JP2008265854A - Self-supportable bag-like container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a self-reliant bag-like container having excellent gas barrier properties, shape-keeping properties and heat resistance. <P>SOLUTION: The self-supporting bag-like container is manufactured of a laminate body including a transparent plastic base material 10, a paper base material layer 20, a gas barrier property laminate film 40 and a heat seal layer 50 as a barrel portion and a laminate body including a transparent plastic base material and a heat seal layer as a bottom portion. By using the gas barrier property laminate film 40, the self-reliant bag-like container has excellent heat resistance, shape-keeping properties and gas barrier properties, and is favorably used for the use in a microwave oven and for the retort processing. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a self-supporting bag-like container, which is a self-supporting bag-like container of the same type as a self-supporting bag whose bottom is formed in a gusset form, and has gas barrier properties, pinhole resistance, deformation prevention strength, etc. The present invention relates to a self-supporting bag-like container that is excellent and can be suitably used in a microwave oven.

  Bags made by heat-sealing laminated films are often used as inexpensive packaging containers that simply seal and wrap the contents for distribution and storage. Such a bag made of laminated film has good processability of the bag making, excellent sealing performance, moisture resistance, gas barrier property, water resistance, heat resistance, content resistance, retort processing suitability, etc. Performance such as microwave oven suitability can be imparted relatively easily by selecting the constituent materials of the laminated film, so in addition to various foods, three-side seal type, four-side seal type, pillow type, etc. in a wide range of fields including non-food Flat bags, gusset bags, standing pouches, or modified or applied bags of these types. Among these, standing pouch-type bags are self-supporting and have the characteristics of a three-dimensional container, and are easy to handle and at the same time can be packaged compactly for their capacity. Conveniently used around the contents you have.

  In addition, since the laminated film bag is flexible and inferior in shape retention, it is soft such as baked confectionery such as rice crackers and biscuits, and other fragile foods such as snack foods, or conversely cakes and castella. When used for foods that are easily crushed, cup-type, brick-type, and paper-belt type containers using laminated cardboard, composite containers made of laminated cardboard and plastic molding, plastic molded containers, metal cans, etc. A method using a sex container has been adopted.

  In addition, in foods that can be heat-filled, such as chocolate sauce, fruit sauce, and soup, and products that are cooked after being cooked in a microwave oven, it is preferable that the container can be self-supporting after opening, and the container has good shape retention. Required.

  As a cup-type paper container using the above laminated cardboard used for such snack foods, liquid distribution, etc., an ethylene-α / olefin copolymer polymerized mainly using a paper layer and using a single site catalyst There has been proposed a paper cup container manufactured using a laminate having a heat seal layer (see, for example, Patent Document 1).

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 is heat-treated in a humid atmosphere at a temperature of 85 ° C. or higher on at least one side has also been proposed (see, for example, Patent Document 2).
JP 2000-229660 A Japanese National Patent Publication No. 11-508502

  However, although the containers described in Patent Document 1 and Patent Document 2 have good shape retention and can improve the protection of the contents, the material cost of the container, the mold for molding the container, and 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. Further, depending on the contents, a higher gas barrier property is required to retain the product, but further improvement is desired.

  In particular, laminating containers including paper bases are widely used, and are foods that can be heat-filled such as chocolate sauce and fruit sauce, and can be used as a sauce after cooking in a microwave oven. In addition, it is convenient if the container after use is folded in a compact manner. There is a stand pouch as a container of such a form, but the stand pouch needs to be self-supporting by line contact at the bottom. If a paper base layer with a predetermined thickness is used to ensure self-supporting and shape retention, it is difficult to secure adhesion between the paper base layer and the gas barrier laminate film. In some cases, the gas barrier properties of the resin may be reduced. Therefore, it is desired to develop a self-supporting bag-like container having excellent gas barrier properties.

  Furthermore, if shape retention can be maintained even after retort sterilization treatment, a self-supporting bag-like retort treatment container can be produced, and such development is desired.

  Therefore, the present invention is excellent in gas barrier properties, preserving, heating suitable for microwave cooking, withstands heat treatment associated with processing such as retort treatment, and is free from delamination, etc., cooked food, marine product, frozen food, It is an object of the present invention to provide a self-supporting bag-like container that is excellent in boiled foods, rice cakes, liquid soups, seasonings, drinking water, and other contents, filling and packaging suitability, quality maintenance, and the like.

  As a result of examining the self-supporting bag-like container in detail, the present inventor can secure shape retention by including a paper base material layer, and when a gas barrier laminate film having a predetermined structure is used, it has an excellent gas barrier against oxygen and water vapor. The present invention has been completed by discovering that it is a self-supporting bag-like container that can be secured and can be suitably used in a microwave oven.

That is, the present invention is a self-supporting bag-like container formed by heat-sealing a laminated body in a bag shape, and the trunk portion of the container is side-sealed on both side edges of the front and rear wall-side laminated bodies. The bottom part is formed in a form having a gusset part formed by heat-sealing and inserting the bottom laminate to the inside between the lower parts of the front and rear wall laminates, The laminate for wall surface is a laminate (I) comprising a transparent plastic substrate, a paper substrate layer having a basis weight of 70 to 280 g / m ² , a gas barrier laminate film and a heat seal layer, and the bottom surface The laminate for use provides a self-supporting bag-like container, which is a laminate (II) including a transparent plastic substrate and a heat seal layer.

  Moreover, this invention provides the retort processing package body which enclosed the content in the said container and heat-processed.

  ADVANTAGE OF THE INVENTION According to this invention, since it is excellent in heat resistance and gas barrier property, the self-supporting bag-like container which can be used conveniently for a microwave oven can be provided.

  Since the self-supporting bag-like container of the present invention uses a paper base material layer, it is excellent in shape retention and can be safely protected even if the contents are easily broken or easily crushed.

  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 self-supporting bag-like container of the present invention will be described in detail.

(1) Self-supporting bag-like container The self-supporting bag-like container according to the present invention and the retort processing package using the same will be described below in more detail with reference to the drawings.

The self-supporting bag-like container of the present invention comprises a laminate (I) comprising a transparent plastic substrate, a paper substrate layer having a basis weight of 70 to 280 g / m ² , a gas barrier laminate film, and a heat seal layer. A laminate for wall surface, a laminate (II) including a transparent plastic substrate and a heat seal layer is used as a laminate for the bottom surface, and the body of the container has side seals on both side edges of the front and back wall laminate. The bottom part was formed in a form having a gusset part formed by folding the bottom laminate to the inside between the lower parts of the front and rear wall laminates and heat-sealing. It is a self-supporting bag-like container.

  The laminate (II) may contain a gas barrier laminate film between the transparent plastic substrate and the heat seal layer. At this time, in the laminates (I) and (II), the base film layer constituting the gas barrier laminate film may be opposed to the heat seal layer or may be laminated opposite to the gas barrier coating film. Although it is good, in this invention, it is preferable to laminate | stack facing a base film layer.

  The laminate (I) used in the present invention further comprises an intermediate substrate film layer between the paper substrate layer and the gas barrier laminate film or between the gas barrier laminate film and the heat seal layer. The laminate (II) may further include an intermediate substrate film layer between the transparent plastic substrate and the gas barrier laminate film or between the gas barrier laminate film and the heat seal layer. In addition, in the laminates (I) and (II), other layers may be included in addition to the above constituent layers. Such other layers include a laminating adhesive layer for laminating each layer by a dry laminating method, a primer layer or an anchor coat layer for laminating a heat seal layer by a melt extrusion method, and other undercoats. There are an agent layer, a surface treatment layer formed by surface treatment, a printing layer, and the like.

  Therefore, as the laminate (I), for example, (a) <transparent plastic substrate / corona treatment layer / printing layer> / extruded laminate resin layer / anchor coat layer / paper substrate layer / anchor coat layer / extruded laminate resin Layer / <gas barrier coating film / inorganic oxide deposition layer / base film layer> / corona treatment layer / laminate adhesive layer / heat seal layer, (b) <transparent plastic substrate / corona treatment layer> / extrusion 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, (c) <transparent plastic substrate / corona treatment layer / printing layer> / extruded laminate resin layer / anchor coat layer / paper substrate layer / anchor coat layer / press Laminate resin layer / <corona treatment layer / base film layer / corona treatment layer / inorganic oxide vapor deposition layer / gas barrier coating film / plasma treatment layer> / laminate adhesive layer / <corona treatment layer / heat seal layer> (D) <Transparent plastic substrate / corona treatment layer / printing layer> / extruded laminate resin layer / anchor coat layer / paper substrate layer / anchor coat layer / extruded laminate resin layer / intermediate substrate film / adhesive layer for lamination / <Gas barrier coating film / inorganic oxide vapor deposition layer / base film layer> / corona treatment layer / laminate adhesive layer / heat seal layer, (e) <transparent plastic base material / corona treatment layer> / extruded laminate resin Layer / anchor coat layer / paper substrate layer / anchor coat layer / extruded laminate resin layer / intermediate substrate film / adhesive layer for lamination / <gas barrier coating / Inorganic oxide deposited layer / base film layer> / corona treatment layer / laminating adhesive layer / heat seal layer can be exemplified.

  As the laminate (II), for example, (a) <transparent plastic substrate> / laminate adhesive layer / heat seal layer, (b) <transparent plastic substrate / corona treatment layer> / laminate adhesive Layer / heat seal layer, (c) <transparent plastic substrate> / laminate adhesive layer / <gas barrier coating film / inorganic oxide deposition layer / substrate film layer> / corona treatment layer / laminate adhesive layer / Heat seal layer, (d) <transparent plastic substrate / corona treatment layer> / laminate adhesive layer / <gas barrier coating film / inorganic oxide deposition layer / substrate film layer> / corona treatment layer / laminate adhesive Layer / heat seal layer, (e) <transparent plastic substrate> / laminate adhesive layer / <corona treatment layer / substrate film layer / corona treatment layer / inorganic oxide deposition layer / gas barrier coating Film / plasma-treated layer> / adhesive layer for laminating / <corona-treated layer / heat seal layer>, (f) <transparent plastic substrate / corona-treated layer / printing layer> / anchor coat layer / intermediate substrate film / laminate Adhesive layer / <gas barrier coating film / inorganic oxide vapor deposition layer / base film layer> / corona treatment layer / laminate adhesive layer / heat seal layer, (g) <transparent plastic base material / corona treatment layer> / Anchor coat layer / Intermediate base film / Adhesive layer for laminating / <Gas barrier coating film / Inorganic oxide deposition layer / Base film layer> / Corona treatment layer / Adhesive layer for laminating / Heat seal layer it can.

  Before forming the laminating adhesive layer, a primer layer may be formed in advance, an undercoat agent layer is provided instead of the laminating adhesive layer, and a heat seal layer is formed by a melt extrusion method. Also good.

  FIG. 1 shows a self-supporting bag-like container in which a transparent plastic substrate (10), a paper substrate layer (20), a gas barrier laminate film (40) and a heat seal layer (50) are laminated. The cross-sectional view of laminated body (I) which has a printed layer (60) in a base material (10) is shown. In the figure, 70 is an extruded laminate layer, 73 is an anchor coat layer, 75 is an adhesive layer for lamination, 80 is a corona-treated layer, 41 is a base film layer constituting a gas barrier laminate film, and 43 is an inorganic oxide vapor deposition layer. 45 show the gas barrier coating film. The print layer (60) shown in FIG. 1 may be omitted.

  FIG. 2 shows a cross-sectional view of a laminate (II) which is a self-supporting bag-like container in which a transparent plastic substrate and a heat seal layer are laminated and has a printing layer on the transparent plastic substrate. The printing layer (60) shown in FIG. 2 may be omitted.

  FIG. 3 shows a self-supporting bag-like container in which the laminate (I) is boxed as a wall laminate. 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 is folded inward and inserted into the bottom laminate return portion (110). In this case, semi-elliptical bottom-layer laminate cutout portions (110a, 110b) are provided in the vicinity of the lower ends on both sides of the bottom-layer laminate that is formed in the form and has a body portion. 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. A vertical ruled line (125) is provided on the front and rear wall laminates (150). Due to the seal pattern of the bottom seal portion (170) and the stamped rule (125) provided in 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-like container of the present invention is not limited to the stand-pouch type shown in FIG. 3, and is also suitable for other self-supporting bag-like containers.

(2) Transparent plastic substrate As the plastic substrate that can be used in the laminate (I) and laminate (II) of the present invention, mechanical, physical, and sufficient for the use of the self-supporting bag-like container of the present invention, A resin having excellent chemical strength, particularly excellent heat resistance, moisture resistance, pinhole resistance, puncture resistance, and the like can be widely used. For example, as resins with excellent heat resistance and water resistance, there are polyesters such as polyethylene terephthalate, polyamides such as various nylons, polypropylene, etc. Other low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) Low density polyethylene, ethylene-α / olefin copolymer polymerized using metallocene 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, and polyolefin resin Acid-modified polyolefin resin, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin modified with unsaturated carboxylic acid such as crylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid Uniaxial or biaxially stretched films such as resins, polyester resins, polyamide resins, polyaramid resins, polycarbonate resins, polyacetal resins, and fluorine resins can be suitably used. In the present invention, a polyester resin such as polypropylene resin and polyethylene terephthalate can be suitably used as a plastic substrate 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 transparent plastic base material uses, for example, one or more of the above-mentioned various resins, and uses 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. , A method for forming the above-mentioned various resins alone, or a method for forming a multi-layer coextrusion film using two or more kinds of resins, and further, using two or more kinds of resins. Various resin films are manufactured by a method of forming a film by mixing before forming into a film, for example, stretching in a uniaxial or biaxial direction using a tenter method or a tubular method. Various resin films 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 plastic substrate layer by melt extrusion lamination to the substrate layer.

  In the present invention, the film thickness of various resin films is preferably about 6 to 100 μm, more preferably about 9 to 50 μm.

(3) Paper base layer As the paper base layer used in the laminate (I) of the present invention, mainly the rigidity of the laminate is moderately increased, and the shape retention of a self-supporting bag-like container is improved. Therefore, the basis weight of the rice is preferably in the range of 70 to 280 g / m ² . When the basis weight of rice is less than 70 g / m ^{2, the} effect of improving the rigidity of the laminate cannot be obtained sufficiently, and the shape retaining property of the container becomes insufficient, such being undesirable. In addition, when the basis weight of the rice exceeds 280 g / m ² , the rigidity of the laminate becomes too strong, the opening of the container becomes worse, the thickness of the cardboard increases, and moisture easily penetrates from the end face of the cardboard. Therefore, it is not preferable. 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 structure 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. Moreover, since the paper base material layer is laminated on the laminate for the wall surface before and after forming the body portion 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, a desired print pattern such as a character, a figure, a pattern, a symbol, or the like may be arbitrarily formed on the paper base layer by a normal printing method.

(4) Gas barrier laminate film The gas barrier laminate film that can be used in the laminate (I) and laminate (II) of the present invention is provided with an inorganic oxide vapor-deposited film on one surface of the base film layer, On the inorganic oxide vapor-deposited film, the general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and 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.), a polyvinyl alcohol-based resin, and / or Or it is the laminated film which provided the gas-barrier coating film by the gas-barrier composition which contains an ethylene vinyl alcohol copolymer and is further polycondensed by the 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 acts synergistically, has excellent gas barrier properties that prevent permeation of oxygen, water vapor, and the like, and also has excellent hot water resistance.

  In particular, when a gas barrier laminate film is laminated on the laminate (II), the container is suitable for a microwave oven, has heat resistance and water resistance to withstand retort sterilization, and has gas barrier properties, such as foodstuffs. Storability can be improved.

(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 heat seal 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 interposed on the printing layer. A heat seal layer may be laminated, a gas barrier coating film is laminated with a primer and a laminating adhesive, and a heat seal layer is laminated by a dry laminating method, or a gas barrier coating film is coated with a primer and an undercoat agent. The molten resin that can constitute the heat seal 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. 4 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. 4, 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 of forming a thin film of an inorganic oxide by physical vapor deposition will be described with reference to FIG. 5 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.

このポリマーは、ＯＲ基（エトキシ基などのアルコキシ基）が、直鎖状のポリマーから分岐した形で有する。このＯＲ基は、存在する酸が触媒となって加水分解されてＯＨ基となり、ゾルゲル法触媒（塩基触媒）の働きにより、まず、ＯＨ基が、脱プロトン化し、次いで、重縮合が進行する。すなわち、このＯＨ基が、下記の式（Ｉ）に示されるポリビニルアルコール系樹脂、または、下記の式（ＩＩ）に示されるエチレン・ビニルアルコール共重合体と重縮合反応し、Ｓｉ−Ｏ−Ｓｉ結合を有する、例えば、下記の式（ＩＶ）に示される複合ポリマー、あるいは、下記の式（Ｖ）及び（ＶＩ）に示される共重合した複合ポリマーを生じると考えられる。

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.

上記の反応は常温で進行し、ガスバリア性組成物は、調製中に粘度が増加する。このガスバリア性組成物を、基材フィルム層上の無機酸化物の蒸着膜の上に塗布し、加熱して溶媒および重縮合反応により生成したアルコールを除去すると重縮合反応が完結し、基材フィルム層上の無機酸化物の蒸着膜の上に透明な塗布膜が形成される。なお、上記の塗布膜を複数層積層する場合には、層間の塗布膜中の複合ポリマー同士も縮合し、層と層との間が強固に結合する。

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.

(5) Intermediate substrate film In the laminate (I) and laminate (II) of the present invention, between the paper substrate layer and the gas barrier laminate film, between the gas barrier laminate film and the heat seal layer, An intermediate substrate film layer may be provided between the transparent plastic substrate layer and the gas barrier laminate film. Thereby, the adhesiveness between lamination | stacking can be improved and the gas barrier characteristic original gas barrier property laminated | multilayer film can be exhibited.

  As such an intermediate substrate film, for example, one or more of a polyolefin resin such as polypropylene, a polyester resin, a polyamide resin, a polyaramid resin, a polycarbonate resin, a polyacetal resin, and a fluorine resin are preferably used. be able to. In the present invention, as the intermediate base film, any of an unstretched film of the resin and 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, a stretched nylon film, or a biaxially stretched polyethylene terephthalate film.

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

(6) Heat-seal layer The heat-seal layer used in the laminate (I) and laminate (II) of the present invention is a low-density polyethylene (hereinafter referred to as LDPE) as such a heat-adhesive resin, Linear low density polyethylene (hereinafter referred to as LLDPE), ethylene-α / olefin copolymer polymerized using a single site catalyst, 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), 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 ( A copolymer having a ethylene content of 10 mol% or less), or a polypropylene resin obtained by graft polymerization or copolymerization of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or an ester monomer, etc. to polypropylene, a medium density polyethylene, An unstretched film such as high-density polyethylene or a resin layer obtained by extrusion coating of 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 heat seal layer has heat resistance, it is necessary to have heat adhesiveness 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 thermal adhesive resin layer, the polypropylene, propylene-ethylene copolymer (copolymer having an ethylene content of 10 mol% or less), or an unsaturated carboxylic acid or 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.

  Thereby, the self-supporting bag-like 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 The heat seal layer can be formed by melt extrusion lamination through a melt extrusion resin layer or the like.

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

(7) Printed layer In the present invention, when a printed layer is formed, it may be formed on a transparent plastic substrate or a paper substrate layer. 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.

  Thus, by applying the design printing layer, the printing effect is enhanced by the whiteness of the cardboard, and the design of the container can be further improved.

(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 processing, plasma is generated by using three types of devices such as direct current glow discharge, radio frequency (AF) discharge, and microwave discharge. Can do. 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 layer and a transparent plastic base material, an anchor coat agent is applied in advance to the laminated surface in contact with the melt-extruded resin layer. Thus, an anchor coat layer can be formed. For example, in order to form an anchor coat layer on a paper base layer when adhering a paper base layer and a transparent plastic base, an organic titanium anchor coat agent such as alkyl titanate, an isocyanate anchor coat agent, polyethyleneimine Examples of such anchor coating agents include 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 the paper base layer in advance, a thin film having high flexibility and flexibility can be formed, acting as a film having flexibility, flexibility, etc. on the melt-extruded resin layer, Processing suitability such as laminating and printing can be improved.

  The anchor coat layer is not limited to the case where it is formed on the paper substrate layer. For example, the anchor coat layer may be formed on a gas barrier coating film or a plasma treatment surface formed on the gas barrier coating film. Adhesion 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 substrate film, a heat seal layer, or the like may be laminated using a dry laminate lamination method via an adhesive layer for lamination. By providing such a primer layer, adhesion between the gas barrier coating film and a laminating adhesive layer, an anchor coat layer, an intermediate substrate film 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 substrate film 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, intermediate base film layer, 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 heat seal layer or the like can be laminated on the transparent plastic substrate via a laminating adhesive using a dry laminating method, and a base film of a gas barrier laminate film Can be bonded using a laminating adhesive when laminating the heat seal layer, and when laminating any two layers, the laminating adhesive can be used to dry Can be glued.

  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 Extrusion Resin In the present invention, as the melt extrusion adhesive resin, a heat sealable resin that can be used when the heat seal layer is a heat sealable resin layer can be used. It is preferable to use linear low density polyethylene or acid-modified polyethylene. 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 material As a material for forming a laminated body constituting the self-supporting bag-like container used in the present invention, for example, low density polyethylene having medium barrier properties such as water vapor, water, medium density polyethylene, Resin film such as high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, etc., or polyvinylidene chloride resin, polyvinyl alcohol resin, ethylene-vinyl having barrier properties against oxygen, water vapor, etc. It has a light-shielding property formed by filming a resin film such as an alcohol copolymer, MXD polyamide-based resin, polynaphthalene terephthalate-based resin, a colorant such as a pigment to the resin, and kneading other desired additives. Various colored resin films 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, ethylene-vinyl acetate copolymer It can be arbitrarily selected from films of known resins such as saponified products, fluorine resins, diene resins, polyacetal resins, polyurethane resins, nitrocellulose, and the like.

  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) Manufacturing method of laminated body The laminated body (I) and laminated body (II) of the present invention use the resin forming each of the layers, and manufacture the laminated body while forming a film by film extrusion or melt extrusion. can do.

  The laminate (I) is provided with an inorganic oxide vapor-deposited film (43) on one surface of the base film layer (41) in advance, and on the surface of the inorganic oxide vapor-deposited film (43), A gas barrier laminated film provided with the gas barrier coating film (45) is produced, the gas barrier laminated film and a heat seal layer are laminated, and a transparent plastic film (10) and a paper base material layer (30) are laminated thereon. Can be prepared by adhering laminates. For example, in the case of the laminate (I) shown in FIG. 1, a base film layer (41), a corona treatment layer (80), an inorganic oxide vapor deposition layer (43), and a gas barrier coating film (45) are sequentially laminated. A corona treatment (80) is performed on the base film layer (41) of the gas barrier laminate film (40) formed, and the corona treatment layer (80) and the heat seal layer (50) are laminated with a laminate adhesive layer (75). On the other hand, a paper layer (20) provided with a printed layer (60) after providing a corona-treated layer (80) on the transparent plastic substrate (10) and provided with an anchor coat layer (73). ) Through an extrusion laminate layer (70), and then an anchor coat layer (73) is formed on the other surface of the paper substrate layer (20), whereby the gas barrier properties of the gas barrier laminate film (40) are formed. Extrude coating film (45) It is an example of a cross-sectional view of Toruso laminate produced by bonding through a (70) (I). If the laminated body used by this invention is a structure which laminated | stacked the transparent plastic base material (10), the paper base material layer (20), the gas-barrier laminated | multilayer film (40), and the heat seal layer (50) in this order, it is the said structure. However, it may be a dry laminate layer instead of an extruded laminate layer, and in that case, an anchor coat layer may not be present. In addition, a plasma treatment or other surface treatment is performed instead of a corona treatment. It may be a dish.

  The laminate (II) can be produced by laminating the transparent plastic film (10) and the paper base layer (30) via the lamination adhesive layer (75). When the laminate (II) includes a gas barrier laminate film between the transparent plastic substrate and the heat seal layer, an inorganic oxide vapor-deposited film (on the surface of the substrate film layer (41) ( 43), and further, a gas barrier laminated film having the gas barrier coating film (45) provided on the surface of the inorganic oxide vapor-deposited film (43) is produced, and the gas barrier laminated film and the heat seal layer are produced. And a transparent plastic film (10) can be laminated thereon. For example, in order to produce the laminate (II) shown in FIG. 2, the corona-treated layer (80) is provided on the transparent plastic substrate (10), the printing layer (60) is then provided, and the extrusion laminate layer (70) is provided. What is necessary is just to adhere | attach with a transparent plastic base material (10). The laminate (II) used in the present invention is not limited to the above-mentioned configuration, and may include a gas barrier laminate film (40) between the transparent plastic substrate (10) and the heat seal layer. Instead of the layer, a dry laminate layer may be used, and in this case, the anchor coat layer may not be present. In addition, a plasma treatment or other surface treatment may be performed instead of the corona treatment.

  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) Self-supporting bag-like container The self-supporting bag-like container of the present invention is formed by heat-sealing the side edge portions of the front and rear wall laminates at the side of the body of the container, The bottom part is formed in a form having a gusset part formed by folding the bottom laminate to the inside between the lower parts of the front and rear wall laminates and heat-sealing, and the gusset part is an inner central part. It is heat-sealed with a bottom-bottom-shaped seal pattern that is low and rises toward both ends.

  FIG. 6 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).

  The self-supporting bag-like container capable of retorting shown in (a) and (b) of FIG. 6 has a bottom part between the lower part of the front and rear wall parts (150) and the bottom part laminated body (155). Is formed in a form having a gusset portion (190) formed by being folded inward and inserted into the bottom-layer laminate folding portion (115), and in the vicinity of the lower ends on both sides of the bottom-layer laminate (155) folded inside, In this case, a semicircular bottom-layer laminate cutout (110a, 110b) is provided, and the gusset (190) rises linearly from the bottom having a predetermined width on the inside to the outside with both sides inclined outward. A ship-bottom-shaped sealing pattern having a shape, 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 edge portions of the front and rear wall laminates (150). 160b) and heat sealed Has been.

  The upper part of the self-supporting bag-like container (100) is filled with the contents from this part and then heat-sealed by the upper seal part (180), but below the upper seal part (180), As an opening means for facilitating opening of the container (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 the ship-bottom-shaped seal pattern of the rising shape is shown, a seal pattern or the like that heat-seals the outer periphery of the bottom gusset portion (190) with a predetermined width may be used. Even in such a case, in order to further improve the self-supporting property of the container, a bottom-layer laminate notch (110a, 110b) having a similar shape is formed in the vicinity of both lower ends of the bottom-layer laminate (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-like container (100) using, for example, a conventional filling machine for a standing pouch, After filling, the upper seal part (180) can be heat sealed by a method such as deaeration sealing.

The container (100) filled with the contents has a hexagonal shape at the bottom and expands in the front and back to form a three-dimensional structure. Therefore, the container (100) can be packaged compactly for its capacity. Since the leg part by the part is reliably formed, the laminate for the front and rear wall surfaces (150) is laminated with thick paper having a basis weight of 70 to 280 g / m ^{2 on} its intermediate layer, and the rigidity is enhanced. The self-sustainability and shape retention of the container are improved, and the contents can be safely protected even in the case of foods containing solid materials that are easily crushed.

  In addition, the self-supporting bag-like container (100) has a front and rear wall laminate (150) at least from the outside, from the transparent plastic substrate (10), the paper substrate layer (30), and the gas barrier laminate film. (40), the heat seal layer (50) is sequentially laminated via the adhesive layers (70, 75), and the bottom laminate (160) is at least from the outside from the transparent plastic substrate (10 ), Gas barrier laminate film (40), and heat seal layer (50) are laminated in order through the adhesive layer (70, 75), so that the heat resistance and water resistance endure retort sterilization as a whole At the same time, it is excellent in gas barrier properties and excellent in long-term storage of contents.

  And when taking out the contents filled in the self-supporting bag-like container (100), a half-cut is provided below the upper seal part (180) as an opening means for facilitating the opening of the container (100). Since the line (130) and the notch (120) are provided at one end thereof, the notch (120) can be 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 by tearing it by hand. Therefore, even when the content contains a solid with a liquid, it can be easily taken out.

  Further, when a design such as a printed pattern is applied to the self-supporting bag-like container (100), the inner surface of the transparent plastic substrate (10) outside the front and rear wall laminates (150) or the paper base By printing on the outer surface of the material layer (20), the whiteness and opacity of the paper base layer (20) can be used, so that the printing effect is enhanced and the design of the container (100) can be further improved. it can.

  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.

  Since the self-supporting bag-like container of the present invention has a form in which the main body portion is provided with self-supporting property by forming the bottom portion in a gusset form in the same manner as a normal standing pouch, It can be manufactured using a pouch bag making machine. 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, a punching device, etc. to a bag making machine for a standing pouch, and when providing a ruled line on the front and back wall laminates, add an additional hot press device or embossing device, etc. Both can be easily manufactured.

(16) Retort processing package body The self-standing structure according to the present invention is filled by filling the contents from the opening of the self-supporting bag-shaped container according to the present invention, and then sealing the opening at the upper end by heat sealing or the like. A self-supporting bag-like container according to the present invention is used by manufacturing a semi-finished packaging product using a pouch-shaped container and then subjecting the semi-packed product to heat treatment such as retorting or boiling. The retort processing package which was made 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 self-supporting bag-like container according to the present invention is excellent in various physical properties such as heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and the like, particularly oxygen gas, water vapor, etc. Excellent barrier properties to prevent permeation, etc., excellent deformation prevention strength, withstand heat treatment associated with processing such as retort processing, no delamination, etc., and further suitable for disposal of paper containers after use Have For this reason, it is a container which heats and fills chocolate sauce, fruit sauce, soup and the like and heats it in a microwave oven at the time of use, and can be suitably used as a bag-like container that can stand by itself after the microwave oven. For example, various foods and beverages such as chocolate sauce, fruit sauce, soup, cooked food, marine products, frozen food, boiled food, seasoning, drinking water, etc., or animal food such as pet food are filled. It is useful for packaging and is excellent in filling / packaging suitability, quality maintenance, and the like.

  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 biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used, and this is attached to a feed roll of a plasma chemical vapor deposition apparatus, and then the corona of the above biaxially stretched polyethylene terephthalate film under the conditions shown below. A 200 nm thick silicon oxide vapor deposition film was formed on the treated surface.

(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 mixed solution composed of an aqueous polyvinyl alcohol solution, a 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.

次に、上記の（２）で形成したプラズマ処理面に、上記で製造したガスバリア性組成物を使用し、これをグラビアロールコート法によりコーティングして、次いで、１００℃で３０秒間、加熱処理して、厚さ０．４ｇ／ｍ²（乾操状態）のガスバリア性塗布膜を形成して、本発明に係るバリア性フィルムを製造した。

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

(2) The surface of the biaxially stretched polyethylene terephthalate film of the barrier film is subjected to a corona discharge treatment, and then a two-component curable polyurethane laminating adhesive is applied to the corona treatment surface using a gravure roll coating method. Then, a laminate adhesive layer is formed by coating to a thickness of 4.0 g / m ² (dry state), and then an unstretched polypropylene film having a thickness of 50 μm is dry-laminated on the surface of the laminate adhesive layer. And laminated.

  (3) Using a normal gravure ink composition on a corona-treated surface of a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, print a printing pattern consisting of letters, symbols, patterns, figures, etc., using a gravure printing method. Thus, a desired printed pattern layer was formed.

(4) A polyethyleneimine anchor coating agent is used on one side of the paper base layer [coated card paper, basis weight 150 g / m ² ], and this is coated with a gravure roll coating method to a film thickness of 0.5 g / m. ^{2 An} anchor coat agent layer is formed by coating so as to be in a dry state, and then the biaxial shaft produced in the above (3) while melt-extruding polypropylene resin to a film thickness of 15 μm on the surface of the anchor coat agent layer. Lamination was carried out facing the printing surface of the stretched polyethylene terephthalate film.

(5) Next, a polyethyleneimine-based anchor coating agent is used on the surface of the gas barrier coating film of the barrier film of the above (1), and this is coated with a film thickness of 0.5 g / m ² (dried by gravure roll coating). State), the anchor coating agent layer is formed, and then the surface of the anchor coating agent layer and the other paper substrate layer surface of (4) are opposed to each other, so that the polypropylene resin has a film thickness of 15 μm. Lamination was performed while melt extrusion to produce a laminate (I).

(Example 2)
(1) Using a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, the above biaxially stretched polyethylene terephthalate film is mounted on a feed roll of a take-up vacuum deposition apparatus, and then this is fed out and biaxially stretched. Using a vacuum deposition method using an electron beam (EB) heating method while supplying oxygen gas to a corona-treated surface of a polyethylene terephthalate film, an aluminum oxide film having a thickness of 200 mm is formed under the following deposition conditions. A deposited film was formed.

(Deposition conditions)
Deposition surface: Corona-treated surface,
Deposition source: Aluminum,
Degree of vacuum in the deposition chamber (before oxygen introduction): 2 to 10 × 10 ⁻⁵ mbar,
Degree of vacuum in the deposition chamber (after oxygen introduction): 1 to 10 × 10 ⁻⁴ mbar,
Line speed: 600 m / min,
Next, immediately after the above-described aluminum oxide vapor deposition film having a thickness of 200 mm was formed, a plasma-treated surface was formed on the aluminum oxide vapor deposition film surface in the same manner as in Example 1 above.

  On the other hand, 100 parts of tetra-i-propoxytitanium and 70 parts of acetylacetone were added to a reactor equipped with a reflux condenser and a stirrer, and stirred at 60 ° C. for 30 minutes to obtain a titanium chelate compound. The purity of this reaction product was 75%.

  On the other hand, according to the composition shown in Table 2 below, composition a. EVOH (ethylene copolymerization ratio 29%) A composition prepared in advance in an EVOH solution dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzate composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, followed by stirring, and a composition prepared in advance c. A mixed liquid composed of an aqueous polyvinyl alcohol solution, acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating liquid.

次に、上記の（１）で形成したプラズマ処理面に、上記で製造したガスバリア性組成物を使用し、これをグラビアロールコート法によりコーティングして、次いで、１００℃で３０秒間、加熱処理して、厚さ０．４ｇ／ｍ²（乾操状態）のガスバリア性塗布膜を形成して、本発明に係るバリア性フィルムを製造した。

Next, the plasma-treated surface formed in the above (1) is coated with the gas barrier composition produced above by the gravure roll coating method, and then heat-treated at 100 ° C. for 30 seconds. Then, a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) was formed to produce a barrier film according to the present invention.

(2) The surface of the biaxially stretched polyethylene terephthalate film of the barrier film is subjected to a corona discharge treatment, and then a two-component curable polyurethane laminating adhesive is applied to the corona treatment surface using a gravure roll coating method. Then, a laminate adhesive layer is formed by coating to a thickness of 4.0 g / m ² (dry state), and then an unstretched polypropylene film having a thickness of 50 μm is dry-laminated on the surface of the laminate adhesive layer. And laminated.

  (3) Using a normal gravure ink composition on a corona-treated surface of a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, print a printing pattern consisting of letters, symbols, patterns, figures, etc., using a gravure printing method. Thus, a desired printed pattern layer was formed.

(4) A polyethyleneimine anchor coating agent is used on one side of the paper base layer [coated card paper, basis weight 150 g / m ² ], and this is coated with a gravure roll coating method to a film thickness of 0.5 g / m. ^{2 An} anchor coat agent layer is formed by coating so as to be in a dry state, and then the biaxial shaft produced in the above (3) while melt-extruding polypropylene resin to a film thickness of 15 μm on the surface of the anchor coat agent layer. Lamination was carried out facing the printing surface of the stretched polyethylene terephthalate film.

(5) Next, a polyethyleneimine-based anchor coating agent is used on the surface of the gas barrier coating film of the barrier film of the above (1), and this is coated with a film thickness of 0.5 g / m ² (dried by gravure roll coating). State), the anchor coating agent layer is formed, and then the surface of the anchor coating agent layer and the other paper substrate layer surface of (4) are opposed to each other, so that the polypropylene resin has a film thickness of 15 μm. Lamination was performed while melt extrusion to produce a laminate (I).

(Comparative Example 1)
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used, and this is attached to a feed roll of a plasma chemical vapor deposition apparatus, and then the corona of the above biaxially stretched polyethylene terephthalate film under the conditions shown below. A vapor-deposited film of organic silicon oxide having a thickness of 100 mm was formed on the treated surface.

(Deposition conditions)
Deposition surface; corona-treated surface,
Introduced gas amount; hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 1.0 (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 forming a silicon oxide vapor deposition film having a thickness of 100 mm 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. Then, the surface tension of the silicon oxide deposition film surface was improved by 54 dyne / cm or more to form a plasma-treated surface, and a barrier film was manufactured.

  (2) Using the barrier film of (1) above, a laminate was produced in the same manner as in (2) to (4) of Example 1.

(Comparative Example 2)
In Example 1 above, after the corona discharge treatment was applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm as the barrier film, a two-component curing type polyurethane-based laminate adhesive was applied to the corona treatment surface. Is coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coating method to form an adhesive layer for laminating, and then a 7 μm thick aluminum layer is formed on the surface of the laminating adhesive layer. A laminate was produced in exactly the same manner as in Example 1 except that a gas barrier film obtained by laminating foil was used.

(Comparative Example 3)
A laminate was produced in the same manner as in Example 1 except that a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used instead of the barrier film produced in (1) of Example 1.

(Comparative Example 4)
In Example 1, a laminate was produced in the same manner as in Example 1 except that no paper substrate was used.

(Experiment 1)
A self-supporting bag-like container having the configuration shown in FIG. 6 is prepared using the laminates manufactured in Examples 1 and 2 and Comparative Examples 1 to 4, and a standing pouch bag making machine is used. Then, a laser beam irradiation device and a punching device for providing the half-cut line 15 and the notch 14 are attached thereto, and with the configuration shown in FIG. 6, the external dimensions are 130 mm wide and 190 mm long, and the length of the gusset portion 11 Was processed to a length of 40 mm to produce a self-supporting bag-like container.

  This self-supporting bag-like container was measured for oxygen permeability, water vapor permeability, pinhole resistance, self-supporting ability, and microwave oven suitability.

(1) Measurement of oxygen permeability The laminates produced in Examples 1 and 2 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 and 2 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 pinhole About the retort processing package manufactured using the self-supporting bag-shaped container manufactured in Examples 1 and 2 and Comparative Examples 1 to 3, using a gelbo tester, After bending 5 times at a temperature of 3 ° C., the oxygen permeability was measured and evaluated.

(4) Self-supporting When the container was made self-supporting, the shape-retaining property on the side of the container was visually observed, and “○” was given when it had shape-retaining property, and “X” when it had no shape-retaining property.

(5) Evaluation of suitability for microwave oven When it is put into a microwave oven, the paper base material is burnt or sparked before the heating of the contents is completed, and “X” is indicated when the microwave oven is not suitable. ○ ”.

The test results are shown in Table 3 below. In Table 3, 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].

  When applied to a microwave oven, Comparative Example 2 using aluminum foil did not have suitability for a microwave oven due to the occurrence of sparks when applied to a microwave oven. It was suitable. In particular, the stand-pack type container tends to improve the heating efficiency because the bottom of the contents is slightly lifted by the container.

(Comparative Example 5)
Using the laminate produced in Example 1 above, a Gavel top type container having a length of 65 mm, a width of 65 mm, and a height of 190 mm was prepared, and oxygen permeability, water vapor permeability, pinhole resistance, self-supporting property and microwave oven were produced. Aptitude was measured. The results are shown in Table 3.

  When the gobber top type container was placed in a microwave oven, the bottom of the container was burned before the contents were heated.

(Comparative Example 6)
Using the laminate produced in Example 2 above, a brick container having a length of 50 mm, a width of 80 mm, and a height of 100 mm was prepared, and oxygen permeability, water vapor permeability, pinhole resistance, self-sustainability, and microwave oven suitability Was measured. The results are shown in Table 3.

  When the brick-type container was placed in a microwave oven, the bottom of the container was burnt before the contents were heated.

  The self-supporting bag-like container according to the present invention is excellent in microwave oven suitability, self-supporting property, gas barrier property, heat resistance, and pinhole resistance, and is particularly useful as a container used in a microwave oven.

FIG. 1 is a cross-sectional view illustrating a laminate (I) constituting a retort processing paper container used in the present invention. FIG. 2 is a cross-sectional view for explaining the laminate (II) constituting the retort processing paper container used in the present invention. It is a figure which shows the external appearance of the self-supporting bag-shaped 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 ... Transparent plastic substrate,
20 ... paper base material layer,
30 ... Intermediate base film,
40 ... Gas barrier laminate film,
41 ... base film layer,
43 ... Inorganic oxide vapor deposition layer,
45 ... Gas barrier coating film,
50 ... heat seal 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 (19)

A self-supporting bag-like container formed by heat-sealing the laminate in a bag shape,
The body of the container is formed by heat-sealing both side edges of the front and rear wall laminates with side seals, and the bottom is a bottom laminate between the lower portions of the front and rear wall laminates. It is formed in a form having a gusset part formed by folding and inserting inside and heat sealing,
The wall surface laminate is a laminate (I) comprising a transparent plastic substrate, a paper substrate layer having a basis weight of 70 to 280 g / m ² , a gas barrier laminate film and a heat seal layer,
The self-supporting bag-like container, wherein the bottom laminate is a laminate (II) including a transparent plastic substrate and a heat seal layer.   The self-supporting bag-like container according to claim 1, wherein the laminate (II) includes a gas barrier laminate film between the transparent plastic substrate and the heat seal 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, 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 obtained by polycondensation by a sol-gel method, which contains at least one alkoxide represented by the formula (1) and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. The self-supporting bag-like container according to claim 1 or 2, wherein the container is a laminated film provided with a gas barrier coating film made of an adhesive composition. The self-supporting bag-like container according to claim 2 or 3, wherein M in the general formula R ¹ _n M (OR ² ) _m is made of silicon, zirconium, titanium, or aluminum.   The self-supporting bag-like container according to any one of claims 2 to 4, wherein the alkoxide is composed of an alkoxysilane, an alkoxide hydrolyzate, or an alkoxide hydrolysis condensate.   The self-supporting bag-like container according to any one of claims 2 to 5, wherein the gas barrier composition contains a silane coupling agent.   The self-supporting property according to any one of claims 2 to 6, wherein the sol-gel method uses a sol-gel method catalyst made of a tertiary amine that is substantially insoluble in water and soluble in an organic solvent. Bag-shaped container.   The self-supporting bag-like container according to any one of claims 2 to 7, wherein the inorganic oxide vapor-deposited film is an inorganic oxide vapor-deposited film formed by chemical vapor deposition or physical vapor deposition.   The self-supporting bag-like container according to any one of claims 2 to 8, wherein the inorganic oxide vapor-deposited film is an organic silicon oxide vapor-deposited film formed by chemical vapor deposition. Said wall for laminate is one which comprises a transparent resin layer, the printing layer between the basis weight amounts 70~280g / m ² paper substrate layer, self-supporting bag according to any one of claims 1 to 9 Shaped container. The paper substrate layer, Stockigt size degree of 400 seconds or more, a thick paper of a basis weight amount 70~280g / m ^2, self-supporting bag-shaped container according to any one of claims 1 to 10.   The gusset part of the bottom part of the said container is heat-sealed by the ship bottom-shaped sealing pattern which becomes low toward the both-ends part while the inner center part is low. Self-supporting bag-like container.   The self-supporting bag-like container according to any one of claims 1 to 12, wherein the transparent plastic substrate is a heat-resistant and water-resistant resin layer.   Any of Claims 1-13 which have an intermediate | middle base film layer between the said paper base material layer and gas-barrier laminated film of laminated body (I), or between the said gas-barrier laminated film and a heat seal layer. A self-supporting bag-like container according to crab.   The laminate (II) has an intermediate substrate film layer between the transparent plastic substrate and the gas barrier laminate film or between the gas barrier laminate film and the heat seal layer. The self-supporting bag-shaped container as described.   The self-supporting bag-like container according to claim 14 or 15, wherein the intermediate base film layer is a polypropylene film.   The self-supporting bag-like container according to any one of claims 1 to 16, wherein the front and rear laminates for wall surfaces are provided with a plurality of vertical creases.   The self-supporting bag-like container according to any one of claims 1 to 17, wherein an opening means is provided at an upper part of the container.   A retort-treated packaging body in which the contents are sealed in the container according to claim 1 and heat-treated.

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