JP2008265855A - Paper container for retort processing, and retort product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a self-reliant paper container for retort processing having excellent gas barrier properties, shape-keeping properties and heat resistance. <P>SOLUTION: The paper container for retort processing is manufactured by making into a box a laminated material prepared by laminating successively an outermost layer, a paper base material, an intermediate base material layer, a gas barrier property laminate film and an innermost layer in this order. The shape keeping properties can be ensured by the paper base material and the adhesiveness can be ensured by laminating the intermediate base material layer between the paper base material and the gas barrier property laminate film. The self-supporting paper container for retort processing has excellent gas barrier properties, shape-keeping properties and heat resistance, and can be favorably used. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a retort-treated paper container, a retort-treated paper container, and a retort-treated packaging body using the same, and has excellent gas barrier properties, heat resistance, pressure resistance, water resistance, heat seal properties, puncture resistance, and self-supporting properties. The present invention relates to a retort processing paper container that excels in resistance and a retort processing package using the same.

Bags are made using a laminated material obtained by laminating plastic film, metal foil, cellophane, etc., and the obtained bag-like container body is filled and packaged with desired food and drink, etc., temperature 110 to 130 ° C., pressure 1 to 3 kgf Retort-processed packaged products having various forms, which have been subjected to a retort treatment by sterilizing under pressure / cm ² · G for 20 to 60 minutes, are manufactured.

  In such a retort-processed packaged product, the laminated material constituting the bag-like container body is, for example, a biaxially stretched polyester resin film having a thickness of 12 μm and a thickness as a laminated material for producing a transparent retort-processed packaged product. A laminated material composed of three layers of a 15 μm biaxially stretched polyamide resin film and an unstretched polypropylene film having a thickness of 50 to 80 μm is known, and as a laminated material for producing a retort-processed packaging product having a barrier property, A laminate comprising four layers of a biaxially stretched polyester resin film having a thickness of 12 μm, an aluminum foil having a thickness of 7 to 9 μm, a biaxially stretched polyamide resin film having a thickness of 15 μm, and an unstretched polypropylene film having a thickness of 50 to 80 μm. In addition, as a laminated material for manufacturing retort-processed packaging products having barrier properties and transparent specifications, Laminated material or the like comprising three layers of cast polypropylene film of biaxially stretched polyamide resin film and the thickness of the polyvinylidene chloride resin film and the thickness of 10 to 20 [mu] m 50 to 80 [mu] m of 15μm are known.

It consists of a laminate type material in the form of a sheet or web, comprising at least one base layer (1), an outer coating (2) and an inner coating (3), and said base layer (1) is paper or It is made of a material that absorbs liquid such as cardboard, and the outer coating (2) is made of polypropylene, stretched polypropylene, metallized stretched polypropylene, high density polyethylene, metallized high density polyethylene, linear low density polyethylene, polyester, metallized polyester and non- A laminate comprising a polymer selected from the group comprising crystalline polyester and the inner coating (3) comprising a polymer selected from the group comprising polypropylene, high density polyethylene, linear low density polyethylene, polyester and amorphous polyester Materials have also been proposed (patents) Document 1). A laminated material including such a paper base is excellent in shape retention and can be easily formed into a standing pouch or a brick type. Further, a group comprising aluminum, aluminum oxide coating, silica coating, ethylene / vinyl alcohol, polyvinyl alcohol, metallized stretched polyester and metallized stretched polypropylene between the base layer (1) and the inner coating (3). Laminates that additionally include a more selected barrier layer (4) have also been proposed. The laminated material having the above structure is made of a packaging material mainly composed of paper, and is used for a temperature of about 110 ° C. to 130 ° C. and a pressure of about 1 to 3 kgf / cm ² · G for about 20 to 60 minutes. Retort processing such as pressure heat sterilization processing can be performed to manufacture retort-processed packaging products having various forms.

In addition, an inorganic oxide vapor deposition film is provided on one surface of the base film, and the general formula R ¹ _n M (OR ² ) _m (wherein , R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m is It contains at least one alkoxide represented by the valence of M), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and is further obtained by polycondensation by a sol-gel method. There is a retort pouch made of a laminated material in which a barrier film provided with a gas barrier coating film made of a gas barrier composition, a barrier resin layer, and a heat sealable resin layer are sequentially laminated (Patent Document 2). As the barrier resin layer, polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer resin, and nylon MXD6 resin are described. The laminated material used for this retort pouch is a so-called soft packaging material.

  Bags made of laminated film such as the above retort pouch have good processability and excellent sealing performance, and also have excellent moisture resistance, gas barrier properties, water resistance, heat resistance, and content resistance. Standing pouch-type bags are self-supporting and have the characteristics of a three-dimensional container, and are easy to handle and can be packaged compactly for their capacity, so they can contain liquid, powdery, granular and other fluid contents. Conveniently used in the center. If these standing pouches are flexible and inferior in shape retention, they are not suitable for use in fragile foods such as snack foods and soft and easily crushed foods such as cakes and castella. A method using a paper container such as a cup type, a brick type, or a gobel top type using a plastic, a composite container using a laminated cardboard and a plastic molded body, a plastic molded container, a metal can, or the like is employed.

  As a cup-type paper container using the above laminated cardboard, a paper cup produced using a laminate comprising a paper layer as a main component and an ethylene-α / olefin copolymer polymerized using a single site catalyst as a heat seal layer A container has been proposed (Patent Document 3).

In addition, at least the intermediate layer uses a material that absorbs liquid such as paper or cardboard as a base layer, and is formed of a laminate type material in the form of a sheet or web in which an outer coating and an inner coating are laminated on the outer side and the inner side. A folded moisture-proof and heat-resistant container that has been heat-treated in a humid atmosphere at a temperature of 85 ° C. or higher on at least one side has also been proposed (Patent Document 4).
Japanese National Patent Publication No. 11-508502 JP 2005-178805 A JP 2000-229660 A Japanese National Patent Publication No. 11-508502

  However, the laminate described in Patent Document 1 has excellent barrier properties when a metal such as aluminum, a metallized stretched polyester, a metallized stretched polypropylene, or the like is used as the barrier layer (4). These metals, metallized stretched polyester, metallized stretched polypropylene, etc. lack in bending resistance and the like, and the laminate strength may decrease. Further, when ethylene / vinyl alcohol, polyvinyl alcohol or the like is used as the barrier layer (4), a predetermined gas barrier property is exhibited in the absolutely dry state, but the gas barrier property in a wet state may be significantly lowered.

  Moreover, although the retort pouch described in Patent Document 2 is excellent in gas barrier properties, it is difficult to use as a standing pouch because it does not include a paper base material and is a soft packaging material.

  In addition, the containers described in Patent Document 3 and Patent Document 4 have good shape retention and can improve the protection of the contents. However, the material cost of the container, the mold for molding the container, the molding apparatus, etc. In addition, the filling and sealing device is expensive, and it is not easy to change the size of the container, which may increase the manufacturing cost. In some cases, gas barrier properties are not sufficient.

  On the other hand, when a paper substrate having a predetermined thickness is used to ensure shape retention, it is difficult to ensure adhesion in the lamination of the paper substrate and the gas barrier laminate film, and the original gas barrier possessed by the gas barrier laminate film is difficult. The characteristics may be reduced. That is, a laminate material that has excellent gas barrier properties, has a laminate strength suitable for retort processing, and has the self-supporting property required for a standing pouch, that is, shape retention, and a retort-treated paper container using such a laminate material, Development of self-supporting bag-like retort processing paper containers and retort products is desired.

  Therefore, the present invention is excellent in self-supporting and gas barrier properties, withstands heat treatment associated with processing such as retort processing, and is free from delamination, and is also a cooked food, marine product, frozen food, boiled food, rice cake, liquid soup, seasoning An object of the present invention is to provide a retort processing paper container, particularly a stand-up pouch type, and a retort processing package using the same, which is excellent in filling and packaging properties, quality maintenance, etc. .

  As a result of detailed examination of the retort-treated paper container, the present inventor can secure shape retention by including a paper base material, and secures excellent gas barrier properties against oxygen and water vapor when a gas barrier laminated film having a predetermined structure is used. When the intermediate base material layer is laminated between the paper base material and the gas barrier laminate film, the laminate property of the paper base material and the gas barrier laminate film is excellent. The present inventors have found that deterioration of characteristics can be prevented and completed the present invention.

That is, the present invention is a retort-treated paper container formed by boxing at least an outermost layer, a paper base material, an intermediate base material layer, a gas barrier laminate film, and a laminated material in which the innermost layer is sequentially laminated, The laminated film is provided with an inorganic oxide vapor-deposited film on one surface of the base film layer, and the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents M A gas barrier property obtained by polycondensation by a sol-gel method, which contains at least one alkoxide represented by valence) and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. Gas barrier coating with composition A laminated film (I) provided with a film, wherein the intermediate base material layer is a laminated film (II) of a polyolefin film and a heat-sealable coating layer. It is.

  Further, the present invention provides a retort product obtained by filling the retort processing paper container with the retort contents and then sealing the container and then heating.

  According to the present invention, by using a polyolefin film and a heat-sealable coating layer as an intermediate base material layer, a retort treatment having excellent gas barrier properties without deteriorating gas barrier properties of a specific gas barrier laminate film Container.

According to the present invention, even if a retort treatment such as pressure heat sterilization treatment is performed at a temperature of about 110 to 130 ° C. and a pressure of about 1 to 3 kgf / cm ² · G for about 20 to 60 minutes, the adhesive strength may be lowered. In addition, a retort processing paper container having excellent gas barrier properties can be provided.

  Since the retort-treated paper container of the present invention uses a paper base material layer, it has excellent shape retention and can be safely protected even if its contents are easily broken or easily crushed. In particular, because of its excellent shape retention, it is most suitable for a self-supporting bag-like retort processing paper container such as a standing pouch that requires a self-supporting property due to line contact.

  The self-supporting bag-like container of the present invention produces a self-supporting bag-like container that is easy to open on the entire top surface of the container, can improve design properties by printing the container, etc. There is an effect that can be provided with good quality.

  Hereinafter, the retort processing paper container of this invention is demonstrated in detail.

(1) Retort processing paper container The retort processing paper container and the retort product using the same according to the present invention will be described below in more detail with reference to the drawings.

The retort-treated paper container of the present invention is a retort-treated paper container formed by boxing at least an outermost layer, a paper base material, an intermediate base material layer, a gas barrier laminated film, and a laminated material obtained by sequentially laminating the innermost layer. The gas barrier laminate film is provided with an inorganic oxide vapor-deposited film on one surface of the base film layer, and the general formula R ¹ _n M (OR ² ) _m (wherein, In the formula, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m Represents at least one alkoxide represented by M), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method. Gas barrier composition obtained It is a laminated film (I) provided with a subbing coating film, and the intermediate base material layer is a laminated film (II) of a polyolefin film and a heat-sealable coating layer.

  In the retort-treated paper container of the present invention, both side edge portions of the front and rear wall laminates are heat-sealed with side seal portions to form a container body, and between the lower portions of the front and rear wall laminates. A standing pouch type can be formed in which the bottom laminated material is folded back and inserted, and a heat-sealed gusset portion is formed as the container bottom. In this invention, it can shape | mold as a laminated material for wall surfaces (A) using the said laminated material, In that case, the kind of laminated material for bottom faces is not ask | required. Preferably, it is a laminate (III) including an outermost layer, a paper base material layer, and an innermost layer, and more preferably, the laminate for wall surface (A) and the laminate for bottom surface (B) are the laminate. Is to configure. When the self-supporting retort processing paper container is a standing pouch, it is necessary to be self-supporting by line contact. However, according to the present invention, the paper base is used to ensure self-supporting and an intermediate base material layer is interposed. By doing so, the gas barrier property of the gas barrier laminate film that is likely to occur when a paper base material is included is not reduced.

  In the present invention, the intermediate substrate layer contained in the laminate may be opposed to the substrate film layer constituting the gas barrier laminate film or may be laminated opposite to the gas barrier coating film. Then, it is preferable to laminate | stack facing a gas-barrier coating film. Moreover, it is preferable that the intermediate | middle base material layer which is laminated | multilayer film (II) of a polyolefin film and a heat-sealable coating layer is laminated | stacked facing the gas barrier coating film which a polyolefin film comprises a gas barrier laminated film.

  The laminated material used in the present invention may contain other layers in addition to the above constituent layers. As such other layers, an adhesive layer for laminating for laminating each layer by a dry laminating method, a primer layer or an anchor coat layer for laminating an innermost layer by a melt extrusion method, and other undercoat agents There are a surface treatment layer formed by surface treatment or a layer, a printing layer, and the like.

  Therefore, as the retort-treated paper container of the present invention including the outermost layer, for example, (a) <plastic base film / corona treatment layer / printing layer> / polyolefin extrusion laminate layer / anchor coat layer / paper base material / anchor coat Layer / polyolefin extrusion laminate layer / <heat-sealable coating layer / polyolefin film / corona treatment layer> / laminate adhesive layer / <gas barrier coating film / inorganic oxide vapor deposition layer / substrate film layer> / corona treatment layer / Laminate adhesive layer / innermost layer, (b) <plastic base film / corona treatment layer> / polyolefin extrusion laminate layer / anchor coat layer / printing layer / paper substrate / anchor coat layer / polyolefin extrusion laminate layer / <heat Sealing coat layer / Polyolefin film / Corona treatment layer> / Laminate Adhesive layer / <gas barrier coating film / inorganic oxide deposition layer / base film layer> / corona treatment layer / laminate adhesive layer / innermost layer, (c) <plastic base film / corona treatment layer / printing Layer> / polyolefin extrusion laminate layer / anchor coat layer / paper substrate / anchor coat layer / <heat-sealable coat layer / polyolefin film / corona treatment layer> / laminate adhesive layer / <corona treatment layer / substrate film layer Examples include: / corona treatment layer / inorganic oxide vapor deposition layer / gas barrier coating film / plasma treatment layer> / laminate adhesive layer / <corona treatment layer / innermost layer>. In addition, before forming the adhesive layer for laminating, a primer layer may be formed in advance, an undercoat agent layer may be provided instead of the laminating adhesive layer, and the innermost layer may be formed by a melt extrusion method. Good.

  FIG. 1 shows a laminate material constituting a retort-treated paper container in which an outermost layer, a paper base material, a <polyolefin film / heat-sealable coating layer>, a gas barrier laminate film and an innermost layer are laminated, and is printed on the outermost layer. FIG. 4 shows a cross-sectional view of a laminate of a retort paper container having a layer.

  Specifically, after the corona-treated layer (80) is provided on the plastic substrate film (10), the printing layer (60) is provided, and this is extruded from the paper substrate (20) provided with the anchor coat layer (73). Adhering via the laminate layer (70), then forming the anchor coat layer (73) on the paper substrate (20), while the substrate film layer (41), corona treatment layer (80), inorganic oxide Corona treatment (80 through the laminated adhesive layer (75) on the gas barrier coating film (45) side of the gas barrier multilayer film (40) obtained by sequentially laminating the vapor deposition layer (43) and the gas barrier coating film (45). ) The heat-sealable coat layer (31) of the intermediate base material layer (30) comprising the polyolefin film (33) and the heat-sealable coat layer (31) and the anchor coat layer (73) provided on the paper base material (20). ) Are bonded via an extruded molten layer (70), and then corona-treated (80) on the base film layer (41) of the gas barrier laminate film (40). The corona-treated layer (80) and the innermost layer It is an example of the cross-sectional view of the laminated material formed by adhere | attaching the corona treatment surface (80) of (50) through the lamination adhesive bond layer (75). The intermediate laminated film (30) is a laminated film of a polyolefin film (33) and a heat-sealable coating layer (31), and the polyolefin film (33) is a gas barrier coating film (45) of the gas barrier laminated film (40). Are stacked facing each other.

  The laminated material used in the present invention may have a configuration in which an outermost layer (10), a paper substrate, (20) an intermediate laminated film (30), a gas barrier laminated film (40), and an innermost layer (50) are laminated in this order. For example, a dry laminate layer may be used instead of the extruded laminate layer, and the anchor coat layer may not be present. In addition, a plasma treatment or other surface may be used instead of the corona treatment. It may be processed. Further, the print layer (60) shown in FIG.

  As described above, when the retort-treated paper container of the present invention is a standing pouch type, the bottom laminate (B) is a laminate (III) including an outermost layer, a paper base material layer, and an innermost layer. Alternatively, the laminated material can be used, and the innermost layer of the laminated body (III) or the laminated material is preferably a heat seal layer.

  As the laminate (III) that can be used for the bottom laminate (B), for example, (a) <transparent plastic substrate film> / extruded laminate resin layer / anchor coat layer / paper substrate layer / anchor coat layer / heat Seal layer, (b) <transparent plastic substrate film / corona treatment layer / printing layer> / extruded laminate resin layer / anchor coat layer / paper substrate layer / anchor coat layer / extruded laminate resin layer / <corona treatment layer / heat Seal layer>, (c) <transparent plastic substrate film> / extruded laminate resin layer / anchor coat layer / paper substrate layer / anchor coat layer / extruded laminate resin layer / <gas barrier coating film / inorganic oxide vapor deposition layer / Base film layer> / Laminate adhesive layer / Heat seal layer, (d) <Transparent plastic base film / Corona treatment layer> / Extruded laminate resin Layer / anchor coat layer / paper base layer / anchor coat layer / extruded laminate resin layer / <gas barrier coating film / inorganic oxide deposition layer / base film layer> / corona treatment layer / laminating adhesive layer / heat seal Layer, (e) <transparent plastic substrate film / corona treatment layer / printing layer> / extruded laminate resin layer / anchor coat layer / paper substrate layer / anchor coat layer / extruded laminate resin layer / <corona treatment layer / substrate Film layer / Inorganic oxide deposition layer / Gas barrier coating film / Plasma treatment layer> // Laminate adhesive layer / <Corona treatment layer / Heat seal layer>, (f) <Transparent plastic substrate film / Corona treatment layer / Printing layer> / Extruded laminate resin layer / Anchor coat layer / Paper substrate layer / Anchor coat layer / Extruded laminate resin layer / <Heat seal coat layer / Polyolefin film> / Laminate adhesive layer / <Gas barrier coating film / Inorganic acid Material deposition layer / Base film layer> / Corona treatment layer / Laminating adhesive layer / Heat seal layer, (g) <Transparent plastic base film / Corona treatment layer> / Extruded laminate resin layer / Anchor coat layer / Paper base Material layer / anchor coat layer / extruded laminate resin layer / <heat-sealable coat layer / polyolefin film> / laminate adhesive layer / <gas barrier coating film / inorganic oxide deposition layer / base film layer> / corona treatment layer / Laminate adhesive layer / heat seal layer, etc.

  FIG. 2 shows a standing pouch-type retort processing paper container made by using the above laminated material. As the opening means for facilitating the opening of the container (100) on the lower side of the upper seal part (180), a half cut line (130) and a notch (120) at one end thereof are provided. Without using a tool such as a scissors, the entire upper part of the container (100) can be opened by easily tearing along the half-cut line (130) starting from the notch (120). Therefore, even when the content is a large solid, the content can be easily taken out.

  In addition, a gusset portion (190) is formed such that the bottom portion is between the lower portions of the front and rear wall laminates (150) and the bottom laminate material is folded inward to the bottom laminate return portion (110). In this case, semi-elliptical bottom laminated material notch portions (110a, 110b) are provided in the vicinity of the lower ends on both sides of the bottom laminated material that is formed in the inner shape, However, it is formed by heat-sealing the edge portions on both sides of the front and rear wall laminates (150) with side seal portions (160a, 160b).

  The seal pattern of the bottom seal portion (170) that heat-seals the bottom gusset portion (190) is a bottom-bottom-shaped seal pattern in which the inside rises linearly from the bottom with a predetermined width to both sides with an inclination toward the outside. The front and back wall laminates (150) are provided with longitudinal creases (125). Due to the seal pattern of the bottom seal portion (170) and the stamped rule (125) provided on the front and rear wall laminates (150), the spreading shape of the bottom of the container (100) after filling the contents becomes a hexagonal shape. Also, since the upper and lower four creases (125) are bent and spread, the container body becomes a stable hexagonal column, and the leg area formed by the heat seal part on the outer periphery of the bottom is large. Therefore, the rigidity of the container (100) can be secured, the self-supporting property of the container (100) can be ensured, the shape retaining property can be further improved, and the swelling of the body can be prevented, so that the appearance can be further improved. However, the self-supporting bag-shaped container of the present invention is not limited to the standing pouch type shown in FIG. 3, and is also suitable for other self-supporting bag-shaped containers.

  Since the self-supporting bag-like container of the present invention as described above has a form in which the main body portion is provided with self-supporting property by forming the bottom portion in the form of a gusset like a normal standing pouch, It can be manufactured using a conventional bag making machine for standing pouches. If necessary, the shape of the sealing head such as a hot plate that heat-seals the bottom gusset portion is changed, and a half-cut line or notch is provided as an opening means on the top of the container. Add an irradiation device, punching device, etc. to the bag making machine for the standing pouch, and if you want to provide stamping on the front and back wall laminates, add a hot press device or embossing device, etc. Both can be easily manufactured.

  However, the retort processing paper container of the present invention is not limited to the type shown in FIG. 2, but is suitable for a brick type or other retort processing paper container.

(2) Outermost layer As the outermost layer that can be used in the present invention, a plastic substrate can be used, and the retort-treated paper container of the present invention, particularly a mechanical and physical enough for use in a self-supporting bag-like container. A resin having excellent chemical strength and particularly excellent heat resistance, moisture resistance, pinhole resistance, puncture resistance, and the like can be widely used. For example, as resins having excellent heat resistance and water resistance, polyesters such as polyethylene terephthalate, polyamides such as various nylons, polypropylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, metallocene Ethylene-α / olefin copolymer polymerized using a catalyst, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid Copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene, polyolefin resin such as acrylic acid, Acid-modified polyolefin resins, polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, polyesters modified with unsaturated carboxylic acids such as phosphoric acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid A uniaxial or biaxially stretched film such as a resin, a polyamide resin, a polyaramid resin, a polycarbonate resin, a polyacetal resin, or a fluorine resin can be suitably used. In the present invention, a polyester resin such as polypropylene resin and polyethylene terephthalate can be suitably used as the outermost layer that is particularly excellent in heat resistance and water resistance. In particular, when the retort processing container of the present invention is a self-supporting bag-like container, it is preferable to have a self-supporting retention formation, and if it is a polypropylene resin or a polyester resin, it has excellent mechanical and chemical strength, And such a waist can be provided. Moreover, since the surface is glossy, the appearance of the container can be improved, and further, printing by printing and the like can be performed. In particular, when used for retort treatment, it is preferable to use polyesters such as polyethylene terephthalate, polyamides such as various nylons, and polypropylene, from the viewpoint of excellent heat resistance and water resistance.

  The outermost layer such as a transparent plastic substrate is made of, for example, one or more of the above-mentioned various resins and formed into a film such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, and others. A method of forming a film of the above-mentioned various resins alone using a method, a method of forming a multilayer co-extrusion film using two or more kinds of resins, and further, two or more kinds of resins Used to produce various resin films by mixing and forming a film before forming a film, for example, using a tenter method or a tubular method in one or two axial directions Various resin films formed by stretching can be used.

  On the other hand, it is not limited to the case of laminating in a laminate as a film, and may be a case of laminating on a paper substrate layer by melt extrusion or the like. That is, one or more of the above resins can be used, stretched or unstretched to be used as a film, or melt-extruded using an extruder or the like, and paper via an anchor coating agent layer or the like. It can be used as a transparent outermost layer by melt extrusion lamination on a base material layer.

  In the present invention, the film thickness of the outermost layer is preferably about 6 to 100 μm, more preferably about 9 to 50 μm.

(3) Paper base material As the paper base material used in the present invention, since it becomes a basic material constituting the paper container, a material having formability, flex resistance, rigidity, waist, strength, etc. is used. It is preferable. For example, it is possible to use a strong-size bleached or unbleached paper substrate, or various paper substrates such as pure white roll paper, kraft paper, paperboard, processed paper, and the like. In the present invention, the paper base has a density of about 0.60 to 1.00 and an edge wick of 0.20 in order to suppress water absorption due to hot water or the like in the retort treatment. It is preferable to use one having a size of ˜0.50 g or less and a sizing degree of about 400 to 1200.

In the present invention, the paper base material has a basis weight of about 50 to 600 g / m ² , preferably a basis weight of about 60 to 450 g / m ² , particularly a basis weight of 70 to 280 g / m ^2. Can be used. In the case of a self-supporting bag-like retort-treated paper container such as a standing pouch, it is particularly preferable to use one having a basis weight of 70 to 280 g / m ² . When the rice basis weight is less than 70 g / m ^{2, the} effect of improving the rigidity of the laminated material cannot be obtained sufficiently, and the shape retention of the container may be insufficient. In addition, when the basis weight of the rice exceeds 280 g / m ² , the rigidity of the laminated material becomes too strong, the openability of the container is deteriorated, and the workability of heat sealing may be lowered. The thickness of the thick paper is preferably 400 seconds or more from the viewpoint of safer retort processing after filling the contents, and the upper limit is not particularly limited, but about 1200 seconds is appropriate from the economical and technical viewpoints. It is. If the thick paper sizing degree is less than 400 seconds, the water resistance is insufficient, and during retort treatment, moisture tends to be absorbed from the end face of the cardboard, which is not preferable. The cardboard is preferably a strong sized cardboard. For example, a cup base paper or a milk carton base paper can be suitably used. In addition, the above-mentioned steecht sizing degree is a value measured according to the steadily sizing degree test method of JIS P8122.

  The above configuration improves the water resistance of the cardboard laminated on the container wall laminate, so that when the self-supporting bag-shaped container filled with the contents is retorted, moisture permeation from the end face of the cardboard is prevented. The amount can be further reduced, and the retort processing can be performed more safely. In addition, since the paper base material layer is laminated on the wall laminate before and after forming the body of the container, moderate rigidity is given, the shape retention of the container is improved, and the contents are easily crushed. Even if you can protect it. Moreover, since the rigidity of the leg part formed by the heat seal part on the outer periphery of the bottom surface is increased at the lower part of the container, the self-supporting property of the container is further improved.

  In the present invention, for example, a desired printed pattern such as a character, a figure, a pattern, a symbol, or the like may be arbitrarily formed on the paper base by a normal printing method.

(4) Intermediate base material layer In this invention, the intermediate base material layer which consists of laminated | multilayer film (II) of a polyolefin film and a heat-sealable coating layer is provided between a paper base material and a gas barrier laminated film. Thereby, the adhesiveness of a paper base material and a gas barrier laminated film can be improved, and the gas barrier characteristic original with a gas barrier laminated film can be exhibited.

  In order to improve the adhesion between the gas barrier laminate film used in the present invention and the paper substrate, it is effective to perform extrusion lamination of the molten resin, but it is necessary to extrude at a high temperature to obtain a high degree of adhesion. This treatment may reduce the gas barrier properties. Further, the adhesion between the paper substrate and the gas barrier laminate film is not easy, and the peel strength may decrease. Furthermore, since the molten resin to be used also has a high degree of adhesion, the price is high, which contributes to an increase in manufacturing cost.

  In the present invention, prior to extrusion lamination with a molten resin, a resin having a heat sealability is previously laminated on a gas barrier laminate film, and when the polyolefin is subjected to melt extrusion lamination on this heat sealable coating layer, the gas barrier properties are reduced. It was found that a low-priced general-purpose product can be used for the melt-extruded resin such as a polyolefin film to be used, and a laminated film (II) of a polyolefin film and a heat-sealable coating layer was used as an intermediate base material layer. .

  Polypropylene is preferred as the polyolefin in such a laminated film (II) because it does not elute particularly during heat sterilization.

  On the other hand, the heat-sealable coating layer is preferably a polyolefin resin or an acrylic resin, such as low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, etc. Polyolefin resin, chlorinated polyolefin resin such as chlorinated polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer Unsaturation such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and the like, a polymer, an ethylene-methyl methacrylate copolymer, a poly (meth) acrylic resin, a polyolefin resin such as polyethylene or polypropylene Modified with carboxylic acid Acrylic resins such as acid-modified polyolefin resins, ethylene-α / olefin copolymers polymerized using metallocene catalysts, ethylene-propylene copolymers, methylpentene polymers, polybutene polymers, polyvinyl acetate resins, polychlorinated resins One or more kinds of films or coating films made of a resin such as vinyl resin can be used. Among these, it is preferable to use a chlorinated polypropylene heat seal coat layer and an acrylic heat seal coat layer.

  For example, as the unstretched film of polyolefin resin, any film such as a film stretched in a uniaxial direction or a biaxial direction can be used. In the present invention, it is particularly preferable to use a biaxially stretched polypropylene film. The laminated film (II) can be prepared by applying and laminating a heat-sealable resin such as a chlorinated polypropylene heat seal coat layer to the polyolefin film.

  The intermediate substrate layer used in the present invention is not limited to the case where a polyolefin film and a heat-sealable coat layer are previously laminated, for example, a polyolefin film is laminated on a gas barrier laminate film, A heat-sealable film may be laminated on the polyolefin film as a heat-sealable coating layer. In this case, the polyolefin film and the heat-sealable coating layer are not limited to the case where a film prepared in advance is used, and may be laminated by melt extrusion or the like. Moreover, as such a laminated film (II), a commercial item can also be used, for example, the brand name "FOH" by the phthalam chemical company can be used.

  In the present invention, the thickness of the intermediate base material layer is not particularly limited as long as adhesion can be secured and shape retention can be maintained, but it is preferably 6 to 100 μm, more preferably 9 to 50 μm.

(5) Gas barrier laminate film The gas barrier laminate film used in the present invention is provided with an inorganic oxide vapor-deposited film on one surface of a base film layer, and the general formula R ¹ _n on the inorganic oxide vapor-deposited film. M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents 1 or an integer greater than or equal to 1 and n + m represents the valence of M.) and contains at least one alkoxide represented by: a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer; Furthermore, it is a laminated film provided with a gas barrier coating film made of a gas barrier composition obtained by polycondensation by a sol-gel method. The gas barrier coating film forms a strong three-dimensional network composite polymer layer by chemically reacting polyvinyl alcohol resin or ethylene / vinyl alcohol copolymer and one or more alkoxides with each other. The vapor deposition film of the product works synergistically, has excellent gas barrier properties that prevent permeation of oxygen, water vapor, etc., and is excellent in transparency, impact resistance, and hot water resistance.

(I) Base film layer The base film layer constituting the gas barrier laminate film has mechanical, physical and chemical strengths sufficient to provide an inorganic oxide vapor-deposited film and a gas barrier coating film. It is preferable to use a resin film that can withstand the conditions for forming a vapor-deposited film of an inorganic oxide and that can be satisfactorily maintained without impairing the properties of the vapor-deposited film of the inorganic oxide.

  Examples of such a base film layer include polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer. (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins Resin, Polyamideimide resin, Polyarylphthalate resin, Silicone resin, Polysulfone resin, Polyphenylene sulfide resin, Polyethersulfone resin, Polyurethane resin, Acetal resin, Cellulose Fat, can be used films composed of various resins other like. In particular, a film of a polypropylene resin, a polyester resin, or a polyamide resin is preferable.

  One or more of the above resins are used, and the resin is formed into a single layer using a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, or the like. Or two or more types of resin formed into a multilayer film by co-extrusion or the like, or a mixture of two or more types of resin to form a film, and a tenter method or a tubular method, etc. Various resin films formed by stretching in the axial direction can be used.

  In this invention, as a film thickness of a base film, about 6-100 micrometers, More preferably, about 9-50 micrometers is preferable.

(Ii) Surface treatment In the present invention, an inorganic oxide vapor-deposited film is formed on one surface of the base film layer, but the base film layer may be subjected to a surface treatment in advance. As a result, the adhesion with an inorganic oxide vapor deposition film or a gas barrier coating film can be improved.

  Such surface treatments include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc., and other pretreatments, etc. is there.

  In addition, a primer coating agent, an undercoat agent, an anchor coating agent, an adhesive, a vapor deposition anchor coating agent, or the like can be optionally applied to the surface of various films used in the present invention in advance. Examples of the coating agent include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyolefins such as polyethylene or polypropylene. A resin composition containing a resin or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used.

  Among such surface treatments, it is particularly preferable to perform corona treatment or plasma treatment. For example, as plasma processing, there is plasma processing in which surface modification is performed using a plasma gas generated by ionizing a gas by arc discharge. In addition to the above, an inorganic gas such as oxygen gas, nitrogen gas, argon gas, helium gas can be used as the plasma gas. In other words, immediately before forming a vapor-deposited film of inorganic oxide by physical vapor deposition or chemical vapor deposition described later, in-line plasma treatment removes moisture, dust, etc. on the surface of the base film. In addition, surface treatment such as smoothing, activation, etc. of the surface can be made possible. Furthermore, in the present invention, it is preferable to perform the plasma discharge treatment in consideration of the plasma output, the kind of plasma gas, the supply amount of the plasma gas, the treatment time, and other conditions. Moreover, as a method for generating plasma, DC glow discharge, high frequency discharge, microwave discharge, and other devices can be used. In addition, plasma treatment can be performed by an atmospheric pressure plasma treatment method.

  In addition, in this invention, in order to improve the adhesiveness with the surface of other resin films other than the said base film layer also on the vapor deposition film | membrane of an inorganic oxide, a gas barrier coating film, a printing layer, and other layers and films. In addition, any of the above surface treatments may be performed. For example, in the present invention, when the innermost layer is formed on the gas barrier coating film, a plasma treatment is performed on the gas barrier coating film, a printing layer is then formed, and a laminating adhesive is formed on the printing layer. The innermost layer may be laminated, the innermost layer is laminated on the gas barrier coating film via a primer and an adhesive for laminating by the dry laminating method, or the above innermost layer is laminated on the gas barrier coating film via a primer and an undercoat agent. A molten resin that can constitute the inner layer may be laminated by melt extrusion.

(Iii) Inorganic oxide vapor-deposited film As the inorganic oxide vapor-deposited film, for example, a chemical vapor deposition method, a physical vapor deposition method, or a combination of these is used to form a single layer of an inorganic oxide vapor-deposited film. It can be produced by forming a layer film or a multilayer film or a composite film composed of two or more layers.

  Examples of the chemical vapor deposition method include chemical vapor deposition methods such as plasma chemical vapor deposition method, low temperature plasma chemical vapor deposition method, thermal chemical vapor deposition method, and photochemical vapor deposition method (Chemical Vapor Deposition method), CVD method). Specifically, on one surface of the base film layer, a monomer gas for vapor deposition such as an organosilicon compound is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen is supplied. An oxygen oxide vapor or the like can be used as a gas, and a vapor deposition film of an inorganic oxide such as silicon oxide can be formed using a low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like.

  In the above, as a low temperature plasma generator, generators, such as high frequency plasma, pulse wave plasma, and microwave plasma, can be used, for example. In view of obtaining highly active and stable plasma, it is preferable to use a high-frequency plasma generator.

  An example of a method for forming a vapor-deposited film of an inorganic oxide by the low temperature plasma chemical vapor deposition method will be described with reference to FIG. 3 which is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus.

  In the present invention, the base film layer 201 is unwound from the unwinding roll 223 disposed in the vacuum chamber 222 of the plasma chemical vapor deposition apparatus 221, and the base film layer 201 is further passed through the auxiliary roll 224 in a predetermined manner. At the speed of cooling / conveying on the circumferential surface of the electrode drum 225. On the other hand, a gas mixture for vapor deposition is prepared by supplying vapor deposition monomer gas such as oxygen gas, inert gas, organosilicon compound, etc. from the gas supply devices 226, 227 and the raw material volatilization supply device 228, etc. Is introduced into the vacuum chamber 222 through the raw material supply nozzle 229. The vapor deposition mixed gas composition is supplied onto the substrate film layer 201 transported on the cooling / electrode drum 225 circumferential surface, and plasma is generated and irradiated by glow discharge plasma 230 to irradiate inorganic oxide such as silicon oxide. The deposited film of the object is formed into a film. Next, if the base film layer 201 on which the inorganic oxide vapor deposition film such as silicon oxide is formed is wound around the winding roll 234 via the auxiliary roll 233, the inorganic oxide vapor deposition is performed by the plasma chemical vapor deposition method. A film can be formed. A predetermined power is applied to the cooling / electrode drum 225 from a power source 231 disposed outside the vacuum chamber 222, and a magnet 232 is disposed in the vicinity of the cooling / electrode drum 225 to promote plasma generation. Has been. Since a predetermined voltage is applied from the power source to the cooling / electrode drum in this way, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. The glow discharge plasma is derived from one or more gas components in the mixed gas. When the base film layer is conveyed at a constant speed in this state, the glow discharge plasma causes the cooling / electrode drum peripheral surface to be conveyed. A vapor-deposited film of an inorganic oxide such as silicon oxide can be formed on the upper base film layer. In FIG. 3, reference numeral 235 represents a vacuum pump.

In the present invention, the vacuum chamber is depressurized by a vacuum pump and adjusted to a vacuum degree of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a vacuum degree of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is preferable to do.

The raw material volatilization supply device volatilizes the organic silicon compound as the raw material, mixes it with oxygen gas, inert gas, etc. supplied from the gas supply device, and introduces this mixed gas into the vacuum chamber through the raw material supply nozzle. . At this time, the content of the organosilicon compound in the mixed gas is preferably 1 to 40%, the oxygen gas content is 10 to 70%, and the inert gas content is preferably 10 to 60%. For example, the mixing ratio of organosilicon compound: oxygen gas: inert gas can be about 1: 6: 5 to 1:17:14. Note that the degree of vacuum in the vacuum chamber when supplying the organosilicon compound, the inert gas, the oxygen gas, and the like is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr is preferable, and the conveying speed of the base film layer is 10 to 300 m / min, preferably 50 to 150 m / min. Formation of a vapor-deposited film of inorganic oxide such as silicon oxide obtained in this way is formed on the base film layer in the form of a thin film in the form of SiO _x while oxidizing the plasmaized source gas with oxygen gas. Therefore, the deposited inorganic oxide vapor deposition film such as silicon oxide is a dense continuous layer having a small gap and rich in flexibility. Therefore, the barrier property of the vapor deposition film of inorganic oxide such as silicon oxide is Compared with a deposited film of an inorganic oxide such as silicon oxide formed by a conventional vacuum deposition method or the like, a sufficiently high barrier property can be obtained with a thin film thickness. In addition, since the surface of the base film layer is cleaned by SiO _x plasma and polar groups, free radicals, etc. are generated on the surface of the base film layer, a deposited film of inorganic oxide such as silicon oxide is formed. The close adhesion with the base film layer is high. Further, the degree of vacuum when forming a continuous film of an inorganic oxide such as silicon oxide is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Since the vacuum degree when forming a deposited film of an inorganic oxide such as silicon oxide by the conventional vacuum deposition method is lower than 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, It is possible to shorten the vacuum state setting time when the material film layer is exchanged, and the degree of vacuum is easily stabilized, and the film forming process is also stabilized.

In the present invention, a vapor deposition film of silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas, and the reaction product is It closely adheres to one surface of the base film layer to form a dense, flexible thin film, and is usually represented by the general formula SiO _x (where X represents a number from 0 to 2). It is a continuous thin film mainly composed of silicon oxide. The silicon oxide vapor deposition film is a silicon oxide vapor deposition represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) in terms of transparency and barrier properties. A thin film mainly composed of a film is preferable. The value of X varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself is yellow. The transparency becomes worse.

In the present invention, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further contains at least one compound of carbon, hydrogen, silicon or oxygen, or a compound composed of two or more elements by chemical bonding or the like. It consists of a vapor deposition film. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the silicon oxide vapor deposition film can be varied by changing the conditions of the vapor deposition process. At this time, the content of the above-mentioned compound in the deposited film of silicon oxide is 0.1 to 50%, preferably 5 to 20%. When the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the deposited silicon oxide film become insufficient, and scratches, cracks, etc. are likely to occur due to bending, and high barrier properties are achieved. On the other hand, it may be difficult to maintain stably, and if it exceeds 50%, the barrier property may be lowered.

  Further, in the present invention, in the silicon oxide vapor-deposited film, it is preferable that the content of the above compound decreases in the depth direction from the surface of the silicon oxide vapor-deposited film. As a result, the impact resistance and the like are enhanced by the above-mentioned compound and the like on the surface of the silicon oxide vapor-deposited film. On the other hand, since the content of the above-mentioned compound is small at the interface with the base film layer, The tight adhesion with the deposited film becomes strong.

  In the present invention, the above-described vapor deposition film of silicon oxide uses, for example, a surface analyzer such as an X-ray photoelectron spectrometer (Xray), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), or the like. The above-mentioned physical properties can be confirmed by performing analysis such as ion etching in the vertical direction and performing elemental analysis of the deposited film of silicon oxide.

  In the present invention, the thickness of the silicon oxide vapor-deposited film is preferably about 50 to 4000 mm, more preferably 100 to 1000 mm. If it is thicker than 4000 mm, cracks or the like may occur in the film. On the other hand, if it is less than 50 mm, it may be difficult to achieve a barrier effect. The film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. As a means for changing the film thickness of the silicon oxide vapor deposition film, a method of increasing the volume velocity of the vapor deposition film, that is, a method of increasing the amount of monomer gas and oxygen gas, a method of slowing the vapor deposition rate, etc. be able to.

  In the present invention, the inorganic oxide vapor-deposited film may be not only one layer of the inorganic oxide vapor-deposited film but also a multilayer film in which two or more layers are laminated, and one or two materials are used. It is also possible to form a vapor-deposited film of an inorganic oxide that is used as a mixture of seeds or more and mixed with different materials.

  In the present invention, as a monomer gas for vapor deposition of an organic silicon compound or the like that forms a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyl Trimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane , Methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. Among these, it is particularly preferable to use 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material because of its handleability and the characteristics of the formed continuous film. In the above, as the inert gas, for example, argon gas, helium gas, or the like can be used.

  On the other hand, in the present invention, an inorganic oxide vapor-deposited film can also be formed by physical vapor deposition. As such a physical vapor deposition method, for example, an inorganic oxide can be formed by a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, an ion plating method, or an ion cluster beam method. A vapor deposition film can be formed.

  Specifically, a metal or metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one of the base film layers, or a metal or metal oxide as a raw material. Vapor deposition using an oxidation reaction deposition method in which oxygen is introduced and oxidized to deposit on one of the base film layers, and further a plasma-assisted oxidation reaction deposition method in which the oxidation reaction is supported by plasma. Can be formed. In addition, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used. A method for forming a thin film of an inorganic oxide by physical vapor deposition will be described with reference to FIG. 4 showing a schematic configuration diagram showing an example of a take-up vacuum deposition apparatus.

  First, the base film layer 201 fed out from the unwinding roll 243 is guided to the cooled coating drum 246 via the guide rolls 244 and 245 in the vacuum chamber 242 of the wind-up type vacuum deposition apparatus 241. The deposition source 248 heated by the crucible 247, for example, metal aluminum or aluminum oxide is evaporated on the base film layer 201 guided on the cooled coating drum 246, and if necessary. Then, an oxygen gas or the like is ejected from the oxygen gas outlet 249, and an inorganic oxide vapor deposition film such as aluminum oxide is formed through the masks 250 and 250 while supplying the oxygen gas. For example, when the base film layer 201 on which an inorganic oxide vapor deposition film such as aluminum oxide is formed is sent out through the guide rolls 251 and 252 and wound around the take-up roll 253, the inorganic oxide formed by physical vapor deposition is used. A vapor deposition film can be formed. In addition, using the above-described winding-type vacuum vapor deposition apparatus, first, a first-layer inorganic oxide vapor-deposited film is formed, and then an inorganic oxide vapor-deposited film is further formed thereon, or A vacuum evaporation apparatus may be connected in series, and an inorganic oxide vapor deposition film may be continuously formed to form an inorganic oxide vapor deposition film composed of a multilayer film of two or more layers.

The vapor deposition film of metal or inorganic oxide may basically be a thin film on which a metal oxide is deposited, for example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca). , Vapor deposition films of metal oxides such as potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) Can be used. Preferably, a vapor-deposited film of a metal oxide such as silicon (Si) or aluminum (Al) can be used. Therefore, the metal oxide vapor deposition film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, and the like, for example, SiO _x , AlO _x , MgO. MO _X (in the formula, M represents a metal element, the value of X is in the range respectively of a metal element different.) as _X, etc. represented by.

  In addition, as the range of the value of X, silicon (Si) exceeds 0 and 2 or less, aluminum (Al) exceeds 0 and 1.5 or less, magnesium (Mg) exceeds 0 and 1 or less, calcium (Ca ) Is greater than 0 and less than or equal to 1, potassium (K) is greater than 0 and less than or equal to 0.5, tin (Sn) is greater than 0 and less than or equal to 2, sodium (Na) is greater than 0 and less than or equal to 0.5, and boron (B) is 0 to 1, 5 or less, Titanium (Ti) is more than 0 to 2 or less, Lead (Pb) is more than 0 to 1 or less, Zirconium (Zr) is more than 0 to 2 or less, Yttrium (Y) is more than 0 to 1 .5 or less. In the above, when X = 0, it is a complete metal, and the upper limit of the range of X is a completely oxidized value. Generally, examples other than silicon (Si) and aluminum (Al) are poor. Therefore, in the present invention, silicon or aluminum is preferable as M. In this case, the value of X is 1.0 to 2.0 for silicon (Si) and 0.5 to 1.5 for aluminum (Al). It is a range. In addition, although the film thickness of the vapor deposition film | membrane of an inorganic oxide changes with kinds etc. of the metal to be used or a metal oxide, it can select arbitrarily within the range of 50-2000 mm, for example, Preferably, it is 100-1000 mm. it can. In addition, as the inorganic oxide vapor deposition film, the metal or metal oxide to be used is used in one kind or a mixture of two or more kinds to constitute a vapor deposition film of an inorganic oxide mixed with different materials. You can also.

  Further, in the present invention, for example, a composite film composed of two or more vapor-deposited films of different kinds of inorganic oxides can be formed by using both physical vapor deposition and chemical vapor deposition.

  As a composite film composed of two or more layers of the above-mentioned different types of inorganic oxide vapor-deposited films, first, on the base film layer, a chemical vapor deposition method is used. An inorganic oxide vapor deposition film capable of preventing generation is provided, and then an inorganic oxide vapor deposition film formed by physical vapor deposition is provided on the inorganic oxide vapor deposition film to form a composite film composed of two or more layers. It is preferable to constitute a vapor-deposited film of inorganic oxide consisting of Contrary to the above, an inorganic oxide vapor-deposited film is first formed on the base film layer by physical vapor deposition, and then dense and flexible by chemical vapor deposition. It is also possible to provide an inorganic oxide vapor-deposited film composed of a composite film composed of two or more layers by providing an inorganic oxide vapor-deposited film that can relatively prevent the occurrence of cracks.

(Iv) Gas barrier coating film The gas barrier coating film used in the present invention has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic having 1 to 8 carbon atoms). Represents a group, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. It contains the above alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. A coating film made of a gas barrier composition, which is coated on the inorganic oxide vapor-deposited film on the substrate film layer to provide a coating film. 10 seconds to 10 seconds at a temperature below the melting point of the base film layer It can be formed by between heat treatment.

  Further, the gas barrier composition is coated on the inorganic oxide vapor-deposited film on the base film layer, and two or more coating films are stacked, and the base film layer has a temperature of 20 to 180 ° C. A composite polymer layer in which two or more gas barrier coating films are stacked may be formed by heat treatment for 10 seconds to 10 minutes at a temperature equal to or lower than the melting point.

As the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , at least one of alkoxide partial hydrolyzate and alkoxide hydrolysis condensate can be used. The partial hydrolyzate is not limited to the one in which all of the alkoxy groups are hydrolyzed, and may be one in which one or more are hydrolyzed, or a mixture thereof, and further a hydrolysis condensate. As a dimer or more of a partially hydrolyzed alkoxide, specifically, a dimer or hexamer may be used.

In the general formula R ¹ _n M (OR ² ) _m , R ¹ is an alkyl group having 1 to 8, preferably 1 to 5, more preferably 1 to 4 carbon atoms which may have a branch. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group, etc. Can be mentioned.

In the general formula R ¹ _n M (OR ² ) _m , R ² is an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 5, and particularly preferably 1 to 4 which may have a branch. Yes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and the like. When a plurality of (OR ² ) are present in the same molecule, (OR ² ) may be the same or different.

Examples of the metal atom represented by M in the general formula R ¹ _n M (OR ² ) _m include silicon, zirconium, titanium, aluminum, and the like.

In the present invention, silicon is preferable. In this case, as an alkoxide that can be preferably used in the present invention, when n = 0 in the general formula R ¹ _n M (OR ² ) _m , the general formula Si (ORa) ₄ (wherein Ra is Represents an alkyl group having 1 to 5 carbon atoms). In the above, Ra includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. Specific examples of such an alkoxysilane include tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si ( OC ₄ H ₉₎ can be exemplified ₄ like.

In the case where n is 1 or more, the general formula RbnSi (ORc) _4-m (wherein m represents an integer of 1, 2, 3 and Rb and Rc are a methyl group, an ethyl group, An alkylalkoxysilane represented by n-propyl group, n-butyl group, etc.) can be used. Examples of such an alkylalkoxysilane include methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OC ₂ H ₅ ) ₃ , dimethyldimethoxysilane (CH ₃ ) ₂ Si (OCH). _{3) 2,} dimethyl diethoxy silane _{(CH 3) 2 Si (OC} 2 H 5) 2, may use other like. In the present invention, the above alkoxysilane, alkylalkoxysilane and the like may be used alone or in combination of two or more.

  In the present invention, a polycondensation product of the above alkoxysilane can also be used, and specifically, for example, polytetramethoxysilane, polytetraemethoxysilane, and the like can be used.

In the present invention, a zirconium alkoxide in which M is Zr can also be suitably used as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m . For example, tetramethoxyzirconium Zr (OCH ₃ ) ₄ , tetraethoxyzirconium Zr (OC ₂ H ₅ ) ₄ , tetra ipropoxyzirconium Zr (iso-OC ₃ H ₇ ) ₄ , tetra n butoxyzirconium Zr (OC ₄ H ₉ ) ₄ , etc. can be exemplified.

Further, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , a titanium alkoxide in which M is Ti can be preferably used. For example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetra Examples include ethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (iso-OC ₃ H ₇ ) ₄ , tetra-n-butoxytitanium Ti (OC ₄ H ₉ ) ₄ , and others.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , an aluminum alkoxide in which M is Al can be used. For example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum _{Al (OC 2 H 5) 4} , tetraisopropoxy aluminum _{Al (is0-OC 3 H 7} ) 4, tetra-n-butoxy aluminum _{Al (OC 4 H 9) 4} , may use other like.

  In the present invention, two or more of the alkoxides may be used in combination. For example, when alkoxysilane and zirconium alkoxide are mixed and used, the toughness, heat resistance and the like of the resulting gas barrier laminate film can be improved, and a decrease in the retort resistance of the film during stretching can be avoided. Under the present circumstances, the usage-amount of a zirconium alkoxide is the range of 10 mass parts or less with respect to 100 mass parts of said alkoxysilanes. When the amount exceeds 10 parts by mass, the formed gas barrier coating film tends to gel, and the brittleness of the film increases, and the gas barrier coating film tends to peel off when the base film layer is coated. Therefore, it is not preferable.

  In addition, when alkoxysilane and titanium alkoxide are mixed and used, the thermal conductivity of the resulting gas barrier coating film is lowered, and the heat resistance is remarkably improved. Under the present circumstances, the usage-amount of a titanium alkoxide is the range of 5 mass parts or less with respect to 100 mass parts of said alkoxysilane. When the amount exceeds 5 parts by mass, the brittleness of the formed gas barrier coating film increases, and the gas barrier coating film may be easily peeled off when the base film layer is coated.

  As the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer used in the present invention, a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer can be used alone, respectively, or polyvinyl alcohol A single resin and an ethylene / vinyl alcohol copolymer can be used in combination. In the present invention, physical properties such as gas barrier properties, water resistance, weather resistance, and the like can be remarkably improved by using a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer.

  When the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is polyvinyl alcohol resin: ethylene / vinyl alcohol copolymer = 10: 0. It is preferable that the position is from 05 to 10: 6.

  The content of the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by mass, preferably 20 to 200 parts by mass with respect to 100 parts by mass of the total amount of the alkoxide. The blending ratio of When it exceeds 500 parts by mass, the brittleness of the gas barrier coating film becomes large, and the water resistance and weather resistance of the resulting barrier film may be lowered. On the other hand, if it is less than 5 parts by mass, the gas barrier property may be lowered.

  In the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, as the polyvinyl alcohol resin, one obtained by saponifying polyvinyl acetate can be generally used. Polyvinyl alcohol resins include partially saponified polyvinyl alcohol resins in which several tens of percent of acetate groups remain, completely saponified polyvinyl alcohols in which no acetate groups remain, and modified polyvinyl alcohol resins in which OH groups have been modified. Well, not particularly limited. Examples of such a polyvinyl alcohol resin include “RS-110 (degree of saponification = 99%, degree of polymerization = 1,000)” manufactured by Kuraray Co., Ltd., and “Kuraray Poval LM-20SO ( “Saponification degree = 40%, polymerization degree = 2,000)”, “GOHSENOL NM-14 (degree of saponification = 99%, polymerization degree = 1,400)” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Can do.

  As the ethylene / vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer can be used. For example, it is not particularly limited, and includes a partially saponified product in which several tens mol% of acetic acid groups remain to a complete saponified product in which only several mol% of acetic acid groups remain or no acetic acid groups remain. However, it is preferable to use a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. In addition, the content of the repeating unit derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. It is preferable. Examples of such an ethylene / vinyl alcohol copolymer include “Eval EP-F101 (ethylene content; 32 mol%)” manufactured by Kuraray Co., Ltd., “Soarnol D2908 (ethylene content; 29 mol) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.” %) "And the like.

The gas barrier composition used in the present invention has the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M is Represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) And a gas barrier obtained by polycondensation by the sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. Composition. In preparing the gas barrier composition, a silane coupling agent or the like may be added.

  As the silane coupling agent that can be suitably used in the present invention, known organic reactive group-containing organoalkoxysilanes can be widely used. For example, an organoalkoxysilane having an epoxy group is suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3,4-epoxy). (Cyclohexyl) ethyltrimethoxysilane or the like can be used. Such silane coupling agents may be used alone or in combination of two or more. In addition, the usage-amount of a silane coupling agent exists in the range of 1-20 mass parts with respect to 100 mass parts of said alkoxysilanes. If 20 parts by mass or more is used, the gas barrier coating film to be formed has increased rigidity and brittleness, and the insulation and workability of the gas barrier coating film may be lowered.

  The sol-gel catalyst is a catalyst mainly used as a polycondensation catalyst, and a basic substance such as tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. For example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc. can be used. In the present invention, N, N-dimethylbenzylamine is particularly preferred. The usage-amount is 0.01-1.0 mass part per 100 mass parts of total amounts of an alkoxide and a silane coupling agent.

  The “acid” used in the gas barrier composition is mainly used as a catalyst for hydrolysis of an alkoxide, a silane coupling agent or the like in the sol-gel method. For example, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, organic acids such as acetic acid and tartaric acid, and the like can be used. The amount of the acid used is preferably 0.001 to 0.05 mol based on the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety).

  Furthermore, in the gas barrier composition, water can be used in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, relative to 1 mol of the total molar amount of the alkoxide. When the amount of water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally crosslinked to form a porous polymer having a low density, Such a porous polymer cannot improve the gas barrier property of the gas barrier laminate film. Moreover, when the amount of the water is less than 0.8 mol, the hydrolysis reaction may hardly proceed.

  Furthermore, as an organic solvent used in said gas-barrier composition, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used, for example. The polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably handled in a state of being dissolved in a coating solution containing the alkoxide, silane coupling agent, or the like. It can be selected appropriately. For example, when a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in combination, it is preferable to use n-butanol. An ethylene / vinyl alcohol copolymer solubilized in a solvent can also be used. For example, trade name “Soarnol” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be preferably used. The amount of the organic solvent used is usually 30 to 500 with respect to 100 mass of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel catalyst. Part by mass.

  In the present invention, the gas barrier laminate film can be produced by the following method.

  First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel catalyst, an acid, water, an organic solvent, and, if necessary, a metal alkoxide Etc. are mixed to prepare a gas barrier composition. By mixing, the gas barrier composition (coating liquid) starts and proceeds with a polycondensation reaction.

  Next, the above gas barrier composition is applied onto the inorganic oxide vapor-deposited film on the base film layer by a conventional method and dried. By this drying step, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer further proceeds, and a coating film is formed. . On the first coating film, the above coating operation may be further repeated to form a plurality of coating films composed of two or more layers.

  Next, the base film layer to which the gas barrier composition is applied is 20 ° C. to 180 ° C. and a temperature not higher than the melting point of the base film layer, preferably at a temperature in the range of 50 ° C. to 160 ° C. for 10 seconds to 10 seconds. Heat for minutes. This makes it possible to produce a barrier film in which one or more gas barrier coating films of the gas barrier composition are formed on the inorganic oxide vapor-deposited film.

  A barrier film obtained by using an ethylene / vinyl alcohol copolymer alone or both a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer is excellent in gas barrier properties after hydrothermal treatment. On the other hand, when a barrier film is produced using only a polyvinyl alcohol-based resin, a first coating film is formed by previously applying a gas barrier composition using a polyvinyl alcohol-based resin, On the coating film, a gas barrier composition containing an ethylene / vinyl alcohol copolymer is applied to form a second coating film, and when these composite layers are formed, the gas barrier properties after hydrothermal treatment It is possible to produce a barrier film with improved resistance.

  Further, a coating film is formed by the gas barrier composition containing the ethylene / vinyl alcohol copolymer, or the gas barrier composition containing a combination of the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer is applied. Even if a film is formed and a plurality of these films are laminated, it becomes an effective means for improving the gas barrier property of the barrier film according to the present invention.

  The production method of the gas barrier laminate film used in the present invention will be described in more detail using alkoxysilane as the alkoxide.

  The alkoxysilane and metal alkoxide blended as the gas barrier composition are hydrolyzed by the added water. During the hydrolysis, the acid acts as a hydrolysis catalyst. Next, protons are taken from the hydroxyl groups generated by the hydrolysis by the action of the sol-gel catalyst, and the hydrolysis products are dehydrated and polycondensed. At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group.

  In addition, the opening of the epoxy group also occurs due to the action of the base catalyst, generating a hydroxyl group. In addition, a polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds. In the reaction system, polyvinyl alcohol resin, ethylene / vinyl alcohol copolymer, or polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer are present, so polyvinyl alcohol resin and ethylene / vinyl alcohol copolymer are present. Reaction with the hydroxyl group of the polymer also occurs. In addition, the polycondensate to be generated includes, for example, an inorganic part composed of a bond such as Si—O—Si, Si—O—Zr, Si—O—Ti, and the like, and an organic part resulting from the silane coupling agent. It is a composite polymer containing.

  In the above reaction, for example, a linear polymer having a partial structural formula represented by the following formula (III) and further having a portion derived from a silane coupling agent is first formed.

  This polymer has an OR group (an alkoxy group such as an ethoxy group) branched from a linear polymer. The OR group is hydrolyzed to become an OH group using an existing acid as a catalyst, and the OH group is first deprotonated by the action of a sol-gel catalyst (base catalyst), and then polycondensation proceeds. That is, this OH group undergoes a polycondensation reaction with a polyvinyl alcohol-based resin represented by the following formula (I) or an ethylene / vinyl alcohol copolymer represented by the following formula (II) to form Si—O—Si. For example, it is considered that a composite polymer represented by the following formula (IV) or a copolymerized composite polymer represented by the following formulas (V) and (VI) is formed.

  The above reaction proceeds at room temperature, and the viscosity of the gas barrier composition increases during preparation. When this gas barrier composition is applied onto an inorganic oxide vapor-deposited film on a base film layer and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed, and the base film A transparent coating film is formed on the inorganic oxide vapor deposition film on the layer. In addition, when laminating | stacking two or more said coating films, the composite polymer in the coating film of an interlayer is also condensed, and a layer couple | bonds firmly between layers.

  Furthermore, the organic reactive group of the silane coupling agent and the hydroxyl group generated by hydrolysis are bonded to the hydroxyl group on the surface of the base film layer, or the deposited film of the inorganic oxide on the base film layer, The adhesion between the base film layer or the surface of the inorganic oxide vapor deposition film and the coating film is also good. Thus, in the present invention, the inorganic oxide vapor-deposited film and the gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by hydrolysis / co-condensation reaction. Adhesion between the oxide vapor deposition film and the gas barrier coating film is improved, and a better gas barrier effect can be exhibited by the synergistic effect of the two layers.

In the present invention, when the amount of water added is adjusted to 0.8 to 2 mol, preferably 1.0 to 1.7 mol, relative to 1 mol of alkoxides, the above linear polymer is used. Is formed. Such a linear polymer has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part. Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the molecular aggregation energy is high. Since the rigidity is also high, it is particularly excellent in gas barrier properties (blocking and blocking permeation of O ₂ , N ₂ , H ₂ O, CO ₂ , etc.).

  Examples of the method for applying the gas barrier composition of the present invention include, for example, once by a roll coater such as a gravure roll coater, spray coat, spin coat, dipping, brush, bar code, applicator or the like. A coating film having a dry film thickness of 0.01 to 30 μm, preferably about 0.1 to 10 μm, can be formed by applying a plurality of times. Further, under a normal environment, 50 to 300 ° C., preferably The gas barrier coating film of the present invention is formed by performing condensation at a temperature of 70 to 200 ° C. by heating and drying for 0.005 to 60 minutes, preferably 0.01 to 10 minutes. Can do.

(6) Innermost layer For the innermost layer, polyolefin resins having various heat sealing properties that can be melted by heat and fused together can be used. Examples of such heat-sealable resins include low-density polyethylene (hereinafter referred to as LDPE), linear low-density polyethylene (hereinafter referred to as LLDPE), and ethylene-α · polymerized using a single-site catalyst. Olefin copolymer, ethylene-vinyl acetate copolymer (hereinafter referred to as EVA), ethylene-acrylic acid copolymer (hereinafter referred to as EAA), ethylene-ethyl acrylate copolymer (hereinafter referred to as EEA) Described), ethylene-methyl acrylate copolymer (hereinafter referred to as EMA), ethylene-methacrylic acid copolymer (hereinafter referred to as EMAA), ionomer, amorphous polyester, polypropylene, propylene-ethylene copolymer Polymer (copolymer with ethylene content of 10 mol% or less) or unsaturated carbon Non-stretched film such as polypropylene resin, medium-density polyethylene, high-density polyethylene, etc., which is graft polymerized or copolymerized with acid, unsaturated carboxylic acid anhydride or ester monomer, or a resin layer obtained by extrusion-coating these resins Can be used.

  The propylene-ethylene copolymer has an ethylene content of 10 mol% or less, for example, in the range of 5 to 10 mol%, and is suitable for extrusion without detracting from the advantages such as heat resistance and rigidity of polypropylene. Heat sealability and impact strength at low temperatures can be improved.

  In the case of graft polymerization of unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or ester monomer to polypropylene with the polypropylene resin, specific examples of the graft component include acrylic acid, methacrylic acid, methacrylic acid. Glycidyl, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethyl maleate, monoethyl maleate, di-n-butyl maleate, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride , 5-norbornene-2,3-anhydride, citraconic acid, citraconic anhydride, crotonic acid, crotonic anhydride, acrylonitrile, methacrylonitrile, sodium acrylate, calcium acrylate, magnesium acrylate, and the like. Among these, a polypropylene resin obtained by graft polymerization of maleic anhydride onto polypropylene can be particularly preferably used because of cost and ease of graft polymerization.

  On the other hand, if the innermost layer has heat resistance, it is necessary to have heat resistance capable of heat-sealing between itself and each other, and at the same time, heat resistance to withstand retort sterilization treatment. As such a heat-resistant heat-sealable resin layer, the polypropylene, the propylene-ethylene copolymer (copolymer having an ethylene content of 10 mol% or less), or an unsaturated carboxylic acid or an unsaturated carboxylic acid on polypropylene. A polypropylene resin obtained by graft polymerization or copolymerization of an anhydride or an ester monomer, an unstretched film such as medium density polyethylene or high density polyethylene, or a resin layer obtained by extrusion coating of these resins can be used. However, in addition to the above, linear low-density polyethylene (hereinafter referred to as LLDPE), amorphous polyester, etc. may also be used when processed under heating conditions called semi-retort processing. it can.

  As a result, the container of the retort processing paper container of the present invention is formed by heat-sealing the side edge portions of the front and back wall laminates with the side seal portions and the bottom portion of the bottom laminate. Since the container is filled in with a gusset part, the bottom of the container is expanded widely in front and back to form a three-dimensional structure. Can be packaged.

  In the present invention, one or more of the above-mentioned resins are used and melt-extruded using an extruder or the like, and the melt-extruded resin layer is melt-extruded and laminated through an anchor coating agent layer or the like. Or by using one or more of the above-mentioned resins, and manufacturing a resin film from the same in advance, and laminating the resin film via a laminating adhesive layer or the like By doing so, the innermost layer can be formed by melt extrusion lamination through a melt extrusion resin layer or the like.

  The thickness of the innermost layer is about 5 to 200 μm, preferably about 10 to 100 μm.

(7) Print layer In the present invention, when a print layer is formed, it may be formed on the outermost layer or on a paper substrate. The printing method is not limited, but gravure printing is preferred. At this time, front printing or back printing may be used.

  Examples of the vehicle constituting the ink composition include polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, poly (meth) acrylic resins, polyvinyl chloride resins, polyvinyl acetate resins, and vinyl chlorides. Vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polybutadiene resin, polyester resin, polyamide resin, Alkyd resin, epoxy resin, unsaturated polyester resin, thermosetting poly (meth) acrylic resin, melamine resin, urea resin, polyurethane resin, phenol resin, xylene resin, maleic acid resin, nitro Cellulose, ethyl cell Cellulose, acetylbutylcellulose, ethyloxyethylcellulose and other fibrous resins, chlorinated rubber, cyclized rubber and other rubber resins, petroleum resins, rosin, casein and other natural resins, linseed oil, soybean oil and other fats and oils A mixture of one or two or more other resins can be used.

  The printing layer is mainly composed of one or more of the above-described ink vehicles, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a curing agent, and a crosslinking agent. Add one or more additives such as lubricants, antistatic agents, fillers, etc., add colorants such as dyes and pigments, and knead well with solvents, diluents, etc. Thus, an ink composition obtained by adjusting the ink composition can be used.

  The above is described in the gravure printing, but an offset ink composition, a relief printing ink composition, a screen ink composition, and other ink compositions are used, for example, a gravure printing method, an offset printing method, a relief printing method, a silk screen. The printing method and other printing methods can be used, for example, by forming a desired printed pattern made up of characters, figures, patterns, symbols, and the like.

(8) Plasma treatment In the present invention, the gas barrier coating film is preferably subjected to a plasma treatment in the surface treatment, whereby the adhesion of the laminated film can be improved.

In the plasma treatment for the gas barrier coating film, an inorganic gas such as oxygen gas, nitrogen gas, argon gas, and helium gas can be used as the plasma gas. In particular, oxygen gas or oxygen gas and argon gas can be used. It is preferable to perform plasma treatment using an inorganic gas containing oxygen gas as a plasma gas, such as a mixed gas. Further, it is possible to perform plasma treatment at a lower voltage, whereby there is no discoloration of the surface of the gas barrier coating film, and the surface of the gas barrier coating film has an OH group, for example, by a chemical reaction or the like. Etc., and Si—C bonds existing in the gas barrier coating film can be converted to SiO ₂ . Furthermore, by the above plasma treatment, the crosslink density of the gas barrier coating film by the gas barrier composition is increased, the humidity dependency thereof is improved, the gas barrier property against oxygen gas, as well as the barrier property against water vapor, Relatively, it is possible to stably maintain a high gas barrier property against oxygen gas, water vapor, etc., and furthermore, a plasma gas composed of an inorganic gas containing oxygen gas is applied to the surface of the gas barrier coating film in a vacuum. When a substrate such as an adhesive layer, an anchor coat layer, a heat-sealable resin layer, or the like is laminated on the plasma treatment layer by forming a plasma treatment layer by performing plasma treatment using the It improves the tight adhesion and the like, and makes it possible to remarkably increase the lamination strength and the like.

Specifically, it is desirable to use a mixed gas of oxygen gas and argon gas, and the gas pressure of the mixed gas of oxygen gas and argon gas is about 1 × 10 ^{−1 to} 10 −10 Torr, More preferably, the 1 × 10 ⁻² to 1 × 10 ⁻⁸ Torr position is desirable, and the ratio of oxygen gas to argon gas is oxygen gas: argon gas = 100: 0 to 30:70 in terms of partial pressure ratio. More preferably, the 90:10 to 70:30 position is desirable, and the plasma output is preferably about 100 to 2500 W, more preferably about 500 to 1500 W, and the processing speed is 100 ˜600 m / min, more preferably 200 to 500 m / min. When the partial pressure ratio between the oxygen gas and the argon gas is increased, if the argon gas partial pressure is increased, oxygen molecules activated by the plasma are reduced, the argon gas acts as a reducing gas, and the introduction of hydroxyl groups is inhibited. Is not preferable. In addition, when the plasma output is less than 100 W, more preferably less than 500 W, the activation of oxygen gas is lowered, and it is difficult to produce highly active oxygen atoms. Furthermore, if it exceeds 2500 W, the plasma output is too high, which is not preferable because it causes a problem that the physical properties of the coating itself deteriorate due to the deterioration of the gas barrier coating film or the like.

  Further, when the above processing speed is less than 100 m / min, further less than 250 m / min, the amount of oxygen plasma is small, and when it exceeds 600 m / min, and further exceeds 500 m / min, a gas barrier is obtained. Oxidation of the conductive coating film proceeds rapidly and the transparency becomes high, but the barrier property is lowered, which is not preferable.

  In the present invention, in plasma treatment, plasma can be generated by using three types of devices such as direct current glow discharge, radio frequency (AF) discharge, and microwave discharge. it can. In the present invention, a high frequency (AF) discharge device of 3.56 MHz can be used.

(9) Anchor coat layer In the present invention, for example, when laminating via a melt-extruded resin, such as a paper base material and the outermost layer, an anchor coat agent is applied in advance to the laminated surface in contact with the melt-extruded resin layer, An anchor coat layer can be formed. For example, in order to form an anchor coat layer on the paper base layer when bonding the paper base and the outermost layer, an organic titanium anchor coating agent such as alkyl titanate, an isocyanate anchor coating agent, or a polyethyleneimine anchor coat Agents, polybutadiene anchor coating agents, isocyanate (urethane), polyethylene imine, and other anchor coating agents. More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. What is made into a component can be used conveniently.

  If these anchor coat layers are formed on a paper substrate in advance, a thin film rich in flexibility and flexibility can be formed, and the melt-extruded resin layer acts as a film having flexibility, flexibility, and lamination. Processing suitability such as processing and printing can be improved.

  The anchor coat layer is not limited to the case where it is formed on a paper base material. For example, the anchor coat layer may be formed on a gas barrier coating film or a plasma-treated surface formed on the gas barrier coating film. Can be improved.

  In the present invention, the anchor coating agent is coated by roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating method, and the solvent, diluent, etc. are dried to form the anchor coating agent layer. can do.

The coating amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

(10) Primer layer In the present invention, for example, a primer is applied to the surface of the gas barrier coating film to form a primer layer, and then an adhesive layer for laminating is formed on the surface of the primer layer, and then the primer layer. In addition, an intermediate base material layer, an innermost layer, and the like may be laminated using a dry laminate lamination method via a laminating adhesive layer. By providing such a primer layer, the adhesion between the gas barrier coating film and the adhesive layer for laminating, the anchor coat layer, the intermediate base material layer, etc., which can be laminated thereon, is improved, and the lamination strength is improved. be able to.

As a primer constituting the primer layer, a polyurethane resin, a polyester resin or the like is a main component of the vehicle, and a silane coupling agent 0.05 to 10% with respect to 1 to 30% by mass of the polyurethane resin or polyester resin. A primer composition containing a mass and preferably 0.1 to 5 mass%, a filler of 0.1 to 20 mass%, preferably 1 to 10 mass%, and additionally containing a solvent and a diluent is used. be able to. If necessary, the primer composition may further contain a stabilizer, a curing agent, a crosslinking agent, a lubricant, an ultraviolet absorber, and other additives. In the present invention, the primer layer has a thickness of 0.1 to 10.0 g / m ² (dry state). The primer composition is coated by roll coating, gravure coating, knife coating, dip coating, spray coating, other coating methods, etc., the coating film is dried to remove the solvent and diluent, and if necessary An aging process etc. can be performed and it can be set as a primer layer.

  As the polyurethane resin, a polyurethane resin obtained by a reaction between a polyfunctional isocyanate and a hydroxyl group-containing compound can be used. For example, polyfunctional isocyanates such as aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate. And a one-component or two-component curable polyurethane resin obtained by a reaction between a polyether-based polyol, a polyester-based polyol, a polyacrylate polyol, and other hydroxyl group-containing compounds.

  On the other hand, as a polyester resin, thermoplasticity produced by polycondensation of one or more aromatic saturated dicarboxylic acids having a benzene nucleus as a basic skeleton such as terephthalic acid and one or more saturated dihydric alcohols. Can be exemplified. Examples of the aromatic saturated dicarboxylic acid having a benzene nucleus include terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether, and 4,4-dicarboxylic acid. Moreover, as saturated dihydric alcohol, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol, neopentyl glycol, etc. Examples thereof include alicyclic glycols such as fatty acid glycol and cyclohexasandimethanol, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, naphthalenediol and other aromatic diols.

  More specifically, as the polyester-based resin, a thermoplastic polyethylene terephthalate resin produced by polycondensation of terephthalic acid and ethylene glycol, and a thermoplastic polybutylene terephthalate resin produced by polycondensation of terephthalic acid and tetramethylene glycol. , Thermoplastic polycyclohexanedimethylene terephthalate resin produced by polycondensation of terephthalic acid and 1,4-cyclohexanedimethanol, thermoplastic polyethylene terephthalate resin produced by copolycondensation of terephthalic acid, isophthalic acid and ethylene glycol, terephthalate Thermoplastic polyethylene terephthalate resin produced by copolycondensation of acid, ethylene glycol and 1,4-cyclohexanedimethanol, terephthalic acid, isophthalic acid and ethylene glycol Thermoplastic polyethylene terephthalate resin produced by copolycondensation of propylene glycol, polyester polyol resins, and other like.

  One or more aliphatic saturated dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanoic acid, in addition to saturated aromatic dicarboxylic acid having a benzene nucleus And may be copolycondensed, and the amount used is preferably in the range of 1 to 10% by mass of the aromatic dicarboxylic acid.

  According to the polyurethane-based resin and the polyester-based resin, the adhesion between the inorganic oxide, in particular, the organic-containing silicon oxide layer and the intermediate base material layer can be improved, and the degree of elongation of the primer layer can be improved. The suitability of post-processing such as laminating can be improved, and the occurrence of cracks and the like of the organic-containing silicon oxide layer during post-processing can be prevented.

  As the silane coupling agent constituting the primer composition, organic functional group silane monomers having binary reactivity can be used. For example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane , Vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane , Γ-mercaptopropylmethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis ( β-hydroxye Le)-.gamma.-aminopropyltriethoxysilane, .gamma.-aminopropyl one such as an aqueous solution of silicones alone or may be used in combination of two or more.

  In the present invention, the inorganic functional group and / or organic functional group of the silane coupling agent can be used to increase the adhesive strength between the gas barrier coating film and the printing layer, primer layer, or the like. Specifically, a functional group at one end of the molecule of the silane coupling agent, usually a chloro, alkoxy, or acetoxy group, is hydrolyzed to form a silanol group (SiOH), which constitutes a gas barrier coating film. It reacts with active groups on the surface of the metal and its film surface, for example, a functional group such as a hydroxyl group, causing a reaction such as a dehydration condensation reaction, and the silane coupling agent is modified with a covalent bond etc. on the film surface of the gas barrier coating film Further, a strong bond is formed on the surface of the gas barrier coating film of the silanol group itself by adsorption or hydrogen bonding. Also, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto at the other end of the silane coupling agent is formed on the silane coupling agent thin film, for example, a primer layer, an adhesive layer for laminating It can react with substances constituting the anchor coat layer, the intermediate base material layer, the melt-extruded resin layer, and other layers to form a strong bond and increase the laminate strength.

  Examples of the filler constituting the primer composition include calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, and resin powder. When a filler is blended, the viscosity of the solution containing the polyurethane resin or polyester resin can be adjusted, the coating suitability can be improved, and a polyurethane resin or polyester resin and a silane coupling agent can be used as a binder resin. Thus, the cohesive strength of the coating film can be improved.

(11) Laminating adhesive In the present invention, a primer layer is formed by applying a primer to the surface of the gas barrier coating film, and then an intermediate base material layer or the like is applied to the surface of the primer layer via a laminating adhesive. It can be laminated using the dry laminating method, and when laminating the base film and the innermost layer of the gas barrier laminate film, it can be adhered using a laminating adhesive. When the two layers are laminated, they can be adhered by a dry lamination lamination method through a laminating adhesive.

  Adhesives for laminating include one-part or two-part cured or non-cured vinyl, (meth) acrylic, polyamide, polyester, polyether, polyurethane, epoxy, rubber, poly, A polyacrylate ester adhesive comprising a vinyl acetate adhesive, a homopolymer such as ethyl acrylate, butyl, 2-ethylhexyl ester or a copolymer thereof with methyl methacrylate, acrylonitrile, styrene, etc., Cyanoacrylate adhesive, ethylene copolymer adhesive consisting of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, cellulose adhesive, polyester adhesive, polyamide Adhesive, polyimide adhesive, urea resin or melamine tree Amino resin adhesives, phenol resin adhesives, epoxy adhesives, polyurethane adhesives, reactive (meth) acrylic acid adhesives, chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc. An inorganic adhesive made of a base adhesive, a silicone adhesive, an alkali metal silicate, a low melting point glass, or the like, or other adhesives can be used. More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. Ingredients. According to these, a thin film rich in flexibility and flexibility can be formed, its tensile elongation is improved, it acts as a film having flexibility, flexibility, and processing suitability such as laminating and printing Can be improved.

  The composition system of these adhesives may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property may be any of a film, a sheet, a powder, a solid, and the like. Furthermore, the reaction mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat welding type, a hot pressure type, and the like.

  As a coating method of the laminating adhesive, for example, direct gravure roll coating method, gravure roll coating method, kiss coating method, reverse roll coating method, fountain method, transfer roll coating method, and other methods can be used.

The coating amount is preferably about 0.1 to 10 g / m ² (dry state), more preferably about 1 to 5 g / m ² (dry state).

  For example, an adhesion promoter such as a silane coupling agent can be arbitrarily added to the laminating adhesive.

(12) Melt-extruded resin In the present invention, as the melt-extrusion adhesive resin, a heat-sealable resin that can be used when the innermost layer is a heat-sealable resin layer can be used. Polypropylene, low-density polyethylene, Linear low density polyethylene, acid-modified polyethylene and the like can be used, and polypropylene is particularly preferable. The thickness of the melt-extruded resin layer made of the melt-extruded adhesive resin is preferably about 5 to 100 μm, more preferably about 10 to 50 μm.

(13) Other laminated materials As materials for forming the laminated material constituting the retort-treated paper container used in the present invention, for example, low density polyethylene having a barrier property such as water vapor and water, medium density polyethylene, high density Film of resin such as polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, or polyvinylidene chloride resin having barrier properties against oxygen, water vapor, polyvinyl alcohol resin, ethylene-vinyl alcohol Copolymer, MXD polyamide resin, resin film such as polynaphthalene terephthalate resin, various colorant such as pigment added to resin, kneading into a film by adding desired additives A colored resin film or the like can be used. These materials can be used alone or in combination. The thickness of the film is arbitrary, but is usually about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

  In addition, since packaging containers are subjected to severe physical and chemical conditions, the packaging materials constituting the packaging containers are required to have strict packaging suitability, deformation prevention strength, drop impact strength, Various conditions such as pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. For this reason, in the present invention, a material that satisfies the above conditions Can be arbitrarily selected and used, specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate. Copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene Fat, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene Copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer , Fluororesin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, and other known resin films can be arbitrarily selected and used.

  In the present invention, the film may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but can be selected from a range of several μm to 300 μm.

  Furthermore, in the present invention, the film may be any film such as extrusion film formation, inflation film formation, and coating film. In addition, for example, a film such as cellophane, a synthetic paper, or the like can be used.

(14) Method for Producing Laminate In the present invention, it is possible to produce a laminate while forming a film by using the resin that forms each of the layers and then extruding it or melt-extruding it.

  An inorganic oxide vapor deposition film (43) is provided in advance on one surface of the base film layer (41), and the gas barrier coating film (45) is further formed on the surface of the inorganic oxide vapor deposition film (43). ) Is provided, and the gas barrier laminate film and the intermediate substrate layer are laminated, and the outermost layer such as a plastic substrate film and a paper substrate are laminated to each other. Then, it can be prepared by laminating the innermost layer on the gas barrier laminate film.

  In addition, when the resin is formed into a film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, mold release properties, flame retardancy, antifungal properties, etc. Various plastic compounding agents and additives can be added for the purpose of improving and modifying the properties, electrical properties, strength, etc., and the addition amount is from a very small amount to several tens of percent, Depending on the purpose, it can be added arbitrarily. Common additives include, for example, lubricants, crosslinking agents, antioxidants, UV absorbers, light stabilizers, fillers, antistatic agents, lubricants, antiblocking agents, colorants such as dyes and pigments, etc. Can be arbitrarily used, and a modifying resin or the like can also be used.

  Lamination can be performed, for example, by wet lamination, dry lamination, solventless dry lamination, extrusion lamination, T-die extrusion, coextrusion lamination, inflation, coextrusion inflation, and others. . In the present invention, when performing the above lamination, if necessary, pretreatment such as corona treatment, plasma treatment, ozone treatment, etc. can be optionally applied, and isocyanate (urethane), polyethyleneimine Anchor coat agents such as polyurethane, polybutadiene, and organic titanium, or known anchor coats such as polyurethane, polyacryl, polyester, epoxy, polyvinyl acetate, cellulose, and other adhesives for laminating. An agent, an adhesive for laminating, and the like can be arbitrarily used. In addition, when the said gas-barrier laminated | multilayer film is marketed, a commercial item can also be used.

(15) Retort processing paper container The retort processing paper container of the present invention can be manufactured by stacking the innermost layers of the above laminated materials so as to face each other, thereby producing a paper container such as a brick type, a flat type, or a gable top type. . Further, the shape can be any of a rectangular container, a cylindrical paper can such as a round shape, and the like.

  On the other hand, in this invention, a standing pouch can be suitably manufactured as a self-supporting bag-like retort processing paper container. The laminate material is excellent in laminate strength and gas barrier properties, and is excellent in shape retention because it contains a paper base material. Particularly, it can be suitably used for a standing pouch that is required to stand by line contact.

  When the retort-treated paper container of the present invention is a self-supporting bag-shaped container, for example, the body of the container is formed by heat-sealing both side edges of the front and rear wall laminates with side seals. The bottom portion is formed in a form having a gusset portion formed by folding and inserting the bottom laminate material between the lower portions of the front and rear wall laminate materials, and heat-sealing. It can be manufactured by heat-sealing with a ship-bottom-shaped seal pattern having a low center portion and a height toward both end portions.

  FIG. 5 shows the configuration of the first embodiment of a self-supporting bag-like container that can be retorted. In the figure, (a) is a schematic front view thereof, and (b) is a schematic cross-sectional view taken along the line AA of the self-supporting bag-like container shown in (a).

  In the self-supporting bag-like container capable of retorting shown in FIGS. 5A and 5B, the bottom portion is between the lower portions of the front and rear wall surface laminates (150), and the bottom surface laminate (155). Is formed in a form having a gusset portion (190) formed by being folded inward and inserted to the bottom surface laminated material folded portion (110), in the vicinity of the lower ends on both sides of the bottom surface laminated material (155) folded inwardly, In this case, a semicircular bottom laminated material notch (110a, 110b) is provided, and the gusset portion (190) rises in a straight line from the bottom having a predetermined width to the inside, with both sides inclined outward. A ship-bottom-shaped seal pattern, that is, formed by heat-sealing at the bottom seal portion (170), and the body portion is connected to the side seal portions (160a) on both side edges of the front and rear wall laminates (150). 160b) and heat sealed Has been. The wall surface laminate (A) is preferably provided with a plurality of vertical creases.

  The upper part of the self-supporting bag-shaped retort processing paper container (100) is filled with the contents from this part and then heat-sealed by the upper seal part 180, but the container ( As the opening means for facilitating the opening of 100), a half cut line (130) and a notch (120) are provided at one end thereof.

  In the figure, the sealing pattern of the bottom seal part (170) for heat-sealing the bottom gusset part (190) shows a more preferable shape, so that the inner side is linear with a predetermined width from the bottom part and both sides are inclined outward. Although a ship-bottom-shaped seal pattern with a rising shape is shown, a seal pattern in which the outer periphery of the bottom gusset portion (190) is heat-sealed with a predetermined width may be used. Even in that case, in order to further improve the self-supporting property of the container, the bottom-layer laminate notch portions (110a, 110b) having a similar shape are formed in the vicinity of both lower ends of the bottom-layer laminate material (155) folded inward. It is preferable that the portion is provided and heat-sealed with the seal pattern having the predetermined width.

  By adopting such a configuration, the filling of the contents can be easily performed from the opening at the top of the self-supporting bag-shaped retort processing paper container (100) using, for example, a conventional filling machine for standing pouches. After the filling, the upper seal part (180) can be heat sealed by a method such as deaeration sealing.

Since the container (100) filled with the contents has a hexagonal shape with a plurality of stamped lines and the shape of the bottom of the ship, the bottom of the container has a three-dimensional structure. In addition, the leg portion by the heat seal portion is surely formed on the outer periphery of the bottom surface, and the front and rear wall laminates (150) are thick paper having a basis weight of 70 to 280 g / m ^{2 on} the intermediate layer. Since the layers are laminated and the rigidity is increased, the self-supporting property and shape retention of the container are improved, and even when the content is a food containing a solid material that tends to be crushed, it can be safely protected.

  Further, by the above-mentioned plurality of creases (100), the front and rear wall laminates (150) are at least from the outermost layer (10) made of a transparent plastic substrate film, and the paper substrate layer (30). The gas barrier laminate film (40) and the innermost layer (50) are sequentially laminated via the adhesive layers (70, 75), and the bottom laminate (160) is transparent at least from the outside. Since the outermost layer (10) made of a plastic substrate film, the gas barrier laminate film (40), and the innermost layer (50) are sequentially laminated via the adhesive layer (70, 75), the retort as a whole It has heat resistance and water resistance that can withstand sterilization treatment, and at the same time has excellent gas barrier properties and excellent long-term storage of contents.

  When the contents filled in (100) are taken out by the above-described plurality of creases, a half as an unsealing means for facilitating the opening of the container (100) is provided below the upper seal portion (180). Since the cut line (130) and the notch (120) are provided at one end thereof, the notch (120) is used as a starting point along the half cut line (130) without using a tool such as a scissors. The entire upper part of the container (100) can be opened easily by tearing by hand. Therefore, even when the content contains a solid with a liquid, it can be easily taken out.

  Furthermore, even when a design such as a printed pattern is applied to the self-supporting bag-like container (100), the inner surface of the outermost layer (10) made of the transparent plastic base film on the outer side of the front and rear wall laminates (150). Alternatively, by printing on the outer surface of the paper base layer (20), the whiteness and opacity of the paper base layer (20) can be used, so the printing effect is enhanced and the design of the container (100) is improved. This can be further improved.

  The ship-bottom-shaped seal pattern has a particularly preferable shape, such as a ship-bottom-shaped seal pattern in which the inside is formed by a curved line such as an arc, or the inside is inclined from the bottom of a predetermined width to the outside on both sides. A ship-bottom seal pattern that rises in a straight line can be mentioned. By adopting such a configuration, the self-supporting bag-shaped container filled with the contents has, for example, a bottom-shaped seal whose bottom is formed by a curved line in accordance with the bottom-shaped seal pattern. In the case of a pattern, it expands in an elliptical shape, and in the case of a ship-bottom-shaped seal pattern that rises linearly from the bottom with a predetermined width toward the outside on both sides, it spreads in a hexagonal shape, both of which are centered in the front and back Moreover, since the leg part by a heat seal part is reliably formed in the outer periphery of a bottom face, the self-supporting property of a container can be improved further.

  Moreover, an opening means may be provided in the upper part of the container. The opening means may be an opening instruction line such as a tear line displayed by printing or an opening instruction mark, and is an easy-opening means as described below that facilitates an opening operation by actual tearing. Also good. Further, a combination of a plurality of these may be provided. Examples of the easy-opening means include, for example, a method of providing a notch frequently used even in a normal pouch, a method of providing a half-cut line by laser light irradiation, or the like, or an easily tearable material in a laminate for a wall of a container. There is a method of laminating a uniaxially stretched film (in this case, the uniaxially stretched film is laminated so that the stretching direction thereof coincides with the opening direction of the container), and these may be used alone, A plurality of means can be used in combination as appropriate, such as lamination of half-cut lines or uniaxially stretched films.

  As the notch, a notch such as a letter shape or a V shape is usually used, but the shape is not particularly limited, and any shape having an acute angle portion in the cutting direction can be used. Also when providing the said half cut line, it is not restricted to a linear half cut line, It can also provide by intermittent half cut lines, such as perforation form. Furthermore, the number of such half-cut lines may be one, but assuming that the tearing direction is deviated, a plurality of half-cut lines such as one or two on each side of the center half-cut line are provided. It can also be provided to converge in parallel or in the center half-cut line.

  As a result, when the contents filled in the container are taken out, an opening means for facilitating the opening of the container is provided at the opening position of the upper part of the container, so that the opening position is not mistaken, making it easier. The entire upper part of the container can be cut out and opened. Moreover, even if the content contains a solid material together with a liquid material or the like, it can be easily taken out.

  The self-supporting bag-like container of the present invention that can be retorted is basically in the form of a self-supporting form formed by forming the bottom part in a gusset form, like a normal standing pouch. It can be manufactured using a conventional bag making machine for standing pouches. If necessary, the shape of the sealing head such as a hot plate that heat-seals the bottom gusset portion is changed, and a half-cut line or notch is provided as an opening means on the top of the container. Add an irradiation device, punching device, etc. to the bag making machine for the standing pouch, and if you want to provide stamping on the front and back wall laminates, add a hot press device or embossing device, etc. Both can be easily manufactured.

(16) Retort processing packaging body The retort processing paper concerning this invention is filled with the contents from the opening part of the retort processing paper container concerning this invention, and the opening part is sealed by the heat seal etc. at the upper end part then. A packaging semi-finished product using a container is manufactured, and then the packaging semi-finished product is subjected to a heat treatment such as a retort treatment or a boil treatment, whereby a retort treatment package using the retort-treated paper container according to the present invention is obtained. It can be manufactured.

In the above, as a method for retorting or boiling, for example, a normal retort kettle is used, and the temperature is about 110 to 130 ° C., preferably about 120 ° C., pressure, 1 to 3 kgf / cm ² · G, Preferably, a method of heating and pressurizing at about 2.1 kgf / cm ² · G, about 20 to 60 minutes, preferably about 30 minutes, or temperature, 90 to 100 ° C., preferably 90 ° C. It can be carried out by a method of performing a boil treatment in about front and rear, time, about 5 to 20 minutes, preferably about 10 minutes. As a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal can be used.

  In the present invention, the contents can be subjected to heat sterilization, heat sterilization cooking, or the like by retort treatment or boil treatment as described above.

  The retort-treated paper container according to the present invention is particularly excellent in laminate strength, excellent in barrier properties to prevent permeation of oxygen gas, water vapor, etc., and excellent in deformation prevention strength, etc., for heat treatment accompanying processing such as retort processing. Withstands and does not allow delamination, and is suitable for disposal of used paper containers. For example, cooked foods, marine products, frozen foods, boiled foods, rice cakes, liquid soups, seasonings It is useful for filling and packaging various foods such as drinking water, etc. or animal food such as pet food, and is excellent in filling and packaging properties and quality maintenance of its contents. .

  EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all.

(Example 1)
(1) A gravure printing method using an ordinary ink composition for cup base paper on one side of a paper base material [density 0.84, edge wick 0.32, size degree 780, basis weight 280 g / m ² ]. Then, a printing pattern composed of characters, symbols, patterns, graphics, etc. was printed to form a desired printing pattern layer.

Next, a polyethyleneimine-based anchor coating agent is used on the printing surface of the paper base material, and this is coated by the gravure roll coating method so as to have a film thickness of 0.5 g / m ² (dry state). An agent layer was formed, and then the polypropylene resin layer was provided on the above-mentioned paper base material by extrusion lamination while melting and extruding a polypropylene resin to a film thickness of 20 μm on the surface of the anchor coat agent layer.

  (2) On the other hand, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm and corona-treated on both sides was used, and this was mounted on a delivery roll of a plasma chemical vapor deposition apparatus. A vapor-deposited film of silicon oxide having a thickness of 200 mm was formed on the corona-treated surface of the axially stretched polyethylene terephthalate film.

(Deposition conditions)
Deposition surface; corona-treated surface,
Introduced gas amount; hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 3.0 (unit: slm),
Degree of vacuum in the vacuum chamber; 2-6 × 10 ⁻⁶ mBar,
Degree of vacuum in the deposition chamber; 2-5 × 10 ⁻³ mBar,
Cooling and electrode drum supply power: 10 kW,
Line speed: 100 m / min,
Next, immediately after the silicon oxide vapor deposition film having a thickness of 200 mm is formed as described above, a glow discharge plasma generator is used on the silicon oxide vapor deposition film surface, and the power is 10 kW, oxygen gas (O ₂ ): argon gas. (Ar) = 8.0: 2.0 (unit: slm) is used, and oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 7 × 10 ⁻⁵ mBar and a processing speed of 100 m / min. The plasma-treated surface was formed by improving the surface tension of the deposited silicon oxide film surface by 54 dyne / cm or more.

  On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixture of polyvinyl alcohol aqueous solution, silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.

Next, the gas barrier composition produced above is used on the plasma-treated surface, and this is coated by a gravure roll coating method, and then heat-treated at 100 ° C. for 30 seconds to obtain a thickness of 0.4 g. A barrier film according to the present invention was produced by forming a gas barrier coating film of / m ² (dry operation state).

(3) A two-component curable polyurethane-based laminating adhesive is used on the gas barrier coating film of the barrier layer formed as described above, and the thickness is 4.0 g / m ² using a gravure roll coating method. Next, the surface of the adhesive layer for laminating is coated with HS-OPP (a heat-sealable biaxially stretched polypropylene film manufactured by Futamura Chemical Co., Ltd .; trade name “FOH”). They were overlapped with the faces facing each other. Next, the surface of the biaxially stretched polyethylene terephthalate film of the barrier film was subjected to a corona discharge treatment, and then a two-component curable polyurethane laminating adhesive was applied to the corona treated surface in the same manner as described above. Is used to form a laminate adhesive layer by coating to a thickness of 4.0 g / m ² (dry state), and then an unstretched propylene film having a thickness of 60 μm is dried on the surface of the laminate adhesive layer. Laminated and laminated.

(4) Next, a polyethyleneimine anchor coating agent is used on the exposed paper surface of the paper substrate of (1) in the same manner as described above, and this is coated with a 0.5 g film thickness by a gravure roll coating method. / M ² (dried state) to form an anchor coating agent layer, and then, on the surface of the anchor coating agent layer, the above-mentioned HS-OPP (Futamura Chemical Co., Ltd. heat seal) Biaxially oriented polypropylene film (trade name “FOH”) with the faces facing each other, and using a polypropylene resin between the layers, extrusion lamination is performed while melt extrusion to a film thickness of 20 μm. The laminated material was prepared by laminating the material and the laminated film.

  (5) To produce a self-supporting bag-shaped container having the configuration shown in FIG. 5 using the above-mentioned laminated material, and to use a standing pouch bag-making machine, and to provide the half-cut line 15 and the notch 14 on this. A laser beam irradiation device and a punching device are attached, and the structure shown in FIG. 5 is processed so that the outer dimensions are 130 mm in width, 190 mm in length, and the length of the gusset portion 11 is 40 mm. A shaped container was produced.

(Example 2)
(1) HS-OPP (Futamura Chemical Co., Ltd. heat-sealable biaxially stretched polypropylene film; trade name “FOH”) is used on one side of the gravure printing system using a normal gravure ink composition, A print pattern composed of characters, symbols, designs, figures, etc. was printed to form a desired print pattern layer.

Next, a polyethyleneimine-based anchor coating agent is used on one surface of a paper base material (density 0.84, edge wick 0.32, size degree 780, basis weight 280 g / m ² ), and this is coated with a gravure roll. The anchor coat agent layer is formed by coating so as to have a film thickness of 0.5 g / m ² (in a dry state), and then a polypropylene resin is used on the surface of the anchor coat agent layer. While being melt-extruded to a thickness of 20 μm, the above-described HS-OPP (a heat-sealable biaxially stretched polypropylene film manufactured by Futamura Chemical Co., Ltd .; trade name “FOH”) was laminated.

  (2) Subsequently, a barrier film was produced in the same manner as in (2) in the same manner as in Example 1, and in the same manner as in (1) in Example 1, HS-OPP (Hutamura Chemical Co., Ltd. heat seal) Biaxially stretched polypropylene film; trade name “FOH”), barrier film and unstretched propylene film were laminated.

(3) A polyethyleneimine-based anchor coating agent is used on the exposed paper surface of the paper substrate of (1) above, and this becomes a film thickness of 0.5 g / m ² (dry state) by a gravure roll coating method. Then, the anchor coat agent layer is formed by coating, and then the HS-OPP (2) heat-sealable biaxially stretched polypropylene film of (Futamura Chemical Co., Ltd.) on the surface of the anchor coat agent layer; “FOH”) facing each other and overlapping, using a polypropylene resin between the layers, extrusion laminating this while melting and extruding to a film thickness of 20 μm, and laminating the above paper substrate and laminated film A laminate was prepared.

(Comparative Example 1)
(1) The same operation as in (1) and (2) of Example 1 was performed.

(2) After the corona discharge treatment is applied to the surface of the biaxially stretched polyethylene terephthalate film of the gas barrier film formed in the above (1), a two-component curable polyurethane laminate adhesive is gravure-coated on the corona treatment surface. Using a roll coating method, a laminate adhesive layer is formed by coating to a thickness of 4.0 g / m ² (in a dry state), and then unstretched propylene having a thickness of 60 μm is formed on the surface of the laminate adhesive layer. The film was laminated by dry lamination.

(3) Next, a polyethyleneimine-based anchor coating agent is used on the exposed paper surface of the paper substrate of (1) above, and this is coated with a film thickness of 0.5 g / m ² (dry state) by a gravure roll coating method. ) To form an anchor coating agent layer, and then, the surface of the anchor coating agent layer is overlapped with the surface of the gas barrier coating film of the barrier film of the above (2) facing each other, A polypropylene resin was used between the layers, and this was extrusion laminated while being melt-extruded to a film thickness of 20 μm, and the above-mentioned paper base material and laminated film were bonded together to prepare a laminated material.

Experimental example 3
The laminates produced in Examples 1 and 2 and Comparative Example 1 were used as the base paper, and this was punched and ruled. Then, after skive hemming, the trunk was frame sealed to create a carton blank. After filling the contents and boxing, a retort sterilization treatment was performed at 120 ° C. for 60 minutes. The retort-treated packaging body thus produced was evaluated for oxygen permeability, water vapor permeability, delamination strength (between the barrier layer and the biaxially stretched polypropylene film), and appearance. The test results are shown in Table 2 below. In Table 2, the unit of oxygen permeability is [cc / m ² / day · 23 ° C./90% RH], and the unit of water vapor permeability is [g / m ² / day · 40 ° C. · 90 % RH].

(1) Measurement of oxygen permeability The laminated materials produced in Examples 1 to 5 and Comparative Examples 1 to 3 above were manufactured by MOCON, USA, under conditions of a temperature of 23 ° C. and a humidity of 90% RH. Measured with a measuring instrument [model name, OXTRAN].

(2) Measurement of water vapor transmission rate The laminates produced in Examples 1 to 5 and Comparative Examples 1 to 3 above were manufactured by MOCON, USA under the conditions of a temperature of 40 ° C and a humidity of 90% RH. The measuring instrument [model name, PERMATRAN] was used.

(3) Measurement of delamination strength This uses a peeling tester (Orientec Co., Ltd., model name, Tensilon universal testing machine), sample 15 mm wide, peeling angle 90 degrees, load cell 5 kgf, peeling speed 300 mm / min. It measured on condition of this.

(4) Appearance The independence was evaluated from the appearance.

  The retort-treated paper container according to the present invention is excellent in gas barrier properties, heat resistance and shape retention, and is particularly useful for a retort-treated paper container.

FIG. 1 is a cross-sectional view for explaining a laminated material constituting a retort processing paper container used in the present invention. It is a figure which shows the external appearance of the retort processing paper container used by this invention. It is a schematic block diagram which shows an example of a low temperature plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows an example of a winding-type vacuum deposition apparatus. It is a figure explaining the retort processing paper container created in the Example.

Explanation of symbols

10: outermost layer,
20 ... paper substrate,
30 ... Intermediate base material layer,
31 ... heat seal coat layer,
33 ... Polyolefin film,
40 ... Gas barrier laminate film,
41 ... base film layer,
43 ... Inorganic oxide vapor deposition layer,
45 ... Gas barrier coating film,
50 ... innermost layer,
60 ... printing layer,
70 ... extruded laminate layer,
73 ... Anchor coat layer,
75 ... Laminating adhesive layer,
80 ... corona treatment layer,
100: Self-supporting bag-like container,
110 ... Laminate cutout for bottom surface,
110 ... Laminate folded portion for bottom surface,
120 ... notch,
130: Half-cut wire,
140 ... pressed ruled line,
150 ... laminate for wall surface,
155 ... Laminate for bottom surface,
160 ... side seal part,
170 ... bottom seal part,
180 ... upper seal part,
190 ... gusset part.

Claims (18)

At least an outermost layer, a paper base material, an intermediate base material layer, a gas barrier laminated film, and a retort-treated paper container formed by boxing a laminated material in which the innermost layer is sequentially laminated,
The gas barrier laminate film is provided with an inorganic oxide vapor-deposited film on one surface of a base film layer, and the general formula R ¹ _n M (OR ² ) _m (wherein , R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m is It contains at least one alkoxide represented by the valence of M), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and is further obtained by polycondensation by a sol-gel method. A laminated film (I) provided with a gas barrier coating film made of a gas barrier composition,
A retort-treated paper container, wherein the intermediate base material layer is a laminated film (II) of a polyolefin film and a heat-sealable coat layer.   The retort-treated paper container according to claim 1, wherein the polyolefin film constituting the intermediate base material layer is a polypropylene film, and the heat-sealable coat layer is a chlorinated polypropylene heat-seal coat layer or an acrylic heat-seal coat layer. . The retort paper container according to claim 1 or 2, wherein M in the general formula R ¹ _n M (OR ² ) _m is made of silicon, zirconium, titanium, or aluminum.   The retort-treated paper container according to any one of claims 1 to 3, wherein the alkoxide is composed of an alkoxysilane, an alkoxide hydrolyzate, or an alkoxide hydrolysis condensate.   The retort-treated paper container according to any one of claims 1 to 4, wherein the gas barrier composition contains a silane coupling agent.   The retort-treated paper container according to any one of claims 1 to 5, wherein the gas barrier coating film is a composite polymer layer in which one layer or two or more layers are laminated.   The gas barrier coating film is a base film on which a gas barrier composition is applied and provided with a coating film, at a temperature of 20 ° C. to 180 ° C. and a temperature equal to or lower than the melting point of the above base film for 10 seconds to 10 seconds. The retort-treated paper container according to any one of claims 1 to 6, wherein the retort-treated paper container comprises a cured film that has been heat-treated for a minute.   The retort-treated paper container according to any one of claims 1 to 7, wherein the sol-gel catalyst is a tertiary amine that is substantially insoluble in water and soluble in an organic solvent.   The retort-treated paper container according to claim 8, wherein the tertiary amine comprises N, N-dimethylbenzylamine.   The retort-treated paper container according to any one of claims 1 to 9, wherein water is used in a ratio of 0.1 to 100 moles per mole of alkoxide.   The retort-treated paper container according to claim 1, wherein the inorganic oxide vapor-deposited film is an inorganic oxide vapor-deposited film formed by chemical vapor deposition or physical vapor deposition. A self-supporting bag-like retort-treated paper container formed by heat-sealing a laminate material according to any one of claims 1 to 11 as a laminate for a wall surface (A),
The body portion of the container is formed by heat-sealing both side edges of the front and rear wall laminates (A) with side seals, and the bottom is the lower part of the front and rear wall laminates (A). Formed in a form having a gusset portion formed by inserting a bottom laminate (B) made of a laminate (III) including an outermost layer, a paper base material layer, and an innermost layer in between, and then heat-sealing. A self-supporting bag-shaped retort processing paper container.   The self-supporting bag-like retort processing paper container according to claim 12, wherein the wall surface laminate (A) and the bottom laminate (B) are both laminates according to claim 1.   The self-supporting bag according to claim 12 or 13, wherein the gusset portion at the bottom of the container is heat-sealed with a bottom-bottom-shaped seal pattern in which an inner central portion is low and increases toward both end portions. Retort processing paper container.   The self-supporting bag-like retort processing paper container according to any one of claims 12 to 14, wherein the front and rear laminates for wall surface (A) are provided with a plurality of vertical ruled lines. .   The self-supporting bag-like container retort processing paper container according to any one of claims 12 to 15, wherein an opening means is provided at an upper part of the container. The paper substrate used in the laminate is a US basis weight 70~280g / m ^2, self-supporting bag-like retort treatment paper container according to any one of claims 12 to 16.   A retort product obtained by filling the retort-treated paper container according to any one of claims 1 to 17 with the retort contents, then sealing the container and then heating.

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