JP2019210021A - Packaging object, packaging body, layered sheet, original fabric sheet, and method of manufacturing packaging object - Google Patents

Abstract

To provide a packaging object storing contents in a packaging body, in which corrosion of end faces of a barrier layer is inhibited effectively, therefore, which is suitable for a use in which the packaging object is in contact with aqueous liquid for a long period.SOLUTION: A packaging object stores contents in a packaging body. The packaging object is used for an application in which aqueous liquid is in contact with an outer face continuously or intermittently. The packaging body is formed by a layered sheet which comprises at least a resin layer which is located at a side of the outer face, a barrier layer, and a thermoplastic resin layer arranged in this order. The contents are stored in the packaging body with the thermoplastic resin layers of the layered sheets fused mutually in peripheral edge portions of the layered sheets. End faces of the barrier layer of the layered sheet are not exposed outward in at least one portion of the peripheral edge portions of the layered sheet.SELECTED DRAWING: None

Description

  The present invention relates to a package, a package, a laminated sheet, an original fabric sheet, and a method for manufacturing the package.

  Traditionally, contents (eg, sensors (temperature, pressure, water flow, water pressure, etc.), wireless devices, power supplies, electronic components, heat exchange in places where there are many opportunities to come into contact with water such as bathrooms, kitchens, water tanks, and outdoors. For the purpose of preventing contact of an object etc.) with an aqueous liquid over a long period of time, a package formed of resin or metal is used.

  On the other hand, as a sheet-like package for protecting the contents from water, various things are known. For example, as a means for protecting the contents from water or light, a retort food packaging material is used. A formed package is common.

  Retort food packaging material has a structure in which a resin layer is arranged on both sides of a barrier layer such as aluminum foil, and after sterilizing the food by heating, it protects the food as the contents from air and light etc. When cooking, it plays the role which prevents a foodstuff from contacting hot water directly (for example, refer patent document 1).

Japanese Patent Laid-Open No. 5-200894

  However, conventional retort food packaging materials are not premised on contact with water for a long period of time. For this reason, when a package made of a packaging material for retort food is used and the package with the contents sealed is brought into contact with water for a long period of time, the end surface of the barrier layer exposed at the end of the package is corroded. There is a problem of doing.

  In the package containing the contents, the corrosion of the end face of the barrier layer at the end of the package leads to the penetration of moisture into the interior of the package and prevents the contents from coming into contact with the aqueous liquid for a long period of time. It is a factor that can not be.

  For this reason, the package that contains the contents using the package formed of the packaging material for conventional retort food is used in places where there are many opportunities to come into contact with water such as bathrooms, kitchens, water tanks, and outdoors. It is not suitable for preventing an object from coming into contact with an aqueous liquid for a long period of time.

  Under such circumstances, the present invention is a package in which the contents are contained in a package body, and even when contacted with an aqueous liquid for a long period of time, corrosion of the end face of the barrier layer is effectively suppressed, The main object is to provide a package suitable for use in contact with an aqueous liquid for a long period of time.

  The present inventors have intensively studied to solve the above problems. As a result, the contents are packaged in a package, and the package is used for an application in which an aqueous liquid contacts the outer surface continuously or intermittently, and the package has at least the outer surface. A laminated sheet comprising a resin layer located on the side, a barrier layer, and a thermoplastic resin layer in this order, and the packaging body includes the thermoplastic resin of the laminated sheet at a peripheral edge of the laminated sheet. The layers are fused together to contain the contents, and at least part of the peripheral edge of the laminated sheet, because the end face of the barrier layer of the laminated sheet is not exposed to the outside, Even when the package is in contact with an aqueous liquid for a long period of time, corrosion of the end face of the barrier layer at the end of the package is effectively suppressed, and the package is suitable for an application that makes contact with the aqueous liquid for a long period of time. It was found that.

  The present invention has been completed by further studies based on these findings.

That is, this invention provides the invention of the aspect hung up below.
Item 1. The contents are packaged in a package,
The package is used for an application in which an aqueous liquid comes into contact with an outer surface continuously or intermittently,
The package is composed of a laminated sheet comprising at least a resin layer located on the outer surface side, a barrier layer, and a thermoplastic resin layer in this order,
The packaging body contains the contents by fusing the thermoplastic resin layers of the laminated sheet to each other at the peripheral edge of the laminated sheet,
The package in which the end surface of the barrier layer of the laminated sheet is not exposed to the outside in at least a part of the peripheral edge of the laminated sheet.
Item 2. Item 2. The package according to Item 1, wherein at least a part of the end face of the barrier layer is located in a fusion peripheral portion where the thermoplastic resin layers of the laminated sheet are heat-sealed.
Item 3. Item 3. The package according to Item 1 or 2, wherein the entire circumference of the end surface of the barrier layer is located in a fusion peripheral portion where the thermoplastic resin layers of the laminated sheet are heat-sealed.
Item 4. Item 4. The package according to any one of Items 1 to 3, wherein at least one of the resin layer and the thermoplastic resin layer covers an end surface of the barrier layer in at least a part of the peripheral edge of the laminated sheet.
Item 5. The package includes a sealing member,
Item 5. The package according to any one of Items 1 to 4, wherein the sealing member covers at least a part of the peripheral edge of the laminated sheet.
Item 6. Item 6. The package according to Item 5, wherein the entire outer surface of the package is composed of the sealing member.
Item 7. Item 7. The package according to Item 5 or 6, wherein the sealing member is made of polyolefin.
Item 8. Item 8. The package according to any one of Items 5 to 7, wherein the sealing member is a heat shrink film.
Item 9. Item 9. The package according to any one of Items 5 to 8, wherein an easy-adhesion layer is provided between the resin layer and the sealing member.
Item 10. Item 10. The package according to any one of Items 1 to 9, wherein the resin layer and the thermoplastic resin layer are made of the same thermoplastic resin.
Item 11. Item 11. The package according to any one of Items 1 to 10, wherein the laminated sheet has at least a concave shape formed so as to be directed from the thermoplastic resin layer side toward the resin layer side.
Item 12. Item 12. The package according to any one of Items 1 to 11, wherein the resin layer contains at least one of polyester and polyolefin.
Item 13. A package used for an application in which an aqueous liquid is in contact with an outer surface continuously or intermittently,
The package is composed of a laminated sheet comprising at least a resin layer located on the outer surface side, a barrier layer, and a thermoplastic resin layer in this order,
The packaging body has a shape that accommodates contents by fusing the thermoplastic resin layers of the laminated sheet at the peripheral edge of the laminated sheet,
The package body in which the end surface of the barrier layer of the laminated sheet is not exposed to the outside in at least a part of the peripheral edge of the laminated sheet.
Item 14. A laminated sheet used for applications in which an aqueous liquid is in contact with an outer surface continuously or intermittently,
The laminated sheet comprises at least a resin layer located on the outer surface side, a barrier layer, and a thermoplastic resin layer in this order,
The laminated sheet in which an end face of the barrier layer is located on an inner side than an end face of the resin layer in at least a part of the peripheral edge of the laminated sheet.
Item 15. A raw sheet for obtaining the laminated sheet according to Item 14,
The raw fabric sheet includes at least a resin layer located on the outer surface side, a barrier layer, and a thermoplastic resin layer in this order,
The said barrier layer is a raw fabric sheet provided partially.
Item 16. A method of manufacturing a package used for an application in which an aqueous liquid contacts an outer surface continuously or intermittently,
As a package that contains the contents of the package, it is composed of a laminated sheet that includes at least a resin layer located on the outer surface side, a barrier layer, and a thermoplastic resin layer in this order. At least a part of the laminated sheet is not exposed to the outside end face of the barrier layer,
The manufacturing method of a package provided with the process of accommodating the said content and obtaining the said package by fuse | melting the said thermoplastic resin layers of the said laminate sheet in the peripheral part of the said laminate sheet.
Item 17. A method of containing contents using a package used for an application in which an aqueous liquid contacts an outer surface continuously or intermittently,
The package is composed of a laminate sheet including at least a resin layer located on the outer surface side, a barrier layer, and a thermoplastic resin layer in this order, and at least a part of the peripheral portion of the laminate sheet includes the laminate sheet. The end face of the barrier layer is not exposed to the outside,
A content accommodation method comprising a step of accommodating the content by fusing the thermoplastic resin layers of the laminate sheet to each other at a peripheral edge of the laminate sheet.
Item 18. A method of manufacturing a package used for an application in which an aqueous liquid is in contact with an outer surface continuously or intermittently,
As a package that contains the contents of the package, it is composed of a laminated sheet that includes at least a resin layer located on the outer surface side, a barrier layer, and a thermoplastic resin layer in this order. At least a part of the laminated sheet is not exposed to the outside end face of the barrier layer,
The manufacturing method of a package provided with the process of accommodating the said content and obtaining the said package by fuse | melting the said thermoplastic resin layers of the said laminate sheet in the peripheral part of the said laminate sheet.
Item 19. The package includes a sealing member,
Item 19. The package manufacturing method according to Item 18, wherein the sealing member is provided so that the sealing member covers at least a part of the peripheral edge of the laminated sheet.

  According to the present invention, even when contacted with an aqueous liquid for a long period of time, corrosion of the end face of the barrier layer at the end of the package is effectively suppressed, and it is suitable for applications that contact the aqueous liquid for a long period of time. Package and its manufacturing method can be provided. Further, according to the present invention, there is provided a package used for an application in which an aqueous liquid comes into contact with the outer surface continuously or intermittently, and the barrier at the end of the package even when contacted with the aqueous liquid for a long period of time. Corrosion of the end face of the layer is effectively suppressed, and it is possible to provide a package and a laminated sheet that are suitable for use in contact with an aqueous liquid for a long period of time, and a raw sheet for obtaining the laminated sheet.

It is a schematic diagram which shows an example of the package of this invention. It is a schematic diagram which shows an example of the package of this invention. It is a schematic diagram which shows an example (1st aspect) of the cross-section (the cross section of the z direction in A-A 'of FIG. 1, 2) of the package of this invention. It is a schematic diagram which shows an example (2nd aspect) of the cross-sectional structure of the package of this invention. It is a schematic diagram which shows an example (3rd aspect) of the cross-sectional structure of the package of this invention. It is a schematic diagram which shows an example (4th aspect) of the cross-sectional structure of the package of this invention. It is a schematic diagram which shows an example (5th aspect) of the cross-sectional structure of the package of this invention. It is a schematic diagram which shows an example (6th aspect) of the cross-sectional structure of the package of this invention. It is a schematic diagram which shows an example (7th aspect) of the cross-sectional structure of the package of this invention. It is a schematic diagram which shows an example (modified example of a 7th aspect) of the cross-sectional structure of the package of this invention. It is a schematic diagram which shows an example of the cross-sectional structure of the lamination sheet of this invention. It is a schematic diagram of the original fabric sheet used in order to obtain the lamination sheet of this invention.

  In the package of the present invention, the contents are contained in a package. The package of this invention is used for the use which an aqueous liquid contacts an outer surface continuously or intermittently. In the package of the present invention, the package is composed of a laminated sheet including at least a resin layer located on the outer surface side, a barrier layer, and a thermoplastic resin layer in this order. Furthermore, the packaging body accommodates the contents by the thermoplastic resin layers of the laminated sheet being fused together at the peripheral edge of the laminated sheet. The package of the present invention is characterized in that the end face of the barrier layer of the laminated sheet is not exposed to the outside in at least a part of the peripheral edge of the laminated sheet. Hereinafter, the package of the present invention, the package, the laminated sheet, the contents storage method, and the package manufacturing method will be described in detail.

  In the present specification, the numerical range indicated by “to” means “above” or “below”. For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. In the present invention, the fact that the end face of the barrier layer is not exposed to the outside means that the end face of the barrier layer is not in contact with the external environment.

1. Use of Package and Package, Structure As shown in the schematic diagrams of FIGS. 3 to 10, the package 10 of the present invention has a structure in which the contents 12 are accommodated in the package 11. The package 10 of this invention is used for the use which an aqueous liquid contacts the outer surface 11a continuously or intermittently. Although the specific use of the package 10 of the present invention is not particularly limited, for example, the contents (for example, a sensor (in a bathroom, a kitchen, a water tank interior, the outdoors) in a place where there is a great opportunity to come into contact with an aqueous liquid. Temperature, pressure, water flow, water pressure, etc.), wireless devices, heat exchangers, electronic components, etc.) are used for the purpose of preventing contact with aqueous liquid for a long period of time. The package 10 of the present invention is used, for example, for the purpose of suppressing, for a long period of time, a material that senses heat, such as a temperature sensor, or a material that exchanges heat, from being decomposed or reacted by direct contact with an aqueous liquid. The In particular, when the content 12 is an electronic member, it may cause a failure when the aqueous liquid contacts the electronic member. Therefore, the package 10 in which the electronic member is sealed by the packaging body 11 of the present invention is used as the electronic device itself or its configuration. By using a part of the member, the electronic device can be suitably used for an application in which the aqueous liquid is in contact with the aqueous liquid continuously or intermittently over a long period of time.

  A package using a conventional packaging material for retort food is usually only in contact with an aqueous liquid for several minutes or at most about 30 minutes, but the package of the present invention. 10 is a package used for an application in which an aqueous liquid contacts continuously or intermittently over a long period of time. The package 10 of the present invention is continuously or over a long period of, for example, 2 hours or more, and further, 12 hours or more, 24 hours or more, 72 hours or more, 7 days or more, 30 days or more, or 1 year or more. You may use for the use which an aqueous liquid contacts intermittently. In addition, the package may be used for applications in which a heated aqueous liquid comes into contact, and the package 10 of the present invention is preferably used for an application in which, for example, an aqueous liquid of about 0 to 98 ° C. comes into contact. Can do.

  For example, as illustrated in FIGS. 3 to 10, the package 11 includes a laminated sheet 13 having at least a resin layer 1, a barrier layer 2, and a thermoplastic resin layer 3 in this order. In the package 11, the resin layer 1 is the outermost layer side, and the thermoplastic resin layer 3 is the innermost layer. When the contents 12 are sealed by the package 11, the contents 12 are accommodated by accommodating the contents 12 such that the thermoplastic resin layer 3 constitutes (inner side) the inner surface 11 b of the package 11. It can be protected for a long time from contact with aqueous liquids.

  In the present invention, the aqueous liquid means a liquid containing water, and the content of water in the aqueous liquid is, for example, 50 mass% or more, 70 mass% or more, 90 mass% or more, 99 Examples include mass% or more and 100 mass%. In addition to water, for example, an organic solvent may be mixed to adjust the freezing point and boiling point. Examples of the organic solvent include ethylene glycol.

  When the contents 12 are accommodated so that the thermoplastic resin layer 3 constitutes the inner surface 11b of the package 11 (becomes inside), for example, the package 11 formed with the laminated sheet 13 is used. The contents 12 can be sealed by fusing together the thermoplastic resin layers 3 located at the periphery. That is, in the package 10 of the present invention, the package 11 is a molded body in which a space for containing the contents 12 is formed, and the contents 12 are arranged in the space to fuse the thermoplastic resin layers 3 together (more Specifically, the contents 12 can be accommodated and sealed by heat-sealing. Specific examples of the contents 12 are as described above.

  3 to 10, the two laminated sheets 13 are each formed in a concave shape from the thermoplastic resin layer 3 toward the resin layer 1, and the thermoplastic resin layer is formed at the peripheral edge portion 13 a of the laminated sheet 13. The contents 12 are accommodated in the package 11 by fusing 3 together.

  The shape for the package 11 to accommodate the contents 12 is not particularly limited as long as a space for accommodating the contents 12 is formed. For example, FIGS. 1 to 10 show various modes in which the laminated sheet 13 has a concave shape formed so as to go from the thermoplastic resin layer 3 side to the resin layer 1 located on the outer surface 11a side. Such a shape can be formed by molding the laminated sheet 13 forming the package 11 with a mold. FIG. 1 shows a shape in which the four peripheral edges 13a are fused so that the thermoplastic resin layers 3 of the two laminated sheets 13 face each other. On the other hand, FIG. 2 shows a shape in which the peripheral edge portions 13a of the three sides are fused so that the thermoplastic resin layers 3 face each other by folding back at the center of one laminated sheet 13.

  The package 11 is not limited to a shape formed by a mold like the shape shown in FIGS. 1 to 10, and may be a bag shape. Specific examples of the bag shape include, for example, a standing pouch, a two-side seal bag, a three-side seal bag, a four-side seal bag, a gusset bag, a pillow packaging bag, a square bottom bag, a bag-in-box bag (inner bag), and the like. It can be selected from various package shapes.

  In addition, in this invention, the peripheral part of a lamination sheet means the area | region of the fixed width (constant distance of the direction which goes to the center from the edge part of a lamination sheet) along the outer peripheral part of a lamination sheet. The fusion peripheral part 30 in which the thermoplastic resin layers 3 of the laminated sheet 13 constituting the package 11 are heat-sealed is formed on the entire periphery of the peripheral part 13a or at least a part of the peripheral part 13a. For example, FIG. 1 shows that two laminated sheets 13 having a rectangular shape are overlapped so that the thermoplastic resin layers 3 face each other, and the entire periphery (four sides) of the peripheral edge portion 13a of the laminated sheet 13 is fused. The top view of the schematic diagram made into the package 10 is represented. The colored area | region of FIG. 1 has shown the area | region currently fuse | melted. In addition, as shown in FIG. 2, as described above, one rectangular sheet 13 is folded back at the position of the center P so that the thermoplastic resin layers 3 face each other, and the peripheral portions 13 a on the three sides are fused. The shape made is illustrated. The colored area | region of FIG. 2 has shown the area | region currently fuse | melted. In the package 10 of FIG. 2, the peripheral part 13a of a lamination sheet respond | corresponds to the area | region currently melt | fused. In addition, in the package 11 of FIG. 2, since the folded part 13b becomes a part which is not opened even if it does not melt | fuse, in FIG. 2, it is not melt | fused. In the present invention, the constant width of the peripheral portion is appropriately set depending on the size of the package 10 and the like, and is not particularly limited. For example, about 0.5 to 100 mm, about 1 to 50 mm, about 2 to 20 mm, etc. Is mentioned.

  When the shape of the package 11 is, for example, a pillow packaging bag, the so-called back-pasted portion also becomes a fusion peripheral portion 30 in which the thermoplastic resin layers 3 are heat-sealed, and the back-attached portion is also the peripheral portion of the laminated sheet 13. 13a. For this reason, it is preferable that the end surface 2a of the barrier layer 2 of the laminated sheet 13 constituting the package is not exposed to the outside in at least a part of the peripheral edge portion 13a of the laminated sheet including the back-pasted portion.

  Although it does not restrict | limit especially as thickness of the lamination sheet 13 which forms the package 11, It is excellent in water resistance over a long period of time, reducing the thickness of the lamination sheet 13, miniaturizing the product which accommodated the content 12 In view of the above, the upper limit is, for example, about 200 μm or less, about 180 μm or less, or about 150 μm or less, and the lower limit is about 50 μm or more, about 60 μm or more. Examples include about 200 μm, about 50 to 180 μm, about 50 to 150 μm, about 60 to 200 μm, about 60 to 180 μm, and about 60 to 150 μm. In the package 11, the thickness of the laminated sheet 13 is a thickness at a portion where the above-described fusion is not performed.

  In the package 10 of the present invention, the package 11 is composed of a laminated sheet 13 including at least the resin layer 1 located on the outer surface side, the barrier layer 2, and the thermoplastic resin layer 3 in this order. The end surface 2a of the barrier layer 2 of the laminated sheet 13 is not exposed to the outside in at least a part of the peripheral edge portion 13a of the sheet 13. In the package 10 of the present invention, in the entire periphery of the peripheral edge portion 13a of the laminated sheet 13 from the viewpoint of more effectively suppressing the corrosion of the end surface 2a of the barrier layer 2 even in contact with the aqueous liquid for a long period of time. The end surface 2a of the barrier layer 2 of the laminated sheet 13 is preferably not exposed to the outside. As specific aspects of the structure of the package 10 of the present invention, the following first to seventh aspects will be described below.

First Embodiment As shown in FIG. 3, in the first embodiment of the package 10 of the present invention, the package 11 includes at least a resin layer 1 located on the outer surface 11a side, a barrier layer 2, and a thermoplastic. It is comprised from the lamination sheet 13 provided with the resin layer 3 in this order. In the first aspect, both the resin layer 1 and the thermoplastic resin layer 3 cover the end surface 2 a of the barrier layer 2 in at least a part of the peripheral edge portion 13 a of the laminated sheet 13. In the schematic diagram of FIG. 3, only the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 are illustrated as the laminated sheet 13 constituting the package 11, but as described later, the package according to the present invention. 10, an adhesive layer may be provided between the resin layer 1 and the barrier layer 2 of the laminated sheet 13 constituting the package 11, or between the barrier layer 2 and the thermoplastic resin layer 3. May be provided with an adhesive layer. Furthermore, a surface coating layer may be provided on the outer side of the resin layer 1. Details of the composition of each layer such as the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 are as described later.

  In the first aspect, as shown in FIG. 3, at least a part of the end surface 2 a of the barrier layer 2 of the package 11 is a fusion peripheral edge in which the thermoplastic resin layers 3 of the laminated sheet 13 are thermally fused. The resin layer 1 and the thermoplastic resin layer 3 both cover the end surface 2 a of the barrier layer 2 in at least a part of the peripheral portion 13 a. Thereby, even when the end surface 2a of the barrier layer 2 of the laminated sheet 13 is not exposed to the outside in at least a part of the peripheral edge portion 13a of the laminated sheet 13, the barrier layer 2 is also in contact with the aqueous liquid for a long period of time. Corrosion of the end face 2a is effectively suppressed, and the package 10 is suitable for use in contact with an aqueous liquid for a long period of time. Since the end surface 2 a of the barrier layer 2 is located in the fusion peripheral portion 30, compared to the case where the end surface 2 a of the barrier layer 2 is not located in the fusion peripheral portion 30, the fusion peripheral portion 30. The water resistance is effectively improved.

  In the first aspect, preferably, the entire circumference of the end surface 2a of the barrier layer 2 of the package 11 is located within the fusion peripheral portion 30 where the thermoplastic resin layers 3 of the laminated sheet 13 are thermally fused. In addition, both the resin layer 1 and the thermoplastic resin layer 3 cover the end surface 2a of the barrier layer 2 over the entire circumference of the peripheral edge portion 13a. Thereby, the end surface 2a of the barrier layer 2 is not exposed to the outside on the entire periphery of the peripheral edge portion 13a of the laminated sheet 13, and the end surface 2a of the barrier layer 2 is more corroded even when it is in contact with the aqueous liquid for a long time. It becomes a package 10 that is more effectively suppressed and is particularly suitable for applications that are in contact with an aqueous liquid for an extended period of time. Compared to the case where the end surface 2 a of the barrier layer 2 is located in the fusion peripheral edge 30 in the entire periphery of the peripheral edge 13 a of the laminated sheet 13, so that it is not located in the fusion peripheral edge 30. The water resistance of the fusion peripheral edge 30 is particularly effectively improved.

  In addition, for example, the sixth aspect described later shows an aspect in which the resin layer 1 covers the end surface 2a of the barrier layer 2 in at least a part of the peripheral edge portion 13a of the laminated sheet 13, and 7 shows an aspect in which the thermoplastic resin layer 3 covers the end surface 2a of the barrier layer 2 in at least a part of the peripheral edge portion 13a of the laminated sheet 13.

  In FIG. 3, both the resin layer 1 and the thermoplastic resin layer 3 cover the end surface 2 a of the barrier layer 2 at the peripheral edge portion 13 a of the laminated sheet 13, and the end surface 2 a of the barrier layer 2 is the resin layer 1. And it is located inside the end surface of the thermoplastic resin layer 3 (center side of the package 11).

  In the package 10 of the present invention, as shown in FIG. 3, in order for both the resin layer 1 and the thermoplastic resin layer 3 to cover the end surface 2 a of the barrier layer 2, for example, When the thermoplastic resin layers 3 are thermally fused together, the resin layer 1 and the thermoplastic resin layer 3 are fused at the peripheral edge portion 13a so that both the resin layer 1 and the thermoplastic resin layer 3 are attached to the end face 2a. Contact.

Second Embodiment As shown in FIG. 4, in the second embodiment of the package 10 of the present invention, the package 11 includes at least a resin layer 1 positioned on the outer surface 11a side, a barrier layer 2, and a thermoplastic. The resin layer 3 is provided in this order, and the package 11 further includes a sealing member 4. In the second aspect, the sealing member 4 covers at least a part of the peripheral edge portion 13 a of the laminated sheet 13. In the schematic diagram of FIG. 4, only the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 are illustrated as the laminated sheet 13 that constitutes the package 11. An adhesive layer may be provided between the layer 2 and an adhesive layer may be provided between the barrier layer 2 and the thermoplastic resin layer 3. Furthermore, a surface coating layer may be provided on the outer side of the resin layer 1. Details of each layer such as the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 and the composition of the sealing member 4 are as described later.

  As shown in FIG. 4, in the second embodiment, at least a part of the end surface 2 a of the barrier layer 2 of the package body 11 is a fusion peripheral edge in which the thermoplastic resin layers 3 of the laminated sheet 13 are thermally fused. It is located in the portion 30, and at least a part of the peripheral edge portion 13 a of the laminated sheet 13 is covered with the sealing member 4. Thereby, even when the end surface 2a of the barrier layer 2 of the laminated sheet 13 is not exposed to the outside in at least a part of the peripheral edge portion 13a of the laminated sheet 13, the barrier layer 2 is also in contact with the aqueous liquid for a long period of time. Corrosion of the end face 2a is effectively suppressed, and the package 10 is suitable for use in contact with an aqueous liquid for a long period of time. Since the end surface 2 a of the barrier layer 2 is located in the fusion peripheral portion 30, compared to the case where the end surface 2 a of the barrier layer 2 is not located in the fusion peripheral portion 30, the fusion peripheral portion 30. The water resistance is effectively improved.

  2nd aspect WHEREIN: The perimeter of the end surface 2a of the barrier layer 2 of the package 11 is located in the fusion | melting peripheral part 30 to which the thermoplastic resin layers 3 of the lamination sheet 13 were heat-seal | fused, Furthermore, The entire periphery of the peripheral edge portion 13 a of the laminated sheet 13 is preferably covered with the sealing member 4. Thereby, the end surface 2a of the barrier layer 2 is not exposed to the outside and the end surface 2a of the barrier layer 2 is exposed to the aqueous liquid for a long period of time on the entire circumference of the peripheral edge portion 13a of the laminated sheet 13. Corrosion is further effectively suppressed, resulting in a package 10 that is particularly suitable for applications that are in contact with an aqueous liquid for an extended period of time. Compared to the case where the end surface 2 a of the barrier layer 2 is located in the fusion peripheral edge 30 in the entire periphery of the peripheral edge 13 a of the laminated sheet 13, so that it is not located in the fusion peripheral edge 30. The water resistance of the fusion peripheral edge 30 is particularly effectively improved.

  The method of covering the peripheral edge portion 13a of the laminated sheet 13 with the sealing member 4 is not particularly limited. For example, the method of fusing the sealing member 4 to the peripheral edge portion 13a of the laminated sheet 13 or the resin layer 1 and sealing. Examples thereof include a method in which an easy-adhesion layer is provided between the member 4 and bonding, and a method using an adhesive or a caulking material. Details of the method of covering the peripheral edge portion 13a of the laminated sheet 13 with the sealing member 4 are as described later.

  In the 2nd aspect shown by FIG. 4, although the sealing member 4 has shown the figure which has covered the end surface 2a of the barrier layer 2 in the peripheral part 13a of the lamination sheet 13, resin like 1st aspect is shown. At least one of the layer 1 and the thermoplastic resin layer 3 may cover the end surface 2 a of the barrier layer 2.

  As shown in FIG. 4, in the second mode, the end surface 2 a of the barrier layer 2 is located on the inner side (center side of the package 11) than the end surfaces of the resin layer 1 and the thermoplastic resin layer 3. It is preferable that the sealing member 4 covers the end surface 2 a of the barrier layer 2 when the sealing member 4 enters inside the end surfaces of the resin layer 1 and the thermoplastic resin layer 3.

Third Aspect As shown in FIG. 5, the package 10 of the third aspect has an end surface 2 a of the barrier layer 2 in which the resin layer 1 and the thermoplastic resin layer 3 are compared with the package 10 of the second aspect. The sealing member 4 covers the end surface 2a of the barrier layer 2 without the sealing member 4 entering inside the end surfaces of the resin layer 1 and the thermoplastic resin layer 3. Although it is different in point, it is common in other points. Also in the third aspect, the sealing member 4 covers at least a part of the peripheral edge portion 13 a of the laminated sheet 13. In the schematic diagram of FIG. 5, only the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 are illustrated as the laminated sheet 13 that constitutes the package 11. An adhesive layer may be provided between the layer 2 and an adhesive layer may be provided between the barrier layer 2 and the thermoplastic resin layer 3. Furthermore, a surface coating layer may be provided on the outer side of the resin layer 1. Details of each layer such as the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 and the composition of the sealing member 4 are as described later.

  In the third aspect, the end surface 2a of the barrier layer 2 of the package 11 reaches the position of the end surface of the resin layer 1 and the thermoplastic resin layer 3 (that is, the end surface 2a of the barrier layer 2 is fused). However, since the sealing member 4 covers the end surface 2a of the barrier layer 2, at least a part of the end surface 2a of the barrier layer 2 of the package 11 is not exposed to the outside. In addition, even when contacted with the aqueous liquid for a long period of time, the corrosion of the end surface 2a of the barrier layer 2 is effectively suppressed, and the package 10 is suitable for use in contact with the aqueous liquid for a long period of time.

  Furthermore, in the third aspect, it is preferable that the entire circumference of the end surface 2 a of the barrier layer 2 of the package 11 is covered with the sealing member 4. As a result, the end surface 2a of the barrier layer 2 is not exposed to the outside and the end surface 2a of the barrier layer 2 is in contact with the aqueous liquid for a long period of time without being exposed to the outside on the entire periphery of the peripheral edge portion 13a of the laminated sheet 13. Corrosion is further effectively suppressed, resulting in a package 10 that is particularly suitable for applications that are in contact with an aqueous liquid for an extended period of time.

  The method for covering the peripheral edge portion 13a of the laminated sheet 13 with the sealing member 4 is not particularly limited, and, for example, a method of fusing the sealing member 4 to the peripheral edge portion 13a of the laminated sheet 13 or the like, Examples thereof include a method of providing an easy-adhesion layer between the resin layer 1 and the sealing member 4 and bonding them, a method using an adhesive or a caulking material, and the like. Details of the method of covering the peripheral edge portion 13a of the laminated sheet 13 with the sealing member 4 are as described later.

4th aspect As FIG. 6 shows, in the 4th aspect of the package 10 of this invention, the package 11 is the resin layer 1 located in the outer surface 11a side, the barrier layer 2, and thermoplasticity at least. The resin layer 3 is provided in this order, and the entire outer surface 11 a of the package 11 is configured by the sealing member 4. That is, in the fourth aspect, the entire outer side of the resin layer 1 located on the outer surface side of the laminated sheet 13 is covered with the sealing member 4. In the schematic diagram of FIG. 6, only the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 are illustrated as the laminated sheet 13 constituting the package 11. An adhesive layer may be provided between the layer 2 and an adhesive layer may be provided between the barrier layer 2 and the thermoplastic resin layer 3. Furthermore, a surface coating layer may be provided on the outer side of the resin layer 1 (however, inside the sealing member 4). Details of each layer such as the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 and the composition of the sealing member 4 are as described later.

  As shown in FIG. 6, in the fourth mode, as in the first mode and the second mode, at least a part of the end surface 2 a of the barrier layer 2 of the package 11 is made of the thermoplastic resin of the laminated sheet 13. The layers 3 are located within the fusion peripheral edge 30 where the layers 3 are thermally fused. Furthermore, in the 4th aspect, the whole outer surface 11a of the package 11 is comprised by the sealing member 4. FIG. For this reason, in the peripheral part 13a of the lamination sheet 13, the end surface 2a of the barrier layer 2 of the lamination sheet 13 is not exposed outside, and even if it contacts with aqueous liquid for a long period of time, the end surface 2a of the barrier layer 2 Corrosion is effectively suppressed, resulting in a package 10 suitable for use in contact with an aqueous liquid for a long period of time. Compared to the case where the end surface 2 a of the barrier layer 2 is not located in the fusion peripheral portion 30 because the end surface 2 a of the barrier layer 2 is located in the fusion peripheral portion 30 between the thermoplastic resin layers 3. Thus, the water resistance of the fusion peripheral edge 30 is effectively improved.

  Also in the fourth aspect, the entire circumference of the end surface 2a of the barrier layer 2 of the package 11 is located within the fusion peripheral portion 30 where the thermoplastic resin layers 3 of the laminated sheet 13 are thermally fused. Preferably it is. Compared to the case where the end surface 2 a of the barrier layer 2 is located in the fusion peripheral edge 30 in the entire periphery of the peripheral edge 13 a of the laminated sheet 13, so that it is not located in the fusion peripheral edge 30. The water resistance of the fusion peripheral edge 30 is particularly effectively improved.

  Furthermore, in the 4th aspect, since the whole outer surface 11a of the package 11 is comprised by the sealing member 4, not only the water resistance of the fusion | melting peripheral part 30 but the water resistance as the package 11 whole is provided. Especially excellent.

  As a method of configuring the entire outer surface 11 a of the package 11 with the sealing member 4, a method of covering the laminated sheet 13 with the sealing member 4 from the outside can be mentioned. As will be described later, for example, by using a heat-shrinkable film as the sealing member 4, the heat-shrinkable film is shrunk by covering and heating the outer side of the laminated sheet 13 with the heat-shrinkable film. The sealing member 4 having a shape along the shape of the outer surface is formed, and the entire outer surface 11 a of the package 11 can be configured by the sealing member 4. The details of the method of configuring the entire outer surface 11a of the package 11 with the sealing member 4 are as described later.

  In the 4th aspect shown by FIG. 6, although the sealing member 4 has shown the figure which has covered the end surface 2a of the barrier layer 2 in the peripheral part 13a of the lamination sheet 13, a 1st aspect and a 2nd Similar to the embodiment, at least one of the resin layer 1 and the thermoplastic resin layer 3 may cover the end surface 2 a of the barrier layer 2.

  As shown in FIG. 6, in the fourth embodiment, the end surface 2 a of the barrier layer 2 is located on the inner side (center side of the package 11) than the end surfaces of the resin layer 1 and the thermoplastic resin layer 3. It is preferable that the sealing member 4 covers the end surface 2 a of the barrier layer 2 when the sealing member 4 enters inside the end surfaces of the resin layer 1 and the thermoplastic resin layer 3.

Fifth Mode As shown in FIG. 7, the difference between the package 10 of the fifth mode and the fourth mode is that, in the fifth mode, the end surface 2a of the barrier layer 2 is the resin layer 1 and It has reached the position of the end surface of the thermoplastic resin layer 3, and the sealing member 4 does not enter the inside of the end surfaces of the resin layer 1 and the thermoplastic resin layer 3 (that is, the end surface 2a of the barrier layer 2 is The sealing member 4 is not located within the fusion peripheral portion 30), and covers the end surface 2 a of the barrier layer 2, and is common in other respects. In the schematic diagram of FIG. 7, only the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 are illustrated as the laminated sheet 13 constituting the package 11. An adhesive layer may be provided between the layer 2 and an adhesive layer may be provided between the barrier layer 2 and the thermoplastic resin layer 3. Furthermore, a surface coating layer may be provided on the outer side of the resin layer 1 (however, inside the sealing member 4). Also in the fifth aspect, details of each layer such as the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 and the composition of the sealing member 4 are as described later.

  As shown in FIG. 7, in the fifth aspect, as in the third aspect, the end surface 2 a of the barrier layer 2 of the package 11 reaches the position of the end surfaces of the resin layer 1 and the thermoplastic resin layer 3. However, since the sealing member 4 covers the entire circumference of the end surface 2a of the barrier layer 2, corrosion of the end surface 2a of the barrier layer 2 is effectively suppressed even when it is in contact with an aqueous liquid for a long period of time. Thus, the package 10 is suitable for use in contact with an aqueous liquid for a long period of time.

  In the fifth aspect, as in the fourth aspect, since the entire outer surface 11a of the package 11 is composed of the sealing member 4, not only the water resistance of the fusion peripheral edge 30 but also the entire package 11 is obtained. The water resistance is particularly excellent.

  As a method of configuring the entire outer surface 11 a of the package 11 with the sealing member 4, a method of covering the outer side of the laminated sheet 13 with the sealing member 4 can be mentioned as in the fourth aspect. As will be described later, for example, by using a heat-shrinkable film as the sealing member 4, the heat-shrinkable film is shrunk by covering and heating the outer side of the laminated sheet 13 with the heat-shrinkable film. The sealing member 4 having a shape along the shape of the outer surface is formed, and the entire outer surface 11 a of the package 11 can be configured by the sealing member 4. The details of the method of configuring the entire outer surface 11a of the package 11 with the sealing member 4 are as described later.

Sixth Aspect and Seventh Aspect As shown in FIG. 8 (sixth aspect) and FIG. 9 (seventh aspect), the packages 10 of the sixth aspect and the seventh aspect are respectively Compared with the package 10 of the embodiment, the difference is as follows. In the sixth aspect, only the resin layer 1 covers the end face 2 a of the barrier layer 2, and in the seventh aspect, only the thermoplastic resin layer 3 covers the end face 2 a of the barrier layer 2. In the sixth aspect, the end surface 2 a of the barrier layer 2 reaches the position of the end surface of the thermoplastic resin layer 3, and the end surface 2 a of the barrier layer 2 is covered with the resin layer 1. On the other hand, in the seventh embodiment, the end surface 2a of the barrier layer 2 is located on the inner side (center side of the package 11) than the end surfaces of the resin layer 1 and the thermoplastic resin layer 3, and the thermoplastic resin layer 3 The end surface 2a of the barrier layer 2 is covered by the above. In these respects, the package 10 of the sixth aspect and the seventh aspect is different from the package 10 of the first aspect, but the other points are common. 8 and 9, only the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 are illustrated as the laminated sheet 13 constituting the package 11, but the present invention is described later. In the package 10, an adhesive layer may be provided between the resin layer 1 and the barrier layer 2 of the laminated sheet 13 constituting the package 11, or the barrier layer 2 and the thermoplastic resin layer 3 An adhesive layer may be provided between them. Furthermore, a surface coating layer may be provided on the outer side of the resin layer 1. Also in the sixth aspect and the seventh aspect, details of each layer such as the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 and the composition of the sealing member 4 are as described later.

  In the seventh aspect, as shown in FIG. 9, at least a part of the end surface 2 a of the barrier layer 2 of the package 11 is a fusion peripheral edge where the thermoplastic resin layers 3 of the laminated sheet 13 are thermally fused. The end surface 2 a of the barrier layer 2 is covered with the thermoplastic resin layer 3. Thereby, even when the end surface 2a of the barrier layer 2 of the laminated sheet 13 is not exposed to the outside in at least a part of the peripheral edge portion 13a of the laminated sheet 13, the barrier layer 2 is also in contact with the aqueous liquid for a long period of time. Corrosion of the end face 2a is effectively suppressed, and the package 10 is suitable for use in contact with an aqueous liquid for a long period of time. In the seventh aspect, the end surface 2 a of the barrier layer 2 is located in the fusion peripheral portion 30, so that the end surface 2 a of the barrier layer 2 is not located in the fusion peripheral portion 30. The water resistance of the fusion peripheral edge 30 is effectively improved.

  In the seventh aspect, the entire circumference of the end surface 2a of the barrier layer 2 of the package 11 is located in the fusion peripheral portion 30 where the thermoplastic resin layers 3 of the laminated sheet 13 are thermally fused, It is preferable that the entire circumference of the end surface 2 a of the barrier layer 2 is covered with the thermoplastic resin layer 3. Thereby, the end surface 2a of the barrier layer 2 is not exposed to the outside and the end surface 2a of the barrier layer 2 is exposed to the aqueous liquid for a long period of time on the entire circumference of the peripheral edge portion 13a of the laminated sheet 13. Corrosion is further effectively suppressed, resulting in a package 10 that is particularly suitable for applications that are in contact with an aqueous liquid for an extended period of time. In the seventh aspect, the end surface 2 a of the barrier layer 2 is positioned in the fusion peripheral portion 30 by being located in the fusion peripheral portion 30 in the entire periphery of the peripheral portion 13 a of the laminated sheet 13. Compared with the case where there is no, the water resistance of the fusion | melting peripheral part 30 improves especially effectively.

  In the package 10 of the present invention, as shown in FIG. 8, in order to cover the end surface 2a of the barrier layer 2 only with the resin layer 1, for example, the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 are provided. When the laminated sheets are sequentially laminated and the resin layer 1 projects outward, and the thermoplastic resin layers 3 of the laminated sheet are heat-sealed, the resin layer 1 is a barrier at the peripheral portion 13a. It shape | molds so that the end surface of the layer 2 and the thermoplastic resin layer 3 may be covered.

  Further, in the package 10 of the present invention, as shown in FIG. 9, in order to cover the end surface 2 a of the barrier layer 2 only with the thermoplastic resin layer 3, for example, as the thermoplastic resin layer 3 of the laminated sheet 13, When the thermoplastic resin layers 3 of the laminated sheet 13 are heat-sealed using a resin that is easily melted, the thermoplastic resin layer 3 is molded so as to cover the end surface 2a of the barrier layer 2 at the peripheral edge portion 13a.

  In the package 10 of the present invention, as shown in FIG. 10, the peripheral portion 13 a of the package 10 of FIG. 9 may be further covered with the sealing member 4.

2. Each layer and sealing member forming the package In the package 10 of the present invention, the package 11 includes at least the resin layer 1 located on the outer surface 11a side, the barrier layer 2, and the thermoplastic resin layer 3 in this order. It comprises a laminated sheet 13 provided. Moreover, the said laminated sheet 13 is provided with the adhesive bond layer, the contact bonding layer, and the surface coating layer as needed. Furthermore, the package 11 includes a sealing member 4 as necessary. Details of each composition, thickness, etc. will be described in detail below.

[Resin layer 1]
In the package 10 of the present invention, the resin layer 1 of the laminated sheet 13 forming the package 11 is a layer located on the outer surface 11a side. The resin layer 1 may constitute at least a part of the outermost surface 11a of the package 11. Specifically, as in the fourth aspect (FIG. 6) or the fifth aspect (FIG. 7), the entire outer surface 11a of the package 11 is configured by the sealing member 4, or the resin layer 1 The resin layer 1 can constitute at least a part of the outermost surface 11 a of the package 11, except for a case where a later-described surface coating layer is further provided on the outer side.

  About the raw material which forms the resin layer 1, if it is excellent in water resistance, it will not restrict | limit in particular. Examples of the material for forming the resin layer 1 include polyester resin, polyolefin resin, polyamide resin, epoxy resin, acrylic resin, fluorine resin, polyurethane resin, silicon resin, phenol resin, polycarbonate, and a mixture or copolymer thereof. The resin film is mentioned. Among these, polyester resins and polyolefin resins are preferable, and polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, polybutylene naphthalate, copolymerized polyester, polypropylene, and the like are more preferable.

  From the viewpoint of excellent water resistance, the resin layer 1 preferably contains at least one of polyethylene naphthalate, polybutylene terephthalate, and polypropylene, and at least of polyethylene naphthalate, polybutylene terephthalate, and polypropylene. More preferably, it is composed of one kind.

  The resin layer 1 may be formed from a single resin film, but may be formed from two or more resin films in order to improve water resistance over a long period of time. Specific examples include a multilayer structure in which a plurality of polyester films are laminated, and a multilayer structure in which a polyester film and a polypropylene film are laminated. Preferred specific examples of the multilayer structure include a multilayer structure in which two polybutylene terephthalate films are laminated, a multilayer structure in which two polyethylene naphthalate films are laminated, and a multilayer structure in which polybutylene terephthalate film and polyethylene naphthalate film are laminated. And a multilayer structure in which a polybutylene terephthalate film and a polypropylene film are laminated, and a multilayer structure in which a polyethylene naphthalate film and a polypropylene film are laminated. When the resin layer 1 has a multilayer structure, the thickness of each layer is preferably about 2 to 25 μm.

  When the resin layer 1 is formed of a multilayer resin film, the two or more resin films may be laminated via an adhesive component such as an adhesive or an adhesive resin. Is the same as that of the adhesive layer described later. In addition, it does not restrict | limit especially as a method of laminating | stacking two or more resin films, A well-known method can be employ | adopted, for example, a dry lamination method, a sandwich lamination method, etc. are mentioned, Preferably the dry lamination method is mentioned. When laminating by the dry laminating method, it is preferable to use a urethane-based adhesive as the adhesive layer. At this time, the thickness of the adhesive layer is, for example, about 2 to 5 μm.

  As thickness of the resin layer 1, Preferably it is about 3-50 micrometers, More preferably, about 10-35 micrometers is mentioned.

[Adhesive layer]
In the laminated sheet 13 forming the package 11, the adhesive layer is a layer provided between the resin layer 1 and the barrier layer 2 as necessary in order to firmly bond the resin layer 1 and the barrier layer 2 (illustration is omitted). ).

  The adhesive layer is formed of an adhesive (resin) that can bond the resin layer 1 and the barrier layer 2 together. The adhesive used for forming the adhesive layer may be a two-component curable adhesive or a one-component curable adhesive. Furthermore, the bonding mechanism of the adhesive used for forming the adhesive layer is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.

  Specific examples of adhesive components that can be used for forming the adhesive layer include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and copolyester; Adhesive; polyurethane adhesive; epoxy resin; phenol resin resin; polyamide resin such as nylon 6, nylon 66, nylon 12, copolymer polyamide; polyolefin resin such as polyolefin, carboxylic acid modified polyolefin, metal modified polyolefin , Polyvinyl acetate resin; cellulose adhesive; (meth) acrylic resin; polyimide resin; polycarbonate; amino resin such as urea resin and melamine resin; chloroprene rubber and nitrile rubber - styrene rubbers such as butadiene rubber; and silicone resins. These adhesive components may be used individually by 1 type, and may be used in combination of 2 or more type. Among these adhesive components, a polyurethane adhesive or an epoxy adhesive is preferable.

  Further, from the viewpoint of further improving the water resistance over a long period of time, it is preferable to use an adhesive component having excellent water resistance as an adhesive component that can be used for forming the adhesive layer. Examples of the adhesive component having excellent water resistance include polyurethane, polyurethane-polyisocyanate (a mixture of a polyurethane compound and a polyisocyanate compound), an epoxy resin, and the like.

Moreover, as resin used for formation of an adhesive bond layer, polyolefin resin, such as polyolefin, cyclic polyolefin, acid-modified polyolefin, acid-modified cyclic polyolefin, can also be used conveniently. That is, the resin constituting the adhesive layer may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. The fact that the resin constituting the adhesive layer contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. However, if the acid modification degree is low, the peak may be small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.

  From the viewpoint of further improving the water resistance over a long period of time while reducing the thickness of the laminated sheet 13, the adhesive layer preferably contains an acid-modified polyolefin. The acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of polyolefin with an acid component such as carboxylic acid. Examples of the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof. Polyolefins to be modified include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, polypropylene block copolymers (for example, block copolymers of propylene and ethylene), polypropylene Polypropylenes such as random copolymers (for example, random copolymers of propylene and ethylene); ethylene-butene-propylene terpolymers and the like. Among these polyolefins, polyethylene and polypropylene are preferable.

  In the adhesive layer, among the acid-modified polyolefins, maleic anhydride-modified polyolefin, and further maleic anhydride-modified polypropylene are particularly preferable.

  Furthermore, from the viewpoint of further improving the water resistance over a long period of time while reducing the thickness of the laminated sheet 13, the adhesive layer may be a cured product of a resin composition containing an acid-modified polyolefin and a curing agent. More preferred. Preferred examples of the acid-modified polyolefin include those described above.

  Hereinafter, various aspects in which the adhesive layer is a cured product of a resin composition containing a curing agent will be described in detail.

  The adhesive layer is a cured product of a resin composition containing an acid-modified polyolefin and at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group. It is particularly preferably a cured product of a resin composition comprising an acid-modified polyolefin and at least one selected from the group consisting of a compound having an isocyanate group and a compound having an epoxy group. In the case where an unreacted substance of a curing agent such as a compound having an isocyanate group, a compound having an oxazoline group, or an epoxy resin remains in the adhesive layer, the presence of the unreacted substance is, for example, infrared spectroscopy, It can be confirmed by a method selected from Raman spectroscopy, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the like.

  Moreover, it is also preferable that an adhesive bond layer contains at least 1 sort (s) selected from the group which consists of a urethane resin, an amide ester resin, and an epoxy resin, and it is more preferable that a urethane resin and an epoxy resin are included. The adhesive layer is more preferably a cured product of a resin composition containing at least one of these resins and the acid-modified polyolefin.

  The adhesive layer is a cured product of a resin composition including a curing agent having at least one selected from the group consisting of an oxygen atom, a heterocyclic ring, a C═N bond, and a C—O—C bond. Is also preferable. Examples of the curing agent having a heterocyclic ring include a curing agent having an oxazoline group and a curing agent having an epoxy group. Examples of the curing agent having a C═N bond include a curing agent having an oxazoline group and a curing agent having an isocyanate group. In addition, examples of the curing agent having a C—O—C bond include a curing agent having an oxazoline group, a curing agent having an epoxy group, and a urethane resin. The adhesive layer is a cured product of a resin composition containing these curing agents, for example, gas chromatography mass spectrometry (GCMS), infrared spectroscopy (IR), time-of-flight secondary ion mass spectrometry (TOF) -SIMS) and X-ray photoelectron spectroscopy (XPS).

  Although it does not restrict | limit especially as a compound which has an isocyanate group, Preferably a polyfunctional isocyanate compound is mentioned. The polyfunctional isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups. Specific examples of the polyfunctional isocyanate-based curing agent include pentane diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and polymerization and nurate of these. And a mixture thereof and a copolymer with another polymer.

  As content of the compound which has an isocyanate group in an adhesive bond layer, it is preferable to exist in the range of 0.1-50 mass% in the resin composition which comprises an adhesive bond layer, 0.5-40 mass% More preferably, it is in the range. At this time, the acid-modified polyolefin may be used as the balance.

  The compound having an oxazoline group is not particularly limited as long as it is a compound having an oxazoline skeleton. Specific examples of the compound having an oxazoline group include those having a polystyrene main chain and those having an acrylic main chain. Moreover, as a commercial item, the Epocross series by Nippon Shokubai Co., Ltd. etc. are mentioned, for example.

  The proportion of the compound having an oxazoline group in the adhesive layer is preferably in the range of 0.1 to 50% by mass, and in the range of 0.5 to 40% by mass in the resin composition constituting the adhesive layer. More preferably. At this time, the acid-modified polyolefin may be used as the balance.

  Examples of the compound having an epoxy group include an epoxy resin. The epoxy resin is not particularly limited as long as it is a resin capable of forming a crosslinked structure with an epoxy group present in the molecule, and a known epoxy resin can be used. As a weight average molecular weight of an epoxy resin, Preferably it is about 50-2000, More preferably, it is about 100-1000, More preferably, about 200-800 is mentioned. In the present invention, the weight average molecular weight of the epoxy resin is a value measured by gel permeation chromatography (GPC) measured under conditions using polystyrene as a standard sample.

  Specific examples of the epoxy resin include trimethylolpropane glycidyl ether derivative, bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether, and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  The ratio of the epoxy resin in the adhesive layer is preferably in the range of 0.1 to 50% by mass and in the range of 0.5 to 40% by mass in the resin composition constituting the adhesive layer. Is more preferable. At this time, the acid-modified polyolefin may be used as the balance.

  The urethane resin is not particularly limited, and a known urethane resin can be used. The adhesive layer may be, for example, a cured product of a two-component curable urethane resin.

  The ratio of the urethane resin in the adhesive layer is preferably in the range of 0.1 to 50% by mass and in the range of 0.5 to 40% by mass in the resin composition constituting the adhesive layer. Is more preferable. At this time, the acid-modified polyolefin may be used as the balance.

  In the present invention, the adhesive layer is a cured resin composition containing at least one selected from the group consisting of an isocyanate group-containing compound, an oxazoline group-containing compound, and an epoxy resin, and the acid-modified polyolefin. When it is a product, the acid-modified polyolefin functions as a main agent, and the compound having an isocyanate group, the compound having an oxazoline group, and the epoxy resin each function as a curing agent.

  The thickness of the adhesive layer is not particularly limited as long as it exhibits a function as a layer to be bonded, but for example, when using what is exemplified as an adhesive component that can be used for forming the adhesive layer, preferably 1 to About 10 micrometers, More preferably, about 1-5 micrometers is mentioned. Moreover, when it comprises by polyolefin resin, such as polyolefin and acid-modified polyolefin resin, Preferably it is about 2-50 micrometers, More preferably, about 10-40 micrometers is mentioned. Moreover, if it is a hardened | cured material of the resin composition containing a hardening | curing agent, Preferably it is about 30 micrometers or less, More preferably, it is about 0.1-20 micrometers, More preferably, about 0.5-5 micrometers is mentioned. When the adhesive layer is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer can be formed by applying the resin composition and curing it by heating or the like.

[Barrier layer 2]
In the laminated sheet 13 that forms the package 11, the barrier layer 2 is a layer having a function of preventing water, oxygen, light, and the like from entering the package 11 in addition to improving the strength of the package 11. . The barrier layer 2 can be formed by, for example, a metal foil, a metal vapor deposition film, an inorganic oxide vapor deposition film, a carbon-containing inorganic oxide vapor deposition film, a film provided with these vapor deposition films, or the like. It is preferable that the layer is formed of Specific examples of the metal constituting the barrier layer 2 include aluminum, stainless steel, and titanium, and preferably aluminum. The barrier layer 2 is preferably formed from a metal foil, and more preferably from an aluminum alloy foil. From the viewpoint of preventing the generation of wrinkles and pinholes in the barrier layer 2 during the manufacture of the package 11, the barrier layer is made of, for example, annealed aluminum (JIS H4160: 1994 A8021H-O, JIS H4160: 1994). A8079H-O, JIS H4000: 2014 A8021P-O, and JIS H4000: 2014 A8079P-O) are more preferable.

  The thickness of the barrier layer 2 is not particularly limited as long as it can exhibit excellent water resistance over a long period of time, but is preferably about 0.1 to 300 μm, more preferably about 10 to 100 μm, and still more preferably about 10 to 80 μm. Can be mentioned.

  The barrier layer 2 is preferably subjected to chemical conversion treatment on at least one surface, preferably both surfaces, for the purpose of stabilizing adhesion, preventing dissolution and corrosion, and the like. Here, the chemical conversion treatment refers to a treatment for forming an acid-resistant film on the surface of the barrier layer. Examples of the chemical conversion treatment include chromate treatment using a chromium compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromic acid acetyl acetate, chromium chloride, potassium sulfate chromium; Phosphoric acid treatment using a phosphoric acid compound such as sodium phosphate, potassium phosphate, ammonium phosphate or polyphosphoric acid; an aminated phenol polymer having a repeating unit represented by the following general formulas (1) to (4) is used And chromate treatment. In the aminated phenol polymer, the repeating units represented by the following general formulas (1) to (4) may be included singly or in any combination of two or more. Also good.

In general formulas (1) to (4), X represents a hydrogen atom, a hydroxy group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group. R ¹ and R ² are the same or different and each represents a hydroxy group, an alkyl group, or a hydroxyalkyl group. In the general formulas (1) to (4), examples of the alkyl group represented by X, R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, C1-C4 linear or branched alkyl groups, such as a tert- butyl group, are mentioned. Examples of the hydroxyalkyl group represented by X, R ¹ and R ² include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 3- A linear or branched chain having 1 to 4 carbon atoms substituted with one hydroxy group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group An alkyl group is mentioned. In the general formulas (1) to (4), the alkyl group and hydroxyalkyl group represented by X, R ¹ and R ² may be the same or different. In the general formulas (1) to (4), X is preferably a hydrogen atom, a hydroxy group or a hydroxyalkyl group. The number average molecular weight of the aminated phenol polymer having the repeating units represented by the general formulas (1) to (4) is, for example, preferably about 500 to 1,000,000, and preferably about 1,000 to 20,000. More preferred.

  Further, as a chemical conversion treatment method for imparting corrosion resistance to the barrier layer 2, a phosphoric acid is coated with a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide or the like and fine particles of barium sulfate dispersed therein. A method of forming an acid-resistant film on the surface of the barrier layer 2 by performing a baking treatment at 150 ° C. or higher can be mentioned. Further, a resin layer obtained by crosslinking a cationic polymer with a crosslinking agent may be further formed on the acid resistant film. Here, examples of the cationic polymer include polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine graft acrylic resin obtained by graft polymerization of a primary amine on an acrylic main skeleton, and polyallylamine. Or the derivative, aminophenol, etc. are mentioned. As these cationic polymers, only one type may be used, or two or more types may be used in combination. Examples of the crosslinking agent include a compound having at least one functional group selected from the group consisting of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent. As these crosslinking agents, only one type may be used, or two or more types may be used in combination.

  In addition, as a method for specifically providing an acid-resistant film, for example, as an example, at least the surface on the inner layer side of the aluminum alloy foil is firstly immersed in an alkali soaking method, electrolytic cleaning method, acid cleaning method, electrolytic acid cleaning method. , Degreased by a known treatment method such as an acid activation method, and then a phosphoric acid metal salt such as chromium phosphate salt, titanium phosphate salt, zirconium phosphate salt, zinc phosphate salt and the like Treatment liquid (aqueous solution) mainly composed of a mixture of metal salts, or treatment liquid (aqueous solution) principally composed of a non-metallic phosphate and a mixture of these non-metallic salts, or acrylic resin In addition, a treatment liquid (aqueous solution) composed of a mixture with a water-based synthetic resin such as a phenol resin or a urethane resin is applied by a known coating method such as a roll coating method, a gravure printing method, or a dipping method. Ri, it is possible to form the acid-resistant coating. For example, when treated with a chromium phosphate salt treatment solution, it becomes an acid-resistant film made of chromium phosphate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride, etc., and treated with a zinc phosphate salt treatment solution. In this case, an acid-resistant film made of zinc phosphate hydrate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride or the like is obtained.

  In addition, as another example of a specific method for providing an acid-resistant film, for example, at least the surface on the inner layer side of the aluminum alloy foil is first subjected to an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid An acid-resistant film can be formed by performing a degreasing process by a known processing method such as an activation method and then performing a known anodizing process on the degreasing surface.

  Other examples of acid-resistant films include phosphate-based and chromic acid-based films. Examples of the phosphate system include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, and chromium phosphate. Examples of the chromic acid system include chromium chromate.

  Another example of an acid-resistant film is to form an acid-resistant film such as phosphate, chromate, fluoride, triazine thiol compound, etc. Prevention of lamination, aluminum surface dissolution and corrosion, especially aluminum oxide present on the aluminum surface is prevented from dissolving and corroding, and the adhesion (wetting) of the aluminum surface is improved, and the resin layer during heat sealing In the embossed type, the effect of preventing delamination between the resin layer and aluminum during press molding is shown. Among substances that form an acid-resistant film, an aqueous solution composed of three components of a phenol resin, a chromium (III) fluoride compound, and phosphoric acid is applied to the aluminum surface, and the dry baking treatment is good.

  The acid-resistant film includes a layer having cerium oxide, phosphoric acid or phosphate, an anionic polymer, and a crosslinking agent that crosslinks the anionic polymer, and the phosphoric acid or phosphate is About 1-100 mass parts may be mix | blended with respect to 100 mass parts of cerium oxides. It is preferable that the acid-resistant film has a multilayer structure further including a layer having a cationic polymer and a crosslinking agent for crosslinking the cationic polymer.

  Further, the anionic polymer is preferably poly (meth) acrylic acid or a salt thereof, or a copolymer containing (meth) acrylic acid or a salt thereof as a main component. Moreover, it is preferable that the said crosslinking agent is at least 1 sort (s) chosen from the group which has a functional group in any one of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent.

  The phosphoric acid or phosphate is preferably condensed phosphoric acid or condensed phosphate.

  As the chemical conversion treatment, only one type of chemical conversion treatment may be performed, or two or more types of chemical conversion treatment may be performed in combination. Furthermore, these chemical conversion treatments may be carried out using one kind of compound alone, or may be carried out using a combination of two or more kinds of compounds. Among the chemical conversion treatments, a chromate treatment, a chemical conversion treatment combining a chromium compound, a phosphate compound, and an aminated phenol polymer are preferable. Of the chromium compounds, chromic acid compounds are preferred.

  Specific examples of the acid resistant film include those containing at least one of phosphate, chromate, fluoride, and triazine thiol. An acid resistant film containing a cerium compound is also preferable. As the cerium compound, cerium oxide is preferable.

  Specific examples of the acid-resistant film include a phosphate film, a chromate film, a fluoride film, and a triazine thiol compound film. As an acid-resistant film, one of these may be used, or a plurality of combinations may be used. Furthermore, as an acid-resistant film, after degreasing the chemical conversion treatment surface of the aluminum alloy foil, a treatment solution comprising a mixture of a metal phosphate and an aqueous synthetic resin, or a mixture of a non-metal phosphate and an aqueous synthetic resin It may be formed of a treatment liquid consisting of

The composition of the acid resistant film can be analyzed using, for example, time-of-flight secondary ion mass spectrometry. By analyzing the composition of the acid-resistant film using time-of-flight secondary ion mass spectrometry, for example, a peak derived from at least one of Ce ⁺ and Cr ⁺ is detected.

  It is preferable that the surface of the aluminum alloy foil is provided with an acid resistant film containing at least one element selected from the group consisting of phosphorus, chromium and cerium. In addition, it is confirmed using X-ray photoelectron spectroscopy that the acid-resistant film on the surface of the aluminum alloy foil of the package 11 contains at least one element selected from the group consisting of phosphorus, chromium, and cerium. be able to. Specifically, first, in the package 11, the thermoplastic resin layer, the adhesive layer, and the like laminated on the aluminum alloy foil are physically peeled off. Next, the aluminum alloy foil is put in an electric furnace, and organic components present on the surface of the aluminum alloy foil are removed at about 300 ° C. for about 30 minutes. Then, it confirms that these elements are contained using the X-ray photoelectron spectroscopy of the surface of aluminum alloy foil.

The amount of the acid-resistant film formed on the surface of the barrier layer 2 in the chemical conversion treatment is not particularly limited. For example, if the above-described chromate treatment is performed, the chromium compound is chromium per 1 m ² of the surface of the barrier layer 2. About 0.5 to 50 mg in terms of conversion, preferably about 1.0 to 40 mg, about 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of phosphorus, and 1 to 200 mg of aminated phenol polymer. It is desirable that it is contained at a rate of about 5.0 to 150 mg.

  The thickness of the acid-resistant film is not particularly limited, but is preferably about 1 nm to 10 μm, more preferably about 1 to 100 nm, from the viewpoint of the cohesive strength of the film and the adhesion with the barrier layer 2 and the thermoplastic resin layer. More preferably, about 1-50 nm is mentioned. The thickness of the acid-resistant film can be measured by observation with a transmission electron microscope or a combination of observation with a transmission electron microscope and energy dispersive X-ray spectroscopy or electron beam energy loss spectroscopy.

  In the chemical conversion treatment, a solution containing a compound used for forming an acid-resistant film is applied to the surface of the barrier layer by a bar coating method, a roll coating method, a gravure coating method, a dipping method, etc. It is carried out by heating to about 200 ° C. In addition, before the chemical conversion treatment is performed on the barrier layer, the barrier layer may be previously subjected to a degreasing treatment by an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or the like. By performing the degreasing process in this manner, it is possible to more efficiently perform the chemical conversion process on the surface of the barrier layer.

[Thermoplastic resin layer 3]
In the laminated sheet 13 forming the package 11, the thermoplastic resin layer 3 corresponds to the innermost layer. For example, when the contents 12 are accommodated, the thermoplastic resin layers are fused to each other, and the contents are formed by the package 11. The object 12 can be sealed.

The resin component used in the thermoplastic resin layer 3 is not particularly limited as long as it can be fused, and examples thereof include polyolefin, cyclic polyolefin, acid-modified polyolefin, and acid-modified cyclic polyolefin. That is, the resin constituting the thermoplastic resin layer 3 may or may not include a polyolefin skeleton, and preferably includes a polyolefin skeleton. The fact that the resin constituting the thermoplastic resin layer 3 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. However, if the acid modification degree is low, the peak may be small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.

  Specific examples of the polyolefin include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, block copolymer of polypropylene (for example, block copolymer of propylene and ethylene), polypropylene Polypropylene, such as a random copolymer of (for example, a random copolymer of propylene and ethylene); a terpolymer of ethylene-butene-propylene, and the like. Among these polyolefins, polyethylene and polypropylene are preferable.

  The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin that is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, butadiene, and isoprene. . Examples of the cyclic monomer that is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornadiene. Among these polyolefins, a cyclic alkene is preferable, and norbornene is more preferable.

  The acid-modified polyolefin is a polymer obtained by modifying the polyolefin by block polymerization or graft polymerization with an acid component such as carboxylic acid. Examples of the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof.

  The acid-modified cyclic polyolefin is obtained by copolymerizing a part of the monomer constituting the cyclic polyolefin in place of the α, β-unsaturated carboxylic acid or its anhydride, or α, β- It is a polymer obtained by block polymerization or graft polymerization of an unsaturated carboxylic acid or its anhydride. The cyclic polyolefin to be modified with carboxylic acid is the same as described above. The carboxylic acid used for modification is the same as the acid component used for modification of the polyolefin.

  Among these resin components, polyolefin such as polypropylene and carboxylic acid-modified polyolefin are preferable; polypropylene and acid-modified polypropylene are more preferable.

  The thermoplastic resin layer 3 may be formed of one kind of resin component alone, or may be formed of a blend polymer in which two or more kinds of resin components are combined. Furthermore, the thermoplastic resin layer 3 may be formed of only one layer, but may be formed of two or more layers using the same or different resin components.

  In the present invention, the resin layer 1 and the thermoplastic resin layer 3 may be made of the same thermoplastic resin.

  Further, the thickness of the thermoplastic resin layer 3 is not particularly limited as long as it exhibits a function as a thermoplastic resin layer, but is preferably 100 μm or less from the viewpoint of exhibiting excellent water resistance over a long period of time. Is about 15 to 60 μm, more preferably about 15 to 40 μm.

[Adhesive layer]
In the laminated sheet 13 forming the package 11, the adhesive layer is a layer provided between the barrier layer 2 and the thermoplastic resin layer 3 as necessary in order to firmly bond the barrier layer 2 and the thermoplastic resin layer 3 (not shown). ).

  The adhesive layer is formed of a resin that can bond the barrier layer 2 and the thermoplastic resin layer 3 together. As the adhesive layer, the same adhesive components and resins exemplified in the adhesive layer can be used.

  Similar to the adhesive layer described above, from the viewpoint of further improving the water resistance over a long period of time, it is preferable to use an adhesive component having excellent water resistance as an adhesive component that can be used for forming the adhesive layer. Examples of the adhesive component having excellent water resistance include polyurethane, polyurethane-polyisocyanate (a mixture of a polyurethane compound and a polyisocyanate compound), an epoxy resin, and the like.

In addition, as the resin used for forming the adhesive layer, polyolefin resins such as polyolefin, cyclic polyolefin, acid-modified polyolefin, and acid-modified cyclic polyolefin can be used. That is, the resin constituting the adhesive layer may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. The fact that the resin constituting the adhesive layer contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. However, if the acid modification degree is low, the peak may be small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.

  From the viewpoint of making the package 11 excellent in shape stability after molding while reducing the thickness of the laminated sheet 13, the adhesive layer preferably contains an acid-modified polyolefin, like the adhesive layer. The acid-modified polyolefin is as described in the adhesive layer.

  In the adhesive layer, among the acid-modified polyolefins, maleic anhydride-modified polyolefin, and further maleic anhydride-modified polypropylene are particularly preferable.

  Furthermore, from the viewpoint of making the package 11 excellent in shape stability after molding while reducing the thickness of the laminated sheet 13, the adhesive layer is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent. More preferably. Preferred examples of the acid-modified polyolefin include those described above.

  Various aspects in which the adhesive layer is a cured product of a resin composition containing a curing agent are the same as those of the above-described adhesive layer.

  The thickness of the adhesive layer is not particularly limited as long as it exhibits a function as an adhesive layer, but for example, those exemplified as an adhesive component that can be used for forming an adhesive layer (that is, an adhesive component that can be used for forming an adhesive layer) ) Is preferably about 1 to 10 μm, more preferably about 1 to 5 μm. Moreover, when it comprises by polyolefin resin, such as polyolefin and acid-modified polyolefin resin, Preferably it is about 2-50 micrometers, More preferably, about 10-40 micrometers is mentioned. Moreover, if it is a hardened | cured material of the resin composition containing a hardening | curing agent, Preferably it is about 30 micrometers or less, More preferably, it is about 0.1-20 micrometers, More preferably, about 0.5-5 micrometers is mentioned. When the adhesive layer is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer can be formed by applying the resin composition and curing it by heating or the like.

[Surface coating layer]
In the laminated sheet 13 forming the package 11, the resin layer 1 (on the side opposite to the barrier layer 2 of the resin layer 1) is optionally used for the purpose of improving design properties, scratch resistance, moldability, and the like. ) May be provided with a surface coating layer if necessary (not shown). A surface coating layer is located in the outermost layer of the package 11 of this invention, when the package 11 does not have the sealing member 4. FIG.

  The surface coating layer can be formed of, for example, a fluororesin, a silicone resin, polyvinylidene chloride, a polyester resin, a urethane resin, an acrylic resin, an epoxy resin, or the like. Of these, the surface coating layer is preferably formed of a two-component curable resin. Examples of the two-component curable resin that forms the surface coating layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Moreover, you may mix | blend additives, such as microparticles | fine-particles, with a surface coating layer. Moreover, a fluororesin and a silicone resin are preferable from a water-resistant viewpoint.

  The method for forming the surface coating layer is not particularly limited, and examples thereof include a method of applying a two-component curable resin for forming the surface coating layer to one surface of the resin layer 1. When blending the additive, the additive may be added to the two-component curable resin, mixed, and then applied.

  Although it will not restrict | limit especially if it sets according to the function which should be provided as a surface coating layer as thickness of a surface coating layer, For example, about 0.5-10 micrometers, Preferably about 1-5 micrometers is mentioned.

[Sealing member 4]
In the package of the package 10 of the present invention, from the viewpoint of more effectively suppressing the corrosion of the barrier layer at the end of the package 11, at least a part of the peripheral portion 13 a of the laminated sheet 13 is sealed with the sealing member 4. Is preferable, and it is particularly preferable that the sealing member 4 covers the entire periphery of the peripheral edge portion 13a of the laminated sheet 13 (see the second and third aspects). Furthermore, it is also preferable that the entire outer surface 11a of the package 11 is composed of the sealing member 4 (see the fourth aspect and the fifth aspect).

  The material constituting the sealing member 4 is not particularly limited as long as it has water resistance. For example, in the case where the sealing member 4 is provided in the package 11 so as to cover the peripheral edge portion 13a of the laminated sheet 13 as in the second and third aspects, the resin film, the adhesive, and the caulking. A material etc. can be used. Moreover, a resin film etc. can be used if it is a case where the whole outer surface 11a of the package 11 is comprised with the sealing member 4 like a 4th aspect and a 5th aspect.

  Moreover, when the sealing member 4 is comprised with the resin film, an easy-adhesion layer is provided between the lamination sheet 13 and the sealing member 4 from a viewpoint of improving the adhesiveness of the sealing member 4 and the lamination sheet 13. You may have.

  The resin film that can constitute the sealing member 4 is not particularly limited as long as it has water resistance. For example, polyester resin, polyolefin resin, polyamide resin, epoxy resin, acrylic resin, fluororesin, polyurethane resin, silicon resin , Phenolic resin, polycarbonate, and a resin film such as a mixture or copolymer thereof. Among these, a polyester resin and a polyolefin resin are preferable, and a resin film composed of polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, polybutylene naphthalate, copolymerized polyester, polypropylene, and the like is more preferable.

  When the entire outer surface 11a of the package 11 is configured by the sealing member 4 as in the fourth aspect and the fifth aspect, the sealing member 4 is particularly formed of a heat shrink film among the resin films. Is preferred. The heat-shrinkable film is shrunk by heat and can constitute the entire outer surface 11a of the package 11 in a state of being in close contact with the shape of the laminated sheet 13. Therefore, the water resistance of the entire package 11 can be effectively increased. It is desirable to seal the heat shrink film so that the seal portion (the position of the joint) does not reach the end of the package 11.

  The heat-shrinkable film only needs to have heat-shrinkability, and polyethylene terephthalate, polystyrene, polypropylene, polyethylene and the like can be used, and a heat-shrinkable film made of polyolefin such as polyethylene and polypropylene is preferable.

  Moreover, the easy-adhesion layer provided as needed between the sealing member 4 and the lamination sheet 13 should just improve the adhesiveness between these layers, for example, with the adhesive illustrated by the above-mentioned adhesive layer Can be formed. As for the thickness of the easy-adhesion layer, the upper limit is preferably about 20 μm or less and about 10 μm or less, and the lower limit is preferably about 0.1 μm or more and about 1 μm or more. 0.1 to 20 μm, 0.1 to 10 μm, 1 to 20 μm, and 1 to 10 μm.

  From the viewpoint of further improving the water resistance over a long period of time while reducing the thickness of the package, when the sealing member 4 is a resin film, the thickness of the sealing member 4 is preferably about the upper limit, The lower limit is preferably about 5 μm or more and about 10 μm or more. Preferred ranges are about 5 to 200 μm, about 5 to 100 μm, about 10 to 200 μm, 10 About 100 micrometers is mentioned. The thickness of the sealing member 4 means the thickness of the sealing member 4 at the peripheral edge portion 13 a of the laminated sheet 13.

  Further, the adhesive that can constitute the sealing member 4 is not particularly limited as long as it has water resistance. For example, the adhesive can be formed of the adhesive exemplified in the above-described adhesive layer.

  The caulking material is a filling material used for the purpose of filling the gaps between objects, and the caulking material that can constitute the sealing member 4 includes acrylic resin, polyurethane, silicone, modified silicone, polysulfide, and the like. Examples include caulking materials.

  From the viewpoint of further improving the water resistance over a long period of time while reducing the thickness of the package, the sealing member 4 is sealed when formed by an adhesive (that is, a cured product of the adhesive). As for the thickness of the member 4, the upper limit is preferably about 2000 μm or less and about 1000 μm or less, and the lower limit is preferably about 10 μm or more, about 50 μm or more. Examples include about 2000 μm, about 10 to 1000 μm, about 50 to 2000 μm, and about 50 to 1000 μm. Further, when the sealing member 4 is formed of a caulking material, the thickness of the sealing member 4 is preferably about 5 mm or less and about 2 μm or less, and preferably about the lower limit. Is about 0.1 mm or more and about 0.5 mm or more, and preferable ranges are about 0.1 to 5 mm, about 0.1 to 2 mm, about 0.5 to 5 mm, and 0.5 to 2 mm. It is done.

3. Package The package of the present invention is a package used for an application in which an aqueous liquid is in contact with an outer surface continuously or intermittently. As shown in FIGS. 1 to 9, the package 11 of the present invention includes a laminated sheet 13 including at least a resin layer 1 located on the outer surface 11 a side, a barrier layer 2, and a thermoplastic resin layer 3 in this order. It is composed of The package 11 of the present invention has a shape that accommodates the contents 12 by fusing the thermoplastic resin layers 3 of the laminated sheet 13 together at the peripheral edge portion 13 a of the laminated sheet 13. Furthermore, the end surface 2a of the barrier layer 2 of the laminated sheet 13 is not exposed to the outside in at least a part of the peripheral edge portion 13a of the laminated sheet 13 of the present invention.

  About the specific aspect of the package 11 of this invention, as demonstrated in the column of above-mentioned "1. Use and structure of a package and a package" and "2. Each layer and sealing member which form a package". It is.

  Moreover, the manufacturing method of the lamination sheet 13 which comprises the package 11 of this invention is as having demonstrated in the column of the below-mentioned "6. lamination sheet".

4). The manufacturing method of the package 10 of this invention is a manufacturing method of the package 10 used for the use which an aqueous liquid contacts an outer surface continuously or intermittently. That is, according to the manufacturing method of the package 10 of the present invention, the present invention described in the above-mentioned sections of “1. Use and structure of package and package” and “2. Each layer and sealing member forming the package”. The package 10 can be suitably manufactured.

  In the manufacturing method of the package 10 of the present invention, the contents of the package 10 when the package 10 does not include the sealing member 4 as in the first aspect, the sixth aspect, and the seventh aspect described above. The package 11 that houses the product 12 includes a laminated sheet 13 that includes at least the resin layer 1 located on the outer surface 11 a side, the barrier layer 2, and the thermoplastic resin layer 3 in this order. In at least a part of 13a, one in which the end surface 2a of the barrier layer 2 of the laminated sheet 13 is not exposed to the outside can be used. Even in the case where the package 10 includes the sealing member 4 as in the second and fourth aspects, the laminated sheet 13 in which the end surface 2a of the barrier layer 2 is not exposed to the outside can be used. . In the manufacturing method of the package 10 of the present invention, at the peripheral edge portion 13a of the laminated sheet 13, the thermoplastic resin layers 3 of the laminated sheet 13 are fused to each other, so that at least the end surface 2a of the barrier layer 2 is exposed to the outside. A process of obtaining the package 10 by accommodating the contents 12 while eliminating exposure is provided.

  The details of the package 11 are as described above. In the manufacturing method of the present invention, the package 12 is obtained by containing the contents 12 by fusing the thermoplastic resin layers 3 of the laminated sheet 13 together at the peripheral edge portion 13a of the laminated sheet 13. The fusion conditions are not particularly limited as long as the thermoplastic resin layers 3 are fused together, and the type of the thermoplastic resin used for the thermoplastic resin layer 3 and the thickness of the thermoplastic resin layer 3 are not limited. For example, the peripheral edge portion 13a of the laminated sheet 13 may be heated and pressurized under the conditions of a temperature of about 120 to 250 ° C. and a pressure of about 0.05 to 3 MPa.

  Moreover, in the manufacturing method of this invention, the package 11 is provided with the sealing member 4, and the sealing member 4 is provided so that the sealing member 4 may cover at least a part of the peripheral edge portion 13a of the laminated sheet. Can do. More specifically, in the case where the package 11 has the sealing member 4, at least a part of the peripheral edge portion 13 a of the laminated sheet 13 is covered with the sealing member 4 (for example, the above-described second mode (FIG. 4 ) And the third mode (FIG. 5)), the peripheral portion 13a of the laminated sheet 13 may be covered with the sealing member 4 after the thermoplastic resin layers 3 are fused together. After the peripheral edge portion 13 a of the laminated sheet 13 is covered with the sealing member 4, the sealing member 4 is fused to the laminated sheet 13 and the thermoplastic resin layers 3 are fused to form the fused peripheral edge portion 30. May be.

  In the case where the package 11 has the sealing member 4 (for example, in the above-described 4 aspect (FIG. 6) or 5th aspect (FIG. 7)), the entire outer surface 11a of the package 11 is sealed with the sealing member 4. When the thermoplastic resin layers 3 of the laminated sheet 13 are fused together and the contents 12 are accommodated, the packaging body 11 is covered with the sealing member 4 from the outside of the laminated sheet 13. The package 10 of the present invention may be obtained at the same time as is completed. When the sealing member 4 is used, the end surface 2a of the barrier layer 2 is the position of the end surface of the resin layer 1 and the thermoplastic resin layer 3 as the laminated sheet 13 as in the third and fifth aspects described above. You can use anything that has reached up to.

5. Method for Accommodating Content The method for accommodating the content 12 of the present invention is a method for accommodating the content 12 using a package used for an application in which an aqueous liquid contacts the outer surface continuously or intermittently. That is, the contents 12 are accommodated in the package 11 by the method for accommodating the contents 12 of the present invention, thereby forming the aforementioned “1. Use and structure of the package and the package” and “2. The package 10 of this invention demonstrated in the column of each layer and a sealing member is obtained suitably.

  In the method for accommodating the contents 12 of the present invention, at least the resin layer 1 located on the outer surface 11a side, the barrier layer 2, and the thermoplastic resin layer 3 are arranged in this order as the package 11 that accommodates the contents 12. The laminated sheet 13 is used, and at least a part of the peripheral edge portion 13a of the laminated sheet 13 is such that the end surface 2a of the barrier layer 2 of the laminated sheet 13 is not exposed to the outside. And in the peripheral part 13a of the said lamination sheet 13, the process of accommodating the content 12 is provided by fuse | melting the thermoplastic resin layers 3 of the lamination sheet 13 mutually. For example, when the thermoplastic resin layers 3 of the laminated sheet 13 are fused together, heat sealing is performed after vacuum sealing to contain the contents.

  The details of the package 11 are as described above. In the accommodation method of the contents 12 of the present invention, the contents 12 are accommodated by fusing the thermoplastic resin layers 3 of the laminated sheet 13 together at the peripheral edge portion 13 a of the laminated sheet 13. The fusion conditions are not particularly limited as long as the thermoplastic resin layers 3 are fused together, and the type of the thermoplastic resin used for the thermoplastic resin layer 3 and the thickness of the thermoplastic resin layer 3 are not limited. Accordingly, it can be set as appropriate, and can be the same as the above-mentioned “4. Manufacturing method of package”.

  Moreover, it can be made to be the same as that of the above-mentioned "4. Manufacturing method of a package" also about the accommodation method of the content 12 in case the package 11 has the sealing member 4. FIG.

6). Laminated sheet The laminated sheet of the present invention is a laminated sheet used for an application in which an aqueous liquid is in contact with an outer surface continuously or intermittently, and is a resin layer 1 located on the outer surface side, a barrier layer 2, and a thermoplastic resin. Layer 3 is provided in this order. For example, as shown in the schematic diagram of FIG. 11, the laminated sheet 13 of the present invention is such that the end surface 2 a of the barrier layer 2 is located on the inner side of the end surface 1 a of the resin layer 1 in at least a part of the peripheral edge portion 13 a. It is characterized by having. Since the laminated sheet of the present invention has such a configuration, it can be suitably used for forming the package 11 of the package 10 of the present invention described above.

  Specifically, for example, the package 11 used in the package 10 of the first aspect as shown in FIG. 3 includes at least the resin layer 1 located on the outer surface 11a side, the barrier layer 2, The laminated sheet 13 having the thermoplastic resin layer 3 in this order is molded to form a concave shape so as to go from the thermoplastic resin layer 3 side to the resin layer 1 side, and further, the thermoplasticity of the peripheral edge portion 13a of the laminated sheet 13 It is obtained by fusing the resin layers 3 together. At this time, for example, the laminated sheet 13 of the present invention as shown in the schematic diagram of FIG. 11 is used, a concave shape is formed so as to go from the thermoplastic resin layer 3 side to the resin layer 1 side, and the peripheral edge of the laminated sheet 13 The shape of the package 11 as shown in FIG. 3 can be formed by fusing the thermoplastic resin layers 3 of the portion 13a to form the fusion peripheral portion 30.

  In the schematic view of FIG. 11, the laminated sheet 13 of the present invention is such that the end surface 2 a of the barrier layer 2 is both the end surface 1 a of the resin layer 1 and the end surface 3 a of the thermoplastic resin layer 3 in at least a part of the peripheral portion 13 a. Is located on the inside. In addition, when using the sealing member 4 like the package 10 of the above-mentioned 3rd aspect and 5th aspect, the end surface 2a of the barrier layer 2 is the end surface 1a of the resin layer 1, and a thermoplastic resin layer. The package 10 can be manufactured using the laminated sheet which is not located inside 3 end surface 3a.

  Moreover, also about the package 11 used for the package 10 of the 2nd aspect as shown in FIG. 4, the laminated sheet 13 of this invention as shown, for example in the schematic diagram of FIG. A concave shape is formed from the resin layer 3 side to the resin layer 1 side, and the thermoplastic resin layers 3 of the peripheral edge portion 13a of the laminated sheet 13 are fused together, and at least one of the peripheral edge portions 13a of the laminated sheet 13 is also fused. By covering the part with the sealing member 4, the shape of the package 11 as shown in FIG. 4 can be formed. Moreover, also about the package 11 used for the package 10 of the 4th aspect as shown in FIG. 6, the laminated sheet 13 of this invention as shown, for example in the schematic diagram of FIG. By forming a concave shape so as to go from the resin layer 3 side to the resin layer 1 side, and further covering the entire outside of the laminated sheet 13 with the sealing member 4, the shape of the package 11 as shown in FIG. Can be formed. Further, for the package 11 used in the package 10 of the seventh embodiment as shown in FIG. 9, for example, the laminated sheet 13 of the present invention as shown in the schematic diagram of FIG. A concave shape is formed from the resin layer 3 side toward the resin layer 1 side, and the thermoplastic resin layers 3 of the peripheral edge portion 13a of the laminated sheet 13 are fused together. The shape of the package 11 as shown in FIG. 9 can be formed by fusing the thermoplastic resin layers 3 so that the plastic resin layer 3 covers the end surface 2a of the barrier layer 2.

  The thickness of the laminated sheet 13 is as described above.

  In the laminated sheet 13 of the present invention, the composition, thickness, etc. of the resin layer 1, the barrier layer 2, the thermoplastic resin layer 3, and the adhesive layer, the adhesive layer, and the surface coating layer provided as necessary are as described above. This is as described for the package 11.

  As an example of the manufacturing method of the lamination sheet of this invention, it is as follows. First, a laminate in which the resin layer 1 and, if necessary, an adhesive layer and a barrier layer 2 are sequentially laminated is formed (hereinafter also referred to as “laminate A”). Specifically, the laminate A is formed by applying an adhesive used for forming an adhesive layer to the resin layer 1 or the barrier layer 2 whose surface is subjected to chemical conversion treatment, if necessary, using a gravure coating method or a roll coating method. After applying and drying by a coating method such as the above, it can be performed by a dry laminating method in which the barrier layer 2 or the resin layer 1 is laminated and the adhesive layer is cured.

  Next, the adhesive layer and the thermoplastic resin layer 3 are laminated in this order on the barrier layer 2 of the laminate A. For example, (1) a method of laminating an adhesive layer and a thermoplastic resin layer 3 by coextrusion on the barrier layer 2 of the laminate A (coextrusion laminating method), (2) a separate adhesive layer and a thermoplastic resin A method of forming a laminated body in which the layers 3 are laminated and laminating the laminated body on the barrier layer 2 of the laminated body A by a thermal laminating method; and (3) forming an adhesive layer on the barrier layer 2 of the laminated body A. (4) A method of laminating a thermoplastic resin layer 3 previously formed into a sheet on the adhesive layer by a thermal lamination method by laminating an adhesive by extrusion method or solution coating, drying at a high temperature and baking method. ) While pouring the molten adhesive layer between the barrier layer 2 of the laminate A and the thermoplastic resin layer 3 formed into a sheet in advance, the laminate A and the thermoplastic resin layer 3 are interposed via the adhesive layer. Those who stick (Sandwich lamination method).

  As a method for producing the laminated sheet 13 of the present invention so that the end surface 2a of the barrier layer 2 is located inside both the end surface 1a of the resin layer 1 and the end surface 3a of the thermoplastic resin layer 3, for example, In the laminating step, there is a method in which the barrier layer 2 is laminated so as to be located inside both the end face 1a of the resin layer 1 and the end face 3a of the thermoplastic resin layer 3. Moreover, after obtaining the laminated body which laminated | stacked the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3, the method of etching the end surface 2a of the barrier layer 2 is also mentioned. Furthermore, as shown in the schematic diagram of FIG. 12, for example, a raw fabric sheet 50 of the resin layer 1, the barrier layer 2, and the thermoplastic resin layer 3 in which the barrier layer 2 is formed in a pattern is prepared. The laminated sheet 13 can also be manufactured by cutting the raw fabric sheet 50 in the thickness direction at the position. In FIG. 12, the hatched area means that the barrier layer 2 is laminated on the original fabric sheet 50.

  When the surface coating layer is provided, the surface coating layer is laminated on the surface of the resin layer 1 opposite to the barrier layer 2. The surface coating layer can be formed, for example, by applying the above resin for forming the surface coating layer to the surface of the resin layer 1. The order of the step of laminating the barrier layer 2 on the surface of the resin layer 1 and the step of laminating the surface coating layer on the surface of the resin layer 1 are not particularly limited. For example, after the surface coating layer is formed on the surface of the resin layer 1, the barrier layer 2 may be formed on the surface of the resin layer 1 opposite to the surface coating layer.

  As described above, surface coating layer provided as necessary / resin layer 1 / adhesive layer provided as needed / barrier layer 2 whose surface is subjected to chemical conversion treatment as needed / provided as needed A laminate composed of the adhesive layer / thermoplastic resin layer 3 is formed. In order to strengthen the adhesiveness of the adhesive layer or the adhesive layer, a hot roll contact type, a hot air type, a near infrared type, or a far infrared ray is further used. You may use for heat processing, such as a formula. Examples of such heat treatment conditions include 150 ° C. to 250 ° C. for 1 minute to 5 minutes.

  In the laminated sheet of the present invention, each layer constituting the laminated body may improve or stabilize film forming properties, lamination processing, suitability of final product secondary processing (pouching, embossing), and the like as necessary. Surface activation treatment such as corona treatment, blast treatment, oxidation treatment, and ozone treatment may be performed.

7). Original Fabric Sheet The original fabric sheet 50 of the present invention is a sheet for obtaining the laminated sheet 13 of the present invention, and comprises at least the resin layer 1 located on the outer surface side, the barrier layer 2 and the thermoplastic resin layer 3. In this order, the barrier layer 2 is partially provided. That is, the raw fabric sheet 50 of the present invention has a portion where the resin layer 1 and the thermoplastic resin layer 3 do not interpose the barrier layer 2. The laminated sheet 13 of the present invention is obtained by cutting at least part of the portion of the raw fabric sheet 50 of the present invention that does not include the barrier layer 2 in the thickness direction.

  In the original fabric sheet 50 of the present invention, for example, when the barrier layer 2 is formed in a pattern as shown in FIG. By cutting in the direction, the laminated sheet 13 in which the end face of the barrier layer 2 is not exposed to the outside at the peripheral edge of the laminated sheet 13 can be suitably manufactured.

  When the shape of the laminated sheet 13 of the present invention is rectangular in plan view, the pattern of the barrier layer 2 of the original fabric sheet 50 of the present invention is preferably rectangular in plan view. The schematic diagram of FIG. 12 shows a state in which six rectangular sheets 13 are obtained from one original sheet 50. The number of laminated sheets 13 obtained from the original fabric sheet 50 can be adjusted by the size of the original fabric sheet 50 and the pattern of the barrier layer 2.

  The original fabric sheet 50 is manufactured, stored and distributed in the form of a wound body wound in a roll shape, and when the laminated sheet 13 of the present invention is manufactured, the original fabric sheet 50 is unwound from the wound body, May be cut. In addition, FIG. 12 shows a view in which the barrier layer 2 is also laminated on the peripheral edge of the original fabric sheet 50, but the barrier layer 2 may not be laminated on the peripheral edge. Moreover, as shown in FIG. 12, the barrier layer 2 may be laminated | stacked on the peripheral part over the perimeter of the original fabric sheet 50, and the barrier layer 2 may be laminated | stacked on a part of peripheral part. .

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

  In the package produced in the following examples, the end face of the barrier layer is not exposed to the outside in the entire periphery of the peripheral edge of the laminated sheet.

[Example 1]
<Manufacture of laminated sheets>
A polyethylene naphthalate film (PEN, thickness 12 μm) was prepared as a resin layer. In addition, an aluminum alloy foil (JIS H4160: 1994 A8021H-O, thickness 35 μm) was prepared as a barrier layer. Next, a two-component polyurethane adhesive (a polyurethane compound having a hydroxyl group and a polyisocyanate compound) was applied to one surface of the aluminum alloy foil to form an adhesive layer (thickness 3 μm) on the aluminum alloy foil. Subsequently, after laminating the adhesive layer and the resin layer on the aluminum alloy foil by a dry lamination method, an aging treatment was performed to produce a laminate of resin layer / adhesive layer / aluminum alloy foil. Chemical conversion treatment is performed on both surfaces of the aluminum alloy foil. The chemical conversion treatment of the aluminum alloy foil is carried out by roll coating of a treatment solution comprising a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m ² (dry mass). It was performed by applying to both sides and baking.

  Next, on the chemical conversion treatment surface of the barrier layer of the laminate obtained above, maleic anhydride-modified polypropylene (PPa, thickness 15 μm) as an adhesive layer and random polypropylene (PP, thickness as a thermoplastic resin layer) 20 μm) was laminated by a coextrusion laminating method, and an adhesive layer / thermoplastic resin layer was laminated on the barrier layer. Next, the laminated sheet of Example 1 in which the resin layer / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer was laminated in this order was obtained by aging the obtained laminated sheet.

<Manufacture of packaging>
A package of Example 1 having a cross-sectional structure as shown in FIG. 5 was produced by the following procedure. First, the laminated sheet obtained above was cut out in a size of 10 cm × 20 cm. Next, it is folded in half so that the thermoplastic resin layer is on the inside, and the sealing member shown in FIG. 5 is placed on both sides (x1 side and x2 side in FIG. 2) of the folded side (y2 side in FIG. 2). 4, a maleic anhydride-modified polypropylene film (PPa, thickness 20 μm) was installed. Next, a bag of 10 cm × 10 cm was produced by heat sealing (temperature 190 ° C., pressure 1.0 MPa, 3 seconds) in a thickness direction with a width of 5 mm together with the maleic anhydride-modified polypropylene film. A temperature sensor (Air Logger (registered trademark) WM2000 series, manufactured by Advantest Co., Ltd.) is inserted as the contents from the opening (y1 side in FIG. 2) at the position facing the bent side. The package of Example 1 having a cross-sectional structure as shown in FIG. 5 was obtained by heat sealing (temperature 190 ° C., pressure 1.0 MPa, 3 seconds) with a thickness of 5 mm along with the acid-modified polypropylene film. . A heat seal tester (TP-701-B manufactured by Tester Sangyo Co., Ltd.) and a chamber type vacuum degassing sealer (FCB-200 manufactured by Fuji Impulse Co., Ltd.) were used for vacuum sealing.

[Example 2]
<Manufacture of packaging>
A laminated sheet of Example 1 having a cross-sectional structure as shown in FIG. 5 was cut out in a size of 10 cm × 20 cm. Next, it is folded in half so that the thermoplastic resin layer is on the inside, and two sides (the x1 side and the x2 side in FIG. 2) of the bent side (in FIG. 2, the x1 side and the x2 side) are 5 mm wide and heat sealed in the thickness direction ( A bag of 10 cm × 10 cm was produced by carrying out a temperature of 190 ° C. and a pressure of 1.0 MPa for 3 seconds. Insert a temperature sensor (AirLogger (registered trademark) WM2000 series, manufactured by Advantest Co., Ltd.) as the contents from the opening (y1 side in FIG. 2) at the position facing the bent side. And heat sealed in the thickness direction (temperature 190 ° C., pressure 1.0 MPa, 3 seconds). Next, as shown in FIG. 5, a caulking material (cemedine 8000 silicone sealant) as the sealing member 4 is applied so as to cover the three heat-sealed sides (thickness (z direction in the cross section of FIG. 5)). ) 1 mm, width (y direction in the cross section of FIG. 5 3 mm)), to obtain a package of Example 2 having a cross-sectional structure as shown in FIG. The vacuum sealing was performed in the same manner as in Example 1.

[Comparative Example 1]
A package was obtained in the same manner as in Example 1 except that the laminated sheet of Example 1 was used and no sealing member was used.

[Example 3]
<Manufacture of laminated sheets>
On both sides of the aluminum alloy foil, a treatment liquid comprising a phenol resin, a chromium fluoride compound, and phosphoric acid is applied to both sides of the aluminum alloy foil by a roll coating method so that the coating amount of chromium is 10 mg / m ² (dry mass). By applying and baking, a chemical conversion treatment was performed to obtain a barrier layer. Next, maleic anhydride-modified polypropylene (PPa, thickness 15 μm) as an adhesive layer and random polypropylene (PP, thickness 20 μm) as a thermoplastic resin layer are coextruded on the chemical conversion treatment surface of the barrier layer by a laminating method. The adhesive layer / thermoplastic resin layer was laminated on the barrier layer. Next, maleic anhydride-modified polypropylene (PPa, thickness 15 μm) as an adhesive layer and random polypropylene (PP, thickness 20 μm) as a resin layer are coextruded on the surface of the barrier layer of the obtained laminate. The laminated sheet of Example 3 was obtained by laminating by a laminating method and laminating a resin layer / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer in this order.

<Manufacture of packaging>
A package of Example 3 having a cross-sectional structure as shown in FIG. 3 was produced by the following procedure. The laminated sheet of Example 3 was cut out in a size of 10 cm × 20 cm, bent in half so that the thermoplastic resin layer was inside, and both sides of the bent side (y2 side in FIG. 2) (x1 side in FIG. 2) A bag of 10 cm × 10 cm was manufactured by heat sealing (temperature 190 ° C., pressure 1.0 MPa, 3 seconds) with a width of 5 mm in the thickness direction of the x2 side. At this time, a heat seal bar having a width of 6 mm was used, and 1 mm from the end portion of the heat seal portion made a space for extruding a resin melted by heat. Insert a temperature sensor as the contents from the opening (y1 side in FIG. 2) at the position facing the bent side (y2 side in FIG. 2), vacuum seal the opening, and then use the same heat seal bar as above The package of Example 3 having a cross-sectional structure as shown in FIG. 3 was obtained by heat sealing (temperature 190 ° C., pressure 1.0 MPa, 3 seconds) in a film thickness direction with a width of 5 mm.

[Example 4]
<Manufacture of laminated sheets>
A polyethylene naphthalate film (PEN, thickness 12 μm) was prepared as a resin layer. In addition, an aluminum alloy foil (JIS H4160: 1994 A8021H-O, thickness 35 μm) was prepared as a barrier layer. Next, a two-component polyurethane adhesive (a polyurethane compound having a hydroxyl group and a polyisocyanate compound) was applied to one surface of the aluminum alloy foil to form an adhesive layer (thickness 3 μm) on the aluminum alloy foil. Subsequently, after laminating the adhesive layer and the resin layer on the aluminum alloy foil by a dry lamination method, an aging treatment was performed to produce a laminate of resin layer / adhesive layer / aluminum alloy foil. Chemical conversion treatment is performed on both surfaces of the aluminum alloy foil. The chemical conversion treatment of the aluminum alloy foil is carried out by roll coating of a treatment solution comprising a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m ² (dry mass). It was performed by applying to both sides and baking. Next, the peripheral portion of the aluminum alloy foil was etched using hydrofluoric acid so that the aluminum alloy foil had a size of 9 cm × 19 cm (the length in the vertical direction and the horizontal direction was reduced by 1 cm each). The surface of the adhesive layer is exposed at the portion where the aluminum alloy foil is etched with hydrofluoric acid. Next, maleic anhydride-modified polypropylene (PPa, thickness 15 μm) as an adhesive layer and a thermoplastic resin layer so as to cover the chemical conversion treatment surface of the barrier layer of the obtained laminate and the exposed adhesive layer Random polypropylene (PP, thickness 20 μm) is laminated by coextrusion laminating method, and an adhesive layer / thermoplastic resin layer is laminated to obtain a resin layer / adhesive layer / barrier layer / adhesive layer / thermoplastic resin A laminated sheet of Example 4 in which the layers were laminated in this order was obtained.

<Manufacture of packaging>
A package of Example 4 having a cross-sectional structure as shown in FIG. 9 was produced by the following procedure. The laminated sheet of Example 4 was cut out with a size of 10 cm × 20 cm. At this time, the center of the package (10 cm × 20 cm) is aligned with the center of the barrier layer (9 cm × 19 cm), and the adhesive layer and the adhesive layer are in contact with each other around the barrier layer Was formed with a width of 1 cm. Next, the package is folded in half so that the thermoplastic resin layer is on the inside, and the two sides (x1 side and x2 side in FIG. 2) of the folded side (in FIG. 2) are 5 mm wide in the thickness direction. Was heat sealed (temperature 190 ° C., pressure 1.0 MPa, 3 seconds) to produce a 10 cm × 10 cm bag. A temperature sensor is inserted as a content from an opening (y2 side in FIG. 2) at a position facing the bent side, and after vacuum-sealing the opening, the opening is heat-sealed in a thickness direction with a width of 5 mm (temperature 190 ° C., By applying a pressure of 1.0 MPa for 3 seconds, a package of Example 4 having a cross-sectional structure as shown in FIG. 9 was obtained.

[Example 5]
<Manufacture of laminated sheets>
An unstretched polypropylene film (CPP, thickness 30 μm) was prepared as a resin layer. In addition, an aluminum alloy foil (JIS H4160: 1994 A8021H-O, thickness 35 μm) was prepared as a barrier layer. Next, a resin composition containing an acid-modified polyolefin resin and an epoxy resin was applied to one surface of the aluminum alloy foil to form an adhesive layer (thickness 3 μm) on the aluminum alloy foil. Subsequently, after laminating the adhesive layer and the resin layer on the aluminum alloy foil by a dry lamination method, an aging treatment was performed to produce a laminate of resin layer / adhesive layer / aluminum alloy foil. Chemical conversion treatment is performed on both surfaces of the aluminum alloy foil. The chemical conversion treatment of the aluminum alloy foil is carried out by roll coating of a treatment solution comprising a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m ² (dry mass). It was performed by applying to both sides and baking. Next, the peripheral portion of the aluminum alloy foil was etched using hydrofluoric acid so that the aluminum alloy foil had a size of 9 cm × 19 cm (the length in the vertical direction and the horizontal direction was reduced by 1 cm each). The surface of the adhesive layer is exposed at the portion where the aluminum alloy foil is etched with hydrofluoric acid. Next, a resin composition (epoxy adhesive) containing an acid-modified polyolefin resin and an epoxy resin is applied so as to cover the chemical conversion treatment surface of the barrier layer of the obtained laminate and the exposed adhesive layer. Then, an adhesive layer (thickness 3 μm) was formed. Next, after laminating an adhesive layer and an unstretched polypropylene film (CPP, thickness 30 μm) by a dry laminating method, an aging treatment is performed to obtain a resin layer / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer. Obtained the package of Example 5 laminated in this order.

<Manufacture of packaging>
A package of Example 5 having a cross-sectional structure as shown in FIG. 6 was produced by the following procedure. The laminated sheet of Example 5 was cut out with a size of 10 cm × 20 cm. At this time, the center of the package (10 cm × 20 cm) is aligned with the center of the barrier layer (9 cm × 19 cm), and the adhesive layer and the adhesive layer are in contact with each other around the barrier layer Was formed with a width of 1 cm. Next, the package is folded in half so that the thermoplastic resin layer is on the inside, and the two sides (x1 side and x2 side in FIG. 2) of the folded side (in FIG. 2) are 5 mm wide in the thickness direction. Was heat sealed (temperature 190 ° C., pressure 1.0 MPa, 3 seconds) to produce a 10 cm × 10 cm bag. A temperature sensor is inserted as a content from an opening (y2 side in FIG. 2) at a position facing the bent side, and after vacuum-sealing the opening, the opening is heat-sealed in a thickness direction with a width of 5 mm (temperature 190 ° C., A bag was obtained with a pressure of 1.0 MPa for 3 seconds. Next, the entire outer surface of the bag was covered with a heat-shrinkable film (polyethylene film) as the sealing member 4, and the sealing members 4 were heat-sealed at positions that do not reach the end of the bag. Thereafter, hot air was applied to the entire surface to obtain a package of Example 5 having a cross-sectional structure as shown in FIG.

[Example 6]
<Manufacture of laminated sheets>
On both sides of the aluminum alloy foil, a treatment liquid comprising a phenol resin, a chromium fluoride compound, and phosphoric acid is applied to both sides of the aluminum alloy foil by a roll coating method so that the coating amount of chromium is 10 mg / m ² (dry mass). By applying and baking, a chemical conversion treatment was performed to obtain a barrier layer. Next, maleic anhydride-modified polypropylene (PPa, thickness 15 μm) as an adhesive layer and random polypropylene (PP, thickness 20 μm) as a thermoplastic resin layer are coextruded on the chemical conversion treatment surface of the barrier layer by a laminating method. The adhesive layer / thermoplastic resin layer was laminated on the barrier layer. Next, after the obtained laminate is cut so as to have a size of 9 cm × 19 cm, a resin composition containing an acid-modified polyolefin resin and an epoxy resin as an adhesive layer on the surface of the barrier layer of the laminate The thing was apply | coated and the adhesive bond layer (thickness 3 micrometers) was formed on aluminum alloy foil. Next, an unstretched polypropylene film (CPP, thickness 30 μm) having a size of 10 cm × 20 cm (the length in the longitudinal direction and the lateral direction is increased by 1 cm) is prepared as the resin layer, and the resin layer (10 cm × 20 cm) is prepared. By laminating the adhesive layer and the resin layer on the aluminum alloy foil so that the center and the center of the barrier layer (9 cm × 19 cm) coincide with each other by the dry laminating method, the resin layer / adhesive A laminated sheet of Example 6 in which the layer / barrier layer / adhesive layer / thermoplastic resin layer was laminated in this order was obtained.

<Manufacture of packaging>
A package of Example 6 having a cross-sectional structure as shown in FIG. 8 was produced by the following procedure. The laminated sheet of Example 6 was folded in half so that the thermoplastic resin layer of the package was on the inside, and the two sides (the x1 side and the x2 side in FIG. 2) of the folded side (y2 side in FIG. 2) were 5 mm. A bag of 10 cm × 10 cm was produced by heat sealing in the thickness direction with a width (temperature 190 ° C., pressure 1.0 MPa, 3 seconds). A temperature sensor is inserted as a content from an opening (y2 side in FIG. 2) at a position facing the bent side, and after vacuum-sealing the opening, the opening is heat-sealed in a thickness direction with a width of 5 mm (temperature 190 ° C., The package of Example 6 was obtained with a pressure of 1.0 MPa for 3 seconds.

[Example 7]
<Manufacture of packaging>
The entire outer surface of the bag was covered with the package of Comparative Example 1 with a heat-shrinkable film (polyethylene film) as the sealing member 4, and the sealing members 4 were heat-sealed at positions not covering the end of the bag. Thereafter, hot air was applied to the entire surface to obtain a package of Example 7 having a cross-sectional structure as shown in FIG.

[Example 8]
<Manufacture of packaging>
As shown in FIG. 10, the caulking material (cemedine 8000 silicone sealant) as the sealing member 4 was applied to the package of Example 4 so as to cover the three heat-sealed sides (thickness (FIG. 10 10 mm in the z direction) and 3 mm in the width (y direction in the cross section of FIG. 10) to obtain a package of Example 8 having a cross sectional structure as shown in FIG.

<Evaluation of water resistance in high temperature environment>
Each package obtained in Examples 1 to 8 and Comparative Example 1 was left in water at 80 ° C. for 3 weeks. As a result, in the packages of Examples 1 to 8, no corrosion of the end face of the barrier layer occurred. On the other hand, in the package of Comparative Example 1, the exposed end face of the barrier layer was corroded.

<Evaluation of water resistance in high temperature environment and salt water>
Each package obtained in Examples 1 to 8 and Comparative Example 1 was allowed to stand for 3 weeks in 80 ° C. and 5% by mass of brine. As a result, in the packages of Examples 1 to 8, no corrosion of the end face of the barrier layer occurred. On the other hand, in the package of Comparative Example 1, the exposed end face of the barrier layer was corroded.

  From these evaluations of water resistance, it can be seen that the packages of Examples 1 to 8 are suitable for use in contact with an aqueous liquid for a long period of time.

DESCRIPTION OF SYMBOLS 1 Resin layer 1a End face 2 of resin layer Barrier layer 2a End face 3 of barrier layer Thermoplastic resin layer 3a End face 4 of thermoplastic resin layer Sealing member 10 Package 11 Package 12 Contents 11a Package outer surface 11b Package body Inner surface 13 Laminated sheet 13a Laminated portion 13b of laminated sheet Folded portion 30 of laminated sheet Fused peripheral portion 50 of thermoplastic resin layer Original sheet

Claims (16)

The contents are packaged in a package,
The package is used for an application in which an aqueous liquid comes into contact with an outer surface continuously or intermittently,
The package is composed of a laminated sheet comprising at least a resin layer located on the outer surface side, a barrier layer, and a thermoplastic resin layer in this order,
The packaging body contains the contents by fusing the thermoplastic resin layers of the laminated sheet to each other at the peripheral edge of the laminated sheet,
The package in which the end surface of the barrier layer of the laminated sheet is not exposed to the outside in at least a part of the peripheral edge of the laminated sheet.   The package according to claim 1, wherein at least a part of an end surface of the barrier layer is located in a fusion peripheral portion where the thermoplastic resin layers of the laminated sheet are heat-sealed.   The package according to claim 1 or 2, wherein the entire circumference of the end face of the barrier layer is located in a fusion peripheral portion where the thermoplastic resin layers of the laminated sheet are heat-sealed.   The package according to any one of claims 1 to 3, wherein at least one of the resin layer and the thermoplastic resin layer covers an end surface of the barrier layer in at least a part of the peripheral edge of the laminated sheet. . The package includes a sealing member,
The package according to any one of claims 1 to 4, wherein the sealing member covers at least a part of the peripheral edge of the laminated sheet.   The package according to claim 5, wherein the entire outer surface of the package is constituted by the sealing member.   The package according to claim 5 or 6, wherein the sealing member is made of polyolefin.   The package according to any one of claims 5 to 7, wherein the sealing member is a heat shrink film.   The package in any one of Claims 5-8 which has an easily bonding layer between the said resin layer and the said sealing member.   The package according to any one of claims 1 to 9, wherein the resin layer and the thermoplastic resin layer are made of the same thermoplastic resin.   The package according to any one of claims 1 to 10, wherein the laminated sheet has at least a concave shape formed so as to go from the thermoplastic resin layer side to the resin layer side.   The package according to any one of claims 1 to 11, wherein the resin layer includes at least one of polyester and polyolefin. A package used for an application in which an aqueous liquid is in contact with an outer surface continuously or intermittently,
The package is composed of a laminated sheet comprising at least a resin layer located on the outer surface side, a barrier layer, and a thermoplastic resin layer in this order,
The packaging body has a shape that accommodates contents by fusing the thermoplastic resin layers of the laminated sheet at the peripheral edge of the laminated sheet,
The package body in which the end surface of the barrier layer of the laminated sheet is not exposed to the outside in at least a part of the peripheral edge of the laminated sheet. A laminated sheet used for applications in which an aqueous liquid is in contact with an outer surface continuously or intermittently,
The laminated sheet comprises at least a resin layer located on the outer surface side, a barrier layer, and a thermoplastic resin layer in this order,
The laminated sheet in which an end face of the barrier layer is located on an inner side than an end face of the resin layer in at least a part of the peripheral edge of the laminated sheet. A raw sheet for obtaining the laminated sheet according to claim 14,
The raw fabric sheet includes at least a resin layer located on the outer surface side, a barrier layer, and a thermoplastic resin layer in this order,
The said barrier layer is a raw fabric sheet provided partially. A method of manufacturing a package used for an application in which an aqueous liquid contacts an outer surface continuously or intermittently,
As a package that accommodates the contents of the package, it is composed of a laminated sheet that includes at least a resin layer located on the outer surface side, a barrier layer, and a thermoplastic resin layer in this order, and the peripheral edge of the laminated sheet At least a part of the laminated sheet is not exposed to the outside end face of the barrier layer,
The manufacturing method of a package provided with the process of accommodating the said content and obtaining the said package by fuse | melting the said thermoplastic resin layers of the said laminate sheet in the peripheral part of the said laminate sheet.