JP2006044162A - Biodegradable gas barrier film having inorganic oxide vapor deposition layer and protective layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a biodegradable gas barrier film having an inorganic oxide vapor deposition layer and a protective layer not deteriorated in gas barrier properties, water vapor barrier properties and adhesion even if post-processing such as printing or the like is applied and reduced in environmental load, and a packaging material using it. <P>SOLUTION: The inorganic oxide vapor deposition layer (2) is provided at least on one side of a biodegradable polymer base material (1) and the protective layer (3) comprising a mixture of melamine and/or its derivative is further provided on the inorganic oxide vapor deposition layer 2. An undercoating layer (4) may be provided between the biodegradable polymer base material (1) and the inorganic oxide vapor deposition layer (2). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a laminate for packaging used in the packaging field of foods, non-foods, and pharmaceuticals. Furthermore, it is related with the laminated body for packaging which considered the environmental load reduction by using a biodegradable base material.

  Various functions are required for the packaging material. Among them, content protection is the most important function. Deterioration and alteration of the contents are promoted mainly by the influence of oxygen, moisture, light, heat and the like. In particular, the influence of oxygen and moisture is great. It is important to consider blocking the contents, that is, the presence of a gas barrier film is required. In addition, in today's diversified preferences and restricted additives, not only from outside, but also from inside, such as inert gas filling packaging, flavor and aroma degeneration prevention It is also necessary to block transmission.

  However, in general, plastic films have poor gas barrier properties, and when used alone, there is no one that satisfies the requirements except for some uses. Therefore, a method of producing a gas barrier film by laminating other layers having excellent gas barrier properties is often employed.

  A film having a layer containing polyvinyl alcohol (PVA) as a component is known to have excellent crystallinity and excellent oxygen barrier properties in a dry state, but the crystallinity decreases under high humidity conditions. The problem is that the barrier properties are significantly reduced (see, for example, Patent Documents 1, 2, and 3).

The said prior art document is shown.
Japanese Patent Laid-Open No. 7-41685. JP-A-7-33909. JP-A-7-251475.

  Various methods have been devised to improve the problem. As a non-PVA system, a gas barrier film provided with a polyvinylidene chloride layer has been put into practical use, but there is a risk of generating harmful dioxins during disposal (for example, see Patent Document 4).

The said prior art document is shown.
JP-A-55-59961.

  Moreover, in order to improve the water resistance of polyvinyl alcohol, an effect of poly (vinyl alcohol-CO-ethylene) in which an ethylene unit is introduced into polyvinyl alcohol is also known, but its resistance to humidity dependency is still sufficient. (For example, refer to Patent Documents 5 and 6).

The said prior art document is shown.
JP-A-6-293118. JP-A-11-170430.

  Moreover, although the composite film of polyacrylic resin salt and polyvinyl alcohol is also devised and it is known that it is excellent in oxygen barrier property, water vapor | steam barrier property is not expressed (for example, refer patent document 7).

The said prior art document is shown.
JP 2001-164174 A.

  Gas barrier films provided with an inorganic oxide vapor deposition layer are also marketed by various companies (see, for example, Patent Document 8), but depending on the application, barrier properties may not be sufficient, and printing as a film for packaging materials is also possible. Some reports have reported that the barrier properties deteriorate.

The said prior art document is shown.
JP-A-6-16848.

  In addition, polyethylene terephthalate, polyamide, etc. are used as the film base of the deposited film, but when these are all discarded, there is no treatment method other than incineration, and the unreasonable waste can be selectively recovered. Not only is it difficult, but wild animals, birds, fish, etc. eat away, causing problems such as indigestion, suffocation, and loss of aesthetic environment.

  Therefore, there has been a demand for a gas barrier material that is free from cracks and pinholes when processed as a packaging material, protects the contents from external oxygen and water vapor, and has a low environmental load.

  The present invention has been made in view of the above-described problems related to a biodegradable polymer substrate provided with an inorganic oxide vapor deposition layer. Even if various stresses such as printing and post-processing are applied, the gas barrier property, water vapor It is an object of the present invention to provide a biodegradable gas barrier film having an inorganic oxide vapor deposition layer and a protective layer with little deterioration in barrier properties and little environmental addition, and a packaging material using the same.

  The present invention has been intensively studied to solve the above-mentioned problems. As described in claim 1, an inorganic oxide vapor deposition layer is provided on at least one surface of a biodegradable polymer substrate, and melamine and / or a derivative thereof are further provided thereon. And a biodegradable gas barrier film having an inorganic oxide vapor-deposited layer and a protective layer, characterized in that a protective layer having a mixture of these components as a component is provided.

  As a further preferred embodiment, as described in claim 2, the biodegradable polymer substrate is a polysaccharide, a polypeptide, polylactic acid, polybutylene succinate, polyethylene succinate, polycaprolactone, polyhydroxybutyrate, Provided is a biodegradable gas barrier film having an inorganic oxide vapor-deposited layer and a protective layer characterized by having at least one of polyglycolic acid and polyvinyl alcohol as a component or a derivative thereof.

As a further preferred embodiment, as described in claim 3, the inorganic oxide vapor deposition layer has at least one of aluminum oxide, silicon oxide, and magnesium oxide as a component, and the inorganic oxide vapor deposition layer and the protective layer A biodegradable gas barrier film is provided.

  Further, as a desirable embodiment, as described in claim 4, the biodegradable gas barrier having an inorganic oxide deposited layer and a protective layer, wherein the melamine and / or derivative thereof has at least one hydroxyl group or amino group. Provide film.

  As a further preferred embodiment, as described in claim 5, the melamine derivative having a hydroxyl group or an amino group has a hydroxyl group or an amino group via a moiety containing an alkyl chain and / or an alkyl ether chain from at least one of the amino groups of melamine. Provided is a biodegradable gas barrier film having an inorganic oxide vapor deposition layer and a protective layer characterized by having a group.

  According to a preferred embodiment of the present invention, there is provided a biodegradable gas barrier film having an inorganic oxide vapor deposition layer and a protective layer, wherein the protective layer is formed by sequentially laminating a melamine derivative and a melamine. .

  As a further preferred embodiment, there is provided a biodegradable gas barrier film having an inorganic oxide vapor deposition layer and a protective layer, wherein the protective layer is formed by a vacuum process.

  As a further desirable embodiment, an inorganic oxide vapor deposition layer and a protective layer, wherein an undercoat layer is provided between the biodegradable polymer substrate and the inorganic oxide vapor deposition layer as described in claim 8. A biodegradable gas barrier film is provided.

  In addition, as a preferred embodiment, as described in claim 9, the undercoat layer has an inorganic oxide deposition characterized in that it has a component composed of a composite of an organosilane or a hydrolyzate thereof, an acrylic polyol and an isocyanate compound. A biodegradable gas barrier film having a layer and a protective layer is provided.

  Furthermore, as described in claim 10, a packaging material produced using the biodegradable gas barrier film having the inorganic oxide vapor deposition layer and the protective layer according to any one of claims 1 to 9 is provided.

  Further, as described in claim 11, the packaging material is formed by laminating a heat seal resin on the biodegradable gas barrier film through at least an adhesive layer and / or an adhesive layer, and the heat seal resin, the adhesive layer, and / or Provided is a packaging material characterized in that the adhesive layer is made of a biodegradable substance.

  Furthermore, as described in claim 12, the biodegradable substance constituting the heat seal resin, the adhesive layer, and the adhesive layer has at least one of polysaccharide, polypeptide (protein), and polyvinyl alcohol as a component. A biodegradable gas barrier film having an inorganic oxide vapor deposition layer and a protective layer is provided.

  According to the present invention, a biodegradable polymer substrate is used, and the environmental load is maintained by maintaining the barrier property by relaxing the physical stress to the inorganic oxide deposited layer by the protective layer and having excellent adhesion. A biodegradable gas barrier film having a small thickness can be obtained.

Embodiments of the present invention will be described in detail with reference to the drawings.
The biodegradable gas barrier film having an inorganic oxide vapor deposition layer and a protective layer according to the present invention has, for example, an inorganic oxide vapor deposition layer (2 on at least one surface of the biodegradable polymer substrate (1) as shown in FIG. ) And a protective layer (3) having a mixture of melamine and / or a derivative thereof as a component.

  The biodegradable polymer substrate (1) in the present invention is a film made of a biodegradable resin, and is a polysaccharide, polypeptides, polylactic acid, polybutylene succinate, polyethylene succinate, polycaprolactone, polyhydroxybutyrate. It is preferable to have at least one of the components among rate, polyglycolic acid, polyvinyl alcohol or derivatives thereof as a component.

If the transparency of the inorganic oxide vapor deposition layer is utilized, it is more preferable that the base material is also transparent. In this regard, polylactic acid or cellophane, which is one of polysaccharides, can be mentioned, but it is limited to these examples. In addition, various well-known additives and stabilizers such as antistatic agents, ultraviolet ray preventing agents, plasticizers, lubricants, etc. may be used on the surface of the base material, and adhesion to the thin film In order to improve the property, corona treatment, low temperature plasma treatment, and ion bombardment treatment can be performed as pretreatment. Furthermore, chemical treatment, solvent treatment, and the like may be performed.

  The thickness of the substrate is not particularly limited, but when considering the workability when laminating other layers, primer layers and inorganic oxide vapor-deposited thin film layers, overcoat layers and other layers. Generally, it is in the range of 5 to 100 μm, and practically in the range of 10 to 50 μm. In consideration of mass productivity, it is desirable to use a long film so that each layer can be formed continuously.

  Next, the inorganic oxide vapor deposition layer (2) is provided to provide gas barrier properties, and is considered to be easy to handle, economical, gas barrier performance, and the like, and is made of aluminum oxide, silicon oxide, magnesium oxide, oxidation. It is preferable to have at least one of titanium as a component. Further, these metal oxides do not necessarily need to be oxidized and saturated. Various additives may be mixed according to the required physical properties. The composition ratio, oxidation degree, additive, and the like of these inorganic oxides may be set in consideration of application, cost, film forming apparatus characteristics, and the like. Examples of film forming means include known methods such as vacuum vapor deposition, sputtering, and chemical vapor deposition (CVD), and electron beam heating vacuum deposition is particularly effective. It is not limited.

  The film thickness is not limited, but is preferably 1 nm to 100 nm. If it is thinner than this, it will be difficult to form a uniform film, so that it will be difficult to express gas barrier performance, and if it is more than this, gas barrier performance will be exhibited, but the flexibility will be reduced later. It becomes poor in processing suitability and practicality and is uneconomical.

  Melamine is generally an alias for 2,4,6-triamino-1,3,5-triazine (Formula 1), but in the present invention, 2,4-diamino-1,3,5-triazine (Formula 2) And 2-amino-1,3,5-triazine (Formula 3). The reason is that each has similar properties and each is effective in the present invention, but the sequential parallel notation is redundant in this specification. In addition, the notation of 2,4,6-triamino-1,3,5-triazine as melamine is common as a raw material for so-called melamine resins, and is therefore unified.

無機酸化物蒸着層の上に設ける保護層（３）とは、主に無機酸化物蒸着層の保護、印刷適性の向上などを目的として設けるものである。メラミンはそれ自体の高結晶性に起因すると推測されるガスバリア性を有するため、バリア性の向上にも寄与する。

The protective layer (3) provided on the inorganic oxide vapor-deposited layer is provided mainly for the purpose of protecting the inorganic oxide vapor-deposited layer and improving printability. Since melamine has gas barrier properties presumed to be due to its high crystallinity, it contributes to the improvement of the barrier properties.

  From previous studies, in the case of melamine alone, the adhesion with the inorganic oxide vapor deposition layer was sometimes insufficient. Therefore, in the present invention, it is recommended to use a melamine derivative in combination. Although it is not always necessary to have a triazine skeleton to improve adhesion, it interacts with the π-conjugated electron cloud of the triazine ring of melamine in order to maintain affinity with melamine used as a component of the protective layer and gas barrier layer. I would like to recommend a melamine derivative that also has a triazine ring.

  The melamine derivative as used herein retains the state in which the amine nitrogen atom (not the constituent nitrogen of the triazine ring) is bonded to the carbon atom of the triazine ring, and the amine is not limited. However, a highly polar hydroxyl group or amino group is provided via an alkyl chain and / or an alkyl ether chain in order to maintain adhesion to the ceramic deposited layer.

  Although the induction method is not limited, the dehydrochlorination reaction between a halogenated alkyl compound having a hydroxyl group at the end and melamine and the reaction between the hydroxyl group-terminated carboxylic acid and carboxylic acid chloride with an amine are simple, and the vacuum process Since it is necessary to suppress the molecular weight to some extent in order to form a film, the former, which is difficult to become a macromolecule, is a preferable method. Although reintroduction of amines is not strongly recommended because reagents may cyclize in the reaction system, substances obtained by controlled synthesis may contribute to adhesion. When an epoxy group, a carboxylic acid, or the like is introduced at the end, the end itself can react with the amine of melamine, so it is easily polymerized and is not suitable for a vacuum process.

  An undercoat layer (4) may be provided between the biodegradable polymer substrate (1) and the inorganic oxide thin film layer (2) (see FIG. 2).

  The undercoat layer (4) is provided on a base material made of a polyamide resin, enhances the adhesion between the biodegradable polymer base material (1) and the inorganic oxide thin film layer (2), and provides a delamination layer. The purpose is to prevent generation and deterioration of gas barrier properties. As a result of intensive studies, it is desirable that a trifunctional organosilane or a hydrolyzate thereof, an acrylic polyol and an isocyanate compound can be used as the undercoat layer in order to achieve the above object.

The trifunctional organosilane is a compound represented by the general formula RSi (OR ′) ₃ (R: substituted / unsubstituted alkyl group, vinyl group, etc., R ′: alkyl group). At this time, it is preferable that the substituent of R contains an epoxy group or an isocyanate group. For example, ethyltrimethoxysilane, vinyltrimethoxysilane, glycidoxypropyltrimethoxysilane containing epoxy group in R, glycidoxytrimethoxysilane, epoxycyclohexylethyltrimethoxysilane, or R containing isocyanate group Γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and the like. These compounds may be used alone or in a mixture of two or more.

  The trifunctional organosilane used in the present invention may be a hydrolyzate such as the above compound. At this time, the substituent of R ′ preferably contains an epoxy group or an isocyanate group. As a method for obtaining a hydrolyzate, a known method such as a method of performing hydrolysis by directly adding an acid, an alkali or the like to a trifunctional organosilane can be used.

The 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, having a hydroxyl group at the terminal. And reacting 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 reactivity with an isocyanate compound, the hydroxyl value is preferably between 5 and 200 (KOHmg / g).

  Furthermore, an isocyanate compound is added in order to improve adhesiveness with a base material or an inorganic oxide layer by the urethane bond which reacts with an acrylic polyol, and acts mainly as a crosslinking agent or a hardening | curing agent. To achieve this, the isocyanate compounds include aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), aliphatic xylene diisocyanate (XDI), hexadiene isocyanate (HMDI), and isophorone diisocyanate (IPDI). Monomers such as these, polymers and derivatives thereof are used, and these are used alone or as a mixture.

  The blending ratio of the acrylic polyol and isocyanate compound used for the undercoat layer (4) is not particularly limited, but if the isocyanate compound is too small, curing may be poor, and if it is too large, blocking or the like may occur and processing may occur. There is a problem above. Therefore, the mixing ratio of the acrylic polyol and the isocyanate compound is preferably such that the isocyanate group derived from the isocyanate compound (—NCO group) is 50 times or less of the hydroxyl group derived from the acrylic polyol (—OH group), particularly preferably − This is a case where NCO groups and —OH groups are blended in equal amounts. As a mixing method, a known method can be used and is not particularly limited.

Furthermore, a metal alkoxide or a hydrolyzate thereof may be added to improve the liquid stability during preparation of the composite. Tetraethoxysilane this metal alkoxide _{[Si (OC 2 H 5)} 4], tripropoxy aluminum _{[Al (OC 3 H 7)} 3] and general formula M (OR) _n (M: a metal element, n: metal Oxidation number) or a hydrolyzate thereof. Among these, tetraethoxysilane, tripropoxyaluminum, or both compounds are preferable because they are relatively stable in an aqueous solvent.

  In addition, a reaction catalyst is added to the composite of the undercoat layer (4). As the reaction catalyst, tin chloride, tin oxychloride, tin alkoxide, various tin compounds such as organic tin, Lewis acid, etc. are used. In addition to the catalyst, the primer agent further includes various additives such as tertiary amines, imidazole derivatives, carboxylic acid metal salt compounds, quaternary ammonium salts, quaternary phosphonium salts and other curing accelerators, phenols, It is also possible to add antioxidants such as sulfur and phosphite, leveling agents, flow regulators, crosslinking reaction accelerators, fillers and the like.

  As a method for forming the undercoat layer (4), 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.

  The thickness of the undercoat layer (4) 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. If the thickness is less than 0.01 μm, it may be difficult to obtain a uniform coating film, and the adhesion may be lowered. If the thickness exceeds 2 μm, the coating film cannot maintain flexibility, and the coating film may be damaged due to external factors. This is not preferable because it may cause a crack. It is particularly preferable that it is in the range of 0.05 to 0.5 μm.

Furthermore, other layers can be laminated on the protective layer (3). For example, they are a printing layer (not shown) and a heat seal layer (not shown). The printing layer is formed for practical use as a mark or character information or for decoration, and has been conventionally used for urethane, acrylic, nitrocellulose, rubber, vinyl chloride, etc. It is a layer composed of ink in which various pigments, extender pigments and additives such as plasticizers, desiccants, stabilizers, and the like are added to the ink binder resin, and letters, pictures, etc. are formed. As a forming method, 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 a roll coating, a knife edge coating, or a gravure coating can be used. The thickness may be 0.1 to 2.0 μm.

  In order to process the biodegradable gas barrier film (10) of the present invention into a packaging material (100), some kind of adhesion processing must be performed. Although not limited, there is a method of bonding by hot melt glue, cold glue, pressure sensitive tack glue, direct lamination with various adhesives (30) or through a heat-sealable polyolefin layer (20). In particular, the latter is suitable for heat-sealing polyolefin layers provided by a dry laminating method or an extrusion method and has high sealing strength. In consideration of easy disposal, it is preferable that these are sufficiently thin. In addition, these layers themselves have to be biodegradable, and examples thereof include polypeptide compounds represented by glue, polysaccharides such as starch paste, and the like. These are preferably selected as appropriate according to the required service life and environment (see FIGS. 3 and 4).

Next, the present invention will be described with reference to examples. However, the examples listed here do not limit the present invention.
<Preparation of melamine derivative>
2,4,5-Triamino-1,3,5-triazine and an equimolar amount of 2-chloroethanol were reacted in the presence of sodium carbonate to introduce a hydroxyl group into melamine. Since the amino groups in melamine are equivalent to each other, in principle, the reactivity is equal, that is, the elimination reaction proceeds competitively at each amino group. Therefore, the obtained derivative became a mixture.
<Example 1>
One side of a 15 μm thick polylactic acid (PLA), which is a biodegradable polymer substrate (1), is evaporated with metallic aluminum by a vacuum vapor deposition device using an electron beam heating method, and oxygen gas is introduced thereto to obtain a thickness. An inorganic oxide thin film layer (2) was formed by vapor-depositing 15 nm of aluminum oxide. Next, the derivative, 2,4,6-triamino-1,3,5-triazine, was sequentially formed into a film by a vacuum process. The cumulative film thickness of melamine and its derivatives is 0.5 μm.
<Example 2>
Same as Example 1 except that the melamine and the derivatives were formed as a mixture simultaneously rather than sequentially.
<Example 3>
As an undercoat layer (4) between the biodegradable polymer substrate (1) and the inorganic oxide thin film layer (2), TDI is used as an acrylic polyol and an isocyanate compound in a diluting solvent (ethyl acetate). The same as Example 1 except that a composite solution obtained by diluting a mixed solution added so that the amount of —NCO group is equal to −0H group to an arbitrary concentration was formed by a gravure coating method to a thickness of 0.15 μm.
<Example 4>
The same as Example 1 except that the inorganic oxide vapor deposition layer (2) is made of silicon oxide by chemical vapor deposition.
<Example 5>
The same as in Example 1 except that the protective layer (3) was melamine alone without using a melamine derivative.
<Example 6>
Same as Example 1 except that no protective layer (3) of melamine and derivative was provided.
<Example 7>
Same as Example 1 except that a PET film was used for the substrate (1).
<Example 8>
The same as Example 7 except that an aluminum foil was used instead of the inorganic oxide vapor deposition layer (2) serving as the barrier layer.

  Finally, in order to give physical stress to the biodegradable gas barrier films of Examples 1 to 8, they were subjected to a gravure printing process. The ink is New LP Super R631 White manufactured by Toyo Ink Co., Ltd., and the gravure plate is a 180-35 μm engraving plate. The printing pattern is a full surface printing.

The oxygen permeability before and after printing of the gas barrier films of Examples 1 to 8 produced in this way, the water vapor permeability, the adhesion between the inorganic oxide vapor-deposited layer and the protective layer before printing, and the disposal after use are as follows. It was measured and evaluated by the method. The results are shown in Table 1.
Oxygen permeability: Measuring device: OXTRAN 2/20 (manufactured by Modern Control), measurement conditions: 30 ° C.-70% RH.
Water vapor permeability: Measuring device: PERMATRAN 3/31 (manufactured by Modern Control), measurement conditions: 40 ° C.-90% RH.
Adhesiveness: Each sample was provided with 10 rows × 10 columns of cuts of about 2 mm square, and a peel test was performed using a cellophane tape to count the remaining number of cells that did not peel. A substrate having a thickness of 50 μm was used instead.
Disposability: A configuration with a small environmental impact at the time of disposal is indicated by a circle, and a configuration with a large environmental load is indicated by a cross. The overall evaluation is excellent (represented by ◎) or slightly inferior (represented by a triangle). 3 levels of evaluation (represented by x) were performed.

表１の評価結果より、メラミン及び誘導物による保護効果が分かる。また、メラミン単体よりも誘導体混合物を用いたものが、さらに誘導体とメラミンを順次積層させたものが密着性良好であることが判る。また、生分解性の基材を用いた場合の包が環境付加が小さいことは明白である。

From the evaluation results in Table 1, the protective effect by melamine and derivatives can be seen. Further, it can be seen that those using a derivative mixture rather than melamine alone, and those obtained by sequentially laminating a derivative and melamine have good adhesion. In addition, it is obvious that the package using a biodegradable substrate has a small environmental load.

It is sectional explanatory drawing which shows one Example of the layer structure of the biodegradable gas barrier film which has an inorganic oxide vapor deposition layer and protective layer of this invention. It is sectional explanatory drawing which shows another Example of the layer structure of the biodegradable gas barrier film which has an inorganic oxide vapor deposition layer and protective layer of this invention. It is sectional explanatory drawing which shows one Example of the packaging material using the biodegradable gas barrier film which has an inorganic oxide vapor deposition layer and protective layer of this invention. It is sectional explanatory drawing which shows another Example of the packaging material using the biodegradable gas barrier film which has an inorganic oxide vapor deposition layer and protective layer of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Biodegradable polymer material 2 ... Deposition layer of inorganic oxide 3 ... Protection layer 4 ... Undercoat layer 10 ... Biodegradable gas barrier film 20 ... Heat seal resin, heat seal polyolefin layer 30 ... ‥adhesive

Claims (12)

  An inorganic oxide vapor deposition layer characterized in that an inorganic oxide vapor deposition layer is provided on at least one surface of a biodegradable polymer substrate, and further a protective layer having a mixture of melamine and / or a derivative thereof as a component is provided thereon. And a biodegradable gas barrier film having a protective layer.   The biodegradable polymer substrate is at least one or more of polysaccharides, polypeptides, polylactic acid, polybutylene succinate, polyethylene succinate, polycaprolactone, polyhydroxybutyrate, polyglycolic acid, polyvinyl alcohol, or The biodegradable gas barrier film having an inorganic oxide vapor-deposited layer and a protective layer according to claim 1, comprising the derivative as a component.   The biodegradability having an inorganic oxide vapor deposition layer and a protective layer according to claim 1 or 2, wherein the inorganic oxide vapor deposition layer has at least one of aluminum oxide, silicon oxide, and magnesium oxide as a component. Gas barrier film.   The biodegradable gas barrier having an inorganic oxide vapor deposition layer and a protective layer according to any one of claims 1 to 3, wherein the melamine and / or derivative thereof has at least one hydroxyl group or amino group. the film.   5. The melamine derivative having a hydroxyl group or an amino group has a hydroxyl group or an amino group through a portion containing an alkyl chain and / or an alkyl ether chain from at least one of the amino groups of melamine. A biodegradable gas barrier film comprising the inorganic oxide vapor-deposited layer and the protective layer described in 1.   The biodegradable gas barrier film having an inorganic oxide vapor deposition layer and a protective layer according to any one of claims 1 to 5, wherein the protective layer is formed by sequentially laminating the melamine derivative and melamine.   The biodegradable gas barrier film having an inorganic oxide deposited layer and a protective layer according to any one of claims 1 to 6, wherein the protective layer is formed by a vacuum process.   The inorganic oxide vapor deposition layer and protective layer according to any one of claims 1 to 7, wherein an undercoat layer is provided between the biodegradable polymer substrate and the inorganic oxide vapor deposition layer. A biodegradable gas barrier film having   The inorganic oxide vapor deposition according to any one of claims 1 to 8, wherein the undercoat layer has a component composed of a composite of organosilane or a hydrolyzate thereof and an acrylic polyol and an isocyanate compound. Biodegradable gas barrier film having a layer and a protective layer.   The packaging material produced using the biodegradable gas barrier film of any one of Claims 1 thru | or 9. The packaging material is formed by laminating a heat seal resin on the biodegradable gas barrier film through at least an adhesive layer and / or an adhesive layer,
The packaging material according to claim 10, wherein the heat seal resin, the adhesive layer, and / or the adhesive layer is made of a biodegradable substance. The biodegradable substance constituting the heat seal resin, the adhesive layer, and the pressure-sensitive adhesive layer has at least one of polysaccharide, polypeptide (protein), and polyvinyl alcohol as a component. A biodegradable gas barrier film having the inorganic oxide vapor-deposited layer and the protective layer.

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