JP2020152066A - Method for producing packaging material laminate, packaging material laminate, and package using the same - Google Patents

Abstract

To provide a method for producing a packaging material laminate in which an adhesive and an anchor coating agent are not used and sealant layers are laminated; the packaging material laminate; and a package produced by using the same.SOLUTION: A method for producing a packaging material laminate that includes: one or more gas barrier layers selected from thin film layers of a metal oxide or an inorganic compound, which have a top coat layer on the top surface of the thin film layers; and a thermoplastic resin layer formed of a fusible resin film, includes: extruding a fusible resin film 27 into a space between a first base material 1 and a second base material 2 which have been fed out from roll bodies 21 and 22 onto which the first base material 1 and the second base material 2 are wound, respectively, and are faced to each other so as to involve a surface on which a thermal adhesive modified layer 6 is formed by surface modification by an atmospheric pressure plasma treatment device 24, without applying an adhesive or an anchor coating agent therebetween; and continuously laminating the first base material 1 and the second base material 2 by a cooling nip roll 25, while applying ozone treatment to the fusible resin film 27.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing a packaging material laminate using a surface-modified resin film, a packaging material laminate, and a packaging body using the same. Further, in detail, various liquid or moisture such as boiled retort foods, liquid detergents, liquid bleaching agents, liquid waxes, hair care products (including shampoos, rinses, conditioners, etc.), chemicals, liquid cosmetics, etc. Low molecular weight components caused by adhesives and anchor coating agents that can be a source of contamination of the contents by not using adhesives and anchor coating agents used in various packaging such as for refilling products containing liquids. A method for manufacturing a packaging material laminate that is clean and has excellent VOC (volatile organic compound) generation and is excellent in environmental measures and energy saving measures, a packaging material laminate, and a packaging made using the same. It is a thing.
In addition, the packaging material laminate according to the present invention is used for various purposes such as decorative sheets, optical films, protective films, and packaging containers. In addition, the packaging container produced by using the packaging material laminate according to the present invention includes liquid seasonings, liquid detergents, liquid bleaching agents, liquid waxes, hair care products (including shampoo, rinse, conditioner, etc.), chemicals, and liquids. Packaging containers for products containing various liquids such as cosmetics or liquids such as water, packaging containers for refilling, boiled / retort foods, general foods, microwave-compatible foods / parts, electronic parts, medical use Widely used in various packaging containers for parts, medical equipment parts, especially radiation sterilization, gas sterilization, autoclave sterilization compatible medical parts, medical equipment parts, precision machine parts, etc.

Traditionally, boiled and retort foods, hair care products, household products, chemicals, general foods, microwave-compatible foods / parts, electronic parts, medical parts, medical equipment parts, precision machine parts, etc. have been stored, stored and transported. For the packaging for supply, a flexible packaging bag or packaging container (hereinafter referred to as a packaging body) in which the peripheral edge of a synthetic resin film having a sealant layer on the inner surface is heat-sealed is used.
The packaging material laminate used for such a packaging is a laminate in which two or more types of films, aluminum foils, vapor-deposited films (thin-film vapor deposition thin films such as aluminum, silica, and alumina are laminated on a base material) and the like. Is used. As the laminate, for example, when the filling port of the packaging container is sealed by welding with a heating bar, so-called heat seal, after filling the contents, the inner surface of the laminate to be the heat seal surface has excellent heat sealability. A polyolefin resin layer such as polypropylene is used as the heat seal layer.
Then, polyamide, polyester, aluminum foil, a vapor-deposited film, etc. are laminated on the laminated body in order to reinforce the strength or impart other functions. For example, a polyamide (PA) resin film / polyethylene terephthalate (PET) resin film having a thin layer of an inorganic compound / unstretched polypropylene (CPP) resin film or a polyethylene terephthalate (PET) resin having a thin layer of a metal oxide or an inorganic compound. Laminates having a structure such as a film / unstretched polyethylene (PE) resin film have been widely used. Further, as a gas barrier layer for aluminum foil, a polyethylene terephthalate (PET) resin film having a thin film layer of a metal oxide or an inorganic compound and a polyamide (PA) resin film having a thin film layer of a metal oxide or an inorganic compound are widely used. ..

Conventionally, as a method of laminating a film used for a laminated body, a dry laminating method in which two or more kinds of resin films are combined and resin films are bonded to each other by using an adhesive, or an anchor coating agent is used. A laminated body in which films are laminated has been produced by a film sand method or an extrusion laminating method performed using the film.
Adhesive strength may be insufficient unless an adhesive or anchor coating agent is used to bond the resin films together. However, the dry laminating method using an adhesive, the film sand method using an anchor coating agent, and the extrusion laminating method have problems in terms of environmental measures and energy saving measures because they use organic solvents, and further, residual solvents and residual solvents Low-molecular-weight components caused by the adhesive and the anchor coating agent may react with the contents filled in the packaging bag to cause contamination of the contents or adversely affect the components of the contents. Further, there is a problem that the influence of contamination on the contents cannot be avoided because there is a risk of migration of the residual solvent and low molecular weight components. Therefore, as a more preferable method for producing a laminate of packaging materials, there is a demand for a method capable of producing a laminate having the required adhesive strength without using an adhesive or an anchor coating agent.

In response to such demands, various proposals have been made regarding a method for producing a laminate without using an adhesive or an anchor coating agent by performing a treatment for increasing the adhesive strength (for example, Patent Documents 1 to 1). 7).
In Patent Document 1, at least one surface of a plastic base material is oxidized by corona treatment, plasma treatment, frame plasma treatment, electron beam irradiation, ultraviolet irradiation, etc., and at least one surface of a melt-extruded film is ozone-treated. , An extrusion laminating method in which both are brought into contact with each other and crimped is described.
Patent Document 2 describes that at least one surface of a plastic base material is subjected to electron beam irradiation treatment, low pressure plasma treatment, atmospheric pressure plasma treatment or corona discharge treatment in an atmosphere of an inert gas such as argon, helium, krypton, neon, xenon, or nitrogen. A method of extrusion laminating in which at least one surface of a melt-extruded film is subjected to ozone treatment and then brought into contact with each other and pressure-bonded is described.

In Patent Document 3, in order to activate the surface of the synthetic resin and improve the adhesiveness to the printing ink and the metal vapor deposition film, a mixed gas atmosphere substantially composed of nitrogen and carbon dioxide (preferably, the oxygen concentration is 0.1 vol). % Or less) describes a surface treatment method for synthetic resins, which comprises corona discharge treatment.
Patent Document 4 describes the number of nitrogen and carbon atoms on the surface of the base film by the ESCA method by corona discharge treatment in a nitrogen gas (oxygen concentration of 3 vol% or less), carbon dioxide gas or a mixed gas atmosphere of nitrogen / carbon dioxide gas. A surface to be treated having a ratio (N / C) in the range of 0.001 to 0.1 is generated, and a water / lower alcohol mixed solution or water is used as a solvent on the surface to be treated, and a water-soluble polymer and an inorganic system are used. A method for producing a gas barrier film in which a coating agent containing a layered compound as a main component is applied and dried to form a coating film is described.

Patent Document 5 discloses a method of laminating at least two or more layers of polyolefin resins such as unstretched polyethylene (PE) and unstretched polypropylene (CPP) without using an adhesive. Specifically, the surface of the resin to be laminated is subjected to low-temperature plasma treatment using a scanning glow discharge plasma device, and then laminated by thermocompression bonding.
Patent Document 6 describes that the base materials whose surface of the fluororesin sheet is plasma-treated by an atmospheric pressure plasma treatment device are equal to or lower than the melting point of the base materials without using an adhesive and without changing the structure and composition thereof. Adhesive devices and methods of bonding by crimping at temperature are shown.
In Patent Document 7, aramid paper composed of plasma surface-treated aramid fibers and aramid pulp and plasma-treated polyester film are continuously laminated and bonded using a pressure roll at a temperature of room temperature to 200 ° C. A non-adhesive aramid-polyester laminate is shown.

Japanese Unexamined Patent Publication No. 7-314629 Japanese Unexamined Patent Publication No. 9-234845 Special Publication No. 57-30854 Japanese Unexamined Patent Publication No. 9-11017 Japanese Unexamined Patent Publication No. 3-162420 Japanese Unexamined Patent Publication No. 2008-075030 Japanese Unexamined Patent Publication No. 2008-183868

However, in the methods proposed in Patent Documents 1 and 2, the adhesive strength may be insufficient only by performing the treatment in combination with the corona treatment in a known air atmosphere and the UV / ozone treatment.

Patent Documents 3 and 4 describe a method of modifying the surface of a synthetic resin to improve adhesiveness by corona discharge treatment in an atmosphere containing nitrogen and substantially no oxygen. However, these patent documents only describe the adhesiveness to a coating film containing a printing ink, a metal vapor deposition film, a water-soluble polymer, and an inorganic layered compound as main constituents. The present inventor has performed a corona discharge treatment in a nitrogen gas atmosphere in order to confirm the adhesiveness between the surface-treated surface of the synthetic resin activated by such a surface treatment method and the resin film by thermal pressure bonding. On the other hand, when an attempt was made to produce a laminated body by a method of heat-laminating a resin film having an untreated surface, sufficient adhesive strength could not be obtained.

Patent Document 5 describes that the surface of a non-polar thermoplastic resin, for example, a polyolefin resin such as unstretched polyethylene (PE), is subjected to low-temperature plasma treatment using a scanning glow discharge plasma apparatus and then thermocompression bonded. It is disclosed to stack. Further, when a polar thermoplastic resin such as polyester and a non-polar thermoplastic resin are laminated, only the non-polar thermoplastic resin is treated with a modulated magnetic field plasma device, but the polar thermoplastic resin is treated. It is said that it is preferable to use the surface of the above without plasma treatment because high interlayer adhesion strength can be obtained. In this case, since it was confirmed by ESCA analysis that CO groups and C = O groups were generated when treated with the modulated magnetic field plasma device, it is said that these generated functional groups contribute to the adhesion.
However, according to the examples, for example, the thermocompression bonding temperature when the PP and LDPE are thermocompression bonded is set to 100 ° C., but the pressing force is not shown, so that it cannot be used industrially.

Patent Document 6 uses an atmospheric pressure plasma processing apparatus for vaporizing a primary alcohol having 4 or less carbon atoms or a lower alcohol which is a secondary alcohol, mixing it with an inert gas, and supplying it to an electrode. A method of surface-modifying a base material whose surface is made of a fluororesin and then thermocompression-bonding the surface-modified base materials at a temperature equal to or lower than the melting point of the base material is disclosed.
It is said that surface modification imparts hydrophilicity to the fluororesin on the surface, but no definition of criteria for determining the preferable treatment state of the plasma-treated resin surface is shown. Further, the thermocompression bonding temperature at the time of thermocompression bonding is set to 200 ° C. or less for polytetrafluoroethylene (PTFE) having a melting point of 327 ° C., but no pressing force is shown, so it should be used industrially. I can't.

In Patent Document 7, aramid paper composed of plasma-treated aramid fibers and aramid pulp and plasma-treated polyethylene terephthalate or polyethylene naphthalate are used at a temperature of room temperature to 200 ° C. under a pressure of 200 kgf / cm or more. A method of continuously laminating using a pressure roll of No. 1 is disclosed.
It is said that by surface modification, certain functional groups such as COOH groups and OH groups can be formed on the film surface, and can be firmly laminated and adhered at a low temperature. However, a preferable treatment state of the plasma-treated resin surface is maintained. No definition of the criteria for judgment is given. Further, since the plasma treatment is a well-known method for enhancing the adhesiveness of various resins, a detailed description of the plasma treatment itself is omitted, and a specific description of the plasma treatment is not described. Therefore, it cannot be used industrially.

In addition, in the dry laminating method using an adhesive, the film sand method using an anchor coating agent, and the extrusion laminating method, since an organic solvent is used, there is a risk of transfer of residual solvent and low molecular weight components. There was a problem that the influence of contamination was unavoidable. For these reasons, it is required to reduce the amount of the adhesive and the anchor coating agent used as much as possible when laminating the resin film to produce the packaging material laminate.

In the prior art, in heat laminating using the same type of film, for example, OPP / CPP or the like was performed without using an adhesive and an anchor coating agent, but different types of films are bonded to each other. When bonding without using an anchor coating agent, the adhesive strength was weak and it was not put into practical use.
As described above, in the prior art, dissimilar films are laminated without using an adhesive and an anchor coating agent, and in particular, a packaging in which a sealant layer is laminated on a resin film having a thin film layer of a metal oxide or an inorganic compound. A method for producing a material laminate, a packaging material laminate, and a packaging produced using the same have not been known.

The present invention has been made in view of the above. That is, an object of the present invention is clean and VOC (volatile) without the generation of low molecular weight components caused by the adhesive and the anchor coating agent, which can be a source of contamination of the contents by not using the adhesive and the anchor coating agent. It completely eliminates the generation of organic compounds), is excellent in environmental measures and energy saving measures, and laminates dissimilar films without using adhesives and anchor coating agents, especially for resin films having a thin layer of metal oxides or inorganic compounds. An object of the present invention is to provide a method for producing a packaging material laminate in which a sealant layer is laminated, a packaging material laminate, and a packaging body produced by using the packaging material laminate.

In the present invention, in order to solve the above problems, a second base material composed of a thin film layer (gas barrier layer) of a metal oxide or an inorganic compound and a thermoplastic resin film having a top coat layer on the surface of the thin film layer, and a molten resin film A method for producing a packaging material laminate including a thermoplastic resin layer comprising a first base material having heat-sealing properties, a thin film layer of a metal oxide or an inorganic compound, and a top coat on the surface of the thin film layer. A molten resin film is extruded between a second base material made of a thermoplastic resin film and bonded to the surface of the molten resin film that meets the second base material by using a film sand method in which the film is laminated while being subjected to ozone treatment. Provided is a method for producing a packaging material laminate, which comprises continuous bonding without applying an agent and an anchor coating agent. When the molten resin film is extruded onto the surface of the second base material without using the first base material, it can be used as an extrusion laminating type laminate.
Further, the adhesive surface of the second base material made of the thin film layer of the metal oxide or the inorganic compound and the thermoplastic resin film having a top coat on the surface of the thin film layer is heated by surface modification using an atmospheric pressure plasma treatment apparatus. Provided is a method for producing a packaging material laminate in which an adhesive modification layer is formed.

In order to solve the above problems, the present invention comprises a thermoplastic consisting of one or more gas barrier layers selected from a thin film layer of a metal oxide or an inorganic compound having a top coat layer on the surface of the thin film layer, and a molten resin film. A method for producing a packaging material laminate including a resin layer, wherein the packaging material laminate has a first base material exposed on one side thereof and having a heat-sealing property, and a top coat layer on a side adjacent thereto. And a second base material made of a thermoplastic resin film having the gas barrier layer, which is laminated through the thermoplastic resin layer without using an adhesive and an anchor coating agent, or the top coat. The thermoplastic resin layer is formed on the side of the second base material made of the layer and the thermoplastic resin film having the gas barrier layer, which has the top coat layer and the gas barrier layer, without using an adhesive and an anchor coating agent. When the packaging material laminate contains the first base material and the second base material, these are used as a base film, and the packaging material laminate is the first base material. When the second base material is contained without containing the above, the second base material is used as a base film, and the film comprises a long film having a thickness of 10 to 500 μm and a length of 3 to 10,000 m. At least one of the base films, which is unwound from the roll body on which the base film is wound, has a surface on which a heat-adhesive modified layer is formed by surface modification by an atmospheric pressure plasma treatment apparatus. When the packaging material laminate contains the first base material and the second base material, the first base material and the first base material so as to include the surface on which the heat-adhesive modified layer is formed. The molten resin film is extruded between the first base material and the second base material without applying an adhesive and an anchor coating agent so that the base materials of 2 are opposed to each other. The surface of the base film to be combined with at least one of the base films is continuously bonded with a cooling nip roll while being subjected to ozone treatment, and the packaging material laminate does not contain the first base material. In the case of containing, the molten resin film is extruded without applying an adhesive and an anchor coating agent to the surface on which the heat-adhesive modified layer of the second base material is formed. Provided is a method for producing a packaging material laminate, characterized in that the surface to be combined with the second base material is continuously bonded with a cooling nip roll while being subjected to ozone treatment.

In the method for producing a laminate of packaging materials, the heat-adhesive modified layer was formed by surface modification of the resin film using an atmospheric pressure plasma treatment device in advance when the base film was bonded. Using the base film and a reference film which is the same or different type of thermoplastic resin film and is treated with air corona, the surface on which the heat-adhesive modified layer of the base film is formed and the air corona. The air corona-treated surfaces of the treated reference film are opposed to each other and thermocompression-bonded without applying an adhesive and an anchor coating agent to obtain a test laminate, and then the adhesive force on the bonded surface of the test laminate is applied. It is preferable to measure the quality of the formed state of the thermoadhesive modified layer of the base film.

A polyethylene terephthalate (PET) resin in which the base film on which a heat-adhesive modified layer is formed using an atmospheric pressure plasma treatment apparatus has a thin film layer of a metal oxide or an inorganic compound and a top coat layer on the surface of the thin film layer. A film or a polyamide (PA) resin film, which is an unstretched polyethylene (PE) resin film treated with air corona as the reference film, is held at a temperature of 160 ° C. and a pressing force of 0.4 MPa for 10 seconds and heat-bonded. The adhesive strength at the time is 5.9N / 25.4mm or more measured by the measuring method specified in JIS K 6854-1 "Adhesive peeling adhesive strength test method Part 1: 90 degree peeling". The process of confirming that,
The base film on which the heat-adhesive modified layer is formed using the atmospheric pressure plasma treatment apparatus is an unstretched polyethylene (PE) resin film, and the polyethylene terephthalate (PET) resin treated with air corona as the reference film. When a film is used and held at a temperature of 160 ° C and a pressing force of 0.4 MPa for 10 seconds and heat-bonded, the adhesive strength is JIS K 6854-1 "Adhesive peeling adhesive strength test method Part 1: 90 degree peeling. The step of confirming that the value measured by the measuring method specified in "" is 5.9 N / 25.4 mm or more,
The base film on which the heat-adhesive modified layer is formed using an atmospheric pressure plasma treatment apparatus is unstretched with unstretched polypropylene (CPP) resin film, cyclic polyolefin (COP or COC) resin film, or unstretched polyethylene. A polypropylene co-extruded film (PE / CPP), using an air corona-treated polyethylene terephthalate (PET) resin film as the reference film, holding at a temperature of 190 ° C. and a pressing force of 0.4 MPa for 10 seconds and heat-pressing. The adhesive strength at the time is 5.9N / 25.4mm or more as measured by the measuring method specified in JIS K 6854-1 "Adhesive peeling adhesive strength test method Part 1: 90 degree peeling". It is preferable to have any of the steps of confirming that.

It is preferable to include an aging step in which the obtained laminate is allowed to stand at room temperature for 10 days to 1 month or at 40 to 60 ° C. for 1 to 3 days after the bonding step of continuously bonding with the cooling nip roll. As a result, the adhesive force can be increased.

The first base material is an unstretched polyethylene (PE) resin film, an unstretched polypropylene (CPP) resin film, a cyclic polyolefin (COP or COC) resin film, and a coextruded film of unstretched polyethylene and unstretched polypropylene (PE / It is one kind selected from the olefin-based film group consisting of CPP), and the thermoplastic resin film contained in the second base material is a polyethylene terephthalate (PET) resin film, a polyamide (PA) resin film, and the like. Polyethylene naphthalate (PEN) resin film, polyacrylonitrile (PAN) resin film, polycarbonate (PC) resin film, polyimide (PI) resin film, polyvinyl chloride (PVC) resin film, ethylene-vinyl alcohol copolymer (EVOH) It is preferably one selected from the group consisting of resin films.
A print layer may be formed on at least one side of the film serving as the second base material.

The present invention also includes one or more gas barrier layers selected from thin film layers of metal oxides or inorganic compounds having a top coat layer on the surface of the thin film layer, and a thermoplastic resin layer made of a molten resin film. A packaging material laminate, wherein the packaging material laminate has a first base material exposed on one side thereof and having a heat-sealing property, and a top coat layer and a gas barrier layer on the side adjacent thereto. A second base material made of a resin film is laminated without an adhesive and an anchor coating agent, or a second group made of a thermoplastic resin film having the top coat layer and the gas barrier layer. The thermoplastic resin layer is laminated on the side of the material having the top coat layer and the gas barrier layer without using an adhesive and an anchor coating agent, and the packaging material laminate is the first. When the base material and the second base material are contained, these are used as a base film, and when the packaging material laminate contains the second base material without containing the first base material, the second base material is contained. The base film is a base film, and the base film is a long film having a thickness of 10 to 500 μm and a length of 3 to 10,000 m, and at least one of the base films is atmospheric pressure. When the packaging material laminate has a surface on which a heat-adhesive modified layer is formed by surface modification by a plasma treatment apparatus and the packaging material laminate contains the first base material and the second base material, the heat adhesion is performed. The first base material and the second base material are opposed to each other so as to include a surface on which the sex-modified layer is formed, and between the first base material and the second base material. The surface of the thermoplastic resin layer that meets at least one of the base films is subjected to ozone treatment through the thermoplastic resin layer, and is bonded without using an adhesive and an anchoring agent to form the packaging. When the material laminate contains the second base material without containing the first base material, the thermoplastic resin layer is formed on the surface on which the heat-adhesive modified layer of the second base material is formed. Is laminated, and the surface of the thermoplastic resin layer that is in contact with the second base material is treated with ozone and bonded without using an adhesive or an anchoring agent. Provide the body.

The first base material is an unstretched polyethylene (PE) resin film, an unstretched polypropylene (CPP) resin film, a cyclic polyolefin (COP or COC) resin film, and a coextruded film of unstretched polyethylene and unstretched polypropylene (PE / It is one kind selected from the olefin-based film group consisting of CPP), and the thermoplastic resin film contained in the second base material is a polyethylene terephthalate (PET) resin film, a polyamide (PA) resin film, and the like. Polyethylene naphthalate (PEN) resin film, polyacrylonitrile (PAN) resin film, polycarbonate (PC) resin film, polyimide (PI) resin film, polyvinyl chloride (PVC) resin film, ethylene-vinyl alcohol copolymer (EVOH) It is preferably one selected from the group consisting of resin films.

Further, in the present invention, when the above-mentioned packaging material laminate is used and the packaging material laminate contains the first base material and the second base material, the first base material is used as a sealant layer. When the packaging material laminate is manufactured so as to be on the inner surface side and contains the second base material without containing the first base material, the thermoplastic resin layer serves as a sealant layer on the inner surface side. Provided is a packaging body characterized in that it is manufactured so as to be.

According to the above invention, since the adhesive and the anchor coating agent are not used to bond the heat seal layer which is the innermost layer of the package, the adhesive and the anchor which can be a source of contamination of the residual solvent and the contents. Since low molecular weight components derived from the coating agent are not generated, the influence of contamination on the contents filled in the package can be reduced.
Further, since the adhesive and the anchor coating agent are not used to bond the heat seal layer which is the innermost layer of the package, the liquid in which the adhesive and the anchor coating agent are filled in the package as in the prior art. It is also possible to reduce the occurrence of adverse effects on the components of the contents due to the reaction with the contents, for example, the decomposition and reduction of the medicinal components.
Moreover, since no adhesive or anchor coating agent is used, it is not necessary to take environmental measures for VOCs (volatile organic compounds) generated by evaporating and drying the solvent.
Further, in the method for producing a laminate of the present invention, since an adhesive and an anchor coating agent are not used, an organic solvent is not used, so that a drying furnace and an exhaust gas treatment device for drying and removing the solvent are not required, and the environment It is very excellent because it can reduce the environmental load from the viewpoint of measures and energy saving measures.
Further, in the present invention, when the top coat layer is provided on the surface of the thin film layer (gas barrier layer) of the metal oxide or the inorganic compound, the top coat layer can be subjected to atmospheric pressure plasma treatment or printing. Further, in the present invention, when the second base material has a printing layer on the top coat layer, the printing layer can be subjected to atmospheric pressure plasma treatment.

It is a conceptual diagram which shows an example of the manufacturing method of the packaging material laminate which concerns on this invention. It is a schematic cross-sectional view which shows an example of the packaging material laminate which concerns on this invention, (a) is the schematic sectional view before film sanding, (b) is the schematic sectional view after film sanding. Another example of the packaging material laminate according to the present invention is a schematic cross-sectional view showing a packaging material laminate made of a film having a printing layer. (A) is a schematic cross-sectional view before film sanding, and (b) is a schematic cross-sectional view after film sanding. It is schematic cross-sectional view which shows an example of the packaging material laminated body which bonded using anchor coat. (A) is a schematic cross-sectional view before film sanding, and (b) is a schematic cross-sectional view after film sanding.

Hereinafter, the present invention will be described with respect to preferred embodiments.

FIG. 1 is a conceptual diagram showing an example of a method for manufacturing a packaging material laminate according to the present invention, in which a first base material and a second base material made of different types of films are bonded together to form a packaging material. It shows a method of manufacturing a laminate.
The first base material 1 and the second base material 2 are each made of a long film, and the roll body 21 on which the first base material 1 is wound and the roll body on which the second base material 2 is wound are respectively. From 22, each is paid out.
The second base material 2 is the second base material 2 on which the heat-adhesive modified layer 6 is formed by surface modification using the atmospheric pressure plasma processing device 24.
Note that FIG. 1 shows a case where the surface is modified online by using the atmospheric pressure plasma processing apparatus 24, but the heat-adhesive modified layer is formed in advance by the surface modification by the atmospheric pressure plasma processing apparatus. A roll body in which the formed second base material is wound may be used.
The surface of the second base material 2 on which the heat-adhesive modified layer 6 is formed faces the first base material 1, and the second base of the molten resin film 27 is formed without applying an anchor coating agent. The molten resin film 27 is extruded from the extrusion die 26 between the first base material 1 and the second base material 2 while performing ozone treatment on the surface to be combined with the material 2, and then bonded with a cooling nip roll 25. (Film sand) is used to obtain the packaging material laminate 10. The obtained packaging material laminate 10 may be wound around a roll body 28, or may be cut to a predetermined size to form a sheet-like laminate (not shown).

2A and 2B are schematic cross-sectional views showing an example of a packaging material laminate according to the present invention, FIG. 2A is a schematic cross-sectional view before film sanding, and FIG. 2B is a schematic cross-sectional view after film sanding. Is.
In this case, at least one surface of the second base material 2 is surface-modified by an atmospheric pressure plasma processing device to form a heat-adhesive modified layer 6. The surface of the second base material 2 on which the thermoplastically modified layer 6 is formed and the first base material 1 face each other, and the second base material 2 is not coated with the anchor coating agent. A thermoplastic resin layer 9 made of a molten resin film whose surface is treated with ozone is bonded (film sanded) between the first base material 1 and the second base material 2 to form a packaging material laminate 10. Is obtained.
The packaging material laminate 10 is a packaging material laminate in which a first base material and a second base material are laminated without using an anchor coating agent. The molten resin film 27 between the first base material and the second base material becomes a solidified thermoplastic resin layer 9 after cooling.
Since a thermoplastic resin film having a heat-sealing property is used for the first base material 1 of the packaging material laminate 10, the packaging material laminate 10 is cut into a predetermined shape and size and heated. A packaging container can be manufactured by heat-sealing the resin of the seal layer on the inner surface side. If the first base material 1 is not used, an extrusion-laminated packaging material laminate (not shown) can be produced in which the thermoplastic resin layer 9 is used as the heat-sealing layer of the packaging container.

Further, FIG. 3 is another example of the packaging material laminate according to the present invention, and is a schematic cross-sectional view showing the packaging material laminate made of a film having a printing layer. (A) is a schematic cross-sectional view before film sanding, and (b) is a schematic cross-sectional view after film sanding.
In FIG. 3, a print layer 11 is formed on one side of the second base material 2 made of a film. A surface modification treatment is performed on the print layer 11 of the second base material 2 on which the print layer 11 is formed by using an atmospheric pressure plasma processing apparatus to print the print layer 11 and the second base material 2. The heat-adhesive modified layer 6 is formed in the portion where the layer is not formed. The surface of the second base material 2 on which the thermoplastically modified layer 6 is formed and the first base material 1 face each other, and the second base material 2 and the second base material 2 are provided without applying an anchor coating agent. A thermoplastic resin layer 9 made of a molten resin film whose mating surfaces are ozone-treated is bonded (film sanded) between the first base material 1 and the second base material 2 to form a packaging material laminate 20. can get.
The packaging material laminate 20 is a laminate on which a printing layer is formed, and the packaging material laminate 20 is cut into a predetermined shape and size and heat-sealed with the resin of the heat-sealing layer as the inner surface side. A practical packaging container having a printing layer can be produced. If the first base material 1 is not used, an extrusion-laminated packaging material laminate (not shown) can be produced in which the thermoplastic resin layer 9 is used as the heat-sealing layer of the packaging container.

The packaging material laminates 10 and 20 according to the present embodiment described above include one or more gas barrier layers 4 selected from a thin film layer (deposited film) of a metal oxide or an inorganic compound.
A first base material 1 having a heat-sealing property is exposed on one surface of the packaging material laminates 10 and 20 according to the present embodiment. On the first base material 1, the second base material 2 composed of the gas barrier layer 4 and the thermoplastic resin film 3 having the top coat layer 5 on the surface thereof heats up without applying an adhesive and an anchor coating agent. It is bonded via the plastic resin layer 9.
Further, in the packaging material laminates 10 and 20, when the first base material 1 is used as the sealant layer, the side of the second base material 2 opposite to the side to which the first base material 1 is attached is , Any layer may be laminated. The first base material 1 may be omitted, and the thermoplastic resin layer 9 may be used as the sealant layer.

The thermoplastic resin film 3 contained in the second base material 2 includes a polyethylene terephthalate (PET) resin film, a polyamide (PA) resin film, a polyethylene naphthalate (PEN) resin film, a polyacrylonitrile (PAN) resin film, and a polycarbonate. One type selected from the group consisting of (PC) resin film, polyimide (PI) resin film, polyvinyl chloride (PVC) resin film, ethylene-vinyl alcohol copolymer (EVOH) resin film and the like can be mentioned.
Further, examples of the metal oxide or the inorganic compound forming the gas barrier layer 4 include gas barrier materials such as silica and alumina. Since these gas barrier materials are not metals such as aluminum and do not have conductivity, they can be heated in a microwave oven. The gas barrier layer 4 can be formed on the surface of the thermoplastic resin film 3 as, for example, a thin-film deposition film.
The topcoat agent used for the topcoat layer 5 is not particularly limited as long as the surface can be modified by an atmospheric pressure plasma treatment apparatus, and for example, an organic topcoat agent such as urethane or polyester. For example, an organic / inorganic mixed topcoat agent such as an organic / inorganic hybrid material using a sol / gel material can be appropriately selected and used depending on the material of the adherend.
The first base material 1 having heat-sealing property includes unstretched polyethylene (PE) resin film, unstretched polypropylene (CPP) resin film, cyclic polyolefin (COP or COC) resin film, and unstretched polyethylene. One type selected from the olefin-based film group composed of a polyethylene co-extruded film (PE / CPP) and the like can be mentioned. The first base material 1 may have an air corona treatment layer 8 formed on the surface of the olefin film 7 by using the air corona treatment device 23.
The packaging material laminates 10 and 20 are composed of a first base material 1 having a heat-sealing property, a thin film layer of a metal oxide or an inorganic compound, and a thermoplastic resin film having a top coat layer on the surface of the thin film layer. The second base material 2 is laminated without using an adhesive and an anchor coating agent.
Since the first base material 1 having a heat-sealing property is laminated on one of the packaging material laminates 10 and 20, the packaging material laminate is cut into a predetermined shape and size. A package can be produced by heat-sealing the first base material 1 with the inner surface side as the inner surface side.
The first base material 1 may be omitted, and the thermoplastic resin layer 9 may be used as the sealant layer. As the thermoplastic resin constituting the thermoplastic resin layer 9 and the molten resin film 27, in the case of the film sand method, a resin suitable for bonding the first base material and the second base material is preferable, and extrusion lamination is used. In the case of the method, a resin suitable for use as a sealant layer is preferable. In either case, it is preferable to mainly use polyethylene (PE) or a carboxylic acid-modified polyolefin resin.

Further, FIG. 4 is a schematic cross-sectional view showing an example of a packaging material laminate bonded by using an anchor coat according to a conventional technique. The packaging material laminate 30 is a thermoplastic resin film having a first base material 1 having heat-sealing properties, a gas barrier layer 4 composed of a thin film layer of a metal oxide or an inorganic compound, and a top coat layer 5 on the surface thereof. The second base material 2 made of 3 is adhered by a film sand using an anchor coating agent. An air corona-treated layer 8 is formed on one surface of the first base material 1, and the surface on which the air corona-treated layer 8 of the first base material 1 is formed and the second base material 2 face each other. After applying the anchor coating agent 31 to the surface of the second base material 2 that meets the molten resin film 27, the molten resin film 27 is subjected to ozone treatment while performing ozone treatment on the surface of the molten resin film 27 that meets the second base material 2. 27 is extruded between the first base material 1 and the second base material 2, and then bonded (film sanded) with a cooling nip roll to obtain a packaging material laminate 30.

(Use of packaging material laminate, etc.)
When the packaging material laminate according to the present embodiment is used for the packaging container, the laminate is prepared using a film having a thickness of about 10 to 100 μm for each of the films of the first base material and the second base material. Is preferable in order to maintain the flexibility of the laminate and improve the processability of the packaging container in the manufacturing process. Further, for the consumer who actually holds the packaging container, the thickness of the laminate used in the packaging container is preferably about 30 to 200 μm from the viewpoint of the feel.
The packaging material laminate according to the present embodiment can be suitably used for a packaging body such as a packaging container. For example, a bag can be obtained by folding this packaging material laminate in half with unstretched polyethylene (PE) as an inner surface in order to form a heat-sealing layer, and heat-sealing on three sides.
In addition, two packaging material laminates cut to a predetermined size are stacked, heat-sealed at both ends, and the packaging material laminate for the bottom folded in half is heat-sealed to allow standing pouch-type self-supporting. A molded package can be obtained.
Further, in the packaging container for refilling, a self-standing standing pouch is used, and a packaging container having various easy-to-pour shapes is provided to obtain a packaging container that simplifies the refilling work of the contents. Can be done.
In addition, for applications such as electronic parts, medical parts, medical equipment parts, precision machine parts, etc., a base film whose cleanliness is maintained and managed is used in a work environment in a clean room where cleanliness is specially controlled. After producing the packaging material laminate according to the present embodiment, a clean packaging body can be produced using the same.
The packaging container (packaging body) of the present embodiment includes various liquid seasonings, liquid detergents, liquid bleaching agents, liquid waxes, hair care products (including shampoo, rinse, conditioner, etc.), chemicals, liquid cosmetics, and the like. Packaging containers for products containing liquids or liquids such as moisture, packaging containers for refilling, boiled / retort foods, general foods, microwave-compatible foods / parts, electronic parts, medical parts, medical equipment parts, Among them, it can be widely used in various packaging containers such as medical parts, medical equipment parts, and precision machine parts that support radiation sterilization, gas sterilization, and autoclave sterilization.
The packaging material laminate of the present embodiment is particularly preferably used as a packaging container material having heat treatment suitability such as boil, retort, and autoclave. Further, the packaging material laminate of the present embodiment is not limited to a packaging body such as a packaging container, and can be used for various purposes such as a decorative sheet, an optical film, and a protective film.

(Steam reforming quality confirmation process)
When the first base material and the second base material are bonded to each other via the molten resin film, or when the molten resin film is bonded to the surface of the second base material, an atmospheric pressure plasma processing apparatus is used in advance. A base material (second base material and / or first base material) on which a heat-adhesive modified layer is formed by surface modification of a resin film using the above, and the same or different type of thermoplastic as this base material. Using a specific resin film that has been treated with air corona, the quality of the surface on which the heat-adhesive modified layer is formed by surface modification by an atmospheric pressure plasma processing apparatus is determined. That is, the surface on which the heat-adhesive modified layer of the base material (second base material and / or the first base material) is formed and the air corona treatment of the specific film (reference film) that has been subjected to the air corona treatment. The adhesive strength when thermocompression bonding is performed with the surfaces facing each other without applying an adhesive or anchor coating agent is JIS K 6854-1 "Adhesive peeling adhesive strength test method Part 1: 90 degree peeling" It is necessary that the surface is modified by using an atmospheric pressure plasma processing apparatus so that the value measured by the measuring method specified in the above is equal to or higher than a predetermined value.
The reference film is only used for determining the quality of the surface, and is not finally included in the laminated body of the product. For example, when the base material (first base material and / or second base material) on which the heat-adhesive modified layer is formed is a long film, a part thereof in the longitudinal direction is used as a reference film. After confirming the quality of the surface modification treatment conditions, a method of continuously bonding the first base material and the second base material can be mentioned. In this case, it is preferable to cut (remove) the portion where the laminate is bonded to the reference film from the product.
The quality confirmation step by bonding with the reference film does not have to be performed every time when the packaging material laminate is produced, but for example, the first base material and / or the second base material to which the atmospheric pressure plasma treatment is performed is performed. When changing the type of base material, changing the processing conditions of atmospheric pressure plasma, cleaning the atmospheric pressure plasma processing equipment, replacing parts, etc., it is possible to carry out a quality confirmation process as necessary. desirable.

In the prior art, surface modification using atmospheric pressure plasma treatment allows certain functional groups, such as COOH groups and OH groups, to be formed on the film surface so that they can be firmly laminated and adhered at low temperatures. However, no criteria have been shown to determine the preferred treatment state of the atmospheric pressure plasma treated film surface.

The present inventors have formed a surface on which a thermoadhesive modified layer of a thermoplastic resin film treated with atmospheric pressure plasma is formed, and a base material having heat-sealing property treated with air corona, for example, unstretched polyethylene (PE). We found that it is possible to confirm a subtle difference in the state of atmospheric pressure plasma treatment by measuring the adhesive strength of the obtained test laminate by thermocompression bonding the resin film with the air corona treated surface facing each other. Furthermore, they have found that the air corona-treated base material (reference film) is not limited to a resin film having a heat-sealing property, and have come to achieve the present invention.

In atmospheric pressure plasma treatment, the treatment conditions such as the time, applied power, and frequency of irradiating the surface of the film with plasma are, for example, a thin film layer of a metal oxide or an inorganic compound and a resin film having a top coat layer on the surface of the thin film layer. In order to search for the plasma treatment conditions for the above, the surface on which the heat-adhesive modified layer of the resin film was formed (which may be a surface having a top coat layer or a printing layer) and air corona treatment were performed. The adhesive strength when heat-bonded under predetermined conditions without applying an adhesive or anchor coating agent to face the air corona-treated surface of the reference film is JIS K 6854-1 "Adhesive peeling adhesive strength test method. Surface modification using an atmospheric pressure plasma processing device is performed so that the strength when peeled at a speed of 5 mm / min by the measuring method specified in "Part 1: 90 degree peeling" is equal to or higher than a predetermined value. Then, a packaging material laminate that can be used for the packaging can be obtained.

A polyethylene terephthalate (PET) resin film in which a base material on which a heat-adhesive modified layer is formed using an atmospheric pressure plasma treatment apparatus has a thin film layer of a metal oxide or an inorganic compound and a top coat layer on the surface of the thin film layer. Alternatively, in the case of a polyamide (PA) resin film, an air corona-treated unstretched polyethylene (PE) resin film is used as the reference film, held at a temperature of 160 ° C. and a pressing force of 0.4 MPa for 10 seconds, and then heat-bonded. The adhesive strength at the time is 5.9N / 25.4mm or more measured by the measuring method specified in JIS K 6854-1 "Adhesive peeling adhesive strength test method Part 1: 90 degree peeling". You just have to confirm that.
When the base material on which the heat-adhesive modified layer is formed using the atmospheric pressure plasma treatment apparatus is an unstretched polyethylene (PE) resin film, the polyethylene terephthalate (PET) resin treated with air corona as the reference film is used. When a film is used and held at a temperature of 160 ° C and a pressing force of 0.4 MPa for 10 seconds and heat-bonded, the adhesive strength is JIS K 6854-1 “Adhesive peeling adhesive strength test method Part 1: 90 degree peeling. It may be confirmed that the value measured by the measuring method specified in "" is 5.9 N / 25.4 mm or more.
The base material on which the heat-adhesive modified layer is formed using the atmospheric pressure plasma treatment apparatus is unstretched polypropylene (CPP) resin film, cyclic polyolefin (COP or COC) resin film, or unstretched polyethylene and unstretched polypropylene. In the case of a co-extruded film (PE / CPP), an air corona-treated polyethylene terephthalate (PET) resin film is used as the reference film, held at a temperature of 190 ° C. and a pressing force of 0.4 MPa for 10 seconds, and then heat-bonded. The adhesive strength at the time is 5.9N / 25.4mm or more measured by the measuring method specified in JIS K 6854-1 "Adhesive peeling adhesive strength test method Part 1: 90 degree peeling". You just have to confirm that.

(Resin film)
Examples of the thermoplastic resin film that can be used as a base material to be subjected to atmospheric pressure plasma treatment include polyethylene terephthalate (PET) resin, polyamide (PA) resin, polycarbonate (PVC) resin, ethylene-vinyl alcohol copolymer (EVOH), and the like. Polyethylene naphthalate (PEN) resin, polyacrylonitrile (PAN) resin, polycarbonate (PC) resin, polyimide (PI) resin, unstretched polyethylene (PE) resin, unstretched polypropylene (CPP) resin, cyclic polyolefin (COP or COC) Examples thereof include a resin film such as resin. The melting points of these thermoplastic resins are polyethylene terephthalate (252 ° C), polyamide (220 ° C), polyvinyl chloride (none), ethylene-vinyl alcohol copolymer (160-190 ° C), and polyethylene naphthalate (about). 270 ° C.), polyacrylonitrile (none), polycarbonate (none), polyimide (none), unstretched polyethylene (105-140 ° C.), unstretched polypropylene (130-165 ° C.). The polyamide resin is a linear polymer in which the main chain is formed by repeating the amide bond (-CONH-) formed by the reaction of acid and amine, and the general trade name is nylon (NY). It is what is called. Further, a film in which two or more kinds of resins are laminated may be used, such as a coextruded film (PE / CPP) of unstretched polyethylene and unstretched polypropylene.

The thickness of the thermoplastic resin film 3 and the first base material 1 having heat-sealing properties used in the packaging material laminate of the present embodiment is preferably about 10 to 500 μm. If the thickness is less than 10 μm, wrinkles are likely to occur, it is difficult to perform roll-to-roll processing, and handling is inconvenient. Further, if the thickness exceeds 500 μm, the rigidity is high and the flexibility is lost, and it is difficult to perform roll-to-roll processing as in the case of being too thin, which causes inconvenience in handling.
Therefore, in the method for producing a laminated body of packaging materials according to the present embodiment, when the surface-modified resin films are bonded to each other with a film sand to produce a laminated film, the laminated resin film is wound as a roll. It is necessary to take care so that the total thickness does not exceed 500 μm.
Further, when the thickness of the laminated resin film exceeds 500 μm, it is difficult to wind the laminated resin film around the roll body, so that the laminated resin film is cut to a certain size and length. It will be manufactured as a sheet of.

(Print layer)
The film as the second base material may have a print layer formed on at least one side thereof. The position of the printing layer is not particularly limited, such as, but is not particularly limited, such as the surface of the second base material to be surface-treated, the surface of the second base material not to be surface-treated, and the inside of the second base material. As shown in FIG. 3, when the print layer 11 is provided on the surface-treated side of the second base material 2, the heat-adhesive modified layer 6 is also formed on the print layer 11. obtain.
In order to form the heat-adhesive modifying layer 6 on the printing layer 11, the printing ink constituting the printing layer 11 needs to contain a resin component that can be modified by atmospheric pressure plasma treatment. Examples of such a resin component include various ink binder resins such as urethane resin and acrylic resin, in addition to the thermoplastic resin used for the base film. Further, various pigments, desiccants, stabilizers and other additives are added to the ink.
The print layer is formed by a known printing method such as an offset printing method, a gravure printing method, or a screen printing method. The thickness of the print layer is usually about 0.05 to 2.0 μm.
Further, when the occupied area of the printing layer is sufficiently smaller than the surface area of the second base material, ozone-treated melting is performed even if the heat-adhesive modified layer is not sufficiently formed on the printing layer. It is possible to bond it with a resin film.

(Manufacturing method of packaging material laminate)
As a method for producing the packaging material laminate of the present embodiment, a first base material made of another thermoplastic resin is placed on a surface of a second base material made of a thermoplastic resin film having a gas barrier layer and a top coat layer. When 1 is bonded, it can be carried out by the following steps (1) and (2).
(1) A surface treatment is performed on the surface of a film of a second base material made of a thermoplastic resin film having a gas barrier layer and a top coat layer using an atmospheric pressure plasma treatment device to form a heat-adhesive modified layer. .. The surface in this case is the surface with the top coat layer.
(2) The second base material of the molten resin film is made by facing the first base material against the surface of the second base material on which the heat-adhesive modified layer is formed, without applying an adhesive and an anchor coating agent. The molten resin film is extruded between the first base material and the second base material while performing ozone treatment on the surface to be combined with the base material, and then bonded (film sand) with a cooling nip roll. Here, if the first base material is not used, it can be used as an extrusion-laminated laminate.

As the molten resin, it is preferable to mainly use an adhesive resin such as a carboxylic acid-modified polyolefin resin. Further, as the molten resin, a thermoplastic urethane resin, a thermoplastic epoxy resin, or the like can be appropriately selected and used according to the material of the adherend and the like.
The reaction gas used in the atmospheric pressure plasma processing apparatus is not limited to one based on nitrogen gas, and may be based on oxygen gas or carbon dioxide gas.

The layer structure of the packaging material laminate is not particularly limited, and examples thereof include the following configurations. In the following example, the right side shows the first base material (which can be omitted) to be the sealant layer. The left side shows the thermoplastic resin film contained in the second base material. Any layer can be further laminated on the left side (outside of the package).
(1-1) PET / silica vapor deposition film / top coat layer / adhesive surface / adhesive resin / PE
(1-2) PET / silica vapor deposition film / top coat layer / adhesive surface / adhesive resin / CPP
(2-1) PET / Alumina vapor deposition film / Top coat layer / Adhesive surface / Adhesive resin / PE
(2-2) PET / Alumina vapor deposition film / Top coat layer / Adhesive surface / Adhesive resin / CPP
(3-1) NY / silica vapor deposition film / top coat layer / adhesive surface / adhesive resin / PE
(3-2) NY / silica vapor deposition film / top coat layer / adhesive surface / adhesive resin / CPP

(Corona discharge processing)
Since the thermoplastic polyolefin resin film such as polyethylene and polypropylene does not have a polar group in the surface layer, the printability of the ink and the adhesiveness with other resins are low. Therefore, in order to improve the printability of the ink and the adhesiveness with other resins, the surface of the resin film is modified by a corona discharge treatment. In the surface modification process by corona discharge, a high-frequency power supply voltage is used to generate corona discharge in the atmosphere, and the electrons and ions generated by the corona discharge are irradiated on the surface of the resin film to form a functional group on the surface of the resin film. By adding the resin film, the surface of the resin film is modified.

(Corona discharge treatment in air atmosphere (air corona treatment))
In the usual surface modification treatment by corona discharge performed in an air atmosphere, the surface of the resin film treated with corona discharge is oxidized, and on the surface of the resin film, carbonyl groups are formed on the main chain and side chains of the polymer. It is considered that oxygen functional groups such as (> CO) and carboxyl group (-COOH) are mainly formed.

(Corona discharge treatment in a nitrogen gas atmosphere)
It is considered that nitrogen functional groups such as amino groups (-NH ₂ ), which are thought to contribute to adhesion, are mainly generated in the main chain and side chains of the polymer on the surface of the resin film by performing the corona discharge treatment in a nitrogen gas atmosphere. Be done. Furthermore, the corona discharge treatment in a nitrogen gas atmosphere is different from the corona discharge treatment in a normal air atmosphere (air corona treatment), and since the discharge occurs in the nitrogen gas atmosphere, the corona discharge treatment in an air atmosphere (air corona treatment) The generation of fragile layers due to impurities in the air generated when the treatment) is performed is suppressed. In some patent documents, it is described that nitrogen gas can also be used as an atmospheric gas for atmospheric pressure glow plasma treatment, but when the discharge state is observed, it is not atmospheric glow plasma discharge. However, the corona discharge in a nitrogen gas atmosphere can be discharged in a streamer-like (linear) shape like lightning, that is, a discharge closer to a gentle (mild) glow than the corona discharge in an air atmosphere by adjusting the discharge conditions. Therefore, it can be used as a more uniform surface modification than air corona treatment.

(Atmospheric pressure glow plasma treatment)
Conventionally, low-temperature plasma treatment that discharges in a vacuum state has been used for surface modification, but there is a drawback that the equipment is large and the operation is complicated because vacuum equipment is required. For this reason, an atmospheric pressure plasma treatment device that generates a glow discharge state that can normally be generated only in a vacuum state under atmospheric pressure and modifies the surface using the reaction radicals, electrons, etc. generated by the glow discharge state is the wettability of the resin film. It has come to be easily used for improvement and adhesiveness improvement.

Atmospheric pressure glow plasma treatment uses rare gas elements such as helium and argon as the atmospheric gas to stably maintain glow discharge, which is more stable than lightning-like streamer-like (linear), that is, corona discharge in an air atmosphere. , Uniform surface modification without unevenness is possible. In some patent documents, it is described that nitrogen gas can also be used as an atmospheric gas for atmospheric pressure glow plasma treatment, but when the discharge state is observed, it is not atmospheric glow plasma discharge.

The atmospheric pressure plasma treatment in the present embodiment is a corona discharge treatment in a nitrogen gas atmosphere or an atmospheric pressure glow plasma treatment in a rare gas atmosphere such as helium or argon.
In atmospheric pressure plasma treatment using oxygen as a reaction gas, oxygen functional groups such as carbonyl group (> CO) and carboxyl group (-COOH) are mainly formed on the main chain and side chains of the polymer on the surface of the resin film. .. Further, by using a nitrogen-based gas as a reaction gas, for example, N ₂ , N ₂ O, NH _3, etc., and further mixing hydrogen (H ₂ ), oxygen (O ₂ ), etc., amino groups, amide groups, etc. can also be obtained. The present inventors have confirmed that it can be introduced intentionally.
Further, CH ₄ , CO _2, etc. may be added to the reaction gas.

In consideration of these, in the present embodiment, when the surface of the resin film is subjected to surface modification treatment using atmospheric pressure plasma treatment, corona discharge treatment in a nitrogen gas atmosphere or a rare gas atmosphere such as helium or argon is used. This can be done using atmospheric pressure glow plasma treatment.
Further, in the present embodiment, in the atmospheric pressure plasma treatment, the time for irradiating the surface of the resin film with the plasma generated by the atmospheric pressure plasma processing apparatus so that the heat-adhesive modified layer is formed on the film surface. The applied power, frequency, etc. can be adjusted.
In the atmospheric pressure plasma treatment, the method of searching for the treatment conditions such as the time for irradiating the surface of the resin film with plasma, the applied power, and the frequency by using the resin film and the reference film is as described above.

(Aging process)
The production method of the present embodiment preferably includes an aging step in which the laminate is allowed to stand at room temperature for 10 days to 1 month or at 40 to 60 ° C. for 1 to 3 days after the bonding step. As a result, the adhesive force can be increased. Here, the normal temperature includes, for example, a temperature range selected within the range of 15 to 25 ° C.
The thermocompression bonding step does not have to be the final step of manufacturing the packaging material laminate. If necessary, it is possible to carry out the aging step during the production of the packaging material laminate, such as after printing.

Hereinafter, the present invention will be specifically described with reference to Examples.

(Measuring equipment, measuring method)
The following experiment was carried out to confirm the effect of surface modification. The treatment conditions by atmospheric pressure plasma treatment are listed for each surface modification example. Since the applied power depends on the scale of the device, the value of the applied power given in the following surface modification example should be understood as a reference indicating the relative strength rather than as an absolute numerical value.

-Measurement of adhesive (peeling) strength: The measurement method specified in JIS K 6854-1 "Adhesive peeling adhesive strength test method Part 1: 90 degree peeling" was followed.
-Boil retort test: A four-sided bag (130 mm x 170 mm) is filled with 200 ml of water, and the boil condition is 95 ° C. x 40 min, and the retort condition is hot water shower type 121 ° C. x 30 min. The appearance was evaluated.

(Confirmation of quality of heat-adhesive modified layer)
In producing the packaging material laminate according to the present embodiment, first, various thermoplastic resin films are surface-modified using an atmospheric pressure plasma treatment device, and then the quality of the heat-adhesive modified layer is determined. Prepare the identified substrate.
Here, the base material A on which the heat-adhesive modified layer is formed and the base material B which is a different type of thermoplastic resin film from the base material A and is treated with air corona are used to heat the base material A. The surface on which the adhesive modification layer was formed and the air corona-treated surface of the base material B were opposed to each other, and thermocompression bonding was performed without applying an adhesive or an anchor coating agent to obtain a test laminate, and then the test was performed. The adhesive strength of the laminated body on the bonded surface is measured to confirm the quality of the thermocompression-bonding modified layer of the base material A.
If the adhesive strength of the test laminate of the base material A on the bonded surface is low, a problem may occur when the packaging material laminate is produced by surface modification using the base material A. For example, when a packaging container is manufactured using a packaging material laminate using the base material A, the packaging material laminate may be peeled off from the bonded surface or may be damaged because it cannot withstand a drop impact. It becomes difficult to obtain a practical packaging material laminate.

Therefore, in order to carry out the method for producing the packaging material laminate according to the present embodiment, the base material A on which the heat-adhesive modified layer is formed by surface modification using the atmospheric pressure plasma processing apparatus to be used in advance. , It is necessary to confirm whether the formation state of the heat-adhesive modified layer is appropriate.
Whether or not the formation state of the thermoadhesive modified layer is appropriate depends on the base material A and the base material B which is a different type of thermoplastic resin film and has been treated with air corona. The surface on which the heat-adhesive modified layer was formed and the air corona-treated surface of the base material B were opposed to each other, and thermocompression bonding was performed without applying an adhesive and an anchor coating agent to obtain a test laminate. It is determined whether or not the adhesive force on the bonded surface of the test laminate exceeds a predetermined value.

(Example of surface modification by atmospheric pressure plasma treatment 1)
An alumina-deposited PET film with a top coat was surface-modified using an atmospheric pressure plasma processing apparatus. The processing conditions are an irradiation time of 0.13 s, an applied power of 2.0 kW, and a frequency of 30 kHz.
Using an alumina-deposited PET film with a top coat of 12 μm in thickness (manufactured by Toray Film Processing Co., Ltd., trade name: 1011HG-CR), surface modification treatment was performed with an atmospheric pressure plasma processing apparatus, and surface modification was performed in Example 1. An alumina-deposited PET film with a surface-modified top coat was obtained.
Next, the surface on which the heat-adhesive modified layer of the resin film of Surface Modification Example 1 was formed and a commercially available unstretched polyethylene (PE) resin film treated with air corona (unstretched polyethylene film manufactured by Tamapoli Co., Ltd.). , Product name; SK615P) is opposed to the air corona treated surface, held at a temperature of 160 ° C. and a pressing force of 0.4 MPa for 10 seconds without applying an adhesive or an anchor coating agent, and heat-pressed to modify the surface. A laminate of the heat seal layer of Example 1 was obtained. The obtained layered body of the heat seal layer of Surface Modification Example 1 had a measured peel strength of 12.9 N / 25.4 mm.

(Example 2 of surface modification by atmospheric pressure plasma treatment)
The same operation as in Surface Modification Example 1 was performed except that the irradiation time, applied power, and frequency of atmospheric pressure plasma in the atmospheric pressure plasma processing apparatus were changed in a weak direction, and the surface was modified in Surface Modification Example 2. An alumina-deposited PET film with a top coat was obtained. The processing conditions are an irradiation time of 0.01 s, an applied power of 10 W, and a frequency of 13.56 MHz.
Next, the obtained resin film of surface modification example 2 was used and bonded to a commercially available air corona-treated unstretched polyethylene (PE) resin film under the same conditions as surface modification example 1. , A laminate of the heat seal layer of Surface Modification Example 2 was obtained. The obtained layered body of the heat seal layer of Surface Modification Example 2 had a measured peel strength of 4.9 N / 25.4 mm.

As described above, the surface-modified resin films of Surface Modified Examples 1 and 2 were obtained by using the atmospheric pressure plasma processing apparatus. The obtained heat-adhesive modified layers of Surface Modified Examples 1 and 2 and an air corona-treated resin film were bonded by thermocompression bonding to obtain a laminate of heat-sealed layers of Surface Modified Examples.
Table 1 shows the results of measuring the peel strength of the obtained laminates of the heat seal layers of Surface Modification Examples 1 and 2.

Next, the surface-modified film of the obtained surface-modified example and the thermoplastic resin film were opposed to each other, and the surface of the molten resin film was modified without applying an adhesive or an anchor coating agent. While performing ozone treatment on the surface to be combined with the film, the molten resin film is extruded between different films and then bonded (film sanded) with a cooling nip roll to obtain the packaging material laminates of Examples 1 to 3 and Comparative Example 1. Made.
Further, in order to compare with the packaging material laminate produced by surface modification, the laminate of Comparative Example 2 was produced by laminating by a film sand method using an anchor coating agent which is a conventional technique.

(Example 1)
The surface on which the heat-adhesive modified layer of the alumina vapor-deposited PET film with the top coat of the above surface modification example 1 was formed, and the commercially available air corona-treated unstretched polypropylene (CPP) resin film (Toray Film Processing Co., Ltd.) The unstretched polypropylene film manufactured by the company, trade name; Trefan ZK207) is opposed to the air corona treated surface, and the thermal adhesiveness of the molten resin film is improved at 80 m / min and 320 ° C. without applying an adhesive or an anchoring agent. While performing ozone treatment on the surface to be combined with the quality layer, the molten resin film is extruded between different films and then bonded (film sand) at 0.23 MPa with a cooling nip roll to obtain the packaging material laminate of Example 1. Obtained. The obtained packaging material laminate of Example 1 had a measured peel strength of 12.0 N / 25.4 mm. Further, after preparing a packaging container for a four-sided seal bag using the obtained packaging material laminate of Example 1, various tests on the packaging container were performed.

(Example 2)
The surface on which the heat-adhesive modified layer of the alumina vapor-deposited PET film with the top coat of the above surface modification example 1 was formed and the commercially available air-corona-treated unstretched polyethylene (PE) resin film (manufactured by Okamoto Co., Ltd.) The unstretched polyethylene film (trade name; LR124) faces the air corona-treated surface and is combined with the heat-adhesive modified layer of the molten resin film at 80 m / min and 320 ° C. without applying an adhesive or an anchoring agent. The molten resin film was extruded between different films while the surface was treated with ozone, and then bonded (film sanded) at 0.23 MPa with a cooling nip roll to obtain a packaging material laminate of Example 2. The obtained packaging material laminate of Example 2 had a measured peel strength of 11.0 N / 25.4 mm. Further, after preparing a packaging container for a four-sided seal bag using the obtained packaging material laminate of Example 2, various tests on the packaging container were performed.

(Example 3)
The surface on which the heat-adhesive modified layer of the alumina vapor-deposited PET film with the top coat of the above surface modification example 1 was formed and the cyclic polyolefin film faced each other, and 80 m without applying an adhesive and an anchoring agent. While performing ozone treatment on the surface of the molten resin film to be combined with the heat-adhesive modified layer at / min and 320 ° C., the molten resin film is extruded between different films and then bonded at 0.23 MPa by a cooling nip roll (film). Sand) to obtain the packaging material laminate of Example 3. The obtained packaging material laminate of Example 3 had a measured peel strength of 12.5 N / 25.4 mm. Further, after preparing a packaging container for a four-sided seal bag using the obtained packaging material laminate of Example 3, various tests on the packaging container were performed.

(Comparative Example 1)
The surface on which the heat-adhesive modified layer of the alumina vapor-deposited PET film with the top coat of the above surface modification example 2 was formed, and the commercially available air corona-treated unstretched polypropylene (CPP) resin film (Toray Film Processing Co., Ltd.) An unstretched polypropylene film manufactured by the same company (trade name; Trefan ZK207) was used for laminating with a film sand under the same conditions as in Example 1 to obtain a packaging material laminate of Comparative Example 1. The obtained packaging material laminate of Comparative Example 1 had a measured peel strength of 4.9 N / 25.4 mm. Further, after preparing a packaging container for a four-sided seal bag using the obtained packaging material laminate of Comparative Example 1, various tests on the packaging container were performed.

(Comparative Example 2)
According to the prior art, the top-coated surface of an alumina-deposited PET film (manufactured by Toray Film Processing Co., Ltd., trade name: 1011HG-CR) with a top coat having a thickness of 12 μm and a commercially available air corona-treated unstretched polypropylene (CPP) An anchor coating agent is applied to the surface of the resin film (unstretched polypropylene film manufactured by Toray Film Processing Co., Ltd., trade name; Trefan ZK207) so that it faces the air corona treated surface, and then on the surface that meets the top coat surface of the molten resin film. A molten resin film was extruded between different films while being treated with ozone, and then bonded (film sanded) with a cooling nip roll to obtain a packaging material laminate of Comparative Example 2 through aging. The packaging material laminate of Comparative Example 2 obtained had a measured peel strength of 15.0 N / 25.4 mm. Further, after preparing a packaging container for a four-sided seal bag using the obtained packaging material laminate of Comparative Example 2, various tests on the packaging container were performed.

Table 2 is a table summarizing the layer configurations of the packaging material laminates of Examples 1 to 2 and Comparative Examples 1 and 2. Table 3 shows the results of various tests performed on the packaging (packaging container) of the four-sided sealed bags of Examples 1 to 3 and Comparative Examples 1 and 2.
Comparative Example 2 is a test result of a packaging container produced by using a laminate produced by a film sand method using an anchor coating agent according to a conventional technique.

Examples 1 to 3 are test results of a package (packaging container) produced by using a package material laminate produced by a film sand method by surface modification. The test results of Examples 1 to 3 which are packaging containers by surface modification have the same or higher performance than the test results of Comparative Example 2 which is a packaging body (packaging container) produced by the prior art. Can be confirmed. Therefore, the packaging material laminate by surface modification has properties equal to or higher than those of the packaging material laminate by the film sand method using the anchor coating agent according to the prior art, and is a constituent material of the packaging body (packaging container). It is possible to use it without causing any problems.

In addition, a boil test was conducted on the packaging containers of Examples 1 to 3, and a retort test was conducted on the packaging containers of Examples 1 and 3. In each case, the phenomenon of delamination (peeling from the bonded surface) does not occur, and the durability is at a level that does not cause any problem in practical use.

Further, Table 4 shows a packaging container produced by using a laminate produced by a film sand method using an anchor coating agent according to a conventional technique, which is a packaging container produced by a film sand method with a base material width of 1,000 mm. This is the calculation of the amount of solvent (kg) required when processing 000 m.

The amount of solvent required for film sand processing using the anchor coating agent according to the prior art was 2.3 (kg). On the other hand, in the case of surface modification, since no anchor coating agent is used, it has become possible to prepare a packaging container without using any solvent.
Since no anchor coating agent is used, the residual solvent in the heat seal layer can be reduced, contamination of the contents can be prevented, and adverse effects on the components can be suppressed.

According to the present invention, a heat-adhesive modified layer of an atmospheric pressure plasma-treated film, which is necessary for obtaining a laminate bonded by a film sand to a film without using an adhesive and an anchor coating agent. By determining the quality of the formed state of the above, it becomes possible to effectively carry out the atmospheric pressure plasma treatment.
Further, according to the present invention, it is possible to obtain a method for producing a laminate bonded by a film sand, a laminate, and a packaging container produced by using the laminate without using an adhesive and an anchor coating agent.
The packaging material laminate according to the present invention can be used for various purposes such as decorative sheets, optical films, protective films, and packaging containers.
In addition, the packaging container produced by using the packaging material laminate according to the present invention includes boiled retort foods, liquid seasonings, liquid detergents, liquid bleaching agents, liquid waxes, hair care products (shampoo, rinse, conditioner, etc.). ), Chemicals, liquid cosmetics, and other packaging containers and refill packaging containers for products containing various liquids such as liquids or water, as well as boiled and retort foods, general foods, microwave-compatible foods, and electronic parts. , Can be used for various packaging containers such as medical parts, medical equipment parts, precision machine parts, etc.
In particular, it is suitably used as a packaging container material having heat treatment suitability for boil, retort, autoclave and the like.
Further, according to the present invention, it is possible to produce a laminate and a packaging container using the same without using an adhesive and an anchor coating agent, that is, without using an organic solvent at all. It is possible to solve the problems of low molecular weight components and residual solvents caused by adhesives and anchor coating agents, which can be sources of contamination, prevent contamination of the contents, and suppress adverse effects on the components. It is also effective as an environmental measure and an energy saving measure.

1 ... 1st base material, 2 ... 2nd base material, 3 ... thermoplastic resin film, 4 ... gas barrier layer, 5 ... top coat layer, 6 ... heat adhesive modification layer, 7 ... olefin film, 8 ... Air corona treatment layer, 9 ... Thermoplastic resin layer, 10 ... Packaging material laminate by surface modification, 11 ... Printing layer, 20 ... Packaging material laminate having printing layer, 21 ... Roll body of first base material, 22 ... 2nd base material roll, 23 ... air corona treatment device, 24 ... atmospheric pressure plasma treatment device, 25 ... cooling nip roll, 26 ... extrusion die, 27 ... molten resin film, 28 ... roll of packaging material laminate , 30 ... Packaging material laminate by anchor coating, 31 ... Anchor coating agent.

Claims (9)

Production of a packaging material laminate including one or more gas barrier layers selected from a thin layer of a metal oxide or an inorganic compound having a top coat layer on the surface of the thin film layer, and a thermoplastic resin layer made of a molten resin film. It's a method
The packaging material laminate is a second group composed of a first base material having heat-sealing properties exposed on one side thereof, and a thermoplastic resin film having the top coat layer and the gas barrier layer on the side adjacent thereto. The material is laminated through the thermoplastic resin layer without using an adhesive and an anchor coating agent, or a second material composed of a thermoplastic resin film having the top coat layer and the gas barrier layer. The thermoplastic resin layer is laminated on the side of the base material having the top coat layer and the gas barrier layer without using an adhesive and an anchor coat agent.
When the packaging material laminate contains the first base material and the second base material, these are used as a base film, and the packaging material laminate does not contain the first base material, and the second base material is not contained. When a base material is contained, the second base material is used as a base film.
At least one of the base films, each unwound from a roll of the base film made of a long film having a thickness of 10 to 500 μm and a length of 3 to 10,000 m, is at atmospheric pressure. It has a surface on which a heat-adhesive modified layer is formed by surface modification by a plasma processing device.
When the packaging material laminate contains the first base material and the second base material, the first base material and the first base material so as to include the surface on which the heat-adhesive modified layer is formed. The molten resin film is extruded between the first base material and the second base material without applying an adhesive and an anchor coating agent so that the second base material is opposed to the second base material. The surface of the film that meets at least one of the base films is continuously bonded with a cooling nip roll while being subjected to ozone treatment.
When the packaging material laminate contains the second base material without containing the first base material, an adhesive and an adhesive and an adhesive are applied to the surface of the second base material on which the heat-adhesive modified layer is formed. The feature is that the molten resin film is extruded without applying an anchor coating agent, and the molten resin film is continuously bonded with a cooling nip roll while being subjected to ozone treatment on the surface of the molten resin film to be combined with the second base material. Packaging material A method for manufacturing a laminate. The same or different type as the base film in which the heat-adhesive modified layer is formed by surface modification of the resin film using an atmospheric pressure plasma treatment device in advance when the base film is bonded. The surface on which the heat-adhesive modified layer of the base film was formed and the air corona-treated surface of the air-corona-treated reference film were formed by using the thermoplastic resin film of No. 1 and the air-corona-treated reference film. After obtaining a test laminate by thermocompression bonding without applying an adhesive and an anchor coating agent to face each other, the adhesive force on the bonding surface of the test laminate is measured to thermally bond the base film. The method for producing a laminate of packaging materials according to claim 1, wherein the quality of the formed state of the sex-modified layer is confirmed. A polyethylene terephthalate (PET) resin in which the base film on which a heat-adhesive modified layer is formed using an atmospheric pressure plasma treatment apparatus has a thin film layer of a metal oxide or an inorganic compound and a top coat layer on the surface of the thin film layer. A film or a polyamide (PA) resin film, which is an unstretched polyethylene (PE) resin film treated with air corona as the reference film, is held at a temperature of 160 ° C. and a pressing force of 0.4 MPa for 10 seconds and heat-bonded. The adhesive strength at the time is 5.9N / 25.4mm or more measured by the measuring method specified in JIS K 6854-1 "Adhesive peeling adhesive strength test method Part 1: 90 degree peeling". The process of confirming that,
The base film on which the heat-adhesive modified layer is formed using the atmospheric pressure plasma treatment apparatus is an unstretched polyethylene (PE) resin film, and the polyethylene terephthalate (PET) resin treated with air corona as the reference film. When a film is used and held at a temperature of 160 ° C and a pressing force of 0.4 MPa for 10 seconds and heat-bonded, the adhesive strength is JIS K 6854-1 "Adhesive peeling adhesive strength test method Part 1: 90 degree peeling. The step of confirming that the value measured by the measuring method specified in "" is 5.9 N / 25.4 mm or more,
The base film on which the heat-adhesive modified layer is formed using an atmospheric pressure plasma treatment apparatus is unstretched with unstretched polypropylene (CPP) resin film, cyclic polyolefin (COP or COC) resin film, or unstretched polyethylene. A polypropylene co-extruded film (PE / CPP), using an air corona-treated polyethylene terephthalate (PET) resin film as the reference film, holding at a temperature of 190 ° C. and a pressing force of 0.4 MPa for 10 seconds and heat-pressing. The adhesive strength at the time is 5.9N / 25.4mm or more as measured by the measuring method specified in JIS K 6854-1 "Adhesive peeling adhesive strength test method Part 1: 90 degree peeling". The method for producing a laminate of packaging materials according to claim 2, further comprising any of the steps of confirming that. It is characterized by including an aging step in which the obtained laminate is allowed to stand at room temperature for 10 days to 1 month or at 40 to 60 ° C. for 1 to 3 days after the bonding step of continuously bonding with the cooling nip roll. The method for producing a packaging material laminate according to any one of claims 1 to 3. The first base material is an unstretched polyethylene (PE) resin film, an unstretched polypropylene (CPP) resin film, a cyclic polyolefin (COP or COC) resin film, and a coextruded film of unstretched polyethylene and unstretched polypropylene (PE / It is one type selected from the olefin-based film group consisting of CPP).
The thermoplastic resin film contained in the second base material is a polyethylene terephthalate (PET) resin film, a polyamide (PA) resin film, a polyethylene naphthalate (PEN) resin film, a polyacrylonitrile (PAN) resin film, and a polycarbonate ( It is characterized by being one type selected from the group consisting of a PC) resin film, a polyimide (PI) resin film, a polyvinyl chloride (PVC) resin film, and an ethylene-vinyl alcohol copolymer (EVOH) resin film. The method for producing a laminate of packaging materials according to any one of claims 1 to 4. The method for producing a packaging material laminate according to any one of claims 1 to 5, wherein a printing layer is formed on at least one side of the film serving as the second base material. A packaging material laminate including one or more gas barrier layers selected from a thin layer of a metal oxide or an inorganic compound having a top coat layer on the surface of the thin film layer, and a thermoplastic resin layer made of a molten resin film. hand,
The packaging material laminate is a second group composed of a first base material having a heat-sealing property exposed on one side thereof, and a thermoplastic resin film having the top coat layer and the gas barrier layer on the side adjacent thereto. The top coat layer and the material of a second base material made of a material obtained by laminating materials without using an adhesive and an anchor coating agent, or a thermoplastic resin film having the top coat layer and the gas barrier layer. The thermoplastic resin layer is laminated on the side having the gas barrier layer without using an adhesive and an anchor coating agent.
When the packaging material laminate contains the first base material and the second base material, these are used as a base film, and the packaging material laminate does not contain the first base material, and the second base material is not contained. When a base material is contained, the second base material is used as a base film.
The base film is a long film having a thickness of 10 to 500 μm and a length of 3 to 10,000 m, and at least one of the base films is heated by surface modification by an atmospheric pressure plasma treatment apparatus. It has a surface on which an adhesive modification layer is formed,
When the packaging material laminate contains the first base material and the second base material, the first base material and the first base material so as to include the surface on which the thermoplastically modified layer is formed. The second base material is opposed to each other, and at least the base film of the thermoplastic resin layer is placed between the first base material and the second base material via the thermoplastic resin layer. The surface to be combined with one is ozone-treated and bonded without using adhesives and anchors.
When the packaging material laminate contains the second base material without containing the first base material, the thermoplasticity is formed on the surface on which the heat-adhesive modified layer of the second base material is formed. The packaging is characterized in that the resin layers are laminated, and the surface of the thermoplastic resin layer that meets with the second base material is treated with ozone and bonded without using an adhesive or an anchoring agent. Material laminate. The first base material is an unstretched polyethylene (PE) resin film, an unstretched polypropylene (CPP) resin film, a cyclic polyolefin (COP or COC) resin film, and a coextruded film of unstretched polyethylene and unstretched polypropylene (PE / It is one type selected from the olefin-based film group consisting of CPP).
The thermoplastic resin film contained in the second base material is a polyethylene terephthalate (PET) resin film, a polyamide (PA) resin film, a polyethylene naphthalate (PEN) resin film, a polyacrylonitrile (PAN) resin film, and a polycarbonate ( It is characterized by being one type selected from the group consisting of a PC) resin film, a polyimide (PI) resin film, a polyvinyl chloride (PVC) resin film, and an ethylene-vinyl alcohol copolymer (EVOH) resin film. The packaging material laminate according to claim 7. Using the packaging material laminate according to claim 7 or 8,
When the packaging material laminate contains the first base material and the second base material, the first base material is manufactured so as to be on the inner surface side as a sealant layer.
When the packaging material laminate contains the second base material without containing the first base material, the thermoplastic resin layer is manufactured so as to be on the inner surface side as a sealant layer. Packaging body.

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