JP5104207B2 - Strong adhesion gas barrier transparent film and laminated packaging material using the same - Google Patents

Description

  The present invention relates to a strong adhesion gas barrier transparent film suitably used for packaging foods and pharmaceuticals and a laminated packaging material using the same, and particularly excellent in transparency and physical strength, and further has high gas barrier properties. Further, the present invention relates to a packaging material in which adhesion to a thermoplastic polymer film as a substrate is maintained even when boil sterilization, retort sterilization, or the like is performed, and a laminated portion is not easily peeled off.

  In recent years, packaging materials used for packaging foods and pharmaceuticals have oxygen, water vapor, and other gases that alter the contents so that the functions and properties of the contents can be maintained by suppressing the alteration of the contents. It is required to have a gas barrier property for blocking. Therefore, conventionally, a metal foil made of a metal such as aluminum, which is less affected by temperature, humidity, etc., has been generally used as a gas barrier layer.

  However, a packaging material using a metal foil made of a metal such as aluminum is excellent in gas barrier properties, but the contents cannot be confirmed through it, and is treated as an incombustible material at the time of disposal after use. There are problems such as having to do it, not being able to use a metal detector when inspecting the packaged contents, and so on.

  Therefore, in order to overcome these drawbacks, for example, silicon oxide, aluminum oxide, magnesium oxide and the like are formed by thin film forming means such as vacuum deposition and sputtering as described in Patent Document 1 and Patent Document 2 and the like. A vapor deposition film formed by forming a vapor deposition thin film made of an inorganic oxide on a polymer film has been developed. These vapor-deposited films are known to have transparency and gas barrier properties against oxygen, water vapor, etc., and are suitable as packaging materials having both transparency and gas barrier properties that cannot be obtained with metal foils and the like. Yes.

In addition, for example, a film using a base material subjected to plasma treatment as described in Patent Document 3 and Patent Document 4 has been developed.
U.S. Pat. No. 3,442,686 Japanese Patent Publication No.63-28017 Japanese Patent Application Laid-Open No. 1991-247750 JP 1994-172966 A

  However, even if it is a vapor deposition film suitable as a packaging material as mentioned above, packaging bodies, such as a packaging container and a packaging bag, are not produced without giving some process there. In general, for these vapor-deposited films, as a post-processing, letters, designs, etc. are printed on the surface of the vapor-deposited film, other films are laminated on the surface, and further molded to form a package. Etc., and are provided as packaging containers and packaging bags. In particular, when the package is subjected to processing such as boil sterilization, retort sterilization, autoclave sterilization, etc., sufficient care must be taken in the design of the packaging material constituting the sterilization.

By the way, after making a bag using the packaging material formed by laminating the above-mentioned vapor-deposited film with a sealant film, filling the contents in the obtained packaging bag and trying boil sterilization or retort sterilization, sterilization There were many cases where delamination occurred in a part of the seal portion of the packaging bag after the processing, resulting in poor appearance, gas barrier properties were lowered at the delamination occurrence portion, and the contents were altered.

  Under such circumstances, the contents to be packaged are transparent so that the contents can be directly seen through, have a high gas barrier property to block the gas etc. affecting the quality of the contents, and further boil sterilization. There is a strong demand for the development of packaging materials that do not deteriorate the gas barrier properties that were initially possessed even when processing such as retort sterilization or autoclave sterilization is performed.

  The present invention has been made under the circumstances as described above. The object of the present invention is to have transparency capable of directly seeing through the contents, and an advanced gas barrier comparable to that of aluminum foil. A highly adhesive gas barrier film that is versatile and can be used for general packaging of foods and pharmaceuticals, without causing delamination or gas barrier deterioration even after being treated for boil sterilization or retort sterilization. And providing a laminated packaging material using this film.

In order to achieve the above-described problems, the invention according to claim 1 is characterized in that a double-bond-containing silane coupling agent is added in an amount of 1 weight by weight in a diluent solvent (ethyl acetate) on at least one surface of a thermoplastic polymer film. Each was mixed and stirred so that the hydroxyl group-containing acrylic resin was 100 parts by weight, and then the aromatic isocyanate compound was added to this mixed solution with NCO groups 3 times the OH groups of the hydroxyl group-containing acrylic resin, etc. It is a strong adhesion gas barrier transparent film in which at least a transparent inorganic thin film layer is laminated via a transparent primer layer made of a primer agent prepared so as to be an amount, and the transparent primer layer is subjected to ESCA analysis (analysis condition: X-ray source monochrome AlK, the X-ray output 30 W), C, N, O, presence of Si has been confirmed, the element ratio (O / C, N / C , Si Each C) is 0.40 or less, 0.10 or less, a strong adhesion barrier transparent film, characterized in that it is 0.05 or less.

Further, the invention according to claim 2 is directed to at least one surface of the thermoplastic polymer film, in which a hydroxyl group / methacrylic group-containing aromatic is added to 1 part by weight of an N group-containing silane coupling agent in a diluting solvent (ethyl acetate). The acrylic resin is mixed and stirred so that the acrylic resin is 100 parts by weight, and then the aliphatic isocyanate compound is added to this mixed solution in an amount equivalent to 3 times the NCO group with respect to the OH group of the hydroxyl / methacrylic group-containing aromatic acrylic resin. A transparent gas barrier transparent film in which at least a transparent inorganic thin film layer is laminated via a transparent primer layer made of a primer agent prepared in addition so that the transparent primer layer is subjected to ESCA analysis ( analysis condition: X-ray source) Monochrome AlKα, X-ray output 30 W) confirms the presence of C, N, O, and Si, and their element ratios (O / C , N / C, Si / C) ) Is 0.40 or less , 0.10 or less, 0.05 or less .

Furthermore, the invention described in claim 3 is the strong adhesion gas barrier transparent film according to claim 1 or 2 , wherein a gas barrier coating layer is laminated on the transparent inorganic thin film layer. To do.

Furthermore, the invention according to claim 4 is the strong adhesion gas barrier transparent film according to any one of claims 1 to 3 , wherein the thermoplastic polymer film is either a polyethylene terephthalate film or a polyamide film. It is characterized by being.

Furthermore, the invention according to claim 5 is the strong adhesion gas barrier transparent film according to any one of claims 1 to 4 , wherein the transparent inorganic thin film layer is made of either silicon oxide or aluminum oxide. It is a thin film.

Furthermore, the invention according to claim 6 is the strong adhesion gas barrier transparent film according to any one of claims 3 to 5 , wherein the gas barrier coating layer comprises a hydroxyl group-containing polymer compound, a metal alkoxide and / or It is characterized by having at least one of the hydrolyzate and / or polymer thereof as a component.

Furthermore, the invention according to claim 7, on the strong adhesion barrier transparent film according to any one of claims 1 to 6, through an adhesive layer, that at least the heat-sealable resin layer are laminated Is a laminated packaging material characterized by

  In the present invention, as described above, the presence of C, N, O, and Si is confirmed by ESCA analysis (analysis conditions: X-ray source monochrome AlKα, X-ray output 30 W) on at least one surface of the thermoplastic polymer film. Thus, even if a treatment such as boil sterilization, retort sterilization, or autoclave sterilization is performed, it is possible to ensure the excellent adhesiveness that was initially possessed.

  The strong adhesion gas barrier transparent film of the present invention and the laminated packaging material using the same have excellent gas barrier properties similar to those of aluminum foil, and package foods, pharmaceuticals, precision electronic parts, etc. It can be widely used as a packaging material.

  Hereinafter, an embodiment of a strong adhesion gas barrier transparent film according to the present invention and a laminated packaging material using the same will be described with reference to the drawings.

  FIG. 1 is an explanatory view for explaining the schematic cross-sectional structure of the strong adhesion gas barrier transparent film of the present invention. The strong adhesion gas barrier transparent film 10 has a configuration in which a transparent inorganic thin film layer 3 made of an inorganic oxide and a gas barrier coating layer 4 are sequentially laminated on one surface of a thermoplastic polymer film 1 with a transparent primer layer 2 interposed therebetween. Is.

  On the other hand, FIG. 2 is explanatory drawing explaining the general | schematic cross-sectional structure of the laminated packaging material of this invention. This laminated packaging material 20 has a transparent inorganic thin film layer 23 made of an inorganic oxide, a gas barrier coating layer 24, an adhesive layer 25, and heat sealability on one side of a thermoplastic polymer film 21 via a transparent primer layer 22. The resin layers 26 are sequentially stacked.

  The thermoplastic polymer films 1 and 21 are transparent film substrates. For example, polyethylene terephthalate (PET), polyester film made of polyethylene naphthalate, polyolefin film made of polyethylene or polypropylene, polystyrene film, polyamide film, polyvinyl chloride film, polycarbonate film, polyacrylonitrile film, polyimide film, polylactic acid It consists of a biodegradable plastic film such as a film. These may be stretched or unstretched, but those excellent in mechanical strength and dimensional stability are preferred. In particular, a polyethylene terephthalate film or a polyamide film arbitrarily stretched in the biaxial direction is preferably used. Further, a thin film made of various known additives and stabilizers such as an antistatic agent, an ultraviolet ray preventing agent, a plasticizer, and a lubricant may be provided on the surface of these films. Furthermore, in order to improve the adhesion with the thin film layer laminated thereon, as a pretreatment, corona treatment, low temperature plasma treatment, ion bombardment treatment, chemical treatment, solvent treatment, or the like may be performed.

  Examples of the dicarboxylic acid component constituting the polyester-based thermoplastic polymer film include terephthalic acid, naphthalenecarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodiumsulfoisophthalic acid, phthalate Aromatic dicarboxylic acids such as acids, alicyclic dicarboxylic acids such as cyclohexyne dicarboxylic acid, oxalic acid, oxalic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, p-oxy Examples thereof include oxycarboxylic acids such as benzoic acid. Examples of alcohol components include aliphatic glycols such as ethylene glycol, propanediol, 1,4 butanediol, 1,6 hexanediol, and neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, and 1,4 cyclohexane. Examples thereof include polyoxyalkylene glycols such as dimethanol, aromatic glycols such as bisphenol A and bisphenol S, and derivatives thereof. Among polyester-based thermoplastic polymer films having these components, polyethylene terephthalate is mainly used from the viewpoints of film-forming properties such as biaxial stretching properties, humidity properties, heat resistance, chemical resistance, and low cost. What has been used is preferably used. And within the range where the excellent physical properties of polyethylene terephthalate can be maintained, other alcohol components are controlled so as to be incorporated into the main chain in the polymerization stage and copolymerized, so that a segment with a small rotational hindrance in the molecular chain (soft segment) ), And the force caused by external impact or bending can be absorbed by the soft segment in the molecular chain, and is excellent in impact resistance and flexibility. Further, a copolyester in which 50 mol% or more of each of the carboxylic acid component and the alcohol component of the polyester is terephthalic acid, ethylene glycol, and derivatives thereof is also preferably used.

  The stretching of such a polyester film is based on the process of sequential biaxial stretching and simultaneous biaxial stretching, but the stretching ratio (vertical stretching ratio × horizontal stretching ratio) during stretching should be in the range of 2 to 30 times. Is preferred. Moreover, it is preferable that the hot-water heating shrinkage | contraction rate on 120 degreeC 30 minute conditions at the time of forming into a film on the said conditions shall be 5% or less in MD / TD direction. If it exceeds 5%, the shrinkage is large, so that the gas barrier property after post-processing is greatly reduced.

  As the polyamide-based material, a thermoplastic polymer film made of homopolyamide, copolyamide or a mixture thereof can be used.

  Examples of homopolyamides include polycaprolactam (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecanamide (nylon 11), polylaurin lactam (nylon). 12), polyethylenediamine adipamide (nylon 2,6), polytetramethylene adipamide (nylon 4,6), polyhexamethylenediadipamide (nylon 6,6), polyhexamiethylene sebacamide (nylon) 6,10), polyhexamethylene decanamide (nylon 6,12), polyoctamethylene adipamide (nylon 8,6), polydecamethylene adipamide (nylon 10,6), polydecamethylene sebacamide (Nylon 10, 10), polydecamethylene dodecamide (nylon 12, 12), meta And xylenediamine-6 nylon (MXD6).

  Examples of copolyamides include caprolactam / laurin lactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurin lactam / hexamethylenediamine ammonium sebacate copolymer, hexamethylene diammonium adipate / hexamethy Examples include a diammonium sebacate copolymer and a caprolactam / hexamethylene diammonium adipate / hexamytylene diammonium sebacate copolymer. From these, an appropriate one may be selected and used in consideration of the use environment, the type of package, workability, economy, and the like.

  The thickness of the thermoplastic polymer films 1 and 21 is not particularly limited, but is suitable as a packaging material, may be laminated with other layers, transparent primer layers 2 and 22 and inorganic Considering workability in the case of laminating the transparent inorganic thin film layers 3 and 23 made of an oxide, the gas barrier coating layers 4 and 24, etc., it is practically in the range of about 3 to 300 μm and 6 to 100 μm depending on applications. It is preferable.

  In consideration of mass productivity, it is desirable to use a long film so that each layer can be formed continuously.

  On such thermoplastic polymer films 1 and 21, transparent primer layers 2 and 22 are provided in order to improve adhesion with transparent inorganic thin film layers 3 and 23 made of an inorganic oxide described later. This layer improves the adhesion between the thermoplastic polymer films 1 and 21 and the transparent inorganic thin film layers 3 and 23 made of an inorganic oxide, and has been subjected to treatments such as boil sterilization, retort sterilization, and autoclave sterilization. It is provided in order to prevent the adhesiveness from being deteriorated later and delamination from occurring.

  As a result of intensive studies, the transparent primer layers 2 and 22 that can achieve the above-mentioned purpose are obtained by ESCA analysis (analysis conditions: X-ray source monochrome AlKα, X-ray output 30 W), and C, N, O, and Si elements. The knowledge that it is a layer where existence is confirmed was obtained.

  And the surface of such transparent primer layers 2 and 22 has an element ratio (O / C) of 0.40 or less obtained from the result of ESCA analysis (measurement conditions: X-ray source monochrome AlKα, X-ray output 30 W). Or when the element ratio (N / C) obtained from the result of ESCA analysis (measurement conditions: X-ray source monochrome AlKα, X-ray output 30 W) is 0.10 or less, ESCA analysis ( Measurement conditions: When the element ratio (Si / C) obtained from the results of X-ray source monochrome AlKα, X-ray output 30 W) is 0.05 or less, and ESCA analysis (measurement conditions: X-ray source monochrome AlKα, X More excellent adhesion when the element ratio (O / C, N / C, Si / C) obtained from the result of the line output 30 W) is 0.40 or less, 0.10 or less, 0.05 or less. Gained It was confirmed that.

  The transparent primer layers 2 and 22 are formed by applying a coating agent obtained by mixing a curing agent and a silane compound to a main resin and heating and drying.

  As the main resin, any resin such as urethane, polyester, or acrylic can be used. For example, in urethane resins, in addition to polyether polyols such as polyethylene glycol and polytetramethylene glycol, polyester polyols such as polyethylene adipate and polyhexamethylene adipate, diisocyanates such as tolylene diisocyanate and hexamethylene diisocyanate, ethylene glycol and the like The thing which uses chain length agents, such as hexamethylene diamine, as a raw material is mentioned. Examples of the polyester resin include polyester resins prepared by polycondensation of an acid component such as dicarboxylic acid or tricarboxylic acid and a glycol component using a known method. Examples of the acid component of such a base resin include terephthalic acid, isophthalic acid, adipic acid, trimellitic acid, and the like. Examples of glycol components include ethylene glycol, neopentyl glycol, butanediol, and ethylene glycol. Examples thereof include modified bisphenol A. Examples of acrylic resins include acrylic resins obtained by copolymerizing acrylic acid derivative monomers and other monomers. Among them, preferred are those obtained by polymerizing acrylic acid derivative monomers such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxylbutyl methacrylate alone, and those obtained by copolymerizing with other monomers. As these main resin, those having two or more hydroxyl groups at the polymer terminal are more desirable.

  Moreover, as a hardening | curing agent, an isocyanate compound, a melamine compound, etc. are mentioned. These are added in order to improve the adhesiveness between the thermoplastic polymer films 1 and 21 and the transparent inorganic thin film layers 3 and 23 by a urethane bond formed by reacting with a polyol. Isocyanate compounds include aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), aliphatic xylene diisocyanate (XDI), hexadiisocyanate (HMDI) monomers, and polymers and derivatives thereof. Etc. can be used alone or in appropriate combination.

  Examples of silane compounds include trichlorosilane, vinyltrichlorosilane, hexamethyldisilazane, etc., and any organic functional group such as ethyltrimethoxysilane, vinyltrimethoxysilane, and γ-chloropropylmethyldimethoxysilane. A silane coupling agent can be mentioned. Of these silane compounds, those having a reactive group such as an amino group, an isocyanate group or a double bond are particularly preferred. For example, 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-isocyanatopropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacrylic Roxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and the like.

  In the coating agent containing such components, various additives such as tertiary amines, imidazole derivatives, carboxylic acid metal salt compounds, quaternary ammonium salts, quaternary phosphonium salts and other curing accelerators, phenolic, Addition of sulfur-based and phosphite-based antioxidants, leveling agents, flow regulators, catalysts, crosslinking reaction accelerators, fillers, and the like may be performed in one direction.

  In general, the thickness of the transparent primer layers 2 and 22 formed of a thin film layer of the coating agent as described above is preferably in the range of about 0.001 to 5 μm. When the thickness is less than 0.001 μm, it is difficult to obtain a uniform thin film, and the adhesion may be lowered. On the other hand, when the thickness exceeds 5 μm, it is difficult to maintain the flexibility of the thin film because it is thick, and it is not preferable because the thin film may be cracked due to external factors. Particularly preferred is a range of 0.003 to 1.5 μm.

  As a method for forming the transparent primer layers 2 and 22, for example, a known printing method such as an offset printing method, a gravure printing method, a silk screen printing method, or a known coating method such as roll coating, knife edge coating, or gravure coating is used. be able to. About drying conditions, generally used conditions may be used. In order to promote the reaction, it can be left in a high temperature aging chamber for several days.

  The transparent inorganic thin film layers 3 and 23 made of an inorganic oxide laminated on the transparent primer layers 2 and 22 are, for example, vapor deposited thin films of silicon oxide, aluminum oxide, tin oxide, magnesium oxide, or a mixture thereof. Any layer may be used as long as it is transparent and has a gas barrier property against oxygen, water vapor, and the like. Therefore, the constituent material is not limited to the above-described inorganic oxide, and various materials can be used as long as they are inorganic materials that meet the above conditions.

Examples of a method for forming the transparent inorganic thin film layers 3 and 23 made of the inorganic oxide on the transparent primer layers 2 and 22 include a normal vacuum vapor deposition method, but other thin film formation methods such as sputtering and An ion plating method, a plasma vapor deposition method (CVD), or the like can also be used. From the viewpoint of productivity, the vacuum deposition method is the best at present. As a heating means of the vacuum evaporation method, it is preferable to use any one of an electron beam heating method, a resistance heating method, and an induction heating method, but the electron beam heating method should be used in consideration of the wide selection of evaporation materials. Is more preferable. In order to increase the transparency of the deposited thin film, reactive deposition in which various gases such as oxygen are blown during deposition may be used.

  The optimum thickness of the transparent inorganic thin film layers 3 and 23 varies depending on the type and configuration of the inorganic compound used, but is generally in the range of about 1 to 500 nm, and the value can be appropriately selected. However, if the thickness is less than 1 nm, it is difficult to form a uniform film, and the function as a gas barrier layer may not be sufficiently achieved. On the other hand, if the thickness exceeds 500 nm, it is difficult to maintain flexibility in the thin film layer, and if a force such as bending or pulling is applied after the film is formed, cracks are likely to occur, which is also preferable from an economical viewpoint. Absent.

  On the other hand, the gas barrier coating layers 4 and 24 provided on the transparent inorganic thin film layers 3 and 23 described above protect the transparent inorganic thin film layers 3 and 23 and have a high gas barrier due to a synergistic effect with the transparent inorganic thin film layers 3 and 23. It is a layer provided in order to express sex. For example, a coating agent having at least one of hydroxyl group-containing polymer compound, metal alkoxide and / or hydrolyzate thereof and / or polymer thereof as a component is applied and dried by heating.

  More specifically, a solution in which a water-soluble polymer and tin chloride are dissolved in an aqueous (water or water / alcohol mixed) solvent, or a metal alkoxide directly or a metal alkoxide previously hydrolyzed in this solution. A coating agent comprising the mixed solution as a main component is applied on a transparent vapor-deposited thin film layer made of an inorganic oxide, and then the coated thin film is heated and dried. Each component contained in the coating agent will be described in more detail.

  Examples of the water-soluble polymer used in the coating agent include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like. In particular, when polyvinyl alcohol (hereinafter abbreviated as PVA) is used, the gas barrier property is most excellent, which is preferable. PVA here is generally obtained by saponifying polyvinyl acetate. As PVA, for example, complete PVA in which only several percent of acetic acid groups remain from so-called partially saponified PVA in which several tens percent of acetic acid groups remain can be used, and is not particularly limited.

Further, the metal alkoxide is a compound represented by a general formula, M (OR) n (M: metal such as Si, Ti, Al, Zr, or alkyl group such as R: CH ₃ or C ₂ H ₅ ). Specific examples include tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], triisopropoxyaluminum [Al (O-iso-C3H7) ₃ ] and the like. Among them, tetraethoxysilane and triisopropoxyaluminum are added. After decomposition, it is preferably used because it is relatively stable in an aqueous solvent.

  In the coating agent, known additives such as isocyanate compounds, silane coupling agents, dispersants, stabilizers, viscosity modifiers, colorants and the like are appropriately added as necessary, as long as the gas barrier properties are not impaired. Is also possible.

  As a method for applying the coating agent, conventionally known methods such as a dipping method, a roll coating method, a screen printing method, a spray method, and a gravure printing method that are usually used can be used.

  When the thickness of the gas barrier coating layers 4 and 24 is less than 0.01 μm after drying, it is difficult to obtain a uniform coating film, and when the thickness exceeds 50 μm, the coating film is cracked. In the range of about 0.01 to 50 μm.

Furthermore, other layers can be laminated on the transparent inorganic thin film layers 3 and 23 and the gas barrier coating layers 4 and 24. For example, a printing layer, an intermediate layer, a heat seal layer, and the like. The printing layer is provided for practical use as a packaging bag, etc., and various pigments, extender pigments and plasticizers, additives such as desiccants, stabilizers, etc. are added to the ink binder resin. Letters, designs, etc. composed of acrylic, nitrocellulose, rubber and vinyl chloride inks. The formation may be performed by a known printing method such as an offset printing method, a gravure printing method, a silk screen printing method, or a known coating method such as roll coating, knife edge coating, or gravure coating. The thickness may be about 0.1 to 2.0 μm.

  On the other hand, the laminated packaging material 20 according to the present invention is obtained by laminating the heat-sealable resin layer 26 via the adhesive layer 25 on the gas barrier coating layer 4 of the strong adhesion gas barrier transparent film 10 having the above-described configuration. Obtainable.

  As the adhesive constituting the adhesive layer 25, a general-purpose laminating adhesive can be used. For example, poly (ester) urethane, polyester, polyamide, epoxy, poly (meth) acrylic, polyethylene imine, ethylene- (meth) acrylic acid, polyvinyl acetate, (modified) polyolefin, A solvent type such as a polybutadiene type, a wax type, or a casein type, an aqueous type, and a hot melt type adhesive may be used.

The adhesive layer 25 is formed by a thin film forming means such as a direct gravure coating method, a reverse gravure coating method, a kiss coating method, a die coating method, a roll coating method, a dip coating method, a knife coating method, a spray coating method, or a fountain coating method. Can be formed. Further, the coating amount at that time is preferably about 0.1 to 8 g / m ² (dry state).

  The heat-sealable resin layer 26 is provided as a seal layer when a bag-shaped package or the like is formed, and may be any layer that can be melted by heat and fused to each other. For example, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, other polyethylene resins, polypropylene, ethylene-propylene copolymer resin, polyester resin, polyamide resin, ethylene-vinyl acetate copolymer Copolymers and saponified products thereof, polycarbonate resins, polyacrylonitrile resins, nitrocellulose, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers and their metal cross-linked products, polylactic acid It is made of biodegradable resin such as resin and other known resins. The thickness may be determined according to the purpose, and generally may be in the range of about 10 to 200 μm.

  As a method for laminating the heat-sealable resin layer 26 on the strong adhesion gas barrier transparent film 10, for example, a dry lamination method, a non-solvent lamination method, an extrusion lamination method, or the like can be used. Moreover, the laminated packaging material 20 of the present invention having excellent adhesion and gas barrier properties can be applied to a printed layer or other substrate on the gas barrier coating layer 4 of the strong adhesion gas barrier transparent film 10 according to the use and demand. The heat-sealable resin layer 6 may be laminated after laminating a film or the like.

  Hereinafter, an embodiment of the present invention will be described in more detail with reference to the drawings. However, the present invention is not limited thereto. “Parts” and “%” are based on weight unless otherwise specified.

First, primer agents A to F were prepared as follows.
<Adjustment of various primer agents>
(1) In a diluting solvent (ethyl acetate), each was mixed and stirred so that a hydroxyl-containing acrylic resin might be 100 weight part with respect to 1 weight part of double bond containing silane coupling agents. Next, an aromatic isocyanate compound is added to the mixed solution with an OH of a hydroxyl group-containing acrylic resin.
The primer agent A was added in such a manner that the NCO group was three times as much as the group.

  (2) In a diluting solvent (ethyl acetate), each was mixed and stirred so that a hydroxyl-containing acrylic resin might be 100 weight part with respect to 1 weight part of double bond containing silane coupling agents. Next, an aromatic isocyanate compound was added to this mixed solution so that the NCO group was 10 times equivalent to the OH group of the hydroxyl group-containing acrylic resin, and primer agent B was obtained.

  (3) In a diluting solvent (ethyl acetate), with respect to 1 part by weight of the N group-containing silane coupling agent, the hydroxyl group / methacrylic group-containing aromatic acrylic resin was mixed at 100 parts by weight and stirred. Next, an aliphatic isocyanate compound was added to this mixed solution so that the NCO group was 3 times equivalent to the OH group of the hydroxyl / methacrylic group-containing aromatic acrylic resin, thereby preparing primer agent C.

  (4) In a diluting solvent (ethyl acetate), each of the N group-containing silane coupling agent was mixed and stirred so that the hydroxyl group / methacryl group-containing aromatic acrylic resin would be 10 parts by weight. . Subsequently, an aliphatic isocyanate compound was added to the mixed solution so that the NCO group was 3 times equivalent to the OH group of the hydroxyl / methacrylic group-containing aromatic acrylic resin, thereby preparing a primer agent D.

  (5) In a diluting solvent (ethyl acetate), 1 part by weight of a double bond-containing silane coupling agent is added so that the hydroxyl / methacrylic group-containing aromatic acrylic resin is 100 parts by weight. A primer agent E was obtained by adding a solvent.

  (6) In a diluting solvent (ethyl acetate), an aliphatic isocyanate compound is added to an OH group of a hydroxyl group / methacrylic group-containing aromatic acrylic resin with respect to 1 part by weight of the hydroxyl group / methacrylic group containing aromatic acrylic resin. A primer solution F was prepared by diluting each of the mixed solutions added so that the group was 3 times equivalent.

  Next, on the corona-treated surface of a 12 μm thick biaxially stretched polyethylene terephthalate film (thermoplastic polymer film), a thin film made of the primer agent A is formed by a gravure coating method to a thickness of 0.1 μm, and a transparent primer layer is formed. Provided. Then, the transparent vapor deposition thin film layer (transparent inorganic thin film layer) which consists of aluminum oxide with a thickness of 20 nm was laminated | stacked on the transparent primer layer with the vacuum vapor deposition apparatus by an electron beam heating system. Further, a gas barrier coating liquid having the composition shown below was applied onto the transparent vapor-deposited thin film layer by heat and dried, and a gas barrier coating layer having a thickness of 0.5 μm was laminated. A strong adhesion gas barrier transparent film was obtained.

The gas barrier coating solution was prepared by adding 10 parts by weight of hydrochloric acid to 1 part by weight of a tetrafunctional silane coupling agent, stirring the mixture for 30 minutes, and hydrolyzing it with a solid content of 5 wt% (in terms of SiO ₂ ) and polyvinyl alcohol. It was obtained by mixing a 3 wt% aqueous solution.

  A strong adhesion gas barrier transparent film according to Example 2 was obtained in the same manner as in Example 1 except that the transparent primer layer was provided using the primer agent C.

  A gas barrier transparent film according to Example 3 for comparison was obtained in the same manner as in Example 1 except that the transparent primer layer was provided using the primer agent B.

  A gas barrier transparent film according to Example 4 for comparison was obtained in the same manner as in Example 1 except that the transparent primer layer was provided using the primer agent D.

  A gas barrier transparent film according to Example 5 for comparison was obtained in the same manner as in Example 1 except that the transparent primer layer was provided using Primer E.

  A gas barrier transparent film according to Example 6 for comparison was obtained in the same manner as in Example 1 except that the transparent primer layer was provided using the primer agent F.

<Manufacture of packaging materials>
On the gas barrier coating layer surfaces of the gas barrier transparent films of Examples 1 to 6, an intervening film made of a biaxially stretched polyamide film having a thickness of 15 μm was dry-laminated via an adhesive layer made of a two-component curable urethane adhesive. Furthermore, a low-density polyethylene film with a thickness of 50 μm is laminated on this intervening film by an adhesive layer made of a two-component curable urethane adhesive, and a polyolefin heat seal layer is provided. A laminated packaging material was obtained.

<Test 1>
The strong adhesion gas barrier transparent films according to Examples 1 and 2 and the transparent primer layers of the gas barrier transparent films according to Examples 3 to 5 were analyzed by ESCA. For the measurement, a measuring machine (Quantum 2000) manufactured by ULVAC-PHI was used, monochrome AlKα was used as the X-ray source, and the output was measured at 30 W (15 kV).

  In the gas barrier transparent films of Examples 1 to 4, the presence of C, N, O, and Si was confirmed. However, N was not detected in Example 5, and Si was not detected in Example 6. These detected elements are shown in [Table 1].

  Moreover, also about the element ratio (O / C, N / C, Si / C) in the surface of the transparent primer layer of the strong adhesion gas barrier transparent film of Examples 1-2 and the gas barrier transparent film of Examples 3-6 [ Table 1].

<Test 2>
Using each of the tightly adhered gas barrier transparent film according to Examples 1 and 2 and the gas barrier transparent film according to Examples 3 to 6, a pouch having a four-side seal portion is prepared, and each is filled with 150 g of water as a content, Retort sterilization treatment was performed at 121 ° C. for 30 minutes.

The oxygen transmission rate (cc / m ² / day) and peel strength (gr / 15 mm) before and after the retort sterilization treatment were measured, and the delamination occurrence after the retort was further observed by visual observation. Moreover, in the seal | sticker part, the part which detected the aluminum element with the fluorescent X ray apparatus from the biaxial polyethylene terephthalate film and the sealant film was estimated as the peeling part. The results are shown in [Table 1].

１）剥離強度は、３００ｍｍ／分の剥離速度で引っ張り測定した。

1) The peel strength was measured by pulling at a peel speed of 300 mm / min.

2) Oxygen transmission rate is an oxygen transmission measuring device; OXTRAN-1 manufactured by Modern Control
Measurement was performed in an atmosphere of 30 ° C. and 70% RH using 0 / 50A.

3) In the evaluation of the peeled surface, AlO is the cohesive failure of the inorganic oxide thin film layer, and ADH is the covered surface.
Represents peeling between the membrane layer and the adhesive layer.

  4) Observation of the occurrence of delamination was performed by bending the seal part of the pouch by 180 ° after the retort sterilization treatment. As a result of visual observation, the inorganic oxide thin film layer was found to be completely delaminated, x if partially delaminated, and ◯ if delamination was not found. expressed.

  As shown in [Table 1], before the retort sterilization treatment, all of the pouches have no problem in adhesion (there is no problem in practical use) and gas barrier properties. However, when the results after the retort sterilization treatment are seen, the pouch made of the strong adhesion gas barrier transparent film according to Examples 1 and 2 is not deteriorated in gas barrier properties, and is peeled off by the adhesive layer even when viewed from the peeled surface. It turns out that the sex is maintained. On the other hand, the pouch composed of the gas barrier transparent film according to Examples 3 to 6 has a deteriorating appearance after the retort sterilization treatment, and the adhesion between the film substrate and the transparent inorganic oxide thin film layer from the observation of the peeled surface. It turns out that there is not enough sex. Therefore, the strong adhesion gas barrier transparent film of the present invention does not deteriorate after gas retort sterilization, and there is no occurrence of delamination, etc. It was found to have resistance to retort treatment.

It is explanatory drawing which shows the general | schematic cross-section structure of the strong adhesion gas barrier transparent film of this invention. It is explanatory drawing which shows the general | schematic cross-section structure of the laminated packaging material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 21 ... Thermoplastic polymer film 2, 22 ... Transparent primer layer 3, 23 ... Transparent inorganic thin film layer 4, 24 ... Gas barrier coating layer 25 ... Adhesive layer 26 ... Heat-sealable resin layer 10 made of an inorganic oxide ... Strong adhesion gas barrier transparent film 20 ... Laminated packaging material

Claims (7)

At least one surface of the thermoplastic polymer film is mixed and stirred in a diluting solvent (ethyl acetate) so that the hydroxyl group-containing acrylic resin becomes 100 parts by weight with respect to 1 part by weight of the double bond-containing silane coupling agent. Then, a transparent inorganic thin film is formed through a transparent primer layer made of a primer agent prepared by adding an aromatic isocyanate compound to this mixed solution so that the NCO group is 3 times equivalent to the OH group of the hydroxyl group-containing acrylic resin. It is a strong adhesion gas barrier transparent film in which at least layers are laminated, and the transparent primer layer has the presence of C, N, O, Si by ESCA analysis (analysis conditions: X-ray source monochrome AlKα, X-ray output 30 W). confirmed, the element ratio (O / C, N / C , Si / C) each is 0.40, 0.10, is 0.05 or less Strong adhesion barrier transparent film characterized in that there. On at least one surface of the thermoplastic polymer film, the hydroxyl group / methacrylic group-containing aromatic acrylic resin is 100 parts by weight with respect to 1 part by weight of the N group-containing silane coupling agent in the diluent solvent (ethyl acetate). Mixing and stirring, and then adding an aliphatic isocyanate compound to this mixed solution so that the NCO group is 3 times equivalent to the OH group of the hydroxyl / methacrylic group-containing aromatic acrylic resin. a strong adhesion barrier transparent film transparent inorganic thin layer through the transparent primer layer is at least stacked, the surface of the transparent primer layer, ESCA analysis (analysis conditions: X-ray source monochrome AlK, X-ray output 30 W) by , C, N, O, presence of Si has been confirmed, the element ratio (O / C, N / C , Si / C) each is 0.40 or more , 0.10, strong adhesion barrier transparent film you characterized that it is 0.05 or less. The gas barrier coating film according to claim 1 or 2, wherein a gas barrier coating layer is laminated on the transparent inorganic thin film layer. The strong adhesion gas barrier transparent film according to any one of claims 1 to 3 , wherein the thermoplastic polymer film is a polyethylene terephthalate film or a polyamide film. The strong adhesion gas barrier transparent film according to any one of claims 1 to 4 , wherein the transparent inorganic thin film layer is a vapor-deposited thin film made of either silicon oxide or aluminum oxide. The gas barrier coating layer, the hydroxyl group-containing polymer, from claim 3, characterized by having a component at least one metal alkoxide and / or a hydrolyzate thereof and / or a polymer of claim 5 The strong adhesion gas barrier transparent film according to any one of the above. A laminated packaging material, wherein at least a heat-sealable resin layer is laminated on the strong adhesion gas barrier transparent film according to any one of claims 1 to 6 via an adhesive layer.

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