JPH11978A - Barrier composite film and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To largely improve adhesive strength and barrier properties of a base material film layer and an inorganic thin film layer by interposing a specific anchor coating layer between the film layer and the thin film layer. SOLUTION: The composite film comprises an inorganic thin film layer formed on at least one surface of a base material film layer via an anchor coating layer. In this case, the coating layer contains ether type polyester, polyisocyanate compound, and substantially nonreactive saturated polyester resin to the polyisocyanate compound and having glass transition temperature of -10 to 20 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in barrier properties against water vapor, oxygen and aroma components, etc., and is used for preserving films of dried foods, retorting and heating microwaves of foods, packaging of pharmaceuticals, precision electronic parts and the like. The present invention relates to a barrier composite film suitable as a film for producing films, balloons, balloons and the like, 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 properties of the base film layer can be greatly improved, and the selection range of the base material is determined in relation to other properties such as heat resistance and mechanical properties. Can be expanded. The composite film provided with the inorganic oxide thin film layer can be roughly classified as follows.

(I) A composite film having an inorganic oxide thin film layer directly formed on a base film. For example, JP-A-60-27532 discloses a composite film in which a transparent thin film layer of magnesium oxide is formed on a polyolefin film, and a polymer layer is formed on the thin film layer by dry lamination or extrusion lamination. JP-A 1-220235 and JP-A 1-2
Japanese Patent Publication No. 02436 discloses a packaging material for a microwave oven and a packaging material for a retort food in which a vapor deposited layer of silicon oxide and a heat sealing layer or a protective layer are formed on the surface of a substrate film. 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. JP-A 1-2
No. 9723 discloses lamination of a biaxially stretched nylon film on a thin film of an inorganic oxide of a film.
No. 6539 discloses lamination or coating of a thin film of an inorganic oxide on a film with a vinylidene chloride resin or the like. However, these composite films (i)
Characteristics such as barrier properties are liable to fluctuate, and it is difficult to stably express high barrier properties. Therefore, usually 10
When used as a film for retort treatment that is sterilized or sterilized in a steam pot at 0 ° C. or higher, properties such as adhesion between layers and barrier properties are significantly reduced after retort treatment. Further, when the inorganic oxide layer is formed directly on the substrate film, the composite film is easily curled, and the handleability in the processing step is impaired.

(Ii) A composite film having an inorganic oxide thin film layer formed on a pretreated surface of a base film. For example, JP-A-53-12953 discloses a composite film in which a silicon oxide transparent thin film is formed on a pre-treated surface of a base film, and JP-A-63-237940 discloses indium oxide and oxide. A composite film in which a heat seal layer such as an ethylene-propylene copolymer is formed on a film obtained by sputtering tin or the like is disclosed. However, when the composite film (ii) is used as a film for retort treatment, the adhesion between the substrate film and the inorganic oxide thin film layer is greatly reduced, and the barrier property is also significantly reduced.

(Iii) A composite film comprising a resin layer or an undercoat layer formed on a base film, and an inorganic oxide thin film layer formed on the undercoat layer. For example, JP-A-4-173137 discloses that a thin film layer of an inorganic oxide is formed on an undercoat layer formed on a film, and a vinyl chloride-vinyl acetate copolymer, polyamide, polyester, acrylic, A balloon laminate having high barrier properties against helium and hydrogen gas by applying a resin or applying a hot melt coating agent is disclosed. JP-A-3-86539 discloses that
On the surface of the base film, apply a reactive two-part curable resin composition composed of a polyisocyanate compound and a saturated polyester polyol, form a silicon oxide thin film layer on the application surface, and have retort suitability It is disclosed to obtain a packaging film. In addition, Tokuhei 8-183
No. 95 discloses that a mixture layer of a two-component curable polyurethane and 5 to 30% by weight of a vinyl chloride-vinyl acetate copolymer is formed on a base film, and a metal oxide such as magnesium oxide is formed on the mixture layer. A vapor deposition film having a vapor deposition layer formed thereon is disclosed. According to this document, in order to prevent the penetration of moisture, a reactive two-part curable polyurethane composed of a polyol component and a polyisocyanate compound is used. The use of a copolymer is disclosed. In these composite films (iii), the adhesion between the base film and the inorganic oxide thin film layer can be improved. However, even if the composite film has high adhesion and barrier properties in the normal state (the film before retort treatment), if it is used as a film for retort treatment, not only the adhesion between the base film and the inorganic oxide thin film layer but also the barrier film The properties are also greatly reduced. In particular, both in the normal state and after the retort treatment, the adhesion between the base film and the inorganic oxide thin film layer and the barrier property cannot be compatible at a high level. Furthermore, since the coated surface of the reactive two-part curable resin composition has tackiness, it is easy to block, and it becomes difficult to wind and rewind the film, resulting in a decrease in productivity. Moreover, since the polyol component and the polyisocyanate compound have reactivity, the two-part curable polyurethane once prepared cannot be used repeatedly, and must be discarded. for that reason,
The undercoat resin composition cannot be used effectively. Japanese Patent Application No. 8-113082 (Japanese Patent Application No. Hei 8-13082) is an improvement of these, and contains a chlorine-containing resin, has an inorganic oxide thin film, and is one of the characteristics of a barrier film. The effect of not generating any gas is lost.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a barrier composite film having significantly improved adhesion, barrier properties, and environmental suitability between a base film layer and an inorganic thin film layer, and a method for producing the same. To provide. Another object of the present invention is to maintain barrier properties while maintaining high adhesion between the base film layer and the inorganic thin film layer even when exposed to severe conditions such as retort treatment and microwave heating as well as normal conditions. It is an object of the present invention to provide a barrier composite film capable of suppressing the reduction and a method for producing the same. Still another object of the present invention is to provide a barrier composite film useful for preserving contents for a long time due to high adhesion and high barrier properties, and a method for producing the same. Another object of the present invention is to provide a barrier composite film having a high productivity while effectively utilizing an anchor coat agent and a method for producing the same. Still another object of the present invention is to provide a barrier composite film having high transparency and visibility of contents, and useful as a packaging film for foods, pharmaceuticals, precision electronic components and the like, and a method for producing the same. .

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that an inorganic thin film is formed on a non-curable specific anchor coat layer formed on the surface of a base film layer. The inventors have found that the formation of the layer can greatly improve not only the adhesion of the inorganic thin film layer to the base film layer but also the gas barrier property even after the retort treatment, and thus completed the present invention.

That is, the barrier composite film of the present invention is a composite film in which an inorganic thin film layer is formed on at least one surface of a base film layer via an anchor coat layer, wherein the anchor coat layer comprises: (A) an ether-type polyester, (B) a polyisocyanate compound, and (C) a saturated polyester resin having a glass transition temperature of −10 to 20 ° C. and substantially non-reactive with the polyisocyanate compound. Have been. In this barrier composite film, the ether type polyester includes:
An ethylene terephthalate-diethylene glycol-based copolymer and the like are included, and the polyisocyanate compound includes a compound having at least two isocyanate groups in a molecule and having a molecular weight of 150 to 1,000. The saturated polyester resin has a hydroxyl value of 0 to 15 mgKOH / g.
Alternatively, a non-crystalline saturated polyester having an acid value of about 0 to 10 mgKOH / g may be used. The proportion of the components of the anchor coat layer is, for example, (A) ether type polyester 1
(B) 10 to 500 parts by weight of the polyisocyanate compound, (C) 1 to 1 part by weight of the saturated polyester resin
It is about 50 parts by weight.

The base film layer contains polypropylene, polyalkylene terephthalate, polyamide or the like, and the inorganic thin film layer is made of, for example, a 2A group element, a transition element, a 2B group element, a 3B group element, or a 4B group element. Group element,
It can be composed of a metal oxide such as a Group 6B element.

The barrier composite film of the present invention includes, for example, (i) a barrier composite film having an inorganic thin film layer formed on at least one surface of a base film layer via an anchor coat layer. A barrier composite film in which the anchor coat layer has an elastic modulus of 0.1 × 10 ¹ to 1 × 10 ³ N / mm ² , (ii) an anchor coat layer on at least one surface of the base film layer. A barrier composite film having an inorganic thin film layer formed thereon, wherein the anchor coat layer has a peel strength of 100 g / 1 with respect to the base film layer after the retort treatment at a temperature of 120 ° C. for 30 minutes.
A barrier composite film having a thickness of 5 mm or more is also included. These barrier composite films also exhibit high gas barrier properties even when exposed to severe conditions such as retort treatment.

In the method of the present invention, (A) an ether-type polyester is provided on at least one surface of the substrate film layer.
(B) a polyisocyanate compound; and (C) an anchor coat layer having a glass transition temperature of −10 ° C. to 20 ° C. and comprising a saturated polyester resin substantially non-reactive with the polyisocyanate compound. After that, a barrier composite film can be produced by forming an inorganic thin film layer on this anchor coat layer.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

[Base Film Layer] As the polymer constituting the base film layer, various polymers capable of forming a film, for example, polyethylene, ethylene-ethyl acrylate copolymer, ionomer, polypropylene, ethylene-propylene copolymer, poly Polyolefins such as -4-methylpentene-1; polyesters such as polyalkylene terephthalate (polyethylene terephthalate, polybutylene terephthalate, etc.) and polyethylene-2,6-naphthalate; nylon 6, nylon 11, nylon 12, nylon 66, nylon 610; Polyamides such as nylon 6/66, nylon 66/610, nylon MXD; polyvinyl chloride; polyvinylidene chloride, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer, vinylidyl chloride Vinylidene chloride resins such as den- (meth) acrylate copolymer; polystyrene, styrene-acrylonitrile copolymer, styrene-
Styrene resins such as acrylonitrile-butadiene copolymer; polyvinyl alcohol: polyamide imide; polyimide; polyether imide; polycarbonate; polysulfone; polyether sulfone; polyether ether ketone; polyarylate; polyphenylene sulfide; polyphenylene oxide; Polyacrylonitrile; Fluororesins such as polytetrafluoroethylene, polytrifluorochloroethylene, fluorinated ethylene-propylene copolymers; Cellulosic polymers such as cellophane; Hydrochloric acid rubber; Copolymers containing components of the above various polymers Is exemplified. These polymers can be used alone or in combination of two or more.

The base film layer is made of 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, Hydrocarbon polymers such as petroleum resin, dicyclopentadiene resin, cumarone resin such as coumarone indene resin, phenolic resin, rosin and its derivatives and hydrogenated resins thereof; plasticizer; filler; higher fatty acid amide, higher fatty acid And its salts, higher fatty acid esters, mineral waxes and waxes such as natural waxes such as vegetable and synthetic waxes such as polyethylene; inorganic lubricants such as silica fine powder and alumina fine powder; polyethylene fine powder; acrylic fine powder And fine powdery lubricants such as organic lubricants; coloring agents and the like.

The light transmittance of the substrate film layer can be appropriately selected. For the sake of visibility and aesthetics of the package contents, the total light transmittance in white light is usually 40% or more, preferably 60%. %, More preferably 80% or more.

The base film layer is made of an olefin polymer (especially a polypropylene polymer), a polyester (especially a polyalkylene terephthalate such as polyethylene terephthalate), a polyamide, a styrene polymer, an ethylene-vinyl alcohol copolymer, a polycarbonate, a polyacrylonitrile. It is preferred to be constituted by such as. Olefin polymers, polyesters, and polyamides are excellent in transparency, mechanical strength, and packaging suitability.

[0016] Packaging materials for foods for retort treatment and electromagnetic wave heating include high heat-resistant polymers having excellent transparency, mechanical strength and packaging suitability, such as polypropylene, polyester, polyamide, ethylene-vinyl alcohol copolymer, and polycarbonate. And polyacrylonitrile are preferred. Particularly preferred polymers constituting the layer include polypropylene, polyester, polyamide and the like.

The substrate film layer may be a single-layer film or a laminated film in which one or two or more polymer layers are laminated. The thickness of the substrate 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 substrate 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).
It is about. 100μm thickness for boiling and retort
The following base film layers are often used.

The base film layer can be formed by a conventional film forming method, for example, a melt forming method such as an inflation method or a T-die method, or a casting method using a solution. Further, the base film layer may be unstretched, or may be subjected to uniaxial or biaxial stretching treatment. 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 thereof can be applied. The stretching ratio can be appropriately set according to the desired film properties, and is, for example, about 1.5 to 20 times, preferably about 2 to 15 times in at least one direction.

At least one surface of the substrate film layer is
Surface treatment may be performed. 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, if an anchor coat layer is formed on the surface-treated surface of the base film layer, the adhesion can be improved.

[Anchor coat layer (undercoat layer)] The main feature of the present invention is that an inorganic thin film layer (particularly a transparent inorganic layer) is formed on at least one surface of the substrate film layer via a specific anchor coat layer. ) Is to greatly improve the adhesion and barrier properties between the base film layer and the inorganic thin film layer. The anchor coat layer,
(A) an ether type polyester, (B) a polyisocyanate compound, and (C) a specific glass transition temperature,
It is composed of a saturated polyester resin substantially non-reactive with the polyisocyanate compound. (C)
When a polyester polyol having reactivity with the polyisocyanate compound (B) is used as the saturated polyester resin, the adhesion and the gas barrier property after the retort treatment are greatly reduced, possibly due to a crosslinking reaction.
Therefore, in the present invention, (C) a soft and substantially non-reactive saturated polyester resin is used. Also,
Even when (B) the polyisocyanate compound is combined with (C) a soft, non-reactive saturated polyester resin, the blocking property of the anchor coat layer is improved by (A) the ether-type polyester. In addition, "substantially non-reactive" means that a crosslinked cured product is not generated.

[(A) Ether type polyester] The ether type polyester used in the present invention is conventionally known only in that ethylene glycol and a compound represented by the following general formula (I) are used as a glycol component. It is needless to say that a conventionally known reaction temperature, reaction pressure, reaction method and polymerization catalyst can be used in the synthesis thereof.

Formula (I)

The ether type polyester used in the present invention can also be obtained from a ternary system of a diol component, ethylene glycol and terephthalic acid represented by these general formulas.

Incidentally, among these diols represented by the general formula (I), and (Where n, m, x, y, R ₁ , and R ₃ each represent the same as those proposed above). Particularly, polyesters obtained from those represented by the general formula: It is valid.

Further, polyesters derived from a combination of at least one of the compounds represented by the above general formula (I) and ethylene glycol, diethylene glycol or triethylene glycol are particularly excellent.

Although it is possible to use an acid component and a specific diol component, from the viewpoint of prevention of so-called pollution or effective use of waste plastics, a material once derived from polyester is used as a more effective material. It is desired to use as. Therefore, a detailed discussion will be made below from the standpoint of effective use of this waste plastic.

Unless otherwise specified, the polyesters described below are polyesters consisting essentially of terephthalic acid and ethylene glycol.

The aromatic dibasic acids include, for example, terephthalic acid, isophthalic acid, p-β-oxyethoxybenzoic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, adipic acid, sebacic acid, azelaic acid, -Sodium sulfoisophthalic acid, diphenylenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and the like.

The ether type polyester is substantially non-reactive with the polyisocyanate compound. That is, the (A) ether-type polyester is non-reactive with the (B) polyisocyanate compound or has a low concentration of active hydrogen atoms even if it has reactive active hydrogen atoms. The acid value of the ether type polyester is, for example, 0 to 30 mgKOH / g, preferably 0 to 20 mgKOH / g.
It is about KOH / g. The acid value of the chlorine-containing resin is
It originates in a polymerizable carboxylic acid or its derivative (s).

The ether type polyester has a glass transition temperature of, for example, 15 to 80 ° C. (for example, 15 to 60 ° C.).
° C), preferably about 20 to 60 ° C, and 20 to 50 ° C.
It is often about ° C.

The molecular weight of the ether-type polyester can be selected within a range that does not impair the adhesion. For example, the number average molecular weight is 0.5 × 10 ⁴ to 10 × 10 ⁴ , preferably 1 × 10 ⁴ to
It is about 5 × 10 ⁴ , more preferably about 1 × 10 ^{4 to} 3 × 10 ⁴ .

[(B) Polyisocyanate compound] As the polyisocyanate compound, at least 2
Compounds having two isocyanate groups are used. Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenyl diisocyanate, xylylene diisocyanate, tetramethyl xylene diisocyanate,
Aromatic diisocyanates such as diphenylmethane diisocyanate, tolidine diisocyanate [bis (4-isocyanate-3-methylphenyl) methane], triphenylmethane triisocyanate, 1,5-naphthalenediisocyanate, 1,4-tetramethylene diisocyanate, 1,6- Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,10-
Aliphatic diisocyanate such as decamethylene diisocyanate, lysine diisocyanate, 1,3,6-hexamethylene triisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and modified polyisocyanate. Is exemplified. In the modified polyisocyanate, for example, an adduct in which polyisocyanate is added to a polyhydric alcohol, a dimer, a trimer having an isocyanurate ring,
Alohanate modified, urea modified polyisocyanate,
Bullet-modified polyisocyanate and the like are included. The polyhydric alcohol in the adduct includes low molecular weight polyols having three or more hydroxyl groups, for example, triols such as glycerin, trimethylolpropane, and trimethylolethane, and tetraols such as pentaerythritol. One or more of these polyisocyanates can be used.

Preferred polyisocyanate compounds include
Low molecular weight compounds having three or more isocyanate groups in the molecule, for example, adducts obtained by adding 3 mol of a polyisocyanate compound (such as diisocyanate) to 1 mol of trimethylolpropane are included. The molecular weight of the polyisocyanate compound can be selected, for example, from the range of about 150 to 1,000, preferably about 300 to 1,000.

[(C) Saturated Polyester Resin] As the saturated polyester resin, various polyesters obtained by a condensation reaction of a polyhydric carboxylic acid or an acid anhydride or lower alcohol ester thereof with a polyhydric alcohol can be used. Oxycarboxylic acid may be used in the overall reaction.

Examples of the polyvalent carboxylic acid component include aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid, and acid anhydrides thereof; succinic acid, glutaric acid, adipic acid And aliphatic carboxylic acids such as azelaic acid and sebacic acid and acid anhydrides thereof. As the polycarboxylic acid component, an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid and terephthalic acid or an acid anhydride thereof, and a saturated aliphatic dicarboxylic acid such as adipic acid, azelaic acid and sebacic acid are often used. The oxycarboxylic acids include, for example, β-oxypropionic acid, β-oxybutyric acid, and the like.

Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Aliphatic dihydric alcohols such as neopentyl glycol; polyoxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and polytetramethylene ether glycol; glycerin;
Aliphatic polyhydric alcohols such as trimethylolpropane, trimethylolethane, and pentaerythritol; alicyclic polyhydric alcohols such as cyclohexanediol and hydrogenated bisphenol A; 2,2-bis (4-dihydroxyethylphenyl) propane; Bisphenol A such as 2-bis (4-dihydroxypropylphenyl) propane
And aromatic polyhydric alcohols such as adducts of alkylene oxides.

In order to block the remaining hydroxyl groups and carboxyl groups, a monohydric alcohol, a monocarboxylic acid or the like may be used as a terminal blocking agent.

Preferred saturated polyester resins are usually
Polyesters other than polyalkylene terephthalate, which are often (C1) non-crystalline polyesters soluble in organic solvents (for example, non-crystalline linear polyesters). Such polyester resins include terephthalic acid,
A polyester having an aromatic ring derived from an aromatic polycarboxylic acid such as phthalic acid or isophthalic acid (eg, an oil-free aromatic polyester); and (C2) a polyalkylene ether glycol unit (a polytetramethylene ether glycol unit). The thermoplastic elastomer includes a soft segment and a polyalkylene terephthalate unit (such as a polyethylene terephthalate or polybutylene terephthalate unit) as a hard segment. In the saturated polyester resin (C1), a part of the alkylene glycol of polyalkylene terephthalate and / or terephthalic acid may be partially converted to another diol (for example, a soft diol component such as diethylene glycol or triethylene glycol) and / or a dicarboxylic acid (phthalic acid). Modified polyester (modified polyalkylene terephthalate) substituted with an acid, isophthalic acid, adipic acid, and the like, and isophthalic acid-based polyester containing isophthalic acid and glycol (such as ethylene glycol) as main components are included.

Saturated polyester resins are clearly distinguished from polyols (polyester polyols, polyether polyols, acrylic polyols, etc.) for constituting two-part curable adhesives in combination with polyisocyanate compounds. That is, the polyol constituting the two-component cured adhesive usually has a hydroxyl value of 40 mg KOH / g or more due to a crosslinking reaction with the polyisocyanate compound.
The saturated polyester resin is substantially non-reactive with the polyisocyanate compound, like the above-mentioned ether type polyester. The hydroxyl value of the saturated polyester resin is
For example, 0 to 15 mgKOH / g, preferably 0 to 10 mgKOH / g
It is about mgKOH / g, and often about 0 to 5 mgKOH / g. The acid value of the saturated polyester resin is, for example, 0 to 10 mgKOH / g, preferably 0 to 10 mgKOH / g.
It is about 7 mgKOH / g, and often about 0 to 5 mgKOH / g.

In the present invention, irrespective of whether the substrate film is exposed to severe conditions such as retort treatment or the like, the adhesion between the base film layer and the inorganic thin film layer and the barrier property are maintained at a high level. In the combination of the ether type polyester, the polyisocyanate compound and the saturated polyester resin, a soft, non-reactive saturated polyester resin is used. The glass transition temperature of the saturated polyester resin is, for example, about −10 ° C. to 20 ° C., preferably about −5 ° C. to 15 ° C. (eg, 0 to 15 ° C.), and often about 0 to 20 ° C.

The molecular weight of the saturated polyester resin depends on the adhesiveness.
Can be selected within a range that does not impair the barrier properties.
Average molecular weight 0.5 × 10^Four -10 × 10^Four , Preferably 1 ×
10 ^Four ~ 5 × 10^Four , More preferably 1 × 10^Four ~ 3x
10^Four It is about.

[Ratio of Components of Anchor Coat Layer] The ratio of the components of the anchor coat layer can be selected within a range that does not impair the adhesiveness and barrier properties. For example, (A) B) 10 to 500 parts by weight of a polyisocyanate compound (preferably 25 to 4 parts by weight)
00 parts by weight, more preferably 30 to 300 parts by weight),
(C) 1 to 50 parts by weight of a saturated polyester resin (preferably 2 to 50 parts by weight, more preferably 5 to 30 parts by weight)
It is about. The proportion of each component is (A) 30 to 200 parts by weight of a polyisocyanate compound (for example, 30 to 15 parts by weight) per 100 parts by weight of an ether type polyester.
(0 parts by weight) and (C) about 3 to 20 parts by weight (e.g., 5 to 20 parts by weight) of the saturated polyester resin, it is possible to secure high adhesion and barrier properties.

The proportion of the (C) saturated polyester resin is usually smaller than the amount of the (B) polyisocyanate compound used.
It is about 5 to 50 parts by weight, preferably about 7 to 40 parts by weight, more preferably about 10 to 30 parts by weight with respect to parts by weight.

The anchor coat layer may contain various additives, for example, stabilizers such as antioxidants, ultraviolet absorbers and heat stabilizers; plasticizers; fillers;

The thickness of the anchor coat layer (undercoat layer) is such that the adhesion to the inorganic thin film layer is improved and the barrier property is not impaired, for example, 0.01 to 5 μm (for example, 0.1 to 5 μm).
1-5 μm), preferably 0.1-1 μm (for example,
0.2 to 1 μm).
Even when the thickness is about 0.7 μm, high adhesion to the inorganic thin film layer is exhibited without deteriorating gas barrier properties.

[Inorganic Thin Film Layer] The inorganic material constituting the inorganic thin film layer is preferably an inorganic material capable of forming a transparent thin film. Examples of such inorganic materials include beryllium, magnesium, calcium, strontium, and barium. Group 2A elements of the periodic table such as titanium; zirconium;
Periodic table transition elements such as ruthenium, hafnium, and tantalum; Periodic table group 2B elements such as zinc; Periodic table group 3B elements such as aluminum, gallium, indium, and thallium;
A group 4B element of the periodic table such as silicon, germanium, and tin; a simple substance such as a group 6B element of the periodic table such as selenium and tellurium; and inorganic compounds containing these elements, for example, oxides, halides, carbides, and nitrides. Can be These can be used alone or in combination of two or more.

Preferred inorganic substances include, for example, Group 2A elements of the periodic table such as magnesium, calcium and barium; transition elements of the periodic table such as titanium, zirconium, tantalum and ruthenium; Group 2B elements of the zinc and the like; aluminum, indium, A simple substance of a Group 3B element of the Periodic Table such as thallium; a Group 4B element of the Periodic Table such as silicon or tin; a selenium or other Group 6B element, or an oxide containing them. In particular, it is preferable that the inorganic thin film layer is formed of a simple substance of a Group 3B element or a 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, composite oxides thereof, and silicon oxide) are excellent in transparency and barrier properties. In particular, silicon oxide, in addition to the above properties, can form a dense thin film, and can maintain high barrier properties even at high temperatures for a long period of time. The silicon oxide includes not only silicon monoxide and silicon dioxide but also a silicon oxide represented by a composition formula SiOx (where 0 <x ≦ 2, preferably 0.8 ≦ x ≦ 1.5). Things are included.

In the electromagnetic wave heating packaging material, non-conductive inorganic compounds such as oxides, halides, carbides, nitrides and the like can be used. Preferred non-conductive inorganics include oxides, such as silicon oxide.

The thickness of the inorganic thin film layer is usually from 100 to 5
000 Å (0.01-0.5 μm), preferably 200-3000 Å (0.02
To 0.3 μm), and more preferably in the range of about 300 to 1500 Å (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 the thickness exceeds 5000 angstroms, the barrier properties are not so much improved, and the transparency and There are problems such as impairing the appearance, which is economically disadvantageous.

The barrier composite film of the present invention comprises an anchor
-It has the characteristic that the coat layer is soft. That is,
The barrier composite film of the present invention includes the barrier composite
In addition to the film, at least one of the base film layers
On the surface, a soft anchor coat layer (having an elastic modulus of 0.1 × 10
¹ ~ 1 × 10^Three N / mm^TwoThrough the anchor coat layer)
The barrier composite film with the inorganic thin film layer formed
included. A preferable elastic modulus of the anchor coat layer is 0.1.
5 × 10¹ ~ 7 × 10^Two N / mm^Two , Especially 1 × 10¹ ~ 5x
10^Two N / mm^TwoIt is about.

Furthermore, the barrier composite film of the present invention is characterized by exhibiting high adhesion and a high level of gas barrier properties even when exposed to severe conditions such as retort treatment. The barrier composite film of the present invention is a barrier composite film in which an inorganic thin film layer is formed on at least one surface of a base film layer via an anchor coat layer, the temperature being 120 ° C. and the time being 30 minutes. The peel strength of the anchor coat layer with respect to the substrate film layer after the retort treatment is 100 g / 15 mm or more (for example, 100 to 500 mm).
g / 15 mm). The peel strength of the anchor coat layer relative to the base film layer is preferably about 150 to 500 g / 15 mm, and more preferably about 200 to 400 g / 15 mm.

[0053] These barrier composite films have high gas barrier properties.
When the thickness of the coating layer composed of 30 μm, the anchor coat layer and the inorganic thin film layer is 0.1 to 0.5 μm, the oxygen gas permeability after the retort treatment at a temperature of 120 ° C. for 30 minutes is, for example, , 5cc / m ² · 24 hours or less (e.g., 0.01~3cc / m ² · 24 hr), preferably 3cc / m ² · 24 hours or less (e.g., 0.01 to 2
cc / m ² · 24 hours), more preferably ² cc / m ²
· 24 hours or less (e.g., 0.01~1cc / m ² · ²
4 hours) and the water vapor transmission rate is, for example, 10 g
/ M ² · 24 hours or less (0.01 to 10 g / m ² · 24 hours), preferably 0.1 to 5 g / m ² · 24 hours, more preferably about 0.1 to 3 g / m ² · 24 hours It is.

[Polymer Layer] In the present invention, at least one polymer layer may be formed on the inorganic thin film layer of the barrier composite film. This polymer layer can be selected according to the application of the barrier composite film, such as protection of the inorganic thin film layer, improvement of barrier properties, imparting of printability (colorability) and adhesion, and may be transparent. . Preferred polymer layers include, for example, a barrier resin layer, a heat seal layer, and the like.

The “barrier resin layer” has a thickness of 2 μm.
m, oxygen gas permeability 20 cc / m at a temperature of 25 ° C.
² · 24 hours or less, the temperature 40 ° C., to mean a layer comprising a water vapor permeability 20 g / m ² · 24 hours or less of the barrier resin at 90% relative humidity. In addition, the term “heat seal layer” means a layer that can be thermally bonded by a method such as impulse seal, high frequency bonding, or ultrasonic bonding, without being limited to thermal bonding using a heat sealer.

Examples of the barrier resin include a vinylidene chloride copolymer, an ethylene-vinyl alcohol copolymer, a polyamide polymer, a polyvinyl alcohol polymer, a polyacrylonitrile polymer, and a urethane polymer. Can be Note that, depending on the composition of the barrier resin, some resins do not exhibit the barrier properties. For example, one example is a thermoplastic polyurethane having a relatively long segment (such as a polyalkyleneoxy segment). These barrier resins can be used alone or in combination of two or more.

Preferred barrier resins include, for example, vinylidene chloride copolymers and ethylene-vinyl alcohol copolymers. The vinylidene chloride copolymer is a copolymer of vinylidene chloride and another polymerizable monomer.Examples of such a copolymerizable monomer include vinyl chloride, vinyl acetate, crotonic acid, acrylic acid, and methyl acrylate. Acrylates such as ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate (eg, C _1-8 alkyl-acrylate), acrylonitrile, methacrylonitrile, methacrylic acid And methacrylates corresponding to the above acrylates. Among these vinylidene chloride-based copolymers, vinylidene chloride-acryloniloryl copolymer, vinylidene chloride-methacrylic acid copolymer, vinylidene chloride-acrylate copolymer, vinylidene chloride-methacrylate copolymer, vinylidene chloride-vinyl acetate copolymer Polymers and the like are preferred. The vinylidene chloride content in the vinylidene chloride copolymer is usually from 85 to 99.
% By weight, preferably about 90 to 97% by weight.

As an ethylene-vinyl alcohol copolymer
Solvent-soluble or dispersible ethylene-vinyl alcohol
Preferred are polyester copolymers. Such ethylene-vinyl
In the alcohol copolymer, the ethylene content is usually 5
~ 50 mol%, preferably 10-45 mol%, more preferably
About 25 to 35 mol%, and the molecular weight (weight average
Molecular weight) is, for example, 1 × 10^Four -10 × 10^Four , Preferred
2x10^Four ~ 7 × 10^Four , Preferably 4 × 10^Four ~ 5
× 10^Four It is about. Degree of saponification is 99.5% or more
Is preferred. Such solvent-soluble ethylene-vinyl
Alcohol copolymers are made of water or a mixture of water and alcohol.
Soluble or dispersible in solvent, forming thin film by coating
it can.

The barrier resin layer is formed of the above-mentioned barrier resin (preferably vinylidene chloride-based resin) in accordance with desired barrier properties (barrier properties against odor components such as oxygen, water vapor, carbon dioxide, gas of organic solvent, limonene and the like). (Copolymer and ethylene-vinyl alcohol copolymer), or a plurality of resins. Further, the barrier resin layer may be composed of a plurality of layers containing a barrier resin. For example, the barrier resin layer is a layer containing a vinylidene chloride-based copolymer,
It may be composed of a plurality of layers including an ethylene-vinyl alcohol copolymer-containing layer. The content of the barrier resin in the barrier resin layer is 50% by weight or more, preferably 75 to 100% by weight, more preferably 90 to 10% by weight.
It is about 0% by weight.

The barrier resin layer is made of another polymer,
For example, olefin polymers such as ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer;
Acrylic polymer; Styrene polymer; Polyester; Polyacetal; Polyvinyl acetate; Polyvinyl chloride; Vinyl chloride-vinyl acetate copolymer; Polyamide; Urethane polymer; Acrylonitrile polymer; Polycarbonate; Chlorinated polyolefin; And the like.

The barrier resin layer may contain the above-mentioned additives as required.

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

The thickness ratio between the inorganic thin film layer and the barrier resin layer can be appropriately set, but the thickness ratio affects the gas barrier properties. In order to obtain high barrier properties and resistance, the ratio T / t of the thickness T (μm) of the barrier resin layer to the thickness t (μm) of the inorganic thin film layer is, for example, 0.1 to 1500, preferably. Is 0.5 to 500
(For example, about 0.5 to 60, preferably about 1 to 200), more preferably about 1 to 100, and 2 to 5
It is often about 0 (for example, about 5 to 50). When the thickness ratio is out of the above range, it is difficult to provide a high barrier property. When the thickness ratio is less than 0.1, defects are likely to occur in the inorganic thin film layer due to external force. It is not economical because its properties are not improved.

When a bag is formed using the barrier composite film of the present invention, the inorganic thin film layer or the barrier resin layer may be covered with a heat seal layer in order to easily form the bag. When the inorganic thin film layer and the barrier resin 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 such as an olefin polymer, a vinyl acetate-vinyl chloride copolymer, a polyester,
Examples include polyamide and rubber-based polymers. These heat bonding polymers can be used alone or in combination of two or more.

Preferred examples of the heat-bondable olefin-based polymer include polyethylene (such as low-density polyethylene and linear low-density polyethylene), and ethylene-based copolymers (ethylene-butene-1 copolymer, ethylene- (4- Methylpentene-1) copolymer, ethylene-hexene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer), ionomer ,polypropylene,
Propylene-based copolymers (propylene-butene-1 copolymer, ethylene-propylene copolymer, ethylene-propylene-butene-1 copolymer, ethylene-propylene-diene copolymer, etc.), maleic anhydride-modified polyethylene, Modified polyolefins such as maleic anhydride-modified polypropylene are exemplified. Preferred olefin-based polymers include polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, amorphous polyolefin (eg, amorphous polypropylene and the like), ethylene-propylene copolymer and the like.
When the heat-sealing layer is formed by lamination, preferable heat-bondable films include a non-stretched polypropylene film and a non-stretched ethylene-propylene copolymer film.

The heat bonding polyester includes an aliphatic polyester containing aliphatic diol and aliphatic dicarboxylic acid as constituents. Examples of the heat-bondable polyamide include nylon 11, nylon 12, nylon 6/12, and the like. The rubber-based polymer includes, for example, butyl rubber, isobutylene rubber, chloroprene rubber, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-acrylonitrile-butadiene copolymer, and the like.

The thickness of the heat seal layer can be appropriately selected, for example, in the range of about 3 to 100 μm depending on the use of the packaging material. １００100 μm, preferably about 30-80 μm.

The heat seal layer may be formed on a predetermined portion of the surface of the inorganic thin film layer or the barrier resin layer, for example, on a portion to be subjected to heat sealing, and may be either a part coat or a full coat. Is often formed on the entire surface of the inorganic thin film layer or the barrier resin layer. Further, as described above, the heat seal layer may be formed on the heat seal portion on the other surface of the base film layer or on the entire surface.

[0070] The heat seal layer may contain the above additives as necessary.

As the polymer layer, a resin layer of a polyester resin such as a vinyl chloride resin (polyvinyl chloride and a copolymer thereof) and a polyalkylene terephthalate (polyethylene terephthalate) may be formed.

[Production Method of Barrier Composite Film] The barrier composite film of the present invention can be produced by sequentially covering at least one surface of the base film layer with the anchor coat layer and the inorganic thin film layer. .

Another barrier composite film of the present invention can be obtained by further forming a barrier resin layer and / or a heat seal layer on the surface of the inorganic thin film layer or the other surface of the base film layer. it can. More specifically,
(I) a method of sequentially covering at least one surface of the base film layer with the anchor coat layer, the inorganic thin film layer, and the barrier resin layer or the heat sealing layer; and (ii) at least one of the base film layers. In which the surface of the base material layer is coated with the anchor coat layer, the inorganic thin film layer, the barrier resin layer, and the heat seal layer in order, and (iii) at least one surface of the base film layer is coated with the anchor coat layer. ,
Obtained by a method of sequentially covering with an inorganic thin film layer and, if necessary, a barrier resin layer and / or a heat sealing layer, and covering the other surface of the base film layer with the barrier resin layer and / or the heat sealing layer. be able to.

The method for forming the anchor coat layer is not particularly limited, and the coating agent containing the components (A) to (C) of the anchor coat agent and a solvent is roll-coated,
The coating can be carried out by applying by a conventional coating method such as a gravure coating method, a reverse coating method, a spray coating method and the like, followed by drying. The coating agent may be a solution or a dispersion. Examples of the solvent include hydrocarbons such as hexane, cyclohexane, benzene, and toluene, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, and mixed solvents thereof. it can.

The anchor coat layer is non-adhesive and has high blocking resistance, unlike a two-component cured adhesive composed of a polyisocyanate compound and a polyol. Therefore, even if the anchor coat layer is formed by coating, winding and rewinding of the film can be performed smoothly, and productivity of the barrier composite film can be improved.

The inorganic thin film layer is formed by a conventional method, for example,
Physical methods (vacuum deposition, reactive deposition, sputtering
Method, reactive sputtering method, ion plating
Method, reactive ion plating method, etc.), chemical method
(CVD, plasma CVD, laser CVD, etc.
The surface of the anchor coat layer with the inorganic material
It can be formed by coating. Do not deposit inorganic thin film layers
It is often formed by any physical method. Vacuum evaporation method
The thin film is formed by using a roll-shaped anchor
-While feeding the base film layer having the coat layer,
^-3-10^-6 Winding vacuum evaporator reduced to about Torr
While passing through the inside, the electron beam, high-frequency induction heating,
Inorganic compounds are heated and evaporated by an anti-heating method, etc.
It can be deposited continuously.

The polymer layer can be formed by a conventional method, for example, coating or laminating. The barrier resin layer can be formed by applying a coating solution containing a barrier resin to the surface of the inorganic thin film layer. The coating solution can be prepared by selecting an appropriate solvent according to the type of the barrier resin, and may be in the form of either a solution or a dispersion.

For example, the solvent of the solution coating solution containing the vinylidene chloride-based copolymer can be appropriately selected according to the type of the vinylidene chloride-based copolymer. For example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone;
Ethers such as dioxane, diethyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; amides such as dimethylformamide and a mixture thereof. Also, the dispersion is usually O / W
It is commercially available in the form of a type emulsion.

The coating solution 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 above-mentioned coating liquid may contain the above-mentioned various additives, and in order to enhance the coating property, for example, an antifoaming agent,
Conventional additives such as viscosity modifiers may be included.

The coating method is not particularly limited, and a conventional method such as an air knife coating method, a roll coating method,
A gravure coating method, a blade coating method, a dip coating method, a spraying method and the like can be employed. After the application of the coating liquid, the barrier resin layer can be formed, for example, by drying at a temperature of about 50 to 150 ° C.

The surface of the barrier resin 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 the heat seal layer. An adhesive layer or a protective layer may be formed partially or entirely without being applied.

The heat seal layer can be formed by a conventional method, for example, a dry laminating method, an extruding laminating method, a coating method, etc., depending on the kind of the heat-bondable polymer.

The barrier composite film of the present invention may include various coating layers and laminate layers such as a lubricating 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 made of a film or the like may be formed.

The barrier composite film of the present invention has greatly improved not only the adhesion of the inorganic thin film layer to the base film layer but also the barrier properties, and can be used even under severe conditions such as retort treatment and microwave heating. It shows high barrier properties as described above. In addition, the transparency is high, and the contents can be easily visually recognized. Therefore, the packaging material is suitably used as various packaging materials such as foods for microwave ovens, retort foods, frozen foods, microwave sterilization, flavor barriers, pharmaceuticals, precision electronic components, and balloon-making materials such as balloons and balloons. Can be used. In addition, when packaging foods and the like, the contents can be stored for a long period of time while suppressing deterioration and deterioration due to high adhesion and high barrier properties. in this way,
The present invention also discloses the use of the barrier composite film for packaging various contents such as the foods, pharmaceuticals, and electronic components.

The form of the package using the film of the present invention is not particularly limited. For example, it can be used as a packaging bag for a solid material or a packaging bag for a liquid material. The packaging bag containing these foods can be subjected to retort treatment or microwave heating as it is.

The packaging form of the packaging material of the present invention includes containers such as bags, cups, tubes, standing bags and trays, lids, and paper packs such as sake, soy sauce, mirin, oil, milk and juice. Materials are exemplified.

[0088]

According to the barrier composite film of the present invention, since a specific anchor coat layer is interposed between the base film layer and the inorganic thin film layer, the adhesion between the base film layer and the inorganic thin film layer and the barrier property are improved. Performance can be greatly improved. In addition, even when exposed to severe conditions such as retort treatment and microwave oven heating, it exhibits high barrier properties over a long period of time while maintaining high adhesion between the base film layer and the inorganic thin film layer even when exposed to severe conditions such as retort processing and microwave oven heating. it can. Furthermore, it has high barrier properties and high transparency. Therefore, it has high transparency and visibility of the contents, and is useful for long-term storage of contents such as foods, pharmaceuticals, and precision electronic components.

Further, the resin component constituting the anchor coat layer is substantially non-reactive with the polyisocyanate compound, and the anchor coat layer is non-adhesive and does not exhibit blocking property. Therefore, the anchor coating agent can be used repeatedly and effectively, and the film can be smoothly wound and unwound, and the productivity of the barrier composite film can be increased.

[0090]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Examples 1 to 10 and Comparative Example 1 Biaxially stretched polyethylene terephthalate film having a thickness of 12 μm
An anchor coat having the composition shown in Table 1 on one side of the film
After applying the agent with a thickness of 0.3 μm after drying, and drying,
5 × 10 with iO as evaporation source^Three Under Torr vacuum,
500 angstrom thick silicon by vacuum evaporation
The oxide deposited layer is formed as an inorganic thin film layer,
A composite film was obtained. In addition, the following anchor coating agents
The components were used. The proportion of the anchor coating agent component in Table 1 is
All of the figures are in terms of solid content. (A1) Ether type polyester: Fuji Photo Film
Stix SOC-30-M, Etch
Renterephthalate-triethylene glycol copolymer
Body, solid content 30% by weight, glass transition temperature 22 ° C (B1) Polyisocyanate compound: Nippon Polyurethane
Industrial Co., Ltd., Coronate L, Tolylene diisocyanate
To-trimethylolpropane adduct, solid content 75 weight
%, Isocyanate content 12% (C) Saturated polyester resin: manufactured by Toyobo Co., Ltd.
Ron 30SS, terephthalic acid and ethylene glycol
Polyester resin as the main component, number average molecular weight 22,0
00, glass transition temperature 7 ° C, hydroxyl value 4.8mgKOH
/ G (B2) polyisocyanate compound: Nippon Polyurethane
Industrial Co., Ltd., Coronate HL, hexamethylene diiso
Cyanate-trimethylolpropane adduct, solid
(B3) Polyisocyanate compound: Huls AG
Manufactured by Vestanat T1890L, isophorone diisocyanate
Nitrate trimer, solid content 70% by weight, contains isocyanate
12%

Comparative Examples 2 to 7 Barrier composite films were produced in the same manner as in Example 6, except that the following two-component curable polyurethane adhesive was used instead of the anchor coating agent of Examples 1-8. In Comparative Example 2, the two-component curable polyurethane adhesive was applied in a thickness of 0.4 μm after drying. Comparative Example 2: Two-part curable polyurethane adhesive (AC1) Polyether polyol (manufactured by Toyo Morton Co., Ltd., Adcoat AD76H5, hydroxyl value 38 mg KOH / g, glass transition temperature 20 ° C.) and polyisocyanate component (Toyo Morton Co., Ltd.) Comparative Example 3: Two-component curable polyurethane adhesive (AC2) polyester polyol (Adcoat AD335AE, manufactured by Toyo Morton Co., Ltd., hydroxyl value 85 mgKOH / g, manufactured by Toyo Morton Co., Ltd.)
Anchor coating agent composed of 100 parts by weight of glass transition temperature (-15 ° C.) and 5 parts by weight of polyisocyanate (CAT-10, manufactured by Toyo Morton Co., Ltd.) Comparative Example 4: Two-part curable polyurethane adhesive (AC3) Anchor coating agent composed of 100 parts by weight of the polyester polyol of Comparative Example 3 and 10 parts by weight of the polyisocyanate of Comparative Example 3 Comparative Example 5: Two-part curable polyurethane adhesive (AC4) 100 parts by weight of the polyester polyol of Comparative Example 3 Comparative Example 6: Two-part curable polyurethane adhesive (AC5) 100 parts by weight of the polyester polyol of Comparative Example 3 and 30 parts by weight of the polyisocyanate of Comparative Example 3 Comparative Example 7: Two-part curable polyurethane adhesive (A 6) An anchor coating agent composed of 100 parts by weight of the polyester polyol of Comparative Example 3 and 50 parts by weight of the polyisocyanate of Comparative Example 3 Comparative Example 8 Barrier properties in the same manner as in Example 1 without applying the anchor coating agent. A composite film was obtained.

For preparing a test sample for the barrier composite films obtained in Examples and Comparative Examples,
A heat seal layer was formed on the inorganic thin film layer by a dry lamination method. That is, a laminating adhesive (Adcoat AD-810 / CAT-RT8, two-part curable polyurethane-based adhesive manufactured by Toyo Morton Co., Ltd.) is applied on the inorganic thin film layer at a thickness of about 2 μm after drying,
Sealant (Senesi C15, manufactured by Daicel Chemical Industries, Ltd.)
3 # 40, unstretched polypropylene, thickness 40 μm) were laminated to form a heat seal layer.

Then, for each sample, 1
Before and after the retort treatment at 20 ° C for 30 minutes,
The coating strength, oxygen gas transmission rate and water vapor transmission rate are as follows.
And measured. Oxygen gas permeability: same pressure method (Measuring instrument: Morcon, O
XTRAN TWIN), 20 ° C, relative humidity 65
%. The unit is cc / m^Two ・ 24 hours
You. Water vapor transmission rate: Measuring instrument (MORCON, PERMAT)
RAN W200) at 40 ° C. and 90% relative humidity.
It was measured under the conditions. The unit is g / m^Two ・ 24 hours. Adhesion strength: Peel strength between base film layer and heat seal layer
Degree measuring instrument (ORIENTEC, RTM-100)
It was measured at a tensile speed of 300 mm / min. Also,
Anchor core 5mm wide, 10mm long, 0.5mm thick
A sample of the coating layer is prepared and a viscoelasticity measuring device
(VES-FIII, manufactured by Co., Ltd.)
(N / mm^Two ) At a temperature of 30 ° C and a frequency of 1 Hz
Was. Table 1 shows the results.

[0095]

[Table 1]Unit of elastic modulus: N / mm^Two , Unit of adhesion strength: g / 1
5mm, O_Two-TR: oxygen gas permeability (cc / m^Two ・ 2
4 hours), WV-TR: water vapor transmission rate (g / m^Two ・ 2
4 hours)

Example 11 Biaxially stretched polyethylene terephthalate film having a thickness of 12 μm
Anchor coat used in Example 6 on one side of the film
After applying the agent with a thickness of 0.3 μm after drying, and drying,
5 × 10 with iO as evaporation source^Three Under Torr vacuum,
500 angstrom thick silicon by vacuum evaporation
The oxide deposited layer was formed as an inorganic thin film layer.

Examples 12 to 15 Biaxially stretched polyethylene terephthalate film having a thickness of 12 μm
Anchor coat used in Example 6 on one side of the film
After applying the agent with a thickness of 0.3 μm after drying, and drying,
5 × 10 with iO as evaporation source^-3 Under Torr vacuum,
500 angstrom thick silicon by vacuum evaporation
The oxide deposited layer was formed as an inorganic thin film layer. Also salt
Vinylidene fluoride copolymer (manufactured by Asahi Kasei Corporation)
Name: Saran Resin F216) was converted to toluene / tetrahydroxide
Dissolved in a mixed solvent of lofran = 1/2 (weight ratio)
A coating solution having a concentration of 15% by weight was prepared. Apply this coating solution
0.5 g / m coating amount after drying on the inorganic thin film layer^Two (application
Example 1, thickness about 0.3 μm), 1.0 g / m^Two (Application example
2, thickness about 0.6μm, 2.0g / m^Two (Application example 3, thickness
About 1.2 μm), 3.0 g / m^Two (Application example 4, thickness approx.
(1.8 μm) to form a barrier resin layer. Real
About the barrier composite film obtained in Examples 11 to 15,
The oxygen gas permeability and the water vapor permeability at 120 ° C.
Measured before and after the retort treatment for 30 minutes
In addition, the results shown in Table 2 were obtained.

[0098]

[Table 2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08G 18/42 C08G 18/42 C08L 67/00 C08L 67/00 75/06 75/06

Claims (20)

[Claims] 1. A composite film having an inorganic thin film layer formed on at least one surface of a substrate film layer via an anchor coat layer, wherein the anchor coat layer comprises:
(A) an ether-type polyester, (B) a polyisocyanate compound, and (C) a glass transition temperature of -10 to 20 ° C.
And a barrier composite film comprising a saturated polyester resin substantially non-reactive with the polyisocyanate compound. 2. The barrier composite film according to claim 1, wherein (A) the ether-type polyester is a polyester-based compound containing at least an aromatic dibasic acid and glycol as monomer components. 3. The polyester (A) is a polyester compound containing at least an aromatic dibasic acid and glycol as a monomer component, wherein the glycol component is (i) ethylene glycol (ii) diethylene glycol or triethylene glycol. (Iii) The barrier composite film according to claim 1 or 2, which is a mixture of at least one glycol represented by the following general formula (I). General formula (I) 4. The barrier composite film according to claim 1, wherein the polyisocyanate compound (B) is a compound having at least two isocyanate groups in the molecule and having a molecular weight of 150 to 1,000. (C) a saturated polyester resin having a hydroxyl value of 0 to 15 mg KOH / g or an acid value of 0 to 10 mg KOH;
The barrier composite film according to claim 1, which is a non-crystalline saturated polyester / g. 6. The barrier composite film according to claim 1, wherein (C) the saturated polyester resin has a number average molecular weight of 1 × 10 ^{4 to} 5 × 10 ⁴ . 7. The composition of the anchor coat layer, wherein:
(A) For 100 parts by weight of the ether type polyester,
(B) 10 to 500 parts by weight of a polyisocyanate compound,
The barrier composite film according to claim 1, wherein (C) 1 to 50 parts by weight of a saturated polyester resin. 8. An anchor coat layer having a glass transition temperature of 15 to 60 ° C. and an acid value of 0 to 30 mg KOH / g per 100 parts by weight of a non-crystalline thermoplastic ether type polyester, and (B) 3 or more in the molecule. 25 to 400 parts by weight of a polyisocyanate compound having an isocyanate group having a molecular weight of 150 to 1000, and (C) a glass transition temperature of 0
２０20 ° C., number average molecular weight 1 × 10 ⁴ -3 × 10 ⁴ , hydroxyl value 0-10 mgKOH / g or acid value 0-10 mgKOH
The barrier composite film according to claim 1, comprising 1 to 50 parts by weight of a non-crystalline saturated polyester resin / g / g. 9. The barrier composite film according to claim 1, wherein the base film layer is made of polypropylene, polyalkylene terephthalate or polyamide. 10. The barrier composite film according to claim 1, wherein the inorganic thin film layer has transparency. 11. The inorganic thin film layer comprises a Group 2A element of the periodic table,
The barrier composite film according to claim 1, comprising at least one metal oxide selected from a transition element, a group 2B element, a group 3B element, a group 4B element, and a group 6B element. 12. The barrier composite film according to claim 1, wherein the inorganic thin film layer is composed of an oxide of a group 3B element or a group 4B element of the periodic table. 13. The barrier composite film according to claim 1, wherein the inorganic thin film layer is composed of silicon oxide. 14. The inorganic thin film layer has a thickness of 100 to 50.
The barrier composite film according to claim 1, which has a thickness of 00 Å. 15. An anchor coat layer on at least one surface of a base film layer composed of polypropylene, polyalkylene terephthalate or polyamide, and a composition formula S
a transparent non-conductive inorganic thin film layer composed of silicon oxide represented by iOx (where 0 <x ≦ 2) and having a thickness of 100 to 5000 angstroms is formed in this order; Anchor coat layer,
(A) a substantially non-reactive ether type polyester having a glass transition temperature of 15 to 60 ° C .;
A low molecular weight polyisocyanate compound having the above isocyanate group, and (C) a glass transition temperature of 0 to 15 ° C,
2. The barrier composite film according to claim 1, comprising a substantially non-reactive saturated polyester resin having a number average molecular weight of 1 × 10 ^{4 to} 5 × 10 ⁴ . 16. A barrier composite film having an inorganic thin film layer formed on at least one surface of a substrate film layer via an anchor coat layer, wherein the elastic modulus of the anchor coat layer is 0.1 × A barrier composite film having a density of 10 ¹ to 1 × 10 ³ N / mm ² . 17. A barrier composite film in which an inorganic thin film layer is formed on at least one surface of a substrate film layer via an anchor coat layer, wherein the barrier composite film has been subjected to a retort treatment at a temperature of 120 ° C. for 30 minutes. A barrier composite film having a peel strength of the anchor coat layer with respect to the base film layer of 100 g / 15 mm or more. 18. The base film layer has a thickness of 10 to 30 μm.
m, when the thickness of the coating layer composed of the anchor coat layer and the inorganic thin film layer is 0.1 to 0.5 μm, the temperature is 12
Oxygen gas permeability after retort treatment at 0 ° C. for 30 minutes is 5 cc / m ² · 24 hours or less, and water vapor permeability is 10
A barrier composite film according to claim 17, wherein less g / m ² · 24 hours. 19. A substantially non-reactive saturated polyester resin having an anchor coat layer having (A) an ether type polyester, (B) a polyisocyanate compound, and (C) a glass transition temperature of -10 ° C. to 20 ° C. The barrier composite film according to claim 17, wherein the composite film is formed of a resin composition having an elastic modulus of 1 × 10 ^{1 to} 5 × 10 ² N / mm ² . 20. At least one surface of the substrate film layer is provided with (A) an ether-type polyester, (B) a polyisocyanate compound, and (C) a glass transition temperature of −10 ° C. or more.
After forming an anchor coat layer having a saturated polyester resin having a temperature of 20 ° C. and substantially non-reactive with the polyisocyanate compound, a barrier composite having an inorganic thin film layer formed on the anchor coat layer Film production method.