JPH08309913A - Barrier composite film and production thereof - Google Patents

Abstract

PURPOSE: To suppress the lowering of barrier properties and the close adhesiveness of a coating film even when mechanical external force acts on a barrier film or the barrier film is preserved under a high temp. and high humidity condition. CONSTITUTION: At least one surface of a base material film composed of polyester or the like is successively covered with an inorg. layer composed of silicon oxide or the like and a coating layer containing a silane coupling agent and a barrier resin (e.g. vinylidene chloride copolymer, an ethylene/vinyl alcohol copolymer) to obtain a barrier composite film. The addition amt. of the silane coupling agent is set to about 0.05-10 pts.wt. per 100 pts.wt. of the barrier resin. A heat-sealing layer may be formed on the coating layer or the other surface of the base material film. This barrier composite film is high in transparency and can keep high gas barrier properties and the close adhesiveness of the coating film over a long period of time even if the coating film is thin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has excellent gas barrier properties against water vapor, oxygen, aroma components, etc., and is a film for storing dried foods, a film for retort processing of foods, a film for heating microwave ovens, pharmaceuticals, precision electronic parts, etc. the film,
The present invention relates to a barrier composite film suitable as a film for producing balloons and balloons, and a method for producing the same.

[0002]

2. Description of the Related Art When a base film is coated with an extremely thin inorganic oxide, the barrier property of the base film can be greatly improved, and the selection range of the base can be selected in consideration of other properties such as heat resistance and mechanical properties. Can be expanded. Further, it has been proposed that a synthetic resin layer is formed on a thin film of an inorganic oxide to impart heat-sealing property to a barrier film or protect the thin film layer of an inorganic oxide. For example, JP-A-60-27532 discloses that a polymer layer is formed on a thin film of an inorganic oxide of a polyolefin film by dry lamination or extrusion lamination.
No. 237940 discloses a composite film in which a heat-sealing layer such as an ethylene-propylene copolymer is formed on a film formed by sputtering indium oxide, tin oxide or the like. JP-A-1-202435 and JP-A-1-202436 disclose a microwave oven packaging material or retort in which a silicon oxide vapor deposition layer and a heat-sealing layer or a protective layer are formed on the surface of a substrate film. A food packaging material is disclosed, wherein the heat-sealing layer is formed by laminating a heat-sealing resin film such as polypropylene, and the protective layer is formed by laminating a film or coating with a thermosetting resin. Japanese Patent Application Laid-Open No. 1-293723 discloses a laminate of a biaxially stretched nylon film on a thin film of an inorganic oxide of a film, and Japanese Patent Application Laid-Open No. 3-86539 discloses a vinylidene chloride-based film on a thin film of an inorganic oxide. Lamination and coating of resins and the like are disclosed, and Japanese Patent Application Laid-Open No. 4-173137 discloses coating of vinyl chloride-vinyl acetate copolymer, polyamide, polyester, acrylic resin on a thin film of an inorganic oxide of the film, and hot melt. Application of coating agents is disclosed.

However, when the polymer layer is formed by extrusion laminating, heat and mechanical external force during the processing cause
Cracks and defects occur in the inorganic thin film layer that covers the base film, and the barrier properties are significantly reduced. Further, even when films are laminated by dry lamination, mechanical external force acts during bonding or application of an adhesive, and the inorganic thin film layer on the base film is easily broken. Furthermore, when forming a protective layer or the like on the inorganic thin film layer by coating, not only does the improvement of the barrier property due to the coating not appear, but the inorganic thin film layer is immediately destroyed by the action of mechanical external force, and the barrier property is greatly reduced. . Furthermore, the above-mentioned films, including the case of laminating or applying a vinylidene chloride resin to the thin film of the inorganic oxide formed on the film, are all intimately adhered to the thin film layer of the inorganic oxide to the base film. It is difficult to maintain high adhesion and high barrier properties for a long period of time when it is used as a packaging material that is not only poor in properties but also subjected to mechanical external force, or as a packaging material that is used under high temperature and high humidity. . In addition, food,
Packaging films used for pharmaceuticals, precision electronic parts, etc. are required to have high transparency in order to make the contents visible and aesthetic. However, the transparency tends to decrease as the adhesion of the inorganic thin film layer decreases. As described above, it is difficult for the conventional film to suppress the deterioration of the barrier property due to the action of the mechanical external force associated with the processing and the use. In particular, in addition to flexibility and transparency, it is not possible to obtain a film having excellent barrier properties even if the coating layer is thin, and the effect of protecting the contents and the visibility of the contents are still insufficient.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a barrier composite film in which the adhesion between the base film and the inorganic thin film layer and the gas barrier property are greatly improved, and a method for producing the same. . Another object of the present invention is to exert a gas barrier property while maintaining high adhesion between the base film and the inorganic thin film layer even when a mechanical external force such as bending or rubbing acts, or when used under high temperature and high humidity. It is to provide a barrier composite film and a method for producing the same, which can suppress deterioration of the film. Still another object of the present invention is to provide a barrier composite film having high barrier properties and high transparency even when the coating layer is thin, and a method for producing the same. Another object of the present invention is to provide a barrier composite film having an extremely small amount of residual solvent after printing and laminating, and a method for producing the same. Still another object of the present invention is that mechanical external force acts, microwave heating, even when exposed to a high temperature and high humidity environment such as retort treatment, deterioration of transparency and gas barrier property can be suppressed, and deterioration and It is an object of the present invention to provide a barrier composite film capable of storing contents for a long time while suppressing deterioration, and a method for producing the same.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above-mentioned object. As a result, the inorganic layer formed on the surface of the base film layer contains a barrier resin and a silane coupling agent. By coating with an adhesive, it was found that not only the adhesiveness of the inorganic layer to the base film layer but also the gas barrier property can be improved, and the barrier property does not deteriorate even under the action of mechanical external force or high temperature and high humidity, and the present invention has been completed. . That is, in the barrier composite film of the present invention, at least one surface of the base film layer is covered with the barrier resin layer containing the silane coupling agent via the inorganic layer. The base film layer is made of various polymers,
For example, it can be formed of an olefin polymer, polyester, polyamide or the like. The inorganic layer may be, for example, Periodic Table 2
It can be composed of various metal simple substances such as group A elements, transition elements, group 2B elements, group 3B elements, group 4B elements, and group 6B elements, or inorganic compounds thereof. Further, the barrier resin coating layer is a silane coupling agent (for example, a halogen atom,
A silicon compound having an alkoxy group and at least one functional group selected from an epoxy group, an amino group, a hydroxyl group, a mercapto group, a vinyl group, and a (meth) acryloyl group, and a barrier resin (a vinylidene chloride-based resin). It can be formed by applying a coating liquid containing a polymer, an ethylene-vinyl alcohol copolymer, etc.). The other surface of the base film layer or the barrier resin coating layer may be covered with a heat seal layer. The inorganic layer may have a thickness of about 100 to 5000 Å, and the barrier resin coating layer may have a thickness of about 0.05 to 15 μm. The ratio T / t of the thickness T (μm) of the barrier resin coating layer to the thickness t (μm) of the inorganic layer can be selected from the range of about 0.1 to 1500. In the barrier composite film of the present invention, an inorganic oxide thin film layer is formed on at least one surface of the base film layer, and a coating layer containing a barrier resin as a main component is formed on the thin film layer. A barrier composite film,
The peel strength of the coating layer to the base film layer after storage for 1 week at a temperature of 40 ° C. and a relative humidity of 90% RH is 1
A barrier composite film having a weight of 00 g / 15 mm or more is also included.

In the present specification, the "barrier resin coating layer" means that the thickness is 2 μm and the temperature is 25.
Oxygen gas permeability of 20 cc / m ² at 24 ° C for 24 hours or less, water vapor permeability of 20 g / m ^{2 at} a temperature of 40 ° C and 90% relative humidity
-It means a layer containing a barrier resin for 24 hours or less. Further, the “heat seal layer” means a layer that can be thermally bonded by a method such as impulse sealing, high frequency bonding, ultrasonic bonding, or the like, without being limited to thermal bonding by a heat sealer.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As the polymer constituting the base film layer, various polymers capable of forming a film, such as polyethylene, ethylene-ethyl acrylate copolymer, ionomer, polypropylene, ethylene-propylene copolymer, Polyolefin such as poly-4-methylpentene-1; Polyalkylene terephthalate (polyethylene terephthalate, polybutylene terephthalate etc.), Polyester such as polyethylene-2,6-naphthalate; Nylon 6, Nylon 11, Nylon 12, Nylon 66, Nylon 610 Polyamide, nylon 6/66, nylon 66/610, nylon MXD, etc .; polyvinyl chloride; polyvinylidene chloride, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride Den - (meth) vinylidene chloride resin such as acrylic acid ester copolymers; polystyrene, styrene - acrylonitrile copolymer, styrene -
Styrene resins such as acrylonitrile-butadiene copolymer; polyvinyl alcohol; polyamideimide; polyimide; polyetherimide; polycarbonate; polysulfone; polyethersulfone; polyetheretherketone; polyarylate; polyphenylene sulfide; polyphenylene oxide; polyparaxylene; Polyacrylonitrile; Fluorine resins such as polytetrafluoroethylene, polytrifluorochloroethylene, fluorinated ethylene-propylene copolymers; Cellulosic polymers such as cellophane; Hydrochloric acid rubber; Copolymers containing the components of the various polymers Is exemplified. These polymers may be used alone or in combination of two or more.

The base film layer contains various additives,
For example, stabilizers such as antioxidants, ultraviolet absorbers and heat stabilizers; antistatic agents such as cationic, anionic, nonionic and amphoteric antistatic agents; crystal nucleus growth agents; styrene resins, terpene resins, Petroleum resins, dicyclopentadiene resins, coumarone resins such as coumarone indene resins, phenolic resins, hydrocarbon polymers such as rosin and its derivatives and hydrogenated resins thereof; plasticizers; fillers; higher fatty acid amides, higher fatty acids And its salts, higher fatty acid esters, natural waxes such as mineral-based and plant-based waxes, waxes such as synthetic waxes such as polyethylene; silica-based fine powders, inorganic lubricants such as alumina-based powders, polyethylene-based powders, acrylic-based powders Fine powdered lubricants such as organic lubricants; colorants and the like may be contained.

The light transmittance of the base film layer can be appropriately selected, and for the visibility and aesthetics of the package contents, the total light transmittance for white light rays is usually 40% or more, preferably 60. % Or more, and more preferably 80% or more.

The base film layer comprises an olefin polymer (especially polypropylene polymer), polyester (especially polyalkylene terephthalate such as polyethylene terephthalate), polyamide, styrene polymer, ethylene-vinyl alcohol copolymer, polycarbonate, polyacrylonitrile. It is preferable to be composed of Olefin-based polymers, polyesters and polyamides are excellent in transparency, mechanical strength and packaging suitability. For retort processing and food packaging materials for electromagnetic heating,
Polymers having excellent transparency, mechanical strength and suitability for packaging and having high heat resistance, such as polypropylene, polyester, polyamide, ethylene-vinyl alcohol copolymer, polycarbonate and polyacrylonitrile are preferable.
Particularly preferable polymer for the base film layer,
Includes polypropylene, polyester, polyamide and the like.

The base film layer may be a monolayer film or a laminated film in which one or more polymer layers are laminated. The thickness of the base film layer is not particularly limited and is appropriately selected in consideration of packaging suitability, mechanical strength, flexibility and the like. The thickness of the base film layer is usually 3 to 200 μm, preferably 5 to 100 μm, more preferably 10 to 50 μm (for example, 10 to 30 μm).
m).

The substrate film layer can be formed by a conventional film forming method, for example, an inflation method, a melt forming method such as a T-die method, or a casting method using a solution. The base film layer may be unstretched or may be uniaxially or biaxially stretched. As the stretching method, for example, a conventional stretching method such as roll stretching, rolling stretching, belt stretching, tenter stretching, tube stretching, or a combination of these can be applied. The stretching ratio can be appropriately set according to the desired characteristics of the film, and is, for example, 1.5 to 20 times, preferably about 2 to 15 times in at least one direction.

At least one surface of the base film layer is
It may be surface-treated. Examples of the surface treatment include corona discharge treatment, plasma treatment, glow discharge treatment, reverse sputtering treatment, flame treatment, chromic acid treatment, solvent treatment and surface roughening treatment. In addition, when the inorganic layer and the barrier resin coating layer are formed on the surface-treated surface of the base film layer, the adhesion can be improved.

An undercoat layer may be formed on the surface of the base film layer instead of or in addition to the surface treatment. The undercoat layer can be composed of various resins such as thermoplastic resins, thermosetting resins, light curable resins (electron beam curable resins, ultraviolet curable resins, etc.) and coupling agents. Specific components of the undercoat layer include
For example, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polycarbonate, cellulosic polymer such as nitrocellulose and cellulose acetate, thermoplastic resin such as rosin-modified maleic acid resin; urethane resin, urea resin, Melamine resin,
Examples include thermosetting resins such as urea-melamine resins and epoxy resins; photocurable resins such as epoxy (meth) acrylates and urethane (meth) acrylates; and silane coupling agents. These may be used alone or in combination of two or more. The undercoat layer may contain a colorant such as a general-purpose dye or pigment. The content of the colorant is appropriately selected within a range that does not impair the transparency of the film, and is usually 1 to 3 with respect to the resin forming the undercoat layer.
It is about 0% by weight. The thickness of the undercoat layer is not particularly limited and is usually about 0.1 to 5 μm. The method for forming the undercoat layer is not particularly limited, and an organic or aqueous coating agent containing the components of the undercoat layer is applied by a conventional coating method such as a roll coating method, a gravure coating method, a reverse coating method, or a spray coating method. And then dried or cured. When a photocurable resin is used, it may be irradiated with an actinic ray.

The main feature of the present invention is to combine an inorganic layer (in particular, an inorganic layer having transparency) with a barrier resin coating layer containing a silane coupling agent,
The point is to cover the surface of the base film. Originally, the inorganic layer (especially the inorganic layer having transparency) formed on the substrate film is not a thin film that is entirely uniform, unlike an aluminum foil, glass, or tile, and an inhomogeneous interface with poor barrier properties. It is assumed that this is a thin film with pinholes and pinholes. In the present invention, the barrier resin coating layer is embedded in the portion having a poor barrier property scattered in the inorganic layer, so that unlike the laminating process of the barrier resin film, the deterioration of the barrier property can be efficiently suppressed. Further, by forming the coating layer of the non-barrier resin, diffusion of gas passing through the inorganic layer may be suppressed to some extent, but the gas barrier property is still small. On the other hand, in the present invention, since the barrier resin coating layer is formed, gas diffusion can be effectively prevented. Furthermore, even if a crack or defect occurs in the inorganic layer due to a mechanical external force acting during processing, the barrier resin coating layer can suppress the diffusion of gas to an extremely small level. Furthermore, by increasing the adhesion between the inorganic layer and the barrier resin coating layer with the inclusion of the silane coupling agent, the occurrence of damage to the inorganic layer against mechanical external force is suppressed, and by any chance cracks or defects. Even in the case of occurrence of, the barrier resin coating layer can minimize the deterioration of the barrier property.

With such a structure, not only the adhesion between the base film layer and the inorganic layer can be remarkably improved, but also the barrier property can be greatly improved. Further, even when a mechanical external force is applied or under high temperature and high humidity, it is possible to remarkably suppress the deterioration of the adhesiveness and the gas barrier property. Furthermore, it is possible to obtain a film having high transparency, probably due to the high affinity between the inorganic layer and the barrier resin coating layer, and having excellent barrier properties even when the coating layer is thin. Further, the combination of the inorganic layer and the coating layer can maintain a high barrier property even when exposed to a high temperature by retort treatment, electromagnetic wave heating, etc., and there is little microwave loss during electromagnetic wave heating of a microwave oven or the like.

The inorganic substance forming the inorganic layer is preferably an inorganic substance capable of forming a transparent thin film. Examples of such an inorganic substance include elements of Group 2A of the periodic table such as beryllium, magnesium, calcium, strontium and barium; Titanium, zirconium, ruthenium, hafnium,
Periodic table transition elements such as tantalum; Periodic table 2B such as zinc
Group elements: Periodic table 3B group elements such as aluminum, gallium, indium, and thallium; Periodic table 4B group elements such as silicon, germanium, tin; Periodic table 6B group elements such as selenium and tellurium; Inorganic compounds such as oxides, halides, carbides, nitrides and the like can be mentioned. These may be used alone or in combination of two or more. Preferred inorganic substances include, for example, magnesium, calcium, barium and other periodic table group 2A elements;
Periodic table transition elements such as titanium, zirconium, tantalum and ruthenium; Periodic table 2B group elements such as zinc; Periodic table 3B group elements such as aluminum, indium and thallium;
Elements of Group 4B of the periodic table such as silicon and tin; simple substances of elements of Group 6B of the periodic table such as selenium, and oxides containing them are included. In particular, it is preferable that the inorganic layer is formed of a simple metal of Group 3B element or Group 4B element of the periodic table or an oxide thereof.

Among the above-mentioned inorganic substances, oxides containing the above-mentioned elements (for example, tin oxide, aluminum oxide, indium oxide or their composite oxides and silicon oxides) are excellent in transparency and barrier properties. In particular, silicon oxide is
In addition to the above characteristics, it is possible to form a dense thin film, has a high affinity with the polymer forming the barrier resin coating layer containing a silane coupling agent, and even if a mechanical external force acts, cracks or defects in the inorganic layer Is not generated, and high barrier properties can be maintained for a long period of time even at high temperatures. The silicon oxide includes not only silicon monoxide and silicon dioxide but also silicon oxide represented by the composition formula SiOx (wherein 0 <x ≦ 2, preferably 0.8 ≦ x ≦ 1.5). Things are included. In the electromagnetic wave heating packaging material, an inorganic compound having a low electric conductivity, for example, a non-conductive inorganic material such as an oxide, a halide, a carbide or a nitride can be used. Preferred non-conductive inorganic materials include oxides such as silicon oxide.

The thickness of the inorganic layer is usually 100 to 500.
0 angstrom (0.01-0.5 μm), preferably 200-3000 angstrom (0.02-
0.3 μm), and more preferably in the range of about 300 to 1500 angstrom (0.03 to 0.15 μm). If the thickness is less than 100 angstroms, it is difficult to form a uniform thin film, and sufficient barrier properties and mechanical strength cannot be obtained. Even if it exceeds 5000 angstroms, the barrier properties are not improved so much, and the transparency and There are problems such as a loss of appearance, which is economically disadvantageous.

As the barrier resin of the coating layer,
Resins having high gas barrier properties as described above, for example, vinylidene chloride-based copolymers, ethylene-vinyl alcohol copolymers, polyamide-based polymers, polyvinyl alcohol-based polymers, polyacrylonitrile-based polymers, urethane-based polymers and the like. Can be mentioned. Depending on the composition of the barrier resin of the coating layer, some resins do not exhibit the gas barrier property. For example, one example thereof is thermoplastic polyurethane having a relatively long segment (polyalkyleneoxy segment or the like). These barrier resins can be used alone or in combination of two or more.

The preferred barrier resin includes, for example, vinylidene chloride copolymer and ethylene-vinyl alcohol copolymer. The vinylidene chloride-based copolymer is a copolymer of vinylidene chloride and another polymerizable monomer, and examples of such a copolymerizable monomer include vinyl chloride, vinyl acetate, crotonic acid, acrylic acid, and methyl acrylate. , Various acrylates such as ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, pentyl acrylate, and hexyl acrylate (for example, C _1-8 alkyl-acrylate), acrylonitrile, methacrylonitrile, methacrylic acid. Examples thereof include methacrylates corresponding to the above acrylates. Among these vinylidene chloride-based copolymers, vinylidene chloride-acrylonylolyl copolymer, vinylidene chloride-methacrylic acid copolymer, vinylidene chloride-acrylate copolymer, vinylidene chloride-methacrylate copolymer, vinylidene chloride-vinyl acetate copolymer Polymers and the like are preferable. The vinylidene chloride content in the vinylidene chloride-based copolymer is usually 85 to 9
It is about 9% by weight, preferably about 90 to 97% by weight.

The ethylene-vinyl alcohol copolymer is preferably a solvent-soluble or dispersible ethylene-vinyl alcohol copolymer. In such ethylene-vinyl alcohol copolymer, the ethylene content is usually
5 to 50 mol%, preferably 10 to 45 mol%, more preferably about 25 to 35 mol%, and the molecular weight (weight average molecular weight) is, for example, 1 × 10 ⁴ to 10 × 10 ⁴ , preferably 2 ×. 10 ^{4 to} 7 × 10 ⁴ , preferably 4 × 10
It is about ^{4 to} 5 × 10 ⁴ . The saponification degree is preferably 99.5% or more. Such solvent-soluble ethylene
The vinyl alcohol copolymer is soluble or dispersible in water or a mixed solvent of water and alcohol, and a thin film can be formed by coating.

The barrier resin coating layer has a desired barrier property (oxygen, water vapor, carbon dioxide, organic solvent gas,
It may contain at least one resin of the barrier resin (preferably vinylidene chloride-based copolymer and ethylene-vinyl alcohol copolymer) depending on its barrier property against aroma components such as limonene). It may contain a resin. Further, the barrier resin coating layer may be composed of a plurality of layers containing a barrier resin. For example, the barrier resin coating layer may be composed of a plurality of layers including a layer containing a vinylidene chloride copolymer and a layer containing an ethylene-vinyl alcohol copolymer. The content of the barrier resin in the barrier resin coating layer is 50% by weight or more, preferably 75 to 100% by weight, more preferably 90 to 100%.
It is about% by weight.

The barrier resin coating layer is formed of another polymer such as ethylene-vinyl acetate copolymer,
Olefin-based polymers such as ethylene-ethyl acrylate copolymers; acrylic-based polymers; styrene-based polymers; polyesters; polyacetals; polyvinyl acetate;
Polyvinyl chloride; vinyl chloride-vinyl acetate copolymer; polyamide; urethane-based polymer; acrylonitrile-based polymer; polycarbonate; chlorinated polyolefin; cellulose-based polymer and the like may be contained. The barrier resin coating layer may optionally contain the above-mentioned additives, anti-blocking agents; adhesion improvers such as polyethyleneimine and polyisocyanate.

As the silane coupling agent, various compounds capable of improving the adhesion to the inorganic layer, the base film layer and the barrier coating layer, for example, halogen atom, epoxy group, amino group, hydroxyl group, mercapto group, vinyl are used. A silicon compound having an alkoxy group and at least one functional group selected from the group, a (meth) acryloyl group. The halogen atom is fluorine,
It contains chlorine, bromine and iodine atoms, and is often a chlorine or bromine atom. The epoxy group is an epoxy ring formed by oxidation of an unsaturated bond of a hydrocarbon group (for example, an unsaturated double bond of a cycloalkenyl group such as a cyclopentenyl group, a cyclohexenyl group or a cyclooctenyl group) or an epoxy of a glycidyl group. It may be composed of a ring. The amino group may be substituted with 1 or 2 lower alkyl groups (eg, C _1-4 alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl groups). Furthermore, the (meth) acryloyl group may be composed of a (meth) acryloyloxy group. Alkoxy groups include, for example, methoxy, ethoxy, furopoxy,
Included are C _1-4 alkoxy groups such as isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy groups. A preferred alkoxy group is a hydrolyzable alkoxy group (particularly a methoxy group or an ethoxy group). In the silicon compound, the number of reactive functional groups is about 1 to 3 (particularly 1 or 2), and the number of alkoxy groups is about 1 to 3 (particularly 2 or 3). Preferred silane coupling agents, in the following formulas Y- (R) _n -SiX ₃ (wherein, Y is a halogen atom, an epoxy group, an amino group,
A functional group selected from a mercapto group, a vinyl group and a (meth) acryloyl group, R is a hydrocarbon residue, and X is the same or different alkoxy group. n is 0 or 1)
A silicon compound represented by

The functional group represented by Y and the alkoxy group represented by X are as described above. The hydrocarbon residue represented by R includes an alkylene group (for example, a straight-chain or branched-chain C such as methylene, ethylene, trimethylene, propylene, 2,2-dimethylmethylene, tetramethylene, pentamethylene, and hexamethylene). _1-6 alkylene groups, etc.), cycloalkene residues (eg, cycloheptene,
C _4-10 cycloalkene residues such as cyclohexene, cyclopentene and cyclooctene), cycloalkene-
Alkyl residue (eg C _4-10 cycloalkene-C such as cycloheptene, cyclohexene, cyclopentene, etc.
_1-6 alkyl group, etc.) and the like. The cycloalkene residue and the cycloalkene-alkyl residue are
As described above, it is often a residue produced by epoxidation of a double bond. Preferred hydrocarbon residue R is C
_1-4 alkylene residue (especially C _2-4 alkylene residue), C
Included are _{5-8 cyclohairken} -C _1-4 alkyl residues, especially cyclohexene-C _2-4 alkyl residues. Furthermore, n is 0 or 1. When Y is a vinyl group, n
Is 0, and when Y is another functional group, n is often 1.

Examples of the silane coupling agent include halogen-containing silane coupling agents (2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane). Etc.), epoxy group-containing silane coupling agent [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-
Epoxycyclohexyl) ethyltriethoxysilane,
3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane Etc.], amino group-containing silane coupling agents (2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- [N- (2-aminoethyl) amino] ethyltri) Methoxysilane, 3- [N- (2-aminoethyl)
Amino] propyltrimethoxysilane, 3- (2-aminoethyl) amino] propyltriethoxysilane, 3-
[N- (2-aminoethyl) amino] propyl methyldimethoxysilane, etc., mercapto group-containing silane coupling agent (2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-
Mercaptopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agents (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), (meth) acryloyl group-containing silane coupling agents (2-methacryloyloxyethyltrimethoxysilane, 2- Methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane and the like) can be exemplified. These silane coupling agents can be used alone or in combination of two or more.

The amount of the silane coupling agent used can be selected within a range capable of improving the adhesiveness of the inorganic layer.
0.05 to 10 parts by weight (for example, 0.1 to 10 parts by weight), preferably 0.1 to 100 parts by weight of the barrier resin.
To 7 parts by weight (eg 0.2 to 7 parts by weight), more preferably 0.5 to 5 parts by weight (eg 0.5 to 3 parts by weight).
It is a degree.

The thickness of the barrier resin coating layer can be appropriately selected within a range that does not impair the characteristics of the film, and is, for example, 0.05 to 15 μm, preferably 0.1 to 10 μm.
(For example, 0.2 to 7 μm), more preferably 0.25 to
It is about 5 μm (for example, 0.3 to 3 μm). When the thickness of the coating layer is less than 0.05 μm, it is difficult to impart high gas barrier properties, and when it exceeds 15 μm, the gas barrier properties are not so improved, which is economically disadvantageous.

The thickness ratio between the inorganic layer and the barrier resin coating layer can be set appropriately, but the thickness ratio affects the gas barrier property. In order to obtain high gas barrier properties and resistance, the thickness t (μm) of the inorganic layer
Thickness of barrier resin coating layer against T (μm)
The ratio T / t is, for example, 0.1 to 1500, preferably 0.5 to 500 (for example, 0.5 to 60, preferably 1 to 200), more preferably 1 to 100, and 2 It is often about 50 (for example, about 5 to 50). When the thickness ratio is out of the above range, it becomes difficult to impart high gas barrier properties, and the above ratio is 0.1.
If it is less than 15%, defects are likely to occur in the inorganic layer due to external force.
Even if it exceeds 00, the gas barrier properties are not so improved,
Not economical.

In the barrier composite film of the present invention, in addition to the composite film, an inorganic oxide thin film layer is formed on at least one surface of the base film layer, and a barrier resin is formed on the thin film layer. A barrier composite film having a coating layer as a main component is also included. These composite films have a peel strength of the coating layer of 100 g / 15 mm or more (for example, 100 to 40) with respect to the base film layer after being stored at a temperature of 40 ° C. and a relative humidity of 90% RH for one week.
0 g / 15 mm), preferably 120-350 g / 15
mm, and more preferably about 150 to 300 g / 15 mm. Further, these composite films have a high gas barrier property, and for example, the thickness of the base film layer is 10 to 3.
When the thickness of the coating layer composed of the inorganic layer and the coating layer is 0 to 5 μm, the oxygen gas permeability at a temperature of 25 ° C. is, for example, 5 cc / m ² · 24 hours or less (for example, 0 .01~3cc / m ² · 24 hr), preferably 0.01~1cc / m ² · 24 hours, more preferably 0.01~0.5cc / m about ² · 24 h, temperature 40 ° C. and The water vapor transmission rate at 90% relative humidity is
For example, 5 g / m ² · 24 hours or less (0.01 to 4 g /
m ² · 24 hours), preferably 0.1 to 3.5 g / m ²
・ 24 hours, more preferably 0.1 to 3 g / m ² · 2
It takes about 4 hours.

In order to form the bag easily, the barrier resin coating layer may be covered with a heat seal layer. When the inorganic layer and the coating layer are formed on one surface of the base film layer, the heat seal layer may be formed on the other surface of the base film layer. As the polymer constituting the heat seal layer, a heat-bonding polymer, for example, an olefin polymer, vinyl acetate-
Examples thereof include vinyl chloride copolymers, polyesters, polyamides and rubber polymers. These heat-bondable polymers can be used alone or in combination of two or more.

Preferred heat-bonding olefin polymers include, for example, polyethylene such as low density polyethylene and linear low density polyethylene, ethylene-butene-1 copolymer, ethylene- (4-methylpentene-1) copolymer. Polymer, ethylene-hexene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer, ionomer, polypropylene, propylene-butene-1 copolymer Polymer, ethylene-propylene copolymer, ethylene-propylene-butene-1 copolymer, ethylene-propylene-
Examples thereof include diene copolymers and modified polyolefins such as maleic anhydride-modified polyethylene and maleic anhydride-modified polypropylene. Preferred olefin-based polymers include polyethylene, ethylene-vinyl acetate copolymer,
Ethylene-ethyl acrylate copolymer, amorphous polyolefin (for example, amorphous polypropylene),
An ethylene-propylene copolymer and the like are included. When forming the heat-sealing layer by laminating, the preferred heat-bondable film is a non-stretched polypropylene film,
An unstretched ethylene-propylene copolymer film and the like are included. The heat-bondable polyester includes an aliphatic polyester having an aliphatic diol and an aliphatic dicarboxylic acid as constituent components. As the heat-bondable polyamide, for example,
Nylon 11, nylon 12, nylon 6/12, etc. may be mentioned. Examples of the rubber-based polymer include butyl rubber, isobutylene rubber, chloroprene rubber, styrene-
Acrylonitrile copolymers, styrene-butadiene copolymers, styrene-acrylonitrile-butadiene copolymers, etc. are included. The thickness of the heat-sealing layer can be appropriately selected in the range of, for example, about 3 to 100 μm according to the application of the packaging material, and when the heat-sealing layer is formed by laminating films, the thickness of the heat-sealing layer is, for example, 20 to 100 μm.
m, preferably about 30 to 80 μm.

The heat seal layer may be formed on a predetermined portion of the surface of the barrier resin coating layer, for example, a portion to be used for heat sealing, but it is often formed on the entire surface of the barrier resin coating layer. . Further, the heat seal layer may be formed on the heat seal site or the whole of the other surface of the base film layer as described above. In addition,
The heat seal layer may contain the above-mentioned additive as needed.

The barrier film of the present invention can be obtained by sequentially coating at least one surface of the base film with an inorganic layer and a barrier resin coating layer containing a silane coupling agent. Another barrier film of the present invention is a method of sequentially coating at least one surface of a base film with an inorganic layer, a barrier resin coating layer containing a silane coupling agent, and a heat seal layer, or a base material. It can be obtained by a method in which one surface of the film is sequentially coated with an inorganic layer and a barrier resin coating layer containing a silane coupling agent, and the other surface of the substrate film is coated with a heat seal layer.

The inorganic layer is formed by a conventional method such as a physical method (vacuum vapor deposition method, reactive vapor deposition method, sputtering method,
Reactive sputtering method, ion plating method, reactive ion plating method, etc., chemical method (CV)
D method, plasma CVD method, laser CVD method, etc.), the surface of the substrate film can be formed by coating with the above-mentioned inorganic substance. The inorganic layer is often formed by a physical method such as vapor deposition, and the inorganic layer can be formed on one side or both sides of the base film layer.

The barrier resin coating layer can be formed by applying a coating solution containing a silane coupling agent and a barrier resin on the surface of the inorganic layer. The coating solution can be prepared by selecting an appropriate solvent according to the types of the silane coupling agent and the barrier resin, and may be in the form of a solution or a dispersion. For example, the solvent of the solution coating solution containing the vinylidene chloride copolymer can be appropriately selected according to the type of the vinylidene chloride copolymer, for example, acetone, methyl ethyl ketone, ketones such as cyclohexanone; dioxane, diethyl. Ethers such as ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate;
Amides such as dimethylformamide and mixed solvents thereof are included. Further, the dispersion liquid is usually commercially available in the form of an O / W type emulsion. The coating liquid containing the ethylene-vinyl alcohol copolymer can be usually prepared using a mixed solvent of water and alcohol. Examples of such alcohols include methanol, ethanol, propanol, isopropanol, cyclohexanol and the like. The coating liquid may contain the above-mentioned various additives, and may further contain conventional additives such as antifoaming agents and viscosity modifiers in order to enhance the coating property.

The coating method is not particularly limited as long as it does not generate cracks or defects in the inorganic layer, and it is a conventional method such as air knife coating method, roll coating method, gravure coating method, blade coating method, dip coating method, spraying. The law etc. can be adopted. After applying the coating solution, for example,
The barrier resin coating layer can be formed by drying at a temperature of about 50 to 150 ° C.

The surface of the barrier resin coating layer may be subjected to the conventional surface treatment exemplified in the section of the base film layer, if necessary, regardless of the presence or absence of a heat seal layer. It is also possible to form an adhesive layer or a protective layer on a part or the entire surface without applying. The heat-sealing layer can be formed by a conventional method such as a dry laminating method, an extrusion laminating method, or a coating method depending on the kind of the heat-bonding polymer.

The barrier composite film of the present invention contains various coating layers and laminate layers such as a slipping layer, an antistatic layer, a decorative printing film layer, and a nylon layer, depending on the type and use of the film. A reinforcing layer such as a film may be formed.

The barrier composite film of the present invention is greatly improved in not only the adhesiveness of the inorganic layer to the base film layer but also the gas barrier property, and even when a mechanical external force acts or it is exposed to high temperature and high humidity, It exhibits a high gas barrier property as described above. Further, even if the coating layer is extremely thin, it exhibits a high gas barrier property and not only has high transparency, but also can reduce flexibility, and can greatly suppress peeling of the coating layer and generation of defects. Therefore, packaging materials are microwave oven food, retort food, frozen food, microwave sterilization, flavor barrier,
Various packaging materials such as pharmaceuticals and precision electronic parts, balloons,
It can be suitably used as a material for producing balloons such as balloons. In addition, by packaging food or the like, the contents can be stored for a long period of time while suppressing deterioration and deterioration. Thus, the present invention also discloses the use of a barrier composite film for packaging various contents such as foods, pharmaceuticals, electronic parts and the like.

The form of the package using the film of the present invention is not particularly limited, and for example, it can be used as a solid packaging bag or a liquid packaging bag. The packaging bag containing these foods can be subjected to retort treatment or microwave heating as it is. Examples of the packaging form of the packaging material of the present invention include bags, cups, tubes, standing bags, containers such as trays, lid materials, and inner packaging materials for paper packs such as sake, soy sauce, mirin, oil, milk and juice. It is illustrated.

[0043]

EFFECT OF THE INVENTION In the barrier composite film of the present invention, the inorganic layer is covered with the barrier resin coating layer containing the silane coupling agent, so that the adhesive force between the base film layer and the inorganic thin film layer and the gas barrier Can greatly improve the sex. In addition, even when mechanical external forces such as bending and rubbing act, and even when used under high temperature and high humidity, while maintaining high adhesion between the base film and the inorganic thin film layer, it has excellent gas barrier properties over a long period of time. Can be demonstrated. Furthermore, even if the coating layer is thin,
It has high barrier properties and high transparency. Therefore, even if mechanical external force acts or is exposed to a high temperature and high humidity environment such as microwave heating, retort treatment, etc., it is possible to suppress the adhesion, transparency and gas barrier property of the inorganic layer from deteriorating and degrading. The contents can be stored for a long time while suppressing the above. Further, the barrier composite film of the present invention, when printed or laminated on the barrier resin coating layer side by a conventional method, penetrates into the base film such as the solvent contained in the printing ink and the laminating adhesive. And the amount of residual solvent is extremely low. for that reason,
High safety can be ensured in food packaging.

[0044]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples. Comparative Example 1 On one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, 5 × 10 5 was used as an evaporation source of SiO 2.
A silicon oxide vapor deposition layer having a thickness of 1000 Å was formed as an inorganic layer by a vacuum vapor deposition method under a vacuum of ⁻⁵ Torr to obtain a composite film.

Examples 1 and 2 For 100 parts by weight of vinylidene chloride-based copolymer (Asahi Kasei Kogyo KK, trade name: Saran Resin F216), γ
-Glycidoxypropyltrimethoxysilane (that is, 3-glycidyloxypropyltrimethoxysilane) (manufactured by Toshiba Silicone Co., Ltd., trade name: TSL835)
0) 1.0 part by weight was added and dissolved in a mixed solvent of toluene / tetrahydrofuran = 1/2 (weight ratio) to prepare a coating solution for a barrier resin coating layer having a resin concentration of 15% by weight. The vinylidene chloride-based copolymer is a copolymer containing 85 mol% or more of vinylidene chloride monomer as a main component and at least one selected from acrylic acid, methyl methacrylate, and methacrylonitrile as a comonomer. is there. 1. The coating liquid was applied to the vapor deposition surface of the silicon oxide vapor deposition film obtained in Comparative Example 1 with a bar coater to give a thickness of 0.5 μm (Example 1) and 2.
After coating so as to have a thickness of 5 μm (Example 2), 105 ° C.
Was dried in an oven for 30 seconds to form a barrier resin coating layer to obtain a composite film.

Example 3 Based on 100 parts by weight of vinylidene chloride copolymer (Asahi Kasei Kogyo KK, trade name: Saran resin F216), γ
-Aminopropyltriethoxysilane (i.e., 3-
Aminopropyltriethoxysilane) (Toshiba Silicone Co., Ltd., trade name: TSL8331) (1.0 part by weight) is added and dissolved in a mixed solvent of toluene / tetrahydrofuran = 1/2 (weight ratio) to give a resin concentration of 15% by weight. % Coating solution for the barrier resin coating layer was prepared. This coating solution was applied to the vapor deposition surface of the silicon oxide vapor deposition film obtained in Comparative Example 1 using a bar coater to give a thickness of 2.5 μm after drying.
m to 30 m in an oven at 105 ° C.
Dry for 2 seconds to form a barrier resin coating layer,
A composite film was obtained.

Example 4 Vinyltrimethoxysilane (manufactured by Toshiba Silicone Co., Ltd., trade name: TSL8311) based on 100 parts by weight of vinylidene chloride copolymer (Asahi Kasei Kogyo Co., Ltd. trade name: Saran Resin F216) 1.0 part by weight was added and dissolved in a mixed solvent of toluene / tetrahydrofuran = 1/2 (weight ratio) to prepare a coating solution for a barrier resin coating layer having a resin concentration of 15% by weight. This coating solution was used as Comparative Example 1
It is applied to the vapor deposition surface of the silicon oxide vapor deposition film obtained in 1. using a bar coater so that the thickness after drying is 2.5 μm, and then dried in an oven at 105 ° C. for 30 seconds to form a barrier resin coating layer. To form a composite film.

Example 5 γ with respect to 100 parts by weight of a vinylidene chloride copolymer (Asahi Kasei Kogyo KK, trade name: Saran Resin F216)
-1.0 parts by weight of mercaptopropyltriethoxysilane (manufactured by Toshiba Silicone Co., Ltd., trade name: TSL8380) was added, dissolved in a mixed solvent of toluene / tetrahydrofuran = 1/2 (weight ratio), and the resin concentration was 15% by weight. % Coating solution for the barrier resin coating layer was prepared. This coating solution was applied to the vapor deposition surface of the silicon oxide vapor deposition film obtained in Comparative Example 1 using a bar coater to obtain a thickness of 2.5 after drying.
After coating to a thickness of 3 μm, use an oven at 105 ° C for 3
After drying for 0 seconds, a barrier resin coating layer was formed to obtain a composite film.

Example 6 100 parts by weight of an ethylene-vinyl alcohol copolymer (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Soanol 30L) was added to γ-glycidoxypropyltrimethoxysilane (Toshiba Silicone Co., Ltd. ), Product name: TSL835
0) 1.0 part by weight was added, and water / isopropanol = 1
It was dissolved in a mixed solvent of 1/1 (weight ratio) to prepare a coating liquid for a barrier resin coating layer having a resin concentration of 12% by weight. This coating solution was applied to the vapor deposition surface of the silicon oxide vapor deposition film obtained in Comparative Example 1 by using a bar coater so that the thickness after drying was 4.0 μm, and then 1 degree in an oven at 115 ° C. After drying for a minute, a barrier resin coating layer was formed to obtain a composite film.

Comparative Example 2 A composite film was obtained in the same manner as in Example 1 without using the silane coupling agent. Comparative Example 3 A composite film was obtained in the same manner as in Example 2 without using the silane coupling agent. Comparative Example 4 A composite film was obtained in the same manner as in Example 3 without using the silane coupling agent.

Comparative Example 5 On one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, Al ₂ O ₃ was used as a vapor deposition source and 5 ×
Thickness of 1000 by vacuum deposition under 10 ^-5 Torr vacuum.
An aluminum oxide vapor deposition layer of angstrom was formed as an inorganic layer to obtain a composite film.

Examples 7 and 8 With respect to 100 parts by weight of vinylidene chloride copolymer (Asahi Kasei Kogyo KK, trade name: Saran resin F216), γ
1 part by weight of glycidoxypropyltrimethoxysilane (manufactured by Toshiba Silicone Co., Ltd., trade name: TSL8350) was added, dissolved in a mixed solvent of toluene / tetrahydrofuran = 1/2 (weight ratio), and the resin concentration was 15% by weight. % Coating solution for barrier resin coating was prepared. This coating solution was applied to the vapor deposition surface of the aluminum oxide vapor deposition film obtained in Comparative Example 5 using a bar coater to obtain a thickness O.V.
After coating so as to have a thickness of 5 μm (Example 7) and 2.5 μm (Example 8), it was dried in an oven at 105 ° C. for 30 seconds to form a barrier resin coating layer to obtain a composite film.

Example 9 100 parts by weight of an ethylene-vinyl alcohol copolymer (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Soarnol 30L) was added to γ-glycidoxypropyltrimethoxysilane (Toshiba Silicone Co., Ltd. ), Product name: TSL835
0) Add 1 part by weight, water / isopropanol = 1/1
It was dissolved in a mixed solvent (weight ratio) to prepare a coating liquid for barrier resin coating having a resin concentration of 12% by weight. This coating solution was applied to the vapor deposition surface of the aluminum oxide vapor deposition film obtained in Comparative Example 5 using a bar coater so that the thickness after drying was 4.0 μm, and then in an oven at 115 ° C. for 1 minute. After drying, a barrier resin coating layer was formed to obtain a composite film.

Comparative Example 6 A composite film was obtained in the same manner as in Example 7 without using the silane coupling agent. Comparative Example 7 A composite film was obtained in the same manner as in Example 8 without using the silane coupling agent. Comparative Example 8 A composite film was obtained in the same manner as in Example 9 without using the silane coupling agent.

Comparative Example 9 Instead of the coating liquid containing a vinylidene chloride copolymer, a general urethane resin solution having no barrier performance defined in this specification [Takelac, trade name, manufactured by Takeda Pharmaceutical Co., Ltd.] was used. A615] on the surface of the inorganic layer with a thickness of 5.0 μm.
A composite film was obtained in the same manner as in Example 1 except that the coating layer of 1 was formed.

Comparative Example 10 Instead of the barrier resin coating layer, a urethane adhesive [trade name: ADCOTE 33, manufactured by Toyo Morton Co., Ltd., was used on the surface of the inorganic layer of the vapor-deposited film obtained in Comparative Example 1.
3E] is applied so that the thickness after drying is about 2 μm,
An unstretched ethylene-propylene copolymer film having a thickness of 30 μm was laminated by a dry lamination method to obtain a composite film.

Comparative Example 11 Instead of the coating liquid containing the vinylidene chloride copolymer, a vinyl chloride-vinyl acetate copolymer solution [Denki Kagaku Kogyo KK] was used.
Manufactured by Denka 1000C, trade name, was used to obtain a composite film in the same manner as in Example 2 except that a coating layer having a thickness of 2.5 μm was formed on the surface of the inorganic layer.

Comparative Example 12 Instead of a coating solution containing γ-glycidoxypropyltrimethoxysilane (manufactured by Toshiba Silicone Co., Ltd., trade name: TSL8350), a vinylidene chloride copolymer (manufactured by Asahi Kasei Kogyo KK, 1 part by weight of polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: Coronate L) is added to 100 parts by weight of product name: Saran resin F216), and toluene / tetrahydrofuran = 1/2 (weight ratio).
To prepare a coating liquid for a barrier resin coating layer having a resin concentration of 15% by weight. This coating solution was applied to the vapor deposition surface of the silicon oxide vapor deposition film obtained in Comparative Example 1 using a bar coater to give a thickness of 2.5 μm after drying.
m to 30 m in an oven at 105 ° C
After being dried for 2 seconds, a barrier resin coating film was formed to obtain a composite film.

Comparative Example 13 Instead of a coating solution containing γ-glycidoxypropyltrimethoxysilane (manufactured by Toshiba Silicone Co., Ltd., trade name: TSL8350), a vinylidene chloride copolymer (manufactured by Asahi Kasei Kogyo KK, 1 part by weight of polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: Coronate L) is added to 100 parts by weight of product name: Saran resin F216,
It was dissolved in a mixed solvent of toluene / tetrahydrofuran = 1/2 (weight ratio) to prepare a coating liquid for a barrier resin coating layer having a resin concentration of 15% by weight. This coating solution
Using a bar coater on the vapor deposition surface of the aluminum oxide vapor deposition film obtained in Comparative Example 5, the thickness after drying was 2.5.
After coating so as to have a thickness of 3 μm, use an oven at 105 ° C for 3
After drying for 0 seconds, a barrier resin coating film was formed to obtain a composite film.

Comparative Example 14 Coating for a barrier resin coating layer containing the vinylidene chloride copolymer of Example 1 at a resin concentration of 15% by weight in the same manner as in Example 1 without adding a silane coupling agent. A liquid was prepared. The above coating solution was applied to one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm using a bar coater without vapor deposition of silicon oxide so that the thickness after drying was 2.5 μm. After that, it was dried in an oven at 105 ° C. for 30 seconds to form a barrier resin coating film to obtain a composite film.

Comparative Example 15 The coating solution (containing a silane coupling agent) obtained in Example 1 was applied to a thickness of 12 without vapor deposition of silicon oxide.
Using a bar coater on one surface of the biaxially stretched polyethylene terephthalate film of μm, the thickness after drying was 2.
After coating so as to have a thickness of 5 μm, it was dried in an oven at 105 ° C. for 30 seconds to form a barrier resin coating film, thus obtaining a composite film.

Then, the oxygen gas permeability, the water vapor permeability and the adhesion strength of the coating film of the composite films obtained in Examples and Comparative Examples were evaluated as follows. Oxygen gas permeability: Same pressure method (Measuring instrument: Morcon, OXTRAN T
WIN) at 20 ° C. and 65% relative humidity. The unit is cc / m ² · 24 hr. Water vapor transmission rate: measured using a measuring instrument (Morcon, PERMATRAN W200) under the conditions of 40 ° C. and 90% relative humidity. The unit is g / m ² · 24 hr.

Adhesion strength of coating film: An unstretched ethylene-propylene copolymer film having a thickness of about 50 μm was laminated on the coating layer by the dry lamination method, and then the test film and the unstretched ethylene-propylene copolymer film were laminated. The peel strength was measured using a measuring instrument (ORIENTEC, RTM-100) at a pulling speed of 300 mm / min.

Further, the film was rubbed once by hand, the oxygen gas permeability and the water vapor permeability before and after the rubbing were measured, and the change in the gas barrier property due to the action of mechanical external force was evaluated. Further, the film was stored under conditions of 40 ° C. and 90% relative humidity for 1 week, and the adhesion strength of the coating film before and after storage was measured,
The change in adhesion under high temperature and high humidity was evaluated. The results are shown in Table 1. In the film of Comparative Example 7, the oxygen transmission rate before hand rubbing was below the measurement limit.

[0065]

[Table 1] Evaluation of test results 1) In the film in which the barrier resin coating layer is not formed (Comparative Example 1 or Comparative Example 5), Examples 1 to 1 are used.
Compared with 6 or Examples 7 to 9, the gas barrier property is significantly reduced. 2) In the film (Comparative Examples 2 to 4 or Comparative Examples 6 to 8) not using the silane coupling agent, the adhesion of the coating film before storage was higher than that of Examples 1 to 6 or Examples 7 to 9. It is small, and the adhesiveness is significantly reduced after storage. 3) In each of the films (Comparative Examples 11 to 13) in which a low barrier resin is used instead of the barrier resin, not only the barrier properties but also the adhesiveness are significantly reduced as compared with Examples 1 to 9. 4) Instead of the silane coupling agent, the film using polyisocyanate, which is a polyfunctional compound reactive at room temperature, has a larger gas barrier property and adhesiveness of the coating film in the normal state than the film using the silane coupling agent. Although there is no difference, when it is stored under high temperature and high humidity, the adhesiveness is significantly reduced.

5) In the film which does not form the inorganic layer,
The gas barrier property is lowered, and the adhesiveness is remarkably lowered when stored under high temperature and high humidity.

Example 10 Instead of the polyethylene terephthalate film, a thickness of 1
A composite film was obtained in the same manner as in Example 2 except that a 5 μm biaxially stretched nylon 6 film was used.

Example 11 A thickness of 2 was used instead of the polyethylene terephthalate film.
A composite film was obtained in the same manner as in Example 2 except that a 0 μm biaxially oriented polypropylene film was used.

Example 12 A coating solution having a ratio of γ-aminopropyltriethoxysilane of 0.2 part by weight to 100 parts by weight of vinylidene chloride copolymer was prepared in the same manner as in Example 3. Then, a composite film was obtained in the same manner as in Example 3 except that the obtained coating liquid was used instead of the coating liquid of Example 3.

Example 13 A coating solution having a ratio of γ-aminopropyltriethoxysilane of 5 parts by weight to 100 parts by weight of a vinylidene chloride copolymer was prepared in the same manner as in Example 3. Then, a composite film was obtained in the same manner as in Example 3 except that the obtained coating liquid was used instead of the coating liquid of Example 3.

Example 14 The coating solution obtained in Example 3 was applied to the vapor deposition surface of the silicon oxide vapor deposition film obtained in Comparative Example 1 to give a thickness of 12 μm after drying.
It was applied so as to have a thickness of m, and a barrier resin coating layer was formed to obtain a composite film.

Example 15 The coating solution obtained in Example 3 was applied on the vapor deposition surface of the silicon oxide vapor deposition film obtained in Comparative Example 1 to a thickness of 5 μm after drying.
And a barrier resin coating layer were formed to obtain a composite film.

Then, the oxygen gas permeability, the water vapor permeability and the adhesion strength of the coating film of the obtained composite film were examined in the same manner as above, and the results shown in Table 2 were obtained.

[0074]

[Table 2]

Claims (25)

[Claims] 1. A barrier composite film in which at least one surface of a base film layer is covered with a barrier resin layer containing a silane coupling agent via an inorganic thin film layer. 2. The barrier composite film according to claim 1, wherein the base film layer is composed of polypropylene, polyalkylene terephthalate or polyamide. 3. The barrier composite film according to claim 1, wherein the inorganic thin film layer has transparency. 4. The inorganic layer is composed of at least one metal oxide selected from 2A group elements, transition elements, 2B group elements, 3B group elements, 4B group elements and 6B group elements of the periodic table. 1. The barrier composite film as described in 1. 5. The inorganic layer is an element of Group 3B or 4B of the periodic table.
The barrier composite film according to claim 1, which is composed of an oxide of a group element. 6. The barrier composite film according to claim 1, wherein the inorganic layer is composed of silicon oxide. 7. The barrier composite film according to claim 1, wherein the inorganic layer has a thickness of 100 to 5000 angstroms. 8. The barrier composite film according to claim 1, wherein the barrier resin coating layer contains a vinylidene chloride copolymer or an ethylene-vinyl alcohol copolymer. 9. The barrier resin coating layer comprises a vinylidene chloride-acrylonylolyl copolymer, vinylidene chloride-methacrylic acid copolymer, vinylidene chloride-acrylate copolymer, vinylidene chloride-methacrylate copolymer, vinylidene chloride-vinyl acetate. 9. The barrier composite film according to claim 8, comprising a copolymer and at least one barrier resin selected from the group consisting of solvent-soluble or dispersible ethylene-vinyl alcohol copolymers having an ethylene content of 5 to 50 mol%. . 10. The silane coupling agent comprises an alkoxy group and at least one functional group selected from a halogen atom, an epoxy group, an amino group, a hydroxyl group, a mercapto group, a vinyl group and a (meth) acryloyl group. The barrier composite film according to claim 1, which has. 11. A silane coupling agent has the formula Y- (R) _n -SiX ₃ (wherein Y is a halogen atom, an epoxy group, an amino group,
A functional group selected from a mercapto group, a vinyl group and a (meth) acryloyl group, R is a hydrocarbon residue, and X is the same or different alkoxy group. n is 0 or 1)
The barrier composite film according to claim 1, which is a compound represented by: 12. The hydrocarbon residue represented by R is C _1-4
C _5-8 in which an alkylene group or a double bond is epoxidized
A cycloalkene-C _1-4 alkyl residue, wherein X is the same or different and is a methoxy group or an ethoxy group.
1. The barrier composite film as described in 1. 13. The barrier composite film according to claim 11, wherein n is 0 when Y is a vinyl group. 14. The barrier composite film according to claim 1, wherein the ratio of the silane coupling agent is 0.05 to 10 parts by weight with respect to 100 parts by weight of the barrier resin. 15. The barrier composite film according to claim 1, wherein the ratio of the silane coupling agent is 0.1 to 7 parts by weight with respect to 100 parts by weight of the barrier resin. 16. The barrier composite film according to claim 1, wherein the barrier resin coating layer has a thickness of 0.05 to 15 μm. 17. The ratio T / μ of the thickness T (μm) of the barrier resin coating layer to the thickness t (μm) of the inorganic layer.
The barrier composite film according to claim 1, wherein t is 0.1 to 1500. 18. The ratio T / μ of the thickness T (μm) of the barrier resin coating layer to the thickness t (μm) of the inorganic layer.
The barrier composite film according to claim 1, wherein t is 0.5 to 500. 19. A composition formula SiOx (wherein 0 <0 <0) is formed on at least one surface of a base film layer made of polypropylene, polyalkylene terephthalate or polyamide.
x ≦ 2), which is composed of a silicon oxide and has a transparency of 100 to 5000 angstroms in thickness, a silane coupling agent, a vinylidene chloride copolymer or an ethylene-vinyl alcohol copolymer. And a barrier resin coating layer containing the barrier resin coating layer are formed in this order, and the ratio T (μm) of the barrier resin coating layer to the thickness t (μm) of the inorganic layer is T.
The barrier composite film according to claim 1, wherein / t is 1 to 200. 20. A non-conductive inorganic material is formed on at least one surface of a base film layer made of polypropylene, polyalkylene terephthalate or polyamide,
The barrier composite film according to claim 1, further comprising an inorganic layer having a thickness of 200 to 3000 angstroms and a barrier resin coating layer having a thickness of 0.1 to 10 μm. 21. A barrier composite film comprising an inorganic oxide thin film layer formed on at least one surface of a base film layer, and a coating layer containing a barrier resin as a main component formed on the thin film layer. Yes, temperature 40 ° C, relative humidity 9
A barrier composite film in which the peel strength of the coating layer from the base film layer after storage at 0% RH for 1 week is 100 g / 15 mm or more. 22. The thickness of the base film layer is 10 to 30 μm.
m, the thickness of the coating layer composed of the inorganic layer and the coating layer is 0.5 to 5 μm, the oxygen gas permeability is 5 cc / m ² · 24 hours or less at a temperature of 25 ° C., a temperature of 40 ° C. and 90%. The barrier composite film according to claim 21, which has a water vapor transmission rate of 5 g / m ² · 24 hours or less at a relative humidity. 23. The barrier composite film according to claim 1, wherein the other surface of the base film layer or the barrier resin coating layer is covered with a heat seal layer. 24. A barrier composite film, which comprises forming an inorganic thin film layer on at least one surface of a base film and then applying a coating solution containing a silane coupling agent and a barrier resin on the inorganic layer. Production method. 25. The method for producing a barrier composite film according to claim 24, wherein a heat-sealing layer having a thickness of 3 to 100 μm is formed on the other surface of the coating layer or the base film.