JP2000025145A - Barrier laminate, packaging material using the same, and packed body using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent barrier properties depending upon a process from changing and deteriorating by a method wherein a covering film, which is produced by forming a thin film layer on a polymer film base material, is laminated through an adhesive having a gas barrier layer onto a heat sealing resin. SOLUTION: A covering film is produced by forming a thin film layer 3 made of metal or metal oxide on one side of a polymer film base material 2. Next, a barrier laminate is produced by bonding the thin film layer, on the surface of which a barrier adhesive 6 is applied, of the covering film 1 having a transparency with a heat sealing resin 7. Through this constitution, minute pin hole parts existing in advance are filled up with an inorganic material super-finely dispersed in a barrier adhesive. Thus, high grade barrier properties are realized. A massive gas transmission through he cracks and fractures, which develop through the expansion and contraction of the film caused at the printing thereon and the lamination of other base material thereon and through the thermal stress due to heat shock, in the thin film layer can be checked by the layer made of the adhesive.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer film substrate and a coating layer made of a metal or a metal compound formed on at least one surface of the substrate by a dry process method such as vapor deposition or sputtering. In regard to laminates of coated films that can be widely used for packaging materials such as industrial materials, pharmaceuticals, foods, etc., especially printing, lamination,
The present invention relates to a barrier laminate improved so as not to cause a significant decrease in gas barrier properties after secondary processing such as bag making, a packaging material using the same, and a packaging body using the same.

[0002]

2. Description of the Related Art A thin film of a metal or a metal compound is formed on a polymer film substrate by a dry process method such as a vacuum evaporation method, and is used as a material for medical drugs, foods, and industrial materials. In addition, vapor-deposited films using metal oxides, which are more transparent in the visible wavelength region than metals such as aluminum, as vapor-deposited materials are superior in terms of easy incineration and are regarded as important due to recent global environmental issues. Have been.

[0003] Among them, those represented by silicon oxide and aluminum oxide have been partially put to practical use, but they are originally used for finishing packaging materials through various secondary processes such as printing, laminating, and bag making. Problems such as deterioration of gas barrier properties and adhesiveness of the coating film remain.

[0004] As described above, in the packaging material using the oxide-deposited film, the know-how of the converting greatly affects the performance of the final product, and it is difficult to handle the same as a general-purpose film, and the use range is restricted. I was

[0005] In order to solve such a problem, the following improvements have been intensively studied.

[0006] When laminating a heat-sealable resin film, the tension of a vapor-deposited film substrate is reduced as much as possible in order to reduce the deterioration of barrier properties. Various processes such as extrusion lamination at low temperature and improvement of special adhesive resin that has adhesiveness even at low temperature.When processing thin film materials by mixing two or more oxides to form a multilayer structure Although the thin film material itself has been improved by reducing the occurrence of cracks, there have been practical problems.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and has a strong adhesive force with a thin film material;
Provide a barrier laminate having a barrier property that is superior to a coated film without barrier property deterioration when performing processing such as printing, laminating, and forming on a coated film that highly maintains the gas barrier property of a thin film material. It is intended to be.

[0008]

According to the first and second aspects of the present invention,
At least one surface of a base material such as a polymer film is provided with an anchor coat layer as required to form a thin film layer of a metal or a metal compound. It is a barrier laminate which is bonded via an agent.

[0009] Since the coating film on which the metal or metal oxide thin film is formed and the heat-sealable resin are laminated via a specific barrier adhesive, cracks in the coating layer and oxygen, nitrogen and the like passing through pinholes are formed. Since gas, water vapor and the like are absorbed and blocked by the adhesive layer, a higher barrier property can be achieved than a conventional laminate having an adhesive having no barrier property.

The invention according to claims 3 and 4 is intended to improve the transparency by forming an anchor coat layer on at least one surface of a base material such as a polymer film as required and forming a thin film of a metal or a metal compound and a protective coat layer in that order. It is a barrier laminate obtained by adhering a covering film and a heat-sealing resin having the same via a barrier adhesive.

As in the first and second aspects of the present invention, the adhesive layer absorbs and blocks gas, water vapor and the like passing through cracks and pinholes through the coating thin film layer and the protective layer, so that a higher barrier property can be obtained. Can be achieved.

The invention of claims 2 and 4 is a structure in which an anchor coat layer is required when adhesion is a problem. When the adhesion is not a problem, the number of steps is small and the cost is low. And 3 are preferred.

[0013] The invention of claim 5 is a barrier laminate in which the barrier adhesive is a cured film of an unsaturated acid and a polyamine derivative.

Since a composition obtained from at least a carboxylic acid of an unsaturated acid and a polyamine derivative forms an amide bond and exhibits gas barrier properties, it is possible to adsorb and block gas components permeating through the coating film. It can be a high barrier laminate.

The invention according to claim 6 is the invention according to claims 1, 2, 3, and 4.
Based on the premise of the invention, the thin film layer is a silicon oxide, aluminum oxide, magnesium oxide, or a mixture of two or more or a multi-layer coating film laminated with a heat sealing resin via a barrier adhesive It is.

The invention according to claim 7 is the barrier laminate according to any one of claims 1 to 6, wherein the protective layer is a coating layer comprising at least a hydrolyzate of a metal alkoxide and a water-soluble binder.

The invention according to claim 8 is the barrier laminate according to any one of claims 1 to 6, wherein the protective layer is a coating layer comprising at least a hydrolyzate of a metal alkoxide and a water-insoluble binder. .

According to a ninth aspect of the present invention, a packaging material base is provided on a surface of the polymer film substrate of the barrier laminate according to any one of the first to eighth aspects opposite to the surface on which the metal or metal compound thin film layer is formed. It is a packaging material characterized by being laminated.

According to a tenth aspect of the present invention, there is provided a package obtained by heat-sealing the heat-sealing resin of the packaging material according to the ninth aspect to form a bag.

According to the present invention, since a coating film having a metal or metal oxide thin film layer formed thereon and a heat-sealable resin are laminated with a two-part curable adhesive having gas barrier properties, the coating film is several cm ³ from the coating film. / M ² / day / at
m, a few g / m ² / day, very small molecules such as oxygen and water vapor leaking in a very small amount can be further blocked by the shielding effect of the adhesive layer, so that it is very superior to those laminated with a conventional non-barrier adhesive. Barrier properties are achieved.

According to the third and fourth aspects of the present invention, similarly to the first and second aspects of the present invention, an extremely small amount of gas permeation leaking through the coating layer and the protective layer can be blocked by the adhesive layer.
Further, the amount of gas permeating from cracks in the thin film layer generated by expansion and contraction of the coating film during the secondary processing can be reduced by the adhesive layer.

The invention of claim 5 relates to a barrier adhesive comprising at least a cured composition of an unsaturated acid and a polyamine derivative. Therefore, the polyamide bond of the cured composition restricts the molecular movement of the adhesive so that the adhesive is bonded. Since it has the function of suppressing the diffusion of low molecules through the agent layer, gas such as trace amounts of oxygen and water vapor molecules that have passed through the thin film layer or the protective layer formed on the thin film layer pass between the adhesives. Diffusion can be blocked, and as a result, the amount of gas permeated and dissolved in the heat-sealing resin layer can be reduced.

According to the sixth aspect of the present invention, since the thin film layer has one of silicon oxide, aluminum oxide, and magnesium oxide, or has a mixed or multi-layered structure of two or more kinds, it is generated in the thin film layer during the secondary processing. Microcracks that propagate into the thin film can be reduced, and a barrier product having a very high barrier property against inorganic gases such as oxygen and nitrogen, water vapor, and organic vapor can be obtained.

Further, in the invention according to claims 7 and 8,
Because a specific protective layer is formed directly on the thin film layer,
Part of the fine inorganic particles contained in the protective layer coating penetrate into microcracks and pinholes with the underlying thin film layer to make the thin film structure more dense and form an independent interface between the protective layer and the thin film layer By forming a hybrid structure that does not have such a structure, gas permeation can be suppressed low, so that a more advanced barrier laminate can be obtained.

According to the ninth and tenth aspects of the present invention, a packaging material or a package which exhibits the above effects even after the secondary processing can be obtained.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The barrier laminate of the present invention has a transparency in which a thin film layer 3 made of a metal or a metal compound is formed on one surface of a polymer film substrate 2 as shown in FIG. The laminate has a basic structure in which a thin film layer surface of the covering film 1 and a heat-sealable resin 7 are adhered via a barrier adhesive 6.

As another layer constitution, as shown in FIG. 2, for example, an anchor coat layer 4, a thin film layer 3 made of a metal or a metal compound, and a protective layer 5 are sequentially formed on one surface of a polymer film substrate 2. A laminate in which the protective layer surface of the coated film 1 having transparency and the heat-sealable resin 7 are bonded via the barrier adhesive 6 is also conceivable.

The polymer film substrate 1 used in the present invention is preferably a material having excellent dimensional stability, heat resistance and mechanical strength. Examples thereof include polyolefins such as polyethylene, polypropylene and polybutene, ethylene-vinyl alcohol copolymers, and the like. Polyvinyl alcohol, formalized polyvinyl alcohol (vinylon), polymethyl acrylate, polystyrene, polyethylene terephthalate, polyethylene 2,6 naphthalate, polyethylene butyrate, polyester, nylon 6, nylon 6
6, Nylon 6-10, Nylon 6-12, Nylon 1
1. Polyamides such as nylon 12, polymethylpentene, polyphenylene sulfide, polyether ketone,
Polyetheretherketone, Polyetherimide, Polyimide, Polycarbonate, Polyketone, Polyacrylonitrile, Polyvinylchloride, Polyvinylidene chloride, Polyfuccavinyl, Polyfuccavinylidene, Polytrifucachloride ethylene, Polytetrafucaethylene, Cellulose, Methylcellulose, Carboxy A film such as methyl cellulose can be exemplified. Naturally, the film is not limited to these films, and a film obtained by laminating two or more kinds of the above films by a known method as needed may be used as the film.

Further, these films can be used as so-called stretched films which are stretched at an arbitrary magnification in at least one of the longitudinal and transverse directions during film formation in view of strength, dimensional stability and heat resistance. Of course, it may be used as an unstretched film that is not stretched.

The above film contains an antioxidant, a heat stabilizer, an ultraviolet absorber, a plasticizer, an antistatic agent, a lubricant, a pigment,
Known additives such as dyes and anti-fogging agents can be blended and used as necessary.

Examples of the antioxidant include 2,6-di-ter
Examples include t-butyl-4-methylphenol, 2,2′-methylenebis (6-tert-butyl-4-ethylphenol), dilaurylthiodipropionate, and the like.

Examples of lubricants and heat stabilizers include polyethylene wax, liquid wax, barium stearate, calcium stearate, dibutyltin dilaurate, metal organic phosphates, organic phosphite compounds, phenols, β-diketone compounds, bisamides, ricinol Examples thereof include inorganic fine particles such as barium acid, silica, alumina, talc, and barium sulfate, and fatty acid amide.

Examples of the ultraviolet absorber include benzotriazole, benzophenol, benzoate, cyanoacrylate, phenyl salicylate and the like.

Examples of the plasticizer include phthalic acid derivatives, isophthalic acid derivatives, itaconic acid derivatives, citric acid derivatives, maleic acid derivatives, adipic acid derivatives, oleic acid derivatives, ricinoleic acid derivatives, and epoxidized soybeans.

Examples of pigments and dyes include phthalone cyanine blue, phthalocyanine green, titanium oxide, alizarin lake, hansa yellow, zinc white, ultramarine, quinacdrine, carbon black, permanent red and the like.

Examples of the antistatic agent include cationic surfactants, anionic surfactants, and nonionic surfactants.

Examples of the antifogging agent include sorbitan fatty acid esters, ethylene oxide adducts of sorbitan fatty acid esters, and fatty acid monoglycerides.

The thickness of the film is not particularly limited, but a film having a thickness of 3 to 500 μm can be used from the viewpoint of strength and handling. Preferably it is in the range of 6 to 100 μm.

The thin film layer 3 is formed by vacuum deposition, sputtering, ion plating, plasma deposition, or chemical deposition (C) of metal, metal oxide, metal nitride, metal carbide, or the like.
A thin film can be formed by a known dry process method such as VD method) or a thin film forming method by wet plating or the like.

Specifically, silicon, aluminum, magnesium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, molybdenum, palladium, silver, indium, tin,
This is a thin film layer having a multilayer structure composed of a single material selected from a metal selected from tantalum, tungsten, platinum, gold, lead and the like, an oxide thereof, a nitride thereof, a plurality of mixed materials, or two or more thereof.

The thickness of the thin film layer is 5 to 2000 n
When the thickness is less than 5 nm, the thin film layer does not form a uniform layer, and does not exhibit the desired gas barrier properties.

When the thickness exceeds 2000 nm, the thin film layer has no flexibility and cracks and cracks occur,
Further, the adhesiveness to the film may be reduced and the thin film layer may fall off, which is not preferable. Preferably, 10
範 囲 100 nm.

As the protective layer 5, polyester, polyimide, polyurethane, polymethacrylate, styrene-
Acrylic copolymer, styrene-acryl-hydroxyethyl methacrylate copolymer, polyurethane, ethylene-vinyl acetate copolymer, chlorinated polyethylene-vinyl acetate copolymer, polyamide, polyvinyl butyl ether, chlorinated polypropylene, vinyl chloride Water-insoluble resin such as vinyl acetate copolymer or polyvinyl alcohol;
Water-soluble resins such as polyvinyl acetate, hydroxymethylcellulose, cellulose, carboxymethylcellulose, and alginic acid, as well as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyl (meth) acrylate, and 2-hydroxyl Resins selected from ultraviolet- or electron-curable resins such as propyl (meth) acrylate, cyclohexyl (meth) acrylate, and epoxy (meth) acrylate have an average agglomerated particle diameter of at least several μm, preferably 2 μm or less, more preferably 1 μm or less. This is a cured coating film obtained by adding fine particles such as anhydrous intangible silica, colloidal silica, silica sol, alumina sol, and lithium silicate, which are fine particles of about 0.1 to 10 wt% to the above-mentioned resin amount. Iron, sodium,
20 impurities such as potassium, calcium, magnesium
About 500 ppm may be contained.

In order to improve the dispersibility of the fine particles, about 0.1 to several% of various silane coupling agents may be added.

When a fine particle having a diameter of more than several microns is used, fine cracks in the thin film layer and particles cannot enter the porous portion, resulting in insufficient densification of the thin film layer.
It is not preferable because it is insufficient to make the protective layer itself thin and hard.

As still another method of forming a protective layer, a protective layer can be formed by heating and drying a coating solution containing one or more metal alkoxides or hydrolysates thereof as a main component. Examples of the coating liquid include those having a catalytic role of promoting hydrolysis of tin chloride, aluminum chloride and the like, and an isocyanate compound having at least two or more isocyanate groups in a molecule such as tolylene diisocyanate (TDI); Isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (H
Monomers such as MDI) and 4-4'diphenylmethane diisocyanate (MDI) and polymers or derivatives thereof can also be added as appropriate.

Specific examples of the metal alkoxide include a general formula M (OR) n (M: Si, Ti, Zr, A) such as tetraethoxysilane and triisopropoxyaluminum.
l, a metal such as Zr, R: an alkyl group such as CH ₃ or C ₂ H ₅ , and n = valence of M).

In addition to the above-mentioned coating components, known additives such as dispersants, stabilizers, and viscosity modifiers can be added.

As a method of forming the protective layer 5, it is possible to form the above-mentioned coating solution on the above-mentioned thin film layer by a known coating method such as a tipping method, a gravure coating method, a roll coating method, and a spraying method. The coating layer can be dried and cured by heating and drying in a conventional hot air circulation or by ultraviolet rays or electron beams.

As described above, since the metal alkoxide and its hydrolyzate are directly coated on the thin film layer to form the protective layer, the coating liquid permeates into the thin film from the porous portion on the surface of the thin film layer to protect the thin film layer. Hybridization regions form at the layer interface. The concentration gradient of the metal alkoxide, which is the main component of the coating solution forming the protective layer, gradually increases from the thin film layer to the protective layer, and the concentration of the fine metal oxide particles, which are hydrolysates generated from the main component material by heating during drying, is reduced. It is considered that the outermost layer increases and the hardness increases as a result.

The thickness of the above-mentioned protective layer is about 0.0
It is in the range of 1-50 μm, preferably 0.01-0.
The range is 8 μm. If the thickness is less than 0.05 μm, the thin film layer is undesirably subjected to stress during secondary processing such as printing or lamination, and the thin film may be cracked or cracked.

When the thickness is more than 50 μm, the above protective function can be maintained, but when the base film is thin, curling, deformation and the like occur during lamination, which is not preferable.

At least one of the protective layer side and the base film side of the coating film of the present invention is provided with a sealant material which is a heat-sealable thermoplastic material shown below via a barrier adhesive 6 as described below, if necessary. It can be laminated and used as the heat sealable resin 7.

Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer Copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene- (meth) acrylic acid copolymer and sodium or Examples thereof include a crosslinked product (ionomer) with a metal ion such as zinc, an ethylene-acrylonitrile copolymer, and an ethylene-vinyl acetate copolymer.

The thickness of the heat-sealable resin varies depending on the application, but is in the range of 1 to 300 μm, preferably 10 to 120 μm, more preferably 15 to 120 μm.
１００100 μm.

The heat-sealing temperature of the heat-sealing resin can be appropriately selected depending on the material to be used, but the heat-sealing can be performed in a temperature range of 80 ° C. to 200 ° C. The method for forming the heat-sealable resin on the protective layer is not particularly limited, and the method of dispersing and dissolving in an organic solvent for coating or the method in which the thermoplastic material is melted by heat and directly extruded into the protective layer. Examples of the method include a coating method and a method in which the thermoplastic material is melted in advance by heat and then formed into a film or sheet and laminated via the following adhesive.

The barrier adhesive 6 is a cured composition obtained from at least an unsaturated acid and a polyamine derivative, and has the following structural formula. A; R2 · N (R1) 2 B; R1 · N (R2) 1 C; (R2) 3N where R1 is hydrogen, an alkyl group, a substituted alkyl group, an allyl group, a substituted allyl group R2; A chain or branched alkyl group or alkylene group, or an arylene group or substituted arylene group having 6 to 18 carbon atoms.

The polyamine used in the present invention has a molecular weight of 1
In the range of 00 to 2,000,000, preferably 4
00 to 400,000.

Examples of the polyamine include polyvinylamine, polyacrylamine, polyvinylpyrrolidone, and a reaction product of polyethyleneamine and ethyldiamine. Polyethyleneimine is economically preferred.

The unsaturated acid is a general term for an acid having a vinyl group, and examples thereof include fumaric acid, maleic acid, acrylic acid, methacrylic acid, cinamic acid, vinyl phosphoric acid, sorbitol acid, vinyl sulfate, and itaconic acid. it can.

The blending ratio of the unsaturated acid and the polyamine derivative is 10:
1-1: 100.

Auxiliary organic crosslinking agents such as polyfunctional (meth) acrylates, epoxy isocyanates, thionates, acid anhydrides, acid grafts, alkyl halides, aldehydes and the like, and reactive silane compounds shown below are used to develop barrier properties. You may blend in the range which does not spoil.

The reactive silane is a compound having a functional group that binds to the nitrogen atom of the polyamine derivative. Those having a trialkoxy or triacryloxysilane group can be exemplified, and are represented by the following structural formula. A-SiR _m (OR) _3- mA; (meth) acrylate, aldehyde, (meth) acrylamide, isocyanate, isocyanate m; 0, 1, 2 R; C ₁ -C _4, preferably γ- (meth) acryl Roxypropyltrimethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, γ-isocyanate propylpropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, ethyltrimethoxysilane, chloropropyltrichlorosilane, chloropropylethylenedimethoxy Silane, methyldimethoxysilane, glycidoxypropylmethyldimethoxysilane, more preferably chloropropyltrimethoxysilane, chloropropyltriethoxysilane, γ-trimethoxysilylpropylglycidyl ether Is Le.

The blending ratio of the polyamine derivative and the reactive silane compound may be in the range of 100: 1 to 1:10, preferably in the range of 10: 1 to 1: 1.

As a method for curing the barrier adhesive, a coating solution obtained by dissolving the above materials in a solvent containing water and alcohol as a main component is coated by a known method such as a gravure method, a roll coating method, or a blade coating method described later. It can be applied to a body to be cured and cured by heat, ultraviolet light, or electron beam.

In addition to the above-mentioned essential components of the unsaturated acid and the polyamine derivative, known silane coupling agents, dispersants,
Any amount of an anti-blocking agent such as stearic acid amide and oleic acid amide can be blended and used as an auxiliary.

The resin of the third component shown below may be added and used within a compatible range. For example, acrylic resin, urethane resin, epoxy resin, polyester resin, polyamide resin, vinyl acetate resin, phenol resin, olefin, ethylene-vinyl acetate copolymer resin,
Polyvinyl acetal resin, natural rubber, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, vinyl acetate-acryl copolymer, ethylene-ethylene acrylate copolymer, polyester polyol, polyester polyurethane polyol, polyether polyurethane polyol, Examples of the resin include a single component selected from resins such as the above-mentioned resins or two kinds of resins.

As the electron beam accelerator used for electron beam irradiation, known types such as a scanning type, a double scanning type, a broad beam type, and a curtain beam type can be used and are not particularly limited.

The accelerating voltage that can be used is 50 to 30
It can be cured at 0 KV with an absorbed dose of 1 to 100 KGy, preferably 2 to 50 KGy.

The thickness of the adhesive layer is 0.1 to 10 μm
And preferably about 0.2 to 5 μm.

Examples of the method of applying the adhesive include the following known application methods, which are not particularly limited.

Specifically, there are a roll coating method, a gravure coating method, a blade coating method, an air knife coating method, a nozzle coating method, a die coating method, a kiss coating method and the like.

The amount of the adhesive applied can be appropriately selected depending on the application, but the amount after drying is in the range of 0.01 to 10 gr / m ² . Preferably it is 0.1-5 gr / m < ² >.

Further, instead of directly laminating the above-mentioned heat-sealing resin layer on the protective layer, the heat-sealing resin layer may be laminated with at least one or more other base material layers exemplified below. I do not care.

Specifically, it is a base material such as paper, polyethylene, polypropylene, polyester, polyamide and non-woven fabric. The thickness is in the range of 10 to 200 μm and is not particularly limited.

In the present invention, the anchor coat layer 4 provided on the polymer film substrate 2 as required
Corona treatment, low temperature plasma treatment, atmospheric pressure plasma treatment,
A method in which a polymer film substrate is formed into a surface-modified layer at a level of 0.1 to several nm by a wet treatment such as a chromic acid treatment, including a dry treatment such as an ion bombardment treatment and a flame treatment, and the resin described below. There are two methods of forming a layer.

The purpose of each of them is to improve the adhesiveness between the polymer film substrate and the thin film layer formed thereon.

Specific examples of the resin forming the anchor coat layer 4 include those selected from saturated polyester resins, unsaturated polyester resins, polyamide resins, polyurethane resins, polyolefin resins, polyethyleneimines, polyethylene oxides, organometallic alkoxides, and the like. Alternatively, an anchor coat layer can be formed by dispersing and dissolving a mixture of two or more of these in an appropriate organic solvent on at least one surface of the film by a known method and drying.

The amount of the anchor coat layer to be applied is set to 0.1.
It is in the range of 01 to 10 gr / m ² . Preferably, 0.
It is in the range of 1 to 1.5 gr / m ² .

Further, the anchor coat layer may contain additives such as the above-mentioned known plasticizers, lubricants, antioxidants, and the like. Alternatively, it is preferable to use a resin layer containing no resin.

The printing may be performed on the barrier laminate itself, but may be provided on the above-mentioned other base material layer. The printing may be performed on the entire surface, partially, or may not be performed. It may not be done.

[0082]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below.

Example 1 Silicon oxide was formed to a thickness of 40 nm on one side of a biaxially stretched polyester film 12 μm as a polymer film substrate 2 by vacuum evaporation to form a thin film layer 3.
The coating film 1 was obtained. On the thin film layer surface of the coating film 1, an adhesive of the following formula 1, which is a barrier adhesive 6, is applied by a gravure coating method so that the coating amount is 3.5 g / m ² , and the heat-sealing resin is applied. 7, low-density polyethylene film 40 μm, and 125KV-2K
Laminated by the electron beam curing method under the irradiation condition of Gy,
The barrier laminate of Example 1 was obtained.

(Example 2) A polyurethane-based anchor coat layer having a thickness of 0.1 µm was formed as an anchor coat layer 4 on one surface of the biaxially stretched polyester film 2 used in Example 1. On the anchor coat layer, silicon oxide was formed to a thickness of 40 nm as a thin film layer 3 in the same manner as in Example 1 to form a coating film 1, and a barrier adhesive 6 as an adhesive of Formulation 1 was prepared in the same manner as in Example 1. Then, the resultant was laminated with a low-density polyethylene film 40 μm as the heat-sealable resin 7 through the above to obtain a barrier laminate of Example 2.

Example 3 Aluminum oxide was formed to a thickness of 25 nm on one side of a biaxially stretched polyester film 12 μm as a polymer film substrate 2 by vacuum evaporation to form a thin film layer 3. Further, the following coating solution 1 is applied on the aluminum oxide thin film by a roll coating method,
By drying in a 120 degree drier for 1 minute, the mixture is dried.
A protective layer 5 having a thickness of 4 μm was formed to obtain a coated film 1. The low-density polyethylene film 40 as the heat-sealable resin 7 is applied to the protective layer surface of the coating film 1 via the adhesive of the prescription 1 as the barrier adhesive 6 in the same manner as in Example 1.
μm was laminated to obtain a barrier laminate of Example 3.

Example 4 An acrylic anchor coat layer 4 having a thickness of 0.1 μm was formed on one side of a biaxially stretched polyester film 12 μm serving as a polymer film substrate 2 and then oxidized by vacuum evaporation on this coat layer. Aluminum was formed to a thickness of 25 nm to form a thin film layer 3. In the same manner as in Example 3, a low-density polyethylene film 4 as a heat-sealable resin 7 was applied to the thin film layer surface of the coated film via a barrier adhesive 6 as an adhesive of Formula 1 as in Example 3.
0 μm was laminated to obtain a barrier laminate of Example 4.

(Example 5) Using the coating film of Example 3, the adhesive of Formula 1 was used, and the irradiation condition was 125 KV.
Instead of -1.5 KGy, a low-density polyethylene film was laminated with 40 μm in the same manner as in Example 4 to obtain a barrier laminate of Example 5.

(Embodiment 6) Irradiation conditions were 125 KV-2.
A laminate was produced by the same material method as in Example 5 except that the thickness was changed to 5 KGy, and a barrier laminate of Example 6 was obtained.

Example 7 A laminate was prepared using the same materials and under the same conditions as in Example 3 except that the adhesive of Formula 2 shown below was used, and a barrier laminate of Example 7 was obtained.

(Example 8) A laminate was produced using the same materials and conditions as in Example 4 except that the adhesive of Formula 2 shown below was used, to obtain a barrier laminate of Example 8.

Example 9 An acrylic anchor coat layer 4 having a thickness of 0.1 μm was formed on one side of a biaxially stretched polyester film 12 μm serving as a polymer film substrate 2 and then oxidized on this coat layer by a vacuum deposition method. Aluminum was formed to a thickness of 25 nm to form a thin film layer 3. Further, the same coating liquid 1 as in Example 3 was applied on this aluminum oxide thin film by a roll coating method, and dried with a dryer at 120 ° for 1 minute to form a protective layer 5 of 0.4 μm to obtain a coating film 1. . On the protective layer surface of the coating film 1,
In the same manner as in Example 1, a low-density polyethylene film 40 μm as a heat-sealable resin 7 was laminated via a barrier adhesive 6 as an adhesive of Formula 1 to obtain a barrier laminate of Example 9.

(Comparative Example 1) In the same manner as in Example 1, 40 nm of silicon oxide was formed on one surface of a biaxially stretched polyester film 12 μm by a known vacuum evaporation method, and a 40 μm low-density polyethylene film was formed on the thin film layer by a conventional method. Dry lamination was performed using a two-part curable urethane-based adhesive (A536 manufactured by Takeda Pharmaceutical Co., Ltd.) to produce a laminate of Comparative Example 1.

Comparative Example 2 A laminate of Comparative Example 2 was produced using the same material and method as in Comparative Example 1, except that aluminum oxide was formed to a thickness of 20 nm as a thin film layer.

<Protective Layer Forming Paint> (Coating Solution Formulation 1) Tetraethoxysilane 1
89.1 g of 0.1N hydrochloric acid was added to 0.4 g, and the mixture was stirred for 30 minutes and hydrolyzed with a solid content of 3% by weight and isopropyl alcohol / water (10/90) consisting of 3% by weight of polyvinyl alcohol. Was mixed to obtain a coating material for forming a protective layer.

<Adhesive> (Adhesive Formulation 1) N- (isopropoxymethoxy) silylpropylpolyethyleneimine and itaconic acid in a ratio of 1: 1
Was dissolved in a water / isopropyl alcohol solvent mixed in the above to prepare a barrier adhesive having a solid content of 20%.

(Adhesive Formulation 2) N- (isopropoxymethoxy) silylpropylpolyethyleneimine, itaconic acid and methacryloxypropyltrimethoxysilane
The mixture mixed at 0:30:20 parts by weight was dissolved in a water / isopropyl alcohol solvent to prepare a barrier adhesive having a solid content of 20%.

The oxygen permeability and water vapor permeability (before and after the gelbo flex test) and the lamination strength of a total of 10 kinds of laminates prepared in Example 8 and Comparative Example 2 were measured by the following methods. did. Table 1 shows the results. <Physical property evaluation method> Oxygen permeability JIS K7126 method B method (same pressure method) Measured at 27 ° C-75% RH atmosphere MoconOxtran Measurement unit: cm ³ / m ² / day / atm. Water vapor permeability 法 JIS K7129 method B (infrared sensor method) Measured at 40 ° C.-90% RH atmosphere Device MoconPermatran Measurement unit: g / m ² / day Laminate strength ‥ Instron type tensile tester based on JIS K7127 method Gelbo Flex Test: Performed 20 times at room temperature using a Gelbo Flex Tester manufactured by Rigaku Corporation.

[0098]

[Table 1]

[0099]

As described above, according to the present invention, a coating film having a thin film layer formed on a polymer film substrate is laminated via an adhesive having a specific gas barrier property.
Higher barrier properties can be achieved by previously filling the fine pinholes in the thin film layer with the ultrafinely dispersed inorganic material contained in the barrier adhesive.

Further, the film can be suppressed by a large amount of the gas-permeable adhesive layer from cracks and cracks in the thin film layer generated due to expansion and contraction of the film generated during printing or lamination with other substrates or thermal stress due to heat shock. Excellent barrier properties can be achieved as a laminate.

Therefore, the barrier property of the final product changes depending on the converting process which has been conventionally employed,
Problems such as deterioration can be solved, and a very practical and valuable packaging material can be provided.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a barrier laminate of the present invention.

FIG. 2 is a sectional view showing another embodiment of the barrier laminate of the present invention.

[Explanation of symbols]

 1) Coating film 2) Polymer film base 3) Thin film layer 4) Anchor coat layer 5) Protective layer 6) Barrier adhesive 7) Heat sealing resin

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08J 7/04 CES C08J 7/04 CESP C08L 101/16 C23C 14/08 N C23C 14/08 C08L 101/00 (72) Inventor Takeshi Shimatani 1-5-1, Taito, Taito-ku, Tokyo Letterpress Printing Co., Ltd.

Claims (10)

[Claims] A heat-sealing resin and a metal or metal compound thin film surface of a transparent coated film having a metal or metal compound thin film layer formed on at least one surface of a polymer film substrate, via a barrier adhesive. A barrier laminate, characterized in that the laminate is adhered by bonding. 2. A metal or metal compound thin film layer surface of a transparent coated film in which a metal or metal compound thin film layer is formed on at least one surface of a polymer film substrate via an anchor coat layer; Characterized by being bonded via a barrier adhesive. 3. A protective film surface of a transparent coated film in which a metal or metal compound thin film layer and a protective layer are sequentially formed on at least one surface of a polymer film substrate, and a heat-sealable resin via a barrier adhesive. A barrier laminate, characterized in that the laminate is adhered by bonding. 4. A polymer film substrate, on at least one side of which
Barrier properties wherein the protective layer surface of a transparent coated film having an anchor coat layer, a metal or metal compound thin film layer, and a protective layer formed sequentially and a heat-sealable resin are bonded via a barrier adhesive. Laminate. 5. The barrier laminate according to claim 1, wherein the barrier adhesive is a cured film of an unsaturated acid and a polyamine derivative. 6. The method according to claim 1, wherein the thin film layer has one of silicon oxide, aluminum oxide, and magnesium oxide, a mixture of two or more thereof, or a multilayer structure. Barrier laminate. 7. The barrier laminate according to claim 1, wherein the protective layer is a coating layer comprising at least a hydrolyzate of a metal alkoxide and a water-soluble binder. 8. The barrier laminate according to claim 1, wherein said protective layer is a coating layer comprising at least a hydrolyzate of a metal alkoxide and a water-insoluble binder. 9. A packaging material base is laminated on the surface of the polymer film substrate of the barrier laminate according to any one of claims 1 to 8 opposite to the surface on which the metal or metal compound thin film layer is formed. And packaging material. 10. A package obtained by heat-sealing the heat-sealing resin of the packaging material according to claim 9 to form a bag.