JPH08230115A - Gas barrier paper laminate package - Google Patents

Abstract

PURPOSE: To give a gas barrier function sufficient adhesion strength and prevent a manufacturing process from becoming complex by surface oxidation treatment, ozone treatment, and crimping processes where relations as expressed by formulas I and II are valid. CONSTITUTION: If the base material of a gas barrier plastic base material layer D is a polyester resin or other than that, a surface oxidation treatment is given to both sides so that relations as expressed by formulas I and II (ΔO/C=O/ C*-O/C<0> ; O/C<0> , O/C* show the ratio of the number of atoms for oxygen and carbon atoms which are measured by the ESCA method before and after surface oxidation treatment. O/C<0> is a lower atom ratio and the reference plane of the base material). The package is obtained in a process where resin layers C, E for extruded laminates are melt and extruded into a film form at 180 deg.C to 340 deg.C and an ozone treatment is given to the plane where the film is adhered to the base material layer D and a process where a resin layer A for an extruded laminate, the paper base material layer B, the resin layer C for an extrusion laminate, the gas barrier plastic base material layer D, and the resin layer E for an extrusion laminate are crimped together.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas barrier paper laminated packaging container comprising a gas barrier paper laminated sheet laminated without using an anchor coating agent (hereinafter referred to as AC agent) and an adhesive resin. . The present invention also relates to a gas barrier paper laminated packaging container comprising a gas barrier paper laminated sheet excellent in low odor and the like when used in a specific place even if an AC agent or an adhesive resin is used.

[0002]

2. Description of the Related Art In recent years, the development of packaging materials for packaging foods, industrial materials, etc. has made remarkable progress, and as a result, for example, foods can be stored for a long period of time. These packaging materials
Properties such as plastic, paper, metal, etc. that cannot be possessed by laminating film-like molded products of different materials such as strength, gas barrier property, moisture resistance, heat sealing property, appearance,
It is composed of laminated sheets that complement the shape, and is designed as a composite material that combines the advantages of each material.

As a method for producing such a laminated sheet, there are, for example, a dry lamination method, a wet lamination method, a hot lamination method, an extrusion lamination method and a coextrusion lamination method, which are applied according to their characteristics. .. In packaging materials and the like, when forming a heat-sealing layer on a base material or when sticking base materials to each other, an extrusion lamination method or a sandwich extrusion lamination method, which is advantageous in terms of cost, is widely used. As a heat seal layer and a sandwich layer,
For example, polyolefin resins such as polyethylene, polypropylene and ethylene copolymers, ionomer resins, etc. are generally used, but much larger amounts of polyolefin resins are used from the viewpoint of cost.

Containers made of laminated materials manufactured by these methods can be remarkably lighter than containers made of metal or glass material, and greatly reduce energy consumption in a physical distribution process, for example. It has been useful. However, these containers are usually called one-way type, and they are disposable containers that can be used only once and cannot be reused.

However, due to the increasing awareness of global environmental protection in recent years, there has been a demand for reuse of resources, and it has been strongly developed to collect the used containers, sort them by the constituent materials, and reuse the resources. It has been requested. However, for example, in order to impart a gas barrier property and a light blocking function, a composite type container formed by using an aluminum foil as an intermediate layer of a packaging material is used, but it is laminated between a paper base material and a resin layer. Not only is it difficult to separate and collect the aluminum foil easily, but when incinerating a used container containing aluminum foil, a large amount of ash is generated, which may damage the incinerator, which requires landfill treatment. There was a problem that it was difficult to recover the resources themselves.

For this reason, various containers have been developed which use paper having a superior gas barrier property as a main base material without using a metal foil film such as an aluminum foil. For example, a container formed from a packaging material having a five-layer constitution of a polyethylene resin layer / paper layer / adhesive resin layer / ethylene-vinyl alcohol copolymer layer / polyethylene resin layer from the outside of the container (Japanese Patent Laid-Open No. 63-121143). Gazette), formed from the outside of the container with a packaging material having a seven-layer structure of polyethylene resin layer / paper layer / adhesive resin layer / ethylene-vinyl alcohol copolymer layer / nylon resin layer / adhesive resin layer / polyethylene resin layer. Container (see Japanese Patent Application Laid-Open No. 2-160551), and the surface of the polyethylene resin layer of the material in which the paper layer / polyethylene resin layer is laminated is treated with an AC agent, and the surface is treated with an adhesive resin and a nylon resin. A structure in which polyethylene resin is laminated by coextrusion lamination molding, or A
Instead of bonding using the agent C, a gas barrier resin layer produced in a step different from the laminating step is used as an intermediate layer, and a polyethylene resin layer is provided on both outer layers through an adhesive resin layer as a multilayer. A container (see JP-A-5-50564) has been developed in which a film product and a laminate material of a paper layer / polyethylene resin layer are laminated by sandwich extrusion lamination.

However, for example, in the method of using an AC agent for molding a sealant that comes into contact with the contents to be packaged, AC agent components such as an organic solvent remain on the sheet and the resulting odor causes the sheet to be used for food packaging. There was a problem of limiting the application to such cases.

As a method of laminating on a plastic substrate without using these AC agents, (a) ethylene, (b) unsaturated polybasic acid, (c) acrylic acid lower alkyl ester, methacrylic acid lower alkyl ester,
The ethylene-based copolymer obtained by copolymerizing an unsaturated monomer selected from vinyl ester is melt-kneaded,
It is reported that a laminate is produced by extruding a film at a temperature of 330 ° C., subjecting the film to ozone treatment, and then pressure-bonding the ozone-treated surface to a base material as an adhesive surface to form a laminate (Japanese Patent Application Laid-Open No. 4-410). 368845). However, the method of using an ethylene-based copolymer having an adhesive function, which uses an unsaturated polybasic acid as a comonomer component, has a roll-releasing property at the time of extrusion lamination processing due to the manufacturing cost and the increase of the low melting point component. In addition to being restricted by the processing temperature and the like, it is not preferable because the resin change in the extruder is complicated.

Further, the ethylene-α-olefin copolymer is subjected to ozone treatment on the adhesive surface to the base material using a known ozone treatment device, and pressure-bonded to the base material without applying an AC agent to obtain a laminate. Or a method of producing a laminate or using an adhesive resin obtained by graft-modifying an unsaturated carboxylic acid or the like with a polyolefin-based resin to produce a laminate by pressureless laminating to a base material in combination with a coextrusion laminating device. Methods have been reported (Convertec (8), 3rd
Page 6, 1991). However, the adhesive strength between the laminate resin and the base material of the laminate obtained by these methods is not sufficient, and its application range is restricted. Furthermore, in the method of using an adhesive resin obtained by graft-modifying an unsaturated carboxylic acid or the like on a polyolefin resin, not only the coextrusion apparatus is required and the manufacturing cost is increased, but also the trouble of changing the resin in the extruder is complicated. This is not preferable.

[0010]

Generally, the basic structure of a container mainly composed of these paper base materials and having a gas barrier property is to provide a polyolefin resin layer, a paper base material, and a polyolefin resin from the outside of the container. It has a five-layer structure including a layer, a gas barrier resin layer, and a polyolefin resin layer. But,
The interlayer adhesion between the resin layer having a gas barrier function and the sealant resin layer using a non-polar polyolefin resin such as polyethylene is such that it can be practically used even if the coextrusion laminating method is used. Since sufficient adhesive strength cannot be obtained, an expensive adhesive resin that has the function of adhering to both resins is required, or after applying an AC agent to a gas barrier plastic substrate, polyethylene resin, etc. It is necessary to extrusion laminate the sealant resin of. The sealant resin is the innermost layer resin that comes into contact with the object to be packaged.

Furthermore, as another method for laminating a gas barrier resin layer on a paper base material, at least five layers in which a gas barrier resin layer is used as an intermediate layer and a polyethylene resin is disposed on both outer layers via an adhesive layer are provided. There is a method in which a coextrusion-molded multilayer film product is manufactured in a step different from the laminating step and is laminated by a sandwich extrusion minate method with a paper base material and a polyethylene resin interposed therebetween. However, these manufacturing methods require not only a multi-layer coextrusion laminating apparatus in terms of processing equipment and a multi-layer film forming machine of at least 5 layers including a gas barrier resin layer in the film manufacturing step, but also a laminating machine. The manufacturing process of the product is very complicated and the productivity is poor.

The present invention has been made based on the above-mentioned circumstances, and an object of the present invention is to combine a gas barrier function and a sufficient adhesive strength, and at a low cost without complicating the manufacturing process. A gas barrier paper laminated packaging container that can be manufactured and has a reduced odor by using an AC agent or an adhesive resin in a specific place, and does not include an aluminum foil in the constituent materials. It is intended to provide a gas barrier paper laminated packaging container having excellent recyclability of paper resources.

[0013]

In view of the present situation, the present inventors have made a gas barrier paper laminated packaging container comprising a gas barrier paper laminated sheet which does not use an adhesive resin and an anchor coating agent, or an adhesive resin. And a gas barrier paper laminated packaging container consisting of a gas barrier paper laminated sheet which is excellent in low odor even when an anchor coating agent is used. As a result, a paper base material, a gas barrier plastic base material and a resin for extrusion laminating are used. A gas barrier paper produced by a specific surface oxidation treatment step, ozone treatment step and pressure bonding step without using an AC agent and an adhesive resin that cause odors The present invention has been completed by finding a gas barrier paper laminated packaging container comprising a laminated sheet. Further, even when the present invention uses the AC agent or the adhesive resin, the present invention specifies the location to be used, and from the specific surface oxidation treatment step, ozone treatment step and pressure bonding step in forming the sealant. Finding a gas barrier paper laminated packaging container comprising the produced gas barrier paper laminated sheet,
The present invention has been completed.

That is, according to the present invention, (A) a resin layer for extrusion lamination, (B) a paper base layer, (C) a resin layer for extrusion lamination, (D) a gas barrier plastic base layer and (E) extrusion. A gas barrier paper laminated sheet comprising at least five laminating resin layers, the gas barrier property being obtained by the following (X) surface oxidation treatment step, (Y) ozone treatment step and (Z) pressure bonding step. A gas barrier paper laminated packaging container comprising a paper laminated sheet is provided. (X) Surface oxidation treatment step (D) Step of subjecting both surfaces of the gas barrier plastic base material layer to surface oxidation treatment. (Y) Ozone treatment step (C) Extrusion laminating resin layer and (E) Extrusion laminating resin layer are melt extruded into a film at a temperature of 180 to 340 ° C., and the film is (D) gas barrier plastic substrate layer. A step of applying ozone treatment to the surface to be bonded. (Z) Pressure bonding step (A) Extrusion laminating resin layer, (B) Paper base material layer,
(C) Extrusion laminating resin layer, (D) Gas barrier plastic base material layer, and (E) Extrusion laminating resin layer are pressure-bonded. A step in which the relationship represented by the following formula is established for the surface oxidized surface. When the gas barrier plastic substrate is a polyester resin Δ (O / C) ≧ 0.08 When the gas barrier plastic substrate is other than a polyester resin Δ (O / C) ≧ 0.05 where Δ (O / C) = (O / C) ^* -(O / C) ⁰ , where (O / C) ⁰ is the surface of the gas barrier plastic substrate before the surface oxidation treatment of the present invention, E
The surface having the smaller value represented by the ratio of the number of oxygen atoms and the number of carbon atoms measured by the SCA method was used as the reference surface of the base material, and (O / C) of this surface was defined as (O / C) of the base material. / C) ⁰ is defined. Further, (O / C) ^* represents the ratio of the number of oxygen atoms to the number of carbon atoms measured by the ESCA method on the surface of the gas barrier plastic substrate having the surface subjected to the surface oxidation treatment of the present invention.

The present invention also includes (A) a resin layer for extrusion laminating, (B) a paper base layer, (C) a resin layer for extrusion laminating, (D) a gas barrier plastic base layer, and (E).
A gas barrier paper laminated sheet comprising at least 6 layers of a resin layer for extrusion laminating and an original film substrate layer (F), which comprises the following (X) surface oxidation treatment step:
The present invention provides a gas barrier paper laminated packaging container comprising a gas barrier paper laminated sheet obtained by (Y) ozone treatment step and (Z) pressure bonding step. (X) Surface oxidation treatment step (D) Step of subjecting both surfaces of the gas barrier plastic base material layer to surface oxidation treatment. (Y) Ozone treatment step (C) Extrusion laminating resin layer and (E) Extrusion laminating resin layer are melt extruded into a film at a temperature of 180 to 340 ° C., and the film is (D) gas barrier plastic substrate layer. A step of applying ozone treatment to the surface to be bonded. (Z) Pressure bonding step (A) Extrusion laminating resin layer, (B) Paper base material layer,
A step of pressure-bonding (C) resin layer for extrusion lamination, (D) gas barrier plastic substrate layer, (E) resin layer for extrusion lamination and (F) film original substrate layer,
A step in which the relationship represented by the following formula is established with respect to the surface oxidation treated surface of the gas barrier plastic base material layer subjected to pressure bonding (D). When the gas barrier plastic substrate is a polyester resin Δ (O / C) ≧ 0.08 When the gas barrier plastic substrate is other than a polyester resin Δ (O / C) ≧ 0.05 where Δ (O / C) = (O / C) ^* -(O / C) ⁰ , where (O / C) ⁰ is the surface of the gas barrier plastic substrate before the surface oxidation treatment of the present invention, E
The surface having the smaller value represented by the ratio of the number of oxygen atoms and the number of carbon atoms measured by the SCA method was used as the reference surface of the base material, and (O / C) of this surface was defined as (O / C) of the base material. / C) ⁰ is defined. Further, (O / C) ^* represents the ratio of the number of oxygen atoms to the number of carbon atoms measured by the ESCA method on the surface of the gas barrier plastic substrate having the surface subjected to the surface oxidation treatment of the present invention.

The present invention also includes (A) a resin layer for extrusion lamination, (B) a paper base layer, (C) a resin layer for extrusion lamination, (D) a gas barrier plastic base layer, and (E) extrusion. A gas-barrier paper laminated sheet comprising at least 5 layers of laminating resin layers, comprising (D)
An anchor coating agent is applied to the surface of the gas barrier plastic substrate layer that is to be bonded to the resin layer for extrusion lamination (C), and the following (X) surface oxidation treatment step, (Y) ozone treatment step and (Z) pressure bonding step are performed. The present invention provides a gas barrier paper laminated packaging container comprising the gas barrier paper laminated sheet obtained by the above. (X) Surface Oxidation Treatment Step (D) A step of subjecting the gas barrier plastic substrate (E) to the surface to be bonded to the resin layer for extrusion laminating, to a surface oxidation treatment. (Y) Ozone treatment step (E) The resin layer for extrusion lamination is melt extruded into a film at a temperature of 180 to 340 ° C., and the surface where the film adheres to the (D) gas barrier plastic substrate layer is subjected to ozone treatment. Process. (Z) Pressure bonding step (A) Extrusion laminating resin layer, (B) Paper base material layer,
(C) Extrusion laminating resin layer, (D) Gas barrier plastic base material layer, and (E) Extrusion laminating resin layer are pressure-bonded. A step in which the relationship represented by the following formula is established for the surface oxidized surface. When the gas barrier plastic substrate is a polyester resin Δ (O / C) ≧ 0.08 When the gas barrier plastic substrate is other than a polyester resin Δ (O / C) ≧ 0.05 where Δ (O / C) = (O / C) ^* -(O / C) ⁰ , where (O / C) ⁰ is the surface of the gas barrier plastic substrate before the surface oxidation treatment of the present invention, E
The surface having the smaller value represented by the ratio of the number of oxygen atoms and the number of carbon atoms measured by the SCA method was used as the reference surface of the base material, and (O / C) of this surface was defined as (O / C) of the base material. / C) ⁰ is defined. Further, (O / C) ^* represents the ratio of the number of oxygen atoms to the number of carbon atoms measured by the ESCA method on the surface of the gas barrier plastic substrate having the surface subjected to the surface oxidation treatment of the present invention.

The present invention also includes (A) a resin layer for extrusion lamination, (B) a paper base layer, (C) a resin layer for extrusion lamination, (D) a gas barrier plastic base layer, and (E).
A gas barrier paper laminated sheet comprising at least 6 layers of an extrusion laminating resin layer and a (F) original film base material layer, wherein (D) gas barrier plastic base material layer (C) for extrusion laminating Gas barrier property obtained by applying an anchor coating agent on the surface to be adhered to the resin layer and obtained by the following (X) surface oxidation treatment step, (Y) ozone treatment step and (Z) pressure bonding step A paper laminated packaging container is provided. (X) Surface oxidation treatment step (D) A step of subjecting the gas barrier plastic base material layer (E) to the surface to be adhered to the resin layer for extrusion laminating, a surface oxidation treatment. (Y) Ozone treatment step (E) The resin layer for extrusion lamination is melt extruded into a film at a temperature of 180 to 340 ° C., and the surface where the film adheres to the (D) gas barrier plastic substrate layer is subjected to ozone treatment. Process. (Z) Pressure bonding step (A) Extrusion laminating resin layer, (B) Paper base material layer,
A step of pressure-bonding (C) resin layer for extrusion lamination, (D) gas barrier plastic substrate layer, (E) resin layer for extrusion lamination and (F) film original substrate layer,
A step in which the relationship represented by the following formula is established with respect to the surface oxidation treated surface of the gas barrier plastic base material layer subjected to pressure bonding (D). When the gas barrier plastic substrate is a polyester resin Δ (O / C) ≧ 0.08 When the gas barrier plastic substrate is other than a polyester resin Δ (O / C) ≧ 0.05 where Δ (O / C) = (O / C) ^* -(O / C) ⁰ , where (O / C) ⁰ is the surface of the gas barrier plastic substrate before the surface oxidation treatment of the present invention, E
The surface having the smaller value represented by the ratio of the number of oxygen atoms and the number of carbon atoms measured by the SCA method was used as the reference surface of the base material, and (O / C) of this surface was defined as (O / C) of the base material. / C) ⁰ is defined. Further, (O / C) ^* represents the ratio of the number of oxygen atoms to the number of carbon atoms measured by the ESCA method on the surface of the gas barrier plastic substrate having the surface subjected to the surface oxidation treatment of the present invention.

The present invention also includes (A) a resin layer for extrusion lamination, (B) a paper base layer, (C ') an adhesive resin layer,
A gas barrier paper laminated sheet comprising at least five layers of (D) a gas barrier plastic base material layer and (E) a resin layer for extrusion laminating, comprising the following (X) surface oxidation treatment step and (Y) A gas barrier paper laminated packaging container comprising a gas barrier paper laminated sheet obtained by an ozone treatment step and a (Z) pressure bonding step. (X) Surface Oxidation Treatment Step (D) A step of subjecting the gas barrier plastic substrate (E) to the surface to be bonded to the resin layer for extrusion laminating, to a surface oxidation treatment. (Y) Ozone treatment step (E) The resin layer for extrusion lamination is melt extruded into a film at a temperature of 180 to 340 ° C., and the surface where the film adheres to the (D) gas barrier plastic substrate layer is subjected to ozone treatment. Process. (Z) Pressure bonding step (A) Extrusion laminating resin layer, (B) Paper base material layer,
A step of pressure-bonding (C ′) the adhesive resin layer, (D) the gas-barrier plastic base material layer, and (E) the resin layer for extrusion laminating, which comprises subjecting the (D) gas-barrier plastic base material layer to pressure-bonding. A step in which the relationship represented by the following formula is established for the surface oxidized surface. When the gas barrier plastic substrate is a polyester resin Δ (O / C) ≧ 0.08 When the gas barrier plastic substrate is other than a polyester resin Δ (O / C) ≧ 0.05 where Δ (O / C) = (O / C) ^* -(O / C) ⁰ , where (O / C) ⁰ is the surface of the gas barrier plastic substrate before the surface oxidation treatment of the present invention, E
The surface having the smaller value represented by the ratio of the number of oxygen atoms and the number of carbon atoms measured by the SCA method was used as the reference surface of the base material, and (O / C) of this surface was defined as (O / C) of the base material. / C) ⁰ is defined. Further, (O / C) ^* represents the ratio of the number of oxygen atoms to the number of carbon atoms measured by the ESCA method on the surface of the gas barrier plastic substrate having the surface subjected to the surface oxidation treatment of the present invention.

The present invention also includes (A) a resin layer for extrusion lamination, (B) a paper base layer, (C ') an adhesive resin layer,
A gas barrier paper laminated sheet comprising at least 6 layers of (D) a gas barrier plastic base material layer, (E) a resin layer for extrusion laminating and (F) an original film base material layer, comprising: Provided is a gas barrier paper laminated packaging container comprising a gas barrier paper laminated sheet obtained by (X) surface oxidation treatment step, (Y) ozone treatment step and (Z) pressure bonding step. (X) Surface oxidation treatment step (D) A step of subjecting the gas barrier plastic base material layer (E) to the surface to be adhered to the resin layer for extrusion laminating, a surface oxidation treatment. (Y) Ozone treatment step (E) The resin layer for extrusion lamination is melt extruded into a film at a temperature of 180 to 340 ° C., and the surface where the film adheres to the (D) gas barrier plastic substrate layer is subjected to ozone treatment. Process. (Z) Pressure bonding step (A) Extrusion laminating resin layer, (B) Paper base material layer,
(C ') adhesive resin layer, (D) gas barrier plastic substrate layer, (E) extrusion laminating resin layer, and (F)
A step of pressure-bonding the raw film base material layer, wherein the relationship represented by the following formula is established for the surface oxidation treated surface of the gas barrier plastic base material layer (D) subjected to pressure bonding. When the gas barrier plastic substrate is a polyester resin Δ (O / C) ≧ 0.08 When the gas barrier plastic substrate is other than a polyester resin Δ (O / C) ≧ 0.05 where Δ (O / C) = (O / C) ^* -(O / C) ⁰ , where (O / C) ⁰ is the surface of the gas barrier plastic substrate before the surface oxidation treatment of the present invention, E
The surface having the smaller value represented by the ratio of the number of oxygen atoms and the number of carbon atoms measured by the SCA method was used as the reference surface of the base material, and (O / C) of this surface was defined as (O / C) of the base material. / C) ⁰ is defined. Further, (O / C) ^* represents the ratio of the number of oxygen atoms to the number of carbon atoms measured by the ESCA method on the surface of the gas barrier plastic substrate having the surface subjected to the surface oxidation treatment of the present invention.

The present invention also provides a gas barrier paper laminated packaging container for liquid foods or wet foods, and a non-food packaging container for industrial chemicals or industrial materials.

The present invention will be described in detail below. Examples of the (D) gas barrier plastic substrate used in the present invention include ethylene-vinyl alcohol copolymer (hereinafter referred to as EVOH), polyvinyl alcohol resin (hereinafter referred to as PVA), acrylonitrile resin,
Vinylidene chloride resin (hereinafter referred to as PVDC), nylon resin (hereinafter referred to as Ny), polyester resin (hereinafter referred to as PET), polyarylate resin, polychlorotrifluoroethylene resin and polyfluorination At least one resin selected from vinylidene resins can be used. Among these, EVOH, PVA, P
VDC, Ny and PET are preferred.

These base materials may be a simple substance, or may be a multi-layer laminate laminated with another resin by a coextrusion molding method, a dry lamination method or the like, and the above resin serves as a surface layer. Any base material may be used. As the laminate, for example, a two-kind two-layer laminate composed of EVOH and Ny, EV
A two-kind and three-layer laminate composed of OH, Ny, and EVOH, E
At least one kind of laminated body selected from a laminated body of three kinds and three layers composed of VOH, an adhesive resin and a polyethylene resin and a laminated body of two kinds and three layers composed of Ny, EVOH and Ny can be mentioned. The shape of these base materials may be a film or sheet shape, or a stretched product thereof.

The (D) gas-barrier plastic substrate used in the present invention is obtained by coating the above-mentioned resin having a gas-barrier function in the form of an emulsion or a solvent on at least one surface of another plastic material to form a gas. It may be a base material having a further improved barrier property or a base material having a new gas barrier property. That is, (D) the gas barrier plastic substrate was coated with a resin coated with an emulsion containing PVDC as a main component, a resin coated with an emulsion containing PVA as a main component, and an emulsion containing EVOH as a main component. Examples include base materials selected from resins. Examples of the (D) gas-barrier plastic substrate coated with an emulsion containing PVDC as a main component (hereinafter, the coated surface is referred to as K) include KNy, KPET, and KP.
Examples thereof include VA and KOPP (biaxially oriented polypropylene) KPT (cellophane). Similarly, an emulsion containing PVA as a main component is applied (hereinafter, the applied surface is referred to as P).
As the (D) gas barrier plastic substrate,
Examples thereof include PPET and POPP. further,
Examples of the (D) gas barrier plastic substrate coated with an emulsion containing EVOH as a main component (hereinafter, the coated surface is referred to as E) include ENy, EPET, and EOPP.

Further, the (D) gas-barrier plastic substrate used in the present invention has one or both surfaces of the gas-barrier plastic substrate, such as silica (SiO _x ), and oxide, in order to further improve the gas barrier property. Zinc (Z
(nO) or a glass material or a metal material such as nickel, chromium or aluminum may be vapor-deposited to a thickness of several tens to several thousand angstroms to physically provide a gas barrier property. Examples of such a base material include silica vapor deposition PET, silica vapor deposition Ny, silica vapor deposition EVOH, aluminum vapor deposition PET, and aluminum vapor deposition Ny.

(D) Gas barrier property used in the present invention, the gas barrier property of the plastic base material varies depending on the function originally possessed by the resin, the function of the coating material, the function of the vapor deposition material, etc., but the oxygen transmission amount is preferably 100 cc. / M ² · 24
Hr · atm or less, more preferably 10 cc / m ² ·
A material having a performance of 24 Hr · atm or less is preferable.

These (D) gas barrier plastic base materials may be coated with a coating agent that promotes easy adhesion in order to impart printability, adhesiveness, vapor deposition property and the like to at least one surface. . In addition, the (D) gas barrier plastic substrate may be subjected to surface treatment such as corona discharge treatment, plasma treatment, or flame treatment in advance on one side or both sides, if necessary.

The wall thickness of the gas barrier plastic substrate used in the present invention is not particularly limited as long as it does not cause any inconvenience in the extrusion lamination process or the container manufacturing process, but is preferably 3 to 40 μm, Preferably 5
A range of 20μ is preferable.

The (B) paper base material used in the present invention includes, for example, bleached wrapping paper and unbleached wrapping paper, and examples of the bleached wrapping paper include pure white roll paper and bleached kraft paper.

The weight of the paper base material used in the present invention is not particularly limited as long as it has a function as a packaging material and is suitable as a base material for extrusion lamination, but preferably 100 to 100. 600 g / m ^2, even more preferably in the range of 150~500g / m ^2. Further, the paper base material used in the present invention may be printed.

Extrusion laminating resins used as (A), (C) and (E) of the present invention are polyethylene resins,
It is at least one resin selected from polypropylene-based resins, ethylene-vinyl ester-based copolymer resins, and ethylene- (meth) acrylic acid ester-based copolymer resins. Furthermore, if necessary, other resins may be mixed in a range of less than 50% by weight. (A), (C) and (E)
The resin for extrusion laminating is properly used depending on the function of the resin such as processability, heat resistance, easy heat sealability, moisture resistance, oil resistance, and chemical resistance, and the property of the object to be packaged.

(A), (C) and (E) used in the present invention
The resin for extrusion laminating may be a single layer or a multilayer of two or more layers. In the case of two or more layers, the same resin may be used, or a combination of different resins that are resins for extrusion laminating may be used. In addition, (E)
Even if the resin for extrusion laminating is a multi-layer using the same resin, it is treated as one layer because of its structure.

The (F) film raw substrate used in the present invention is a polyethylene resin, a polypropylene resin, an ethylene-vinyl ester copolymer resin and an ethylene-based resin similar to the resins mentioned in the resin for extrusion lamination. It is at least one resin selected from (meth) acrylic acid ester-based copolymer resins, as long as these are film-formed, and particularly suitable as a substrate for sandwich extrusion lamination. However, the thickness is preferably 10 to 80 μm, more preferably 15 to 60 μm.

The resins mentioned in (A), (C), (E) and (F) will be described respectively. The production method of the polyethylene-based resin is not limited, and it can be produced by, for example, a radical polymerization method or an ionic polymerization method. Examples of the polyethylene-based resin include low-density polyethylene produced by radical polymerization, high-density polyethylene produced by ionic polymerization, and ethylene-α-olefin obtained by copolymerizing ethylene and α-olefin. Examples thereof include copolymers. Examples of the α-olefin include propylene, butene-1, 4-methylpentene-1,
C3-C18 α-olefins such as hexene-1, octene-1, decene-1, and octadecene-1 are used, and these α-olefins can be used alone or in combination of two or more. The content of the α-olefin contained in the ethylene-α-olefin copolymer is preferably 1 to 30.
%, And more preferably 5 to 20% by weight.

The production method of the polypropylene resin is not limited, and it can be produced by, for example, an ionic polymerization method. Examples of the polypropylene-based resin include a homopolymer of propylene or a copolymer of propylene and α-olefin such as a copolymer of propylene and ethylene or butene-1. The α-olefin copolymerized with propylene may be used alone or in combination of two or more. The content of α-olefin contained in the propylene-α-olefin copolymer is preferably 0.1.
-40% by weight, more preferably 1-30% by weight.

The ethylene-vinyl ester-based copolymer resin and the ethylene- (meth) acrylic acid ester-based copolymer resin can be produced by a radical polymerization method, and are obtained by copolymerizing ethylene and a radically polymerizable monomer. To be

Examples of the vinyl ester of the ethylene-vinyl ester copolymer include vinyl acetate, vinyl propionate and vinyl neoate.

Examples of the (meth) acrylic acid ester of the ethylene- (meth) acrylic acid ester type copolymer include methyl acrylate, ethyl acrylate and acrylic acid n.
-Propyl, isopropyl acrylate, acrylic acid n-
Acrylic esters such as butyl, t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, methacrylic acid Examples of the methacrylic acid ester such as isobutyl include unsaturated carboxylic acid esters having 4 to 8 carbon atoms. These comonomers may be used alone or in combination of two or more.

The content of the comonomer component contained in the ethylene-vinyl ester copolymer and the ethylene- (meth) acrylic acid ester copolymer is preferably 30% by weight or less, more preferably 20% by weight or less. .

From the standpoint of processability, the melt flow rate (M) at 190 ° C. for polyethylene resin, ethylene-vinyl ester copolymer resin and ethylene- (meth) acrylic acid ester copolymer resin.
FR) is preferably in the range of 1 to 100 g / 10 minutes, and for polypropylene resins, 230 ° C.
It is preferable that the MFR in is in the range of 1 to 100 g / 10 minutes.

The AC agent used in the present invention is not particularly limited, and examples thereof include those commonly used.
For example, an organic titanate-based adhesive, an organic isocyanate-based adhesive, a polyethyleneimine-based adhesive, or the like can be used.

The method for producing the adhesive resin used in the present invention is not limited, and it can be produced by, for example, a radical polymerization method or a graft polymerization method. Examples of the adhesive resin that can be produced by the radical polymerization method include a copolymer of ethylene and an unsaturated polybasic acid, a copolymer of ethylene, an unsaturated polybasic acid and acrylic acid lower alkyl ester, an ethylene and an unsaturated polybasic acid. Examples thereof include a copolymer of a basic acid and a methacrylic acid lower alkyl ester, a copolymer of ethylene, an unsaturated polybasic acid and a vinyl ester. Specifically, ethylene (hereinafter referred to as E) and maleic anhydride (hereinafter referred to as MAH
Copolymer) and ethyl acrylate (hereinafter referred to as EA), ethylene, maleic anhydride and methyl acrylate (hereinafter referred to as MA), ethylene and acrylic acid (hereinafter referred to as AA) ) Copolymer, ethylene and methacrylic acid (hereinafter referred to as MAA)
And the like. Further, ionomer resins obtained by partially or completely neutralizing these adhesive resins with metal ions such as zinc and sodium can be mentioned. Further, as the adhesive resin that can be produced by the graft polymerization method,
For example, a resin obtained by graft-polymerizing maleic anhydride or the like with a polyolefin resin such as polyethylene or polypropylene to give an adhesive function can be used.

From the viewpoint of workability, the adhesive resin is
Melt flow rate (MFR) at 190 ° C is 1 to
It is preferably in the range of 100 g / 10 minutes.

In the surface oxidation treatment step of the present invention, both surfaces of the (D) gas barrier plastic base material are subjected to surface oxidation treatment so that the adhesive surface of the (D) gas barrier plastic base material is oxidized to a certain level or higher. Generate activation points,
This is a process that enables strong adhesion. Here, regarding the oxidation activation point above the certain level, Δ (O /
C).

The surface oxidation treatment step is specifically carried out by a corona treatment step, a plasma treatment step, a flame plasma treatment step, an electron beam irradiation treatment step, an ultraviolet ray irradiation treatment step and the like. Details will be described later.

In the ozone treatment step of the present invention, when the (B) paper base material and the (D) gas barrier plastic base material are laminated, the (C) extrusion laminating resin is melt-extruded into a film to obtain a film ( D) This is a step of subjecting the adhesive surface to the gas barrier plastic substrate to ozone treatment. When the ozone treatment step of the present invention is a laminate of (D) a gas barrier plastic substrate and a (E) resin for extrusion laminating that serves as a sealant in contact with an article to be packaged, (E) a resin for extrusion laminating is formed into a film. In this step, the film is melt-extruded into a uniform shape, and the surface of the film (D) that is adhered to the gas barrier plastic substrate is subjected to ozone treatment. Further, in the ozone treatment step of the present invention, a sandwich extrusion lamination method using (E) a resin for extrusion lamination is used for laminating (D) a gas barrier plastic substrate and (F) a film original substrate layer. This is a step of melt-extruding a resin for extrusion laminating into a film shape, and subjecting the adhesive surface of the film (D) to the plastic substrate having a gas barrier property to ozone treatment.

The location where the AC agent is used in the present invention is the surface of the (D) gas barrier plastic substrate (C) which is bonded to the resin layer for extrusion laminating.
After the AC agent is applied to the (D) gas barrier plastic base material layer, it can be laminated by the sandwich extrusion lamination method with the (B) paper base material layer using the extrusion laminate resin as the intermediate layer. The location where the adhesive resin is used in the present invention is between the (D) gas barrier plastic base material layer and the (B) paper base material layer. As the laminating method, the adhesive resin is used as the intermediate layer (B). The paper substrate layer and the (D) gas barrier plastic substrate layer can be laminated by the sandwich extrusion lamination method. When an adhesive resin is used, the surface of the (D) gas barrier plastic base material that is to be adhered to the adhesive resin is preferably subjected to surface treatment such as corona treatment.

The ozone treatment is carried out, for example, by blowing a gas containing ozone (for example, air) from a nozzle provided in an air gap under the T-die or a slit-shaped blowout port onto the molten film. When the ozone nozzle cannot be installed under the T-die, it may be sprayed onto the gas barrier plastic substrate immediately before pressure-bonding and laminating. The amount of ozone sprayed is preferably 1 mg / m ² or more, and more preferably 5 mg / m ² or more per unit area of passage of the molten film. The temperature at which the resin for extrusion lamination is melt extruded into a film is 18
The temperature is 0 to 340 ° C, preferably 210 to 330 ° C. If the temperature is less than 180 ° C., the spreadability of the resin will be poor,
Not only is it difficult to obtain a molten thin film having a uniform wall thickness, but also the adhesive strength with the gas barrier plastic substrate becomes insufficient. On the other hand, when the gas barrier plastic substrate and the innermost layer sealant resin are pasted together, if the resin temperature exceeds 340 ° C., the surface oxidation of the molten resin will increase and the odor of the laminate film will deteriorate, making it suitable for food packaging applications. If used, it may be subject to restrictions.

In the pressure-bonding step of the present invention, the surface-oxidized surface of the (D) gas barrier plastic substrate obtained in the surface-oxidized step is brought into contact with the ozone-treated surface of the film obtained in the ozone-treatment step. In the step of pressure-bonding the film and the (D) gas-barrier plastic base material, the relationship represented by the following formula is established for the surface-oxidized surface of the (D) gas-barrier plastic base material subjected to the pressure-bonding. It is a process. (1) When the gas barrier plastic substrate is a polyester resin Δ (O / C) ≧ 0.08 (2) When the gas barrier plastic substrate is other than a polyester resin Δ (O / C) ≧ 0. 05 where Δ (O / C) = (O / C) ^* − (O / C) ⁰ , where (O / C) ⁰ is the gas barrier plastic before the surface oxidation treatment of the present invention. E of the substrate surface
The surface having the smaller value represented by the ratio of the number of oxygen atoms and the number of carbon atoms measured by the SCA method is the reference surface of the base material, and the (O / C) of the reference surface is the (O / C) of the base material. O / C) ⁰ . Further, (O / C) ^* represents the ratio of the number of oxygen atoms to the number of carbon atoms measured by the ESCA method on the surface of the gas barrier plastic substrate having the surface subjected to the surface oxidation treatment of the present invention.

The (O / C) ^* of the gas barrier plastic substrate is a value measured 30 minutes after the resin of the present invention is laminated by extrusion lamination or sandwich extrusion lamination. However, in the actual measurement, a gas barrier plastic base material that is not subjected to the extrusion laminating or sandwich extrusion laminating step is prepared separately, and the base material is subjected to surface oxidation treatment in the same manner as the base material subjected to the above-mentioned step,
I went to the surface.

The method of measuring the (O / C) value will be described later. Here, the pressure bonding method of the (B) paper base material and the (D) gas barrier plastic base material is not particularly limited, and for example, a sandwich extrusion lamination method is used. The method for pressure-bonding the gas barrier plastic substrate and the sealant resin layer is not particularly limited, and an extrusion lamination method or a sandwich extrusion lamination method is used.

The pressure-bonding step of the present invention is carried out, for example, by a sandwich extrusion lamination method in which a (B) paper base material and (D) gas barrier plastic base material are interposed (C) an extrusion laminating resin layer in the laminating step. Stacking process,
Either of the steps of (D) laminating the gas barrier plastic substrate and the (E) resin for extrusion laminating as a sealant by an extrusion lamination method may be performed first,
There is no particular restriction on the processing order.

In the pressure bonding step of the present invention, the resin layer for extrusion laminating (E) laminated with the gas barrier plastic substrate (D) may be used as a sealant. Furthermore, when the (F) film original fabric base material layer produced in a process different from the laminating process is used as a sealant, the (E) resin layer for extrusion lamination of the present invention is used as an intermediate layer, and (D) gas barrier property The plastic substrate and the (F) film original substrate layer can be laminated by the sandwich extrusion lamination method.

In the pressure-bonding step of the present invention, in the case where the base material used for the (D) gas-barrier plastic base material is a multilayer film molded product containing a gas-barrier resin produced in a step different from the pressure-bonding step, for example, EVOH / Adhesive resin / PE
In the case of a three-kind three-layer structured base material consisting of or a three-kind three-layer structured base material consisting of Ny / adhesive resin / PE, E of the base material
By stacking the VOH surface and the Ny surface so as to face the (B) paper base material layer by the sandwich extrusion lamination method, (D) PE of the gas barrier plastic base material layer
Can also be a sealant.

In the pressure-bonding step of the present invention, (D) a resin for extrusion laminating, which serves as a sealant, is laminated on one side of a gas barrier plastic substrate by an extrusion lamination method, and then obtained. The laminated film is subjected to an aging treatment described below to promote the adhesiveness with the (D) gas barrier plastic base material, and then the surface of the (D) gas barrier plastic base material of the laminated film is transferred to the (B) paper base. You may arrange | position so that it may face a material, and may laminate | stack it by the sandwich extrusion lamination method.

The number of layers of the sheets constituting the container of the present invention is
It may be at least 5 layers or 6 layers, and from the viewpoint of productivity and economical efficiency, 10 layers or less are preferable, and 8 layers or less are more preferable.

The laminated sheet constituting the container of the present invention may be processed by, for example, tandem processing or double laminating processing.

A known extrusion laminator can be used in the pressure bonding step of the present invention.

In the present invention, it is preferable that the surface oxidation treatment step and the pressure-bonding step are provided in-line, and the (D) gas barrier plastic substrate after the surface oxidation treatment step is immediately subjected to the pressure-bonding step. As a result, a higher level of adhesive strength is exhibited and undesired blocking of the film is prevented. It should be noted that the above-mentioned "providing the pressure bonding step in-line and immediately subjecting the (D) gas barrier plastic substrate after the surface oxidation treatment step to the pressure bonding step" means that in the extrusion lamination process, the (D) gas barrier plastic substrate is used. Material feeding process, surface oxidation treatment process,
It means that the crimping step and the product winding step use (D) a device sequentially installed on the same line along the flow direction of the gas barrier plastic substrate, and perform these steps promptly in a series of operations. To do.

In the present invention, from the viewpoint of further improving the adhesive strength, the gas barrier plastic substrate (D) to be subjected to the surface oxidation treatment step before the surface oxidation treatment step is kept at 40 ° C. or higher and (D). It is preferable to provide a heating step before surface oxidation, which is a step of heating at a temperature below the melting point of the gas barrier plastic substrate.

The heating temperature is not lower than 40 ° C. and not higher than the melting point of the (D) gas barrier plastic substrate, preferably not lower than 60 ° C. and not higher than 30 ° C. lower than the melting point of the substrate. Here, the temperature refers to the surface temperature of the (D) gas barrier plastic substrate, and can be measured, for example, by a contact thermometer. (D) The gas barrier plastic substrate is optimally heated by using a far infrared heater, a heating roll or the like. For example,
(D) In the process of transporting the gas barrier plastic substrate to the surface oxidation treatment step, it may be passed under a far infrared heater. For example, if (D) the gas barrier plastic substrate has a width of 500 mm, The far-infrared heater has an output of about 1 to 30 kW (when a plurality of heaters are used, the total output), and the distance between the heater and the surface of the (D) gas barrier plastic substrate is 1
The temperature may be maintained at about 30 cm for about 0.05 to 5 seconds.

In the present invention, from the viewpoint of further improving the adhesive strength, it is preferable to provide, after the pressure-bonding step, an aging step of aging the laminated film or laminated sheet obtained in the pressure-bonding step under heat retention.

The aging temperature is usually 30 ° C. or higher and lower than 50 ° C., preferably 40 to 45 ° C. If the aging temperature is too low, the improvement of the adhesive strength may be insufficient, while if it is too high, if the laminated resin is a sealant resin, the heat seal performance is deteriorated or the resin deteriorates, and the odor This can cause problems.

The aging time is usually 1 to 120 hours, preferably 10 to 120 hours. If the aging time is too short, the improvement of the adhesive strength may be insufficient. On the other hand, if it is too long, the extrusion-laminated resin may be deteriorated, which is also disadvantageous in terms of economy and productivity. Is.

To carry out the aging step, an ordinary oven or a room in which the temperature can be adjusted may be used.

In the present invention, a heating step before surface oxidation,
By carrying out all of the surface oxidation treatment step, the ozone treatment step, the pressure bonding step and the aging step in combination, the container of the present invention can realize stronger adhesive strength.

Next, a specific embodiment of the surface oxidation treatment step will be described.

The surface oxidation treatment step is specifically carried out by a corona treatment step, a plasma treatment step, a flame plasma treatment step, an electron beam irradiation treatment step, an ultraviolet ray irradiation treatment step and the like.

The corona discharge treatment step is a step of performing the corona discharge treatment on both surfaces of the (D) gas barrier plastic substrate. The corona discharge treatment is carried out, for example, by using a known corona discharge treatment device and passing the (D) gas barrier plastic substrate through the generated corona atmosphere. Here, from the viewpoint of maintaining the adhesive strength at a high level, the corona discharge density is preferably 40 (W · min / m ² ) or more, and more preferably 50 (W · min / m ² ) or more. However, the preferable corona discharge density when using the heating step before surface oxidation and / or the aging step is 10 (W
-Min / m ² ) or more.

In the plasma treatment step, a simple substance or a mixed gas such as argon, helium, krypton, neon, xenon, hydrogen, nitrogen, and air is electronically excited by a plasma jet, and then the charged particles are removed and electrically charged. This can be carried out by blowing a neutralized excited inert gas onto the surface of the (D) gas barrier plastic substrate.

The flame plasma treatment step can be carried out by blowing ionized plasma in the flame produced when burning natural gas or propane onto the surface of the (D) gas barrier plastic substrate.

The electron beam irradiation treatment step is carried out by irradiating the surface of the (D) gas barrier plastic substrate with an electron beam generated by an electron beam accelerator. As the electron beam irradiation device, for example, a device "Electron Curtain" (trade name) that can irradiate a curtain-shaped uniform electron beam from a linear filament can be used.

The ultraviolet irradiation treatment step is, for example, 200 to 4
It is carried out by irradiating the surface of the (D) gas barrier plastic substrate with an ultraviolet ray having a wavelength of 00 mμ.

A method of measuring the Δ (O / C) value will be described. (D) On both sides of the gas barrier plastic substrate,
In the case of using a (D) gas barrier plastic base material which has not been previously subjected to surface oxidation treatment such as corona discharge treatment or coating treatment such as a coating agent for promoting easy adhesion, the following method is used. O / C) value is calculated. That is,
In this case, either surface may be defined as the reference surface of the base material. Therefore, (B) Δ (O /
The C) value is the value obtained by subtracting (O / C) ⁰ of the substrate from (O / C) ^* after subjecting the surface to the surface oxidation treatment of the present invention. On the other hand, (B) Δ (O /
The value C) is a value obtained by subtracting (O / C) ⁰ of the substrate from (O / C) ^* after the surface oxidation treatment of the present invention is applied to the surface.

Among the gas barrier plastic base materials, in order to further improve the gas barrier properties of these gas barrier plastic base materials, a glassy material or a metal material is vapor-deposited on one surface of the resin to form a physical layer. There is a base material having a gas barrier property, but in the case of such a base material, the Δ (O / C) value is determined by the following method. That is, in this case, the plastic substrate surface is defined as the reference surface of the substrate. Therefore, the Δ (O / C) value of this surface is
After the surface is subjected to the surface oxidation treatment of the present invention (O /
C) ^* is the value obtained by subtracting (O / C) ⁰ of the base material.

Here, ESCA means Electron
Spectroscopy for Chemica
l Analysis, and (O / C) ^* and (O / C) ⁰ are calculated as follows. That is, the abundance ratio (O / C) of oxygen and carbon is obtained from the ratio of the values of the respective peak intensities of O _1S and C _1S multiplied by the relative sensitivity of each peak (for details, see, for example, Raito Yoshihito). , "Fundamentals and Applications of Polymer Surfaces (1)," Kagaku Dojin, 1986, Chapter 4.).

The change with time of the Δ (O / C) value will be described. FIG. 1 shows the change with time of Δ (O / C) value in the case where the gas barrier plastic substrate is a biaxially stretched nylon film and the surface is treated by corona discharge. As is clear from FIG. 1, the Δ (O / C) value sharply decreases with time, and for example, the corona treatment density is 100 (w · min / m ² ).
In the case of, the Δ (O / C) value becomes less than 0.05 after one day. Further, in the case of 30 (w · min / m ² ), the degree of surface oxidation treatment was low, and Δ (O
/ C) value is less than 0.05. Therefore, when the corona discharge treatment density is 30 (w · min / m ² ), sufficient adhesive strength cannot be obtained unless the corona discharge treatment is performed in-line in the same process as the ozone treatment process and the pressure bonding process. If the value of Δ (O / C) is too small, sufficient adhesive strength cannot be obtained.

Here, the polyester resin means an aromatic dicarboxylic acid such as terephthalic acid or 2,6-naphthalenedicarboxylic acid and an aliphatic glycol such as ethylene glycol, diethylene glycol or 1,4-cyclohexanedimethanol. It is a resin composed of a polymer obtained by polycondensation. Typical examples of the polymer include polyethylene terephthalate (PET) and polyethylene 2,6-naphthalene dicarboxylate (PE).
N), polybutylene terephthalate (PBT), etc. are illustrated. In addition to the homopolymer, the polymer is 2
It may be a copolymer containing 0 mol% or less of the third component. In this case, as the dicarboxylic acid component, for example, one or more of isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid and oxycarboxylic acid (for example, p-oxybenzoic acid). Can be used. As the glycol component, one kind or two or more kinds of ethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, neopentyl glycol and the like can be used.

By the way, in order to improve the printability on the surface of the commercially available gas barrier plastic substrate, the AC
In order to improve the adhesiveness of the agent to the base material, there is a base material that has been subjected to surface oxidation treatment such as corona discharge treatment on one or both sides. When used without being carried out, the sufficiently strong adhesive force aimed by the present invention cannot be obtained.

In the present invention, (D) the resin extruded and laminated on the gas barrier plastic substrate is applied to the heat seal layer of the laminated film or sheet,
Also, it can be applied to the intermediate layer of sandwich extrusion lamination, but they are properly used depending on the function of the resin, such as easy heat sealing property and moisture proof property.

The resin for extrusion lamination used in the present invention is
To the extent that the effects of the present invention are not impaired, known additives such as antioxidants, antiblocking agents, weathering agents, neutralizing agents,
It may contain a flame retardant, an antistatic agent, an antifogging agent, a lubricant, a dispersant, a pigment, an organic or inorganic filler, and the like.

The gas barrier paper laminated packaging sheet obtained by each of the above-mentioned steps has no AC agent component such as an organic solvent remaining in the sheet, and there is no fear of odor resulting from it, and it is extrusion laminated. Since the resin for processing can be processed at low temperature, the odor surface does not deteriorate due to the evaporation of low molecular weight components and volatile components contained in the resin. Therefore, it is most suitable for food packaging materials. Furthermore, coextrusion laminating of a gas barrier plastic base material using an adhesive resin, or processing that requires the production of a multilayer film molded product containing a gas barrier plastic base material in a step different from the laminating step. Compared with the law, it is characterized by superior productivity and economic efficiency. Further, the gas barrier paper laminated packaging sheet used in the present invention does not contain aluminum foil in the material constitution of the packaging container, and thus not only excels in easy recyclability of paper resources, but also when incinerated. Since it does not generate ash, it has the advantage of being less likely to damage the incinerator.

Next, the laminated constitution of the gas barrier paper laminated packaging container of the present invention will be specifically described. The laminated sheet constituting the packaging container of the present invention includes (A) resin layer for extrusion lamination / (B) paper base material layer / (C) resin layer for extrusion lamination / (D) gas barrier plastic base material layer / A sheet having at least five layers of (E) a resin layer for extrusion lamination, or (A) a resin layer for extrusion lamination / (B) a paper base material layer / (C) a resin layer for extrusion lamination /
A sheet having at least 6 layers of (D) gas barrier plastic substrate layer / (E) resin layer for extrusion laminating / (F) film original substrate layer can be mentioned.

More specifically, (A) PE / (B) paper / (C) PE // (D) EVOH // (E)
PE (A) PE / (B) Paper / (C) PE // (D) PVA // (E) P
E (A) PE / (B) Paper / (C) PE // (D) PVDC // (E)
PE (A) PE / (B) Paper / (C) PE // (D) ONy // (E) P
E (A) PE / (B) Paper / (C) PE // (D) PET // (E) P
E (A) PE / (B) Paper / (C) PE // (D) EVOH // (E)
PE / (F) Original film (A) PE / (B) Paper / (C) PE // (D) PVA // (E) P
E / (F) Raw film (A) PE / (B) Paper / (C) PE // (D) PVDC // (E)
PE / (F) Original film (A) PE / (B) Paper / (C) PE // (D) Ny // (E) PE
/ (F) Original film (A) PE / (B) Paper / (C) PE // (D) PET // (E) P
E / (F) Original film (A) PE / (B) Paper / (C) PE // (D) [EVOH / N
y] // (E) PE (A) PE / (B) Paper / (C) PE // (D) [Ny / EVO
H] // (E) PE (A) PE / (B) Paper / (C) PE // (D) [EVOH / Ny
/ EVOH] // (E) PE (A) PE / (B) Paper / (C) PE // (D) [Ny / EVOH
/ Ny] // (E) PE (A) PE / (B) Paper / (C) PE // (D) KONy // (E)
PE (A) PE / (B) Paper / (C) PE // (D) KPET // (E)
PE (A) PE / (B) Paper / (C) PE // (D) KPVA // (E)
PE (A) PP / (B) Paper / (C) PE // (D) KOPP // (E)
PP (A) PE / (B) Paper / (C) PE // (D) KPT // (E) P
E (A) PE / (B) Paper / (C) PE // (D) PPET // (E)
PE (A) PP / (B) Paper / (C) PE // (D) POPP // (E)
PP (A) PE / (B) Paper / (C) PE // (D) EONy // (E)
PE (A) PE / (B) Paper / (C) PE // (D) EPET // (E)
PE (A) PP / (B) Paper / (C) PE // (D) EOPP // (E)
PP (A) PE / (B) Paper / (C) EMMA // (D) Silica evaporation E
VOH // (E) PE (A) PE / (B) Paper / (C) EMMA // (D) Silica vapor deposition O
Ny // (E) PE (A) PE / (B) Paper / (C) EMMA // (D) Silica vapor deposition P
ET // (E) PE (A) PE / (B) Paper / (C) EMMA // (D) Aluminum vapor deposition O
Ny // (E) PE (A) PE / (B) Paper / (C) EMMA // (D) Aluminum vapor deposition P
ET // (E) PE

Here, // is a portion representing that the pressure bonding step is performed after the ozone treatment and the surface oxidation treatment according to the present invention. PE is polyethylene resin, PP is polypropylene resin, EMMA is ethylene- (meth)
Acrylic ester copolymer resin, EVOH is ethylene-vinyl alcohol copolymer, PVA is polyvinyl alcohol resin, PVDC is vinylidene chloride resin, O
Ny is a biaxially stretched nylon resin, PET is a biaxially stretched polyester resin, KONy is a biaxially stretched nylon resin coated with an emulsion containing PVDC as a main component, KP
ET is a biaxially stretched polyester resin coated with an emulsion containing PVDC as a main component, KPVA is a biaxially stretched polyvinyl alcohol resin coated with an emulsion containing PVDC as a main component, and KOPP is an emulsion containing PVDC as a main component. Coated biaxially oriented polypropylene, KP
T is cellophane coated with PVDC-based emulsion, PPET is biaxially oriented polyester resin coated with PVA-based emulsion, and POPP is biaxially coated with PVA-based emulsion. Stretched polypropylene resin, EONy is emulsion-coated biaxially stretched nylon resin whose main component is EVOH, E
PET represents an emulsion-coated biaxially stretched polyester-based resin containing EVOH as a main component, and EOPP represents an emulsion-coated biaxially-stretched polypropylene-based resin containing EVOH as a main component. In addition, (D) [EVOH / Ny]
The parentheses such as [] represent a laminate.

Next, the laminated constitution of the gas barrier paper laminated packaging container of the present invention, in which the location where the AC agent or the adhesive resin is used is specified, will be specifically described.
For example, as a laminated sheet using an AC agent,
(A) Extrusion laminating resin layer, (B) Paper base material layer,
A gas barrier paper laminated sheet comprising at least 5 layers of (C) resin layer for extrusion lamination, (D) gas barrier plastic substrate layer, and (E) resin layer for extrusion lamination, or (A) resin for extrusion lamination Layer, (B) paper base material layer, (C) extrusion laminating resin layer, (D) gas barrier plastic base material layer, (E) extrusion laminating resin layer and (F) original film base material layer An example is a gas barrier paper laminated sheet having a six-layer structure.

When the adhesive resin is used as the laminated sheet, (A) resin layer for extrusion lamination, (B) paper base material layer, (C ') adhesive resin layer, (D) gas barrier property A gas barrier paper laminated sheet comprising at least 5 layers of a plastic substrate layer and (E) resin layer for extrusion lamination, or (A) resin layer for extrusion lamination, (B) paper substrate layer, (C '). A gas barrier paper laminated sheet comprising at least 6 layers of an adhesive resin layer, (D) gas barrier plastic base material layer, (E) resin layer for extrusion laminating and (F) original film base material layer is mentioned. To be

Specific examples of the constitution using the AC agent include (A) PE / (B) paper / (C) PE / (AC agent) (D) EVOH
// (E) PE (A) PE / (B) Paper / (C) PE / (AC agent) (D) PVA /
/ (E) PE (A) PE / (B) Paper / (C) PE / (AC agent) (D) PVDC
// (E) PE (A) PE / (B) Paper / (C) PE / (AC agent) (D) ONy /
/ (E) PE (A) PE / (B) Paper / (C) PE / (AC agent) (D) PET /
/ (E) PE (A) PE / (B) Paper / (C) PE / (AC agent) (D) EVOH
// (E) PE / (F) Original film (A) PE / (B) Paper / (C) PE / (AC agent) (D) Silica vapor deposition EVOH // (E) PE (A) PE / ( B) Paper / (C) PE / (AC agent) (D) Silica vapor deposition PET // (E) PE (A) PE / (B) Paper / (C) PE / (AC agent) (D) Silica vapor deposition ONy // (E) PE (A) PE / (B) Paper / (C) PE / (AC agent) (D) KONy
// (E) PE (A) PE / (B) Paper / (C) PE / (AC agent) (D) KONy
// (E) PE / (F) Original film (A) PE / (B) Paper / (C) PE / (AC agent) (D) KPET
// (E) PE (A) PE / (B) Paper / (C) PE / (AC agent) (D) KPVA
// (E) PE (A) PE / (B) Paper / (C) PE / (AC agent) (D) KONy
// (E) PE (A) PE / (B) Paper / (C) PE / (AC agent) (D) EPET
// (E) PE etc. are mentioned.

Specific examples of the constitution using the adhesive resin include (A) PE / (B) paper / (C ') adhesive resin / (D) EVOH //
(E) PE (A) PE / (B) Paper / (C ') Adhesive resin / (D) PVA //
(E) PE (A) PE / (B) Paper / (C ') Adhesive resin / (D) PVDC //
(E) PE (A) PE / (B) Paper / (C ') Adhesive resin / (D) ONy //
(E) PE (A) PE / (B) Paper / (C ') Adhesive resin / (D) PET //
(E) PE (A) PE / (B) Paper / (C ') Adhesive resin / (D) EVOH //
(E) PE / film original fabric (A) PE / (B) paper / (C ') adhesive resin / (D) silica vapor deposition E
VOH // (E) PE (A) PE / (B) Paper / (C ') Adhesive resin / (D) Silica vapor deposition P
ET // (E) PE (A) PE / (B) Paper / (C ') Adhesive resin / (D) Silica vapor deposition O
Ny // (E) PE (A) PE / (B) Paper / (C ') Adhesive resin / (D) KONy //
(E) PE (A) PE / (B) Paper / (C ') Adhesive resin / (D) KONy //
(E) PE / Film original (A) PE / (B) Paper / (C ') Adhesive resin / (D) KPET //
(E) PE (A) PE / (B) Paper / (C ') Adhesive resin / (D) KPVA //
(E) PE (A) PE / (B) Paper / (C ') Adhesive resin / (D) EONy //
(E) PE (A) PE / (B) Paper / (C ') Adhesive resin / (D) EPET //
(E) PE and the like can be mentioned.

Further, (AC agent) is a portion showing that the AC agent is applied to the gas barrier plastic base material layer and then the pressure bonding step is performed. Further, the adhesive resin is a portion showing that the (B) paper base material layer and the (D) gas barrier plastic base material layer are pressure-bonded and laminated by the sandwich extrusion lamination method.

The gas barrier paper laminated packaging container of the present invention can be used for liquid foods and wet foods. Examples of liquid foods include milk such as milk, dairy products such as fresh creams and lactic acid drinks, fruit drinks, sake alcohols, shochu, coffee drinks, oolong tea, tea, vegetable juice, mineral water, soy milk, honey drinks. , Soy sauce, sauces, dressings, edible oil, various sauces such as sauce and noodle soup, and the like. Examples of moist foods include tofu.

The gas barrier paper laminated packaging container of the present invention is used for non-food products such as industrial chemicals and industrial materials. For example, liquid synthetic detergents, surfactants, shampoos, rinses, liquid fertilizers, developers, various Examples include paints, bleaching agents, organic solvents, lubricating oils and motor oils.

The method for producing the gas barrier paper laminated packaging container of the present invention is not particularly limited. For example, after punching a gas barrier paper laminated packaging sheet into a predetermined shape, hot air heating, flame heating, etc. Is heat-sealed to form a container having a capacity of 100 milliliters to several liters.

The shape of the gas barrier paper laminated packaging container of the present invention is not particularly limited, and examples thereof include a Gobel type container and a brick type container.

[0094]

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The measurement and evaluation methods used in Examples and Comparative Examples are as follows. (1) Measurement of (O / C) ^* and (O / C) ⁰ FI Surface Science System
Using ESCA LAB MR-II manufactured by K.K., the ratio of the values obtained by multiplying the area ratio of the respective peak intensities of O _1S and C _1S by the relative sensitivity of each peak was used to determine the abundance ratio of oxygen and carbon (O /
C) was determined. The (O / C) ^* of the gas barrier plastic substrate is a value measured 30 minutes after laminating the resin of the present invention by extrusion lamination or sandwich extrusion lamination. However, in the actual measurement, a gas barrier plastic base material that is not subjected to extrusion lamination or sandwich extrusion lamination process is prepared separately, and the base material is subjected to the same surface treatment as the substrate subjected to extrusion lamination or sandwich extrusion lamination process. Oxidation treatment was performed on the surface.

(2) Evaluation method Measurement of film adhesive strength A laminated sheet having a width of 15 mm was measured at 200 mm / min using an auto strain type tensile tester manufactured by Toyo Seiki Co., Ltd.
The film adhesiveness was evaluated from the peel strength when peeled by 180 degrees at a tensile speed of. However, the film adhesion strength 1: represents the film adhesion strength between the paper base material and the gas barrier plastic base material layer. Membrane adhesion strength 2: represents the membrane adhesion strength between the gas barrier plastic substrate layer and the sealant resin layer.

Odor sensory test The odor sensory test was conducted by the following method. From the obtained gas-barrier paper laminated sheet, a laminated film (15 cm x 7 cm) obtained by mechanically peeling the gas-barrier plastic base material and the sealant resin layer was placed in a 1-liter wide-mouthed bottle and covered with an aluminum foil. 50 ° C, 1 using a heating oven
After heating under the condition of hr, the sample was gradually cooled for 30 minutes. Then, eight selected panelists smelled the odor of the laminated film held in the wide-mouthed bottle to determine the odor intensity. The odor intensity at that time was evaluated as 4 ranks, and the rank with the largest number of the 8 panelists was used as the evaluation result of the sample. The odor sensory test represents the following judgment. “A”: The level is almost odorless and may be applicable to all packaging materials. "○": The odorless level is low and the packaging material is widely used. "△": There is no odor, but there is no problem depending on the use of the packaging material. “X”: There is no odor, and its use as a packaging material is limited.

Gas Barrier Property The oxygen permeability of the gas barrier paper laminated sheet is measured according to JIS K.
It measured according to 7126.

Presence or absence of ash content The presence or absence of ash content was evaluated when the gas barrier paper laminated sheet was burned using an electric furnace combustion test apparatus (manufactured by Yamato Scientific Co., Ltd.). “None”: There was no generation of ash. “Yes”: There was generation of ash.

Comprehensive Evaluation The results of comprehensive evaluation of the adhesive strength, gas barrier property, odor strength and ash content of the base material are shown. “A”: Very good in comprehensive evaluation. "○": Excellent in overall evaluation. “X”: Inferior to the comprehensive evaluation.

Example 1 First, a paper base material and a gas barrier plastic base material were laminated as follows. Here, the gas barrier plastic substrate was made by using a biaxially stretched EVOH which was already corona-treated on one side at the time of purchase. First, the treated surface of the gas barrier plastic base material is arranged so as to face the paper base material, is fed from the main feeding machine of the laminator, and the adhesive surface with the molten resin is attached by the corona discharge treatment machine provided in the laminator inline. Corona treatment was performed at a treatment density of 59 (w · min / m ² ). △ of the surface at this time
O / C was 0.109. Next, weigh 180 (g /
The paper base material of m ² ) is fed from the sand base material feeding machine,
LDPE (low density polyethylene: Sumikasen manufactured by Sumitomo Chemical Co., Ltd., L718-H, MFR 8 g / 10 min, density 0.919 g / cm ³ ) is melt-kneaded using an extruder having a diameter of 65 mmφ, and resin is melted from the T-die. Temperature 305 ℃, width 4
Extruded into a molten film with a thickness of 50 mm and a thickness of 15 μm.
The laminating speed at this time was 140 (m / min). Next, air having an ozone concentration of 15 (g / m ³ ) was applied to the surface of the molten film, which was bonded to the biaxially stretched EVOH substrate, at a position 30 mm below the die to supply air of 2 (m ³ / h) with an ozone concentration of 15 (g / m ³ ).
The molten film was treated with ozone by spraying under the condition of r). The ozone treatment amount at this time was 7.9 (mg / m ² ) with respect to the passing unit area of the molten film. Then, the obtained laminate of the paper base material and the biaxially stretched EVOH base material was wound up on a winder.

Next, a sealant was laminated on the other surface of the biaxially stretched EVOH substrate of the laminate as follows. The laminate was arranged so that the biaxially stretched EVOH surface was the laminate surface, and the laminate was fed out from the main feeding machine of the laminator. Then, the in-line corona discharge machine was used to treat the adhesive surface with the molten resin at a treatment density of 59 (w / min /
Corona treatment was performed at an intensity of m ² ). △ O of the surface at this time
/ C was 0.087. Next, the same LDPE as described above was supplied to each of two extruders having a diameter of 65 mm and melt-kneaded.
Extruded into a molten film having a width of 450 mm and a total thickness of 50 μ (25 μ each). The laminating speed at this time was 140 (m / min). Then, 30 mm below the die on the surface of the molten film to be bonded to the biaxially stretched EVOH substrate.
From the nozzle provided at the position of ozone concentration 15 (g / m ³ )
The molten film was subjected to ozone treatment by blowing the above air under the condition of 2 (m ³ / hr). The ozone treatment amount at this time was 7.9 with respect to the passing unit area of the molten film.
(Mg / m ² ). Then, the obtained paper base material and 2
A four-layer laminate composed of axially stretched EVOH and a sealant was wound by a winder.

Next, a low density polyethylene layer was laminated on the other side of the paper base material of the laminate as follows.
The paper substrate surface of the laminate was made to be the laminating surface, and the laminate was delivered from the main delivery machine of the laminator. Then, the same LDPE as the above is melt-kneaded using an extruder having a diameter of 65 mm, and the resin temperature is set to 315 from a single T-die.
It was extruded at a temperature of 450 ° C. and a width of 450 mm and a thickness of 15 μm to obtain a molten film, which was subjected to a pressure bonding step with a paper substrate. The laminating speed at this time was 140 (m / min). Then, LDPE was laminated on the laminated body, and a laminated body having a total of 5 layers was wound by a winding machine.

Through the above three steps, from the outermost layer of the laminated sheet, LDPE / paper base material layer / LDPE / EV
A gas barrier paper laminated packaging sheet composed of a total of 5 layers of OH / LDPE was prepared. Then, the obtained gas barrier paper laminated packaging sheet was aged using a commercially available oven under the conditions of 40 ° C. and 24 hours.
A packaging container was prepared using the obtained gas barrier paper laminated packaging sheet, and evaluated according to the above evaluation method. The processing conditions are shown in Tables 1 and 2, and the evaluation results are shown in Table 3.

Example 2 (D) Unstretched E as Gas Barrier Plastic Base Material
Example 1 was repeated except that VOH and LLDPE were used as the (E) layer of the sealant layer. Table 1 shows processing conditions
2 and 2 show the evaluation results, respectively.

Example 3 (D) Except that biaxially oriented nylon was used as the gas barrier plastic substrate, EMMA was used as the (C) layer, and LDPE and LLDPE were used as the (E) layer of the sealant layer.
The same procedure as in Example 1 was performed. The processing conditions are shown in Tables 1 and 2, and the evaluation results are shown in Table 3.

Example 4 (D) Same as Example 1 except that biaxially oriented polyester was used as the gas barrier plastic substrate, EMMA was used as the (C) layer, and EMMA and LLDPE were used as the (E) layer of the sealant layer. went. Table 1 and 2 for processing conditions
Table 3 shows the evaluation results.

Example 5 (D) A biaxially stretched nylon film was used as a gas barrier plastic substrate, EMMA was used as the (C) layer, and the substrate and the sealant resin layer were laminated by the following method.
Sandwich extrusion lamination processing was performed. The innermost layer sealant film used was an inflation molding film of LDPE. Other conditions were the same as in Example 1. Processing conditions are shown in Tables 4 and 5, evaluation results are shown in Table 6,
Shown respectively.

Example 6 (D) PVDC as Gas Barrier Plastic Base Material
A coated biaxially stretched nylon was used, and the PVDC coated surface was arranged so as to face the (B) paper substrate. And (C)
Adhesive resin (E-EA-MAH) was used as the layer, and sandwich extrusion laminating was used as the method for laminating the base material and the sealant resin layer. As the innermost layer sealant film, an LDPE inflation molding film was used. In the sandwich extrusion laminating process of the (B) paper base material and the (D) gas barrier plastic base material, the ozone treatment was not applied to the (C) layer in contact with the (B) paper base material. Other conditions were the same as in Example 5. The processing conditions are shown in Tables 4 and 5, and the evaluation results are shown in Table 6.

Example 7 (D) PVDC as Gas Barrier Plastic Base Material
A coated biaxially stretched nylon was used, and the PVDC coated surface was arranged so as to face the (B) paper substrate. And (C)
LDPE was used as the layer, and sandwich extrusion laminating was used as the method for laminating the base material and the sealant resin layer. The innermost sealant film is L
A DPE blown film was used. Also,
In the sandwich extrusion laminating process of the (B) paper base material and the (D) gas barrier plastic base material, the AC agent was applied to the (D) gas barrier plastic base material. Other conditions were the same as in Example 5. The processing conditions are shown in Tables 4 and 5, and the evaluation results are shown in Table 6.

Comparative Examples 1 to 10 The same procedure as in Example 1 was carried out except that the conditions were as shown in Tables 7, 8, 10, 11, 13 and 14. The evaluation results are shown in Tables 9 and 12.
And 15 respectively.

Comparative Example 11 As a gas barrier plastic substrate, an aluminum foil as a metallic barrier material was used instead of the plastic substrate. Furthermore, when extrusion-laminating a sealant on the aluminum foil, a dual slot die was used and a coextrusion lamination method of an adhesive resin and LDPE was used.
The processing conditions are shown in Tables 13 and 14, and the evaluation results are shown in Table 15.

Comparative Example 12 A biaxially stretched polyester was used as a gas barrier plastic substrate, and when a sealant was extrusion laminated on the substrate, the gas barrier plastic substrate was subjected to anchor coat treatment. The processing conditions are shown in Table 13 and
The evaluation results are shown in 14 and Table 15 is shown in Table 15.

[0113]

[Table 1] ─────────────────────────────────── Actual Examples 1 2 3 4 ──── ──────────────────────────────── Substrate / Resin Extrusion laminating resin 1 LD LD LD LD Substrate 1 Paper Paper Paper Paper Extrusion laminating resin 2 LD LD EMMA EMMA Substrate 2 EVOH CEVOH ONy PET Extrusion laminating resin 3 LD LL LD EMMA Extrusion laminating resin 4 LD LL LL LL Processing conditions Melt extrusion temperature 1 (° C) 315 315 315 315 315 Melt extrusion Temperature 2 (° C) 305 305 305 305 305 Melt Extrusion Temperature 3 (° C) 280 260 295 295 Melt Extrusion Temperature 4 (° C) 280 260 280 280 AC Treatment 1 No No No No AC Treatment 2 No No No No Speed m / min 14 0 140 140 140 Thickness 1 (μ) 15 15 15 15 15 Thickness 2 (μ) 15 15 20 20 Thickness 3 (μ) 25 25 20 20 20 Thickness 4 (μ) 25 25 40 40 40 ──────────── ─────────────────────────

[0114]

[Table 2] ─────────────────────────────────── Actual Examples 1 2 3 4 ──── ─────────────────────────────── Machining condition ESCA1 (O / C) ^* 0.410 0.330 0.242 0.530 (O / C) ⁰ 0.301 0.238 0.153 0.402 Degree of oxidation 1 ΔO / C 0.109 0.092 0.089 0.133 ESCA2 (O / C) ^* 0.388 0.320 0.205 0.525 (O / C) ⁰ 0.301 0.238 0.153 0.402 Degree of oxidation 2 ΔO / C 0.087 0.082 0.052 0.123 Corona discharge treatment 1 treatment Density W / min / m ² 59 59 59 59 59 Corona discharge treatment 2 Treatment density W / min / m ² 59 59 59 59 59 Ozone treatment 1 Treatment mg / m ² 7.9 7.9 7.9 7.9 Ozone treatment 2 Treatment mg / m ² 7.9 7.9 7.9 7.9 Aging treatment Temperature ℃ 40 ── 40 40 hours hr 48 ── 48 48 ──────────────────────────────── ────

[0115]

[Table 3] ─────────────────────────────────── Actual Examples 1 2 3 4 ──── ─────────────────────────────── Evaluation film adhesive strength 1 g / 15mm Peeling impossible Peeling impossible Resin cut Resin cut Film adhesion strength 2 g / 15mm Peeling is not possible Peeling is not possible 820 700 Gas barrier property 0.3 1.5 40 60 cc / m ² · 24hr · atm Odor intensity ◎ ◎ ○ ○ With or without ash formation No No No No Total evaluation ◎ ◎ ○ ○ ───────────────────────────────────

[0116]

[Table 4] ─────────────────────────────── Actual example 5 6 7 ────────── ────────────────────── Substrates / Resin Extrusion laminating resin 1 LD LD LD Substrate 1 Paper Paper Paper Extrusion laminating resin 2 EMMA E-EA- MAH LD Base material 2 ONy KONy KONy Extrusion laminating resin 3 LD LD LD Sealant film LD Raw fabric LD Raw fabric LD raw fabric Processing conditions Melt extrusion temperature 1 (° C) 315 315 315 Melt extrusion temperature 2 (° C) 305 305 305 305 Melt Extrusion temperature 3 (° C) 305 305 305 Melt extrusion temperature 4 (° C) ─── ─── ─── AC treatment 1 No No Yes AC treatment 2 No No No Speed m / min 140 140 140 Thickness 1 (μ) 15 15 15 Thickness 2 (μ) 20 20 20 Thickness 3 (μ) 20 20 20 Film thickness 4 (μ) 30 30 30 ────────────────────────────────

[0117]

[Table 5] ─────────────────────────────── Actual Examples 5 6 7 ────────── ────────────────────── Machining conditions ESCA1 (O / C) ^* 0.242 ─── ─── (O / C) ⁰ 0.153 ─── ── ─ Degree of oxidation 1 ΔO / C 0.089 ─── ──── ESCA2 (O / C) ^* 0.205 0.205 0.205 (O / C) ⁰ 0.153 0.153 0.153 Degree of oxidation 2 ΔO / C 0.052 0.052 0.052 Corona discharge treatment 1 Treatment density W ・Min / m ² 59 59 ── Corona discharge treatment 2 Treatment density W ・ min / m ² 59 59 59 Ozone treatment 1 Treatment amount mg / m ² 7.9 ───── Ozone treatment 2 Treatment amount mg / m ² 7.9 7.9 7.9 Aging Treatment temperature ℃ 40 40 40 hours hr 48 48 48 48 ────────────────────────────────

[0118]

[Table 6] ─────────────────────────────── Actual example 5 6 7 ────────── ────────────────────── Evaluation Membrane bond strength 1 g / 15mm Resin break Resin break Resin break Membrane bond strength 2 g / 15mm 770 770 770 Gas barrier property 40 7 7 cc / m ²・ 24hr ・ atm Odor intensity ◎ ◎ ◎ Presence or absence of ash formation No No No Total evaluation ○ ○ ○ ─────────────────────── ─────────

[0119]

[Table 7] ─────────────────────────────────── Comparative Examples 1 2 3 4 ──── ──────────────────────────────── Substrate / Resin Extrusion laminating resin 1 LD LD LD LD Substrate 1 Paper Paper Paper Paper Resin for extrusion lamination 2 LD LD LD LD Base material 2 EVOH EVOH CEVOH CEVOH Resin for extrusion lamination 3 LD LD LL LL Resin for extrusion lamination 4 LD LD LL LL Processing conditions Melt extrusion temperature 1 (° C) 315 315 315 315 Melt extrusion Temperature 2 (° C) 305 305 305 305 305 Melt extrusion temperature 3 (° C) 280 280 260 260 260 Melt extrusion temperature 4 (° C) 280 280 260 260 260 AC treatment 1 No No No No AC treatment 2 No No No No Speed m / min 140 1 0 140 140 Thickness 1 (μ) 15 15 15 15 Thickness 2 (μ) 15 15 15 15 Thickness 3 (μ) 25 25 25 25 Thickness 4 (μ) 25 25 25 25 25 ──────────── ────────────────────────

[0120]

[Table 8] ─────────────────────────────────── Comparative Examples 1 2 3 4 ──── ─────────────────────────────── Machining condition ESCA1 (O / C) ^* 0.329 0.410 0.254 0.330 (O / C) ⁰ 0.301 0.301 0.238 0.238 Oxidation degree 1 ΔO / C 0.028 0.109 0.016 0.092 ESCA2 (O / C) ^* 0.301 0.388 0.238 0.320 (O / C) ⁰ 0.301 0.301 0.238 0.238 Oxidation degree 2 ΔO / C 0 0.087 0 0.082 Corona discharge treatment 1 treatment Density W · min / m ² ─── 59 ─── 59 Corona discharge treatment 2 Treatment density W · min / m ² ─── 59 ──── 59 Ozone treatment 1 Treatment amount mg / m ² ─────── ─── ─── Ozone treatment 2 Treatment mg / m ² ─── ─── ─── ─── Aging temperature ℃ ─── ─── ─── ─── Time hr ─── ── ─────────────────────────── ───────────────

[0121]

[Table 9] ─────────────────────────────────── Comparative Examples 1 2 3 4 ──── ─────────────────────────────── Evaluation Membrane bond strength 1 g / 15mm 20 20 20 30 Membrane bond strength 2 g / 15mm 30 40 30 30 Gas barrier property 0.3 0.3 1.5 1.5 1.5 cc / m ² · 24hr · atm Odor intensity ◎ ◎ ◎ ◎ ◎ Whether or not ash content is generated No No No No Total evaluation × × × × ── ──────────────────────────────────

[0122]

[Table 10] ─────────────────────────────────── Comparative Examples 5 6 7 8 ──── ──────────────────────────────── Substrate / Resin Extrusion laminating resin 1 LD LD LD LD Substrate 1 Paper Paper Paper Paper Resin for extrusion lamination 2 EMMA EMMA LD EMMA Substrate 2 ONy ONy ONy PET Resin for extrusion lamination 3 LD LD LD EMMA Resin for extrusion lamination 4 LL LL LL LL Processing conditions Melt extrusion temperature 1 (° C) 315 315 315 315 315 Melt extrusion Temperature 2 (℃) 305 305 305 305 305 Melt extrusion temperature 3 (℃) 295 295 295 295 Melt extrusion temperature 4 (℃) 280 280 280 280 AC treatment 1 No No No No AC treatment 2 No No No No Speed m / min 14 0 140 140 140 Thickness 1 (μ) 15 15 15 15 15 Thickness 2 (μ) 20 20 20 20 20 Thickness 3 (μ) 20 20 20 20 20 Thickness 4 (μ) 40 40 40 40 40 ──────────── ─────────────────────────

[0123]

[Table 11] ─────────────────────────────────── Comparative example 5 6 7 8 ──── ─────────────────────────────── ESCA1 (O / C) ^* 0.191 0.242 0.191 0.469 (O / C) ⁰ 0.153 0.153 0.153 0.402 Oxidation degree 1 ΔO / C 0.038 0.089 0.038 0.067 ESCA2 (O / C) ^* 0.153 0.205 0.153 0.402 (O / C) ⁰ 0.153 0.153 0.153 0.402 Oxidation degree 2 ΔO / C 0 0.052 0 0 Corona discharge treatment 1 Treatment density W・ Min / m ² ── 59 ── ── Corona discharge treatment 2 Treatment density W ・ min / m ² ── 59 ── ── Ozone treatment 1 Treatment amount mg / m ² ── ── 7.9 ── Ozone treatment 2 Processing amount mg / m ² ── ── 7.9 ── Aging temperature ℃ ── ── ── ── Time hr ── ── ── ── ─────────────── ────────────────────

[0124]

[Table 12] ─────────────────────────────────── Comparative example 5 6 7 8 ──── ─────────────────────────────── Evaluation membrane adhesion strength 1 g / 15mm 30 40 40 160 160 membrane adhesion strength 2 g / 15mm 40 60 210 260 Odor intensity ○ ○ ○ ○ Gas barrier property 40 40 40 60 cc / m ²・ 24hr ・ atm Presence of ash content No No No No No Overall evaluation × × × × ─────────── ─────────────────────────

[0125]

[Table 13] ─────────────────────────────────── Comparative example 9 10 11 12 12 ──── ──────────────────────────────── Substrate / Resin Extrusion laminating resin 1 LD LD LD LD Substrate 1 Paper Paper Paper Paper Extrusion Laminating Resin 2 EMMA EMMA LD EMMA Substrate 2 PET PET PET AL PET Extrusion Laminating Resin 3 EMMA EMMA E-EA-MAH LD Extrusion Laminating Resin 4 LL LL LD LD Processing Conditions Melt Extrusion Temperature 1 (° C) 315 315 315 315 Melt extrusion temperature 2 (° C) 305 305 315 315 315 Melt extrusion temperature 3 (° C) 295 295 290 315 Melt extrusion temperature 4 (° C) 280 280 290 290 AC treatment 1 No No No No AC treatment 2 No No No Yes Yes Speed m / min 140 140 140 140 140 Thickness 1 (μ) 15 15 15 15 15 Thickness 2 (μ) 20 20 15 20 20 Thickness 3 (μ) 20 20 20 20 20 Thickness 4 (μ) 40 40 30 30 30 ──────── ────────────────────────────

[0126]

[Table 14] ─────────────────────────────────── Comparative example 9 10 11 12 12 ──── ─────────────────────────────── Machining condition ESCA1 (O / C) ^* 0.535 0.469 ── 0.469 (O / C) ⁰ 0.402 0.402 ── 0.402 Degree of oxidation 1 ΔO / C 0.133 0.067 ── 0.067 ESCA2 (O / C) ^* 0.530 0.402 ── ── (O / C) ⁰ 0.402 0.402 ── ── Degree of oxidation 2 ΔO / C 0.128 0 ──── Corona discharge treatment 1 Treatment density W · min / m ² 59 ── ── 59 Corona discharge treatment 2 Treatment density W · min / m ² 59 ── ───── Ozone treatment 1 Treatment amount mg / m ² ── 7.9 ── 7.9 Ozone treatment 2 Treatment amount mg / m ² ── 7.9 ── ── Aging treatment temperature ℃ ── ── ── 40 hours hr ── ── ── 48 ──────── ──────────────────────────

[0127]

[Table 15] ─────────────────────────────────── Comparative Examples 9 10 11 12 12 ──── ─────────────────────────────── Evaluation film adhesion strength 1 g / 15mm 100 100 380 Resin cut film adhesion strength 2 g / 15mm 280 290 640 Not peelable Odor strength ○ ○ △ × Gas barrier property 60 60 0 60 cc / m ² , 24hr, atm Ashes ash generation Yes No No Yes No No Overall evaluation × × × × ──────── ────────────────────────────

Substrate 1: Paper Substrate Substrate 2: Gas Barrier Plastic Substrate or Metallic Gas Barrier Substrate Extrusion Laminating Resin 1: Resin Laminating Outside Paper Substrate Extrusion Laminating Resin 2: Paper Substrate Sandwich Extrusion Laminate Resin for Laminating Material and Gas Barrier Plastic Base Material Extrusion Laminating Resin 3: Sealant Resin Adhering to Gas Barrier Plastic Base Material Extrusion Laminating Resin 4: Sealant Resin of Innermost Layer in Contact with Contents Laminating resins 3 and 4 are co-extruded by dual slot die Sealant film: Gas barrier property Sealant film of innermost layer in contact with plastic base material and sandwich extrusion laminate AC treatment 1: Paper base material and gas barrier property Plastic substrate sandwich extrusion lamine It was used to laminated in Deployment method. AC treatment 2: Used in extrusion laminating a sealant resin layer on a gas barrier plastic substrate.

Thickness 1: Laminate thickness of extruded laminated resin 1 Thickness 2: Laminate thickness of extruded laminated resin 2 Thickness 3: Laminate thickness of extruded laminated resin 3 Thickness 4: Laminate thickness of extruded laminated resin 4 Film thickness 4: Sealant film Thickness

ESCA1: ESCA measurement value of gas-barrier plastic base material on the surface directly facing the paper base material Oxidation degree 1: Oxidation degree by ESCA measurement value of gas-barrier plastic base material on the surface facing the paper base material ESCA2: ESCA measurement value of gas barrier plastic base material surface not facing paper base material Oxidation degree 2: Oxidation degree by ESCA measurement value of gas barrier plastic base material surface not facing paper base material Corona discharge treatment 1: Paper base material Corona discharge treatment density applied to the surface of the gas barrier plastic substrate facing the surface Corona discharge treatment 2: Corona discharge treatment density applied to the surface of the gas barrier plastic substrate that does not face the paper substrate Ozone treatment 1: Paper Gas barrier plastic on the surface facing the base material Amount of ozone treatment applied to the surface of the molten film that adheres to the base material Ozone treatment 2: Paper base The amount of ozone treatment applied to the surface of the molten film that adheres to the surface of the gas barrier plastic substrate that does not face the material

Paper base material: Nippon Paper Pulp Trading Co., Ltd. paperboard base paper Weighing 180 (g / m ² ) Gas barrier plastic base material EVOH: Biaxially stretched EVOH (where EVOH is an ethylene-vinyl alcohol copolymer) ), Kuraray EF-XL type 15μ CEVOH: unstretched EVOH, Kuraray EF-E type 20μ ONy: biaxially stretched nylon, Unitika's ON type 15μ PET: biaxially stretched polyester, Toyobo. Company E
5100 type 15μ KONy: PVDC-coated biaxially stretched nylon, manufactured by Unitika Ltd. DCR type 15μ Here, the gas barrier plastic base material excluding KONy was one that had been subjected to corona treatment at the time of purchase. The EVOH, CEVOH, ONy, and PET base materials were arranged so that the treated surface faced the paper base material. KO
Ny was placed so that the PVDC coated surface was directly facing the paper substrate. Metallic barrier substrate AL: Aluminum foil, thickness 7 μ Extrusion laminating resin LD: Low density polyethylene, Sumikasen L718-H manufactured by Sumitomo Chemical Co., Ltd., MFR 8 g / 10 min, density 0.
919 g / cm ³ LL: Linear low density polyethylene, Sumitomo Chemical Co., Ltd.
Sumikasen α, CS8026, MFR 10g / 10
Min, density 0.914 g / cm ³ EMMA: ethylene-methyl methacrylate copolymer, Sumitomo Chemical Co., Ltd. Acryft, WH302, M
FR 7 g / 10 min, density 0.930 g / cm ³ , methyl methacrylate content 15 wt% E-EA-MAH: ethylene-ethyl acrylate-maleic anhydride copolymer, Sumitomo Chemical Co., Ltd. Bondine, L
X4110, MFR 7 g / 10 min, density 0.930, ethyl acrylate content 6 wt%, maleic anhydride content 3 wt% LD raw material: low density polyethylene, Sumitomo Chemical Co., Ltd.
Sumikasen L405, MFR 3.7 g / 10 min, density 0.924 g / cm ³ , inflation molded film

Processing conditions "-" in the table indicates that the treatment was not carried out. No AC treatment: No anchor coat treatment Yes: Anchor coat treatment (using Nippon Soda Co., Ltd. Citabond 120)

[0133]

As described above in detail, according to the present invention, a gas barrier function and sufficient adhesive strength are provided without using an AC agent or an adhesive resin, and the manufacturing process is not complicated. It is a gas barrier paper laminated packaging container with excellent productivity and economical efficiency, and because it can be laminated with resin at low temperature, it has excellent low odor, and because it does not contain aluminum foil in the constituent materials, it is easy to use paper resources. It is possible to provide a gas barrier paper laminated packaging container having excellent recyclability and incineration processability. Further, the present invention, even if using an AC agent or adhesive resin which is not preferable for low odor, by specifying the location, the odor component contained in the organic solvent or adhesive resin used in the AC agent applying step, (D) It is possible to prevent transfer to the sealant which is blocked by the gas barrier plastic base material layer and is in contact with the contents of the container. Moreover, similar to the above, it is a gas barrier paper laminated packaging container that has both a gas barrier function and sufficient adhesive strength, and that does not complicate the manufacturing process and is excellent in productivity and economic efficiency, and is made of resin. Since it can be laminated at a low temperature, it has excellent low odor properties, and since it does not contain aluminum foil in the constituent materials, it is possible to provide a gas barrier paper laminated packaging container that has excellent recyclability of paper resources and excellent incineration processability. it can. Further, the gas barrier paper laminated packaging container of the present invention has excellent properties as described above, and therefore, packaging container for liquid food or wet food and packaging container for non-food such as industrial chemicals or industrial materials. Is useful as

[Brief description of drawings]

Fig. 1 △ O / of corona treated biaxially stretched nylon surface
It is a figure showing the time-dependent change of C value.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroaki Takahata 5-1 Anezaki Kaigan, Ichihara-shi, Chiba Sumitomo Chemical Co., Ltd. (72) Inventor Hirotsugu Goto 5-1 Anesaki Kaigan, Ichihara-shi, Chiba Sumitomo Chemical Within the corporation

Claims (16)

[Claims] 1. A resin layer for extrusion lamination, a paper base layer for (B), a resin layer for extrusion lamination, a gas barrier plastic base layer for (D), and a resin layer for extrusion lamination (E). A gas-barrier paper laminated sheet having a constitution of at least 5 layers, which is obtained by the following (X) surface oxidation treatment step, (Y) ozone treatment step and (Z) pressure-bonding step. Gas barrier paper laminated packaging container. (X) Surface oxidation treatment step (D) Step of subjecting both surfaces of the gas barrier plastic base material layer to surface oxidation treatment. (Y) Ozone treatment step (C) Extrusion laminating resin layer and (E) Extrusion laminating resin layer are melt extruded into a film at a temperature of 180 to 340 ° C., and the film is (D) gas barrier plastic substrate layer. A step of applying ozone treatment to the surface to be bonded. (Z) Pressure bonding step (A) Extrusion laminating resin layer, (B) Paper base material layer,
(C) Extrusion laminating resin layer, (D) Gas barrier plastic base material layer, and (E) Extrusion laminating resin layer are pressure-bonded. A step in which the relationship represented by the following formula is established for the surface oxidized surface. When the gas barrier plastic substrate is a polyester resin Δ (O / C) ≧ 0.08 When the gas barrier plastic substrate is other than a polyester resin Δ (O / C) ≧ 0.05 where Δ (O / C) = (O / C) ^* -(O / C) ⁰ , where (O / C) ⁰ is the surface of the gas barrier plastic substrate before the surface oxidation treatment of the present invention, E
The surface having the smaller value represented by the ratio of the number of oxygen atoms and the number of carbon atoms measured by the SCA method was used as the reference surface of the base material, and (O / C) of this surface was defined as (O / C) of the base material. / C) ⁰ is defined. Further, (O / C) ^* represents the ratio of the number of oxygen atoms to the number of carbon atoms measured by the ESCA method on the surface of the gas barrier plastic substrate having the surface subjected to the surface oxidation treatment of the present invention. 2. (A) Extrusion laminating resin layer, (B) Paper substrate layer, (C) Extrusion laminating resin layer, (D) Gas barrier plastic substrate layer, (E) Extrusion laminating resin layer. And (F) a gas barrier paper laminated sheet comprising at least 6 layers of the film original fabric base layer,
A gas barrier paper laminated packaging container comprising a gas barrier paper laminated sheet obtained by the following (X) surface oxidation treatment step, (Y) ozone treatment step and (Z) pressure bonding step. (X) Surface oxidation treatment step (D) Step of subjecting both surfaces of the gas barrier plastic base material layer to surface oxidation treatment. (Y) Ozone treatment step (C) Extrusion laminating resin layer and (E) Extrusion laminating resin layer are melt extruded into a film at a temperature of 180 to 340 ° C., and the film is (D) gas barrier plastic substrate layer. A step of applying ozone treatment to the surface to be bonded. (Z) Pressure bonding step (A) Extrusion laminating resin layer, (B) Paper base material layer,
A step of pressure-bonding (C) resin layer for extrusion lamination, (D) gas barrier plastic substrate layer, (E) resin layer for extrusion lamination and (F) film original substrate layer,
A step in which the relationship represented by the following formula is established with respect to the surface oxidation treated surface of the gas barrier plastic base material layer subjected to pressure bonding (D). When the gas barrier plastic substrate is a polyester resin Δ (O / C) ≧ 0.08 When the gas barrier plastic substrate is other than a polyester resin Δ (O / C) ≧ 0.05 where Δ (O / C) = (O / C) ^* -(O / C) ⁰ , where (O / C) ⁰ is the surface of the gas barrier plastic substrate before the surface oxidation treatment of the present invention, E
The surface having the smaller value represented by the ratio of the number of oxygen atoms and the number of carbon atoms measured by the SCA method was used as the reference surface of the base material, and (O / C) of this surface was defined as (O / C) of the base material. / C) ⁰ is defined. Further, (O / C) ^* represents the ratio of the number of oxygen atoms to the number of carbon atoms measured by the ESCA method on the surface of the gas barrier plastic substrate having the surface subjected to the surface oxidation treatment of the present invention. 3. (A) Extrusion laminating resin layer, (B) Paper base layer, (C) Extrusion laminating resin layer, (D) Gas barrier plastic base layer and (E) Extrusion laminating resin layer. A gas-barrier paper laminated sheet having a constitution of at least 5 layers, wherein an anchor coating agent is applied to a surface of the (D) gas-barrier plastic base material layer which is bonded to the (C) resin layer for extrusion laminating, A gas barrier paper laminated packaging container comprising the gas barrier paper laminated sheet obtained by (X) surface oxidation treatment step, (Y) ozone treatment step and (Z) pressure bonding step. (X) Surface Oxidation Treatment Step (D) A step of subjecting the gas barrier plastic substrate (E) to the surface to be bonded to the resin layer for extrusion laminating, to a surface oxidation treatment. (Y) Ozone treatment step (E) The resin layer for extrusion lamination is melt extruded into a film at a temperature of 180 to 340 ° C., and the surface where the film adheres to the (D) gas barrier plastic substrate layer is subjected to ozone treatment. Process. (Z) Pressure bonding step (A) Extrusion laminating resin layer, (B) Paper base material layer,
(C) Extrusion laminating resin layer, (D) Gas barrier plastic base material layer, and (E) Extrusion laminating resin layer are pressure-bonded. A step in which the relationship represented by the following formula is established for the surface oxidized surface. When the gas barrier plastic substrate is a polyester resin Δ (O / C) ≧ 0.08 When the gas barrier plastic substrate is other than a polyester resin Δ (O / C) ≧ 0.05 where Δ (O / C) = (O / C) ^* -(O / C) ⁰ , where (O / C) ⁰ is the surface of the gas barrier plastic substrate before the surface oxidation treatment of the present invention, E
The surface having the smaller value represented by the ratio of the number of oxygen atoms and the number of carbon atoms measured by the SCA method was used as the reference surface of the base material, and (O / C) of this surface was defined as (O / C) of the base material. / C) ⁰ is defined. Further, (O / C) ^* represents the ratio of the number of oxygen atoms to the number of carbon atoms measured by the ESCA method on the surface of the gas barrier plastic substrate having the surface subjected to the surface oxidation treatment of the present invention. 4. (A) Extrusion laminating resin layer, (B) Paper base layer, (C) Extrusion laminating resin layer, (D) Gas barrier plastic base layer, (E) Extrusion laminating resin layer. And (F) a gas barrier paper laminated sheet comprising at least 6 layers of the film original fabric base layer,
An anchor coating agent is applied to the surface of the (D) gas barrier plastic base material layer that is bonded to the (C) resin layer for extrusion lamination, and the following (X) surface oxidation treatment step, (Y) ozone treatment step and (Z) are performed. ) A gas barrier paper laminated packaging container comprising a gas barrier paper laminated sheet obtained by a pressure bonding step. (X) Surface oxidation treatment step (D) A step of subjecting the gas barrier plastic base material layer (E) to the surface to be adhered to the resin layer for extrusion laminating, a surface oxidation treatment. (Y) Ozone treatment step (E) The resin layer for extrusion lamination is melt extruded into a film at a temperature of 180 to 340 ° C., and the surface where the film adheres to the (D) gas barrier plastic substrate layer is subjected to ozone treatment. Process. (Z) Pressure bonding step (A) Extrusion laminating resin layer, (B) Paper base material layer,
A step of pressure-bonding (C) resin layer for extrusion lamination, (D) gas barrier plastic substrate layer, (E) resin layer for extrusion lamination and (F) film original substrate layer,
A step in which the relationship represented by the following formula is established with respect to the surface oxidation treated surface of the gas barrier plastic base material layer subjected to pressure bonding (D). When the gas barrier plastic substrate is a polyester resin Δ (O / C) ≧ 0.08 When the gas barrier plastic substrate is other than a polyester resin Δ (O / C) ≧ 0.05 where Δ (O / C) = (O / C) ^* -(O / C) ⁰ , where (O / C) ⁰ is the surface of the gas barrier plastic substrate before the surface oxidation treatment of the present invention, E
The surface having the smaller value represented by the ratio of the number of oxygen atoms and the number of carbon atoms measured by the SCA method was used as the reference surface of the base material, and (O / C) of this surface was defined as (O / C) of the base material. / C) ⁰ is defined. Further, (O / C) ^* represents the ratio of the number of oxygen atoms to the number of carbon atoms measured by the ESCA method on the surface of the gas barrier plastic substrate having the surface subjected to the surface oxidation treatment of the present invention. 5. (A) Extrusion laminating resin layer, (B) Paper base layer, (C ') Adhesive resin layer, (D) Gas barrier plastic base layer and (E) Extrusion laminating resin layer. A gas barrier paper laminated sheet having a constitution of at least 5 layers of the following (X) surface oxidation treatment step,
A gas barrier paper laminated packaging container comprising a gas barrier paper laminated sheet obtained by (Y) ozone treatment step and (Z) pressure bonding step. (X) Surface Oxidation Treatment Step (D) A step of subjecting the gas barrier plastic substrate (E) to the surface to be bonded to the resin layer for extrusion laminating, to a surface oxidation treatment. (Y) Ozone treatment step (E) The resin layer for extrusion lamination is melt extruded into a film at a temperature of 180 to 340 ° C., and the surface where the film adheres to the (D) gas barrier plastic substrate layer is subjected to ozone treatment. Process. (Z) Pressure bonding step (A) Extrusion laminating resin layer, (B) Paper base material layer,
A step of pressure-bonding (C ′) the adhesive resin layer, (D) the gas-barrier plastic base material layer, and (E) the resin layer for extrusion laminating, which comprises subjecting the (D) gas-barrier plastic base material layer to pressure-bonding. A step in which the relationship represented by the following formula is established for the surface oxidized surface. When the gas barrier plastic substrate is a polyester resin Δ (O / C) ≧ 0.08 When the gas barrier plastic substrate is other than a polyester resin Δ (O / C) ≧ 0.05 where Δ (O / C) = (O / C) ^* -(O / C) ⁰ , where (O / C) ⁰ is the surface of the gas barrier plastic substrate before the surface oxidation treatment of the present invention, E
The surface having the smaller value represented by the ratio of the number of oxygen atoms and the number of carbon atoms measured by the SCA method was used as the reference surface of the base material, and (O / C) of this surface was defined as (O / C) of the base material. / C) ⁰ is defined. Further, (O / C) ^* represents the ratio of the number of oxygen atoms to the number of carbon atoms measured by the ESCA method on the surface of the gas barrier plastic substrate having the surface subjected to the surface oxidation treatment of the present invention. 6. (A) Extrusion laminating resin layer, (B) Paper base material layer, (C ') Adhesive resin layer, (D) Gas barrier plastic base material layer, (E) Extrusion laminating resin layer And (F) a gas barrier paper laminated sheet comprising at least 6 layers of the original film base material layer, which comprises the following (X) surface oxidation treatment step, (Y) ozone treatment step and (Z) pressure-bonding step. A gas barrier paper laminated packaging container comprising the gas barrier paper laminated sheet obtained by. (X) Surface oxidation treatment step (D) A step of subjecting the gas barrier plastic base material layer (E) to the surface to be adhered to the resin layer for extrusion laminating, a surface oxidation treatment. (Y) Ozone treatment step (E) The resin layer for extrusion lamination is melt extruded into a film at a temperature of 180 to 340 ° C., and the surface where the film adheres to the (D) gas barrier plastic substrate layer is subjected to ozone treatment. Process. (Z) Pressure bonding step (A) Extrusion laminating resin layer, (B) Paper base material layer,
(C ') adhesive resin layer, (D) gas barrier plastic substrate layer, (E) extrusion laminating resin layer, and (F)
A step of pressure-bonding the raw film base material layer, wherein the relationship represented by the following formula is established for the surface oxidation treated surface of the gas barrier plastic base material layer (D) subjected to pressure bonding. When the gas barrier plastic substrate is a polyester resin Δ (O / C) ≧ 0.08 When the gas barrier plastic substrate is other than a polyester resin Δ (O / C) ≧ 0.05 where Δ (O / C) = (O / C) ^* -(O / C) ⁰ , where (O / C) ⁰ is the surface of the gas barrier plastic substrate before the surface oxidation treatment of the present invention, E
The surface having the smaller value represented by the ratio of the number of oxygen atoms and the number of carbon atoms measured by the SCA method was used as the reference surface of the base material, and (O / C) of this surface was defined as (O / C) of the base material. / C) ⁰ is defined. Further, (O / C) ^* represents the ratio of the number of oxygen atoms to the number of carbon atoms measured by the ESCA method on the surface of the gas barrier plastic substrate having the surface subjected to the surface oxidation treatment of the present invention. 7. A resin for extrusion laminating of (A), (C) and (E) is a polyethylene resin, a polypropylene resin, an ethylene-vinyl ester copolymer resin and an ethylene- (meth) acrylic ester copolymer. 7. At least one resin selected from polymer resins.
The gas barrier paper laminated packaging container according to any one of 1. 8. The adhesive resin (C ') is an ethylene-unsaturated polybasic acid copolymer, an ethylene-unsaturated polybasic acid-acrylic acid lower alkyl ester copolymer, an ethylene-unsaturated polybasic acid-polymer. The gas barrier paper laminated packaging container according to claim 5 or 6, which is at least one adhesive resin selected from a methacrylic acid lower alkyl ester copolymer and an ethylene-unsaturated polybasic acid-vinyl ester copolymer. 9. A (D) gas barrier plastic substrate comprises an ethylene-vinyl alcohol copolymer, a polyvinyl alcohol resin, an acrylonitrile resin, a vinylidene chloride resin, a nylon resin, a polyester resin,
The gas barrier paper laminated packaging container according to any one of claims 1 to 6, which is at least one resin selected from polyarylate-based resins, polychlorotrifluoroethylene-based resins, and polyvinylidene fluoride-based resins. 10. The (D) gas barrier plastic substrate is at least one resin selected from ethylene-vinyl alcohol copolymers, nylon resins and polyester resins. A gas-barrier paper laminated packaging container according to. 11. A (D) gas barrier plastic substrate, a two-kind two-layer laminate comprising an ethylene-vinyl alcohol copolymer and a nylon resin, an ethylene-vinyl alcohol copolymer, a nylon resin and ethylene. -A two-kind three-layer laminate made of a vinyl alcohol copolymer, a three-kind three-layer laminate made of an ethylene-vinyl alcohol copolymer, an adhesive resin and a polyethylene resin, and a nylon resin, an ethylene-vinyl alcohol copolymer The gas barrier paper laminated packaging container according to any one of claims 1 to 6, which is at least one kind of laminated body selected from a laminated body of two kinds and three layers made of a polymer and a nylon resin. (D) The gas barrier plastic substrate (D) is a resin coated with an emulsion containing a vinylidene chloride resin as a main component, a resin coated with an emulsion containing a polyvinyl alcohol resin as a main component, and ethylene- The gas barrier paper laminated packaging container according to any one of claims 1 to 6, which is a substrate selected from resins coated with an emulsion containing a vinyl alcohol copolymer as a main component. 13. A (D) gas barrier plastic substrate, a nylon resin layer having silica deposited on at least one surface, a polyester resin having silica deposited on at least one surface, or ethylene-vinyl alcohol having silica deposited on at least one surface. The gas barrier paper laminated packaging container according to any one of claims 1 to 6, which is a base material comprising a copolymer layer. 14. The (F) film original substrate is selected from polyethylene resin, polypropylene resin, ethylene-vinyl ester copolymer resin and ethylene- (meth) acrylic acid ester copolymer resin. The gas barrier paper laminated packaging container according to claim 2, 4 or 6, which is at least one resin. 15. The gas barrier paper laminated packaging container is a packaging container for liquid food or wet food.
4. The gas barrier paper laminated packaging container according to any one of 4 above. 16. The gas barrier paper laminated packaging container according to any one of claims 1 to 14, wherein the gas barrier paper laminated packaging container is a non-food packaging container for industrial chemicals or industrial materials.