JP4865750B2 - Laminated body - Google Patents

Description

  The present invention is a plastic film excellent as a container for medical pharmaceuticals for packaging, transporting and storing plastic containers filled with liquids such as Ringer's solution and blood transfusion, and food packaging containers for maintaining quality such as taste. It is related with the laminated body.

  More specifically, it has excellent barrier properties against external light, oxygen gas, water vapor, and the like, and has less elution from the film, and has flexibility, impact resistance, friction resistance, pinhole resistance, and puncture resistance. The present invention relates to a laminate of plastic films having excellent properties, transparency, heat resistance, low-temperature heat sealability, quality retention, printability, openability, filling packaging suitability, and the like.

  Conventionally, various packaging materials have been developed and proposed for filling and packaging various articles such as foods and drinks, pharmaceuticals, chemicals, daily necessities, miscellaneous goods, and others.

  Therefore, the above-mentioned packaging material is strongly required to have a blocking property against light, oxygen gas or water vapor gas from outside, so-called light shielding property and gas barrier property, in order to prevent deterioration of contents. It is.

By the way, as a barrier material against external light, oxygen gas, water vapor gas or the like, for example, an aluminum-deposited resin film obtained by vacuum-depositing aluminum on a aluminum foil or a plastic film by a vacuum deposition method or the like. Etc. are known.
Furthermore, examples of the barrier material against oxygen gas or water vapor gas include, for example, polyvinylidene chloride resin on the surface of a film made of polyvinylidene chloride resin or a copolymer resin of vinylidene chloride and other monomers, or a plastic film. A resin film coated with a resin, a film made of a silicide of polyvinyl alcohol or an ethylene-vinyl acetate copolymer, or a physical vapor phase such as a vacuum deposition method on one surface of a substrate film such as a plastic film. Using a growth method (PVD method), for example, a vapor deposition film provided with a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide, or a chemical vapor deposition method (CVD method) such as a low temperature plasma chemical vapor deposition method. For example, a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is used. Only vapor-deposited film, and the like are known was.

  These barrier materials are laminated with other materials such as plastic films, and for example, packaging materials useful for filling and packaging various articles such as foods and drinks, pharmaceuticals, chemicals, daily necessities, miscellaneous goods, etc. providing.

  By the way, in the field of medical packaging materials such as those filled in flexible bag-shaped plastic containers (hereinafter referred to as “infusion bags”), quality due to barrier properties such as oxygen against Ringer's solution, blood transfusions, etc. Stability is required.

  Furthermore, as a packaging form in the case of transporting an infusion solution, the infusion solution is usually filled in an infusion bag, and the infusion bag made of a plastic laminate is put in an outer bag made of a plastic laminate, and further packaged. This is a form in which several outer bags are stacked and packed in cardboard.

  As an outer bag of the infusion bag used above, a biaxially stretched nylon film having a printed layer on the back surface as an outermost layer, a nylon resin layer, an ethylene-vinyl alcohol copolymer layer, and a nylon resin layer as a barrier layer Co-pressed co-stretched film, unstretched polyethylene film as the innermost layer sequentially laminated via dry laminate adhesive, biaxially stretched polypropylene film with printed layer on the back as outermost layer, biaxially stretched as barrier layer MXD nylon film or co-extrusion co-stretched film consisting of nylon resin layer, ethylene-vinyl alcohol copolymer layer and nylon resin layer, and unstretched polyethylene film as the innermost layer were sequentially laminated via dry laminate adhesive Things are widely known.

  However, in the packaging material having the above specifications, all have excellent barrier properties, but since it is laminated between each film layer constituting the packaging material via a dry laminate adhesive, it is flexible. The chipped and bent portions have an acute angle, and the above packaging material is used to produce a bag-like container by manufacturing the bag, and then the desired article is placed and the bag-like container is hermetically sealed. In the case of transporting in a package, there is a problem in that, due to vibration, intensive wear is caused in the portion where the package is repeatedly bent, so that pinholes are easily generated and the barrier property is remarkably impaired.

  In the packaging bag having the above specifications, the biaxially stretched polypropylene layer and the biaxially stretched nylon film layer, which are the outermost layers, are less slidable with respect to corrugated cardboard. There is a problem that pinholes are easily generated and the barrier property is remarkably impaired.

  Furthermore, in the packaging bag having the above specifications, the unstretched polyethylene layer, which is the innermost layer, is poorly slidable with respect to the infusion bag, so that it is likely to rub due to vibration and generates pinholes from the rubbed portion. There is a problem that the barrier property is remarkably impaired.

  Further, the packaging bag having the above specifications has a problem that although it is excellent in transparency, light from the outside cannot be blocked, so that deterioration may occur depending on the contents.

  In addition, when a packaging material having the above specifications is used as a packaging material for food, since it is laminated via a dry laminating adhesive between each film layer constituting the packaging material, residual solvent and unreacted Since a monomer component etc. transfer to a film, there exists a problem that a film smells in the contents.

  Therefore, in order to solve the above problems, the present inventors, as a result of earnest research, the present invention is at least an unstretched polyolefin-based film as the outermost layer, a stretched polyamide-based resin film as a barrier layer, a light-shielding film, And a laminate comprising a structure in which unstretched polyolefin films are sequentially laminated as the innermost layer, wherein the innermost layer is a film formed from a resin having a melting point lower than that of the outermost layer, and The interlayer between the outermost layer and the barrier layer, and the interlayer between the light-shielding film layer and the innermost layer are laminated via a melt-extruded resin layer, and the interlayer between the barrier layer and the light-shielding film layer is interposed via an adhesive layer for dry lamination. Produced a laminated structure characterized in that it has excellent barrier properties against oxygen gas and water vapor, etc. Since there are few extracts, it has excellent quality retention, and it has excellent flexibility, impact resistance, friction resistance, pinhole resistance, and puncture resistance, so it has excellent transportability, heat resistance, and heat sealability. In addition, the present invention relates to a medical pharmaceutical bag packaging and food packaging laminate having excellent light shielding properties, printability, and the like.

  Moreover, in the above, the outermost layer can provide a laminate characterized by an unstretched polypropylene film.

  The barrier layer is a co-extrusion co-stretched film comprising a nylon resin layer, an ethylene-vinyl alcohol copolymer layer and a nylon resin layer, and a co-extrusion comprising a nylon resin layer, an MXD nylon resin layer and a nylon resin layer. A laminate characterized by being a co-stretched film or a stretched film made of MXD nylon can be provided.

  Moreover, the said light-shielding film consists of a structure which provided the metal vapor deposition film in one surface of the stretched film, and can provide the laminated body characterized by the above-mentioned.

  Moreover, the laminated body characterized by the said innermost layer being formed in the shape which has fine unevenness | corrugation in an inner surface can be provided.

  Moreover, the laminated body characterized by the said innermost layer being an unstretched film which consists of a linear low density polyethylene can be provided.

  Moreover, the laminated body which can be used as an infusion bag packaging container or a food packaging container can be provided.

  Hereinafter, the laminated body concerning this invention, a packaging container using the same, and a packaging body are demonstrated in detail using drawing etc. below.

  FIG. 1 is a schematic cross-sectional view showing a layer configuration of an example of a laminate according to the present invention.

  As shown in FIG. 1, the laminate according to the present invention is provided with a metal vapor deposition film on at least one surface of an unstretched polyolefin film as an outermost layer, a stretched polyamide resin film as a barrier layer, and a base film. And a non-stretched polyolefin film, which is an innermost layer made of a resin having a melting point lower than that of the outermost layer, is a laminate having a structure in which layers are sequentially laminated, and a stretched barrier film layer The interlayer between the light-shielding film layer is interposed between the adhesive layer for dry lamination, the interlayer between the outermost layer and the stretched barrier film layer, and the interlayer between the light-shielding film layer and the innermost layer. The basic structure is a configuration in which the layers are stacked via each other.

  The above illustrations are examples of the laminate according to the present invention, and the present invention is not limited thereby.

  For example, in the present invention, if necessary, a desired printed pattern layer made of, for example, letters, symbols, figures, patterns, etc., may be provided on the front surface or the back surface of the stretched barrier film, although not shown. It can be done.

  Further, for example, the stretch barrier polyamide resin film is a co-pressed co-stretched film comprising a nylon resin layer, an ethylene-vinyl alcohol copolymer layer, and a nylon resin layer, a nylon resin layer, an MXD nylon resin layer, and a nylon resin. It is desirable that the film is formed from a co-pressed and co-stretched film composed of layers or a stretched film composed of MXD nylon.

  Moreover, it is desirable that the innermost layer is formed in a shape having fine irregularities on the inner surface.

  FIG. 2 is a schematic front view showing an example of a bag-like plastic container according to the present invention using the laminate shown in FIG.

  As shown in FIG. 2, the bag-shaped plastic container according to the present invention is formed by stacking the two laminates shown in FIG. 1 and sealing three sides of two side seal portions and one bottom seal portion. In addition to a bag shape, the opening is provided with a notch for opening.

  The above illustrations are examples of bag-like packaging containers according to the present invention, and the present invention is not limited thereby.

  For example, in addition to the four-side seal type, the packaging container is a side seal type, a two-side seal type, a three-side seal type, an envelope-attached seal type, a center joint seal type (pillow seal type), a pleated seal type, a flat bottom seal type, or It may be a bag having any one of the square bottom seal type.

  FIG. 3 is a schematic front view showing an example of a package using the bag-shaped plastic container shown in FIG. 2, in which an article such as an infusion bag is packaged, and the opening is heat sealed. is there.

  As shown in FIG. 3, the package according to the present invention is a package in which the infusion bag is accommodated in the above-described bag body, and the opening is heat sealed to form a top seal portion, and the contents are packaged. Is the body.

  Next, in the present invention, the laminate material according to the present invention as described above, the material constituting the packaging container, the production method thereof, etc. will be described. First, as the outermost layer constituting the laminate material according to the present invention, Any film or sheet having excellent flexibility can be used.

  Moreover, since the material of the outermost layer constituting the packaging container is a part that is most susceptible to heat during heat sealing, it needs to have a higher melting point than the innermost layer (heat sealing layer).

  Specifically, medium density polyethylene, high density polyethylene, ethylene-α olefin polymer polymerized using a metallocene catalyst, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene -Polyolefin resins such as methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene are treated with acrylic acid. Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meth) acrylic diameter resins, polyvinyl chloride resins, etc. Polyolefin It is preferred to use fat.

  In particular, a film formed from a homo-type polypropylene resin has excellent moisture resistance, and when an ethylene-vinyl alcohol copolymer or the like is used as a barrier layer, it prevents permeation of oxygen gas, water vapor, and the like in a completely dry state. Although it has the desired effect as a gas barrier property, the gas barrier property is deteriorated in a wet state, so that this can be prevented and the cost performance is excellent, which is more preferable.

  In the above, since the outermost resin film or sheet is unstretched and has flexibility and excellent followability with the shape of the contents, a bent portion is formed with the thickness of the contents. Without the need for pinhole resistance.

  On the other hand, when an unstretched film or sheet is used as the outermost resin film or sheet, the thickness of the content when storing the content is high because the rigidity is high and the elasticity is poor. In this case, a bent portion is formed and the force is concentrated on the bent portion and rubbed due to vibrations or the like when transported, thereby generating a pinhole.

  Further, in the above, the resin film or sheet is preferably excellent in slipperiness because it can prevent pinholes due to external rubs such as cardboard rubs when transporting. .

  In the present invention, the thickness of the outermost layer is preferably about 5 to 200 μm, and more preferably about 10 to 60 μm.

  The stretched barrier polyamide resin film constituting the barrier layer according to the present invention includes a polyamide system having gas barrier properties against impact, strength, oxygen gas, water vapor, impact resistance, flex pinhole resistance, puncture resistance, etc. Any stretched film or sheet of resin can be used.

  Specifically, for example, MXD nylon 6 film, MXD nylon resin and nylon 46, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, and other various polyamide resins such as 2 to 3 A multilayer laminated film comprising at least layers, or an ethylene-vinyl alcohol copolymer and various polyamide-based resins such as nylon 46, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, etc. A multilayer laminated film composed of 2 to 3 or more layers can be used.

  Among them, a multilayer laminated film formed by coextrusion with an ethylene-vinyl alcohol copolymer and the above-mentioned nylon has high gas barrier properties, and further has an aroma retaining property, transparency, impact resistance, flex pinhole resistance, Since it is excellent in piercing property, flexibility, and chemical resistance, it is more preferable.

  Thus, the MXD nylon 6 film or the multilayer laminated film is made of a biaxially stretched barrier nylon film stretched in the biaxial direction by a normal biaxial stretching method such as a tenter method or a tubular method. It is desirable to use it. The film thickness is about 10 to 200 μm, preferably about 10 to 50 μm.

  In addition, the polyamide resin film or the multilayer laminated film described above may be subjected to any surface treatment coated with an anchor coating agent or the like, if necessary, before corona discharge treatment, plasma discharge treatment, flame treatment, ozone treatment, etc. Processing can also be performed.

  In the present invention, by using the above-mentioned stretched polyamide resin film as a base material, it has a barrier property against oxygen gas, water vapor, etc., and further has strength, impact resistance, and puncture resistance. The laminated material which has those characteristics is manufactured using toughness, such as.

  In the present invention, the production method of the above multilayer laminated film will be described. As the production method, for example, a molding method for forming a resin having different properties into a multilayer film, for example, a T-die method, an inflation method or the like is adopted. is there.

  Specifically, using a multi-layer T die-cast molding method such as a feed block method or a multi-manifold method, or a molding method such as a multi-layer inflation molding method, for example, an adhesive composed of a nylon resin layer / acid-modified polyolefin resin. Multi-layer laminated film consisting of 3 layers and 5 layers such as adhesive resin layer / ethylene-vinyl alcohol copolymer layer / adhesive resin layer made of acid-modified polyolefin resin / nylon resin layer, or nylon resin layer / ethylene-vinyl alcohol A multilayer laminated film composed of two types and three layers such as a copolymer layer / nylon resin layer, and a multilayer laminated film composed of two types and three layers such as a nylon resin layer / MXD nylon 6 resin layer / a nylon resin layer, etc. It is something that can be done.

  Next, in the present invention, as the thickness of each layer constituting the multilayer laminated film according to the present invention as described above, for example, the thickness of the nylon resin layer is about 1 to 200 μm, preferably 5 to 5 μm. About 100 μm is desirable, and the ethylene-vinyl alcohol copolymer layer or MXD nylon resin layer is preferably about 1 to 100 μm, preferably about 5 to 50 μm, and further, an adhesive resin layer between the layers. Is about 1 to 100 μm, preferably about 5 to 50 μm.

  In the above, as the ethylene-vinyl alcohol copolymer film, for example, an ethylene content of about 25 to 50 mol% obtained by completely saponifying an ethylene-vinyl acetate copolymer having a vinyl acetate content of about 79 to 92 wt%. The ethylene-vinyl alcohol copolymer can be used.

  The ethylene-vinyl alcohol copolymer has a high gas barrier property and is excellent in aroma retention and transparency.

  Thus, in the above-mentioned ethylene-vinyl alcohol copolymer, an ethylene content of 50 mol% or more is not preferable because the oxygen gas barrier property is drastically lowered and the transparency is also deteriorated. On the other hand, those having a content of 25 mol% or less are not preferable because the thin film becomes brittle and the oxygen gas barrier property is lowered under high humidity.

  In addition, if necessary, an optional print layer such as characters, designs, figures, symbols, etc. may be used for displaying decoration, contents, display of the best-before period, display of manufacturers, sellers, etc. Those provided on the front surface or the back surface of the barrier film layer are preferable.

  Since a film layer is formed on the printing ink layer and the printing layer is protected, there is an advantage that there is no ink peeling due to rubbing or the like.

  Such a printing layer can be formed, for example, by a normal printing method such as offset printing or gravure printing, flexographic printing, letterpress printing, silk screen printing, or the like using a normal ink composition.

  As the light-shielding film according to the present invention, a material having a property of shielding light from the outside can be used.

  Specifically, as this light-shielding material, it is preferable to use a metal such as aluminum by forming a deposited film on a base film such as a PET film by vacuum deposition. A light-shielding ink layer may be provided, or a white film may be used.

  Among them, a base film on which a metal vapor-deposited film is formed is more preferable because it has an advantage that it can impart a property that does not transmit water vapor, oxygen gas, or the like in addition to light shielding properties.

  As a metal to be formed on such a metal deposition film, metals such as aluminum (Al), chromium (Cr), silver (Ag), copper (Cu), tin (Sn), etc. can be used. It is desirable to use aluminum (Al).

  Further, in the above, the aluminum foil has a thickness of about 5 to 30 μm, and the metal deposition film preferably has a thickness of about 50 to 3000 mm, preferably about 100 to 1000 mm. Is desirable.

As such a light-shielding ink, specifically, an ink containing a light-shielding pigment such as an aluminum paste can be used.
In the above, the thickness of the ink layer is preferably about 1 to 8 μm, and more preferably about 2 to 5 μm.

  The white film contains a white pigment mainly giving a light shielding property to the polyolefin resin.

  Specific examples of the white pigment used in the white film include titanium oxide, zinc oxide, extender pigments such as aluminum hydroxide, magnesium carbonate, calcium carbonate, precipitated barium sulfate, silica, and talc.

  In the above, the content of the white pigment is preferably about 10 to 40%.

  In addition, the resin film that supports the above-described vapor-deposited film is provided with a vapor-deposited layer, and therefore has excellent properties in mechanical, physical, chemical, etc., particularly strong and tough. In addition, a heat-resistant resin film or sheet can be used.

  Specifically, in the present invention, examples of the resin film that supports the above-described deposited film include polyester resin films such as polyethylene terephthalate, polyamide resin films such as various nylons, polyethylene resins, and polypropylene resins. Resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyolefin film such as polybutene resin film, polyvinyl chloride resin, polycarbonate resin Resin, polyimide resin, polyamideimide resin, polyaryl phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, cell Over scan resins, poly (meth) acrylic resins, polyvinylidene chloride film, acetal resin film, fluorine-based resin, it is possible to use other like.

  In the present invention, it is particularly preferable to use a film or sheet of polypropylene resin, polyester resin, or polyamide resin.

  In the present invention, as the base film or sheet, for example, one or more of the above-mentioned various resins are used, and an extrusion method, a casting method, a T-die method, a cutting method, an inflation method, etc. Using the film-forming method, the above-mentioned various resins can be formed into a film alone, or two or more kinds of various resins can be used and mixed to form a film before forming the film, etc. To produce various resin films or sheets, and further use, for example, the above-mentioned base film or sheet stretched uniaxially or biaxially using a tenter method or a tubular method can do.

  In the present invention, the film thickness of the base film or sheet is preferably about 6 to 100 μm, more preferably about 9 to 50 μm.

  Next, in the present invention, a method for forming a metal vapor deposition film constituting the barrier layer will be described. Examples of such a method include physical vapor deposition methods such as vacuum vapor deposition, sputtering, and ion plating (for example, (Physical Vapor Deposition method, PVD method) or Chemical Vapor Deposition method (Chemical Vapor Deposition method, CVD method) such as Plasma Chemical Vapor Deposition method, Thermal Chemical Vapor Deposition method, Photochemical Vapor Deposition method, etc. it can.

  In the present invention, the method for forming a metal vapor deposition film will be described in detail. The metal as described above is used as a raw material, and this is heated and vapor deposited on a flexible film, or the metal is used as a raw material. Use an oxidation reaction deposition method in which oxygen gas is introduced to oxidize and deposit on a flexible film, and a plasma-assisted oxidation reaction deposition method in which the oxidation reaction is supported by plasma. Can be formed.

  As the innermost layer constituting the laminated material according to the present invention, any film or sheet having a heat sealing property that can be melted by heating and fused to each other and having a lower melting point than the outermost layer can be used. But it can be used.

  Specifically, it is preferable to use a film formed from a polyolefin-based resin such as low-density polyethylene or linear low-density polyethylene. Among them, it is highly heat-sealable to use a linear low-density polyethylene resin. It is more preferable because it is excellent in slipperiness and pinhole resistance.

  The layer made of the polyolefin film is formed in advance by, for example, the T-die method or the inflation method, and after forming the film, the surface is matted in various ways by various methods described later. It is more preferable that the film is made of a film that is not easily rubbed between the contents and the innermost layer during transportation, can prevent pinholes, and the inner surfaces of the laminated films on both sides are less likely to be in close contact with each other.

  The above-mentioned polyolefin film can be matted by various methods.

  For example, a mechanical method such as embossing a film obtained by the T-die method using a chill roll with a mesh, a chill roll or a pinch roll of an inflation method, etc. are heated, and the thermal and mechanical There are a method of embossing and a method of polishing with a brush or the like.

  Moreover, in film formation, the surface can also be made into a film | membrane with an uneven | corrugated shape by using the material which mixed resin with low compatibility with the main component of polyolefin resin in advance.

  In the case of embossing with a mesh, it is preferable to have an uneven state of about 60 to 80 mesh.

On the inner surface side of the innermost layer, the fine irregularities are preferably irregularities having a height of about 0.5 to 15.0 μm, and more preferably 1.0 to 3.0 μm.
If the inner surface of the innermost layer is smooth, the contents of the infusion bag and the innermost layer tend to rub during transportation, which is not preferable.

  Moreover, the inner surfaces of the laminated films on both sides are easily adhered to each other, and the openability of the bag is deteriorated, which is not preferable.

  In addition, when the height of the fine irregularities is less than 0.5 μm, it is not preferable because there is no effect of preventing rubbing between the contents and the inner surface of the laminated film, and the inner surfaces of the laminated film are easily adhered to each other. .

  Further, when the height of the unevenness exceeds 15 μm, the effect of preventing the friction between the contents and the inner surface of the laminated film and the effect of preventing the adhesion between the inner surfaces of the laminated film are good, but it is preferable because the heat sealability is reduced. Absent.

  In addition, when one or more of the above-mentioned various resins are used and the film is formed, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipping, etc. Various plastic compounding agents, additives, and the like can be added for the purpose of improving and modifying properties, mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc.

  The addition amount can be arbitrarily added from a very small amount to several tens of percent depending on the purpose.

  In the above, general additives include, for example, colorants such as lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, antiblocking agents, dyes, pigments, and the like. Etc. can be used, and further, a modifying resin or the like can also be used.

  Next, in the present invention described above, a method of laminating various resin films or sheets and each layer will be described. The outermost layer, the barrier layer, the light-shielding film layer, and the innermost layer are usually used as such methods. For example, a wet lamination method, a dry lamination method, a solvent-free dry lamination method, an extrusion lamination method, a T-die extrusion molding method, a co-extrusion lamination method, and the like can be used.

  Among them, in the present invention, in order to adhere the interlayer between the outermost layer and the barrier layer and the interlayer between the light-shielding film layer and the innermost layer, one or more thermoplastic resins described later are used, and this is used. The method of melt extrusion using an extruder, etc., is not sticky, flexible, has few leachables from the film, excellent hygiene, and does not require adhesive aging, etc. Is also excellent and desirable.

  In the present invention, a resin layer composed of a thermoplastic resin layer is used as the melt-extruded resin layer, and specific examples of such a material include a low density polyethylene resin, a medium density polyethylene resin, a high density polyethylene resin, Chain low density polyethylene resin, copolymer resin with ethylene / α olefin polymerized using metallocene catalyst, ethylene / polypropylene copolymer resin, ethylene / vinyl acetate copolymer resin, ethylene / acrylic acid copolymer Resin, ethylene / ethyl acrylate copolymer resin, ethylene / methacrylic acid copolymer resin, ethylene / methyl methacrylate copolymer resin, ethylene / maleic acid copolymer resin, ionomer resin, polyolefin resin and unsaturated carboxylic acid , Unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, ester monomer DOO polymerization, or can be used copolymerized resins, resins of maleic anhydride was graft-modified polyolefin resin.

  These materials can be used alone or in combination.

  The thickness of the resin layer is preferably about 5 to 30 μm.

  Next, in the present invention, a method for laminating the barrier layer and the light-shielding film constituting the laminate will be described. Between the barrier layer and the light-shielding film, a dry lamination method, a solventless lamination method, A wet lamination method, an extrusion lamination method, a coextrusion lamination method, a sandwich lamination method, or the like can be used, and among these, a dry lamination method is preferable.

  When performing the above lamination, if necessary, pretreatment such as corona treatment and ozone treatment can be applied to the film.

  In the present invention, by using a laminating adhesive, the adhesion between the barrier layer and the metal vapor-deposited film of the light-shielding film layer is improved, and the degree of elongation of the laminating adhesive layer is improved, and the laminating process is performed. Or, improving the post-processability of the box making process, preventing cracks in the metal deposited film such as aluminum during the post-process, and having the advantage that the laminate strength can be obtained without delamination It is.

  The composition system of the adhesive for laminating may be any form such as an aqueous type, a solvent type, an emulsion type, and a dispersion type, and the property is any of film / sheet, powder, solid, etc. Further, the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.

  Examples of such an adhesive for laminating include anchor coating agents such as isocyanate (urethane), polyethyleneimine, polybutadiene, and organic titanium, or polyurethane, ethyl polyacrylate, polybutyl acrylate, 2- Polyacrylic type such as ethylhexyl ester, polyester type, epoxy type, polyvinyl acetate type, cellulose type, polyamide type, polyimide type, urea resin, melamine resin and other amino resin type, phenol resin type, epoxy resin type, reactive type ( (Meth) acrylic, chloroprene rubber, nitrile rubber, rubber system such as styrene-butadiene rubber, inorganic adhesive composed of silicone, alkali metal silicate, low melting point glass, etc., and other adhesives can be preferably used. , Isocyanate resin And curing agent), polyester resin having a hydroxyl group, polyether-based resin, urethane-modified polyol, two-component curable adhesive and an epoxy compound (base resin) is preferable.

  Among these, it is preferable to use polyester from the viewpoint of heat resistance.

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

  In the silane coupling agent, a functional group, chloro, alkoxy, or acetoxy group at one end of the molecule is hydrolyzed to form a silanol group, which dehydrates and condenses with active groups on the surface of the metal deposition film. An organic functional group such as a vinyl group, a methacryloxy group, an amino group, or an epoxy group at the other end of the silane coupling agent is formed on the other end of the silane coupling agent, causing a pinhole-resistant layer and an innermost layer. By reacting strongly with the substances constituting these, the laminate strength is increased, and a strong interlayer strength is made possible.

  That is, utilizing the inorganic and organic properties of the silane coupling agent, through a metal foil, an inorganic oxide vapor deposition film, an adhesive layer, an anchor coating agent layer, and other layers, a paper substrate, Adhesiveness with a synthetic resin film base material is improved, thereby increasing the laminate strength.

Thus, methods for forming these adhesives include, for example, direct roll coating, reverse roll coating, gravure (direct) coating, air knife coating, squeeze coating, blade coating, comma coating, curtain flow coating, kiss coating, and extrusion. It can be formed by coating or other methods. The coating amount of the adhesive is preferably from 0.1 to 10 g / m ² (dry state), and preferably from 1 to 5 g / m ² (dry state).

  Thus, when laminating various resin films or sheets and each layer, if necessary, pretreatment such as corona treatment, ozone treatment, flame treatment, and the like can be performed and laminated.

  The above-mentioned surface pretreatment is carried out as a method for improving the adhesion and the like when laminating each resin film or sheet and each layer. As a method for improving the above adhesion, for example, A primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, and the like can be arbitrarily formed in advance on the surface of various resin films or sheets to form a surface treatment layer.

  Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene, and polypropylene. A resin composition containing a polyolefin resin or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used.

  As the above-mentioned anchor coating agent, either a solvent type or an aqueous type can be used as the anchor coating agent, but when the substrate is paper, toluene, methyl ethyl ketone in a diluting solvent and the anchor coating agent Since organic solvents and the like harmful to the human body such as (MEK) remain in the laminate, when used in food packaging, the residual solvent tends to migrate to the food, which is not preferable for food hygiene.

  Therefore, (chlorinated) polypropylene, modified polyolefin, ethyl vinyl alcohol, polyethylene imine, polybutadiene, polyurethane, polyester polyurethane emulsion, polyvinyl chloride emulsion, urethane acrylic emulsion, silicon acrylic emulsion, vinyl acetate acrylic emulsion , Acrylic emulsion, styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, methyl methacrylate-butadiene copolymer latex, chloroprene latex, polybutadiene latex rubber latex, polyacrylate latex, poly Vinylidene chloride latex, polybutadiene latex, or carboxyl modification of these latexes And water-soluble substances such as polyvinyl alcohol, water-soluble ethylene-vinyl acetate copolymer, polyethylene oxide, aqueous acrylic resin, aqueous apoxy resin, aqueous cellulose derivative, aqueous polyester and aqueous lignin derivative, etc. An emulsion or dispersion anchor coat agent is used.

As an application method of the anchor coating agent, for example, it can be applied by a method such as a gravure coating method, a reverse roll coating method, a knife coating method, a kiss coating method, and the like. 0.1 to 5 g / m ² is preferable.

  Next, in the present invention, a method for making a bag using the above-described laminated material will be described. The inner surface of the heat-sealable film layer is opposed to each other, and the two layers are folded. A bag body can be formed by stacking and further heat-sealing the peripheral edge portion to provide a seal portion.

  Thus, as the bag making method, the above-mentioned laminated material is folded with the inner layer faces facing each other, or two of them are overlapped, and the peripheral edge of the outer periphery is, for example, a side seal type , Two-side seal type, three-side seal type, four-side seal type, envelope sticker seal type, jointed sticker seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, etc. It is possible to produce various types of packaging containers according to the present invention by heat sealing.

  In the above, 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, and an ultrasonic seal can be used.

  In the present invention, it is possible to attach to the packaging container as described above as an easy-opening means, for example, a spout such as a one-piece type, a two-piece type, or the like, or a zipper for opening and closing. .

  As the above-mentioned easy-opening means, in addition to notches commonly used for ordinary bags, half-cut lines by laser light irradiation, etc., or lamination of uniaxially stretched films (stretching direction matches the direction of the cut line) These may be used alone or in combination with a plurality of notches and half-cut lines, or uniaxially stretched film, or cut tape. They can be used in combination.

  By adopting such a configuration, it can be easily opened by tearing by hand at a suitable position.

  Thus, in the present invention, the packaging container having various forms formed by using the laminated material according to the present invention has flexibility, impact resistance, friction resistance, pinhole resistance, Excellent piercing property, heat resistance, low temperature heat sealing property, excellent barrier property against light from outside, oxygen gas, water vapor, etc., little elution from film, excellent hygiene, for example, food and beverage, infusion bag, It is excellent in filling and packaging suitability, storage suitability, etc. for various articles such as chemicals such as pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, and adhesives, and cosmetics and other cosmetics.

  The present invention will be described more specifically with reference to examples.

Example 1
FIG. 4 is a schematic cross-sectional view showing the layer configuration of an example of a laminate according to the present invention.
As shown in FIG. 4, the laminate according to the present invention first has a nylon resin layer 2a (8 μm) / ethylene-vinyl alcohol copolymer layer 2b (9 μm) / nylon resin layer 2a having a thickness of 25 μm as an intermediate layer. (8 μm) Coextruded biaxially stretched nylon film 2 ′ composed of 2 types and 3 layers, urethane ink composition on the back side, and gravure printing method, letters, symbols, patterns, figures, etc. A desired printing layer 7 was formed by printing a printing pattern consisting of

Furthermore, a 12 μm-thick biaxially stretched polyethylene terephthalate film in which a polyurethane-based laminate adhesive layer 8 is applied at a coating amount of 3.0 g / m ² on the printed layer 7 to form a 100-mm aluminum vapor-deposited film 2c. 22 laminated aluminum vapor-deposited surface 2c, layered structure, co-extruded biaxially stretched nylon film 2 'layer / printing layer 7 / laminated adhesive layer 8 / aluminum vapor deposited film 2c / 2-stretched polyethylene terephthalate film 22 Got.

  On the other hand, as an outermost layer, an unstretched film 1a formed from a homopolypropylene resin having a thickness of 30 μm was prepared.

In the unstretched polypropylene film 1a, one side is subjected to corona treatment, a polyurethane-based anchor coat layer 6a having a coating amount of 0.1 g / m ² is applied to the corona-treated surface, and the outermost anchor coat layer 6a is applied. The surface and the anchor coat layer 6b application surface of the laminated film are opposed to each other and laminated through a melt-extruded resin layer 4 made of polyethylene resin having a thickness of 15 μm. As a result, the layer structure, unstretched polypropylene film 1a / Polyurethane-based anchor coat layer 6a / melt-extruded polyethylene resin layer 4 / polyethyleneimine-based anchor coat layer 6b / co-extruded biaxially stretched nylon film 2 'layer / printing layer 7 / laminate adhesive layer 8 / aluminum deposited film 2c / 2-axis A laminated film comprising the stretched polyethylene terephthalate film layer 22 was obtained.

On the other hand, as an innermost layer, a 60 μm linear low density polyethylene unstretched film 3a provided with unevenness of 1.0 to 3.0 μm on one side was formed and used.
In addition, the unevenness | corrugation was type | molded using the cooling roll which has an unevenness | corrugation on the surface in the case of T die-casting film forming.

  The unevenness was measured using a three-dimensional surface roughness / contour shape measuring machine (manufactured by Nippon Denki Co., Ltd.). In this method, the surface of an object is three-dimensionally measured by a direct contact needle method.

A polyurethane-based anchor coating agent 6a is applied to the biaxially stretched polyethylene terephthalate film layer side of the laminated film obtained above (coating amount 0.1 g / m ² ), and a melt-extruded resin layer made of polyethylene resin having a thickness of 15 μm. 4 was laminated on the surface of the linear low density polyethylene unstretched film 3a that had not been subjected to the uneven treatment, to obtain a laminate of Example 1 according to the present invention.

In addition, the layer structure of the following Example 1 is shown in order from the outermost layer to the innermost layer.
Layer structure: unstretched polypropylene film layer 1a / polyurethane anchor coat layer 6a / melt-extruded polyethylene resin layer 4 / polyethyleneimine anchor coat layer 6b / co-extruded biaxially stretched nylon film 2 '/ printing layer 7 / laminate adhesive Layer 8 / Aluminum vapor-deposited film 2c / biaxially stretched polyethylene terephthalate film layer 22 / melt extruded polyethylene resin layer 4 / linear low density polyethylene unstretched film layer 3a

The types of materials used in Example 1 are shown below.
Unstretched polypropylene film: Trade name “SC” (manufactured by Tosero)
Melt Extruded Polyethylene Resin: Trade name “SUMIKAcene 11P” (Mitsui Chemicals, Inc.)
Co-extruded biaxially stretched nylon film: Trade name “HP” (manufactured by Gunze Co., Ltd.)
Printing ink: Trade name “gravure ink CLIOS” (manufactured by The Inktec Co., Ltd.)
Biaxially stretched polyethylene terephthalate film: Trade name "800" (manufactured by Nippon Metallizing Industry Co., Ltd.)
Unstretched linear low-density polyethylene film: Trade name “SP-UMSL” (Dainippon Resin Co., Ltd.)

Next, two sheets of the laminated material produced above were prepared, the surfaces of the linear low-density polyethylene film were overlapped facing each other, and then the outer peripheral edge part was 5 mm wide and three-way heat sealed (conditions 180 ° C., 2 kg / cm ² , 0.5 seconds) to form a sealed portion and a flat bag of 630 mm × 320 mm having an opening on the upper side.

  After storing the infusion bag from the opening in the flat bag manufactured above, the opening is then heat sealed to form an upper seal, and a notch is made in the seal, according to the present invention. A package was produced.

  The package manufactured above blocks light from the outside, has excellent barrier properties against oxygen gas, water vapor, etc., and has little elution from the film, and has flexibility, impact resistance, friction resistance, pin resistance It was excellent in hole property, puncture resistance, heat resistance, low temperature heat seal property, quality retention, printability, opening property, filling packaging property, and content filling property.

(Comparative Example 1)
FIG. 5 is a schematic cross-sectional view showing the layer structure of the laminate (conventional product) of Comparative Example 1.
As shown in FIG. 5, first, as the outermost layer, a biaxially stretched nylon film 1b having a thickness of 20 μm is used, and a urethane ink composition is used on the back surface thereof. A desired printed layer 7 was formed by printing a printed pattern composed of a pattern, a figure, and the like.

Thereafter, a polyurethane-based laminating adhesive 8 is applied on the printing layer 7 (amount applied: 3.0 g / m ² ), and an intermediate layer of 25 μm thick nylon resin layer 2a (8 μm) / ethylene-vinyl alcohol co-polymerized As a result of laminating a co-extruded biaxially stretched nylon film 2 ′ composed of two types and three layers such as a combined layer 2b (9 μm) / nylon resin layer 2a (8 μm), the layer structure, biaxially stretched nylon film 1b / printing layer 7 / A laminated film comprising a laminate adhesive layer 8 / coextruded biaxially stretched nylon film 2 'was obtained.

Next, polyurethane adhesive 8 is applied to the intermediate layer side of the laminated film obtained above (coating amount 3.0 g / m ² ), and the innermost layer is a 50 μm linear low density polyethylene unstretched film. 3a was laminated and the laminated body of the comparative example 1 was obtained.

In addition, the layer structure of the following comparative example 1 is shown in order of the innermost layer from the outermost layer.
Layer structure: biaxially stretched nylon film layer 1b / printing layer 7 / laminate adhesive layer 8 / coextruded biaxially stretched nylon film layer 2 ′ / laminate adhesive layer 8 / linear low density polyethylene unstretched film layer 3a

The types of materials used in Comparative Example 1 are shown below.
Biaxially stretched nylon film: Trade name “ON” (manufactured by Unitika Ltd.)
Printing ink: Trade name “gravure ink CLIOS” (manufactured by The Inktec Co., Ltd.)
Co-extruded biaxially stretched nylon film: Trade name “HP” (manufactured by Gunze Co., Ltd.)
Unstretched linear low-density polyethylene film: Trade name “SR-X” (Dainippon Resin Co., Ltd.)

(Comparative Example 2)
FIG. 6 is a schematic cross-sectional view showing the layer configuration of the laminate of Comparative Example 2.
As shown in FIG. 6, using the same material and method as in Example 1 except that a biaxially stretched nylon film 1b having a thickness of 15 μm is used as the outermost layer and a light-shielding film is not used, the laminate is formed. Manufactured.

In addition, the layer structure of the following comparative example 2 is shown in order of outermost layer to innermost layer.
Layer structure of Comparative Example 2: Biaxially stretched nylon film layer 1b / polyurethane anchor coat layer 6a / melt-extruded polyethylene resin layer 4 / polyethyleneimine anchor coat layer 6b / co-extruded biaxially stretched nylon film 2 ′ / printing layer 7 / Polyurethane anchor coat layer 6a / melt extruded polyethylene resin layer 4 / linear low density polyethylene unstretched film layer 3a

The types of materials used in Comparative Example 2 are shown below.
Biaxially stretched nylon film: Trade name “ON” (manufactured by Unitika Ltd.)

(Experiment 1: Heat seal strength measurement)
About the laminated body manufactured in Example 1 and Comparative Examples 1 and 2, a sample was cut into a strip having a width of 15 mm, and the laminated body was sealed under a sealing condition of 1 kg / cm ² , 180 ° C. for 1 second, and then a tensile test. T-peeling was measured with a machine (Orientec).

  The tensile speed was 300 mm / min, the knob interval was 50 mm, and the load cell was 5 kgf.

  The measurement results are shown in Table 1 below.

  In Table 1, the heat seal strength per 15 mm (unit: N / 15 mm) is shown.

(Experiment 2: Bending pinhole measurement)
About the laminated body manufactured in Example 1 and Comparative Examples 1 and 2, the sample was cut into A4 size (30 cm × 21 cm), and the surface of the outermost layer of each sample film was a test surface with a gelbo flex tester. After bending at a temperature of 23 ° C., the number of gelbos, 1000 times, and 5000 times, the number of pinholes generated within an area of 30 cm × 21 cm of each sample was counted.

  The measurement results are shown in Table 1 below.

(Experiment 3: slipperiness measurement)
About the outermost layer surface and the innermost layer surface of the laminates manufactured in Example 1 and Comparative Examples 1 and 2, using a sliding tester manufactured by Toyo Seiki Co., Ltd., according to ASTM 1894, the static friction coefficient μs and dynamic friction coefficient μd were measured.

(Experiment 4: Oxygen permeability measurement)
About the laminated body manufactured in Example 1 and Comparative Examples 1 and 2 under the conditions of a temperature of 23 ° C. and a humidity of 60% RH, a measuring instrument manufactured by Mocon (USA) (model name, OXTRAN) And measured according to JIS K7126B.

In Table 1, the unit of oxygen permeability is cc / m ² · day · atm.

(Experimental result)

  As is clear from the above measurement results, the film according to Example 1 was excellent in flexibility of the film and excellent in bending resistance, slipping property, barrier property and sealing strength.

  On the other hand, in Comparative Example 1, compared to the laminate of Example 1, each layer is stiff because it is laminated via a dry laminate adhesive, and since a stretched film is used as the outermost layer, bending resistance Inferior, pinholes are generated in the bent part, barrier properties are deteriorated, and the innermost layer is smooth, so that it is inferior in slipperiness. It was.

  Further, in Comparative Example 2, since a stretched film was used as the outermost layer, it was inferior in bending resistance, and pinholes were generated in the bent portion, resulting in deterioration of barrier properties, which was not preferable.

  As is clear from the above description, the present invention sequentially comprises at least an unstretched polyolefin film as the outermost layer, a stretched polyamide resin film as a barrier layer, a light-shielding film, and an unstretched polyolefin film as the innermost layer. A laminate having a laminated structure, wherein the innermost layer is a film formed from a resin having a melting point lower than that of the outermost layer, the interlayer between the outermost layer and the barrier layer, and a light-shielding film A layer characterized in that the layer between the innermost layer and the innermost layer is laminated via a melt-extruded resin layer, and the layer between the barrier layer and the light-shielding film layer is laminated via an adhesive layer for dry lamination When the body was manufactured, it blocked light from the outside, was excellent in barrier properties against oxygen gas, water vapor, and the like, and had less elution from the film. Excellent in flexibility, impact resistance, friction resistance, pinhole resistance, puncture resistance, light shielding, heat resistance, low temperature heat sealability, quality retention, printability, openability, filling packaging suitability, etc. When a concave-convex shape is formed on the innermost layer, it is possible to provide a laminate having excellent inner surface slipperiness.

  Furthermore, when the laminated body is used to produce a packaging container, it is possible to provide a packaging container for foods and medical drugs, which are required to maintain quality in distribution and storage processes.

It is a schematic sectional drawing which shows the layer structure of an example of the laminated body concerning this invention. It is a schematic front view which shows an example of the bag-shaped plastic container concerning this invention using the laminated body shown in FIG. It is a schematic front view which shows an example of the package which used the bag-shaped plastic container shown in FIG. 2, packaged articles | goods, such as an infusion bag, and heat-sealed and sealed the opening part. It is a schematic sectional drawing which shows the layer structure of the Example of the laminated body concerning this invention. It is a schematic sectional drawing which shows the layer structure of the laminated body (conventional product) of the comparative example 1. 6 is a schematic cross-sectional view showing a layer configuration of a laminate of Comparative Example 2. FIG.

Explanation of symbols

1 Unstretched polyolefin film layer (outermost layer)
1a Unstretched polypropylene film layer (outermost layer)
1b Biaxially stretched nylon film layer (outermost layer)
21 Stretched barrier polyamide resin film layer (barrier layer)
2 'Coextruded biaxially stretched nylon film (barrier layer)
2a Nylon resin layer 2b Ethylene-vinyl alcohol copolymer layer 2c Metal vapor deposition layer 22 Base film 2 ″ light-shielding film 3 Unstretched polyolefin film layer (innermost layer)
3a Linear low density polyethylene unstretched film (innermost layer)
4 Melt extruded resin layer 5 Uneven shape 6a Anchor coat layer (polyurethane)
6b Anchor coat layer (polyethyleneimine)
7 Print layer 8 Laminate adhesive layer 9a Side seal 9b Bottom seal 9c Top seal 10 Laminate 11 Notch 12 Contents (infusion bag)
20 Packaging container (flat bag)
30 Package

Claims (4)

A laminate for an infusion bag packaging container comprising at least an unstretched polyolefin film as an outermost layer, a stretched polyamide resin film as a barrier layer, a light-shielding film, and an unstretched polyolefin film as an innermost layer in order. The innermost layer is a film formed from a resin having a melting point lower than that of the outermost layer, the interlayer between the outermost layer and the barrier layer, and the interlayer between the light-shielding film layer and the innermost layer. , Laminated via a melt-extruded resin layer, and the interlayer between the barrier layer and the light-shielding film layer is laminated via an adhesive layer for dry lamination,
The light shielding film has a configuration in which a metal vapor deposition layer is provided on the barrier layer side,
The innermost layer is formed in a shape having fine irregularities on the inner surface.   The laminate according to claim 1, wherein the outermost layer is an unstretched polypropylene film.   The barrier layer is a co-pushing co-stretched film composed of a nylon resin layer, an ethylene-vinyl alcohol copolymer layer, and a nylon resin layer, and a co-pushing co-stretched film composed of a nylon resin layer, an MXD nylon resin layer, and a nylon resin layer. It is a stretched film which consists of a film or MXD nylon, The laminated body in any one of Claims 1-2 characterized by the above-mentioned.   The laminate according to any one of claims 1 to 3, wherein the innermost layer is an unstretched film made of linear low-density polyethylene.

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