JP2005178149A - Low adsorbent laminated packaging material, and package and lid material using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low adsorbent lamainated packaging material for preventing the adsorption of a medicinally effective component, an aroma component or the like contained in content such as food, a beverage, a toiletry article, a medicine and the like and the reduction of the medicinally effective component or the aroma component with the elapse of time, improving the adhesion of a thermal adhesive resin layer to the surface of a vapor deposition layer comprising an inorganic oxide, especially imparting gas barrier properties such as aluminum oxide, silicon oxide, magnesium oxide or the like, excellent in low temperature heat sealability, heat sealing strength, gas barrier properties, processing properties such as bag making or the like and so on, a package such as a bag or the like using the same and a lid material. <P>SOLUTION: The low adsorbent laminated packaging material is constituted by laminating at least a heat-sealable thermoplastic resin layer on the vapor deposition thin film layer or a gas barrier film layer comprising the inorganic oxide on a transparent gas barrier film by coating. A molded product and a lid material using the papckaging material are also disclosed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a low adsorptive laminated packaging material, and more specifically, by reducing the thickness of a heat-sealable thermoplastic resin layer (sealant layer) in the innermost layer of the packaging material, food, beverage, toiletry products, Thermoplastics that adsorb to packaging materials such as medicinal ingredients and fragrance ingredients contained in the contents of pharmaceuticals, etc., prevent the medicinal ingredients and fragrance ingredients from decreasing over time, and that can be heat-sealed especially with gas barrier films Regarding low-adhesive laminated packaging materials that are excellent in adhesion between the resin layer, low-temperature heat sealability and heat seal strength, gas barrier properties, bag processing, etc. It is used as a packaging body such as a bag using the packaging material and a lid.

  Generally used packaging materials have a structure in which a gas barrier layer is laminated on a base material via an adhesive layer or a polyethylene resin layer having a thickness of 15 μm or more, and a polyolefin resin film is laminated thereon as a sealant layer. Is often used. When packaging containing volatile menthol, naphthalene, other scent ingredients or medicinal ingredients in a bag using this packaging material, those ingredients will be adsorbed by the film of the innermost sealant layer There are many cases. In order to prevent such adsorption, a method of thinning the film of the sealant layer, a method of using a polyester film, or a method of coating the whole surface or part of the heat sealant as the sealant layer has been studied.

However, the current method for thinning the sealant film is that the minimum thickness is about 15 μm due to the limitations of the film forming technology, and the polyester film has a high cost and is resistant to content. Was also insufficient. In addition, the method of applying the heat sealant as the sealant layer is, in particular, the resin system used for the heat sealant is polyester, ethylene vinyl acetate, chlorinated polypropylene, chlorinated polyethylene, ethylene copolymer, In the case of polyurethane, vinyl chloride / vinyl acetate copolymer, etc., a dry coating amount of at least 5 g / m ^{2 is} required to maintain the heat seal strength due to the cohesive strength of the coating film. There was a limit to the reduction of the amount of adsorbed medicinal ingredients to the heat sealant coating layer. Furthermore, those using chlorinated substances may generate harmful substances when incinerated after disposal, and should be avoided in the future. In addition, when the sealant layer is formed by the part coat method, the gas barrier layer comes into contact with the contents when the contents are packaged. Therefore, the active ingredient of the contents attack the inner surface of the packaging material violently. There have been problems such as deterioration of the layer and deterioration of the heat seal strength due to deterioration of the part-coated heat sealant itself. Furthermore, when formed by the above part coat method, when post-processing such as bag making using the packaging material, there is a difference in the presence or absence of tack, slipperiness, etc. in the application part and non-application part of the heat sealant. As a result, the processability is poor, and the gas barrier layer of the packaging material is damaged due to friction with various machines in the post-processing step, and the gas barrier property is deteriorated.

Patent documents are described below.
JP-A-10-329264 JP, 10-45176, A Furthermore, in the conventional packaging material, the thing which laminated the barrier base material and sealant base materials, such as aluminum foil and a vapor deposition plastic film, is used widely. In a packaging bag in which a base material layer is provided on one side and a heat-adhesive resin layer is provided on the entire other surface, and the heat-adhesive resin layer is thermally bonded with the heat-adhesive resin layer. It is composed of at least one of a coalesced resin, an ethylene copolymer resin, an ester resin, a urethane resin, and a modified polyolefin, and the coating amount at the time of drying of the thermal adhesive resin layer is 5 to 10 g / m 2. A packaging bag has been proposed as a low-absorption packaging bag (see Patent Document 1) When the application amount in a dry state is at least 5 g / m 2 or more, the application of this heat sealant There was a limit to reducing the amount of adsorbed medicinal components on the layer, and a non-adsorbing material in which a heat-adhesive resin layer was formed on the aluminum foil surface or the vapor-deposited surface of an inorganic material such as aluminum, silicon oxide, or aluminum oxide was proposed However, the adhesion of the heat-adhesive resin layer to the surface of the vapor deposition layer of an inorganic material such as aluminum, silicon oxide, and aluminum oxide is not sufficient, and there is a problem in adhesion.

  The present invention has been made in order to solve the above-mentioned problems, and adsorbs it to packaging materials such as medicinal ingredients and aroma ingredients contained in the contents of foods, beverages, toiletries, pharmaceuticals, etc. Improves adhesion of heat-adhesive resin layer to the surface of deposited thin film layers of inorganic oxides such as aluminum oxide, silicon oxide and magnesium oxide, which prevents components and fragrance components from decreasing over time, especially providing gas barrier properties And providing a low-adsorptive laminated packaging material having excellent low-temperature heat sealability and heat seal strength, gas barrier properties, processing suitability such as bag making, etc., and a bag-like package body and lid material using the packaging material. With the goal.

In order to achieve the above object, that is, the invention according to claim 1,
A low-adsorption multilayer packaging characterized by laminating at least a thermoplastic resin layer heat-sealable by coating on a vapor-deposited thin film layer or gas barrier coating layer made of an inorganic oxide provided on a transparent gas barrier film Material.

The invention according to claim 2
A low-adsorption multilayer packaging material, wherein another substrate is laminated on a film substrate made of a transparent plastic constituting the low-adsorption multilayer packaging material according to claim 1.

The invention according to claim 3
The transparent gas barrier film has a general formula R′Si (OR) ₃ (R ′: alkyl group, vinyl group, glycidoxypropyl group, R: alkyl group, etc.) on at least one surface of a substrate made of a transparent plastic material. A transparent primer layer composed of a trifunctional organosilane or a hydrolyzate of the organosilane, a composite of acrylic polyol and an isocyanate compound, and a deposited thin film layer composed of an inorganic oxide having a thickness of 5 to 300 nm. The low-adsorption multilayer packaging material according to claim 1 or 2.

The invention according to claim 4
The deposited thin film layer made of the inorganic oxide is obtained by at least one of a physical vapor deposition method (PVD method) and a chemical vapor deposition method (CVD method), and includes Al, Si, Mg, Sn, Zr, The low-adsorption multilayer packaging material according to any one of claims 1 to 3, wherein the low-adsorption multilayer packaging material is made of an oxide of at least one metal selected from the group consisting of Ti, In, Zn, and Sb. is there.

The invention according to claim 5
The low-adsorbent laminated packaging material according to any one of claims 1 to 4, wherein the heat-sealable thermoplastic resin contains a maleic anhydride-modified polypropylene resin as a main component.

The invention according to claim 6
The coating amount of the heat-sealable thermoplastic resin layer is in a dry state, is a low absorptive laminated packaging material according to claim 5, wherein the range of 0.5 to 5.0 g / m ² .

The invention according to claim 7
The low-adsorption multilayer packaging material according to any one of claims 1 to 6, wherein an epoxy group is contained in R 'constituting the trifunctional organosilane.

The invention according to claim 8 is
The low-adsorption multilayer packaging material according to any one of claims 1 to 7, wherein a reaction catalyst is added to the composite.

The invention according to claim 9 is
9. The low adsorptive laminated packaging material according to claim 8, wherein the reaction catalyst is a tin compound.

The invention according to claim 10 is
In the composite, a metal alkoxide represented by the general formula M (OR) n (M: metal element, R: alkyl group such as CH ₃ and C ₂ H ₅ , n: oxidation number of metal element) or The low adsorptive laminated packaging material according to any one of claims 1 to 9, wherein a hydrolyzate of the metal alkoxide is added.

The invention according to claim 11 is
In the composite, a metal alkoxide represented by the general formula M (OR) n (M: metal element, R: alkyl group such as CH ₃ and C ₂ H ₅ , n: oxidation number of metal element) or The low adsorptive laminated packaging material according to any one of claims 1 to 10, wherein a hydrolyzate of the metal alkoxide is added.

The invention according to claim 12
The thickness of the said transparent primer layer is the range of 0.01-2 micrometers, It is a low adsorptive laminated packaging material in any one of Claims 1-11 characterized by the above-mentioned.

The invention according to claim 13 is
The thickness of the said transparent primer layer is the range of 0.01-2 micrometers, The low adsorptive laminated packaging material in any one of Claims 1-12 characterized by the above-mentioned.

The invention according to claim 14 is
A gas barrier coating layer is further laminated on the vapor-deposited thin film layer made of an inorganic oxide provided on the transparent gas barrier film, and the gas barrier coating layer comprises a water-soluble polymer and (a) one type It is a layer formed by applying a coating agent mainly comprising an aqueous solution containing at least one of the above metal alkoxide and its hydrolyzate or at least one of (b) tin chloride or a water / alcohol mixed solution, followed by heating and drying. The low adsorptive laminated packaging material according to any one of claims 1 to 13.

The invention according to claim 15 is
The low-adsorption multilayer packaging material according to claim 14, wherein the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof.

The invention according to claim 16 provides
The low-adsorbent laminated packaging material according to claim 14 or 15, wherein the water-soluble polymer is polyvinyl alcohol.

The invention according to claim 17 provides
It is a package formed by shape | molding the heat-sealable thermoplastic resin layer laminated | stacked on the low adsorptivity laminated packaging material of any one of Claims 1-16 as an innermost layer.

The invention according to claim 18 provides
A cover material comprising a heat-sealable thermoplastic resin layer laminated on the low-adsorption multilayer packaging material according to any one of claims 1 to 16 as an innermost layer.

  According to the present invention, it is adsorbed to packaging materials such as medicinal components and aroma components contained in the contents of foods, beverages, toiletries, pharmaceuticals, etc., and the medicinal components and aroma components are prevented from decreasing over time, in particular. Improves the adhesion of the heat-adhesive resin layer to the vapor-deposited thin film layer surface of inorganic oxides such as aluminum oxide, silicon oxide, and magnesium oxide that impart gas barrier properties, low-temperature heat sealability and heat seal strength, gas barrier properties, bag making It is possible to provide a low-adsorption multilayer packaging material having excellent processability and the like, a low-adsorption package such as a low-adsorption bag using the packaging material, and a lid.

  Specifically, as the heat-sealable heat-adhesive resin layer in the present invention, by using a polypropylene resin mainly composed of maleic anhydride-modified polypropylene resin, aluminum oxide, silicon oxide provided on the transparent gas barrier film, The adhesion due to the bonding of acidic groups of the heat-adhesive resin layer to the surface of the vapor-deposited thin film layer of inorganic oxide such as magnesium oxide is improved, and the content resistance is improved.

  Then, a heat-adhesive resin layer that can be heat-sealed is applied to the entire surface of the vapor-deposited thin film layer of an inorganic oxide such as aluminum oxide, silicon oxide, or magnesium oxide provided on the transparent gas barrier film. It is possible to avoid the deterioration of the gas barrier property accompanying the deterioration of the deposited thin film layer of the object. Further, by applying a heat-sealable heat-adhesive resin layer over the entire surface of the inorganic oxide vapor-deposited thin film layer, processability such as bag making is improved.

  Moreover, as a heat-sealable heat-adhesive resin layer used in the present invention, it is excellent in hygiene by using a polypropylene resin mainly composed of maleic anhydride-modified polypropylene resin. It can be used as a low adsorption packaging material in a wide range of fields. In addition, by using an ethylene-polypropylene copolymer as a heat-adhesive resin layer that can be heat-sealed, it is possible to lower the baking temperature at the time of coating processing, and it is possible to prevent damage to the transparent gas barrier film due to the baking temperature, The temperature can be lowered during heat sealing.

Furthermore, a dispersion type coating liquid in which a polypropylene resin containing a maleic anhydride-modified polypropylene resin as a main component is present as a polymer crystal in a coating state has a molecular weight equivalent to that of an extruded film by baking after coating. Since a heat-adhesive resin layer that can be heat-sealed is obtained, a heat-adhesive resin layer composed of a very thin coating film can be formed. Since a heat-adhesive resin layer consisting of a very thin polymer film can be formed, the adsorption of medicinal components and aroma components contained in the contents to the packaging material is reduced, and the cost and weight of the packaging material are reduced. Possible and environmentally friendly. In addition, since a heat-adhesive resin layer composed of a stable coating film is obtained immediately after coating, an aging step such as a reactive heat seal lacquer is not required, and stable sealing strength can be obtained from the initial stage of coating. Furthermore, since the cohesive strength of the heat-adhesive resin layer is high, deterioration of the heat-adhesive resin layer due to the contents, stickiness, etc. can be avoided as compared with the solvent-based emulsion type heat seal lacquer. The content is excellent in take-out property without adhering to the inner surface of the packaging material.

  Hereinafter, a low-adsorption multilayer packaging material and a bag-like package using the packaging material as an embodiment of the present invention will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view showing an example of the laminated packaging material of the present invention. FIG. 2 is a cross-sectional view showing another example of the laminated packaging material of the present invention. FIG. 3 is a plan view showing a packaging bag made of pillow bags as an example of a package using the low-adsorption multilayer packaging material of the present invention. 4 is a perspective view of the pillow packaging bag shown in FIG.

  As an example of the low adsorptive laminated packaging material of the present invention, as shown in FIG. 1, the low adsorptive laminated packaging material A is composed of a trifunctional organosilane, acrylic polyol, isocyanate on a film substrate 1 made of a transparent plastic material. Heat that can be heat-sealed on a gas barrier coating layer 6 of a transparent gas barrier film 5 in which a transparent primer layer 2 made of a compound or the like, a vapor deposition thin film layer 3 made of an inorganic oxide, and a gas barrier coating layer 4 are sequentially laminated. This is a laminated packaging material having a configuration in which the adhesive resin layer 6 is formed by application and laminated. In this case, the gas barrier coating layer 6 may not be provided depending on the required quality.

  In addition, as another example of the low adsorptive laminated packaging material of the present invention, as shown in FIG. 2, the adsorptive laminated packaging material B is composed of a trifunctional organosilane and acrylic on a film substrate 1 made of a transparent plastic material. A film substrate 1 made of a transparent plastic material of a transparent gas barrier film 5 in which a transparent primer layer 2 made of a composite such as a polyol or an isocyanate compound, a vapor deposition thin film layer 3 made of an inorganic oxide, and a gas barrier coating layer 4 are sequentially laminated. It is a laminated packaging material having a configuration in which another base material 7 is laminated via an adhesive layer 8. In this case, the gas barrier coating layer 6 may not be provided depending on the required quality.

  The substrate 7 laminated on the transparent gas barrier film 5 used in the present invention is not particularly limited. For example, paper or a plastic film can be used. Examples of the plastic film include polyethylene terephthalate (PET) and polyethylene naphthalate. Polyester films such as (PEN), polyolefin films such as polypropylene, polystyrene films, polyamide films such as 6-nylon, polycarbonate films, polyacrylonitrile films, polyimide films, etc. are used and have mechanical strength and dimensional stability Is good. In particular, among these, a film arbitrarily stretched in the biaxial direction is preferably used.

  In addition, a printing layer can be suitably provided in the base material 7 as needed. The printed layer is formed for practical use as a balloon or the like. For example, various types of pigments, extender pigments, plasticizers, drying agents, stabilizers and other additives are added to conventionally used ink binder resins such as urethanes, acrylics, nitrocelluloses, and rubbers. It is a layer composed of ink. Characters, pictures, and the like are formed by this printing. As a forming method, for example, a known printing method such as an offset printing method, a gravure printing method, or a silk screen printing method, or a known coating method such as a roll coating, a knife edge coating, or a gravure coating can be used. The dry film thickness (solid content) of the printing layer may be 0.1 to 2.0 μm.

  Below, the transparent gas barrier film 5 used by this invention is demonstrated in detail.

  The film substrate 1 made of a transparent plastic material of the transparent gas barrier film 5 used in the present invention is preferably a transparent film in order to make use of the transparency of the deposited thin film layer. For example, polyethylene terephthalate (PET), polyester film such as polyethylene naphthalate, polyolefin film such as polyethylene and polypropylene, polystyrene film, polyamide film, polyvinyl chloride film, polycarbonate film, polyacrylonitrile film, polyimide film, etc. are used. Either stretched or unstretched, and those having mechanical strength and dimensional stability are preferred. These are processed into a film and used. In particular, polyethylene terephthalate arbitrarily stretched in the biaxial direction is preferably used. In addition, various known additives and stabilizers such as antistatic agents, ultraviolet inhibitors, plasticizers, lubricants, and the like may be used on the surface of the substrate 1 to improve the adhesion to the thin film. In addition, corona treatment, low temperature plasma treatment, ion bombardment treatment may be performed as pretreatment, and chemical treatment, solvent treatment, and the like may be performed.

  The thickness of the film substrate 1 made of a transparent plastic material is not particularly limited, but is suitable as a packaging material, may be laminated with other layers, and comprises a transparent primer layer 4 and an inorganic oxide. Considering the workability when forming the vapor-deposited thin film layer 3 and the gas barrier coating layer 4, it is practically in the range of 3 to 200 μm and preferably 6 to 30 μm depending on the application.

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

  The transparent primer layer 2 of the present invention is provided on a film substrate 1 made of a transparent plastic material, enhances the adhesion between the substrate 1 and the deposited thin film layer 3 made of an inorganic oxide, and generates delamination. The purpose is to prevent.

  As a result of intensive studies, the present inventors have been able to use a trifunctional organosilane or a hydrolyzate thereof, an acrylic polyol, an isocyanate compound, etc. as a primer resin in order to achieve the above object in the present invention. I found out that it was a thing.

Furthermore, the composite which comprises the transparent primer layer 2 is demonstrated in detail. The trifunctional organosilane is a general formula R′Si (OR) ₃ such as ethyltrimethoxysilane, vinyltrimethoxysilane, glycidoxypropyltrimethoxysilane (where R ′ is an alkyl group, vinyl group, glycidoxypropyl group, etc.) , R is an alkyl group or the like), or a hydrolyzate thereof. Of these, glycidoxytrimethoxysilane, epoxycyclohexylethyltrimethoxysilane, and the like in which an epoxy group is contained in R ′ are particularly preferable. A method for obtaining a hydrolyzate can be obtained by a known method such as a method of performing hydrolysis by directly adding an acid, an alkali or the like to a trifunctional organosilane.

  An acrylic polyol is a polymer compound obtained by polymerizing an acrylic acid derivative monomer, or a polymer compound obtained by copolymerizing an acrylic acid derivative monomer and other monomers, and has a hydroxyl group at the terminal. It is to be reacted with an isocyanate group of an isocyanate compound added later. Among these, those obtained by polymerizing acrylic acid derivative monomers such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate alone, and acrylic polyols obtained by copolymerizing with other monomers such as styrene are preferably used. In consideration of the reactivity with the isocyanate compound, the hydroxyl value is preferably between 5 and 200 (KOHmg / g).

The mixing ratio of acrylic polyol and trifunctional organosilane is from 1/1 to 100 / by weight.
It is preferably in the range of 1, more preferably in the range of 2/1 to 50/1. The dissolving and diluting solvent is not particularly limited as long as it can be dissolved and diluted. For example, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as methyl ethyl ketone, A mixture of aromatic hydrocarbons such as toluene and xylene alone and arbitrarily can be used. However, since an aqueous solution of hydrochloric acid or the like may be used to hydrolyze trifunctional organosilane or the like, it is more preferable to use a solvent in which isopropyl alcohol or the like and ethyl acetate that is a polar solvent are arbitrarily mixed as a cosolvent.

In addition, a reaction catalyst may be added to accelerate the reaction when the trifunctional organosilane and acrylic polyol are blended. The catalyst to be added is a tin compound such as tin chloride (SnCl ₂ , SnCl ₄ ), tin oxychloride (SnOHCl, Sn (OH) ₂ Cl ₂ ), tin alkoxide and the like in terms of reactivity and polymerization stability. Is preferred. These catalysts may be added directly at the time of blending, or may be added after being dissolved in a solvent such as methanol. If the addition amount is too small or too large, the catalytic effect cannot be obtained, so the molar ratio with respect to the trifunctional organosilane is preferably in the range of 1/10 to 1/10000, and more preferably 1/100 to 1 More preferably, it is in the range of / 2000.

  Furthermore, the isocyanate compound to be mixed is added in order to increase the adhesion with the base material 1 or the vapor-deposited thin film layer 3 made of an inorganic oxide by a urethane bond formed by reacting with an acrylic polyol. Acts as a curing agent. To achieve this, as isocyanate compounds, monomers such as aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), aliphatic xylene diisocyanate (XDI), and hexadiisocyanate (HMDI); These polymers and derivatives are used, and these are used alone or as a mixture.

  The blending ratio of the acrylic polyol and the isocyanate compound is not particularly limited, but if the isocyanate compound is too small, curing may be poor, and if it is too much, blocking or the like occurs and there is a problem in processing. Therefore, the blending ratio of the acrylic polyol and the insocyanate compound is preferably that the NCO group derived from the isocyanate compound is 50 times or less of the OH group derived from the acrylic polyol, and particularly preferably the NCO group and the OH group are blended in an equivalent amount. This is the case. As a mixing method, a known method can be used and is not particularly limited.

Furthermore, in order to improve the liquid stability during preparation of the composite, it is possible to add a metal alkoxide or a hydrolyzate thereof. The metal alkoxide is a general formula M (OR) n (M is Si, Al, Ti, Zr) such as tetraethoxysilane [Si (OC ₄ H ₅ ) ₄ ], tripropoxy aluminum [Al (OC ₃ H ₇ ) ₃ ], etc. Or a metal such as R, an alkyl group such as CH ₃ or C ₂ H ₅ ), or a hydrolyzate thereof. Among these, tetraethoxysilane, tripropoxyaluminum, or a mixture of both is preferable because it is relatively stable in an aqueous solvent. The metal alkoxide hydrolyzate may be hydrolyzed with the trifunctional organosilane, or a metal alkoxide hydrolyzate may be added.

  The mixing ratio of the trifunctional organosilane and the metal alkoxide is preferably in the range of 10: 1 to 1:10 in terms of molar ratio from the viewpoint of liquid stability. Preferably, both are blended in equimolar amounts.

The composite coating is obtained by hydrolyzing such trifunctional organosilane in advance or by hydrolyzing trifunctional organosilane with metal alkoxide (
At this time, the above-mentioned reaction catalyst may be used) is mixed with an acrylic polyol or an isocyanate compound to prepare a composite solution, or trifunctional organosilane and acrylic polyol are mixed in advance in a solvent (at this time) The above-mentioned reaction catalyst or metal alkoxide may be added) Hydrolyzed reaction, or a mixture of trifunctional organosilane and acrylic polyol (In this case, the above-mentioned reaction catalyst or metal alkoxide may be added) The substrate 1 is formed by coating the base material 1 with an isocyanate compound added to prepare a composite solution.

  Various additives such as tertiary amines, imidazole derivatives, metal salt compounds of carboxylic acids, quaternary ammonium salts, quaternary phosphonium salts and other curing accelerators, phenolic, sulfur-based, phosphite-based, etc. It is also possible to add an antioxidant, a leveling agent, a flow regulator, a catalyst, a crosslinking reaction accelerator, a filler and the like.

  The thickness of the transparent primer layer 2 is not particularly limited as long as a uniform coating film can be formed, but is generally preferably in the range of 0.01 to 2 μm. When the thickness is less than 0.01 μm, it is difficult to obtain a uniform coating film, and the adhesion may be lowered. On the other hand, when the thickness exceeds 2 μm, the coating film cannot be kept flexible because it is thick, and the coating film may be cracked due to external factors, which is not preferable. Particularly preferred is a range of 0.05 to 0.5 μm.

  As a method for forming the transparent primer layer 2, 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 may be used. it can. About drying conditions, generally used conditions may be used.

  Moreover, as a vapor deposition material which comprises the vapor deposition thin film layer 5 which consists of an inorganic oxide of the transparent gas barrier film used by this invention, at least one of a physical vapor deposition method (PVD method) and a chemical vapor deposition method (CVD method) is used. An oxide of at least one metal selected from the group consisting of Al, Si, Mg, Sn, Zr, Ti, In, Zn, and Sb can be given.

  The metal oxide preferably used for the vapor deposition thin film layer 5 made of such an inorganic oxide is one or more selected from Al, Si, Mg, Zr, Ti, Sn, In, Zn, and Sb. Specifically, silicon oxide, silicon carbide oxide, aluminum oxide, magnesium oxide, cerium oxide, hafnium oxide, tantalum oxide, titanium oxide (for example, titanium dioxide, titanium trioxide, or titanium monoxide) ), Yttrium oxide, zirconium oxide (for example, zirconium monoxide), and the like. In particular, silicon oxide and / or silicon carbide oxide are more preferably used from the viewpoint of production stability, safety, and cost. .

  As the film thickness of the vapor-deposited thin film layer 3 made of the above inorganic oxide in the present invention, the optimum condition varies depending on the type and configuration of the inorganic compound to be used, but generally within the range of 5 to 300 nm is desirable. It is selected appropriately. However, if the film thickness is less than 5 nm, a uniform film may not be obtained or the film thickness may not be sufficient, and the function as a gas barrier material may not be sufficiently achieved. On the other hand, when the film thickness exceeds 300 nm, flexibility cannot be maintained in the thin film, and the thin film may be cracked due to external factors such as bending and pulling after the film formation. The thickness of the deposited thin film layer 5 is preferably in the range of 10 to 150 nm.

There are various methods for forming the vapor-deposited thin film layer 3 made of an inorganic oxide on the transparent primer layer 2, and it can be formed by a normal vacuum vapor deposition method, but other thin film forming methods such as sputtering and ion plating. Alternatively, a plasma vapor deposition method (CVD) or the like can be used. However, considering productivity, the vacuum deposition method is the best at present. As the heating means of the vacuum deposition apparatus by the vacuum deposition method, an electron beam heating method, a resistance heating method, or an induction heating method is preferable. In order to improve the adhesion between the thin film and the base material and the denseness of the thin film, a plasma assist method or an ion It is also possible to use a beam assist method. In addition, in order to increase the transparency of the deposited film, it is possible to carry out reactive deposition by blowing oxygen gas or the like during deposition.

  The gas barrier coating layer 4 used in the present invention is provided on the vapor-deposited thin film layer 4 made of an inorganic oxide in order to provide a gas barrier property as high as that of an aluminum foil depending on the required quality.

  The gas barrier coating layer 4 is mainly composed of an aqueous solution or a water / alcohol mixed solution containing at least one of a water-soluble polymer and (a) one or more metal alkoxides and hydrolysates or (b) tin chloride. It is formed using a coating agent. Mineralize a solution in which water-soluble polymer and tin chloride are dissolved in an aqueous (water or water / alcohol mixed) solvent, or a solution in which metal alkoxide is directly or hydrolyzed beforehand. The deposited thin film layer 3 made of oxide is formed by coating and heating and drying. Each component contained in the coating agent will be described in more detail.

  Examples of the water-soluble polymer used in the coating agent in the present invention 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 as the coating agent of the laminate of the present invention, the gas barrier property is most excellent. The PVA here is generally obtained by saponifying polyvinyl acetate, and includes from so-called partially saponified PVA in which several dozen percent of acetate groups remain to complete PVA in which only several percent of acetate groups remain. There is no particular limitation.

The tin chloride may be stannous chloride (SnCl ₂ ), stannic chloride (SnCl ₄ ), or a mixture thereof, and may be used as an anhydride or a hydrate.

Furthermore, the metal alkoxide is represented by a general formula M (OR) n (M) such as tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], triisopropoxy aluminum [Al (O-2′-C ₃ H ₇ ) ₃ ]. : Metal such as Si, Ti, Al, Zr, R: alkyl group such as CH ₃ and C ₂ H ₅ ). Among these, tetraethoxysilane and triisopropoxyaluminum are preferable because they are relatively stable in an aqueous solvent after hydrolysis.

  Each of the above components can be added to the coating agent alone or in combination, and further, an isocyanate compound, a silane coupling agent, or a dispersant, stabilizer, viscosity adjustment, as long as the gas barrier properties of the coating agent are not impaired. Known additives such as coloring agents and coloring agents can be added.

  For example, the isocyanate compound added to the coating agent has two or more isocyanate groups (NCO groups) in the molecule. For example, monomers such as tolylene diisocyanate, triphenylmethane triisocyanate, and tetramethylxylene diisocyanate. And their polymers and derivatives.

As a method for applying the coating agent, conventionally known means such as a dipping method, a roll coating method, a screen printing method, a spray method and the like that are usually used can be used. The thickness of the coating varies depending on the type of coating agent and the processing conditions, but it is sufficient that the thickness after drying is 0.01 μm or more. However, if the thickness exceeds 50 μm, cracks are likely to occur in the film. The range of 01-50 micrometers is preferable.

  The heat-sealable heat-adhesive resin layer 6 used in the present invention is provided as an adhesive layer when a package body such as a bag is formed. As the heat-adhesive resin that can be heat-sealed, a resin mainly composed of maleic anhydride-modified polypropylene resin is used, and it is formed by applying on the transparent gas barrier film 5 as a dispersion coating liquid.

  As the heat-sealable heat-adhesive resin layer in the present invention, an inorganic material such as aluminum oxide, silicon oxide, and magnesium oxide provided on the transparent gas barrier film by using a polypropylene resin mainly composed of maleic anhydride-modified polypropylene resin. The adhesion due to the bonding of acidic groups of the heat-adhesive resin layer to the oxide vapor-deposited thin film layer surface is improved, and the content resistance is improved.

  Then, a heat-adhesive resin layer that can be heat-sealed is applied to the entire surface of the vapor-deposited thin film layer of an inorganic oxide such as aluminum oxide, silicon oxide, or magnesium oxide provided on the transparent gas barrier film. It is possible to avoid the deterioration of the gas barrier property accompanying the deterioration of the deposited thin film layer of the object. Further, by applying a heat-sealable heat-adhesive resin layer over the entire surface of the inorganic oxide vapor-deposited thin film layer, processability such as bag making is improved.

  Moreover, as a heat-sealable heat-adhesive resin layer used in the present invention, it is excellent in hygiene by using a polypropylene resin mainly composed of maleic anhydride-modified polypropylene resin. It can be used as a low adsorption packaging material in a wide range of fields. In addition, by using an ethylene-polypropylene copolymer as a heat-adhesive resin layer that can be heat-sealed, it is possible to lower the baking temperature at the time of coating processing, and it is possible to prevent damage to the transparent gas barrier film due to the baking temperature, The temperature can be lowered during heat sealing.

  Furthermore, a dispersion type coating liquid in which a polypropylene resin containing a maleic anhydride-modified polypropylene resin as a main component is present as a polymer crystal in a coating state has a molecular weight equivalent to that of an extruded film by baking after coating. Since a heat-adhesive resin layer that can be heat-sealed is obtained, a heat-adhesive resin layer composed of a very thin coating film can be formed. Since a heat-adhesive resin layer consisting of a very thin polymer film can be formed, the adsorption of medicinal components and aroma components contained in the contents to the packaging material is reduced, and the cost and weight of the packaging material are reduced. Possible and environmentally friendly. In addition, since a heat-adhesive resin layer composed of a stable coating film is obtained immediately after coating, an aging step such as a reactive heat seal lacquer is not required, and stable sealing strength can be obtained from the initial stage of coating. Furthermore, since the cohesive strength of the heat-adhesive resin layer is high, deterioration of the heat-adhesive resin layer due to the contents, stickiness, etc. can be avoided as compared with the solvent-based emulsion type heat seal lacquer. The content is excellent in take-out property without adhering to the inner surface of the packaging material.

As an adhesive constituting the adhesive layer 8 for laminating the base material 7 and the film base material 1 made of the transparent plastic material of the transparent gas barrier film 5 used in the present invention, for example, an adhesive layer for dry lamination is used. Specifically, the constituting adhesive is a two-component curable urethane adhesive, a polyester urethane adhesive, a polyether urethane adhesive, an acrylic adhesive, a polyester adhesive used in dry lamination, etc. Adhesives, polyamide adhesives, epoxy adhesives, and the like can be used. In general, a two-component mixed adhesive in which a main agent having a hydroxyl group and a curing agent having an isocyanate group are mainly used, and the application method is a gravure coating method, a roll coating method, or the like. The application amount of the adhesive is 1 to 5 g / m ² (dry state).

  Using the low-adsorption multilayer packaging material of the present invention obtained above, a heat-sealable thermoplastic resin layer laminated on the low-adsorption multilayer packaging material is formed as the innermost layer, for example, when making bags There are various forms such as a three-side seal bag, a four-side seal bag, a gusset packaging bag, and a pillow packaging bag.

  For example, as shown in FIG. 5, in order to form a three-side sealed bag from the low-adsorption multilayer packaging material of the present invention, for example, a known die roll type automatic filling packaging machine 13 is used, and the inner layer side of the multilayer packaging material is On the upper side, the laminated packaging material 14 is supplied to the guide roll 15 so that the substrate is on the lower side, the laminated packaging material 14 is folded in half by the lead 16, and a filling machine (not shown) is sandwiched between the folded folded packaging materials. 2), the left end of the laminated packaging material folded in half with the vertical seal roll 17 is heat-sealed.

  Next, after the horizontal seal 19, after filling a certain amount of content, the horizontal seal roll 18 heats it in the horizontal direction, the horizontal heat seal portion 19 is cut with a knife 20, and the three-way filled with the content The seal bag 21 is manufactured. If a four-side sealed die roll automatic filling and packaging machine is used, a four-side sealed bag can be obtained.

  In the method for producing a pillow packaging bag using the low-adsorption multilayer packaging material according to the present invention, examples of the heat seal method include a bar seal, a rotary roll seal, It can be performed by a known method such as a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal or the like. Heat seal forms such as joint-sealed seal type, pleated seal type, flat bottom seal type, square bottom seal type, boat bottom seal type, etc. Various types of pillow-packaging bags can be manufactured.

  For example, FIG. 3 shows an example of a pillow packaging bag as a package using the low-adsorption multilayer packaging material of the present invention. This pillow packaging bag has a size of 70 mm in length and 60 mm in width, and is formed by forming an upper end seal portion 10 and a lower end seal portion 11 having a seal width of 5 mm and a back-sealed seal portion 12 having a seal width of 7 mm. This is a pillow packaging bag 9. FIG. 4 shows a schematic perspective view thereof.

  Further, the low-adsorbent laminated packaging material of the present invention is used to form a lid with the heat-sealable thermoplastic resin layer laminated on the low-adsorbent laminated packaging material as the innermost layer, and various low-adsorbent lids Used as

  Specific examples of the low adsorptive laminated packaging material of the present invention will be described below, but the present invention is not limited to these examples.

<Example 1>
First, as a substrate, a composite solution obtained by adjusting the following composite solution as a transparent primer layer on one side of a 12 μm thick biaxially stretched polyethylene terephthalate (PET) film was formed by a gravure coating method to a thickness of 0.2 μm. . Next, the aluminum vapor is evaporated on the transparent primer layer by a vacuum vapor deposition apparatus using an electron beam heating method, oxygen gas is introduced therein, aluminum oxide having a thickness of 20 nm is vapor-deposited, and a vapor-deposited thin film layer made of an inorganic oxide is formed. Formed. Further, a coating agent having the following composition was applied thereon with a bar coater and dried at 120 ° C. for 1 minute with a dryer to form a gas barrier coating layer having a thickness of 0.3 μm to obtain a transparent gas barrier film in the present invention.

[Preparation of complex solution]
In a diluting solvent, 2- (epoxycyclohexyl) ethyltrimethylsilane (hereinafter abbreviated as EETMS) and acrylic polyol are mixed in an amount of 5.0 times (weight ratio) with respect to EETMS and further mixed with tin chloride (SnCl ₂ ) / A methanol solution (prepared to 0.003 mol / g) is added to EETMS so as to be 1/135 mol and stirred. Then, a mixed solution obtained by diluting a mixed solution of triidyl isocyanate (hereinafter abbreviated as TDI) as an isocyanate compound so that NCO groups are equivalent to OH groups of the acrylic polyol to an arbitrary concentration is used as a composite solution.

[Composition of coating agent]
(1) Liquid: A hydrolyzed solution having a solid content of 3 wt% (in terms of SiO ₂ ) obtained by adding 89.6 g of hydrochloric acid (0.1N) to 10.4 g of tetraethoxysilane and stirring for 30 minutes for hydrolysis.
(2) Liquid: 3 wt% water / isopropyl alcohol solution of polyvinyl alcohol (90:10 by weight ratio of water: isopropyl alcohol).
(1) Liquid and (2) liquid mixed at a blending ratio (wt% / wt%) of 60/40.

On the other hand, a dispersion coating solution [manufactured by Mitsui Chemicals, R-300] comprising a maleic anhydride-modified copolymer polypropylene resin as a main component as a heat-sealable thermoplastic resin is used for the transparent gas barrier film obtained above. The low-adsorbent laminated packaging material of the present invention is formed by applying a heat-sealable thermoplastic resin layer by coating the entire surface of the gas barrier coating layer so that the coating amount (dry solid content) is 2.0 g / m ² . An evaluation sample for evaluating basic characteristics was prepared.

<Example 2>
In Example 1, an evaluation sample for evaluating the basic characteristics of the low adsorptive laminated packaging material in the present invention was prepared in the same manner as in Example 1 except that a transparent gas barrier film without a gas barrier coating layer was used.

<Example 3>
Example 1 was the same as Example 1 except that a dispersion coating solution (manufactured by Mitsui Chemicals, Inc., R-200) containing maleic anhydride-modified homopolypropylene resin as a main component was used as the heat-sealable thermoplastic resin. Thus, an evaluation sample for evaluating the basic characteristics of the low adsorptive laminated packaging material in the present invention was prepared.

  Below, the comparative example of this invention is demonstrated.

<Comparative example 1>
In Example 1, an application amount (dry solid content) is 6.0 g / m ² to form a heat-sealable thermoplastic resin layer, and the basic characteristics of the low-adsorption multilayer packaging material of the present invention A sample for comparative evaluation was made.

<Comparative example 2>
In Example 1, the heat-sealable thermoplastic resin layer is formed by coating in a pattern so that the coating amount (dry solid content) is 2.0 g / m ^2. A sample to be compared and evaluated with the basic characteristics was prepared.

<Comparative Example 3>
In Example 1, the low adsorptivity in the present invention was the same as in Example 1 except that a polyester solvent heat seal lacquer [Dainippon Ink & Chemicals, A904] was used as the heat-sealable thermoplastic resin. An evaluation sample for evaluating the basic characteristics of the laminated packaging material was prepared.

<Comparative example 4>
In Example 1, the low adsorptive laminated packaging material in the present invention was used in the same manner as in Example 1 except that an ionomer (IO) aqueous emulsion [N75B, manufactured by Mitsui Chemicals, Inc.] was used as the heat-sealable thermoplastic resin. An evaluation sample for evaluating the basic characteristics of was prepared.

  Various laminated packaging materials obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were subjected to the following bag making processing conditions using a horizontal pillow bag making machine [manufactured by Fujikikai Co., Ltd., “αWRAPPER FW3400”]. Bath seal preparation (containing limonene as a fragrance, powdered form) as content: 70 mm long and 60 mm wide, top seal part 10 and bottom seal part 11 with a seal width of 5 mm, back-sealed seal with a seal width of 7 mm A pillow packaging bag having a configuration in which the portion 12 was formed to form a bag was produced.

[Bag making conditions]
・ Set temperature of seal bar 180 ℃
・ Processing speed 50 shots / min
The pillow packaging bags filled with the contents obtained above were each stored at 40 ° C. for 1 month, and then evaluated for water vapor permeability, bag making suitability, contents take-out suitability, limonene adsorption amount, and seal strength based on the following evaluation methods. did. The results are shown in Table 1.

<Water vapor permeability>
The water vapor permeability at 40 ° C.-90% RH was measured by the MOCON method.

<Pability for bag making>
The suitability at the time of bag making processing was evaluated, and the suitability was indicated by ○ mark and the lack of suitability was indicated by × mark.

<Appropriate content removal>
After opening, the contents were shaken out, and the presence or absence of adhesion of the preparation to the sealant thermoplastic resin sealant was confirmed and evaluated. The case where no adhesion was observed was indicated by a circle, and the case where adhesion was observed was indicated by a cross.

<Limonene adsorption amount>
The laminated packaging material was cut to a size of 10 × 10 mm, sampled, washed twice with pure water, then wiped off and sealed in a 20 ml vial, SPME fiber was inserted here, heated at 80 ° C. for 30 min, volatilized The components were collected and the amount of limonene adsorbed was analyzed with a GC / MS measuring device. The limonene adsorption peak area in Comparative Example 4 was set as 1, and the ratio of the limonene adsorption peak area in other examples was evaluated by the adsorption amount ratio obtained.

<Seal strength>
It measured by 90 degree peeling by the method based on JIS-Z1707 before and after preservation | save.

表１の結果より、実施例１〜３における内容物として入浴製剤を充填したピロー包装袋を構成する本発明の低吸着性積層包装材料は、比較例１〜４におけるピロー包装袋を構成する積層包装材料と比較して、ヒートシール可能な熱可塑性樹脂として、耐内容物性に優れる無水マレイン酸変性プロピレン樹脂を主成分とするシーラント層を少ない塗布量で、全面に塗布し、ヒートシールすることにより、本発明の低吸着性積層包装材料を用いて製袋する際の製袋適性も良好であり、また水蒸気等のガスバリア性、取り出し適性も良好である。さらに、内容物としてリモネンを含有する入浴製剤を充填包装した場合でもリモネンの吸着がなく、また製袋直後および内容物としてリモネンを含有する入浴製剤を充填包装した場合でもヒートシール強度を維持し、かつ透明ガスバリアフィルムとヒートシール
可能な熱可塑性樹脂層との層間の密着性を向上改善したことでラミネーションの発生もない。以上のことから、本発明の低吸着性積層包装材料は、薬効成分や香気成分等の包装材料への低吸着性を有することで、薬効成分や香気成分等が包装材料へ吸着し、薬効成分や香気成分が経時的に減少することを防止することが可能であることを示すものである。

From the results of Table 1, the low-adsorbent laminated packaging material of the present invention constituting the pillow packaging bag filled with the bath preparation as the contents in Examples 1 to 3 is the laminated constituting the pillow packaging bag in Comparative Examples 1 to 4. Compared with packaging materials, as a heat-sealable thermoplastic resin, a sealant layer mainly composed of maleic anhydride-modified propylene resin, which has excellent content resistance, is applied to the entire surface with a small coating amount and heat-sealed. The bag making suitability for making a bag using the low-adsorption multilayer packaging material of the present invention is also good, and the gas barrier properties such as water vapor and the take-out suitability are also good. Furthermore, there is no adsorption of limonene even when the bath preparation containing limonene is filled and packaged as the contents, and the heat seal strength is maintained immediately after bag making and even when the bath preparation containing limonene is filled and packaged as the contents, In addition, there is no occurrence of lamination by improving and improving the adhesion between the transparent gas barrier film and the heat-sealable thermoplastic resin layer. From the above, the low adsorptive laminated packaging material of the present invention has a low adsorptivity to packaging materials such as medicinal ingredients and aroma components, so that medicinal ingredients and aroma components are adsorbed to the packaging material, and the medicinal ingredients This shows that it is possible to prevent the odor component and the fragrance component from decreasing with time.

  Therefore, the packaging body such as a bag and the lid material using the low-adsorption laminated packaging material of the present invention are suitably used in the packaging field for packaging foods, beverages, toiletries, pharmaceuticals and the like containing medicinal ingredients, aroma ingredients, and the like. Used.

  Low adsorptive laminated packaging material that adsorbs to packaging materials such as medicinal ingredients and aroma ingredients contained in the contents of food, beverages, toiletries, pharmaceuticals, etc., and prevents the medicinal ingredients from decreasing over time and its packaging It can be suitably used as a package or a cover material such as a low adsorbent bag shape using the material.

It is sectional drawing which shows an example of the low adsorptive laminated packaging material of this invention. It is sectional drawing which shows an example of the low adsorptive laminated packaging material of this invention. It is a top view which shows the pillow bag making as an example of the package using the low adsorptivity laminated packaging material of this invention. FIG. 4 is a perspective view of the pillow packaging bag shown in FIG. 3. It is explanatory drawing explaining the process of manufacturing a 3-way heat seal bag using a die roll type automatic filling and packaging machine as an example of a method for manufacturing a package body such as a bag in the present invention.

Explanation of symbols

A, B: Low adsorptive laminated packaging material 1 ... Film base layer 2 made of transparent plastic material ... Primer layer 3 ... Evaporated thin film layer 4 made of inorganic oxide ... Gas barrier coating Layer 5 ... Transparent gas barrier film 6 ... Heat-sealable thermoplastic resin layer 7 ... Base material layer 8 ... Adhesive layer 9 ... Pillow packaging bag 10 ... Top end seal 11 ... -Lower end seal part 12 ... Back-attached seal part 13 ... Main part 14 of die roll type automatic filling and packaging machine ... Laminated material 15 ... Roll 16 ... Lead 17 ... Vertical seal metal Roll 18 ... Horizontal seal Metal roll 19 ... Seal part 20 ... Knife 21 ... Three-sided seal bag

Claims (18)

  A low-adsorption multilayer packaging characterized by laminating at least a thermoplastic resin layer heat-sealable by coating on a vapor-deposited thin film layer or gas barrier coating layer made of an inorganic oxide provided on a transparent gas barrier film material.   A low-adsorption multilayer packaging material, wherein another substrate is laminated on a film substrate made of a transparent plastic constituting the low-adsorption multilayer packaging material according to claim 1. The transparent gas barrier film has a general formula R′Si (OR) ₃ (R ′: alkyl group, vinyl group, glycidoxypropyl group, R: alkyl group, etc.) on at least one surface of a substrate made of a transparent plastic material. A transparent primer layer composed of a trifunctional organosilane or a hydrolyzate of the organosilane, a composite of acrylic polyol and an isocyanate compound, and a deposited thin film layer composed of an inorganic oxide having a thickness of 5 to 300 nm. The low-adsorption multilayer packaging material according to claim 1 or 2.   The deposited thin film layer made of the inorganic oxide is obtained by at least one of a physical vapor deposition method (PVD method) and a chemical vapor deposition method (CVD method), and includes Al, Si, Mg, Sn, Zr, The low adsorptive laminated packaging material according to any one of claims 1 to 3, comprising an oxide of at least one metal selected from the group consisting of Ti, In, Zn, and Sb.   The low-adsorption multilayer packaging material according to any one of claims 1 to 4, wherein the heat-sealable thermoplastic resin contains a maleic anhydride-modified polypropylene resin as a main component. The coating amount of heat-sealable thermoplastic resin layer is in a dry state, low absorptive laminated packaging material according to claim 5, wherein the range of 0.5 to 5.0 g / m ^2.   The low-adsorption multilayer packaging material according to any one of claims 1 to 6, wherein an epoxy group is contained in R 'constituting the trifunctional organosilane.   The low-adsorption multilayer packaging material according to any one of claims 1 to 7, wherein a reaction catalyst is added to the composite.   9. The low adsorptive laminated packaging material according to claim 8, wherein the reaction catalyst is a tin compound. In the composite, a metal alkoxide represented by the general formula M (OR) n (M: metal element, R: alkyl group such as CH ₃ and C ₂ H ₅ , n: oxidation number of metal element) or The low adsorptive laminated packaging material according to any one of claims 1 to 9, wherein a hydrolyzate of the metal alkoxide is added. In the composite, a metal alkoxide represented by the general formula M (OR) n (M: metal element, R: alkyl group such as CH ₃ and C ₂ H ₅ , n: oxidation number of metal element) or The low adsorptive laminated packaging material according to any one of claims 1 to 10, wherein a hydrolyzate of the metal alkoxide is added. The low-adsorption multilayer packaging material according to any one of claims 1 to 11, wherein the metal in the metal alkoxide or the hydrolyzate of the metal alkoxide is Si, Al, Ti, Zr or a mixture thereof. .   The thickness of the said transparent primer layer is the range of 0.01-2 micrometers, The low adsorptivity laminated packaging material in any one of Claims 1-12 characterized by the above-mentioned.   A gas barrier coating layer is further laminated on the vapor-deposited thin film layer made of an inorganic oxide provided on the transparent gas barrier film, and the gas barrier coating layer comprises a water-soluble polymer and (a) one type It is a layer formed by applying a coating agent mainly comprising an aqueous solution containing at least one of the above metal alkoxide and its hydrolyzate or at least one of (b) tin chloride or a water / alcohol mixed solution, followed by heating and drying. The low adsorptive laminated packaging material according to any one of claims 1 to 13.   The low-adsorption multilayer packaging material according to claim 14, wherein the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof.   The low-adsorption multilayer packaging material according to claim 14 or 15, wherein the water-soluble polymer is polyvinyl alcohol.   A package comprising the heat-sealable thermoplastic resin layer laminated on the low-adsorption multilayer packaging material according to any one of claims 1 to 16 as an innermost layer.   A lid material comprising a heat-sealable thermoplastic resin layer laminated on the low-adsorption multilayer packaging material according to any one of claims 1 to 16 as an innermost layer.

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