JP5152634B2 - Oxygen-absorbing coextrusion multilayer laminate sheet - Google Patents

Description

  The present invention relates to an oxygen-absorbing coextruded multilayer laminated sheet, and more particularly to a lid member that seals an opening of a plastic molded container and captures oxygen that is present or generated in a packaging container.

  Conventionally, plastic packaging products in various forms have been developed for filling and packaging various foods and drinks, chemical products such as liquid detergents, cosmetics, pharmaceuticals, miscellaneous goods, industrial components, and other various articles. ,Proposed. In these plastic packaging products, the opening of the plastic molding container is often sealed with a sheet. In general, this sheet has excellent heat sealability and satisfactory sealability due to the protection of the quality of the contents, extension of the storage period, and other requirements. It is required that the packaging container has an easy opening property that can be easily opened. Therefore, in recent years, various types of materials, materials, etc. have been used to develop packaging sheet materials having various layer configurations, and packaging bags, packaging products, etc. having various forms using such sheets have been developed. Has been proposed.

In recent years, as one of such sheets, a cohesive failure type easy peel sealant as a lid material used for polypropylene molded containers and paper cup containers in which polypropylene is laminated in the innermost layer, and polypropylene is a heat bonding component A cohesive fracture easy peel sealant using a mixture of ethylene / α-olefin copolymer, low density polyethylene, linear low density polyethylene, high density polyethylene, polystyrene or a modified product thereof. Proposed. (See JP 2001-301831 A: Patent Document 1). Further, depending on the contents to be filled and packaged, for example, it may be required to have a gas barrier property that prevents permeation of oxygen gas, water vapor, and the like. Assuming such a situation, it is suitable as a container that prevents oxidation of the contents of the container by removing oxygen from the container and by preventing oxygen from entering the container from outside the container. Articles of manufacture have been proposed, such as packaging articles, multilayer films, containers comprising an oxygen scavenging composition comprising a polymer backbone, a cyclic olefin pendant group, a linking group binding the olefin pendant group to the backbone and a transition metal catalyst A manufacturing method and others have been proposed (Japanese Patent Publication No. 2003-521552: Patent Document 2).
JP 2001-301831 A Special table 2003-521552 gazette

  However, a lid using a cohesive failure type heat sealable film in which a sealing layer is formed by blending the above polypropylene and polyethylene, the surface of the heat sealable film is formed on a molded container such as polyethylene or polypropylene, or polyethylene. Laminating a film made of polypropylene resin, polypropylene resin, etc., and superimposing it on the surface of the flange part that constitutes the opening part of a paper container or the like using the film as a surface layer. When a packaged product is manufactured by punching along the shape of the part, the resin crimp phenomenon of the punched part frequently occurs, and the lid material adheres very firmly and tightly to the flange surface, causing problems when opening the container. There is a problem that it occurs.

  Furthermore, the above-mentioned easy peel sealant can have a gas barrier property that reduces the permeation of oxygen gas, water vapor, etc. by laminating a barrier substrate film, but cannot completely prevent permeation, and the container It was difficult to prevent the internal oxygen concentration from increasing (passive barrier).

  Also, when using the same film and an easy-to-peel sealant and an oxygen scavenging composition at the same time, it is necessary to manufacture them individually and bond them together by a method such as dry lamination. However, not only does the production cost increase, but there is a problem in that the oxygen scavenging ability is lowered by directly contacting the oxygen scavenging composition with an adhesive or the like.

  Therefore, the present invention is excellent in heat-sealability and can sufficiently satisfy its sealing performance, protects the quality of the contents, satisfies other requirements, and prevents the resin-bonding phenomenon of the punched portion, It has excellent easy peelability, can easily open the opening of a plastic molded container when consumed, has an easy opening property that can constitute a very beautiful peeling interface, and penetrates the package. A sealant sheet having a function of preventing oxygen from entering into the package and further sufficiently capturing oxygen that is present or generated in the package (active barrier) is manufactured as a co-extruded multilayer laminate sheet (ie, (Manufacturing co-extruded multi-layer laminate sheet that combines heat sealability, easy peel property and oxygen absorption), useful for protecting the quality of contents and extending shelf life Packaging materials, packaging bags, and to provide a packaged product or the like.

  As a result of various studies to solve the above problems, the present inventors laminated a first film having a specific composition, a second film that is an oxygen-absorbing resin layer, and a third film in this order. The present inventors have found that this problem can be solved by using the coextruded multilayer laminated sheet.

  Here, the co-extruded multilayer laminate sheet of the present invention is a co-extrusion multilayer laminate sheet in which at least a first film, a second film, and a third film are provided in this order, and the first film comprises: A film comprising one or two or more resin layers, the outermost layer being a resin layer containing at least 50 to 90% by weight of high-density polyethylene and 10 to 50% by weight of polybutene-1; Is a film consisting of an oxygen-absorbing resin layer containing an oxidizing resin and a transition metal catalyst, and the third film is a film consisting of one or more resin layers having a resin layer containing a thermoplastic resin It is characterized by being.

In a preferred embodiment of the coextruded multilayer laminated sheet of the present invention, the first film is composed of two or more resin layers, and the resin layer adjacent to the outermost surface layer among the resin layers constituting the first film is , An ethylene-α / olefin copolymer, a high-density polyethylene having a density of 0.935 g / cm ³ or more, or a polypropylene-based resin.

  In another preferred embodiment of the coextruded multilayer laminated sheet of the present invention, the first film is composed of two or more resin layers, and faces the second film out of the resin layers constituting the first film. It is assumed that the layer is an adhesive resin layer.

In another preferred embodiment of the coextruded multilayer laminated sheet of the present invention, the third film is an ethylene-α / olefin copolymer polymerized using a single site catalyst, and the density is 0.935 g / cm ³ or more. And a resin layer mainly composed of high-density polyethylene or polypropylene-based resin.

  In another preferred embodiment of the coextruded multilayer laminated sheet of the present invention, the third film is composed of two or more resin layers, and a layer facing the second film among the resin layers constituting the third film. Is a resin layer made of an adhesive resin.

  In another preferred embodiment of the coextruded multilayer laminated sheet of the present invention, the thickness of the outermost surface layer of the first film is 30 μm or less.

  In another preferred embodiment of the coextruded multilayer laminated sheet of the present invention, the base film is further provided in the order of the first film, the second film, the third film, and the base film. It shall be.

  In another preferred embodiment of the coextruded multilayer laminated sheet of the present invention, the base film is a biaxially stretched polyester resin film.

In another preferred embodiment of the coextruded multilayer laminated sheet of the present invention, the high-density polyethylene contained in the outermost surface layer of the first film has a density of 0.950 to 0.980 g / cm ³ , a melt flow rate ( MFR) is 8.0 to 40.0 g / 10 min.

In another preferred embodiment of the coextruded multilayer laminated sheet of the present invention, the polybutene contained in the outermost surface layer of the first film has a density of 0.880 to 0.930 g / cm ³ and a melt flow rate (MFR). Is 0.1 to 10.0 g / 10 min.

In another preferred embodiment of the coextruded multilayer laminated sheet of the present invention, the high-density polyethylene and polybutene contained in the outermost surface layer of the first film are 60 to 80% by weight and 20 to 40% by weight, respectively. In another preferred embodiment of the coextruded multilayer laminated sheet of the present invention, an ethylene / α-olefin copolymer obtained by polymerizing a resin layer adjacent to the outermost surface layer using a single site catalyst is used. And the density of the copolymer is 0.910 to 0.930 g / cm ³ .

  The packaging container according to another aspect of the present invention is a packaging container using the coextruded multilayer laminated sheet.

<Co-extrusion multilayer laminate sheet>
The coextruded multilayer laminated sheet of the present invention includes a first film having a cohesive failure layer that exhibits easy peel properties by adhering to a container or the like, a second film that exhibits oxygen absorption, a second film, and a substrate. A third film that prevents direct contact of the adhesive and imparts strength to the sheet is provided at least in this order. In the coextruded multilayer laminated sheet of the present invention, for example, a base film may be further laminated on the third film. In that case, the coextruded multilayer laminated sheet includes the first film, the second film, the third film, It becomes what was provided in order of the base film. In this case, typically, the first film, the second film, and the third film are laminated by coextrusion, and then the base film is laminated.

<First film>
The first film in the coextruded multilayer laminate sheet of the present invention includes at least a cohesive failure layer that adheres to the container or the like on the outermost surface and exhibits easy peel properties, and when used as a lid of a packaging container, It is assumed to be located between the second film exhibiting oxygen absorbability and the container. This first film may be formed of one or more resin layers.

-Outermost surface layer of first film-
The outermost surface layer of the first film (that is, the layer farthest from the second film when the first film is assumed to be in direct contact with a container and the first film is formed of two or more resin layers) is a cohesive failure layer And a resin layer containing at least 50 to 90% by weight of high-density polyethylene and 10 to 50% by weight of polybutene-1.

The high-density polyethylene resin preferably has a density of 0.950 to 0.980 g / cm ³ and a melt flow rate (MFR) of 8.0 to 40.0 g / 10 min. 30.0 g / 10 min (190 ° C.) is preferred. As such a high-density polyethylene-based resin, as a monomer, ethylene, further propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, Α-olefin such as 1-nonene, 1-decene, etc. is used, for example, by using a polymerization method such as slurry method, solution method, gas phase method, etc., ethylene alone or ethylene and other An ethylene homopolymer obtained by copolymerizing an olefin, a copolymer of ethylene and another olefin, or the like can be used. If the melt flow rate (MFR) is less than 8.0 g / 10 minutes, the melt flow rate (MFR) of the polybutene resin becomes close, and the degree of dispersion becomes high (finely dispersed state). When the peel performance cannot be expressed and the melt flow rate (MFR) exceeds 40.0 g / 10 min, the film-forming stability is deteriorated and the compatibility with the polybutene resin is deteriorated. This is not preferable for reasons such as the possibility of visible unevenness and irregularities (complete separation). If the density is less than 0.950 g / cm ³ , low-temperature sealing is possible, but there is a possibility that stringing (feathering), lowering of the waist problem, etc. may occur. There is. Here, the melt flow rate (MFR) is measured from a method based on JIS K6922, and the density is measured from a method based on JIS K7112.

The polybutene resin preferably has a density of 0.880 to 0.930 g / cm ³ and a melt flow rate (MFR) of 0.1 to 10.0 g / 10 minutes.

  A melt flow rate (MFR) of 0.5 to 5.0 g / 10 min (230 ° C.) is particularly preferable because of excellent peelability. When the melt flow rate (MFR) is less than 0.1 g / 10 minutes, the resin pressure rises in the extruder due to the decrease in flowability, and the compatibility with the polyethylene resin is poor, and visible unevenness, It is not preferable because of the possibility of high density (complete separation), and when the melt flow rate (MFR) exceeds 10.0 g / 10 min, it is relatively compatible with the polyethylene resin, There is a concern that the intended easy peel performance may not be achieved due to the fine dispersion state. Here, the melt flow rate (MFR) is measured from a method based on JIS K6921.

  The blending ratio of the resin composition used for the outermost surface layer of the first film can be freely selected from 50 to 90% by weight for the polyethylene resin and 10 to 50% by weight for the polybutene resin. Among these, the former is particularly preferably 60 to 80% by weight and the latter is preferably 20 to 40% by weight. If the former is larger than this range, the adhesive strength with the oxygen barrier container whose surface layer is made of polypropylene is insufficient, and if the latter is large, the adhesive strength with the polypropylene cup is excessive. The cohesive fracture strength is preferably 5 to 15 N / 15 mm width, more preferably 10 to 15 N / 15 mm width. If necessary, for example, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, antiblocking agents, lubricants (fatty acid amides, etc.), flame retardants, inorganic or organic fillers, crosslinking agents, dyes In addition, one or two or more additives such as a colorant such as a pigment, a modifying resin, and the like may be added, and a solvent, a diluent, and the like may be added as necessary.

  The thickness of the outermost surface layer is preferably 30 μm or less, more preferably 5 to 10 μm. If the film thickness is extremely thin, it is difficult to form a layer stably during film formation, and if it is 30 μm or more, stringing or the like may occur.

−Cushion layer−
The first film may be preferably two or more resin layers. In that case, a cushion layer may be provided as a resin layer adjacent to the outermost surface layer among the resin layers constituting the first film. . As a component of the cushion layer, an ethylene-α / olefin copolymer, a high density polyethylene having a density of 0.935 g / cm ³ or more, or a polypropylene resin can be preferably used as a main component. Specifically, the same material as the base layer of the third film described later can be used. Among these, relatively preferred for use in the cushion layer is high density polyethylene having a density of 0.935 g / cm ³ or more. The cushion layer can be omitted, and the film thickness can also be selected freely. In the present specification, the main component means not only the cushion layer component but also a component contained at least 50% by weight, preferably 70% by weight, more preferably 90% by weight.

-Adhesive resin layer-
Moreover, when making a 1st film into 2 or more resin layers, the layer facing a 2nd film can be made into an adhesive resin layer among the resin layers which comprise a 1st film. Preferably, when the first film is made of three resin layers, the outermost surface layer, the cushion layer, and the adhesive resin layer can be used. It is not always necessary to provide an adhesive resin layer on the surface of the first film that faces the oxygen absorbing layer, but it should be provided if the adhesiveness between the oxygen absorbing resin composition and the thermoplastic resin on the surface facing it is low. Is desirable. The adhesive strength is preferably 2 N / 15 mm width or more, more preferably 5 N / 15 mm width. The film thickness is preferably 5 to 15 μm. If it is extremely thin, it is difficult to form a layer stably at the time of film formation, and if it is thicker than necessary, the adhesive resin is relatively expensive, which increases the cost of the film.

  Examples of the adhesive resin layer include an adhesive layer for laminating with an adhesive for laminating, an adhesion assistant layer with an anchor coating agent, and the like. Examples of laminating adhesives include polyvinyl acetate adhesives, homopolymers such as ethyl acrylate, butyl, and 2-ethylhexyl ester, or co-polymerization of these with methyl methacrylate, acrylonitrile, styrene, and the like. Polyacrylic acid ester adhesives composed of coalescence, cyanoacrylate adhesives, ethylene copolymer adhesives composed of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, Cellulose adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive, amino resin adhesive made of urea resin or melamine resin, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, Reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber It can be used rubber-based adhesives consisting of styrene-butadiene rubber, a silicone-based adhesive, an alkali metal silicate, inorganic adhesive made of a low-melting-point glass or the like, an adhesive other like. As the anchor coating agent constituting the anchor coating agent layer, for example, various aqueous or oil-based anchor coating agents such as organotitanium-based, isocyanate-based, polyethyleneimine-based, polyptadiene-based, etc. such as alkyl titanate are used. be able to.

  Another layer may be provided on the first film.

<Second film>
The second film in the coextruded multilayer laminated sheet of the present invention is a film composed of an oxygen-absorbing resin layer, and is provided between the first film and the third film, and includes an oxidizing resin, a transition metal catalyst, Is an oxygen-absorbing resin layer.

  In the coextruded multilayer laminated sheet of the present invention, any oxygen-absorbing resin can be used for the oxygen-absorbing layer of the second film. For example, the oxidizing resin that forms the oxygen-absorbing resin layer includes an ethylenically unsaturated hydrocarbon polymer, a main chain ethylenically unsaturated hydrocarbon polymer, a polyether unit polymer, a copolymer of ethylene and a distorted cyclic alkylene, and a polyamide resin. , Acid-modified polybutadiene, hydroxyaldehyde polymer, and the like can be used. Among these, as the oxidizing resin, it is preferable to use a resin having a melting point and MFR close to those of polyethylene and polypropylene used for the first film and the third film, because film formation by coextrusion becomes easy.

  Examples of the transition metal catalyst constituting the oxygen-absorbing resin layer include, for example, transition metals selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Sn, Cu, or mixtures thereof, and compounds thereof. Can be used. Examples of the transition metal compound include halides such as chlorides, sulfur oxyacid salts such as sulfates, nitrogen oxyacid salts such as nitrates, phosphorus oxyacid salts such as phosphates, silicas, and the like. Acid salts, carboxylate salts, sulfonate salts, phosphonate salts, etc., more specifically, acetic acid, propionate, isopropionic acid, butanoic acid, isobutanoic acid, pentanoic acid, isopentanoic acid, hexanoic acid, heptane Acid, isoheptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, 3,5,5-trimethylhexanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, Stearic acid, arachidic acid, lindelic acid, tuzuic acid, petroceric acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, formic acid, oxalic acid, Rufamin acid, transition metal salts such as naphthenic acid.

  It is desirable to select the oxygen-absorbing resin according to the oxygen-absorbing performance required for the coextruded multilayer laminated sheet. When oxygen absorption is required over a long period of time, as described in this example, the oxygen absorption rate is low, but nylon MXD6 is used as the oxidizing resin, and cobalt stearate is used as the transition metal catalyst. An oxygen-absorbing resin containing can be used. Since this oxygen-absorbing resin has a low oxygen absorption rate, it is preferable to perform nitrogen substitution or the like by a gas flash method or the like in order to reduce the initial oxygen concentration after filling the contents. Further, it is desirable to select the film thickness according to the required oxygen absorption amount.

<Third film>
The third film in the coextruded multilayer laminated sheet of the present invention prevents the adhesive between the second film and the substrate from coming into direct contact, suppresses the deterioration reaction of the second film, and the coextruded multilayer laminated sheet of the present invention. While providing strength and making the layer structure of the coextruded multilayer laminate sheet close to symmetry, the layer prevents curling of the sheet and has a base layer containing a thermoplastic resin.

  This third film may be formed of one or more resin layers.

-Base layer-
The third film is made of a base layer, preferably an ethylene-α / olefin copolymer polymerized using a single site catalyst, a high density polyethylene having a density of 0.935 g / cm ³ or more, or a polypropylene resin. A base layer as a main component is included. Among these, an ethylene-α / olefin copolymer polymerized using a single site catalyst is relatively preferable for use in the base layer.

  Among these, as the ethylene-α / olefin copolymer polymerized using a single site catalyst, for example, a catalyst by a combination of a metallocene complex and an alumoxane such as a catalyst by a combination of zirconocene dichloride and methylalumoxane, An ethylene-α / olefin copolymer obtained by polymerization using a single site catalyst (metallocene catalyst) can be used. The above metallocene catalyst is also called a single site catalyst because the current catalyst is called a multi-site catalyst with heterogeneous active sites, while the active sites are uniform. Specifically, the product name “Kernel” manufactured by Mitsubishi Chemical Corporation, the product name “Epolyu” manufactured by Mitsui Petrochemical Industry Co., Ltd., and the product name “EXACT” manufactured by Exxon Chemical Company, USA ”, Ethylene-α and olefin polymerized using a single site catalyst (metallocene catalyst) such as“ AFFINITY ”, trade name“ ENGAGE ”, etc., manufactured by Dow Chemical Co., USA Polymers can be used.

As the high density polyethylene having a density of 0.935 g / m ³ or more, for example, a density generated by polymerization using a chromium oxide catalyst or a Ziegler-Natta catalyst is 0.00. Homopolymer of ethylene of 935 g / m ³ or more, or ethylene and propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene Copolymers with α-olefins such as 1-decene and others can be used. In addition, said density is measured from the method based on JISK7112.

  As the polypropylene resin, general polypropylene can be used.

  In forming the base layer, if necessary, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antiblocking agent, a lubricant (fatty acid amide, etc.), a flame retardant, an inorganic or organic filler. Add one or two or more additives such as cross-linking agents, dyes, pigments, and other modifiers, and further add solvents, diluents, etc. as necessary. You can also. If the film thickness is extremely thin, it is difficult to form a layer stably at the time of film formation.

-Adhesive resin layer-
Moreover, when making a 3rd film into 2 or more resin layers, the layer facing a 2nd film can be made into an adhesive resin layer among the resin layers which comprise a 3rd film. It is not always necessary to provide an adhesive resin layer on the surface of the third film that faces the oxygen absorbing layer, but it should be provided if the adhesiveness between the oxygen absorbing resin composition and the thermoplastic resin on the surface facing it is low. Is desirable. The adhesive strength is preferably 2 N / 15 mm width or more, more preferably 5 N / 15 mm width. The film thickness is preferably 5 to 15 μm. If it is extremely thin, it is difficult to form a layer stably at the time of film formation, and if it is thicker than necessary, the adhesive resin is relatively expensive, which increases the cost of the film.

  Specifically, the same adhesive resin as the first film adhesive resin can be used.

  This third film may be provided with another layer.

<Base film>
In the coextruded multilayer laminated sheet of the present invention, a base film can be further provided on the outer side of the third film (surface far from the second film). Therefore, when a base film is provided, it is provided in the order of the first film, the second film, the third film, and the base film.

  The material of the base film is preferably excellent in mechanical, physical, chemical, etc., excellent in strength, toughness, etc., and further heat resistant, moisture proof, pin hole resistant A base film excellent in puncture resistance, transparency, etc. can be used. Specifically, for example, films of various resins such as polyester resins, polyamide resins, polyaramid resins, polyethylene resins, polypropylene resins, polycarbonate resins, polyacetal resins, fluorine resins, and the like are used. Can be used. These films can be any of unstretched films or stretched films stretched in a uniaxial direction or a biaxial direction. In the present invention, the thickness of the substrate film may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, rigidity, etc., and if it is too thick, the cost increases. On the contrary, if it is too thin, the strength, puncture resistance, rigidity, etc. are undesirably lowered. Therefore, about 10 μm to 100 μm, preferably about 12 μm to 50 μm is desirable. In the present invention, among the above base films, a biaxially stretched polyester resin, a biaxially stretched polyamide resin, or a biaxially stretched polypropylene resin having a thickness of about 9 μm to 30 μm is used. Is preferred. More preferably, the base film is a biaxially stretched polyester resin film.

Alternatively, as the base film, it is possible to impart formability, bending resistance, rigidity, etc., for example, a strong or small bleached or unbleached paper base, or pure white roll paper, kraft paper, paperboard Paper base materials such as processed paper, and the like can also be used. In this case, as the paper substrate constituting the paper layer, it is desirable to use a paper having a basis weight of about 80 to 600 g / m ² , preferably a basis weight of about 100 to 450 g / m ² . Furthermore, the paper base material which comprises a paper layer, the film of various resin as the base film mentioned above, etc. can be used together.

  The base film may have a barrier property, and as such a barrier base film, for example, an aluminum foil having a light shielding property and a barrier property against oxygen gas, water vapor, or the like, or vapor deposition of the aluminum foil is provided. Resin film having a film, silicon oxide having a barrier property against oxygen gas, water vapor, etc., a resin film having a deposited film of an inorganic oxide such as aluminum oxide, low density polyethylene having a barrier property against water vapor, water, etc. Polyvinylidene chloride resin having a barrier property against a film or sheet of resin such as density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, oxygen gas, water vapor, etc., polyvinyl alcohol -Sulfur resin, saponified ethylene-vinyl acetate copolymer Film or sheet of a resin such as nylon MXD6 - DOO, may use other like. Here, an aluminum foil having a thickness of about 5 μm to 30 μm can be used, and an aluminum or inorganic oxide deposited film having a thickness of about 100 mm to 2000 mm can be used. Examples of the resin film that supports the vapor-deposited film include a polyester resin film, a polyamide resin film, a polyolefin resin film, a polyvinyl chloride resin film, a polycarbonate resin film, and a polyvinylidene chloride resin film. Polyvinyl alcohol-based resin film, ethylene-vinyl acetate copolymer saponified film, and the like can be used.

  A plurality of substrate films may be laminated, for example, a base layer of a third film, a normal substrate film, or a barrier substrate film can be laminated.

  In laminating the base film, for example, a laminating adhesive layer such as a laminating adhesive is provided, and then laminating via the laminating adhesive layer, a dry lamination laminating method, or , By using a melt extrusion laminating method in which an adhesion assistant layer, a melt-extruded resin layer, etc. are provided with an anchor coating agent, etc., and then laminated via the adhesion assistant layer, the melt-extruded resin layer, etc. Can do. Further, for example, a wet lamination method, a solventless dry lamination method, and the like can be used. When this lamination is performed, pretreatment such as corona discharge treatment, ozone treatment, plasma treatment, flame treatment, and the like can be optionally performed on the surface of the substrate to be laminated, if necessary. Also, for example, anchor coating agents such as isocyanate (urethane), polyethyleneimine, polybutadiene, and organic titanium, or polyurethane, polyacryl, polyester, epoxy, polyvinyl acetate, cellulose -Known anchor coating agents, adhesives, etc., such as adhesives for laminating, etc., can be arbitrarily used.

<Packing container>
The packaging container which is another aspect of the present invention is a packaging container using the coextruded multilayer laminated sheet of the present invention. The coextruded multilayer laminated sheet of the present invention is typically used as a container lid, but is not limited thereto. As this container, for example, as a molding resin, polyethylene resin, polypropylene resin, ethylene-propylene copolymer, polyacrylic or polymethylmethacrylic resin, polyvinyl chloride resin, vinyl chloride-vinylidene chloride copolymer , Polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, Use molding resin such as fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc., for example, extrusion molding, injection molding, blow molding, foam molding, vacuum / pressure air, etc. Thermoforming, cast molding, compression molding, etc. Various plastic molded container molded using the processing method can be used.

  The contents of the packaging container according to the present invention are not limited to food, but may be non-food, solid or liquid. The filling state of the packaging container may be a full filling state or a state with a head space, and can be used regardless of the state and shape of the contents. For example, various articles | goods, such as various foods and drinks, chemicals, such as an adhesive agent and an adhesive, cosmetics, detergent, a pharmaceutical, miscellaneous goods, such as a chemical warmer, etc. can be mentioned.

  In the present invention, the heat sealing method between the lid member and the plastic molding container may be, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal. It can carry out by well-known methods, such as.

<Example 1>
(1). Preparation of Resin Compositions (a) to (f) (a). Resin composition 1 constituting the first film (outermost surface layer: for cohesive failure layer)
70 parts by weight of high-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name, Novatec HJ580, density = 0.960 g / cm ³ , melt flow rate: MFR = 11 g / 10 min) and polybutene resin (ethylene-propylene-butene) -1 copolymer resin, manufactured by Mitsui Chemicals, Inc., trade name, Toughmer BL4000, density = 0.915 g / cm ³ , melt flow rate: MFR = 1.8 g / 10 min) 30 parts by weight and synthetic silica 0.5% The resin composition was prepared by sufficiently kneading the parts.
(B) Resin composition 2 (for cushion layer) constituting the first film
An ethylene-α / olefin copolymer copolymerized using a single site catalyst (metallocene catalyst) (manufactured by Prime Polymer Co., Ltd., trade name, Evolu-SP2020, density = 0.916 g / cm ³ , melt flow rate, A resin composition comprising 100 parts by weight of MFR = 1.5 g / 10 minutes was prepared.
(C) Resin composition 3 (for adhesive resin layer) constituting the first film
A resin composition comprising 100 parts by weight of an adhesive polyolefin (Mitsui Chemicals, trade name, Admer NF308, density = 0.932 g / cm ³ , melt flow rate, MFR = 1.7 g / 10 min) was prepared.
(D). Resin composition constituting the second film As an oxidizing resin, nylon MXD6 (manufactured by Mitsubishi Gas Chemical Co., Ltd., MX nylon 6007) 100.0 parts by weight, and as a transition metal catalyst, 0.004 parts by weight of cobalt stearate An oxygen-absorbing resin composition was prepared.
(E). Resin composition 1 (for adhesive resin layer) constituting the third film
An adhesive polyolefin similar to (c) of Example 1 was prepared.
(What). Resin composition 2 (for base layer) constituting the third film
A resin composition similar to (b) of Example 1 was prepared.

(2). Manufacture of multilayer laminated sheet Using the resin composition prepared above, using a 7-type 7-layer top-blown air-cooled inflation co-extrusion film-forming machine, the layer of the resin composition of (A) is 5 μm. (B) 15 μm of the resin composition layer, (c) 5 μm of the resin composition layer, (d) 10 μm of the resin composition layer, (e) 5 μm of the resin composition layer, The layers of the resin composition in (i) were co-extruded to 10 μm to produce a co-extruded multilayer laminated sheet having a total thickness of 50 μm.

(3). Measurement of oxygen concentration in the prepared pouch Next, the multilayer laminated sheet manufactured above was vacuum-packed in a pouch prepared with an oxygen barrier film, and the oxygen concentration in the container after gas flushing was assumed in the pouch. 100 ml of the oxygen / nitrogen mixed gas having an oxygen concentration of 2% was injected and the inlet was sealed. This was stored at 60 ° C. for 7 days, and then the oxygen concentration in the pouch was measured with a nondestructive oxygen measuring device (PreSens, model name, Fibox 3).

(4). Manufacture of multi-layer laminated sheet (covering material) laminated with base film A corona discharge treatment is applied to one side of a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and a two-component curable polyurethane system An adhesive layer is formed by applying a laminating adhesive with a thickness of 3.0 g / m ² (dry), and then a biaxially stretched polyethylene terf that has been subjected to corona treatment on both sides of the adhesive layer. A two-part curable polyurethane laminating adhesive is thickened on the surface of the biaxially stretched polyethylene terephthalate film laminated on the turret film and treated in the same manner as above. An adhesive layer was formed by applying 3.0 g / m ² (dry) to obtain a base film.

  On the other hand, the surface of the resin layer made of the resin composition (f) of the coextruded multilayer laminated sheet produced in (2) above was subjected to corona discharge treatment.

  The surface of the adhesive layer of the substrate film and the corona-treated surface of the coextruded multilayer laminate sheet were overlapped to obtain a multilayer laminate sheet (covering material) on which the substrate film of the present invention was laminated.

(5) Performance measurement of multilayer laminated sheet (cover material) laminated with a base film First, the film thickness of the cover material produced above was measured by μ-meter (manufactured by Sony Corporation).

Next, peel strength was measured. An oxygen barrier container (oxygen permeability: 0.015 cc / pkg · day · atm) in which a sheet of polypropylene 200 μm / EVOH 20 μm / polypropylene 200 μm was molded into a cup shape with a flange inner diameter of 74 mm and an inner volume of 120 ml was prepared. On the surface of the flange portion of the opening of the container, the lid material produced above is overlapped with the co-extruded multilayer laminated sheet facing the surface, and thereafter, the seal temperature from the flat seal is 200 ° C., 3 kg / cm ^2. Sealing was performed for 1 second. Subsequently, the peel strength was measured at 15 mm width and 300 mm / min with a tensile tester. The easy-openability (easy peel property) of the manufactured packaged product was good, and no tearing, tearing, stringing, etc. were observed during peeling. Table 1 shows the measurement results of peel strength. Further, when shear cutting with scissors was performed with the polypropylene container and the lid material overlapped, the crimping phenomenon did not occur, and the cut surface peeled smoothly.

Using the lid material produced above, first, the oxygen barrier container (oxygen permeability: 0.015 cc / pg · day · atm) having an inner diameter of 74 mm and an inner volume of 120 ml was filled with water in a fully-filled state. Then, the lid manufactured as described above is overlapped on the surface of the flange portion of the opening with the co-extruded multilayer laminated sheet facing the surface, and then the seal temperature of 200 ° C. and 3 kg / cm from the flat seal. ^2. Sealing was performed under conditions of 1 second, and a packaged product was produced by filling and packaging water in a cup-shaped molded container. Furthermore, when the drop test was performed three times from 1 m on the packaged product, no tearing, leakage, or the like was observed. The packaged product filled and packed with water was stored at 23 ° C. for 7 days, and then the dissolved oxygen in the container was measured with a nondestructive oxygen measuring device (PreSens, model name, Fibox 3).

<Example 2>
(1). Preparation of Resin Compositions (a) to (f) (a). Resin composition 1 constituting the first film (outermost surface layer: for cohesive failure layer)
A resin composition similar to (a) of Example 1 was prepared.
(B) Resin composition 2 (for cushion layer) constituting the first film
A resin composition similar to (b) of Example 1 was prepared.
(C) Resin composition 3 (for adhesive resin layer) constituting the first film
An adhesive polyolefin similar to (c) of Example 1 was prepared.
(D). Resin Composition Constructing Second Film An oxygen-absorbing resin composition similar to (d) of Example 1 was prepared.
(E). Resin composition 1 (for adhesive resin layer) constituting the third film
An adhesive polyolefin similar to (c) of Example 1 was prepared.
(What). Resin composition 2 (for base layer) constituting the third film
A resin composition similar to (b) of Example 1 was prepared.

  (2). Next, the resin composition prepared above was used, and these were formed using a 7-type 7-layer top-blown air-cooled inflation coextrusion film-forming machine, and the layer of the resin composition of (A) was 10 μm, ( (B) a layer made of the resin composition of 10 μm, (c) a layer of the resin composition of 5 μm, (d) a layer of the resin composition of 10 μm, (e) a layer of the resin composition of 5 μm, (f) Each layer of the resin composition was coextruded to 5 μm to produce a multilayer laminated sheet having a total thickness of 50 μm.

  About (3)-(5), it carried out similarly to Example 1. FIG. The results were the same as in Example 1 except for those shown in Table 1.

<Example 3>
(1). Preparation of Resin Compositions (a) to (f) (a). Resin composition 1 constituting the first film (outermost surface layer: for cohesive failure layer)
High-density polyethylene (trade name, Novatec HJ590N, manufactured by Nippon Polyethylene Co., Ltd., density = 0.960 g / cm 3, melt flow rate: MFR = 40 g / 10 min) and 70 parts by weight of polybutene resin (ethylene-propylene-butene- 1 copolymer resin, manufactured by Mitsui Chemicals, Inc., trade name, TAFMER BL4000, density = 0.915 g / cm 3, melt flow rate: MFR = 1.8 g / 10 min)) 30 parts by weight and 0.5 parts by weight of synthetic silica Were sufficiently kneaded to prepare a resin composition.
(B) Resin composition 2 (for cushion layer) constituting the first film
A resin composition similar to (b) of Example 1 was prepared.
(C) Resin composition 3 (for adhesive resin layer) constituting the first film
An adhesive polyolefin similar to (c) of Example 1 was prepared.
(D). Resin Composition Constructing Second Film An oxygen-absorbing resin composition similar to (d) of Example 1 was prepared.
(E). Resin composition 1 (for adhesive resin layer) constituting the third film
An adhesive polyolefin similar to (c) of Example 1 was prepared.
(What). Resin composition 2 (for base layer) constituting the third film
A resin composition comprising 100 parts by weight of block polypropylene (manufactured by Sun Allomer Co., Ltd., trade name, PF380A, density = 0.900 g / cm 3, melt flow rate, MFR = 1 g / 10 min) was prepared.

  About (2)-(5), it carried out similarly to Example 1. FIG. The results were the same as in Example 1 except for those shown in Table 1.

<Comparative Example 1>
(1). Preparation of Resin Compositions (A) to (B) (A). Resin composition composing the first film (outermost surface layer: for cohesive failure layer) A resin composition similar to (i) of Example 1 was prepared.
(B) Resin composition constituting the second film A resin composition similar to (b) of Example 1 was prepared.

  About (2)-(5), it carried out similarly to Example 1. FIG. The results were the same as in Example 1 except that oxygen absorption did not start and that shown in Table 1.

<Comparative example 2>
(1). Preparation of Resin Compositions (a) to (f) (a). Resin composition 1 constituting the first film (outermost surface layer: for cohesive failure layer)
High-density polyethylene (trade name, Novatec HJ580, manufactured by Nippon Polyethylene Co., Ltd., density = 0.960 g / cm ³ , melt flow rate: MFR = 11 g / 10 min) and 70 parts by weight of block polypropylene (manufactured by Sun Allomer Co., Ltd., product) Name, PF380A, density = 0.000 g / cm3, melt flow rate, MFR = 1 g / 10 min) 30 parts by weight and synthetic silica 0.5 part by weight were sufficiently kneaded to prepare a resin composition.
(B) Resin composition constituting the second film A resin composition similar to (b) of Example 1 was prepared.

(2). Manufacture of multilayer laminated sheet Using the resin composition prepared above, using a three-layer, three-layer top-blown air-cooled inflation coextrusion film-forming machine, the layer of the resin composition of (A) is 5 μm. The layers of the resin composition of (b) were coextruded to 45 μm to produce a coextruded multilayer laminated sheet having a total thickness of 50 μm.

About (3)-(4), it carried out similarly to Example 1, and when the shear cut by scissors was performed by superimposing a polypropylene container and the said cover material, the crimping | compression-bonding phenomenon was confirmed.

Claims (12)

At least a first film, a second film, a third film, and a base film are coextruded multilayer laminated sheets provided in this order,
The first film includes a resin layer containing at least 50 to 90% by weight of high-density polyethylene and 10 to 50% by weight of polybutene-1 and having a cohesive fracture strength of 5 to 15 N / 15 mm width as an outermost surface layer. Is a film composed of one or more resin layers,
The second film is a film composed of an oxygen-absorbing resin layer containing an oxidizing resin and a transition metal catalyst,
The third film has a resin layer containing a thermoplastic resin, and is a film composed of one or more resin layers,
A co-extruded multilayer laminate sheet, characterized in that The first film is composed of two or more resin layers, and the resin layer adjacent to the outermost surface layer among the resin layers constituting the first film,
Ethylene-α-olefin copolymer,
High density polyethylene having a density of 0.935 g / cm ³ or more, or
Polypropylene resin,
The coextruded multilayer laminated sheet according to claim 1, wherein the coextruded multilayer laminated sheet is a resin layer mainly comprising:   The 1st film consists of two or more resin layers, and the layer facing the 2nd film among the resin layers which constitute the 1st film is an adhesive resin layer. Co-extrusion multilayer laminate sheet. The third film is
An ethylene-α / olefin copolymer polymerized using a single-site catalyst,
High density polyethylene having a density of 0.935 g / cm ³ or more, or
Polypropylene resin,
The co-extrusion multilayer laminated sheet according to any one of claims 1 to 3, comprising a resin layer containing as a main component.   The third film is composed of two or more resin layers, and a layer facing the second film among the resin layers constituting the third film is a resin layer made of an adhesive resin. The co-extruded multilayer laminated sheet according to item 1.   The coextruded multilayer laminated sheet according to any one of claims 1 to 5, wherein the thickness of the outermost surface layer of the first film is 30 µm or less. The coextruded multilayer laminated sheet according to claim 1 , wherein the base film is a biaxially stretched polyester resin film. The high-density polyethylene contained in the outermost surface layer of the first film has a density of 0.950 to 0.980 g / cm ³ and a melt flow rate (MFR) of 8.0 to 40.0 g / 10 minutes. Item 2. A coextruded multilayer laminated sheet according to Item 1. The polybutene contained in the outermost surface layer of the first film has a density of 0.880 to 0.930 g / cm ³ and a melt flow rate (MFR) of 0.1 to 10.0 g / 10 minutes. Coextruded multilayer laminated sheet as described in 1.   The coextruded multilayer laminated sheet according to claim 1, wherein the high-density polyethylene and polybutene contained in the outermost surface layer of the first film are 60 to 80% by weight and 20 to 40% by weight, respectively. The resin layer adjacent to the outermost surface layer contains an ethylene / α-olefin copolymer polymerized using a single site catalyst, and the density of the copolymer is 0.910 to 0.930 g / cm ³ . The coextruded multilayer laminated sheet according to claim 2. Packaging container using the coextruded multilayer laminated sheet according to any one of claims 1 to 11.