JP6478137B2 - Laminated body and package using the same - Google Patents

Description

  The present invention relates to a laminate, and more particularly to a laminate used for a packaging container suitable for packaging a liquid material containing alcohol at a high concentration.

  Alcohol disinfectants, deodorants and the like are commercially available in the form of being packaged in a dispenser container having a bottle container made of a resin such as polyethylene terephthalate resin, polyvinyl chloride resin, or polyethylene resin, and a spout. In recent years, a refill bottle container filled with contents has been marketed to reduce the environmental load, and the spout can be used repeatedly by attaching the spout to the refill bottle container. However, currently used bottle containers themselves are discarded. On the other hand, sanitary products such as liquid detergents are marketed as refillable containers that are hermetically sealed in flexible packaging bags such as standing pouches, and bottles can be transferred by transferring the liquid from the packaging bag to the bottle container. The container body can be used repeatedly.

  The packaging bag as described above is composed of a laminated film in which a base film and a sealant layer made of polyethylene resin or the like are laminated via an adhesive layer, and is filled into the packaging bag by heat-sealing the sealant layer. The contents such as liquids can be sealed and packaged. When a packaging bag made of such a laminated film is filled with a liquid substance containing alcohol at a high concentration, the alcohol component penetrates into the laminated film and the adhesive layer component dissolves when stored for a long period of time. There was a problem that the packaging bag was damaged due to peeling (delamination) from the sealant layer. For this reason, as described above, alcohol sanitizers, deodorants, etc. cannot be used as refillable containers, and bottle containers made of resins such as polyethylene terephthalate resin, polyvinyl chloride resin, and polyethylene resin. Is used.

  By the way, as a packaging bag capable of hermetically filling an alcohol-containing material, a laminated film in which each layer of a base material layer, a barrier layer and a sealant layer is laminated via an adhesive layer is used. In general, an adhesive for dry lamination such as polyurethane adhesive is used. However, even such a packaging bag has a problem that delamination as described above occurs when a high-concentration alcohol-containing material having an alcohol concentration exceeding 40% by mass is filled.

  In order to solve the above problems, JP 2008-94471 A (Patent Document 1) applies an aqueous dispersion containing fine particles made of a specific modified polyolefin resin on the surface of a barrier layer made of aluminum foil. And forming an anchor coat layer, by extruding and laminating a polyolefin resin or the like on the anchor coat layer surface to form a sealant layer, even for a high concentration alcohol-containing material such that the alcohol concentration exceeds 40% by mass, It is disclosed that a packaging bag having high alcohol resistance can be realized.

JP 2008-94471 A

  The inventors of the present invention now have a high-concentration alcohol-containing material in which an alcohol concentration exceeds 40% by mass in a packaging container composed of a laminate obtained by dry lamination through a barrier layer, a sealant layer, and an adhesive layer. When filled, moisture (water vapor) that enters through the barrier layer from the outside of the packaging container acts on the adhesive layer, and the cohesive force of the adhesive layer is reduced by the alcohol component that has exuded from the inside of the packaging container through the sealant layer. Thus, it was found that the barrier layer and the sealant layer were peeled off. And, by using a metal foil as a barrier layer, by using a polyurethane adhesive in which a specific main agent and a curing agent are blended at a predetermined ratio, as an adhesive when dry laminating a metal foil and a sealant layer, It was found that a packaging container having high alcohol resistance can be realized even for a high-concentration alcohol-containing material. The present invention is based on such knowledge.

  Therefore, the objective of this invention is providing the laminated body which can implement | achieve the package which has high alcohol resistance also with respect to the high concentration alcohol containing material whose alcohol concentration exceeds 40 mass%.

The laminate according to the present invention is a laminated film in which a base material layer, a barrier layer, and a sealant layer are laminated in this order via an adhesive layer,
The barrier layer is made of a metal foil,
The adhesive layer between the barrier layer and the sealant layer comprises a urethane-based adhesive containing a polyester polyol and an epoxy compound as main components and a polyisocyanate as a curing agent,
The ratio of the main agent to the curing agent is 10: 1.269 to 10: 2.885 in terms of solid content mass ratio.

  In the aspect of the present invention, the metal foil may be an aluminum foil.

  In an embodiment of the present invention, the epoxy compound may be a bisphenol type epoxy compound.

  In the aspect of this invention, 5-40 mass% in conversion of solid content may be sufficient as content of the said epoxy compound in the said main ingredient.

  In the aspect of the present invention, the urethane adhesive may further contain a silane coupling agent.

  In an aspect of the present invention, an intermediate layer is further provided between the barrier layer and the sealant layer, and the barrier layer, the intermediate layer, and the sealant layer are laminated via the adhesive layer. It may be.

  Moreover, according to another aspect of this invention, the package which consists of an above described laminated body is also provided.

  According to the present invention, a polyurethane adhesive containing a specific main agent and a curing agent in a predetermined ratio is used as an adhesive when a metal foil is used as a barrier layer and the metal foil and the sealant layer are dry-laminated. Since it uses, when the obtained laminated body is used as a packaging body, the packaging body which has high alcohol resistance also with respect to a high concentration alcohol containing material is realizable.

It is sectional drawing which showed one Embodiment of the laminated body by this invention. It is sectional drawing which showed another embodiment of the laminated body by this invention. It is an external appearance perspective view which shows an example of the package body bag-made using the laminated body by this invention. It is a top view which shows another example of the package body bag-made using the laminated body by this invention.

<Laminate>
Hereinafter, although the laminated body by this invention is demonstrated, referring drawings, this invention is not limited by embodiment shown in figure. FIG. 1 is a cross-sectional view showing an embodiment of a laminate according to the present invention. When the laminate 1 is a package (not shown), the base material layer 10 located in the outermost layer, the barrier layer 20, and the sealant layer 30 located as the innermost layer are interposed via the adhesive layer 40. It is the laminated body laminated | stacked in this order. In the present invention, as shown in FIG. 2, an intermediate layer 50 may be further provided between the barrier layer 20 and the sealant layer 30. In the case where the laminate 1 is an embodiment as shown in FIG. 2, an adhesive layer 40 is provided between each of the barrier layer 20, the intermediate layer 50, and the sealant layer 30. Hereinafter, each layer which comprises a laminated body is demonstrated.

  The base material layer 10 is a layer for supporting the laminate and improving strength characteristics and impact resistance when the laminate is a packaging body such as a packaging container. Examples of the material used as the base material layer include resin films or sheets having the above-mentioned properties, for example, polyolefin resins such as polyethylene resins or polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile. -Styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate and other polyester resins, various nylons And various resins such as polyamide resins, polyurethane resins, acetal resins, cellulose resins, and the like. Among these, from the viewpoint of practicality and the like, a film or sheet of a polyester resin, a polyolefin resin, or a polyamide resin can be preferably used.

  The above-mentioned resin film or sheet uses, for example, one or more of the above-mentioned various resins and uses a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, or the like. A method of forming the above various resins alone, or a method of forming a multi-layer coextrusion film using two or more kinds of resins, and further using two or more kinds of resins, Various resin films or sheets are manufactured by a method of forming a film by mixing before forming a film, and if desired, for example, using a tenter method or a tube llama method, a uniaxial Furthermore, various resin films or sheets stretched in the biaxial direction can be used.

  Although the thickness of a base material layer can be suitably changed also with the usage application of a package, it is 6-200 micrometers normally from a viewpoint of a moldability or transparency, Preferably, it is about 9-100 micrometers.

  In addition, the base material layer has heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipping properties, mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. For the purpose of improvement and modification, various plastic compounding agents and additives may be blended. Examples of such additives include a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, and a pigment.

  In addition, the surface of the base material layer may be subjected to a surface treatment as necessary in order to improve adhesion to a barrier layer described later. As the surface treatment, pre-treatment such as corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. is optionally given, For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, and the like can be given.

  Next, the barrier layer 20 provided on the base material layer 10 will be described. The barrier layer is a layer for suppressing the penetration of gas (especially water vapor gas) from the outside, preventing the contents from being deteriorated, and preventing the deterioration of the adhesive layer, which will be described later, when the laminate is a package. . Conventionally, in the gas barrier film, metal foil such as aluminum foil or metal or metal oxide vapor deposition film was interposed, but in the present invention, by interposing the metal foil in the laminate, A package that can prevent moisture (water vapor) from the outside of the package from entering the adhesive layer described later, prevent the adhesive layer from being affected by moisture, and can withstand a high-concentration alcohol solution. It has been found that can be realized. Without being bound by theory, it is likely that the permeability of water vapor gas is remarkably high because the barrier layer is dense at the molecular level as compared to conventional deposited films of metal or metal oxide. It is thought that it can be reduced.

  As the barrier layer, for example, a layer made of a metal foil obtained by rolling a metal or an alloy can be used. As the metal foil, one or more materials selected from the group consisting of aluminum, copper, zinc, gold, silver, and alloys thereof can be used, and among these, aluminum foil is preferably used. As a material for the aluminum foil, a pure aluminum-based or aluminum-iron-based alloy is generally used.

  Examples of the method for forming the barrier layer include a dry laminating method in which a metal foil is provided on the base material layer via an adhesive layer. The thickness of the barrier layer is about 1 to 30 μm, preferably about 5 to 15 μm, in view of ensuring workability and water vapor gas permeability.

  As the adhesive for laminating the base material layer and the barrier layer, conventionally known adhesives can be used, for example, polyvinyl acetate adhesive, homopolymers such as ethyl acrylate, butyl, 2-ethylhexyl ester, etc. Or polyacrylic acid ester adhesives, cyanoacrylate adhesives, ethylene and vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc. made of a copolymer of these with methyl methacrylate, acrylonitrile, styrene, etc. Ethylene copolymer adhesive made of copolymer with other monomers, cellulose adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive, amino resin adhesive made of urea resin or melamine resin, etc. , Phenolic resin adhesive, epoxy adhesive, polyurethane adhesive, reaction Use (meth) acrylic adhesives, chloroprene rubber, nitrile rubber, rubber adhesives made of styrene-butadiene rubber, etc., silicone adhesives, alkali metal silicates, inorganic adhesives made of low melting glass, etc. Can do.

  Next, the adhesive layer 40 interposed between the barrier layer 20 and the sealant layer 30 will be described. The adhesive layer is formed of a so-called two-component curable adhesive composed of a main agent containing polyester polyol and an epoxy compound and a curing agent containing polyisocyanate. Conventionally, a polyester-based urethane adhesive has been used as an adhesive for dry lamination of a laminated film for packaging material, but it is included in moisture entering from the outside of the package or a material constituting the laminated film (for example, nylon). Due to moisture, the ester bond portion of the polyester urethane adhesive may be hydrolyzed, and the cohesive strength of the adhesive may be reduced. In the present invention, the addition of an epoxy compound as a main component in addition to the polyester polyol suppresses a decrease in the cohesive strength of the adhesive due to moisture. The reason for this is not clear, but it is considered that the epoxy group in the epoxy compound reacts with a carboxyl group generated by hydrolysis of the ester bond, thereby suppressing a decrease in the molecular weight of the adhesive component. In other words, the barrier layer described above suppresses the entry of moisture into the adhesive layer as much as possible, and suppresses the adhesive itself from being denatured by a small amount of moisture reaching the adhesive layer or moisture entering from another layer. Thus, it is possible to effectively prevent the cohesive force of the adhesive layer from being reduced by the alcohol component exuded from the sealant layer side.

  As the polyester polyol as the main component of the adhesive, those composed of various polycarboxylic acids and polyols can be used, but dicarboxylic acids composed of aliphatic dibasic acids and aromatic dibasic acids, and fats. What is comprised with a group glycol is more preferable at the point that adhesiveness becomes high. Examples of the aliphatic dibasic acid include malonic acid, succinic acid, tartaric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, alkyl succinic acid, linolenic acid, maleic acid, fumaric acid , Mesaconic acid, citraconic acid, itaconic acid, glutaconic acid and the like, or reactive derivatives such as acid anhydrides, alkyl esters, acid halides, and the like. These aliphatic dicarboxylic acids can be used alone or in combination of two or more. Examples of the aromatic dibasic acid include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, tetrahydro Examples thereof include phthalic acid and the like, or reactive derivatives thereof such as acid anhydrides, alkyl esters, and acid halides. These aromatic dicarboxylic acids can be used alone or in combination of two or more.

  Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 1,6-hexanediol, A propylene glycol etc. can be illustrated and these can be used individually or in combination of 2 or more types.

  The production method of the polyester polyol itself may be a known method, and may be a known method such as dehydration condensation or transesterification condensation. These polyester polyols have a number average molecular weight of 700 to 3000, preferably 1000 to 2000, and an acid value of 3.0 mgKOH / g or less, preferably 1.0 mgKOH / g.

  The epoxy compound contained in the main agent of the adhesive is not particularly limited as long as it has at least one epoxy group or glycidyl group, but considering the cohesive strength of the adhesive, it is aromatic. It is preferable to use an epoxy compound of the type. Examples of such an epoxy compound include bisphenol type epoxy compounds such as bisphenol A type epoxy compounds and bisphenol F type epoxy compounds, novolak type epoxy compounds such as novolac epoxy compounds and cresol novolac epoxy compounds, biphenyl type epoxy compounds, and stilbene type epoxy compounds. And epoxy compounds such as a triphenolmethane type epoxy compound, an alkyl-modified triphenolmethane type epoxy compound, a triazine nucleus-containing epoxy compound, and a dicyclopentadiene-modified phenol type epoxy compound. These epoxy compounds can be used alone or in combination of two or more. Among these aromatic epoxy compounds, hydrophobic bisphenol type epoxy compounds can be preferably used because they have a high effect of suppressing hydrolysis of the ester bond of the polyester polyol.

  The above-mentioned epoxy compound preferably has a number average molecular weight of 1000 to 3000. An epoxy compound having a small number average molecular weight may ooze out from the inside of the package through each layer in the laminate, and the low molecular weight of an aromatic epoxy compound such as a bisphenol type epoxy compound is filled in the package. There is a risk of impact. On the other hand, if the number average molecular weight is 3000 or more, the cohesive force of the adhesive may be reduced.

  The epoxy compound is preferably contained in the main component in an amount of 5 to 40% by mass in terms of solid content, more preferably 20 to 30% by mass. If the content of the epoxy compound is small, the effect of suppressing the hydrolysis of the ester bond as described above cannot be expected. On the other hand, if the content of the epoxy compound is too large, the cohesive force of the adhesive may be reduced.

  As the curing agent for the adhesive used in the present invention, polyisocyanate that reacts with the hydroxyl group of the polyester polyol to form a urethane bond is used. As the polyisocyanate, known aliphatic, alicyclic, aromatic, and aromatic-aliphatic isocyanate compounds can be used.

  Examples of the aliphatic isocyanate compound include aliphatic diisocyanate compounds such as hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, and lysine diisocyanate.

  Examples of the alicyclic isocyanate compound include alicyclic diisocyanate compounds such as isophorone diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylene diisocyanate. .

  Examples of the aromatic isocyanate compound include tolylene diisocyanate (TDI) such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, etc., diphenylmethane diisocyanate (MDI), orthotoluidine diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4 ' -Diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenol Diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, aromatic diisocyanate compounds such as 3,3'-dimethoxy-4,4'-diisocyanate.

  Examples of the aromatic-aliphatic isocyanate compound include aromatic-aliphatic diisocyanate compounds such as xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, and polymethylene polyphenylene polyisocyanate. These may be used individually by 1 type and may use 2 or more types together.

  Among the above-mentioned isocyanate curing agents, aromatic-aliphatic diisocyanate compounds are preferred from the viewpoint of adhesive strength after curing, and trimethylolpropane / tolylene diisocyanate trimer adducts and trimethylolpropane / xylylene diisocyanate. A trimer adduct of (3), a trimethylolpropane / hexamethylene diisocyanate trimer adduct, and the like can be preferably used.

  In the present invention, the blending ratio of the main agent (that is, polyester polyol and epoxy compound) and the curing agent is in the range of 10: 1.269 to 10: 2.885 in terms of solid content mass ratio. Usually, the compounding ratio of the main agent and the curing agent is about 10: 1.154 in terms of solid content, but by increasing the compounding amount of the curing agent more than usual, the water molecules are added to the isocyanate group (- NCO) and the reaction, and it can be further suppressed that the adhesive is hydrolyzed by moisture. A more preferred blending ratio is in the range of 10: 1.384 to 10: 2.308, and a more preferred blending ratio is in the range of 10: 1.546 to 10: 2.308.

  The adhesive may contain a curing catalyst for promoting the curing reaction of the polyester polyol. Examples of the reaction catalyst include trimethylene bis (4-aminobenzoate), dimethylethanolamine, triethyleneamine, tetramethylpolymethylenediamine, amines such as tris (dimethylaminomethyl) phenol, tin octylate, tin naphthenate, Examples thereof include metal salts such as cobalt naphthenate, zinc naphthenate, and dibutyltin laurate, and higher bismuth carboxylates. These curing catalysts are usually used in the range of 0.001 to 1 mol% with respect to the polyester polyol.

  In the present invention, a chain extender may be contained in the adhesive. The chain extender reacts with the isocyanate group of the prepolymer, and the prepolymer is interconnected and polymerized through the functional group of the chain extender, and the molecular weight of the resulting polyurethane gradually increases as the reaction proceeds. To increase. The addition amount of the chain extender can be appropriately adjusted in consideration of the coatability during dry lamination.

  Examples of the chain extender include low-molecular diamines and low-molecular diols used in ordinary polyurethane production. Examples of the diamine include aliphatic diamines such as ethylene diamine, 1,2-propylene diamine, and hexamethylene diamine; isophorone diamine (IPDA), dicyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1,3-bis. There are alicyclic diamines such as aminomethylcyclohexane, and these can be used alone or in admixture of two or more.

  Examples of the low molecular diol include aliphatic glycols such as ethylene glycol and 1,4-butanediol, and aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene. Among these chain extenders, diamine-based ones have high reactivity, so that the molecular weight of polyurethane can be easily increased.

  The adhesive may contain a silane coupling agent. By using a silane coupling agent in combination, the adhesion between the metal foil (barrier layer) and the adhesive is further improved. As the silane coupling agent, conventionally known silane coupling agents can be used. For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , Epoxy group-containing silane coupling agents such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, Amino group-containing silane coupling agents such as 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, (methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. ) Acrylic group-containing silane coupling , Etc. Inshianeto group-containing silane coupling agents such as 3-isocyanate propyl triethoxysilane and the like. These may be used alone or in combination of two or more. Among these, a silane coupling agent having a mercapto group, which is used for improving adhesiveness for rubber applications such as butyl rubber and isoprene rubber, can be preferably used. Examples of such silane coupling agents include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, and alkoxy oligomers having these structures, mercapto groups and epoxy groups, Examples include alkoxy oligomers having a plurality of functional groups such as a combination of a mercapto group and an amino group. These can be used alone or in combination of two or more. The addition amount of the silane coupling agent is usually about 0.1 to 10% by mass with respect to the main agent.

  In addition, the adhesive includes, for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, For the purpose of improving and modifying electrical properties, strength, etc., for example, coloring of lubricants, plasticizers, fillers, fillers, antistatic agents, antiblocking agents, crosslinking agents, light stabilizers, dyes, pigments, etc. An agent or the like may be added.

  The adhesive may be diluted with an organic solvent for viscosity adjustment at the time of application, for example, methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, It can be diluted with isopropanol, acetic acid n-propanol or the like.

  In order to form an adhesive layer on the barrier layer, an adhesive prepared by kneading and dispersing the above-described components can be formed by applying to the surface of the barrier layer and drying. The method for applying the adhesive is not particularly limited. For example, roll coat, reverse roll coat, transfer roll coat, gravure coat, gravure reverse coat, comma coat, rod coat, blade coat, bar coat, wire Bar coat, die coat, lip coat, dip coat, etc. can be applied. Although the thickness of an adhesive bond layer can be suitably adjusted with the use use etc. of a package body, it is 5-500 micrometers normally, Preferably it is about 10-100 micrometers.

  Next, the sealant layer will be described. When the laminate is made into a package, the sealant layers of the laminate are fused to each other to seal the package. Therefore, the sealant layer may be any material that can be heat-sealed, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, metallocene catalyst (single site catalyst). ) -Polymerized ethylene / α-olefin copolymer, polypropylene, ethylene / vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid An acid-modified polyolefin resin obtained by modifying a polyolefin resin such as a copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic anhydride, or fumaric acid. Film or sheet consisting of etc. And the like. These can be used alone or in combination of two or more.

  The thickness of the sealant layer is preferably 20 to 200 μm and more preferably 50 to 100 μm from the viewpoint of heat sealability.

  In the present invention, an intermediate layer 40 may be provided between the barrier layer 20 and the sealant layer 30 as shown in FIG. The intermediate layer provides sealing, puncture resistance (pinhole resistance), heat resistance, light resistance, quality maintenance, workability, hygiene, etc. when the laminate is made into a package. is there.

  Examples of the intermediate layer include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, and ethylene-ethyl acrylate copolymer. Polymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (Meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene styrene copolymer (ABS resin), polyester resin, polyamide resin, Police car Any known resin film or sheet such as nate resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. Can be used.

  The film or sheet may be any of unstretched, uniaxially or biaxially stretched, etc., but if puncture resistance (pinhole resistance) is required, a stretched nylon film may be used. Can be used. In addition, a light-shielding film or sheet obtained by adding a desired additive such as a colorant or an ultraviolet absorber and kneading to form a film can also be used. The thickness of the intermediate layer is arbitrary, but can be appropriately selected within a range of several μm to 300 μm.

  When the intermediate layer 50 is provided, the barrier layer 20 and the intermediate layer 50 are laminated via the adhesive layer 40 described above, and the intermediate layer 50 and the sealant layer 30 are further laminated via the adhesive layer 40. When the adhesive layer 40 is provided on the intermediate layer 40, the surface treatment as described above may be performed on the surface of the intermediate layer 50 in advance to improve the adhesion between the intermediate layer 40 and the adhesive layer 50.

  The laminated body by this invention may contain layers other than the above-mentioned layer, and can provide suitably the printing layer, concealment layer, etc. which are provided as a laminated body for packaging bodies. For example, between the base material layer 10 and the barrier layer 20, the printing layer which provides desired printing patterns, such as a character, a figure, a symbol, a pattern, may be provided. The printing layer is usually an ink composition prepared by kneading an ink vehicle and a colorant such as a dye / pigment with a solvent, a diluent, etc., and is used in gravure printing, offset printing, letterpress printing, screen printing, transfer printing. It can be formed by printing a desired printing pattern on the surface of the base material layer (the surface on the side where the barrier layer is provided) by a printing method such as flexographic printing. In the ink composition for forming the printing layer, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a curing agent, a crosslinking agent, a lubricant, an antistatic agent, a filler, etc., as necessary One or more of these additives may be added. The printing layer may be provided on the entire surface or may be provided on a part. The coating amount of the ink composition when forming the printing layer is about 1 μm to 8 μm in the dried state after coating.

  Further, a concealing layer may be provided between the printing layer and the barrier layer. By providing the concealing layer, it is possible to conceal the darkening that occurs when a crack occurs in the barrier layer made of metal foil, and to maintain good visibility of the above-described printed layer. The concealing layer can be formed in the same manner as the printing layer using silver ink or white ink close to metal color.

  The thickness of a laminated body can be suitably determined according to the use. For example, it can be in the form of a film or sheet having a thickness of 30 to 300 μm, preferably 50 to 200 μm.

  The laminate according to the invention has on one or both sides a chemical function, an electrical function, a magnetic function, a mechanical function, a friction / abrasion / lubricating function, an optical function, a thermal function, a biocompatibility. Secondary processing can be performed for the purpose of imparting surface functions and the like. Examples of secondary processing include embossing, painting, adhesion, printing, metalizing (plating, etc.), machining, surface treatment, and the like. Further, as will be described later, a laminate, a bag making process, and other post-treatments can be applied to the laminate to produce a molded product such as a package.

<Packaging body>
The package according to the present invention is made by using the above-described laminate. A packaging bag can be manufactured by heat-sealing the sealant layers of the laminate. The form of the packaging bag is not particularly limited. For example, a standing pouch type, a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, a palm-attached seal type (pillow seal type), a pleat It can be used as a packaging bag of various forms such as an attached seal type, a flat bottom seal type, a square bottom seal type, and a gusset type.

  As an example of a package according to the present invention, a case where a laminate is applied to a standing pouch will be described. FIG. 3 is an external perspective view showing an example of a package (standing pouch) made by using the laminate according to the present invention. As shown in FIG. 3, the standing pouch 2 includes two body parts (side sheet) 60 and a bottom part (bottom sheet) 70. The side sheet 60 and the bottom sheet 70 may be a laminated body having the same configuration or a laminated body having a different configuration. The standing pouch 2 is formed by bag-making so that the sealant layer of the laminate constituting the side sheet 60 and the bottom sheet 70 becomes the innermost layer. Further, as shown in FIG. 4, the standing pouch 2 may be provided with a spout portion 80 in a part of the trunk portion 60.

  A conventionally known method can be applied to the bag making process. For example, the two side sheets 60 are overlapped with the side sheets 60 facing each other so that the sealant layer is the innermost layer, and the two side sheets 60 are formed. By inserting the bottom sheet 70 between them and heat-sealing the side sheet 60 and the bottom sheet 70, a package (stand pouch) can be manufactured. As a heat sealing method, a conventionally 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 employed.

  As described above, the package according to the present invention uses a metal foil as a barrier layer, and a specific main agent and a curing agent are blended at a predetermined ratio as an adhesive when the metal foil and the sealant layer are dry-laminated. Because the laminated body using the polyurethane-based adhesive is used, even when a liquid with a high alcohol concentration (for example, an alcohol concentration of 40% by mass or more) is filled, such as a disinfectant, The laminate does not peel off. The type of alcohol is not particularly limited. For example, methyl alcohol, ethyl alcohol, monohydric alcohols such as propyl alcohol, butyl alcohol, and amyl alcohol including various isomers, ethylene glycol, polymethylene glycol, glycerin, and the like. Or a polyhydric alcohol. The package according to the present invention has high alcohol resistance, but of course, the contents to be filled are not limited to alcohol-containing materials, and include deodorants, fragrances, insecticides, pest control agents, and the like. It goes without saying that it can also function as a package for refilling various drugs, liquid detergents, liquid softeners, liquid soaps and the like.

  The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

Example 1
<Production of laminate>
A corona treatment is performed on one side of a polyethylene terephthalate (PET) film (PTM-RT, manufactured by Unitika Co., Ltd.) having a thickness of 12 μm, and an ester urethane adhesive (main agent: RU-80, Curing agent: H-5, manufactured by Rock Paint, blending ratio of main agent and curing agent = 10: 2.25 (solid content / mass ratio)), dried, and then 7 μm thick aluminum foil (Tokai Aluminum) Made by dry lamination. Further, on this aluminum foil surface, a main agent (Adcoat 502, manufactured by Toyo Morton) containing a polyester polyol and an epoxy compound and a curing agent (CAT-10L, manufactured by Toyo Morton) containing a polyisocyanate are shown in the following table. An adhesive layer was formed by applying an adhesive blended so as to have a solid content mass ratio of 1 to a coating amount of 3.5 g / m ² in a dry state using a gravure coater. . Next, a biaxially stretched nylon film (ONMB-RT, manufactured by Unitika Co., Ltd.) having a thickness of 15 μm and subjected to corona treatment on both sides is dry laminated on the surface of the adhesive layer to form an intermediate layer. The coating amount in the state where the adhesive which mix | blended Adcoat 502 as a main ingredient and CAT-10L as a hardening | curing agent so that it might become the solid content mass ratio shown in following Table 1 using a gravure coater was 3. The adhesive layer was formed by coating so as to be 5 g / m ² . By dry laminating a 100 μm-thick low-density polyethylene film (SP-406, manufactured by DNP Technopack Co., Ltd.) having a corona-treated one side on the surface of this adhesive layer, and aging treatment at a temperature of 40 to 45 ° C. for 120 hours The adhesive layer was cured to produce a laminate. In Table 1 below, PET represents the polyethylene terephthalate film, and LDPE represents the low-density polyethylene film.

Examples 2-3 and Comparative Example 1
A laminate was produced in the same manner as in Example 1 except that the blending ratio of the main agent and the curing agent of the adhesive used for forming the adhesive layer was changed as shown in Table 1 below.

Comparative Example 2
Instead of the adhesive used to form the adhesive layer, an ester urethane adhesive (main agent: RU-80, curing agent: H-5, manufactured by Rock Paint) is used, and the mixing ratio of the main agent and the curing agent A laminated body was produced in the same manner as in Example 1 except that was changed as shown in Table 1 below.

Comparative Example 3
Using a gravure coater on a biaxially stretched nylon film (ONMB-RT, manufactured by Unitika Co., Ltd.) having a thickness of 15 μm with corona treatment on both sides, a main agent (Adcoat 502, manufactured by Toyo Morton Co., Ltd.) containing a polyester polyol and an epoxy compound; The adhesive which mix | blended the hardening | curing agent (CAT-10L, the Toyo Morton company make) containing polyisocyanate so that it might become solid content mass ratio shown in the following Table 1 was dried using the gravure coater. The coating amount was 3.5 g / m ² to form an adhesive layer. Next, a polyethylene terephthalate film having a thickness of 12 μm having an aluminum vapor deposition film provided on one surface was dry-laminated on the surface of the adhesive layer so that the aluminum vapor deposition film faced the biaxially oriented nylon film. Subsequently, the surface of the polyethylene terephthalate film on which the aluminum vapor deposition film is provided is subjected to corona treatment, and on the corona treatment surface, Adcoat 502 as a main agent and CAT-10L as a curing agent are applied. Adhesive layer coated with an adhesive blended so as to have a solid mass ratio shown in Table 1 below so that the coating amount in a dried state using a gravure coater is 3.5 g / m ^2. Formed. By dry laminating a 100 μm-thick low-density polyethylene film (SP-406, manufactured by DNP Technopack Co., Ltd.) having a corona-treated one side on the surface of this adhesive layer, and aging treatment at a temperature of 40 to 45 ° C. for 120 hours The adhesive layer was cured to produce a laminate. In Table 1 below, ONy represents the biaxially stretched nylon film.

<Evaluation of laminate>
Each laminate obtained as described above was cut into a strip shape having a width of 15 mm to prepare a test piece. Further, a package as shown in FIG. 3 is prepared using each laminate, and 350 ml of an aqueous solution containing 60% ethanol is filled from the upper part of the package, and the upper part is heat-sealed and sealed. After storing for 2 weeks in an environment at 0 ° C., the filled aqueous solution was removed from the package, and then a strip-shaped test piece having a width of 15 mm was cut out from the package. About these 2 types of test pieces, the 90 degree | times peeling test was done at the speed | rate of 50 mm / min using the tensile tester (Tensilon universal material tester RTC-1310A, the product made by ORIENTEC). In the peel test, both the peel strength between the aluminum foil and the biaxially stretched nylon film (intermediate layer) and the peel strength between the biaxially stretched nylon film (intermediate layer) and the low density polyethylene film (sealant layer) were measured. The evaluation results were as shown in Table 2 below. The package using the laminate of Comparative Example 3 was peeled off from the base material layer and the barrier layer, and between the barrier layer and the sealant layer when stored for 2 weeks in a state filled with an aqueous ethanol solution. The peel strength could not be measured using

DESCRIPTION OF SYMBOLS 1 Laminated body 2 Packaging 10 Base material layer 20 Barrier layer 30 Sealant layer 40 Adhesive layer 50 Intermediate layer 60 Body part 70 Bottom part 80 Outlet part

Claims (6)

A base material layer, a barrier layer, an intermediate layer, and a sealant layer are laminated in this order via an adhesive layer,
The barrier layer is made of a metal foil,
Urethanes in which both the adhesive layer between the barrier layer and the intermediate layer and between the intermediate layer and the sealant layer contain a polyester polyol and an epoxy compound as main components and a polyisocyanate as a curing agent Made of adhesive,
The ratio of the said main ingredient and the said hardening | curing agent is 10: 1.269-10: 2.885 by solid content mass ratio, The laminated body characterized by the above-mentioned.   The laminate according to claim 1, wherein the metal foil is an aluminum foil.   The laminate according to claim 1 or 2, wherein the epoxy compound is a bisphenol type epoxy compound.   The laminate according to any one of claims 1 to 3, wherein the content of the epoxy compound in the main agent is 5 to 40% by mass in terms of solid content.   The laminate according to any one of claims 1 to 4, wherein the urethane-based adhesive further comprises a silane coupling agent.   The package body which consists of a laminated body as described in any one of Claims 1-5.

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