JP2000006304A - Barrier laminate, packaging material using the same, and package using packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier laminate high in the bonding strength with a membrane material, not generating the deterioration of barrier properties when processing such as printing, lamination and molding is applied to a coating film highly keeping the gas barrier properties possessed by the membrane material and having barrier properties more excellent than those of the coating film. SOLUTION: This laminate is constituted by bonding a coating film 1 having transparency, which is formed by providing an anchor coat layer 4 on at least the single surface of a polymeric film base material 2 as necessary and successively forming a metal or a metal compd. membrane layer 3 and, as necessary, a protective layer 5 on the anchor coat layer 4, to a heat sealable resin layer through a barrier adhesive 6 containing inorg. fine particles.

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;
Provided is a barrier laminate having a barrier property that does not deteriorate when subjected to processing such as printing, laminating, and forming on a coated film that maintains a high gas barrier property of a thin film material, and has better barrier properties than a coated film. It is intended to be.

[0008]

According to the first and second aspects of the present invention,
An anchor coat layer is provided on at least one side of a base material such as a polymer film as necessary to form a thin film of a metal or a metal compound. This is a barrier laminate obtained by bonding via a barrier adhesive containing fine particles.

The invention according to claims 5 and 6 is directed to a transparent coated film in which an anchor coat layer is provided on at least one side of a base material such as a polymer film as required to form a thin film of a metal or a metal compound. A barrier laminate comprising a heat-sealable resin with a barrier adhesive containing inorganic ultrafine particles interposed therebetween, wherein the thin film layer of the coating layer is bonded to each other with the barrier adhesive. .

[0010] 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.

According to the third and fourth aspects of the present invention, a metal or metal compound thin film and a protective layer are sequentially formed by providing an anchor coat layer on at least one surface of a base material such as a polymer film, if necessary, and have transparency. It is a barrier laminate obtained by adhering a coating film and a heat-sealing resin via a barrier adhesive containing inorganic ultrafine particles.

The invention according to claims 7 and 8 has transparency in which an anchor coat layer is provided on at least one surface of a base material such as a polymer film as required, and a metal, a metal compound thin film, and a protective layer are sequentially formed. A barrier laminate comprising a coating film and a heat-sealable resin via a barrier adhesive containing inorganic ultrafine particles, wherein the protective layer surfaces are adhered to each other with the barrier adhesive as in claims 5 and 6. It is a combination.

As in the first and second aspects of the present invention, cracks and gas passing through the pinhole and water vapor passing through the pinhole are absorbed and blocked by the adhesive layer, so that a higher barrier property is obtained. Can be achieved.

The second and fourth aspects of the present invention have a structure in which an anchor coat layer is required when the 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.

According to a ninth aspect of the present invention, the inorganic ultrafine particles are
It is a barrier laminate which is a barrier adhesive containing up to 50% by weight.

Since the ultrafine particles fill the gaps between the adhesive molecules and exhibit a gas barrier property in the adhesive layer, gas components permeating through the coating film can be adsorbed and blocked, so that a very advanced barrier laminate is provided. Can be

According to a tenth aspect of the present invention, based on the premise of the first to eighth aspects, the thin film layer is made of any one of silicon oxide, aluminum oxide, and magnesium oxide, or a mixture or a multi-layer coating film having a multilayer structure. Is laminated with a heat seal resin via a barrier adhesive.

An eleventh aspect of the present invention is a barrier laminate in which the protective layer is a coating layer comprising at least a hydrolyzate of a metal alkoxide and a water-soluble binder.

The invention of claim 12 is a barrier laminate in which the protective layer is a coating layer comprising at least a hydrolyzate of a metal alkoxide and a water-insoluble binder.

A thirteenth aspect of the present invention is a barrier laminate, wherein the protective layer is a coating layer comprising at least an inorganic additive smaller than 1 μm and a water-soluble binder.

The invention according to claim 14 is a barrier laminate in which the protective layer is a coating layer comprising at least an inorganic additive smaller than 1 μm and a water-insoluble binder.

The invention according to claim 15 is a barrier laminate in which the protective layer is a coating layer composed of at least either alumina sol or silica sol or a mixed sol thereof and a water-soluble binder.

The invention according to claim 16 is a barrier laminate in which the protective layer is a coating layer comprising at least either alumina sol or silica sol or a mixed sol thereof and a water-insoluble binder.

[0024] The inventions of claims 17 to 20 are barrier laminates in which the anchor layer described in the claims is a specific coat layer described above.

The invention of claim 21 is a barrier laminate in which another plastic film is provided on the intermediate layer.

According to a twenty-second aspect of the present invention, a packaging material base is provided on the surface of the polymer film substrate of the barrier laminate according to any one of the first to twenty-first 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 twenty-third aspect of the present invention, there is provided a package obtained by heat-sealing the heat-sealing resin of the packaging material of the twenty-second aspect to form a bag.

According to the present invention, since a coating film on which a thin layer of metal or metal oxide is formed and a heat-sealing resin are laminated with a two-part curable adhesive having a gas barrier property, several cm ³ / M ² / day / at
m. And very small molecules such as oxygen and water vapor leaking in a very small amount such as several g / m ² / day can be further blocked by the shielding effect of the ultrafine particles in the adhesive layer. Excellent barrier properties can be 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 adhesive is a barrier adhesive in which ultrafine particles made of an inorganic substance are dispersed in an adhesive component of 2 to 50% by weight, so that the ultrafine particles fill the molecular gaps constituting the adhesive. In addition, since it functions to restrain the diffusion of low molecules through the adhesive layer in order to restrain the molecular movement of the adhesive, a very small amount of light transmitted through the thin film layer or the protective layer formed on the thin film layer is used. Gases such as oxygen and water vapor molecules can be prevented from diffusing between the adhesives, and as a result, the amount of gas permeated by dissolving and diffusing into the heat-sealing resin layer can be reduced.

Conversely, even when the gas concentration on the heat sealing resin side is high, the adhesive layer has a gas barrier function, so that the difference in gas concentration at the interface between the heat sealing resin and the coating film becomes small, so that the gas passes through the coating film. The amount of flowing gas can be reduced.

Further, since the thin film layer has a mixed or multilayer structure composed of any one of silicon oxide, aluminum oxide and magnesium oxide, or a mixture of two or more thereof, microcracks generated in the thin film layer during the secondary processing are introduced into the inside of the thin film. Propagation can be reduced, and a barrier laminate having an extremely high barrier property against inorganic gases such as oxygen and nitrogen, water vapor, and organic vapor can be obtained.

Further, since the specific protective layer is formed directly on the thin film layer, a part of the fine inorganic particles contained in the protective layer coating film may be partially cracked with the underlying thin film layer by a micro crack or pinhole. In addition, the thin film structure is made more dense and the protective layer and the thin film layer do not form an independent interface. By forming a hybrid structure, the gas permeation can be kept low, so that a more advanced barrier laminate can be obtained. .

Then, a packaging material or a package that exhibits the above effects even after the secondary processing is obtained.

[0035]

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 heat sealing resin 7 is adhered to a thin film layer surface of a covering film 1 having a barrier adhesive 6 containing ultrafine particles.

As another layer constitution, for example, as shown in FIG. 2, 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 a heat-sealable resin 7 is adhered to the protective layer surface of the coated film 1 having transparency via a barrier adhesive 6 containing ultrafine particles is also conceivable.

Further, as shown in FIG. 3, for example, two thin transparent films 1 and 1 having a thin film layer 3 made of a metal or a metal compound formed on one surface of a polymer film substrate 2 The layers are opposed to each other and bonded via a barrier adhesive 6 containing inorganic ultrafine particles to form a composite film. A heat-sealable resin 7 is bonded to the polymer film substrate surface on one side of the composite film. It is a laminated body.

Further, as shown in FIG. 4, 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 base material 2 to increase the transparency. The two protective films 1 and 2 having the protective layers are opposed to each other and bonded via a barrier adhesive 6 containing inorganic ultrafine particles to form a composite film. The polymer film base on one side of the composite film This is a laminate in which the heat-sealable resin 7 is adhered to the material surface.

As the polymer film substrate 2 used in the present invention, a material excellent in dimensional stability, heat resistance and mechanical strength is preferable. For example, polyolefin such as polyethylene, polypropylene, polybutene, ethylene-vinyl alcohol copolymer, 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 11, nylon 12, etc., polyamide, 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.

These films can also 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 phthalocyanine 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 a 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 coating 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 is larger than 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
The range is 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 another method of forming the 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 their polymers or derivatives can 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, metals such as Zr, R: alkyl groups such as CH ₃ and C ₂ H ₅ , and n = M).

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

As a method for forming the protective layer 5, the above-mentioned coating solution is formed 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.

Since the protective layer is formed by directly coating the metal alkoxide and its hydrolyzate on the thin film layer as described above, the coating liquid permeates from the porous portion on the surface of the thin film layer to the inside of the thin film, thereby protecting 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 protective layer 5 is about 0.01 to 5
0 μm, preferably 0.01 to 0.8 μm
Range. 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. A heat-sealable resin obtained by laminating a sealant material, which is a heat-sealable thermoplastic material shown below, via a barrier adhesive as described below, if necessary, on at least one of the protective layer side and the base film side of the coating film. Can be used as

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 optimum thickness of the heat-sealable resin varies depending on the type, 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.

As the barrier adhesive 6, 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-butadiun copolymer, acrylonitrile-butadiene copolymer, vinyl acetate-acryl copolymer, Ethylene-ethyl acrylate copolymers, polyester polyols, polyester polyurethane polyols, polyether polyurethane polyols and other single resins or two or more resins selected from resins such as water, isopropyl alcohol, methanol, alcohols such as ethanol, acetic acid Esters such as ethyl, ketones such as methyl ethyl ketone, aromatic hydrocarbons such as toluene, and aliphatic hydrocarbons such as hexane. And when used as a one-component adhesive agent such as solvent-free or hot-melt to the fabric, not particularly limited may be any reactive adhesive obtained by applying a crosslinking system described below as needed.

Examples of the crosslinking system include a hydroxyl group / isocyanate system, an amine / epoxy system, a carboxyl group / epoxy system, an amine / isocyanate system, an amine / carbodiimide system, a carboxyl group / oxazoline system, a hydroxyl group / carbodiimide system, and a carboxyl group / garbodiimide system. System, carbonyl group / hydrazine system, silyl system and the like.

Among them, tolylene diisocyanate, 4
-4 'diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
Xylylene diisocyanate and their adducts,
A two-part reactive urethane-based adhesive with a main component such as polyester polyol, polyester polyurethane polyol, or polyether polyol using an isocyanate compound selected from burette and isocyanurate as a crosslinking agent is preferable.

Further, acrylic or urethane acrylate-based adhesives that cure the adhesive with radiation such as ultraviolet rays or electron beams may be used.

Examples of the glycol constituting the polymer used as the main ingredient include ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, and trimethylolpropane.

Examples of the dicarboxylic acid include adipic acid, azelaic acid, sebacic acid, maleic acid, phthalic anhydride, and isophthal.

Typical polyols include polyesters such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, and polycaprolactone, and polyoxypropylene diol, polytetramethylene glycol ether, and polyoxyethylene diol. It is not limited to.

The ultrafine particles used in the present invention include Si,
AlO_Two, FeO_Three, FeO, CaO, MgO, Mn_Three
O_Four, TiO_Two, ZrO_Two, HfO_Two, ThO_Two, Be
O, Y_TwoO_Three, La_TwoO_Three, CeO_Two, 3Al_TwoO_Three2
SiO_Two, 2Al_TwoO_ThreeSiO_Two, Al_TwoSiO_Five, M
gSiO_Three, Mg_TwoSiO_Four, CaOMgO, Ca_TwoS
iO_Three, Ca_ThreeSi_TwoO₇, MgAl_TwoO_Four, FeCr
_TwoO_Four, MgFe_TwoO _Four, MgCr_TwoO_Four, FeTiO
_Three, CaTiO_Three, 3Y_TwoO_Three, 5Fe_TwoO_Three, BaO
₆Fe_TwoO_Three, Ba_TwoSiO_Four, 3CaOMgO_TwoSi
O_Two, 2CaOMgO_TwoSiO_Two, Li_TwoOAl_TwoO_Three
2SiO_Two, 2CaOAl_TwoO_ThreeSiO _Two, 3CaOA
l_TwoO_Three2SiO_Two, 2Na_TwoOAl_TwoO_Three4SiO_Two
Oxides such as SiC, WC, TiC, TaC, ZrC,
B_FourCarbides such as C, Si_ThreeN_Four, BN, TiN, Zr
One or more materials selected from materials such as nitrides such as N and AlN
Ceramic materials can be used as appropriate.

Further, a tetrahedral layer in which SiO ₄ is two-dimensionally polymerized and a layered viscous mineral in which AlO ₄ (OH) ₂ is bonded to an octahedral layer are represented by pyrophyllite, talc, sericite, Montmorillonite and mica can also be used.

The particle size of the ultrafine powder in the present invention is as follows.
Less than 1 μm, good or 5-50n
m. If it exceeds 1 μm, even if it is added to the adhesive, the particle size is large, so that it is not uniformly dispersed and the expression of the barrier function becomes unstable.

The lower limit is preferably as small as possible, but it is preferable that the lower limit be as small as possible due to restrictions on the dispersion method and the time required for dispersion.

Examples of the dispersion method include a high-speed rotating high-shear type stirrer such as a propeller mixer, a turbine mixer and a dezo lever, a high-speed rotating high-shear stirrer such as a homomixer, a colloid mill, a pressurized nozzle type emulsifier, and an ultrasonic type. The material can be dispersed and dissolved in a solvent as required to form fine particles by a combination of a known stirrer such as an emulsifier, a mechanical vibration stirrer, and a stirrer using an electrostatic field. The method is not particularly limited.

The ultrafine particles are used in an amount of 2 to
It must be in the range of 50% by weight.

When the content is less than 2% by weight, the barrier property is insufficiently developed, and when the content is more than 50% by weight, the viscosity of the adhesive rapidly increases, or the cohesive force of the adhesive decreases and the laminating property decreases. It is not preferable because strength may be affected. Preferably, it is in the range of 5 to 30% by weight.

If necessary, known adhesives such as ultraviolet absorbers, antioxidants, light stabilizers, tackifiers, plasticizers, fillers, lubricants, surface modifiers, etc., do not impair the barrier performance. It does not matter even if it is appropriately added within the range.

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, but are not particularly limited to, the following known application methods.

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 >.

Instead of directly laminating the heat-sealable resin layer 7 on the protective layer 5, the heat-sealable resin layer may be laminated with at least one other base layer exemplified below. I don't 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.

The anchor coat layer 4 provided as needed on the polymer film substrate 2 includes dry treatments such as corona treatment, low-temperature plasma treatment, atmospheric pressure plasma treatment, ion bombardment treatment, and flame treatment. There are two methods of forming a surface modified layer on the polymer film substrate at a level of 0.1 to several nm and a layer made of a resin shown below by wet treatment such as chromic acid treatment.

All of the objects are to improve the adhesion 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, polyethyleneimine, polyethylene oxide, 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 coating amount of the anchor coat layer 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, preferably, the adhesion after boil sterilization, retort sterilization, and autoclave sterilization is excellent by specifying the anchor coat material to the materials described below.

To achieve the above object, a primer resin can be used as a composite of a metal alkoxide or a hydrolyzate thereof, a trifunctional organosilane or a hydrolyzate thereof, and a polyol and an isocyanate compound. Needs to be

Further, the composite will be described in detail. the above
Metal alkoxide is tetraethoxysilane [Si
(OC_TwoH_Five)_Four], Tripropoxy aluminum [A
l (OC_ThreeH₇)_ThreeGeneral formula M (OR) _nCan be represented by
Or a hydrolyzate thereof. Where to get hydrolysates
In this case, add an acid or alkali directly to the metal alkoxide.
It is possible to use an ordinary method or the like that is obtained. What
Even if M in the metal alkoxide is Si, Al, Ti,
Zr or a mixture thereof is superior in various properties.
Is preferred.

The trifunctional organosilane is a compound represented by the general formula R ′ such as methoxytriethylsilane, vinyltrimethoxysilane and glycidoxypropyltrimethoxysilane.
Si (OR) ₃ (R ′ is a functional group such as an alkyl group, a vinyl group, and a glycidoxypropyl group) or a hydrolyzate thereof. When a hydrolyzate is obtained, an ordinary method or the like obtained by directly adding an acid or an alkali to the organosilane can be used. Among them, glycidoxytrimethoxysilane or epoxycyclohexylethyltrimethoxysilane in which an epoxy group is contained in R ′ is particularly preferable because of its excellent physical properties.

The mixing ratio of the metal alkoxide and the trifunctional organosilane is not particularly limited, and may be any type as long as at least one of them is contained. The molar ratio is preferably in the range of 10: 1 to 1:10, and more preferably both are blended in an equimolar amount.

Further, a reaction catalyst may be added to promote the reaction at the time of blending the two. The catalyst to be added includes tin chloride (SnCl ₂ , SnCl ₄ ) and tin oxychloride (SnOH) from the viewpoint of reactivity and polymerization stability.
Cl, Sn (OH) ₂ Cl ₂ ) and tin compounds such as tin alkoxides are preferred. These catalysts may be added directly at the time of compounding, or may be added by dissolving in a solvent such as methanol. If the addition amount is too small or too large, no catalytic effect can be obtained, so the molar ratio is 1 / l with respect to the combined amount of the metal alkoxide and the trifunctional organosilane.
The range is preferably from 10 to 1 / 10,000, and more preferably from 1/100 to 1/2000.

The polyol is a high molecular compound having a hydroxyl group at a terminal, such as a polyester polyol, an acrylic polyol, or a polyether polyol, and is reacted with an isocyanate compound to be added later. Above all, acrylic polyols such as hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate and polyester polyols such as linear saturated polyester are preferably used. In consideration of the reactivity with the isocyanate compound, the hydroxyl value is preferably between 5 and 200 (KOH mg / g).

The compounding ratio of the polyol, the metal alkoxide and the trifunctional organosilane is preferably in the range of 2/1 to 20/1, more preferably 3/1, in terms of the solid content (weight). To 7/1. The dissolving and diluting solvent is not particularly limited as long as it can be dissolved and diluted, and examples thereof include esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as methyl ethyl ketone, toluene, and xylene. And the like can be used alone or arbitrarily blended with aromatic hydrocarbons. Preferably, ethyl acetate and isopropyl alcohol are arbitrarily mixed in view of solubility and processability.

The isocyanate compound to be further mixed is
It is added to enhance adhesion to a substrate or an inorganic oxide by urethane bonds formed by reacting with a polyol, and mainly acts as a crosslinking agent or a curing agent. In order to achieve this, monomers such as aromatic tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), aliphatic xylene diisocyanate (XDI) and hexaylene diisocyanate (HMDI), These polymers,
Derivatives are used, and these are used alone or as a mixture.

The mixing ratio of the polyol and the isocyanate compound is not particularly limited. However, 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. is there. Therefore, the blending ratio of the polyol and the insocyanate compound is preferably such that the NCO group derived from the isocyanate compound is 50 times or less in terms of equivalent weight with respect to the OH group derived from the polyol, and particularly preferred is the NCO group and the OH group.
The groups are blended in equivalent amounts.

The coating film of the composite is prepared by directly or previously subjecting such a metal alkoxide or trifunctional organosilane to a hydrolysis reaction (the reaction catalyst described above may be used at this time). A composite liquid is prepared by mixing with an isocyanate compound and coated on the substrate 1 to form a composite liquid.

Various additives such as curing accelerators such as tertiary amines, imidazole derivatives, metal salt compounds of carboxylic acids, quaternary ammonium salts, and quaternary phosphonium salts; It is also possible to add a phyto-based antioxidant, a leveling agent, a flow regulator, a filler, or the like.

The thickness of the transparent anchor layer 2 is not particularly limited as long as a uniform coating film can be formed, but is generally preferably in the range of 0.01 to 2 μm. When the thickness is less than 0.01 μm, it is difficult to obtain a uniform coating film, and the adhesion may be 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.

It is particularly preferred that the thickness be in the range of 0.05 to 0.5 μm.

Further, the anchor coat layer may contain additives such as the above-mentioned known plasticizers, lubricants, antioxidants, etc., but it may be reduced in consideration of the adhesion to the thin film layer. 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.

[0108]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. <Experiment 1>

(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. Next, a low-density polyethylene film 40 μm as a heat-sealable resin 7 was formed on the thin film layer by dry lamination using an adhesive having a prescription 1 shown below, which is a barrier adhesive 6 containing inorganic ultrafine particles. Lamination was performed to obtain a barrier laminate of Example 1 (see FIG. 1).

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 side of the biaxially stretched polyester film 2 used in Example 1. On this 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 surface of a biaxially stretched polyester film 12 μm as a polymer film substrate 2 by a vacuum evaporation method 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,
Dry by drying in a dryer at 120 ° C. for 1 minute.
A protective layer 5 having a thickness of 4 μm was formed to obtain a coated film 1. In the same manner as in Example 1, a protective adhesive 6 containing inorganic ultrafine particles was applied to the protective layer surface of the coating film 1 via an adhesive having a prescription 1 shown below. A 40 μm-density polyethylene film 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 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. Thereafter, the barrier adhesive 6 was applied to the thin film layer surface of the coating film in the same manner as in Example 3.
Heat-sealable resin 7 via the adhesive of formula 1
Laminated low-density polyethylene film 40μm,
The barrier laminate of Example 4 was obtained.

Example 5 Using the coated film of Example 3, a low-density polyethylene film of 40 μm was laminated in the same manner as in Example 4 using the adhesive of Formula 2 described below. did.

Example 6 Using the coated film of Example 4, a low-density polyethylene film of 40 μm was laminated in the same manner as in Example 4 using the adhesive of Formula 2 described later, and the barrier laminate of Example 6 was used. did.

Example 7 Aluminum oxide was applied to one side of a biaxially stretched polyester film 12 μm by a known method.
A thin film layer 3 was formed to a thickness of 5 nm, and then a coating liquid 2 shown below was coated on the thin film layer by a gravure coating method, dried at 80 ° C. for 1 minute, and then 0.4 μm
m of protective layer 5 was formed to form a coated film. Protective layer surface of this coating film and low density polyethylene film 40μ
and m were bonded via an adhesive having the following formulation 3 to obtain a barrier laminate of Example 7.

Example 8 A barrier laminate of Example 8 was produced using the same materials and method as in Example 7 except that a protective layer was formed using the coating liquid of Formulation 3 shown below. (Detailed description is omitted).

Example 9 A barrier laminate of Example 9 was produced using the same materials and method as in Example 7, except that a protective layer was formed using a coating solution of Formula 4 shown below. (Detailed description is omitted).

Example 10 Example 7 was repeated except that a protective layer was formed using the coating liquid of Formula 5 shown below.
A barrier laminate of Example 10 was manufactured using the same material and method as described above (detailed description is omitted).

Example 11 Example 7 was repeated except that a protective layer was formed using the coating solution of Formula 6 shown below.
A barrier laminate of Example 11 was manufactured using the same material and method as in Example 1 (detailed description is omitted).

(Example 12) Example 7 was repeated except that a protective layer was formed using a coating solution having the following formulation 7.
A barrier laminate of Example 12 was manufactured using the same materials and method as in Example 1 (detailed description is omitted).

Example 13 The same polyurethane-based anchor coat layer as in Example 2 having a thickness of 0.1 μm was formed on one surface of the biaxially stretched polyester film 12 μm used in Example 1 as an anchor coat layer 4. On this anchor coat layer, silicon oxide, which is the same thin film layer 3 as in the first embodiment, is 40 nm thick.
Then, the coating liquid 1 was further applied on the thin film layer 3 in the same manner as in Example 3 to form a protective layer 5 having a thickness of 0.4 μm. As in Example 1, a low-density polyethylene film 40 μm, which is a heat-sealable resin 7, was applied to the protective layer surface of this coating film via an adhesive of Formula 1 which was a barrier adhesive 6 containing inorganic ultrafine particles, as in Example 1. Were laminated to form a barrier laminate of Example 13 (see FIG. 2).

(Comparative Example 1) In the same manner as in Example 1, one side of a biaxially stretched polyester film 12 μm was formed with 40 nm of silicon oxide by a known vacuum deposition method, and a low-density polyethylene film 40 μm was formed on the thin film layer by a conventional method. Two-part curable urethane adhesive (A53 manufactured by Takeda Pharmaceutical Co., Ltd.)
Dry lamination was performed in the same manner as in Example 1 using 6) to produce a laminate of Comparative Example 1.

Comparative Example 2 The barrier laminate of Comparative Example 2 was prepared using the same material and method as in Example 1 except that an adhesive layer was formed using the adhesive of Formula 4 shown below. It was fabricated (detailed description is omitted).

Comparative Example 3 The barrier laminate of Comparative Example 3 was prepared using the same material and method as in Example 1 except that an adhesive layer was formed using the adhesive of Formula 5 shown below. It was fabricated (detailed description is omitted).

<Experiment 2>

Example 14 Silicon oxide was formed to a thickness of 40 nm by vacuum evaporation on one surface of a biaxially stretched polyester film 12 μm as a polymer film substrate 2 to form a thin film layer 3. The two biaxially stretched polyester films on which the thin film layer is formed are laminated by dry lamination via an adhesive of formula 1 which is a barrier adhesive 6 shown below with the thin film layer surfaces facing each other, A film was prepared. A low-density polyethylene film 40 μm as the heat-sealable resin 7 was laminated on one biaxially stretched polyester film surface of the composite film to obtain a barrier laminate of Example 14 (see FIG. 3).

(Example 15) On one surface of the biaxially stretched polyester film used in Example 1 of Experiment 1, an anchor coat paint of Formula 1 shown below was formed to a thickness of 0.1 μm by a gravure coating method. Was formed. Aluminum oxide was formed to a thickness of 20 nm as a thin film layer 3 on this anchor coat layer in the same manner as in Example 1. The two biaxially stretched polyester films on which the anchor coat layer 4 and the thin film layer 3 were sequentially formed were prepared by using the same barrier adhesive 6 as in Example 1 with the thin film layers facing each other.
To form a composite film. A low-density polyethylene film 30 μm as the heat-sealable resin 7 was extruded and laminated on one biaxially stretched polyester film surface of the composite film to obtain a barrier laminate of Example 15.

Example 16 The same biaxially stretched polyester film as in Example 1 was formed on one surface thereof with aluminum oxide to a thickness of 25 nm by vacuum evaporation to form a thin film layer 3. Further, a coating liquid of Formula 2 described below was applied as a protective layer paint on the aluminum oxide thin film by a roll coating method, and dried with a dryer at 120 ° C. for 1 minute to form a 0.4 μm protective layer 5. Biaxially stretched polyester film 2 on which thin film layer 3 and protective layer 5 are sequentially formed
The sheets were laminated by a dry lamination method via a barrier adhesive 6 having the following formulation 2 with the protective layers facing each other to produce a composite film. On one biaxially stretched polyester film surface of this composite film, an unstretched polypropylene film 30 which is a heat-sealable resin 7
μm was laminated to obtain a barrier laminate of Example 16.

(Example 17) A laminate was prepared by using the same material and method as in Example 16 except that a protective layer was formed using a coating liquid of Formula 1 described below as a protective layer paint. Was obtained.

(Example 18) A composite film similar to that of Example 16 was produced using the same materials and method as in Example 16 except that the adhesive of Formula 1 was used instead of the adhesive of Formula 2. A biaxially stretched nylon film 1 was placed on one biaxially stretched polyester film
5μm, low-density polyethylene film 40μm sequentially,
The laminate was laminated with the barrier adhesive 6 of Formulation 1 to obtain a laminate of Example 18.

(Example 19) A laminate was prepared using the same material and method as in Example 14 except that the adhesive of Formula 7 was used as the barrier adhesive 6, and the barrier laminate of Example 19 was used. did.

(Example 20) A laminate was prepared using the same material and method as in Example 14 except that the adhesive of Formulation 5 was used as the barrier adhesive 6, and the barrier laminate of Example 20 was used. did.

Example 21 One side of a biaxially stretched polyester film as a polymer film base material 2 was coated with an anchor coat paint of Formula 1 by gravure coating at a thickness of 0.1 μm.
Then, the anchor coat layer 4 was formed. Aluminum oxide was formed to a thickness of 20 nm on the anchor coat layer as the thin film layer 3 in the same manner as in Example 15, and then the thin film layer 3 was formed.
The coating liquid 1 was applied on the substrate in the same manner as in Example 16 to form a protective layer 5 of 0.4 μm.
And The anchor coat layer 4, the thin film layer 3, and the protective layer 5
Are laminated by a dry lamination method via an adhesive of Formula 1 which is the same barrier adhesive 6 as in Example 1 with the protective layer surfaces facing each other with the protective layer facing each other. To produce a composite film. A low-density polyethylene film 30 μm as the heat-sealable resin 7 was extruded and laminated on one biaxially stretched polyester film surface of the composite film to obtain a barrier laminate of Example 21.

Comparative Example 4 In the same manner as in Example 1 of Experiment 1, silicon oxide was formed to a thickness of 40 nm by a known vacuum deposition method, and a conventional two-part curable urethane-based adhesive (manufactured by Takeda Pharmaceutical Co., Ltd.)
A536) was used for dry lamination in the same manner as in Example 1 to obtain a barrier laminate of Comparative Example 4.

(Comparative Example 5) A laminate was produced using the same material and method as in Example 1 except that the adhesive of Formula 3 described later was used as the adhesive, and the resulting laminate was a barrier laminate of Comparative Example 5. .

(Comparative Example 6) A laminate was prepared using the same material and method as in Example 1 except that an adhesive having a formulation 6 described later was used as an adhesive, and a barrier laminate of Comparative Example 6 was obtained. .

Comparative Example 7 A laminate was produced using the same material and method as in Example 15 except that the same conventional urethane-based adhesive as in Comparative Example 1 was used as the adhesive. A laminate was obtained.

<Paint for Anchor Coat> The formulation of the coating solution for the anchor coat used is as follows. <Coating liquid formulation 1> Acrylic polyol was added to tetraethoxysilane and epoxycyclohexyltrimethoxysilane by adding 1/400 mol of a tin chloride / methanol solution as a catalyst and blending them in a molar ratio of 1: 1. The mixture is stirred at a weight ratio of 5: 1 with respect to the total amount of the above-mentioned tetraethoxysilane and epoxycyclohexyltrimethoxysilane, and then stirred. Then, tolylene diisocyanate as an isocyanate compound is converted to an isocyanate group equivalent to the hydroxyl group of the acrylic polyol. And an additional dilution solvent was added to prepare an anchor coat liquid.

<Paint for forming protective layer> The formulation of the coating liquid for forming the protective layer used is as follows. <Coating liquid 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 to obtain a hydrolysis solution having a solid content of 3% by weight, an acid value of 3, a hydroxyl value of 67, a glass transition point temperature of 88 ° C, and a molecular weight of 10200. Was mixed with a solution of methyl ethyl ketone consisting of 3% by weight of the acrylic polyol to obtain a paint for forming a protective layer.

<Coating liquid formulation 2> 89.1 g of 0.1N hydrochloric acid was added to 10.4 g of tetraethoxysilane, and 3
A hydrolysis solution having a solid content of 3% by weight, which was hydrolyzed by stirring for 0 minutes, and a solution of isopropyl alcohol / water (10/90) consisting of 3% by weight of polyvinyl alcohol were mixed to obtain a coating for forming a protective layer. .

<Adhesive> The formulation of the adhesive used is as follows. <Adhesive Formulation 1> Polyester polyol having a number average molecular weight of 25,000 obtained by polycondensation of terephthalic acid and ethylene glycol, 1,6 hexanediol (solid content: 4
(0%) acetic acid solution (90% by weight) and a silicon oxide particle having an ultrafine particle size of 15 nm with a ball mill and a wet crushing device, which is 10% by weight based on the polyester polyol resin.
Then, 10 parts by weight of a urethane adduct acetic acid solution (solid content: 75%) obtained by reacting 1 mole of trimethylolpropane and 3 moles of tolylene diisocyanate are mixed, and 117 parts by weight of ethyl acetate are further added to the urethane-based barrier adhesive. Agent was obtained.

<Adhesive Formulation 2> 90 parts by weight of an acetic acid solution of a polyester polyol having a number average molecular weight of 25,000 (solid content: 40%) obtained by polycondensation of terephthalic acid with ethylene glycol and 1,6 hexanediol was wet-crushed. A urethane adduct obtained by adding a mixture of silicon oxide and aluminum oxide particles ultrafinely divided to 10 nm and 15 nm to a polyester polyol resin in an amount of 10% by weight and then reacting 1 mol of trimethylolpropane with 3 mol of tolylene diisocyanate. 10 parts by weight of an acetic acid solution (solid content: 75%) was mixed, and 117 parts by weight of ethyl acetate was further added to obtain a urethane-based barrier adhesive.

<Adhesive Formulation 3> An adhesive having the same formulation as the adhesive 1 was prepared except that the amount of ultrafine silicon oxide was 2% by weight.

<Adhesive Formulation 4> An adhesive having the same formulation as the adhesive 1 was prepared except that the amount of the silicon oxide finely divided into particles was 1% by weight.

<Adhesive Formulation 5> An adhesive having the same formulation as that of the adhesive 1 was prepared except that the amount of the finely divided silicon oxide was changed to 50% by weight.

<Adhesive Formulation 6> An adhesive having the same formulation as the adhesive 1 was prepared except that the amount of the ultrafinely divided silicon oxide was 55% by weight.

<Adhesive Formulation 7> An adhesive having the same formulation as the adhesive 1 was prepared except that the amount of the ultrafinely divided silicon oxide was changed to 15% by weight.

<Evaluation Methods for Physical Properties> The oxygen permeability, water vapor permeability and lamination strength of the 28 kinds of barrier laminates of Examples 1 and 2 and the comparative examples thus produced are described below. Was measured. Oxygen permeability: JIS K7126 method B (same pressure method) Measured in an atmosphere of 27 ° C.-75% RH Apparatus MoconOxtran Measurement unit: cm ³ / m ² / day / atm.・ Water vapor permeability: JIS K7129 B method (infrared sensor method) Measured in an atmosphere of 40 ° C.-90% RH Apparatus MoconPermatran Measurement unit: g / m ² / day ・ Laminate strength: Tensileon tensile tester based on JIS K7127 Measure laminate strength

Table 1 summarizes the results of Experiment 1 and Table 2 summarizes the results of Experiment 2.

[0150]

[Table 1]

[0151]

[Table 2]

[0152]

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 base materials 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 an explanatory cross-sectional view showing one example of a barrier laminate of the present invention.

FIG. 2 is an explanatory sectional view showing another example of the barrier laminate of the present invention.

FIG. 3 is an explanatory sectional view showing still another example of the barrier laminate of the present invention.

FIG. 4 is an explanatory sectional view showing still another example 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

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 7/04 C08J 7/04 P // C23C 14/08 C23C 14/08 N (72) Inventor Takeshi Shimatani 1-5-1, Taito, Taito-ku, Tokyo Letterpress Printing Co., Ltd.

Claims (23)

[Claims] 1. A polymer film substrate comprising a metal or metal compound thin film layer formed on at least one side of a polymer film substrate and having a metal or metal compound thin film surface and a heat-sealable resin containing inorganic ultrafine particles. A barrier laminate, wherein the laminate is bonded via a barrier adhesive. 2. 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 an anchor coat layer, and a heat-sealing resin. A barrier laminate which is bonded via a barrier adhesive containing inorganic ultrafine particles. 3. A polymer film substrate comprising at least one surface of a metal or metal compound thin film layer and a protective layer, in which a protective layer surface of a transparent coated film and a heat-sealable resin contain inorganic ultrafine particles. A barrier laminate, wherein the laminate is bonded via a barrier adhesive. 4. A polymer film substrate, on at least one side of which
The anchor layer, the metal or metal compound thin film layer, and the protective layer surface of the transparent coated film having the protective layer formed sequentially were adhered to the heat-sealable resin via a barrier adhesive containing ultrafine inorganic particles. A laminate having a barrier property. 5. A transparent film having a metal or metal compound thin film layer formed on at least one surface of a polymer film substrate.
The thin film layers of the two coated films are opposed to each other and bonded via a barrier adhesive containing inorganic ultrafine particles to form a composite film, and the heat-sealing property is applied to the polymer film substrate surface on one side of the composite film. A barrier laminate having a resin bonded thereto. 6. An ultrafine inorganic particle, wherein two thin film layers of a transparent film having a metal or metal compound thin film layer formed on at least one surface of a polymer film substrate via an anchor coat layer are opposed to each other. A barrier laminate comprising a composite film which is bonded via a barrier adhesive containing the same, and a heat-sealable resin is bonded to a polymer film substrate surface on one side of the composite film. 7. A two-layered transparent film having a metal or metal compound thin film layer and a protective layer sequentially formed on at least one surface of a polymer film substrate, wherein the protective layers are opposed to each other and contain inorganic ultrafine particles. A barrier laminate comprising a composite film which is adhered via a barrier adhesive to form a composite film, and a heat-sealable resin is adhered to the polymer film substrate on one side of the composite film. 8. At least one surface of a polymer film substrate,
Anchor coat layer, metal or metal compound thin film layer, and protective layer of protective film are sequentially formed, and the protective layers of two transparent coated films are opposed to each other and bonded via a barrier adhesive containing ultrafine inorganic particles. A barrier laminate comprising a composite film, wherein a heat-sealable resin is adhered to the polymer film substrate on one side of the composite film. 9. The barrier laminate according to claim 1, wherein the barrier ultra-fine particle is a barrier adhesive containing 2 to 50% by weight of the inorganic ultrafine particles. 10. 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. 11. 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. 12. 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-insoluble binder. 13. The barrier laminate according to claim 1, wherein said protective layer is a coating layer comprising an inorganic additive having a size of at least 1 μm and a water-soluble binder. 14. The barrier laminate according to claim 1, wherein said protective layer is a coating layer comprising an inorganic additive having a size of at least 1 μm and a water-insoluble binder. 15. The method according to claim 1, wherein the protective layer is a coating layer comprising at least one of alumina sol and silica sol or a mixed sol thereof and a water-soluble binder. Barrier laminate. 16. The protective layer according to claim 1, wherein the protective layer is a coating layer comprising at least one of alumina sol and silica sol or a mixed sol thereof and a water-insoluble binder. Barrier laminate. 17. An anchor coat layer according to claim 1, wherein the anchor coat layer is a general formula M (OR) _n (M; a metal element such as Si or Al; R; a general formula C _n H _2n such as CH ₃ or C ₂ H). _A metal alkoxide represented by an alkyl group represented by ₊₁ ; n; an integer of 1 or more); a hydrolyzate of the metal alkoxide; or a trifunctional group represented by the general formula R′Si (OR) ₃ (R ′: functional group) A transparent anchor layer comprising a composite of at least one of an organosilane or a hydrolyzate of the organosilane and a polyol and an isocyanate compound. 18. The barrier laminate according to claim 17, wherein the polyol is a polyester polyol, an acrylic polyol, or a mixture thereof. 19. The method according to claim 19, wherein the metal alkoxide or the metal during hydrolysis of the metal alkoxide is Si, Al, Ti,
The barrier laminate according to claim 17, which is any one of Zr or a mixture thereof. 20. The thickness of the transparent anchor layer is 0.01
The barrier laminate according to claim 17, wherein the thickness is from 2 to 2 µm. 21. The method according to claim 5, wherein at least one uniaxially or biaxially stretched plastic film is provided between the coating film and the barrier adhesive or between the protective layer and the barrier adhesive. Barrier laminate. 22. A packaging material base laminated on the surface of the polymer film substrate of the barrier laminate according to any one of claims 1 to 21 opposite to the surface on which the metal or metal compound thin film layer is formed. And packaging material. 23. A package obtained by heat-sealing the heat-sealing resin of the packaging material according to claim 22 to form a bag.