JP2018024143A - Laminate, packaging bag and manufacturing method of laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a tolerance to a highly permeable content such as an acid and a base in a laminate.SOLUTION: A laminate 10 includes: a barrier layer 13 including a metal or an alloy; an intermediate layer composed of a surface modification layer 14 containing an amino group and formed on the barrier layer 13; a first adhesion layer 15 formed of an adhesive agent having a bifunctional or polyfunctional isocyanate compound as a major component, laminated on the surface modification layer 14; and a sealant layer 16 laminated on the first adhesion layer 15.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a laminate, a packaging bag, and a method for manufacturing the laminate.

2. Description of the Related Art Conventionally, packaging bags for storing contents such as various foods and chemicals are known. In these packaging bags, for example, a laminate having at least a sealant layer is fused to each other in the sealant layer to form a bag.
The laminated body used for such a packaging bag needs to have appropriate tolerance depending on, for example, the characteristics of the contents. In particular, when the contents have strong permeability such as an acid or a base, resistance to an acid or a base that does not cause the laminate to peel off is required.
For example, Patent Document 1 describes a method for producing a laminate in which the laminate strength between a base material and a sealant layer does not decrease even when various strongly permeable contents act. The laminate manufactured by the manufacturing method of Patent Document 1 includes a base material made of polyester, nylon, or polypropylene, an adhesive layer made of an isocyanate compound, and a sealant layer extruded onto the adhesive layer. They are stacked in order.

Japanese Patent No. 4852874

However, the conventional laminate, packaging bag, and laminate manufacturing method as described above have the following problems.
The laminated body of patent document 1 can be used for the packaging bag which accommodates strong permeable contents, such as an acid and a base, by improving the tolerance of the contact bonding layer between a base material and a sealant layer. However, for example, the contents of strong acids and strong bases have a strong odor, so that the laminate used for the packaging bag is required to have not only content resistance but also barrier properties.
However, even if a barrier layer is provided to increase the barrier property of the laminate, the strongly permeable contents penetrate into the inside of the barrier layer in the laminate and attack the adhesive layer. There is a tendency that the adhesive strength of the adhesive layer disposed inside the barrier layer is lowered.
Furthermore, when the strongly permeable content is an acid, a base, or the like, if a metal thin film is used for the barrier layer, there is a problem that the metal thin film reacts with the acid or base to be corroded.

  The present invention has been made in view of the above problems, and provides a laminate, a packaging bag, and a method for producing the laminate that can improve resistance to strongly permeable contents such as acids and bases. The purpose is to do.

  In order to solve the above problems, the laminate of the first aspect of the present invention comprises a barrier layer made of a metal or an alloy, and a surface modification layer containing an amino group and formed on the surface of the barrier layer. An intermediate layer, a first adhesive layer formed by an adhesive mainly composed of a bifunctional or higher functional isocyanate compound, laminated on the intermediate layer, and a sealant layer laminated on the first adhesive layer, Including.

  In the laminate of the first aspect, the bifunctional or higher functional isocyanate compound may be a derivative of an isocyanate monomer obtained by trifunctionalizing a bifunctional isocyanate monomer.

  In the laminate of the first aspect, the thickness of the first adhesive layer may be 0.05 μm or more and 1 μm or less.

  In the laminate of the first aspect, the barrier layer may be made of aluminum or an aluminum alloy having a size of 6 μm to 20 μm.

  In the laminate according to the first aspect, the surface modified layer may include an inorganic film containing a heavy metal or a salt thereof, and an organic polymer film containing a nitrogen atom and covering the inorganic film. .

  The laminate according to the second aspect of the present invention includes a barrier layer made of an inorganic oxide, a polyamide resin, an intermediate layer bonded to the barrier layer through a second adhesive layer, and a bifunctional or higher functional layer. A first adhesive layer formed of an adhesive mainly composed of an isocyanate compound and laminated on the intermediate layer, and a sealant layer laminated on the first adhesive layer are included.

  In the laminate of the second aspect, the bifunctional or higher isocyanate compound may be a derivative of an isocyanate monomer obtained by trifunctionalizing a bifunctional isocyanate monomer.

  In the laminated body of the second aspect, the thickness of the first adhesive layer may be 0.05 μm or more and 1 μm or less.

In the laminated body according to the second aspect, the oxygen transmission amount may be 1.0 cm ³ / (m ² · day · atm) or less.

  In the packaging bag of the third aspect of the present invention, a part of the sealant layer of the laminate is heat-sealed to form an internal space surrounded by the sealant layer.

  According to a fourth aspect of the present invention, there is provided a method for manufacturing a laminate, comprising subjecting a surface of a barrier layer made of a metal or an alloy to a chemical conversion treatment to form an intermediate layer made of a surface modified layer containing an amino group on the surface of the barrier layer. Forming a first adhesive layer by applying an adhesive mainly composed of a bifunctional or higher functional isocyanate compound to the intermediate layer, and drying the polyolefin resin, Extruding the surface of the first adhesive layer.

  According to a fifth aspect of the present invention, there is provided a method for producing a laminate, comprising: forming an intermediate layer made of a polyamide resin layer on a surface of a barrier layer made of an inorganic oxide via a second adhesive layer; And forming an adhesive layer on the surface of the first adhesive layer by applying and drying an adhesive mainly composed of a bifunctional or higher isocyanate compound, and drying the polyolefin resin on the surface of the first adhesive layer. Extruding.

  In the method for producing a laminate, the bifunctional or higher functional isocyanate compound may be a derivative of an isocyanate monomer obtained by trifunctionalizing a bifunctional isocyanate monomer.

  According to the laminate, the packaging bag, and the method for producing a laminate of the present invention, there is an effect that resistance to strongly permeable contents such as acid and base can be improved.

It is a typical front view which shows the structure of the packaging bag of the 1st Embodiment of this invention. It is AA sectional drawing in FIG. It is a typical longitudinal section showing the layer composition of the layered product of a 1st embodiment of the present invention. It is a typical longitudinal cross-sectional view which shows the layer structure of the laminated body of the 2nd Embodiment of this invention.

  Embodiments of the present invention will be described below with reference to the accompanying drawings. In all the drawings, even if the embodiments are different, the same or corresponding members are denoted by the same reference numerals, and common description is omitted.

[First Embodiment]
The packaging bag and laminated body of the 1st Embodiment of this invention are demonstrated.
FIG. 1 is a schematic front view showing the configuration of the packaging bag of the first embodiment of the present invention. 2 is a cross-sectional view taken along line AA in FIG.

As shown in FIG. 1, the packaging bag 1 of the present embodiment is configured by joining three sides of a laminated sheet 1 </ b> A (laminated body) facing each other in the thickness direction at a heat seal part 1 c. Pouch.
At the upper end of each laminated sheet 1A, an opening T surrounded by the laminated sheet 1A is formed. On the inner peripheral surface of the opening T, a heat sealing opening 1d capable of heat sealing is formed. As shown in FIG. 2, an internal space S that communicates from the opening T to the lower end of each laminated sheet 1 </ b> A is formed inside the packaging bag 1.
The laminated sheet 1 </ b> A includes an inner surface layer 1 b that forms the inner surface of the opening T and the inner space S, and an outer surface layer 1 a that forms the outer surface of the packaging bag 1. The inner surface layer 1b is formed by a sealant layer described later. For this reason, the heat sealing opening 1d can be heat-sealed by being heated in an opposed state.
The packaging bag 1 can store and store strongly permeable contents composed of various acids and bases.
Examples of acids that can be accommodated in the packaging bag 1 include acetic acid and sodium hypochlorite. The pH of the acid that can be accommodated is not particularly limited, and may be, for example, pH 3 or less.
For example, examples of bases that can be accommodated in the packaging bag 1 include ammonia and monoethanolamine. The pH of the base that can be accommodated is not particularly limited, and can be, for example, pH 11 or higher.

A detailed configuration of the laminated sheet 1A used for the packaging bag 1 will be described.
FIG. 3 is a schematic longitudinal sectional view showing the layer structure of the laminate according to the first embodiment of the present invention.

As illustrated in FIG. 3, the laminated sheet 1 </ b> A includes the laminated body 10 of the present embodiment.
In the laminate 10, a base material layer 11, a second adhesive layer 12, a barrier layer 13, a surface modification layer 14 (intermediate layer), a first adhesive layer 15, and a sealant layer 16 are laminated in this order.

The base material layer 11 is a layered portion constituting the outer surface layer 1 a in the packaging bag 1. As the base material layer 11, an appropriate resin having properties such as strength necessary for the outermost layer of the packaging bag 1 is used.
Examples of resin materials suitable for the base material layer 11 include polyester, polyamide, polyolefin, polyethylene terephthalate (PET), nylon (ONY), polypropylene (OPP), and the like.
The layer thickness of the base material layer 11 is not particularly limited. For example, the layer thickness of the base material layer 11 may be 5 μm or more and 100 μm or less.

The second adhesive layer 12 is provided for bonding a barrier layer 13 described later to the base material layer 11. The material of the 2nd contact bonding layer 12 will not be specifically limited if the barrier layer 13 mentioned later can be joined to the base material layer 11. FIG.
For example, as the second adhesive layer 12, a urethane adhesive, an epoxy adhesive, an acrylic adhesive, or the like may be used depending on the material of the base material layer 11 and the barrier layer 13.

The barrier layer 13 is a layered portion for suppressing the permeation of volatile components from the contents themselves and the contents contained in the internal space S in the packaging bag 1.
As the barrier layer 13, an appropriate metal or alloy capable of forming a surface modification layer 14 to be described later on the surface is used. As the barrier layer 13, for example, aluminum or an aluminum alloy may be used.
The layer thickness of the barrier layer 13 is not particularly limited as long as barrier characteristics necessary for the packaging bag 1 and flexibility as the packaging bag 1 are obtained.
For example, when the barrier layer 13 is an aluminum foil, the layer thickness of the barrier layer 13 may be 1 μm or more and 50 μm or less. If the thickness of the barrier layer 13 is less than 1 μm, the barrier property may be insufficient. When the thickness of the barrier layer 13 exceeds 50 μm, flexibility may be deteriorated. When the barrier layer 13 is made of aluminum or an aluminum alloy, a more preferable layer thickness of the barrier layer 13 is 6 μm or more and 20 μm or less.

The surface modification layer 14 is an intermediate layer that is formed on the surface opposite to the barrier layer 13 and includes an amino group in order to improve adhesive strength with a sealant layer 16 described later.
In this embodiment, the surface modification layer 14 is formed by subjecting the barrier layer 13 to a chemical conversion treatment with an appropriate surface modification agent.
The surface modification layer 14 includes an inorganic coating containing a heavy metal or a salt thereof, and an organic polymer coating that contains a nitrogen atom and covers the inorganic coating by coordination bonding between the nitrogen atom and the heavy metal. Also good. This organic polymer film is preferably a compound having at least one resin skeleton of an acrylic resin and a polybutadiene resin and formed of a compound having an amino group.
More preferably, the heavy metal contained in the surface modification layer 14 contains at least one of zirconium, molybdenum, tungsten, niobium, nickel, cobalt, manganese, and tantalum, for example.

In the case of such a preferable configuration, the surface modification layer 14 includes an inorganic film containing a heavy metal or a salt thereof, thereby improving the corrosion resistance against acids and bases. Furthermore, since the surface modification layer 14 includes an organic polymer film that covers the inorganic film by coordination of heavy metals and nitrogen atoms of the inorganic film, the adhesive strength with the resin adhesive is improved. In particular, when an adhesive containing an isocyanate group is used as the adhesive, a cross-linked structure is formed by a reaction between an amino group and an isocyanate group in the organic polymer film, so that the adhesive strength is further improved.
As an example of the surface modifier which can form the surface modification layer 14 of such a structure, the metal surface treatment composition as described in patent 3871361 is mentioned, for example.

The coating amount of the surface modification layer 14 is preferably 3.0 mg / m ² or more and 25 mg / m ² or less. If the coating amount of the surface modification layer 14 is thinner than 3.0 mg / m ² , the corrosion resistance may be inferior. If the coating amount of the surface modification layer 14 is thicker than 25 mg / m ² , film cracking may occur.

The first adhesive layer 15 is a layered portion that joins a surface modification layer 14 that is an intermediate layer and a sealant layer 16 described later.
The first adhesive layer 15 is formed of an adhesive mainly composed of a bifunctional or higher functional isocyanate compound, and is laminated on the surface modification layer 14.
The bifunctional or higher isocyanate compound may be a derivative of an isocyanate monomer obtained by trifunctionalizing a bifunctional isocyanate monomer. Here, the “trifunctionalized derivative of isocyanate monomer” may be, for example, any of an adduct type, a burette type, and an isocyanurate type.

  Examples of the isocyanate compound that constitutes the first adhesive layer 15 include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4. Examples include various diisocyanate monomers such as' -diphenylmethane diisocyanate and hydrogenated products thereof. In addition, adduct type obtained by reacting these diisocyanate monomers with trifunctional active hydrogen-containing compounds such as trimethylolpropane and glycerol, burette type obtained by reacting with water, or trimer (isocyanate) utilizing self-polymerization of isocyanate groups. A trifunctional derivative such as a (nurate) type, or a polyfunctional derivative higher than that may be used.

  The layer thickness of the first adhesive layer 15 may be 0.05 μm or more and 1 μm or less. There exists a possibility that adhesive strength may fall that the layer thickness of the 1st contact bonding layer 15 is less than 0.05 micrometer. If the thickness of the first adhesive layer 15 exceeds 1 μm, flexibility may be deteriorated.

The sealant layer 16 is a layered portion for forming the heat seal portion 1c. The sealant layer 16 is bonded to the surface modification layer 14 via the first adhesive layer 15.
The sealant layer 16 is formed of an appropriate resin material that can be heat sealed. Examples of resin materials suitable for the sealant layer 16 include polyolefin resins such as polyethylene resins and polypropylene resins.
Specific examples of the material of the sealant layer 16 include, for example, high density polyethylene, low density polyethylene, medium density polyethylene, ethylene resins such as ethylene-α olefin copolymer, homo-block / random polypropylene resins, propylene- Propylene resin such as α-olefin copolymer, ethylene-α, β unsaturated carboxylic acid copolymer such as ethylene-acrylic acid copolymer and ethylene-methacrylic acid copolymer, ethylene-methyl acrylate and ethylene-acrylic Esterified products of ethylene-α, β unsaturated carboxylic acid copolymers such as ethyl acetate, ethylene-methyl methacrylate and ethylene-ethyl methacrylate, and ethylene-α, β in which the carboxylic acid moiety is crosslinked with sodium ion, zinc ion, etc. Ionic cross-linked product of unsaturated carboxylic acid copolymer, ethylene Epoxy compound-modified polyolefins such as acid anhydride-modified polyolefins, ethylene-glycidyl methacrylate copolymers such as terpolymers such as maleic anhydride graft copolymer and ethylene-ethyl acrylate-maleic anhydride, ethylene -A single resin or a blend of two or more resins selected from vinyl acetate copolymers. The sealant layer 16 may be configured by adding various additives (such as an antioxidant, a tackifier, a filler, and various fillers) to these materials as necessary.

Next, the manufacturing method of the laminated body 10 of this embodiment is demonstrated.
First, an adhesive to be the second adhesive layer 12 is applied to the base material layer 11, and the base material layer 11 and the barrier layer 13 are bonded via the second adhesive layer 12.
Thereafter, a surface modifying agent for forming the surface modifying layer 14 is applied to the surface of the barrier layer 13, and the surface modifying agent is brought into contact with the surface of the barrier layer 13. The surface modifier to be applied may be appropriately heated. The contact time between the surface modifying agent and the barrier layer 13 is not particularly limited as long as the surface modifying layer 14 having a necessary coating amount is formed.
Examples of the method for applying the surface modifier include a spray method, a dipping method, a flow coating method, and a roller coating method.
When the applied surface modifier comes into contact with the barrier layer 13 and the surface modified layer 14 is formed on the surface of the barrier layer 13, for example, a water washing process is performed to remove the excess surface modifier. Is called. When the surface modifying agent is removed, the surface modifying layer 14 is dried.

Thereafter, an adhesive for forming the first adhesive layer 15 is applied to the surface of the surface modification layer 14. Here, the adhesive coating liquid is prepared such that the solid content ratio of the above-described isocyanate compound is 0.1 wt% to 20 wt%, preferably 0.1 wt% to 10 wt%.
The coating thickness of the coating solution is set to be 0.05 μm or more and 1 μm or less when dried. The coating method is not particularly limited, and for example, a coating method such as a roller coating method or a spray coating method is possible.
When the coating solution is applied, the coating solution is dried. Thus, the first adhesive layer 15 is formed.

Thereafter, for example, a polyolefin-based resin is extruded onto the first adhesive layer 15, and the sealant layer 16 is laminated via the extruded polyolefin-based resin. At this time, the surface of the sealant layer 16 may be subjected to ozone treatment. The resin temperature during extrusion of the polyolefin resin may be, for example, 290 ° C. or higher and 330 ° C.
However, the sealant layer 16 may be formed by extruding a polyolefin-based resin on the first adhesive layer 15.
The laminated body 10 is manufactured by the above.

  Such a laminated body 10 is laminated so that the sealant layers 16 face each other by being appropriately cut and then bent as necessary. Then, the location used as the heat seal part 1c is heat-sealed. Thereby, the packaging bag 1 is manufactured.

Since the packaging bag 1 of this embodiment is formed by the laminated body 10 which has the barrier layer 13, it has favorable barrier property. When the metal or alloy which comprises the barrier layer 13 touches an acid or a base, there exists a possibility that it may be corroded. However, in the laminate 10, the surface modification layer 14 is formed on the surface of the barrier bag 13 on the inner space S side of the packaging bag 1.
Since the barrier layer 13 is covered with the inorganic film of the surface modification layer 14, even if the contents permeate from the inner space S side, the contents and the barrier layer 13 are separated by the inorganic film of the surface modification layer 14. Contact is prevented. For this reason, even when the content of the packaging bag 1 is an acid or a base, corrosion of the barrier layer 13 is prevented.

Furthermore, in the surface modification layer 14, the inorganic film is covered with the organic polymer film. This organic polymer film has an amino group, and a nitrogen atom in the amino group is coordinated with a heavy metal in the inorganic film. For this reason, the organic polymer film is firmly bonded to the inorganic film. Further, the amino group on the surface of the organic polymer film opposite to the inorganic film reacts with the isocyanate group of the isocyanate compound applied on the surface modified layer 14. Thereby, for example, a urea bond, a burette bond, an allophanate bond, and the like are generated, and a three-dimensional crosslinked structure is formed. For this reason, the isocyanate compound of the 1st contact bonding layer 15 and the organic polymer membrane | film | coat of the surface modification layer 14 join firmly.
Thereby, the adhesive strength between the 1st contact bonding layer 15 and the surface modification layer 14 improves.

  Further, the sealant layer 16 is laminated via the polyolefin resin extruded onto the first adhesive layer 15, or the resin material constituting the sealant layer 16 is extruded onto the first adhesive layer 15. Thus, it is firmly joined. For this reason, the adhesive strength between the sealant layer 16 and the first adhesive layer 15 is improved.

  Thus, according to the packaging bag 1 using the laminated body 10, the tolerance with respect to strong permeable contents, such as an acid and a base, can be improved.

[Second Embodiment]
The laminated body of the 2nd Embodiment of this invention is demonstrated.
FIG. 4 is a schematic longitudinal sectional view showing the layer structure of the laminate according to the second embodiment of the present invention.

As shown in FIG. 1, the laminated body 20 of this embodiment can be used in place of the laminated body 10 of the first embodiment in the laminated sheet 1A of the packaging bag 1 in the first embodiment.
As shown in FIG. 2, the laminate 20 includes a barrier layer 22, a second adhesive layer 23, and a polyamide resin layer instead of the second adhesive layer 12, the barrier layer 13, and the surface modification layer 14 of the laminate 10. 24 (intermediate layer). Hereinafter, a description will be given centering on differences from the first embodiment.

The barrier layer 22 is a layered portion that is densely formed of an inorganic oxide. The barrier layer 22 can be manufactured, for example, by depositing an inorganic oxide on the base material layer 11.
Examples of the inorganic oxide that can be used for the barrier layer 22 include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), and the like.
The layer thickness of the barrier layer 22 is set to an appropriate layer thickness that provides a necessary gas permeation amount for the packaging bag 1.
Since the barrier layer 22 has poor adhesion to the sealant layer 16, in this embodiment, a polyamide resin layer 24 described later is disposed as an intermediate layer between the barrier layer 22 and the sealant layer 16.
Furthermore, since the barrier layer 22 is sandwiched between the base material layer 11 and the polyamide resin layer 24, even if the laminated body 20 is curved or bent, cracking or peeling hardly occurs. ing.

The second adhesive layer 23 is provided for bonding a polyamide resin layer 24 described later to the barrier layer 22. The material of the 2nd contact bonding layer 23 will not be specifically limited if the polyamide resin layer 24 mentioned later can be joined to the base material layer 11. FIG.
For example, as the second adhesive layer 23, a urethane adhesive, an epoxy adhesive, an acrylic adhesive, or the like may be used depending on the material of the barrier layer 22 and the polyamide resin layer 24.

The polyamide resin layer 24 is an intermediate layer including an amino group on the surface opposite to the barrier layer 13 in order to improve the adhesive strength with the sealant layer 16.
The polyamide resin layer 24 is formed by a thin layer sheet of polyamide resin.
Examples of the material of the polyamide resin layer 24 include nylon.
Since the polyamide resin layer 24 contains an amino group, it is firmly bonded to an adhesive layer made of an isocyanate compound like the first adhesive layer 15 in the first embodiment.
The layer thickness of the first adhesive layer 15 in the present embodiment may be any layer thickness that provides the necessary adhesive strength between the polyamide resin layer 24 and the sealant layer 16. For example, the layer thickness of the first adhesive layer 15 is the same as that of the first embodiment. The same can be said.

Next, the manufacturing method of the laminated body 10 of this embodiment is demonstrated centering on a different point from the said 1st Embodiment.
First, an inorganic oxide is vapor-deposited on the base material layer 11, and the laminated body of the base material layer 11 and the barrier layer 22 is formed.
Thereafter, an adhesive that becomes the second adhesive layer 23 is applied to the surface of the barrier layer 22, and a thin layer sheet that becomes the polyamide resin layer 24 is laminated on the second adhesive layer 23. At this time, the thin layer sheet used as the polyamide resin layer 24 may be subjected to, for example, corona treatment or easy adhesion treatment.

Thereafter, an adhesive for forming the first adhesive layer 15 is applied on the polyamide resin layer 24 in the same manner as in the first embodiment.
When the coating liquid is applied, the coating liquid is dried, and the sealant layer 16 is laminated on the first adhesive layer 15 in the same manner as in the first embodiment.
Thus, the stacked body 20 is formed.

  Such a laminate 20 is as follows. After being cut into a suitable shape, the sealant layers 16 are laminated so as to face each other by being bent as necessary. Then, the location used as the heat seal part 1c is heat-sealed. Thereby, the packaging bag 1 of this embodiment is manufactured.

  Since the packaging bag 1 of this embodiment is formed of the laminated body 20 having the barrier layer 22, it has a good barrier property. The inorganic oxide constituting the barrier layer 22 has higher corrosion resistance to acids or bases than the metal foil. For this reason, even when the content of the packaging bag 1 is an acid or a base, corrosion of the barrier layer 22 is prevented.

Further, the polyamide resin layer 24 and the sealant layer 16 are joined by the first adhesive layer 15 as in the first embodiment.
Since the polyamide resin layer 24 has an amino group, it reacts with the isocyanate group of the isocyanate compound of the first adhesive layer 15. Thereby, for example, a urea bond, a burette bond, an allophanate bond, and the like are generated, and a three-dimensional crosslinked structure is formed. For this reason, the isocyanate compound of the 1st contact bonding layer 15 and the polyamide resin layer 24 join firmly.
Thereby, the adhesive strength between the 1st contact bonding layer 15 and the polyamide resin layer 24 improves.
The adhesive strength between the sealant layer 16 and the first adhesive layer 15 is the same as that in the first embodiment.

  Thus, according to the packaging bag 1 in which the laminated body 20 is used, resistance to strong permeable contents such as acid and base can be improved.

In the above description of each embodiment, the packaging bag 1 has been described as an example in which the three sides are surrounded by the heat seal portion 1c and the heat seal opening 1d at the upper end portion can be heat sealed. However, the structure of the packaging bag 1 is not limited to this.
For example, the heat sealing opening 1d may be heat sealed in a state in which a resin member forming a spout and a plug is attached.
For example, a chuck may be welded to the inner peripheral surface of the opening T.
For example, the packaging bag 1 may be configured by a gusset bag, a standing pouch, or the like.

Hereinafter, Examples 1 and 2 of the laminate and the packaging bag of each of the above embodiments will be described together with Comparative Examples 1 to 4.
The following [Table 1] shows the layer structure of the laminates of Examples 1 and 2 and Comparative Examples 1 to 3.

In [Table 1], materials of some layers are represented by abbreviations. PE represents polyethylene, AL represents an aluminum alloy (aluminum foil), SM represents a surface modified layer, PET represents polyethylene terephthalate, S represents silica (SiO ₂ ), and ONY represents stretched nylon. When a number is described following these abbreviations, the number represents a layer thickness [μm].
Hereinafter, for the sake of simplicity, the abbreviations of these abbreviations may be used in the specification.

[Example 1]
Example 1 is an example relating to the laminate 10 and the packaging bag 1 of the first embodiment.
As shown in [Table 1], the laminate of Example 1 is composed of a polyethylene terephthalate (base material layer 11) having a layer thickness of 12 μm, an aluminum foil (barrier layer 13) having a layer thickness of 7 μm, a surface modification layer 14, and a layer thickness. A 30 μm sealant layer 16 was laminated in this order.
As the base material layer 11, FE2001 (trade name; manufactured by Futamura Chemical Co., Ltd.) was used. As the barrier layer 13, A8079 material (manufactured by Toyo Aluminum Co., Ltd.) was used. As the second adhesive layer 12, Dick Dry (registered trademark) LX-500 (trade name; manufactured by DIC Graphics Co., Ltd.), which is a urethane adhesive, was used.
The surface modification layer 14 was formed by applying Surfcoat (registered trademark) EC1000A / B (trade name; manufactured by Nippon Paint Surf Chemicals Co., Ltd.) to the surface of the barrier layer 13. The sealant layer 16 is T.D. which is L-LDPE (linear low density polyethylene). U. X (registered trademark) FC-S (trade name; manufactured by Mitsui Chemicals Tosero Co., Ltd.) was used.
As the first adhesive layer 15 for joining the surface modification layer 14 and the sealant layer 16, a biuret type of hexamethylene diisocyanate was used.

In this example, after the barrier layer 13 was adhered to the base material layer 11 using the second adhesive layer 12, Surfcoat (registered trademark) EC1000A / B was applied to the surface of the barrier layer 13 by a roll coating method. . Surfcoat (registered trademark) EC1000A / B is a mixture of EC1000A and EC1000B at a weight ratio of 3: 1, and water and IPA (EC1000A so that EC1000A has a concentration of 4.0 wt% and EC1000B has a concentration of 1.3 wt%). After diluting with a mixed solvent of Toyo Ink S503 solvent), it was applied to the barrier layer 13 to a coating amount of 20 mg / m ² and dried. Thereby, the surface modification layer 14 was formed.
Thereafter, a biuret type of hexamethylene diisocyanate was applied and dried on the surface of the surface modification layer 14 to form a first adhesive layer 15 having a layer thickness of 0.3 μm.
Thereafter, Novatec (registered trademark) LD LC600A (trade name; manufactured by Nippon Polyethylene Co., Ltd.) was extruded onto the first adhesive layer 15. U. The sealant layer 16 was laminated by bonding with X (registered trademark) FC-S. The temperature at the time of extrusion of LC600A was 290 ° C. or higher and 330 ° C. or lower.
Thus, the laminate 10 of this example was manufactured.

The packaging bag 1 of this example was manufactured by heat-sealing the three sides of the rectangle in a state where the two laminated bodies 10 cut into a rectangle were stacked with the sealant layers 16 facing each other.
In order to evaluate the packaging bag 1, the heat sealing opening 1 d was heat-sealed in a state where the contents were packed in the internal space S of the packaging bag 1. Thereby, the sample of the packaging bag 1 containing the contents was manufactured.
The contents were packed with acid or base. An acetic acid 5 wt% aqueous solution (pH 3.0 or less) was used as the acid, and a monoethanolamine 10 wt% aqueous solution (pH 11.0 or more) was used as the base.

[Example 2]
Example 2 is an example relating to the laminate 20 and the packaging bag 1 of the second embodiment.
As shown in [Table 1], the laminate of Example 2 was made of polyethylene terephthalate (base material layer 11), silica (barrier layer 22), stretched nylon (polyamide resin layer 24) having a layer thickness of 15 μm, and layer thickness of 100 μm. The sealant layer 16 was laminated in this order. Among these, the material of the sealant layer 16 is the same as that of the first embodiment.
As the base material layer 11 and the barrier layer 22, a transparent high barrier film GL-RD (trade name; manufactured by Toppan Printing Co., Ltd.) having a silica layer deposited on a PET film was used.
As the polyamide resin layer 24, Emblem (registered trademark) ONBC-15 (trade name; manufactured by Unitika Ltd.) was used. As the second adhesive layer 12 that bonds the barrier layer 22 and the polyamide resin layer 24, Dick Dry (registered trademark) LX-500 (trade name; manufactured by DIC Graphics Co., Ltd.), which is a two-component curable urethane adhesive. ) Was used.
As the first adhesive layer 15 that bonds the polyamide resin layer 24 and the sealant layer 16, a biuret type of hexamethylene diisocyanate was used as in Example 1.

In this example, the second adhesive layer 12 was applied to the silica layer in the transparent high barrier film GL-RD, and the polyamide resin layer 24 was laminated.
Thereafter, a biuret type of hexamethylene diisocyanate was applied and dried on the surface of the polyamide resin layer 24 in the same manner as in Example 1 to form the first adhesive layer 15 having a layer thickness of 0.3 μm.
Thereafter, Novatec (registered trademark) LD LC600A was extruded onto the first adhesive layer 15, and T.P. U. By bonding with X (registered trademark) FC-S, a sealant layer 16 having a layer thickness different from that of Example 1 was laminated.
With the above, the laminate 20 of this example was manufactured.

  A packaging bag 1 of this example was manufactured in the same manner as in Example 1 except that the laminate 20 was used, and a sample of the packaging bag 1 filled with the same contents was manufactured.

[Comparative Example 1]
As shown in [Table 1], Comparative Example 1 is an example of a layer configuration having no intermediate layer.
The laminate of Comparative Example 1 was constituted by laminating polyethylene terephthalate (base material layer) having a layer thickness of 12 μm, an aluminum foil (barrier layer) having a layer thickness of 7 μm, and a sealant layer having a layer thickness of 40 μm in this order. Among these, the materials of the base material layer, the barrier layer, and the sealant layer are the same as those of the base material layer 11, the barrier layer 13, and the sealant layer 16 of Example 1, respectively. The base material layer and the barrier layer were bonded by the same second adhesive layer 12 as in Example 1.
In this comparative example, the first adhesive layer that bonds the barrier layer and the sealant layer is mainly composed of Dick Dry (registered trademark) LX-500 (trade name; manufactured by DIC Graphics Co., Ltd.), and Dick Dry (registered). (Trademark) KW-75 (trade name; manufactured by DIC Graphics Co., Ltd.) was used. Dick Dry (registered trademark) LX-500 has a polyester polyol as a main component, and Dick Dry (registered trademark) KW-75 has an isocyanate as a main component.

  In this comparative example, the base material layer, the second adhesive layer, the barrier layer, the first adhesive layer, and the sealant layer were produced by dry lamination in this order.

[Comparative Example 2]
As shown in [Table 1], Comparative Example 2 is an example of a layer configuration having no intermediate layer.
The laminate of Comparative Example 2 differs from Comparative Example 1 only in the material of the first adhesive layer. In Comparative Example 2, the biuret type of hexamethylene diisocyanate was used as the first adhesive layer for bonding the barrier layer and the sealant layer as in Example 1.

[Comparative Example 3]
As shown in [Table 1], Comparative Example 3 is an example of a layer configuration in which ONY is an intermediate layer.
In the laminate of Comparative Example 3, in Comparative Example 2, an intermediate layer made of stretched nylon having a layer thickness of 15 μm is inserted between the barrier layer and the sealant layer. As this intermediate layer, Emblem (registered trademark) ONBC-15 was used. However, in Comparative Example 3, the thickness of the sealant layer was 100 μm.
In Comparative Example 3, the barrier layer and the intermediate layer were bonded by LX-500 as in Example 2. As in Example 2, the biuret type of hexamethylene diisocyanate was used as the first adhesive layer for bonding the intermediate layer and the sealant layer.

[Comparative Example 4]
As shown in [Table 1], Comparative Example 4 is an example of a layer configuration having PET as an intermediate layer.
The laminate of Comparative Example 4 was configured by replacing the intermediate layer made of ONY in Comparative Example 3 with PET having a layer thickness of 12 μm. However, in Comparative Example 4, the thickness of the sealant layer was 30 μm.
Polyester film FE2002 (trade name; manufactured by Futamura Chemical Co., Ltd.) was used as the intermediate layer PET of this comparative example.
The materials of the first adhesive layer and the second adhesive layer in this comparative example were the same as those in Comparative example 3, respectively.

[Packaging bags of Comparative Examples 1 to 4]
In Comparative Examples 1 to 4, except that the laminates of Comparative Examples 1 to 4 were used, the packaging bags of each Comparative Example were produced in the same manner as in Example 1, and the same contents were filled. A sample of packaging bag was produced.

[Evaluation]
As an evaluation of Examples 1 and 2 and Comparative Examples 1 to 4, initial and time-lapse laminate strength measurements and oxygen permeation amounts (OTR) were measured.
The laminate strength was measured before and after the sample storage test. The sample storage test was conducted for 3 months in a thermostatic chamber adjusted to 50 ° C.
The laminate strength was measured by a measurement sample obtained by cutting a sample of the packaging bag with the contents removed into a 15 mm width. The laminate strength of each layer of the measurement sample was measured by T-type peeling using Tensilon (registered trademark) universal material testing machine RTF-1250 (trade name; manufactured by A & D Co., Ltd.). Was done by The peeling rate in the measurement was 300 mm / min.
The OTR of the laminate was measured by OX-TRAN (registered trademark) Model 2/21 (trade name; manufactured by MOCON).

[Evaluation results]
[Table 2] below shows the evaluation results of laminate strength and OTR. In the notation of [Table 2], the same abbreviations as in [Table 1] are used.

  Laminate strength [N / 15 mm] for each peeled surface is immediately before the start of the storage test ("when starting" in [Table 2]) and after the storage test is completed ("after 3 months storage" in [Table 2]). The measured values are shown. After the storage test, the case where the content is an acid and the case where the content is a base are described. However, in the comparative example 4, the sample which made the content an acid was not created.

In Example 1, the sealant layer 16 (PE) was peeled off from the surface modified layer 14 both at the start and after storage for 3 months, but the PE was cut during the measurement, and the laminate strength could not be measured. . However, it was necessary to have such a large peel force that the PE could be cut, so it can be said that the packaging bag 1 of Example 1 had a high laminate strength. In Example 1, it can be said that there was no deterioration of the laminate strength due to the influence of acid and base in the storage test for 3 months.
The OTR was below the measurement limit of the measuring instrument 0.1 [cm ³ / (m ² · day · atm)].
For this reason, Example 1 was excellent in laminate strength and OTR, and was determined to be good (◯, good).

In Example 2, the laminate strength between the base material layer 11 (PET) and the polyamide resin layer 24 (ONY) slightly decreased after the storage test. However, since the laminate strength only needs to exceed 2.0 [N / 15 mm], for example, the laminate strength was reduced to such a level that there is no practical problem.
On the other hand, the laminate strength between the polyamide resin layer 24 (ONY) and the sealant layer 16 (PE) could not be measured because the sealant layer 16 did not peel off. It turns out that the 2nd contact bonding layer 23 is very excellent in acid tolerance and base tolerance.
The OTR was 1.0 [cm ³ / (m ² · day · atm)].
For this reason, Example 2 was excellent in laminate strength and OTR, and was determined to be good (◯, good).

As shown in [Table 2], in Comparative Examples 1 to 4, the measured values of OTR were good, but as described below, the laminate strength had a problem, so that it was defective (x, no good). ).
In Comparative Example 1, the laminate strength after storage for 3 months was 0.0 [N / 15 mm], and it was found that neither the acid nor base contents had resistance. This is considered to be because the acid and base that penetrated into the sealant layer (PE) corroded the aluminum foil of the barrier layer (AL) because it did not have an intermediate layer.

  In Comparative Example 2, no adhesive strength was developed between the aluminum foil of the barrier layer (AL) and the sealant layer (PE). That is, it was found that an adhesive mainly composed of an isocyanate compound cannot bond an aluminum foil and a sealant layer without an intermediate layer. For this reason, a storage test was not performed.

In Comparative Example 3, the laminate strength between the intermediate layer (ONY) and the sealant layer (PE) had no problem as in Example 2. However, after the storage test, the aluminum foil of the barrier layer (AL) was corroded, and the laminate strength between the barrier layer (AL) and the intermediate layer (ONY) could not be measured.
That is, when the intermediate layer is ONY, it is considered that the corrosion of the metal barrier layer has progressed because the penetration of the acid and base into the barrier layer cannot be prevented. On the other hand, in Example 2, even if the acid and the base penetrate, the silica itself of the barrier layer is hardly corroded by the acid and the base.

In Comparative Example 4, there was no particular problem with the laminate strength between the intermediate layer (PET) and the sealant layer (PE). Therefore, the biuret type of hexamethylene diisocyanate is at least base resistant even when PET is the intermediate layer. Is found to be good.
However, after the storage test, corrosion of AL occurred and the strength deteriorated due to hydrolysis of PET. As a result, the peel test could not be performed in any of AL / PET and between PET / PE, and the respective laminate strengths could not be measured.

As mentioned above, although each preferred embodiment of the present invention was described with each example, the present invention is not limited to these embodiments and examples. Additions, omissions, substitutions, and other modifications can be made without departing from the spirit of the present invention.
Further, the present invention is not limited by the above description, and is limited only by the appended claims.

1 Packaging bag 1A Laminate sheet (laminate)
1b Inner surface layer 1c Heat seal part 10, 20 Laminate body 11 Base material layer 12, 23 Second adhesive layer 13, 22 Barrier layer 14 Surface modification layer (intermediate layer)
15 First adhesive layer 16 Sealant layer 24 Polyamide resin layer (intermediate layer)
S Internal space T Opening

Claims (13)

A barrier layer made of metal or alloy;
An intermediate layer comprising an amino group and comprising a surface modification layer formed on the surface of the barrier layer;
A first adhesive layer formed of an adhesive mainly composed of a bifunctional or higher isocyanate compound and laminated on the intermediate layer;
A sealant layer laminated to the first adhesive layer;
A laminate comprising: The bifunctional or higher isocyanate compound is a derivative of an isocyanate monomer obtained by trifunctionalizing a bifunctional isocyanate monomer.
The laminate according to claim 1. The thickness of the first adhesive layer is 0.05 μm or more and 1 μm or less.
The laminate according to claim 1 or 2. The barrier layer is made of aluminum or aluminum alloy having a size of 6 μm or more and 20 μm or less,
The laminated body of any one of Claims 1-3. The surface modification layer is
An inorganic film containing a heavy metal or a salt thereof;
An organic polymer film containing nitrogen atoms and covering the inorganic film;
The laminated body of any one of Claims 1-4 provided with these. A barrier layer made of an inorganic oxide;
An intermediate layer made of a polyamide resin and bonded to the barrier layer via a second adhesive layer;
A first adhesive layer formed of an adhesive mainly composed of a bifunctional or higher isocyanate compound and laminated on the intermediate layer;
A sealant layer laminated to the first adhesive layer;
A laminate comprising: The bifunctional or higher isocyanate compound is a derivative of an isocyanate monomer obtained by trifunctionalizing a bifunctional isocyanate monomer.
The laminate according to claim 6. The thickness of the first adhesive layer is 0.05 μm or more and 1 μm or less.
The laminate according to claim 6 or 7. The oxygen transmission amount is 1.0 cm ³ / (m ² · day · atm) or less,
The laminated body of any one of Claims 6-8.   A packaging bag in which a part of the sealant layer of the laminate according to any one of claims 1 to 9 is heat-sealed to form an internal space surrounded by the sealant layer. Forming a middle layer composed of a surface modified layer containing an amino group on the surface of the barrier layer by subjecting the surface of the barrier layer made of metal or alloy to chemical conversion;
Forming a first adhesive layer by applying an adhesive mainly composed of a bifunctional or higher functional isocyanate compound to the intermediate layer and drying;
Extruding a polyolefin-based resin on the surface of the first adhesive layer;
The manufacturing method of a laminated body containing this. Forming an intermediate layer made of a polyamide resin layer on the surface of the barrier layer made of an inorganic oxide via a second adhesive layer;
Forming a first adhesive layer by applying an adhesive mainly composed of a bifunctional or higher functional isocyanate compound to the intermediate layer and drying;
Extruding a polyolefin-based resin on the surface of the first adhesive layer;
The manufacturing method of a laminated body containing this. The bifunctional or higher isocyanate compound is a derivative of an isocyanate monomer obtained by trifunctionalizing a bifunctional isocyanate monomer.
The manufacturing method of the laminated body of Claim 11 or 12.

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