapor deposition material, J: plasma gun, A1 : vacuum vessel, B1: unwinding section, C1: cooling/electrode drum, D1: winding section, E1: transport roll, F1: glow discharge plasma, G1: reaction gas supply section, H1: raw material supply nozzle, I1: raw material Gas supply unit, J1: magnet, K1: power supply, L1: vacuum pump

Claims (18)

A laminate,
At least, comprising a first base material, a deposited film, a barrier coat layer and a sealant layer,
The first base material includes a polypropylene resin layer, a surface resin layer provided on one surface of the polypropylene resin layer, and an adhesive resin layer between the polypropylene resin layer and the surface resin layer. An axially stretched resin film,
The adhesive resin layer is provided on the polypropylene resin layer,
The surface resin layer is provided on the adhesive resin layer,
The deposited film is provided on the surface resin layer of the first base material,
The surface resin layer contains a resin material having a melting point of 180° C. or higher,
the resin material is vinyl resin, nylon 6, nylon 6,6, MXD nylon or polyester;
The deposited film is composed of an inorganic oxide,
A laminate, wherein the sealant layer comprises a polyolefin having a melting point of 110° C. or higher. The laminate according to claim 1, wherein the surface resin layer contains a resin material having a melting point of 180°C or higher and 265°C or lower. The resin material of the surface resin layer has a melting point TA,
The polypropylene of the polypropylene resin layer has a melting point TB,
3. The laminate according to claim 1, wherein the difference between said melting point TA and said melting point TB is 20[deg.] C. or more and 80[deg.] C. or less. The laminate according to any one of claims 1 to 3, wherein the resin material of the surface resin layer is made of a polymer having a polar group. The laminate according to any one of claims 1 to 4, wherein the ratio of the thickness of the surface resin layer to the total thickness of the first base material is 1% or more and 10% or less. Laminate according to any one of the preceding claims, wherein the sealant layer comprises a sealant material having a melting point of 150°C or higher. Laminate according to any one of the preceding claims, wherein the sealant layer comprises polypropylene having a melting point of 150°C or higher. The laminate according to any one of claims 1 to 7, further comprising a second substrate. 9. The laminate of claim 8, wherein said second substrate comprises polypropylene. 10. The laminate according to claim 8 or 9, wherein said first substrate and said deposited film are located between said second substrate and said sealant layer. An intermediate layer is provided between the deposited film and the sealant layer,
The laminate according to claim 8 or 9, wherein the intermediate layer is the second base material. 12. The laminate according to claim 11, wherein the intermediate layer is composed of a stretched polypropylene resin film. The laminate according to any one of claims 1 to 12, comprising the barrier coat layer between the vapor deposited film and the sealant layer. The barrier coat layer is a gas barrier coating film of a mixture of a metal alkoxide and a water-soluble polymer, or a gas barrier coating film of a mixture of a metal alkoxide, a water-soluble polymer and a silane coupling agent. Item 14. The laminate according to any one of items 1 to 13. The laminate according to any one of claims 1 to 14, which is used for packaging containers. A pouch for retort or boiling, comprising the laminate according to any one of claims 1 to 15. 17. The retort or boil pouch of claim 16, comprising a notch. 18. Retort or boil pouch according to claim 16 or 17, comprising a half cut line.

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