JP5245507B2 - Gas barrier laminated film - Google Patents

Description

  The present invention relates to a gas barrier laminate film, and more particularly to a gas barrier laminate film in which heat resistance and adhesion of a barrier coat layer are improved, deterioration of oxygen permeability after retort treatment is suppressed, and occurrence of delamination and the like is suppressed.

Regarding a method for suppressing barrier deterioration after boiling and retorting, Patent Document 1, a gas barrier vapor deposition layer mainly containing an inorganic compound on a substrate,
One of the silicon compound represented by the general formula Si (OR1) 4 (1) and a hydrolyzate thereof provided on the gas barrier vapor deposition layer, the general formula (R2Si (OR3) 3) n (2) One of the silicon compound represented by the formula (1) and hydrolyzate thereof [wherein R1, R3 are CH3, C2H5, or C2H4OCH3, R2 represents an organic functional group] And a gas barrier coating layer obtained by applying and drying a coating solution containing a water-soluble polymer having a hydroxyl group, and a gas barrier laminate film has been proposed.
However, the addition of the general formula (R2Si (OR3) 3) n has been raised as an effect of improving the water resistance of the film raised here, but this material is a so-called silane coupling when n = 1. It is classified as an agent, and it is expensive and has a drawback of lacking stability of the liquid because it involves a hydrolysis reaction when used in an aqueous system.

Regarding the invention using a water-based curing agent, in Patent Document 2, by using an oxazoline group-containing polymer, it is usually used as a crosslinking agent for a carboxyl group-containing polymer and does not react with the hydroxyl group of polyvinyl alcohol. Nevertheless, the knowledge that the boiling resistance of the PVA film is remarkably improved has been described, suggesting the possibility that PVA itself takes a cross-linked structure with an oxazoline group.
However, the boiling resistance required for the present invention is very high, and the boiling resistance expressed by the reaction between PVA and the oxazoline group was not sufficient.

In Patent Document 3 and Patent Document 4, a compound that promotes hydrolysis / condensation polymerization of an organosilicate, a water-soluble and / or water-dispersible curing agent having a reactive functional group and a hydrophilic group in the molecule, and an alkoxysilane compound. There has been proposed a composition for imparting stain resistance to paints containing.
The action of the water-soluble and / or water-dispersible curing agent having a reactive functional group and a hydrophilic group described here is a micelle-like structure and a structure in which a large amount of organosilicate is present in the hydrophobic portion. This contributes to the uniform dispersion in the water-based paint, and is not intended to reinforce the coating film.
WO2004 / 048081 JP 2000-109630 A JP 2005-15676 A JP 2006-45483 A

  The problem to be solved by the present invention is to provide a laminated film excellent in gas barrier properties in which deterioration of oxygen permeability after retort treatment is suppressed and generation of delamination and the like is suppressed.

  As a result of intensive studies to solve the above problems, the present inventor has added a water-soluble or water-dispersible curing agent having a reactive functional group to an existing gas barrier composition, whereby the heat resistance of the barrier coat layer, We have developed a gas barrier laminate film that improves adhesion, suppresses the deterioration of oxygen permeability after retorting, and suppresses the occurrence of delamination.

  That is, the present invention provides an inorganic oxide vapor deposition layer on at least one surface of a substrate, and further, on the inorganic oxide vapor deposition layer, one or more alkoxides, a water-soluble polymer, The present invention relates to a gas barrier laminate film provided with a barrier coat layer obtained by hydrolysis and polycondensation of a gas barrier composition containing a water-dispersible curing agent by a sol-gel method.

The gas barrier laminate film according to the present application contains a water-soluble or water-dispersible curing agent in the gas barrier composition in order to improve barrier deterioration after boil-retort and adhesion problems. As a result, the water resistance and boiling resistance of the barrier coat layer are improved, and a printing layer, an adhesive layer and an anchor coat are further laminated on the barrier coat layer as well as the deposited film by the effect of introducing an organic functional group into the coating film. Demonstrate the effect of improving adhesion to the layer.
These synergistic effects make it possible to provide a gas barrier laminate film with almost no deterioration in gas barrier properties after hydrothermal treatment.

Hereinafter, the gas barrier laminate film of the present invention will be specifically described.
1. Structure of Gas Barrier Laminate Film of the Present Invention The gas barrier laminate film according to the present application is provided with an inorganic oxide vapor deposition layer on at least one surface of a base film, and further, a barrier coat layer is formed on the inorganic oxide vapor deposition layer. The three layers provided have a basic structure (FIG. 1). In the case where the inorganic oxide vapor deposition layer is deposited using a chemical vapor deposition method, vapor deposition layers having different film qualities can be laminated in multiple layers.
The gas barrier laminate film according to the present application can be directly printed.
In the gas barrier laminate film according to the present application, a heat seal layer can be laminated on the barrier coat layer with or without an adhesive layer or anchor coat layer.
When manufacturing a packaging bag using the gas barrier laminated film according to the present application, it is preferable to create a heat seal layer.

In addition to the dry laminating method in which the heat seal layer is laminated via an adhesive layer or an anchor coat layer, there is an extrusion laminating method in which the resin of the heat seal layer is directly melt bonded.
As a layer structure of the packaging bag using the gas barrier laminate film according to the present application, a gas barrier laminate film / anchor coat layer / extruded resin (heat seal layer), a gas barrier laminate film / anchor coat layer / extruded resin / PEF ( Heat seal layer).
Furthermore, the layer structure of the packaging material for retort using the gas barrier laminate film according to the present application has a gas barrier laminate film / adhesive layer (DL) / nylon substrate (in order to give piercing property and bag breaking strength) ONY) / adhesive layer / CPP (heat seal layer, unstretched polypropylene film) or the like, a nylon base material may be laminated on the intermediate layer. When a nylon base material is laminated, it is preferable to further laminate a heat seal layer.
When a nylon substrate is used as the base film of the gas barrier laminate film, the layer structure of the packaging material for retort using the gas barrier laminate film according to the present application is polyethylene terephthalate (PET) / adhesive layer / gas barrier. The gas barrier laminate film according to the present application can be laminated as an intermediate layer, such as an adhesive laminate film / adhesive layer / CPP.

2. Base Film In the present invention, the base film is preferably provided with an inorganic oxide vapor-deposited layer, and therefore has excellent properties in terms of mechanical, physical, chemical, etc. In particular, a resin that is strong and strong, has heat resistance, can withstand the conditions for forming an inorganic oxide vapor-deposited layer, and can be maintained well without impairing the properties of the inorganic oxide vapor-deposited layer Any film or sheet can be used.

Specifically, in the present invention, as the base film, for example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile- Butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, polyamide resin such as various nylons, Polyimide resin, polyamideimide resin, polyarylphthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cell Over scan based resin, a film or sheet of various resins other like can be used.
In the present invention, it is particularly preferable to use a film or sheet of polypropylene resin, polyester resin, or polyamide resin.

In the present invention, as the above-mentioned various resin films or sheets, for example, one or more of the above-mentioned various resins are used, extrusion method, cast molding method, T-die method, cutting method, inflation method, Using other film forming methods, a method of forming the above-mentioned various resins alone, or a method of forming a multilayer coextrusion film using two or more kinds of resins, Using two or more kinds of resins, by mixing and forming a film before film formation, etc., various resin films or sheets are manufactured, and if necessary, for example, a tenter method, or Various resin films or sheets that are stretched uniaxially or biaxially using a tubular method or the like can be used.
In the present invention, the film thickness of various resin films or sheets is preferably about 6 to 100 μm, more preferably about 9 to 50 μm.

It should be noted that one or more of the above-mentioned various resins are used, and when forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness Various plastic compounding agents and additives can be added for the purpose of improving, modifying, releasability, flame retardancy, antifungal properties, electrical properties, strength, etc. From a very small amount to several tens of percent, it can be arbitrarily added depending on the purpose.
In the above, general additives include, for example, colorants such as lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, antiblocking agents, dyes, pigments, and the like. Etc. can be arbitrarily used, and further, a modifying resin or the like can also be used.

In addition, in the present invention, the surface of the above-described various resin films or sheets may have a desired surface in advance, if necessary, in order to improve close adhesion with an inorganic oxide vapor-deposited film described later. A treatment layer can be provided.
In the present invention, examples of the surface treatment layer include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, or the like can be formed and provided.
The above-mentioned surface pretreatment is carried out as a method for improving the tight adhesion between various resin films or sheets and an inorganic oxide vapor deposition film, which will be described later. In addition, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer, or a vapor deposition anchor coat agent layer is arbitrarily provided on the surface of various resin films or sheets. It can also be formed into a surface treatment layer.
Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene, and polypropylene. A resin composition comprising a main component of a vehicle such as a polyolefin resin or a copolymer or modified resin thereof, a cellulose resin, or the like can be used.

3. Inorganic oxide vapor deposition layer In this invention, as an inorganic oxide vapor deposition layer, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na ), Boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), and other deposited layers.
Preferable examples include a deposited layer made of a metal oxide of silicon (Si) or aluminum (Al).
The metal oxide deposition layer is also a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc., and its notation is, for example, SiO _x , AlO _x , MgO _x, etc. Thus, MO _x (wherein, M represents a metal element, and the value of X varies depending on the metal element).

In addition, as a range of the value of x described above, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1.5, titanium (Ti) is 0 to 2, Lead (Pb) can take values in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5.
In the above, when x = 0, it is a perfect metal and cannot be used because it is not transparent. Further, the upper limit of the range of x is a value when completely oxidized.
Preferably, silicon (Si) having a value in the range of 1.0 to 2.0 and aluminum (Al) in the range of 0.5 to 1.5 can be used.

The layer thickness of the inorganic oxide layer varies depending on the metal used or the type of metal oxide, but can be arbitrarily selected within the range of, for example, 5 to 1000 mm, preferably 50 to 500 mm.
Moreover, the metal or metal oxide to be used as an inorganic oxide layer can be used by 1 type, or 2 or more types of mixtures, and can comprise the inorganic oxide layer mixed with the dissimilar material.
Further, when the inorganic oxide is silicon oxide, it may be a carbon-containing silicon oxide represented by SiOxCy [wherein x is in the range of 1.5 to 2.2, and y is Preferably it is in the range of 0.15 to 0.80, and x is in the range of 1.7 to 2.1 and y is in the range of 0.39 to 0.47. preferable].

4). The vapor deposition method of an inorganic oxide vapor deposition layer The vapor deposition of an inorganic oxide layer can be performed by a chemical vapor deposition method or a physical vapor deposition method, or using these together. When the chemical vapor deposition method is used, vapor deposition layers having different film qualities can be stacked in multiple layers.
(1) Chemical vapor deposition (Chemical Vapor Deposition method, CVD method)
Examples of the chemical vapor deposition method used in the present invention include a plasma CVD method, a thermal chemical vapor deposition method, and a photochemical vapor deposition method.
Specifically, a plasma chemical vapor deposition method (Plasma Chemical Vapor Deposition method), which is one of the chemical vapor deposition methods that can be used in the present invention, is applied to a substrate film, an inorganic oxide layer, or a gas barrier layer. On the surface of the vapor deposition surface, a monomer gas for vapor deposition of inorganic oxide is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen gas or the like is used as an oxygen supply gas. A vapor deposition layer made of an inorganic oxide is formed using a low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like.
In the above, as a low temperature plasma generator, for example, a generator such as high frequency plasma, pulse wave plasma, microwave plasma or the like is used. In the present invention, in order to obtain a highly active stable plasma, a high frequency plasma method is used. It is desirable to use a generator.

An example of the formation method of the inorganic oxide vapor deposition layer by the low temperature plasma chemical vapor deposition method in the present invention will be described. FIG. 2 is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus used in the low temperature plasma chemical vapor deposition method.
In the present invention, as shown in FIG. 2, the film to be deposited 11 is fed out from the unwinding roll 23 disposed in the vacuum chamber 22 of the low-temperature plasma chemical vapor deposition apparatus 21. Then, it is conveyed on the circumferential surface of the cooling / electrode drum 25 through the auxiliary roll 24 at a predetermined speed. Oxygen gas, inert gas, monomer gas for vapor deposition, and the like are supplied from the gas supply devices 26 and 27 and the raw material volatilization supply device 28, and a vacuum chamber is formed through the raw material supply nozzle 29 while adjusting a mixed gas composition for vapor deposition. The mixed gas composition for vapor deposition is introduced into 22, and plasma is generated by the glow discharge plasma 30 on the vapor deposition film 11 conveyed on the cooling / electrode drum 25 peripheral surface. To form an inorganic oxide vapor deposition layer. At that time, the cooling / electrode drum 25 is applied with a predetermined power from a power source 31 disposed outside the vacuum chamber 22, and a magnet 32 is disposed in the vicinity of the cooling / electrode drum 25. The generation of plasma is promoted. Next, the film to be deposited 11 is wound around a winding roll 34 via an auxiliary roll 33 after forming an inorganic oxide vapor deposition layer. In the figure, 35 represents a vacuum pump.
In the low temperature plasma chemical vapor deposition apparatus described above, the inorganic oxide vapor deposition layer is formed in a thin film shape on the film to be vapor deposited using plasmaized source gas, so that it is dense and has few gaps. It becomes a continuous layer rich in flexibility. Accordingly, the barrier property is much higher than that of an inorganic oxide vapor deposition layer formed by a conventional vacuum vapor deposition method or the like, and a sufficient barrier property can be obtained with a thin film thickness.

(2) Physical vapor deposition method (Physical Vapor Deposition method, PVD method)
The physical vapor deposition method includes, for example, a vacuum deposition method, a sputtering method, an ion plating method, an ion cluster beam method, and the like.
An example of the physical vapor deposition method that can be used in the present invention will be described more specifically. FIG. 3 is a schematic configuration diagram of a take-up vacuum deposition apparatus showing an example of the inorganic oxide deposition method in the present invention.
As shown in FIG. 3, in the vacuum chamber 42 of the take-up vacuum deposition apparatus 41, the film to be deposited 11 is fed out from the unwinding roll 43, and the film to be deposited 11 is passed through the guide rolls 44 and 45. To the cooled coating drum 46. Next, an evaporation source 48 heated by a crucible 47 is deposited on the film 11 to be guided guided on the cooled coating drum 46 while supplying oxygen gas or the like from an oxygen gas outlet 49 if necessary. Then, an inorganic oxide vapor deposition layer is formed through the mask 50. In the electron beam vacuum deposition method, the deposition source 48 is overheated by electron beam irradiation. Next, the film 11 to be deposited on which the inorganic oxide vapor deposition layer is laminated is wound around the take-up roll 53 via the guide rolls 51 and 52.

5. Gas barrier composition The barrier coat layer of the present invention comprises a gas barrier composition containing one or more alkoxides, a water-soluble polymer, and a water-soluble or water-dispersible curing agent, hydrolyzed and polymerized by a sol-gel method. It can be formed by condensation. A silane coupling agent may be added to the gas barrier composition.
(1) Water-soluble or water-dispersible curing agent The present invention provides a polymer and an alkoxide by adding a water-soluble or water-dispersible curing agent having a reactive organic functional group to an existing gas barrier composition. The water resistance and boiling resistance of the barrier coat layer can be improved by further reacting with the curing agent in addition to the crosslinking reaction.
Furthermore, by introducing the organic functional group into the barrier coat layer, the effect of improving the adhesion to the printed layer, the adhesive layer, the anchor coat layer, etc. as well as the inorganic oxide vapor deposition layer as well as the barrier coat layer is exhibited. .
In addition, these synergistic effects can make it possible to provide a gas barrier laminated film with almost no deterioration in gas barrier properties after hydrothermal treatment.

The water-soluble or water-dispersible curing agent used in the gas barrier composition according to the present application has a reactive functional group, and the reactive functional group is an isocyanate group, an epoxy group, a vinyl group, a carbodiimide group, an oxazoline group, and A curing agent that is one or more selected from the group consisting of hydrazide groups. For example, there are isocyanate crosslinking agents, epoxy crosslinking agents, vinyl crosslinking agents, carbodiimide crosslinking agents, oxazoline group crosslinking agents, and hydrazide group crosslinking agents.
Specifically, Aquanate 100 manufactured by Nippon Polyurethane Industry Co., Ltd., Epiol E-100 manufactured by Nippon Oil & Fats Co., Ltd., Bremer PP-1000 manufactured by the same company, Carbodilite V-02 manufactured by Nippon Spinning Co., Ltd., and Nippon Shokubai Co., Ltd. Epochros WS-700 manufactured by the company can be used.
The addition amount of the water-soluble or water-dispersible curing agent is 0.1 to 100 wt%, preferably 1 to 30 wt%, based on the total weight of the solid content of the water-soluble polymer.

(2) Alkoxide In the present invention, as the alkoxide, the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and M is a metal atom) N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the number of atoms of M). One or more alkoxides represented by
In the present invention, as the metal atom M, silicon, zirconium, titanium, aluminum or the like can be used as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m . Moreover, in this invention, the alkoxide of a single or 2 or more types of different metal atoms can be mixed and used in the same solution.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples include -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and other alkyl groups.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group and the like.
In the present invention, these alkyl groups may be the same or different in the same molecule.

(3) Water-soluble polymer As the water-soluble polymer, either or both of a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer can be preferably used.
Moreover, in this invention, it is preferable that content of a polyvinyl alcohol-type resin and / or an ethylene vinyl alcohol copolymer is the range of 5-500 weight part with respect to 100 weight part of total amounts of said alkoxide. In the above, if it exceeds 500 parts by weight, the brittleness of the barrier coating is increased, and the weather resistance and the like are also deteriorated.
In the present invention, as the polyvinyl alcohol-based resin, generally obtained by saponifying polyvinyl acetate can be used. Specific examples of the polyvinyl alcohol resin include PVA110 manufactured by Kuraray Co., Ltd. (degree of saponification = 98 to 99%, degree of polymerization = 1,100), PVA117 (degree of saponification = 98 to 99%, degree of polymerization = 1,700). ), PVA124 (degree of saponification = 98-99%, degree of polymerization = 2,400), PVA135H (degree of saponification = 99.7% or more, degree of polymerization = 3,500), RS-made by the company's RS polymer 110 (degree of saponification = 99%, degree of polymerization = 1,000), Kuraray Poval LM-20SO manufactured by the same company (degree of saponification = 40%, degree of polymerization = 2,000), GOHSENOL manufactured by Nippon Synthetic Chemical Industry Co., Ltd. NM-14 (degree of saponification = 99%, degree of polymerization = 1,400), GOHSENOL NH-18 (degree of saponification = 98-99%, degree of polymerization = 1,700) and the like can be used.

  In the present invention, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer should be used. Can do. Such saponification products include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which only several mol% of acetic acid groups remain or no acetic acid groups remain. The Although not particularly limited, it is preferable to use a saponification degree of 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferably used. Specific examples of the ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%). ) Etc. can be used.

(4) Silane Coupling Agent In the present invention, a silane coupling agent can be added to the gas barrier composition to be prepared.
In the present invention, the silane coupling agent comprises an organosilicon compound having both a hydrolyzable group that reacts with an inorganic substance and an organic functional group that reacts with an organic substance in one molecule. Examples of the hydrolyzing group that reacts with an inorganic substance include an alkoxy group such as a methoxy group and an ethoxy group, an acetoxy group, and a chloro group. Moreover, as an organic functional group which reacts with organic substance, the functional group which reacts with the hydroxyl group in a hydroxyl-containing acrylic resin or the isocyanate group of an isocyanate compound is preferable, for example, an isocyanate group, an amino group, an epoxy group, and a mercapto group are mentioned. Moreover, a vinyl group, a methacryloxy group, etc. may be sufficient.
The organosilicon compound may have an alkyl group or a phenyl group that does not react with either an inorganic substance or an organic substance. Further, it can be mixed with a silicon compound having no organic functional group, for example, a compound such as an alkoxysilane having only a hydrolyzable group. In the present invention, the silane coupling agent may be one type or a mixture of two or more types.

In the silane coupling agent as described above, the hydrolyzable group is hydrolyzed to form a silanol group (SiOH), which is an active metal on the surface of the inorganic oxide deposited layer or the metal constituting the inorganic oxide deposited layer. Interacts with a functional group such as a hydroxyl group, for example, causes a reaction such as a dehydration condensation reaction, and a silane coupling agent is modified with a covalent bond or the like on the surface of the deposited inorganic oxide film. A strong bond is formed on the surface of the vapor deposition film of the inorganic oxide of the group itself by adsorption or hydrogen bonding.
On the other hand, the organic functional group at the other end of the organosilicon reacts with the material constituting the deposition surface of the base film or barrier coat layer to form a strong bond, and firmly adheres to the laminate. Increase strength. Thus, in the present invention, it is possible to form a strong laminated structure having a high laminate strength.

  Examples of the silane coupling agent used in the present invention include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, amino group-containing silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane, Contains epoxy groups such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Silane coupling agent, 3-mercap Examples include mercapto group-containing silane coupling agents such as topropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, and isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane. It is done.

6). Preparation of gas barrier composition and formation method of barrier coat layer (1) Preparation of gas barrier composition Water-soluble or water-dispersible curing agent, sol-gel method catalyst, acid, water and organic solvent , And if necessary, a gas barrier composition (coating solution) is prepared by mixing with a silane coupling agent or the like.
In the gas barrier composition (coating liquid), a polycondensation reaction and a crosslinking reaction with a reactive functional group of a water-soluble or water-dispersible curing agent gradually proceed.
In addition, as a sol-gel method catalyst used in the preparation of a gas barrier composition, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent, such as N, N-dimethylbenzylamine, should be used. As the acid, for example, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and tartaric acid, and the like can be used. Furthermore, as an organic solvent, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, etc. can be used, for example.

  Furthermore, regarding the gas barrier composition, the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably in a state of being dissolved in a coating solution containing the alkoxide, the silane coupling agent, or the like. The kind of the organic solvent is appropriately selected. In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, one commercially available as Soarnol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) can be used.

(2) Formation method of barrier coat layer When the above gas barrier composition is applied on the inorganic oxide deposition layer and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed. A transparent gas barrier coating layer is formed.
Furthermore, since the hydroxyl group generated by hydrolysis and the silanol group derived from the silane coupling agent are bonded to the hydroxyl group on the surface of the inorganic oxide deposition layer, the adhesion and adhesion between the inorganic oxide deposition layer and the gas barrier coating layer Good properties and the like.
By being formed as described above, the gas barrier coating layer of the present invention includes a linear polymer having crystallinity, and has a structure in which a large number of minute crystals are embedded in an amorphous portion. . Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the cohesive energy of the molecule is high. Good gas barrier properties.

In the present invention, the inorganic oxide vapor deposition layer and the gas barrier coating layer form, for example, chemical bonds, hydrogen bonds, or coordinate bonds by hydrolysis / co-condensation, and the adhesion between these two layers is improved. In addition, the effect of better barrier properties can be exhibited by a synergistic effect.
In the present invention, the gas barrier composition may be applied by one or more times by a coating means such as a roll coat such as a gravure roll coater, a spray coat, dipping, a brush, a bar coat, or an applicator. With this coating, a barrier coat having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm can be formed. Further, by heating and drying at a temperature of 20 to 300 ° C. for 0.05 to 60 minutes in a normal environment, condensation and a crosslinking reaction by a reactive functional group of a water-soluble or water-dispersible curing agent can be performed. And the gas barrier coating layer of the present invention can be formed.

7. Anchor coat layer, adhesive layer and heat seal layer (1) Anchor coat layer The anchor coat layer is a layer formed by reaction curing of an anchor coat agent containing a hydroxyl group-containing acrylic resin, an isocyanate compound and a silane coupling agent.
Examples of the anchor coating agent include organic titanium anchor coating agents such as alkyl titanates, isocyanate anchor coating agents, polyethyleneimine anchor coating agents, polybutadiene anchor coating agents, and other various aqueous or oil-based anchor coating agents. Can be used. In the present invention, the anchor coating agent is coated by roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating method, and the solvent, diluent, etc. are dried to form the anchor coating agent layer. can do. The application amount of the anchor coating agent is preferably 0.1 to 5 g / m ² (dry state).

(2) Adhesive layer As an adhesive constituting the adhesive layer, for example, a polyvinyl acetate adhesive, a homopolymer such as ethyl butyl acrylate, 2-ethylhexyl ester, or these and methyl methacrylate, From polyacrylic acid ester adhesives composed of copolymers with acrylonitrile, styrene, etc., cyanoacrylate adhesives, copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc. Ethylene copolymer adhesives, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives made of urea resin or melamine resin, phenol resin adhesives, epoxy adhesives Adhesives, polyurethane adhesives, reactive (meth) acrylic adhesives, Chlorop Adhesives such as rubber adhesives such as ren rubber, nitrile rubber, styrene-butadiene rubber, silicone adhesives, alkali metal silicates, low melting point glass and the like, and other adhesives can be used.
The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property is any of film / sheet form, powder form, solid form, etc. Further, the bonding mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.
The above adhesive can be applied by, for example, a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or the like, and the coating amount is 0.1 to 10 g / m ² (dry state). The position is desirable.

(3) Heat-seal layer In the present invention, as the heat-sealable resin constituting the heat-seal layer, resins that can be melted by heat and fused to each other can be used, specifically, low-density polyethylene. , Medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer Polymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride Modified with unsaturated carboxylic acid such as Acid-modified polyolefin resin, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin, polystyrene resin, polyacrylonitrile resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile A butadiene-styrene copolymer (ABS resin) or the like can be used.

In the present invention, the resin film or sheet as described above can be laminated with a heat seal layer by a known laminating method such as a dry laminating method or a non-solvent dry laminating method, or the above resin as a main component. The heat seal layer can be constituted by a coating film or the like made of the resin composition. The thickness is 5 to 300 μm, preferably 10 to 100 μm.
Furthermore, in the present invention, an ethylene-α / olefin copolymer polymerized using a metallocene catalyst can also be used as the heat-sealable resin as described above. Specifically, for example, a catalyst based on a combination of a metallocene complex and an alumoxane, such as a catalyst based on a combination of zirconocene dichloride and methylalumoxane, that is, an ethylene-α / olefin copolymer obtained by polymerization using a metallocene catalyst Can be used. The metallocene catalyst is also called a single site catalyst because the current catalyst is called a multi-site catalyst with heterogeneous active sites, while the active sites are uniform. For example, trade name “Kernel” manufactured by Mitsubishi Chemical Corporation, trade name “Evolue” manufactured by Mitsui Petrochemical Co., Ltd., trade name “EXACT” manufactured by EXXON CHEMICAL, USA, US An ethylene-α / olefin copolymer polymerized using a metallocene catalyst such as “Affinity” or “Engage” manufactured by Dow Chemical Co. can be used. . In the present invention, when an ethylene-α / olefin copolymer polymerized using a metallocene catalyst is used as the heat-sealable resin as described above, low-temperature heat sealing is possible when manufacturing a bag. Has the advantage of being.

Hereinafter, the present invention will be described more specifically with reference to examples.
[Example 1]
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used, and this is attached to a feed roll of a plasma chemical vapor deposition apparatus. Then, under the conditions shown below, the corona of the above biaxially stretched polyethylene terephthalate film is used. A 200 nm thick silicon oxide vapor deposition film was formed on the treated surface.
(Deposition conditions)
Deposition surface; corona-treated surface introduction gas amount; hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 3.0 (unit: slm)
Degree of vacuum in the vacuum chamber; 2-6 × 10 ⁻⁶ mBar
Degree of vacuum in the deposition chamber; 2-5 × 10 ⁻³ mBar
Cooling and electrode drum power supply: 10kW
Line speed: 100 m / min
Next, immediately after the silicon oxide vapor deposition film having a thickness of 200 mm is formed as described above, a glow discharge plasma generator is used on the silicon oxide vapor deposition film surface, and the power is 9 kw, oxygen gas (O ₂ ): argon gas. Using a mixed gas of (Ar) = 7.0: 2.5 (unit: slm), oxygen / argon mixed gas plasma treatment was performed at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 420 m / min. The plasma-treated surface was formed by improving the surface tension of the deposited silicon oxide film surface by 54 dyne / cm or more.

  (2) On the other hand, according to the composition shown in Table 1, the prepared composition a. A composition prepared in advance in a mixture of polyvinyl alcohol, isopropyl alcohol and ion-exchanged water. A water-soluble or water-dispersible isocyanate cross-linking agent, hydrochloric acid, isopropyl alcohol, and ion-exchanged water are added and stirred, and the mixture is colorless and transparent. A barrier coating solution was obtained.

Next, the plasma-treated surface formed in (1) above is coated with the gas barrier composition produced above by the gravure roll coating method, and then heat-treated at 180 ° C. for 60 seconds. A gas barrier coating film having a thickness of 0.3 μm (in a dry operation state) was formed.
(Water-soluble or water-dispersible isocyanate cross-linking agent used: Nippon Polyurentane Aquanate 100)

[ Reference Example 1 ]
The same test as in Example 1 was performed by replacing the water-soluble or water-dispersible isocyanate crosslinking agent of Example 1 with a water-soluble or water-dispersible epoxy crosslinking agent.
(Water-soluble or water-dispersible epoxy-based crosslinking agent used: Nippon Oil & Fats Co., Ltd. Epiol E-100)

[ Reference Example 2 ]
The same test as in Example 1 was performed by replacing the water-soluble or water-dispersible isocyanate crosslinking agent of Example 1 with a water-soluble or water-dispersible vinyl crosslinking agent.
(Water-soluble or water-dispersible vinyl-based crosslinking agent used: Nippon Oil & Fats Co., Ltd. BLEMER PP-1000)

[ Reference Example 3 ]
The same test as in Example 1 was performed by replacing the water-soluble or water-dispersible isocyanate crosslinking agent of Example 1 with a water-soluble or water-dispersible carbodiimide-based crosslinking agent.
(Water-soluble or water-dispersible carbodiimide crosslinking agent used: Nisshinbo Co., Ltd. Carbodilite V-02)

[Example 2 ]
The same test as in Example 1 was performed by replacing the water-soluble or water-dispersible isocyanate crosslinking agent of Example 1 with a water-soluble or water-dispersible oxazoline group-based crosslinking agent.
(Water-soluble or water-dispersible oxazoline group-based crosslinking agent used: Nippon Shokubai Epocross WS-700)

[ Reference Example 4 ]
The same test as in Example 1 was performed by replacing the water-soluble or water-dispersible isocyanate crosslinking agent of Example 1 with a water-soluble or water-dispersible hydrazide group-based crosslinking agent.
(Water-soluble or water-dispersible hydrazide group-based crosslinking agent used: adipic acid dihydrazide)

[Comparative Example 1]
The same test as in Example 1 was performed except that the water-soluble or water-dispersible isocyanate crosslinking agent was not included.

[Comparison test]
Example 21 to, using a gas barrier laminate film obtained in Reference Example 1-4 Contact and Comparative Example 1 to obtain a laminated film for boil and retort evaluated according to the following specifications.
Boil specification: Gas barrier laminate film / DL / PEF 60μm
Retort specification: Gas barrier laminate film / DL / ONY15μm / DL / CPP60μm
A four-way pouch was prepared using the obtained laminate film, each was filled with 200 cc of water, and subjected to a hot water sterilization treatment under a boil condition of 95 ° C./60 min and a retort condition of 135 ° C./60 min.

For boil evaluation, oxygen permeability before and after boil (cc / m ² · day · atm, 23 ° C, under 90% PH) and laminar strength (N / 15mm T-shaped peel measurement speed 50mm / min) and peeling interface The water-resistant laminating strength (N / 15 mm) was measured at a measurement speed of 50 mm / min while dropping water.
For retort evaluation, oxygen permeability before and after retort and laminar strength (N / 15mm T-shaped peeling measurement speed 50mm / min) and delamination occurrence check were made. Fill the pouch with 100cc water, and put a ruled line on the pouch. Then, the retort sterilization treatment was performed at 135 ° C./60 min in a state of being bent at 180 ° and fixed with a clip, and the state after retort was observed.

The comparative test results are summarized in Table 2 and Table 3.
The laminate film using the gas barrier laminate film obtained in the examples hardly affected the oxygen permeability by the boil treatment, and was superior in the barrier property to the boil treatment than the film of the comparative example.
Moreover, also in the retort process, compared with the film of the comparative example, the influence on the oxygen permeability was small, and furthermore, it had excellent barrier properties in terms of laminating strength and appearance.

It is a schematic sectional drawing which shows an example of the layer structure about the gas-barrier laminated film which concerns on this application. It is a schematic block diagram which shows the outline | summary of the example about a plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows the outline | summary of the example about a winding-type vacuum evaporation system.

Explanation of symbols

A: Gas barrier laminated film 1: Base film 2: Inorganic oxide vapor deposition layer 3: Barrier coat layer 11: Film to be vapor deposited 21: Low temperature plasma chemical vapor deposition apparatus 22, 42: Vacuum chamber 23, 43: Unwinding roll 24, 33: Auxiliary roll 25: Cooling / electrode drum 26, 27: Gas supply device 28: Raw material volatilization supply device 29: Raw material supply nozzle 30: Glow discharge plasma 31: Power source 32: Magnet 34, 53: Winding roll 35: Vacuum pump 41: Rewind-type vacuum deposition apparatus 44, 45, 51, 52: Guide roll 46: Coating drum 47: Crucible 48: Deposition source 49: Oxygen gas outlet 50: Mask

Claims (8)

An inorganic oxide vapor deposition layer is provided on at least one surface of the base film, and one or more alkoxides, a water-soluble polymer, and a water-soluble or water-dispersible curing agent are further formed on the inorganic oxide vapor deposition layer. A gas barrier laminate film characterized by comprising a barrier coat layer obtained by hydrolyzing and polycondensing a gas barrier composition containing
Water-soluble or water-dispersible curing agent, possess one or more reactive functional groups selected from isocyanate group and oxazoline group or al group consisting, and,
The gas barrier composition is characterized that it will not contain the synthetic fluorine mica-based mineral, the gas barrier laminate film. The alkoxide is represented by the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents 0 or more) The gas barrier laminate film according to claim 1, wherein the gas barrier laminate film is represented by an integer: m represents an integer of 1 or more, and n + m represents the number of atoms of M).   The gas-barrier laminated film according to claim 1 or 2, wherein the water-soluble polymer contains at least one of a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer.   The gas barrier laminate film according to any one of claims 1 to 3, wherein the gas barrier composition further contains a silane coupling agent.   The gas barrier laminate film according to any one of claims 1 to 4, wherein the barrier coat layer is printed.   The gas barrier laminate according to any one of claims 1 to 5, wherein a heat seal layer is further laminated on the barrier coat layer with or without an adhesive layer or an anchor coat layer. the film.   The gas barrier laminate film according to claim 6, wherein a nylon base material is further laminated between the barrier coat layer and the heat seal layer via an adhesive layer.   The gas barrier laminate film according to any one of claims 1 to 5 using nylon as a base material is used as an intermediate layer, and another base film and a heat seal layer are interposed therebetween through an adhesive layer or an anchor coat layer. A gas barrier laminate film characterized by laminating.

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