JP2001113623A - Gas barrier packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging material for a liquid having high gas barrier properties and high adhesion, friendly even to environment and high in practicality. SOLUTION: A primer layer excellent in dimensional stability and adhesion, a membrane layer comprising inorganic oxide excellent in gas barrier properties and a gas barrier coating film layer are successively laminated on one surface of a plastic base material and an outer base material is further laminated thereon and a sealant layer is formed on the other surface of the base material to constitute a gas barrier packaging material for a liquid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging material used in the field of packaging of foods, non-foodstuffs, pharmaceuticals, etc., and in particular, it requires a gas barrier property and is suitable for filling a liquid material as a content. It is about materials.

[0002]

2. Description of the Related Art In recent years, packaging materials used for packaging foods, non-foodstuffs, pharmaceuticals, etc., include oxygen, water vapor, and the like which penetrate the packaging material in order to suppress deterioration of contents and maintain their functions and properties. In addition, it is necessary to prevent the influence of the gas that alters the contents, and it is required to have a gas barrier property for blocking these gases. In particular, when the content is a liquid substance, if the gas barrier property is insufficient, the weight may be reduced, which may cause a problem. Therefore, conventionally, a vapor-deposited film made of a metal such as aluminum, which is less affected by temperature and humidity, and a packaging material using such a metal foil as a gas barrier layer have been generally used.

However, a packaging material using a metal foil made of a metal such as aluminum has excellent gas barrier properties, but must be disposed of as incombustibles when disposed after use. There are disadvantages, such as high cost, the inability to use a metal detector at the time of inspection, and the difficulty in using it due to the recent increase in environmental awareness.

Accordingly, as a packaging material which overcomes these drawbacks, for example, US Pat.
A film in which an inorganic oxide of silicon oxide or aluminum oxide as described in -28017 or the like is formed on a polymer film by forming a vapor-deposited film by a forming method such as a vacuum vapor deposition method or a sputtering method has been developed. . These vapor-deposited films are known to have transparency and gas barrier properties against oxygen, water vapor, etc., and are suitable as packaging materials having both transparency and gas barrier properties that cannot be obtained with metal foils and the like. I have.

[0005]

However, even a film suitable for the above-mentioned packaging material is rarely used alone as a vapor deposition film as a packaging container or a packaging material. A package is completed through various processes such as printing or laminating characters and pictures on the surface or laminating the film with a film or the like, and shape processing into a package such as a container. In the case of liquids,
In addition to the bag-like packaging material, there are cases where it is made into a container-like packaging material by compounding with paper or the like. Therefore, sufficient care must be taken when designing the packaging.

[0006] Therefore, after the above-mentioned vapor-deposited film or the like is used to form a bag into a bag-like packaging material laminated with a sealant film, the contents are filled with water and stored under high temperature and high humidity, and changes in weight and strength are confirmed. As a result, there was a problem that the rate of change in weight after storage was large and some delamination and the like occurred.

[0007] In other words, the conditions used as a packaging material in such a case include a high gas barrier property of blocking gas and the like which affect the contents, and a high degree of adhesion without a decrease in strength even after the contents are filled and stored. In addition, there is a demand for eco-friendly, recyclable, etc., but at present, no packaging material that satisfies all of them has been found.

In view of the above, the present invention has been devised in view of the above problems, and has as its object to provide a highly practical packaging material which has high gas barrier properties and high adhesion and is environmentally friendly.

[0009]

In order to achieve the above object, the present invention first provides, in one aspect, an acrylic polyol, an isocyanate compound, and a silane coupling agent on one surface of a base material made of a plastic material. A primer layer composed of a composite of the above, and an outer substrate is laminated on the thin film layer side of a laminated material composed of a thin film layer composed of an inorganic oxide, and a thermoplastic material having heat sealability on the substrate side of the laminated material. A gas barrier packaging material characterized by laminating a sealant layer made of a resin.

According to a second aspect of the present invention, an acrylic polyol is provided on one surface of the substrate made of a plastic material.
Isocyanate compound, a primer layer composed of a composite with a silane coupling agent, a thin film layer composed of an inorganic oxide, and an outer substrate laminated on the gas barrier film layer side of a laminated material composed of a gas barrier film layer, Further, a gas barrier packaging material is characterized in that a sealant layer made of a thermoplastic resin having heat sealing properties is laminated on the substrate side of the laminated material.

According to a third aspect of the present invention, the gas barrier coating layer comprises an aqueous solution or a water / alcohol mixed solution containing a water-soluble polymer, at least one metal alkoxide and its hydrolyzate, or tin chloride. 3. A gas barrier packaging material according to claim 2, wherein a coating agent mainly comprising is applied and dried by heating.

According to a fourth aspect of the present invention, the silane coupling agent of the primer layer has an organic functional group which reacts with at least one of a hydroxyl group of an acrylic polyol or an isocyanate group of an isocyanate compound. A gas barrier packaging material according to any one of claims 1 to 3.

According to a fifth aspect of the present invention, there is provided the gas barrier packaging material according to the fourth aspect, wherein the organic functional group of the silane coupling agent of the primer layer comprises an isocyanate group, an epoxy group and an amino group. Things.

According to a sixth aspect of the present invention, there is provided the gas barrier packaging material according to the first or second aspect, wherein the outer substrate is a biaxially stretched polyethylene terephthalate film.

According to the present invention, a primer layer excellent in dimensional stability and adhesion, a thin film layer made of an inorganic oxide excellent in gas barrier properties, and an outer substrate are sequentially laminated on one surface of a plastic substrate. Although a packaging material having a sealant layer formed on the other surface of the base material of the laminated material has a gas barrier effect, a highly practical packaging material for liquids without occurrence of delamination or the like can be obtained. In order to impart gas barrier properties, a primer layer having excellent dimensional stability and adhesion, a thin film layer composed of an inorganic oxide having excellent gas barrier properties, a gas barrier coating layer, and an outer substrate on one surface of a plastic substrate When a packaging material having a structure in which a sealant layer is formed on the other surface of the base material of the laminated material obtained by sequentially laminating the laminated material has a high barrier effect against a highly scatterable liquid substance, it has excellent adhesion and does not generate delamination and the like. Packaging materials for highly practical liquid is obtained.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the drawings. FIG. 1 is a schematic partial sectional view showing one embodiment of the gas barrier packaging material of the present invention. FIG. 2 is a schematic partial sectional view showing another embodiment of the gas barrier packaging material of the present invention. First, the configuration of the gas barrier packaging material of the present invention in FIG. 1 will be described. The substrate 1 is a film made of a plastic material, and a primer layer 2 made of a composite of an acrylic polyol, an isocyanate compound, a silane coupling agent, and the like, and a thin film layer 3 made of an inorganic oxide are sequentially formed on one surface of the substrate 1. An outer base material 5 made of a stretched plastic material is laminated on the thin film layer 3 of the laminated material, and the other surface of the base material 1 of the laminated material is heat-sealed thermoplastic. This is a packaging material having a configuration in which a sealant layer 6 made of a resin is laminated. Next, the configuration of FIG. 2 of the gas barrier packaging material of the present invention will be described. Substrate 1
Is a film made of a plastic material, and a primer layer 2 made of a composite of an acrylic polyol, an isocyanate compound, a silane coupling agent and the like on one surface of a substrate 1, a deposited thin film layer 3 made of an inorganic oxide, and a gas barrier coating The layer 4 is a laminated material in which layers are sequentially laminated, and an outer substrate 5 made of a plastic material stretched on the gas barrier coating layer 4 of the laminated material is laminated, and the other surface of the substrate 1 of the laminated material is heated. This is a packaging material having a configuration in which a sealant layer 6 made of a thermoplastic resin having a sealing property is laminated.

Hereinafter, the individual materials constituting the packaging material will be described. First, the substrate 1 made of a plastic material is preferably a transparent film in order to make use of the transparency of the deposited thin film layer. As the substrate 1, a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate, a polyolefin film such as polyethylene or polypropylene, a polystyrene film, a polyamide film, a polycarbonate film, a polyacrylonitrile film, a polyimide film, or the like can be used. The substrate 1 may be stretched or unstretched, and preferably has mechanical strength and dimensional stability. Among them, polyethylene terephthalate arbitrarily stretched in the biaxial direction is particularly preferred. Further, on the surface of the substrate 1 opposite to the surface on which the deposited thin film layer is provided, a thin film coated with various known additives and stabilizers such as an antistatic agent, an ultraviolet inhibitor, a plasticizer, and a lubricant is formed. May be. Further, in order to improve the adhesiveness with the thin film, a corona treatment, a low-temperature plasma treatment,
Any treatment such as ion bombardment treatment, chemical treatment, and solvent treatment may be performed.

The thickness of the substrate 1 is not particularly limited, and a film obtained by laminating films having different properties other than a single film can be used in consideration of suitability as a packaging material. In addition, the primer layer and the deposited thin film layer,
Further, in consideration of workability in forming the gas barrier coating layer, the thickness is practically preferably in the range of 3 to 200 μm, and more preferably 6 to 30 μm depending on the use.

Further, in consideration of mass productivity, it is desirable to form a long continuous film so that each of the layers can be formed continuously.

Next, the primer layer 2 is formed on one surface of the substrate 1.
To form The role of the primer layer 2 is to smooth the substrate 1, improve the gas barrier properties of the vapor-deposited thin film layer composed of an inorganic oxide, further enhance the adhesion between the vapor-deposited thin film layer, and fill the aqueous content. This also prevents the occurrence of delamination or the like.

As a result of extensive studies, the present inventors have found that a composition comprising an acrylic polyol, an isocyanate compound, and a silane coupling agent is promising as a primer layer having the above performance.

The composition of the primer layer 2 will be described in more detail. 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 another monomer, having a hydroxyl group at a terminal, This is to react with the isocyanate group of the isocyanate compound to be added later. Among them, 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 adding and copolymerizing other monomers such as styrene are preferably used. In consideration of the reactivity with the isocyanate compound, the hydroxyl value is 5 to 200.
(KOH mg / g).

The isocyanate compound is added in order to increase the adhesion to a substrate or a deposited layer composed of an inorganic oxide by urethane bonds formed by reacting with an acrylic polyol, and mainly acts as a crosslinking agent or a curing agent. I do.
In order to achieve this, as an isocyanate compound,
Monomers such as aromatic tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), aliphatic xylene diisocyanate (XDI), hexadiisocyanate (HMDI), and isophorone diisocyanate (IPDI);
Derivatives are used. These are used alone or as a mixture.

The mixing ratio of the acrylic polyol and the isocyanate compound is not particularly limited, but if the amount of the isocyanate compound is too small, the curing may be poor. If the amount is too large, blocking or the like may occur and processing problems may occur. There is. Therefore, the mixing ratio of the acrylic polyol and the insocyanate compound is preferably such that the isocyanate group derived from the isocyanate compound is 50 times or less the hydroxyl group derived from the acrylic polyol. Particularly preferred is a case where isocyanate groups and hydroxyl groups are blended in equal amounts. A known method can be used for the mixing method, and is not particularly limited.

As the silane coupling agent, any silane coupling agent containing an organic functional group can be used. For example, ethyltrimethoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloro Use one or more silane coupling agents such as propyltrimethoxysilane, glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, or a hydrolyzate thereof. be able to.

Further, among these silane coupling agents, those having a functional group which reacts with a hydroxyl group of an acrylic polyol or an isocyanate group of an isocyanate compound are particularly preferable. For example, those containing isocyanate groups such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)
Those containing an amino group such as -γ-aminopropyltriethoxysilane and γ-phenylaminopropyltrimethoxysilane, and further γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxy Those containing an epoxy group, such as silane, can be used alone or as a mixture of two or more. These silane coupling agents have a functional group in which an organic functional group present at one end shows an interaction in a composite composed of an acrylic polyol and an isocyanate compound, or reacts with a hydroxyl group of an acrylic polyol or an isocyanate group of an isocyanate compound. By using a silane coupling agent to give a covalent bond to form a stronger primer layer,
The silanol group generated by hydrolysis of the alkoxy group at the other end expresses high adhesion to the inorganic oxide due to strong interaction with the metal in the inorganic oxide and the highly active hydroxyl group on the surface of the inorganic oxide. It is possible to obtain desired physical properties. Therefore, a silane coupling agent obtained by a hydrolysis reaction with a metal alkoxide may be used. There is no problem even if the alkoxy group of the silane coupling agent is a chloro group, an acetoxy group or the like, and these alkoxy groups, a chloro group, an acetoxy group and the like are hydrolyzed to form a silanol group. It can be used in this composite.

The mixing ratio of the acrylic polyol and the silane coupling agent is preferably in the range of 1/1 to 100/1 by weight, more preferably 2/1 to 50/100.
1 range.

The solvent for dissolving and diluting is not particularly limited as long as it is capable of dissolving and diluting. For example, esters such as ethyl acetate and butyl acetate, methanol,
A mixture of alcohols such as ethanol and isopropyl alcohol, ketones such as methyl ethyl ketone, and aromatic hydrocarbons such as toluene and xylene alone and arbitrarily can be used. However, since an aqueous solution such as hydrochloric acid or acetic acid may be used to hydrolyze the silane coupling agent, it is more preferable to use a solvent in which isopropyl alcohol or the like is arbitrarily mixed with ethyl acetate, which is a polar solvent, as a co-solvent. .

It is preferable to add a reaction catalyst in order to accelerate the reaction when the silane coupling agent is compounded. The catalyst to be added is preferably a tin compound such as tin chloride (SnCl 2, SnCl 4), tin oxychloride (SnOHCl, Sn (OH) 2 Cl 2), and tin alkoxide from the viewpoint of reactivity and polymerization stability. 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, no catalytic effect can be obtained, so that the molar ratio is 1/10 to 1/1000 with respect to the silane coupling agent.
0 is preferable, and 1/100 to 1/1 is more preferable.
More preferably, it is in the range of 2,000.

As a method for preparing a primer solution for forming the primer layer 2, a composite solution is prepared by mixing an acrylic polyol, an isocyanate compound, and a silane coupling agent at an arbitrary mixing ratio. Specifically, first, a silane coupling agent and an acrylic polyol are mixed, a solvent and a diluent are added to dilute the mixture to an arbitrary concentration, and then mixed with an isocyanate compound to prepare a composite solution, or a silane coupling method is used in advance. There is a method in which the composition is mixed in a solvent and then mixed with an acrylic polyol, and the mixture is diluted to an arbitrary concentration by adding a solvent and a diluent, and then a composite solution is prepared by adding an isocyanate compound.

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

A coating film is formed on one surface of the substrate 1 by a known printing / coating method such as gravure printing, roll coating, knife edge coating, gravure coating, etc., and dried and cured to form the primer layer 2. Form. It is preferable that the thickness of the primer layer 2 is generally in the range of 0.01 to 2 μm in dry film thickness. When the thickness is less than 0.01 μm, it is difficult to obtain a uniform coating film, and the adhesion may be reduced.
On the other hand, if the thickness exceeds 2 μm, it is not preferable because the film cannot keep flexibility because of the thickness and there is a possibility that the film may be cracked by external factors. A particularly preferred thickness of the primer layer 2 is 0.05
０．５0.5 μm.

As a method for forming the primer layer, 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 coat, a knife edge coat or a gravure coat may be used. Can be. As the drying conditions, generally used conditions are adopted.

The thin film layer 3 made of an inorganic oxide is made of a vapor-deposited film of an inorganic oxide such as aluminum oxide, silicon oxide, tin oxide, magnesium oxide or a mixture thereof, has transparency, and is made of oxygen, water vapor or the like. Any material having gas barrier properties may be used. Among them, aluminum oxide and silicon oxide are preferable, especially in consideration of gas barrier properties. Among them, silicon oxide is particularly excellent in liquid gas barrier properties. However, the thin film layer of the present invention is not limited to the above-described inorganic oxide, and any material that meets the above conditions can be used.

The optimum conditions for the thickness of the thin film layer 3 vary depending on the type and constitution of the inorganic compound used.
The range is desirably in the range of ~ 300 nm, and the value is appropriately selected. 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, if the thickness exceeds 300 nm, flexibility cannot be maintained in the thin film, and the thin film may be cracked by external factors such as bending and pulling after the film is formed. The thickness of the deposited layer is preferably 10
It is in the range of １５０150 nm.

There are various methods for forming the thin film layer 3 on the primer layer, and the thin film layer 3 can be formed by an ordinary vacuum deposition method. Further, other thin film forming methods such as a sputtering method, an ion plating method, and a plasma vapor deposition (CVD) method can also be used. However, in consideration of productivity, the vacuum deposition method is currently the most excellent. As a heating means of a vacuum deposition apparatus by a vacuum deposition method, any of an electron beam heating method, a resistance heating method, and an induction heating method is preferable. Further, in order to improve the adhesion between the deposited film and the base material and the denseness of the deposited film, the deposition can be performed by using a plasma assist method or an ion beam assist method. In addition, in order to increase the transparency of the deposited film, reactive vapor deposition such as blowing oxygen gas may be performed at the time of vapor deposition.

The gas barrier coating layer 4 is a thin film layer 3 made of an inorganic oxide for imparting a higher gas barrier property.
It is provided above.

The gas barrier coating layer 4 is formed of an aqueous solution or a water / alcohol mixed solution containing a water-soluble polymer and at least one of (a) at least one metal alkoxide and a hydrolyzate or (b) tin chloride. It is formed by using a coating agent as a main agent. For example, a solution obtained by dissolving a water-soluble polymer and tin chloride in an aqueous (water or water / alcohol mixture) solvent, or a solution obtained by mixing a metal alkoxide directly or beforehand with a treatment such as hydrolysis is used. Adjust to make a solution. This solution is coated on a vapor-deposited layer made of an inorganic oxide, and then dried by heating. Each component contained in the coating agent will be described in more detail.

The water-soluble polymer used for the coating agent in the present invention includes polyvinyl alcohol, polyvinylpyrrolidone, starch, methylcellulose, carboxymethylcellulose, sodium alginate and the like. In particular, when polyvinyl alcohol (hereinafter abbreviated as PVA) is used for the coating agent of the present invention, the gas barrier properties are most excellent. The PVA referred to here is generally obtained by saponifying polyvinyl acetate. As PVA, for example,
So-called partially saponified PV in which several tens% of acetic acid groups remain.
It includes from A to complete PVA in which only a few% of acetic acid groups remain, and is not particularly limited.

The tin chloride used for the coating agent includes stannous chloride (SnCl2), stannic chloride (SnC2).
14) or a mixture thereof. These tin chlorides may be anhydrous or hydrated.

Further, the metal alkoxide is represented by the general formula: M (O
R) n (M: metal such as Si, Ti, Al, Zr, R:
CH3, C2H5, etc.). Specifically, tetraethoxysilane [Si
(OC2H5) 4], triisopropoxyaluminum [Al (O-2'-C3H7) 3] and the like. Among them, tetraethoxysilane and triisopropoxyaluminum are hydrolyzed in an aqueous solvent. It is preferable because it is stable.

Known additives such as an isocyanate compound, a silane coupling agent, or a dispersing agent, a stabilizer, a viscosity modifier, and a coloring agent may be added as needed as long as the gas barrier properties of the coating agent are not impaired. it can.

For example, as the isocyanate compound to be added to the coating agent, a compound having two or more isocyanate groups in its molecule is preferable. For example, monomers such as tolylene diisocyanate, triphenylmethane triisocyanate, and tetramethyl xylene diisocyanate, and polymers and derivatives thereof are exemplified.

As a method for applying the coating agent, conventionally known means such as a commonly used dipping method, roll coating method, screen printing method, spray method and the like can be used. The thickness of the coating varies depending on the type of coating agent and processing conditions, but the thickness after drying is 0.01μ.
It is sufficient that the thickness is at least m, but if the thickness is at least 50 μm, cracks are likely to occur in the film.

The outer base material 5 made of a stretched plastic material is laminated on the gas barrier coating layer and placed outside the packaging material, protecting the vapor-deposited layer made of inorganic oxide and the gas barrier coating layer, and protecting the entire packaging material. It is provided for the purpose of raising the waist strength.

Examples of the outer substrate 5 include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefin films such as polypropylene, and polyamide films. It is preferable to use a stretched substrate in consideration of mechanical strength. Among them, polyethylene terephthalate which is stretched arbitrarily in the biaxial direction is particularly preferably used.

The thickness of the outer substrate 5 is determined according to the material and required quality, but is generally in the range of 10 to 30 μm. As a forming method, lamination is performed by a known laminating method such as a dry laminating method of bonding using an adhesive such as a two-component curable urethane-based resin or an extrusion laminating method in which a polyolefin resin is heated and melted and extruded into a curtain shape and used as an adhesive layer. It is possible.

Further, another layer can be laminated on the outer surface or the inner surface of the outer substrate 5. For example, it is a printing layer or a paper material layer. The printing layer is formed for practical use as a packaging bag or the like. For example, additives such as various pigments, extenders and plasticizers, desiccants and stabilizers are added to conventionally used ink binder resins such as urethane, acrylic, nitrocellulose and rubber. It is a layer composed of ink. By this printing, characters, pictures, and the like are formed. As a forming method, for example, a well-known printing method such as an offset printing method, a gravure printing method, or a silk screen printing method, or a well-known coating method such as a roll coat, a knife edge coat, or a gravure coat can be used. Dry thickness of printed layer is 0.1 ~
2.0 μm may be sufficient.

The paper material layer is further laminated on the outer substrate 5 and is used for use as a composite container. For example, the material and thickness of the paper material layer are not particularly limited since they differ according to required quality. As a forming method, a known method such as a dry laminating method of bonding using an adhesive such as a two-component curable urethane-based resin or an extrusion laminating method in which a polyolefin resin is heated and melted and extruded into a curtain shape and used as an adhesive layer. Can be stacked.

Thermoplastic resin layer 6 having heat sealability
Is provided on the other surface of the base material 1 as an adhesive layer when forming a bag-like packaging material or a container packaging material. For example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer and the like A resin such as a metal crosslinked product is used. The thickness is determined according to the purpose, but is generally 15
２００200 μm. As a forming method, it is common to use a dry laminating method or the like in which a film-like material made of the above resin is bonded using an adhesive such as a two-component curable urethane resin, but all are laminated by a known method. be able to.

[0051]

EXAMPLES The gas barrier packaging material of the present invention will be further described with reference to specific examples.

<Preparation of Solution for Primer Layer> A) 2- (Epoxycyclohexyl) ethyltrimethylsilane (hereinafter abbreviated as EETMS) in a diluting solvent (ethyl acetate), and 5.0 times the weight of the EETMS (weight ratio) Of acrylic polyol. The mixture was further added with a tin chloride (SnCl ₂ ) / methanol solution (0.0
03 mol / g) was added to EETMS by 1
/ 135 mol and stirred. Next, triisyl isocyanate (hereinafter abbreviated as TDI) was added as an isocyanate compound so that the isocyanate group of TDI was equivalent to the hydroxyl group of acrylic polyol. 2% by weight of this mixed solution as the total concentration of the added compound
The solution A was diluted so that

B) 1 part by weight of γ-isocyanatopropyltrimethylsilane in a diluting solvent (ethyl acetate)
10 parts by weight of acrylic polyol were mixed and stirred. Then, as an isocyanate compound, a 7: 3 mixture of XDI and IPDI was added so that the isocyanate group of this isocyanate compound mixture was equivalent to the hydroxyl group of the acrylic polyol. A solution obtained by diluting this mixed solution to have a total concentration of the added compound of 2% by weight was designated as solution B.

<Example 1> The substrate 1 was 12 μm thick.
The solution A was applied to one side of a biaxially stretched polyethylene terephthalate (PET) film by a gravure coating method so as to have a dry thickness of 0.1 μm, followed by drying.
Was formed. Next, the silicon oxide was evaporated by a vacuum evaporation apparatus using a resistance heating method to form a layer having a thickness of 4 on the primer layer 2.
A thin film layer 3 made of 0 nm silicon oxide was formed. next,
On the thin film layer 3, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was laminated as the outer substrate 5 by a dry lamination method via a two-component curable urethane-based adhesive. Further, a low-density polyethylene film having a thickness of 60 μm is laminated on the other surface of the base material 1 by a dry lamination method via a two-component curable urethane-based adhesive to form a sealant layer 6, and the gas barrier packaging material of the present invention is formed. Produced.

<Example 2> 12 μm thick substrate 1
The solution A was applied to one surface of a biaxially stretched polyethylene terephthalate (PET) film by a gravure coating method to a dry thickness of 0.1 μm and dried.
Was formed. Next, the silicon oxide was evaporated by a vacuum evaporation apparatus using a resistance heating method to form a layer having a thickness of 4 on the primer layer 2.
A thin film layer 3 made of 0 nm silicon oxide was formed. Further, a coating agent having the following composition was applied thereon by a gravure coating method to form a gas barrier coating layer 4 having a dry thickness of 0.4 μm. Composition of coating agent: A mixture of the following liquids in a mixing ratio of 60/40 (wt%). Liquid: hydrochloric acid (0.1%) in 10.4 g of tetraethoxysilane
N) A hydrolyzed solution having a solid content of 3% by weight (SiO2 equivalent) obtained by adding 89.6 g and stirring for 30 minutes to hydrolyze. Liquid: 10w in 3wt% polyvinyl alcohol aqueous solution
The solution which mixed the isopropyl alcohol solution of t%.
Next, on the gas barrier coating layer 4, as the outer substrate 5,
A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was laminated by a dry lamination method via a two-component curable urethane-based adhesive. Furthermore, a low-density polyethylene film having a thickness of 60 μm is laminated on the other surface of the base material 1 by a dry lamination method via a two-component curable urethane-based adhesive to form a sealant layer 6, and the gas barrier packaging material of the present invention is formed. Obtained.

Example 3 A gas barrier packaging material of the present invention was obtained in the same manner as in Example 2, except that Solution B was used as the primer layer 2.

<Embodiment 4> In Embodiment 3, the thin film layer 3
The thickness is about 20 by the reactive vacuum deposition method by introducing oxygen gas of metallic aluminum by electron beam heating method.
A gas barrier packaging material of the present invention was obtained in the same manner as in Example 3 except that aluminum oxide having a thickness of nm was formed.

Comparative Example A comparative packaging material was obtained in the same manner as in Example 3 except that the primer layer 2 was not provided.

Using the gas barrier packaging material of the present invention obtained in Examples 1 to 4 and the packaging material of the comparative example, a pouch having four sides as a seal portion was produced, and water was used as the content.
g. Then, the pouch is heated to 40 ° C.-90% R
Stored under H atmosphere for 1 month. As an evaluation, an oxygen permeability measurement device (OXTRAN, manufactured by Modern Control Co., Ltd.)
-10/50 A), in an atmosphere of 30 ° C. and 70% RH, oxygen permeability (cc / m ² / day), weight change after storage for 1 month (gr / m ² / day), before and after storage The lamination strength (measured at a peeling speed of 300 mm / min, unit: gr / 15 mm), and the peeled state of the thin film layer 3 after storage were observed by visual observation. Table 1 shows the results.

[0060]

[Table 1]

As a result of the storage test of the contents shown in Table 1, those using the gas barrier wrapping material of the present invention have high gas barrier properties and high lamination strength for blocking gases and the like which affect the contents. Was confirmed. And,
It can be seen that the content has a high gas barrier property even with respect to a liquid substance, and has excellent content resistance without delamination or the like.

On the other hand, in the packaging material of the comparative example, both the appearance after storage and the overall evaluation were poor.

[0063]

As described above, according to the gas barrier packaging material of the present invention, a versatile packaging material having excellent transparency and high gas barrier properties comparable to aluminum foil can be obtained. It has excellent adhesion and gas barrier properties, including suitability for contents, especially for contents, so it can be widely used in the field of packaging.

[Brief description of the drawings]

FIG. 1 is a schematic partial sectional view showing one embodiment of the gas barrier packaging material of the present invention.

FIG. 2 is a schematic partial sectional view showing another embodiment of the gas barrier packaging material of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Primer layer 3 ... Thin film layer 4 ... Gas barrier coating layer 5 ... Outer base material 6 ... Sealant layer

 ──────────────────────────────────────────────────の Continued on the front page F-term (reference) 4F100 AA05C AA17C AA20 AH06B AH08C AK01A AK01C AK01E AK06 AK25B AK42D AK51B AK51G AT00D BA05 BA07 BA10D BA10E CB02 EH46C EH66 JEJBJC12BJJBJJBJJB12

Claims (6)

[Claims] 1. A primer layer comprising a composite of an acrylic polyol, an isocyanate compound, and a silane coupling agent on one surface of a substrate made of a plastic material,
An outer base material is laminated on the thin film layer side of the laminated material composed of the inorganic oxide thin film layer, and a sealant layer composed of a thermoplastic resin having heat sealability is laminated on the substrate side of the laminated material. A gas barrier packaging material characterized by the following. 2. A primer layer comprising a composite of an acrylic polyol, an isocyanate compound and a silane coupling agent, on one surface of a substrate made of a plastic material,
A thin film layer made of an inorganic oxide and a gas barrier coating layer, a laminate material having an outer substrate laminated on the gas barrier film layer side of the laminate material, and a thermoplastic resin having heat sealability on the substrate side of the laminate material A gas barrier packaging material characterized by laminating a sealant layer comprising: 3. The method according to claim 1, wherein the gas barrier coating layer comprises a water-soluble polymer, at least one metal alkoxide and a hydrolyzate thereof.
3. The gas barrier packaging material according to claim 2, wherein a coating agent mainly composed of an aqueous solution containing at least one tin chloride or a water / alcohol mixed solution is applied and dried by heating. 4. The silane coupling agent of the primer layer has an organic functional group that reacts with at least one of a hydroxyl group of an acrylic polyol or an isocyanate group of an isocyanate compound.
The gas barrier packaging material according to any one of the above. 5. The gas barrier packaging material according to claim 4, wherein the organic functional group of the silane coupling agent of the primer layer comprises an isocyanate group, an epoxy group and an amino group. 6. The gas barrier packaging material according to claim 1, wherein the outer substrate is a biaxially stretched polyethylene terephthalate film.