JP5228284B2 - Transparent barrier laminated film and method for producing the same - Google Patents

Description

  The present invention relates to a transparent barrier laminate film and a method for producing the same, and more specifically, has a sufficiently high UV transmittance that is sufficiently transparent as a packaging material, and prevents the transmission of oxygen gas, water vapor, etc. The present invention relates to a transparent barrier laminated film having excellent barrier properties to prevent and a method for producing the same.

Conventionally, gas barrier properties have been improved by forming an alumina vapor deposition film layer on a transparent substrate film and further coating a barrier agent on the alumina vapor deposition layer. For example, in Patent Document 1, a vapor deposition film made of an inorganic compound is used as a first layer on a base material made of a polymer resin composition, and a water-soluble polymer, (a) one or more metal alkoxides and their hydrolysis are disclosed. Of gas barrier properties after retort treatment and adhesion by laminating a gas barrier coating mainly comprising an aqueous solution containing at least one of the above or (b) tin chloride or a water / alcohol mixed solution as a second layer. It is described that a gas barrier laminate film with suppressed strength deterioration is obtained. Patent Document 2 discloses that after a metal oxide layer (A layer) is formed on a transparent polymer film by vapor deposition, component a (polyvinyl alcohol) and component b (alkoxysilane such as tetramethoxysilane) are formed. (Part) hydrolyzate, its (partial) condensate or a mixture thereof), component c (curing catalyst), component d (solvent containing at least 50% by weight of a polyvinyl alcohol-soluble solvent in all solvents), and component a / Component b = 5/1 to 1/2 (weight ratio), and a coating agent layer adjusted to pH 3 to 11 is applied onto the A layer, and then the coating agent is heated to form a cured film. It describes a method for producing a transparent barrier laminate film that is excellent in gas barrier properties, solvent resistance, heat resistance, chemical resistance, water resistance, flexibility, and adhesion. Furthermore, in Patent Document 3, when the total light transmittance of the base plastic film is 100%, an aluminum oxide vapor deposition film is formed on the base plastic film in the range of 90 to 95% of the total light transmittance after aluminum oxide deposition. Gas barrier resin in which at least one of oxygen transmission rate (unit: cc / m ² / day) and water vapor transmission rate (unit: g / m ² / day) is 100 or less when a film of 10 μm is formed on the vapor deposition layer of the vapor deposition film A protective layer is formed by coating with an aqueous solution or an aqueous dispersion, and the total light transmittance is 100% or more when the light transmittance of the base plastic film is 100%. It is described to do.
Japanese Patent No. 2790054 Japanese Patent No. 3403880 Japanese Patent No. 2000-185364

However, Patent Documents 1 to 3 disclose a transparent barrier laminate film having a high ultraviolet transmittance which is sufficiently transparent as a packaging material, a high oxygen barrier property and a high water vapor barrier property, and having retort and boil resistance. There is no mention of considering the vapor deposition conditions for obtaining the film, the drying conditions of the barrier coat layer formed on the vapor deposition layer, and the post-aging treatment after the formation of the transparent barrier laminate film.
The problem to be solved by the present invention is a transparent barrier laminate having a high ultraviolet transmittance that is sufficiently transparent as a packaging material, a high oxygen barrier property and a high water vapor barrier property, and having retort and boil resistance. It is to provide a film and a manufacturing method thereof.

Invention of Claim 1 solves the subject regarding a transparent barrier laminated film, and provides the vapor deposition film of the inorganic oxide whose ultraviolet transmittance in 366 nm is 82 to 94% on a transparent plastic substrate film, On this deposited film layer, a general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² are organic groups having 1 to 8 carbon atoms, M represents a metal atom, and n is 0 or more) M represents an integer of 1 or more, and n + m represents the valence of M), and at least one alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer represented by The gist is a transparent barrier laminate film characterized by comprising a barrier coating formed by coating a coating material comprising a barrier composition obtained by polycondensation by a sol-gel method.

Invention of Claim 2 solves the subject regarding the manufacturing method of a transparent gas-barrier laminated | multilayer film, and the vapor deposition film | membrane of the inorganic oxide whose ultraviolet transmittance in 366nm is 82-94% on a transparent plastic base film On the deposited film layer, a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic groups having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and at least one alkoxide represented by the formula: polyvinyl alcohol resin and / or ethylene / vinyl alcohol A transparent barrier laminate film comprising: a polymer, and further applying a coating material comprising a barrier composition obtained by polycondensation by a sol-gel method to form a barrier coating. Method Is the gist.

  In the manufacturing method of the present invention described above, it is desirable to dry at a temperature of 140 ° C. or higher after the coating material is applied. It is considered that the core whose water vapor barrier property is enhanced by drying at 140 ° C. or higher is a result of not less than the crystallization of PVA due to drying of the coating material contributing to the expression of the water vapor barrier property.

  In the present invention, the vapor-deposited film of inorganic oxide can be composed of aluminum oxide, silicon oxide or the like, but particularly in the case of a vapor-deposited layer of aluminum oxide, aluminum oxide which has been contradictory in the past due to the vapor-deposited film and the gas barrier coating film. The transparency of the vapor deposition layer and the gas barrier property can be made compatible, and a favorable effect can be obtained. In that case, the aluminum oxide vapor deposition film is formed by adjusting the reaction system while reacting aluminum vapor and oxygen in the gas phase so that the ultraviolet transmittance at 366 nm is adjusted in the range of 82 to 94%. When the ultraviolet transmittance is 82% or less, the transparency of the transparent barrier laminate film cannot be improved. If it is 94% or more, the reaction activity of the deposited film itself is low and the reaction with the barrier coating material becomes insufficient, so the effect of improving the oxygen barrier property and water vapor barrier property is impaired.

  The thickness of the aluminum oxide vapor deposition film used in the present invention is preferably 100 to 400 mm. When the thickness is 100 mm or less, the barrier property of the deposited film itself is low, and a sufficient barrier property cannot be obtained even if a barrier coating material is applied on the deposited film. On the other hand, if the vapor deposition film becomes thicker than 400 mm, it becomes a transparent barrier laminate film lacking in post-processing suitability, resulting in a film having poor practicality.

  Instead of the method described in paragraph 0007, a vapor deposition film made of aluminum oxide, silicon oxide, or the like is formed, a plasma-treated surface with oxygen gas is formed thereon, and a barrier coating material is applied onto the plasma-treated surface. You may do it. In that case, the vapor deposition film is formed by adjusting the ultraviolet transmittance at 366 nm in the range of 82 to 94%. When the ultraviolet transmittance is 82% or less, the transparency of the transparent barrier laminate film cannot be improved. If it is 94% or more, the reaction activity of the deposited film itself is low and the reaction with the barrier coating material becomes insufficient, so the effect of improving the oxygen barrier property and water vapor barrier property is impaired. The thickness of the deposited film is preferably 100 to 400 mm. When the thickness is 100 mm or less, the barrier property of the deposited film itself is low, and a sufficient barrier property cannot be obtained even if a barrier coating material is applied on the deposited film. On the other hand, if the vapor deposition film becomes thicker than 400 mm, it becomes a transparent barrier laminate film lacking in post-processing suitability, resulting in a film having poor practicality.

  In this invention, it is preferable to give an aging process to the manufactured gas-barrier laminated | multilayer film at the temperature of 40-80 degreeC. By this aging treatment, not only the ultraviolet transmittance is improved, but also the cross-linking reaction of the gas barrier coating proceeds and the barrier performance is remarkably improved.

  According to the present invention, a transparent barrier laminated film having a high ultraviolet transmittance that is sufficiently transparent as a packaging material, a high oxygen barrier property and a high water vapor barrier property, and having retort and boil resistance is manufactured. be able to.

The above invention will be described below in more detail with reference to the drawings.
1 shows the structure of a transparent barrier laminate film according to the present invention.

The transparent barrier laminate film 1 according to the present invention forms an inorganic oxide vapor deposition film 3 having an ultraviolet transmittance of 82 to 94% at 366 nm on a transparent plastic substrate film 2, and on this vapor deposition film 3, General formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic groups having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents A sol-gel containing at least one alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer represented by the following formula: The barrier coating 4 is formed by applying a coating material made of a barrier composition obtained by polycondensation by a method.

In the present invention, as the transparent plastic substrate film 2, for example, polyolefin resins such as polyethylene, polypropylene, polybutene, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6 naphthalate, nylon 6, nylon 12, etc. Polyamide resin, polyolefin resin such as polyethylene or polypropylene, polyvinyl chloride, polyvinylidene chloride, ethylene vinyl acetate copolymer, polystyrene, polycarbonate, polyacrylonitrile, polysulfone, polyphenylene oxide, aromatic polyamide, polyimide, cellulose, acetic acid A film made of cellulose, a copolymer of these polymers, or a polymer blend can be applied.
A desired surface treatment layer may be provided on the surface of the transparent plastic film, if necessary, in order to improve the adhesion to the deposited inorganic oxide film formed thereon.
As the surface treatment layer, a corona treatment layer, an ozone treatment layer, a low temperature plasma treatment using oxygen gas or nitrogen gas, a glow discharge treatment, an oxidation treatment layer using chemicals, or the like can be provided.

Next, the inorganic oxide vapor-deposited film 3 will be described. As the inorganic oxide vapor-deposited film, for example, a chemical vapor deposition method or a physical vapor deposition method, or a combination of both is applied. can do.
In addition, a vapor deposition film made of aluminum oxide, silicon oxide, or the like can be applied. In particular, by using a vapor deposition film of aluminum oxide, a vapor deposition film and a gas barrier coating film can be used to form an aluminum oxide vapor deposition layer that has been contradictory in the past. Both transparency and gas barrier properties can be achieved, and favorable effects can be obtained. In that case, the aluminum oxide vapor-deposited film is formed by adjusting the reaction system while reacting aluminum vapor and oxygen in the gas phase so that the ultraviolet transmittance at 366 nm is adjusted in the range of 82 to 94%. When the ultraviolet transmittance is 82% or less, the transparency of the transparent barrier laminate film cannot be improved. If it is 94% or more, the reaction activity of the deposited film itself is low and the reaction with the barrier coating material becomes insufficient, so the effect of improving the oxygen barrier property and water vapor barrier property is impaired.
Moreover, the thickness of the aluminum oxide vapor deposition film used in the present invention is preferably 100 to 400 mm. When the thickness is 100 mm or less, the barrier property of the deposited film itself is low, and a sufficient barrier property cannot be obtained even if a barrier coating material is applied on the deposited film. On the other hand, if the vapor deposition film becomes thicker than 400 mm, it becomes a transparent barrier laminate film lacking in post-processing suitability, resulting in a film having poor practicality.

  Further, instead of the above-described method, a vapor deposition film made of aluminum oxide, silicon oxide, or the like is formed, a plasma treatment surface with oxygen gas is formed thereon, and a barrier coating material is applied on the plasma treatment surface. It may be. In that case, the vapor deposition film is formed by adjusting the ultraviolet transmittance at 366 nm in the range of 82 to 94%. When the ultraviolet transmittance is 82% or less, the transparency of the transparent barrier laminate film cannot be improved. If it is 94% or more, the reaction activity of the deposited film itself is low and the reaction with the barrier coating material becomes insufficient, so the effect of improving the oxygen barrier property and water vapor barrier property is impaired. The thickness of the deposited film is preferably 100 to 400 mm. When the thickness is 100 mm or less, the barrier property of the deposited film itself is low, and a sufficient barrier property cannot be obtained even if a barrier coating material is applied on the deposited film. On the other hand, if the vapor deposition film becomes thicker than 400 mm, it becomes a transparent barrier laminate film lacking in post-processing suitability, resulting in a film having poor practicality.

Next, an inorganic oxide vapor deposition film formed by the physical vapor deposition method will be described. As a vapor deposition film of an inorganic oxide by a physical vapor deposition method, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, an ion plating method, or an ion cluster beam method is used. It can be used to form an inorganic oxide vapor-deposited film.
Specifically, a metal oxide is used as a raw material, this is heated and vaporized, and vapor deposition is performed on the transparent plastic substrate film 2, or a metal oxide is used as a raw material and oxygen is introduced. The vapor deposition film can be formed using an oxidation reaction vapor deposition method in which the film is oxidized and vapor-deposited on the surface of the transparent plastic substrate film, and further a plasma-assisted oxidation reaction vapor deposition method in which the oxidation reaction is supported by plasma.
In the physical vapor deposition method, the evaporation material can be heated by, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like.

FIG. 3 shows a schematic configuration of an example of a take-up vacuum deposition apparatus of physical vapor deposition.
As shown in FIG. 3, the transparent plastic substrate film 2 fed out from the unwinding roll 43 in the vacuum chamber 42 of the wind-up type vacuum vapor deposition apparatus 41 is cooled by the coating drum 46 via the guide rolls 44 and 45. Be guided to.
On the transparent plastic film 2 guided on the coating drum 46, a vapor deposition film 48 heated by a crucible 47, for example, metal aluminum or aluminum oxide is evaporated, and if necessary, from an oxygen gas outlet 49. Oxygen gas is ejected, and this is supplied to the transparent plastic substrate film 2 through the masks 50 and 50, while forming a vapor-deposited film of aluminum oxide and then forming the vapor-deposited film. Is fed through the guide rolls 45 ′ and 44 ′ and wound on the take-up roll 51, thereby forming an inorganic oxide vapor-deposited film by physical vapor deposition.

  As an inorganic oxide vapor-deposited film formed by physical vapor deposition, any thin film in which a metal oxide is vapor-deposited can be used. In addition to aluminum oxide, for example, an oxide of silicon (Si) The deposited film can be used.

Next, the barrier coating 4 will be described. Examples of the gas barrier coating 4 include, for example, a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ^{2 each} have 1 to 8 carbon atoms). M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and at least one alkoxide represented by polyvinyl Barrier property obtained by polycondensation by sol-gel method in the presence of sol-gel method catalyst, acid, water and organic solvent, containing alcohol-based resin and / or ethylene / vinyl alcohol copolymer Step of preparing the composition, barrier property of polycondensation by the above-mentioned sol-gel method on the vapor deposition film 3 provided on the transparent plastic substrate film 2 through a plasma-treated surface with oxygen gas if necessary. Barrier properties by applying the composition The step of forming a coating, and the transparent plastic film provided with the above-mentioned barrier coating is heat-treated at a temperature of 20 ° C. to 200 ° C., preferably 140 ° C. or higher and below the melting point of the transparent plastic film for 10 seconds to 10 minutes. And can be manufactured by a manufacturing process including a process of forming the barrier coating 4.

The barrier coating 4 has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic groups having 1 to 8 carbon atoms, M represents a metal atom, and n represents 1 represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M) at least one alkoxide, polyvinyl alcohol resin, and / or ethylene / vinyl alcohol copolymer A barrier composition obtained by polycondensation by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water and an organic solvent, and using this, a transparent plastic film Two or more layers may be stacked on the vapor deposition film 3 provided on the surface of 2 to form a composite polymer layer.

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 .
Thus, in the present invention, examples of preferable metals include silicon and titanium.
In the present invention, the alkoxide can be used singly or in combination of two or more different metal atoms 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.

Thus, in the present invention, as the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , for example, it is preferable to use an alkoxysilane in which the metal atom M is Si.
The alkoxysilane is represented by the general formula Si (ORa) _m (wherein Ra represents a lower alkyl group).
Specific examples of the above alkoxysilane include, for example, tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC ₄ H ₉ ) _{4 and} others can be used.

In the present invention, examples of the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m include, for example, the general formula Rb _n Si (ORc) _4-m (where n is 0 or more). M represents an integer of 1, 2, and 3, and Rb and Rc represent a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like.) can do.
Specific examples of the above alkoxysilane include, for example, methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OHC ₂ H ₅ ) ₃ , dimethyldimethoxysilane (CH ₃ ) ₂ Si ( OCH ₃ ) ₂ , dimethyldiethoxysilane (CH ₃ ) ₂ Si (OC ₂ H5 ₅ ) _{2 and} others can be used.
Said alkoxysilane, alkylalkoxysilane, etc. can be used individually or in mixture of 2 or more types.
In the present invention, a polycondensation product of the above alkoxysilane can also be used. Specifically, for example, polytetramethoxypolytetraethoxysilane or the like can be used.

Next, in the present invention, as the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , for example, a zirconium alkoxide in which the metal atom M is Zr can be used. Specific examples of the zirconium alkoxide include, for example, tetramethoxyzirconium Zr (OCH ₃ ) ₄ , tetraethoxyzirconium Zr (OC ₂ H ₅ ) ₄ , tetra i-propoxyzirconium Zr (iso-OC ₃ H ₇ ) ₄ , tetra n-Butoxyzirconium Zr (OC ₄ H ₉ ) _{4 and} others can be used.

In the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, a titanium alkoxide in which the metal atom is Ti can be used.
Specific examples of the titanium alkoxide include, for example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetraethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetra i-propoxytitanium Ti (iso-OC ₃ H ₇ ) ₄ , Tetra n-butoxy titanium Ti (OC ₄ H ₉ ) _{4 and} others can be used.

Furthermore, in the present invention, as the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , for example, an aluminum alkoxide in which the metal atom M is Al can be used.
Specific examples of the aluminum alkoxide include, for example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum Al (OC ₂ H ₅ ) ₄ , tetra i-propoxytitanium Al (iso-OC ₃ H ₇ ) ₄ , Tetra n-butoxy titanium Al (OC ₄ H ₉ ) _{4 and} others can be used.

In the present invention, the above alkoxides may be used as a mixture of two or more thereof.
Thus, in the present invention, in particular, by using a mixture of alkoxysilane and zirconium alkoxide, it is possible to improve the toughness, heat resistance, etc. of the obtained transparent barrier laminate film, A decrease in retort resistance and the like is avoided.
The amount of the zirconium alkoxide used is in the range of 10 parts by weight or less with respect to 100 parts by weight of the alkoxysilane, preferably about 5 parts by weight.
In the above, if it exceeds 10 parts by weight, the formed barrier coating film is easily gelled, the brittleness of the film is increased, and the barrier coating film tends to peel off, which is not preferable. .

In the present invention, in particular, by using a mixture of alkoxysilane and titanium alkoxide, the thermal conductivity of the resulting barrier coating is lowered, and its heat resistance is remarkably improved.
In the above, the amount of titanium alkoxide used is in the range of 5 parts by weight or less with respect to 100 parts by weight of alkoxysilane, preferably about 3 parts by weight.
In the above, if it exceeds 5 parts by weight, the formed brittle barrier film tends to be brittle, and the barrier coat tends to peel off, which is not preferable.

Next, as the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer for forming the barrier coating film for forming the barrier layer according to the present invention, the polyvinyl alcohol resin or the ethylene / vinyl alcohol copolymer is used. Can be used alone, or a combination of a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer can be used. Thus, in the present invention, by using a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, the barrier properties, water resistance, weather resistance and other physical properties of the barrier coating can be remarkably improved. .
In particular, in the present invention, by using a combination of a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer, in addition to the above physical properties such as barrier properties, water resistance and weather resistance, after hot water treatment and hot water treatment It is possible to form a barrier film having excellent barrier properties.

  In the present invention, when a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer are used in combination, the blending ratio thereof is, as a weight ratio, polyvinyl alcohol-based resin: ethylene / vinyl copolymer resin = 10: 0. .05 to 10: 6 is preferable, and it is more preferable to use at a use ratio of about 10: 1.

  In the present invention, the content of the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by weight with respect to 100 parts by weight of the total amount of the alkoxide, preferably, It is preferable to prepare the barrier composition at a blending ratio of about 20 to 200 parts by weight.

  In the above, if it exceeds 500 parts by weight, the brittleness of the barrier coating becomes large, and the water resistance and weather resistance thereof are also lowered, which is not preferable.

  In the present invention, with respect to the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer, first, a polyvinyl alcohol resin generally obtained by saponifying polyvinyl acetate can be used.

The polyvinyl alcohol resin may be a partially saponified polyvinyl alcohol in which several tens of percent of acetate groups remain, a completely saponified product in which no acetate groups remain, or a modified polyvinyl alcohol resin in which OH groups are modified. There is no particular limitation.
Specific examples of the polyvinyl alcohol resin include RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (degree of saponification = 40%, degree of polymerization = 2,000), GOHSENOL NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, degree of polymerization = 1,000) 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.
Specifically, the present invention is particularly limited from a partially saponified product in which several tens mol% of acetic acid groups remain to a completely saponified product in which only several mol% of acetic acid groups remain or no acetic acid group remains. Although it is not a thing, it is preferable to use the thing with a preferable saponification degree from a viewpoint of barrier property being 80 mol% or more, More preferably 90 mol% or more, More preferably, it is 95 mol% or more.
The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter 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.

Next, in the present invention, the barrier composition for forming the barrier coating according to the present invention will be described. Such a barrier composition has the general formula R ¹ _n M (OR ² ) _m as described above (wherein R ¹ and R ² are organic groups having 1 to 8 carbon atoms, and M represents a metal atom). , N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), a polyvinyl alcohol resin as described above, and / or Or an ethylene / vinyl alcohol copolymer, and further, a barrier composition that is polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent. .

In order to prepare said barrier composition, a silane coupling agent etc. can also be added, for example.
Thus, as the silane coupling agent, known organic reactive group-containing organoalkoxysilanes can be used.
In the present invention, an organoalkoxysilane having an epoxy group is particularly suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
The above silane coupling agents may be used alone or in combination of two or more.
In this invention, the usage-amount of the above silane coupling agents can be used within the range of 1-20 weight part with respect to 100 weight part of said alkoxysilane.
In the above, the use of 20 parts by weight or more is not preferable because rigidity and brittleness of the formed barrier coating film are increased and the insulating property and workability of the barrier coating film tend to decrease.

Next, as the sol-gel method catalyst used in the above-mentioned barrier composition, mainly a polycondensation catalyst, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used.
Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used.
In the present invention, it is preferable to use 0.01 to 1.0 parts by weight, preferably about 0.03 parts by weight per 100 parts by weight of the total amount of alkoxide and silane coupling agent.
Moreover, as an acid used in said barrier property composition, it is used as a catalyst of the said sol-gel method, mainly a catalyst for hydrolysis of an alkoxide, a silane coupling agent, etc.
Examples of the acid include mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and tartaric acid.
The amount of the acid used is about 0.001 to 0.05 mol, preferably about 0.01 mol, relative to the total molar amount of the alkoxide and alkoxide of the silane coupling agent (for example, silicate moiety). preferable.

Furthermore, in said barrier composition, water of 0.1-100 mol with respect to 1 mol of total molar amounts of said alkoxide, Preferably 0.8-2 mol of water can be used. When the amount of water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles crosslink three-dimensionally, resulting in low density and porosity. Therefore, such a porous polymer is not preferable because the barrier property cannot be improved.
Further, if the amount of water is less than 0.8 mol, it is not preferable because the hydrolysis reaction tends to hardly proceed.

Furthermore, as an organic solvent used in said barrier composition, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used, for example.
Further, regarding the barrier composition, the polyvinyl alcohol 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. Therefore, the type of the organic solvent is appropriately selected.
In the case of using a combination of a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer, it is preferable to use n-butanol.
In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, those commercially available as Soarnol (trade name) can be used.
The amount of the organic solvent used is usually 30 per 100 parts by weight of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel method catalyst. ~ 500 parts by weight.

Next, in the present invention, the barrier coating according to the present invention is specifically produced, for example, as follows.
First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel method catalyst, an acid, water, an organic solvent, and, if necessary, A barrier composition (coating liquid) is prepared by mixing metal alkoxide and the like.
After the preparation, the polycondensation reaction gradually proceeds in the above-mentioned barrier composition (coating liquid).
Next, the above-mentioned barrier composition (coating liquid) is applied on an inorganic oxide vapor-deposited film provided on one side of the transparent plastic substrate film by a conventional method and dried.
Thus, by the above drying, polycondensation of the above alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent and polyvinyl alcohol resin / and / or ethylene / vinyl alcohol copolymer proceeds, and the barrier coating is formed. It is formed.
Further, preferably, the above coating operation is repeated to form a barrier film composed of a plurality of coating films composed of two or more layers.
Finally, the vapor-deposited transparent plastic substrate film coated with the coating solution is 20 ° C. to 200 ° C., preferably about 100 ° C. to 200 ° C., more preferably 140 ° C. to 200 ° C. Form a barrier film with the above-mentioned barrier composition (coating liquid) on the inorganic oxide vapor-deposited film formed on the surface of the transparent plastic film by heating at a temperature for 10 seconds to 10 minutes. Can do.
The barrier coating thus obtained has excellent oxygen barrier properties, water vapor barrier properties, and the like.

  In the present invention, in place of the polyvinyl alcohol-based resin, an ethylene / vinyl alcohol copolymer, or both a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer, The transparent barrier laminate film according to the present invention produced by performing drying and heat treatment further improves barrier properties such as oxygen barrier property and water vapor barrier property after hot water treatment such as boil treatment and retort treatment. There is an advantage.

  Further, in the present invention, when the ethylene / vinyl alcohol copolymer or the combination of the polyvinyl alcohol resin and the ethylene / vinyl copolymer is not used as described above, that is, only the polyvinyl alcohol resin is used. In the case of constituting the barrier film according to the present invention, in order to improve the barrier property after the hot water treatment, for example, a barrier composition using a polyvinyl alcohol-based resin is applied in advance to form the first A barrier coating with improved barrier properties by forming a coating layer and then coating a barrier composition containing an ethylene / vinyl alcohol copolymer thereon to form a second coating layer Can also be formed.

  Furthermore, it is formed with the coating layer formed by the barrier property composition containing said ethylene vinyl alcohol copolymer, or the barrier property composition containing polyvinyl alcohol-type resin and ethylene vinyl alcohol copolymer. A plurality of coating layers may be formed as a multilayer, thereby forming a barrier coating with improved barrier properties.

Next, the operation of the method for forming a barrier coating film according to the present invention will be described using a case of using alkoxysilane as an alkoxide. First, the alkoxysilane and the metal alkoxide are hydrolyzed by water added in the coating solution.
At that time, the acid serves as a catalyst for hydrolysis.
Next, protons are taken from the generated hydroxyl groups by the action of the sol-gel method, and hydrolyzed products are dehydrated and polycondensed.
At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group.
In addition, due to the action of the base catalyst, ring opening of the epoxy group also occurs and a hydroxyl group is generated.
A polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds.
Furthermore, since the reaction system includes a polyvinyl alcohol resin, an ethylene / vinyl alcohol copolymer, or both a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer, the polyvinyl alcohol resin and the ethylene / vinyl alcohol Reaction with the hydroxyl group of the copolymer also occurs.
The resulting polycondensate constitutes a composite polymer including, for example, an inorganic part composed of Si—O—Si, Si—O—Zr, Si—O—Ti, and other bonds, and an organic part derived from the silane coupling agent. To do.
In the above reaction, for example, a linear polymer having a partial structural formula represented by the following formula (III) and further having a portion derived from a silane coupling agent is first formed.
This polymer contains an OR group (an alkoxy group such as an ethoxy group) branched from a linear polymer.
This OR group is hydrolyzed to become an OH group using an existing acid as a catalyst. The OH group is first deprotonated by the action of a sol-gel method catalyst (base catalyst), and then polycondensation proceeds. To do.
That is, this OH group undergoes a polycondensation reaction with a polyvinyl alcohol resin represented by the following formula (I) or an ethylene / vinyl alcohol copolymer represented by the following formula (II) to form Si—O—Si. It is considered that a composite polymer having a bond, for example, represented by the following formula (IV) or a copolymerized composite polymer represented by the following formulas (V) and (VI) is formed.

Said reaction advances at normal temperature, and a viscosity increases during preparation of a barrier composition (coating liquid).
When this barrier composition (coating liquid) is applied onto a vapor-deposited film of an inorganic oxide provided on one side of the transparent plastic base film 2, it is heated to remove the solvent and the alcohol produced by the polycondensation reaction. The polycondensation reaction is completed, and a transparent barrier film is formed on the inorganic oxide provided on one side of the transparent plastic substrate film 2.
When a plurality of the above-mentioned coating layers are stacked, the composite polymers in the interlayer coating layers are also condensed, and the layers are firmly bonded to each other.
Furthermore, since the organic reactive group of the silane coupling agent and the hydroxyl group generated by hydrolysis are bonded to the hydroxyl group on the surface of the vapor-deposited inorganic oxide film provided on one side of the transparent plastic substrate film, the transparent plastic substrate film The adhesion between the surface of the vapor-deposited film of the inorganic oxide provided on one side and the coating layer, the adhesiveness, and the like are also good.

The linear polymer as described above has crystallinity and has a structure in which a large number of fine crystals are embedded in an amorphous part.
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 molecular cohesive energy is high. Excellent rigidity due to high rigidity.

Since the barrier coating film according to the present invention has the excellent characteristics as described above, it is useful as a packaging material. In particular, since it is excellent in barrier properties (blocking and blocking permeation of O ₂ , N ₂ , H ₂ O, CO _{2 and} others), it is suitably used as a barrier substrate constituting a packaging film.
In particular, when used in so-called gas-filled packaging filled with N ₂ , CO ₂ gas, or the like, the excellent barrier properties are extremely effective for holding the filled gas.
Furthermore, the gas barrier laminate film according to the present invention is excellent in hot water treatment, particularly high-pressure hot water treatment (retort treatment), and exhibits extremely excellent gas barrier properties.

In the present invention, the inorganic oxide vapor-deposited film and the barrier film form, for example, a chemical bond, hydrogen bond, or coordination bond by hydrolysis / co-condensation, and the inorganic oxide vapor-deposited film and the barrier film are formed. Property and the adhesion between the barrier film and the synergistic effect of the two layers can provide a better barrier effect.
Examples of the method for applying the barrier composition of the present invention include one or more times by application means such as a roll coat such as a gravure roll coater, a spray coat, a dipping, a brush, a bar coat, and an applicator. By coating, a barrier coating 4 having a dry film thickness of 0.01 to 30 μm, preferably about 0.1 to 10 μm can be formed. Furthermore, the condensation is carried out by heating and drying under normal circumstances at a temperature of 50 to 300 ° C., preferably 70 to 200 ° C., for 0.05 to 60 minutes, preferably 0.01 to 10 minutes. Thus, the first or second barrier coating of the present invention can be formed.
Further, pretreatment such as corona discharge treatment or plasma treatment can be performed.

  About the transparent barrier laminated film obtained by apply | coating a barrier coating material on a vapor deposition film, an aging process is performed for one to several days at the temperature of 40-80 degreeC. By this treatment, not only the ultraviolet transmittance is improved, but also in terms of the barrier property, the cross-linking reaction of the coating film of the gas barrier coating material proceeds, and the performance is remarkably improved with respect to the barrier property.

Adjust the oxygen gas supply amount by reactive vapor deposition using an EB vapor deposition device on one side of a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and adjust the ultraviolet transmittance at 366 nm to be 88%, A vapor deposition film of aluminum oxide having a thickness of 200 mm was formed to obtain an aluminum oxide vapor deposition film.
(Deposition conditions)
Vapor deposition raw material: Vacuum degree in aluminum winding side chamber: 2.3 × 10 ⁻³ mbar
Degree of vacuum in the coating chamber on the oxygen gas introduction side: 2.9 × 10 ⁻⁴ mbar
Degree of vacuum in coating chamber after introducing oxygen gas: 4.3 × 10 ⁻⁴ mbar
Film transport speed: 500 m / min
The composition b (a mixture of polyvinyl alcohol, isopropyl alcohol and ion-exchanged water) prepared in accordance with the composition shown in Table 1 on the obtained aluminum oxide vapor-deposited film was prepared in advance with a composition b (ethyl silicate, silane coupling agent). Then, a hydrolyzate composed of hydrochloric acid, isopropyl alcohol and ion-exchanged water) was added and stirred to obtain a colorless and transparent barrier coating material. The obtained barrier coating material was applied and dried at 140 ° C. for 30 seconds to obtain a barrier coating film having a thickness of 0.2 μm. The obtained film was aged at 55 ° C. for 72 hours.

(Table 1)
a Polyvinyl alcohol 2.40 (wt%)
Isopropyl alcohol 2.88
H ₂ O 54.72
b Ethyl silicate 17.00
Silane coupling agent 1.70
Isopropyl alcohol 3.11
0.5N hydrochloric acid aqueous solution 0.53
H ₂ O 17.66
Total 100.0 (wt%)

A transparent barrier laminate film was obtained in the same manner as in Example 1, except that the thickness of the deposited film was 300 mm.
(Deposition conditions)
Vapor deposition raw material: Vacuum degree in aluminum winding side chamber: 2.3 × 10 ⁻³ mbar
Degree of vacuum in the coating chamber on the oxygen gas introduction side: 2.9 × 10 ⁻⁴ mbar
Degree of vacuum in coating chamber after introducing oxygen gas: 4.3 × 10 ⁻⁴ mbar
Film transport speed: 500 m / min
Then, in the same manner as in Example 1, aging treatment was performed at 55 ° C. for 72 hours.

  A transparent barrier laminate film was obtained in the same manner as Example 1. The transparent barrier laminate film was subjected to an aging treatment at 80 ° C. for 24 hours.

Adjust the oxygen gas supply rate by reactive vapor deposition using an EB vapor deposition device on one side of a 12 μm thick biaxially stretched polyethylene terephthalate film, and adjust the ultraviolet transmittance at 366 nm to be 92%, A vapor deposition film of aluminum oxide having a thickness of 200 mm was formed to obtain an aluminum oxide vapor deposition film.
(Deposition conditions)
Vapor deposition raw material: Vacuum degree in aluminum winding side chamber: 2.3 × 10 ⁻³ mbar
Degree of vacuum in the coating chamber on the oxygen gas introduction side: 2.9 × 10 ⁻⁴ mbar
Degree of vacuum in coating chamber after introducing oxygen gas: 4.3 × 10 ⁻⁴ mbar
Film transport speed: 500 m / min
Next, the barrier coating material used in Example 1 was applied to the deposited film surface of the aluminum oxide deposited film and dried at 140 ° C. for 30 seconds to form a barrier film having a thickness of 0.2 μm to form a transparent barrier laminated film. Got. The obtained transparent barrier laminate film was subjected to an aging treatment at 55 ° C. for 72 hours.

  A transparent barrier laminate film was obtained in the same manner as in Example 1, except that the drying temperature was 200 ° C. for 10 seconds. Then, in the same manner as in Example 1, aging treatment was performed at 55 ° C. for 72 hours.

A biaxially stretched polyethylene terephthalate film having a thickness of 12μ is subjected to corona treatment on one side, and then the biaxially stretched polyethylene terephthalate subjected to the corona treatment is attached to a feeding roll of a plasma chemical vapor deposition apparatus. A 150 nm thick silicon oxide vapor deposition film was formed on the corona-treated surface of the biaxially stretched polyethylene terephthalate film.
(Deposition conditions)
Deposition surface; corona-treated surface reaction gas type and mixing ratio; 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
Film transport speed: 100 m / min

Next, immediately after forming a vapor deposition film having a thickness of 150 mm, a glow discharge plasma generator was used on the vapor deposition surface of the silicon oxide, power 9 kW, oxygen gas: argon gas = 7.0: 2.5 (unit: slm) ), A mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 100 m / min is performed, and an oxygen gas / argon gas mixed gas plasma treatment is performed, and the surface tension of the deposited silicon oxide film surface is 54 dyne / A plasma-treated surface improved by at least cm was formed.

  On the other hand, according to the composition shown in Table 2 below, the prepared composition a (mixed solution composed of an aqueous polyvinyl alcohol solution, isopropyl alcohol and ion-exchanged water) was added to the composition b (ethyl silicate, silane coupling agent, isopropyl alcohol, 0.5N hydrochloric acid aqueous solution and ion-exchanged water) was added and stirred well to obtain a colorless and transparent barrier coating material.

(Table 2)
a Polyvinyl alcohol 2.33 (wt%)
Isopropyl alcohol 2.70
H ₂ O 51.75
b Ethyl silicate 16.60
Silane coupling agent 1.66
Isopropyl alcohol 3.90
0.5N hydrochloric acid aqueous solution 0.53
H ₂ O 20.53
Total 100.0 (wt%)

  Next, the barrier coating material is used on the plasma-treated surface of the silicon oxide vapor deposition film formed as described above, and this is coated by a gravure coating method, and then heat-treated at 140 ° C. for 30 seconds, A gas barrier coating film having a thickness of 0.2 μm (dry state) was formed. The obtained transparent barrier laminate film was subjected to an aging treatment at 55 ° C. for 72 hours.

A biaxially stretched nylon film having a thickness of 15 μm is used as a base material, and this is mounted on a feeding roll of a plasma chemical vapor deposition apparatus. A vapor deposited film of 150 mm thick silicon oxide is biaxially stretched nylon under the following conditions. It was formed on the corona-treated surface of the film.
(Deposition conditions)
Deposition surface: Corona-treated surface Reaction gas type and mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1: 11: 10 (Unit: slm)
Degree of vacuum in the vacuum chamber: 5.2 × 10 ⁻⁶ mBar
Degree of vacuum in the deposition chamber: 5.1 × 10 ⁻² mBar
Cooling and electrode drum power supply: 18kW
Film transport speed: 70 m / min
Next, immediately after forming a vapor-deposited film having a thickness of 150 mm, a plasma-treated surface was formed on the silicon oxide vapor-deposited surface in the same manner as in Example 5.

  Next, a barrier coating material having the same composition as the barrier coating material used in Example 6 was applied to the plasma-treated surface of the silicon oxide vapor deposition film formed as described above, and this was coated by a gravure coating method. Then, heat treatment was performed at 140 ° C. for 30 seconds to form a barrier film having a thickness of 0.2 μm (in a dry state), and a transparent barrier laminated film was obtained. The obtained transparent barrier laminate film was subjected to an aging treatment at 55 ° C. for 72 hours.

  In the same manner as in Example 1, immediately after forming a vapor-deposited film having a thickness of 200 mm, a plasma-treated surface was formed on the aluminum oxide vapor-deposited surface in the same manner as in Example 6.

  Next, a barrier coating material having the same composition as the barrier coating material used in Example 6 was applied to the plasma-treated surface of the aluminum oxide vapor deposition film formed as described above, and this was coated by a gravure coating method. Then, heat treatment was performed at 140 ° C. for 30 seconds to form a barrier film having a thickness of 0.2 μm (in a dry state), and a transparent barrier laminated film was obtained. The obtained transparent barrier laminate film was subjected to an aging treatment at 55 ° C. for 72 hours.

  As a base material, a biaxially stretched nylon film having a thickness of 15 μm and subjected to corona treatment on one side is used. First, the biaxially stretched nylon film is attached to a feed roll of a wind-up type vacuum deposition apparatus, and then This was drawn out, and aluminum was used as a deposition raw material on the corona-treated surface of the biaxially stretched nylon film. However, immediately after forming a deposited film with a film thickness of 200 mm at a film conveyance speed of 300 m / min, on the deposited surface of the aluminum oxide, A plasma treated surface was formed in the same manner as in Example 6.

  On the other hand, composition b (ethyl silicate) prepared in advance in composition a (EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solution of isopropyl alcohol and ion-exchanged water) prepared according to the composition shown in Table 3 below. 40, a hydrolyzate composed of isopropyl alcohol, aluminum acetylacetone and ion-exchanged water), sufficiently stirred, and further prepared in advance c (polyvinyl alcohol, silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and A liquid mixture comprising ion-exchanged water) was added and stirred to obtain a colorless and transparent barrier coating material.

(Table 3)
a EVOH (ethylene copolymerization rate) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
b Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
c Polyvinyl alcohol 1.520
Silane coupling agent 0.050
Acetic acid 0.130
Isopropyl alcohol 13.824
H ₂ O 20.53
Total 100.0 (wt%)

  Next, the barrier coating material obtained as described above is applied to the plasma-treated surface of the aluminum oxide vapor-deposited film formed as described above, and dried at 140 ° C. for 30 seconds. A barrier coating having a thickness of 0.2 μm (in a dry state) was formed to obtain a transparent barrier laminate film. The obtained transparent barrier laminate film was subjected to an aging treatment at 55 ° C. for 72 hours.

[Comparative Example 1]
Adjust the oxygen gas supply amount by reactive vapor deposition using an EB vapor deposition device on one side of a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and adjust the ultraviolet transmittance at 366 nm to be 80%, A vapor deposition film of aluminum oxide having a thickness of 200 mm was formed to obtain an aluminum oxide vapor deposition film.
(Deposition conditions)
Vapor deposition raw material: Vacuum degree in aluminum winding side chamber: 2.3 × 10 ⁻³ mbar
Degree of vacuum in the coating chamber on the oxygen gas introduction side: 2.9 × 10 ⁻⁴ mbar
Degree of vacuum in coating chamber after introducing oxygen gas: 4.3 × 10 ⁻⁴ mbar
Film transport speed: 500 m / min
The barrier coating material used in Example 1 was applied to the deposited film surface of the aluminum deposited film on the deposited film surface of the aluminum oxide deposited film and dried at 140 ° C. for 30 seconds to form a barrier coated film having a thickness of 0.2 μm. It formed and obtained the transparent barrier property laminated film. The obtained transparent barrier laminate film was subjected to an aging treatment at 55 ° C. for 72 hours.

[Comparative Example 2]
Adjust the oxygen gas supply amount by reactive vapor deposition using an EB vapor deposition device on one side of a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and adjust the ultraviolet transmittance at 366 nm to be 96%, A vapor deposition film of aluminum oxide having a thickness of 200 mm was formed to obtain an aluminum oxide vapor deposition film.
(Deposition conditions)
Vapor deposition raw material: Vacuum degree in aluminum winding side chamber: 2.3 × 10 ⁻³ mbar
Degree of vacuum in the coating chamber on the oxygen gas introduction side: 2.9 × 10 ⁻⁴ mbar
Degree of vacuum in coating chamber after introducing oxygen gas: 4.3 × 10 ⁻⁴ mbar
Film transport speed: 500 m / min

  The barrier coating material used in Example 1 was applied to the deposited film surface of the aluminum deposited film on the deposited film surface of the aluminum oxide deposited film and dried at 140 ° C. for 30 seconds to form a barrier coated film having a thickness of 0.2 μm. It formed and obtained the transparent barrier property laminated film. The obtained transparent barrier laminate film was subjected to an aging treatment at 55 ° C. for 72 hours.

[Comparative Example 3]
Adjust the oxygen gas supply amount by reactive vapor deposition using an EB vapor deposition device on one side of a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and adjust the ultraviolet transmittance at 366 nm to be 88%, A deposited aluminum oxide film having a thickness of 100 mm was formed to obtain an aluminum oxide deposited film.
(Deposition conditions)
Vapor deposition raw material: Vacuum degree in aluminum winding side chamber: 2.3 × 10 ⁻³ mbar
Degree of vacuum in the coating chamber on the oxygen gas introduction side: 2.9 × 10 ⁻⁴ mbar
Degree of vacuum in coating chamber after introducing oxygen gas: 4.3 × 10 ⁻⁴ mbar
Film transport speed: 500 m / min
The barrier coating material used in Example 1 was applied to the deposited film surface of the aluminum deposited film on the deposited film surface of the aluminum oxide deposited film and dried at 140 ° C. for 30 seconds to form a barrier coated film having a thickness of 0.2 μm. It formed and obtained the transparent barrier property laminated film. The obtained transparent barrier laminate film was subjected to an aging treatment at 55 ° C. for 72 hours.

[Comparative Example 4]
Adjust the oxygen gas supply amount by reactive vapor deposition using an EB vapor deposition device on one side of a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and adjust the ultraviolet transmittance at 366 nm to be 88%, An aluminum oxide vapor-deposited film having a thickness of 500 mm was formed into an aluminum oxide vapor-deposited film.
(Deposition conditions)
Vapor deposition raw material: Vacuum degree in aluminum winding side chamber: 2.3 × 10 ⁻³ mbar
Degree of vacuum in the coating chamber on the oxygen gas introduction side: 2.9 × 10 ⁻⁴ mbar
Degree of vacuum in coating chamber after introducing oxygen gas: 4.3 × 10 ⁻⁴ mbar
Film transport speed: 500 m / min
The barrier coating material used in Example 1 was applied to the deposited film surface of the aluminum deposited film on the deposited film surface of the aluminum oxide deposited film and dried at 140 ° C. for 30 seconds to form a barrier coated film having a thickness of 0.2 μm. It formed and obtained the transparent barrier property laminated film. The obtained transparent barrier laminate film was subjected to an aging treatment at 55 ° C. for 72 hours.

[Comparative Example 5]
A transparent laminated film was obtained in the same manner as in Example 1, except that the drying temperature was 100 ° C. for 1 minute. The obtained transparent barrier laminate film was subjected to an aging treatment at 55 ° C. for 72 hours.

[Experimental example]
About the transparent barrier property laminated | multilayer film of said Examples 1-9 and Comparative Examples 1-5, it measured about the ultraviolet-ray transmittance in 366 nm before and behind an aging process, oxygen permeability, and water vapor permeability.
(1) Measurement of ultraviolet transmittance Using a spectrophotometer (manufactured by Shimadzu Corporation, model name UV-2200), the transmittance is measured with the total value of the linear light and scattered light at 366 nm as transmitted light. did.
(2) Measurement of oxygen permeability Oxygen permeability was measured under conditions of a temperature of 23 ° C and a humidity of 90% RH using OXTRAN manufactured by MOCON.
(3) Measurement of water vapor transmission rate The measurement of water vapor was performed under the conditions of a temperature of 40 ° C. and a humidity of 100% RH using PERMATRAN manufactured by MOCON.

About the transparent barrier property laminated | multilayer film of Examples 1-9 and Comparative Examples 1-5, it investigated about the bran transmittance | permeability in 366 nm before and behind aging, oxygen barrier property, and water vapor | steam barrier property.
Table 4 shows the measurement results.

As shown in Table 4, each of the transparent barrier laminate films of Examples 1 to 9 showed high ultraviolet transmittance after the aging treatment. Moreover, it turned out that the oxidation permeability | transmittance and water vapor | steam permeability | transmittance are low, and show the outstanding barrier property. On the other hand, in Comparative Examples 1 and 4, there was only a slight increase in the ultraviolet transmittance due to the aging treatment, and a high ultraviolet transmittance of 94% or more was not obtained. In Comparative Examples 2 to 3 and 5, a high ultraviolet transmittance of 94% or more was obtained, but the oxygen permeability after the aging treatment was only 0.5 to 0.6 cc / m ² · day · atm. The low oxygen permeability as in Examples 1-9 was not obtained. Moreover, the water vapor permeability after the aging treatment was also stopped at 1.2 to 1.4 g / m ² · day, and the low water vapor permeability as in Examples 1 to 9 was not obtained.

Next, for each transparent barrier laminate film after the aging treatment of Examples 1 to 9 and Comparative Examples 1 to 5, PEF (polyethylene film) 30 μm was dry laminated on the barrier coating surface side of each transparent barrier laminate film, The film obtained by the bonding was subjected to a bending resistance test using a gelboflex tester manufactured by Tester Sangyo Co., Ltd., and the decrease in oxygen permeability and water vapor permeability due to bending was examined.
Table 5 shows the measurement results.

About Examples 1-9, the fall of oxygen permeability and water vapor permeability was not seen until the frequency | count of bending 5 times. However, when the number of bendings was 50, the oxygen permeability decreased to 0.9 to 1.2 cc / m ² · day · atm, and the water vapor permeability decreased to 1.2 to 1.6 g / m ² · day. On the other hand, in Comparative Examples 2 to 5, the oxygen permeability was 0.8 to 10.2 cc / m ² · day · atm and the water vapor permeability was 1.6 to 4.3 g / m ^{2 when the} number of flexing was 5 times.・ As the number of flexing increases, the oxygen permeability is 3.8 to 36.8 cc / m ² · day · atm, and the water vapor permeability is 3.8 to 13.4 g / m ² · day with 50 times flexing. There was a significant decline.

Using the laminate formed by dry laminating 15 μm of biaxially stretched nylon (ON) and 60 μm of polypropylene (CPP) on each transparent barrier laminate film after the aging treatment of Examples 1 to 5 and Comparative Examples 1 to 5 A retort pouch was prepared. A pouch for retort was prepared using a laminate formed by dry laminating PET 12 μm / films of Examples 7 and 9 / CPP 60 μm on the transparent laminated films of Examples 7 and 9.
The pouches produced as described above were each filled with water and subjected to retort treatment under conditions of 121 ° C./2 atm / 30 minutes, and the oxygen permeability and water vapor permeability before and after the retort treatment were examined.
Table 6 shows the measurement results.

For Examples 1-9, the oxygen permeability decreases from the retort before 0.2cc / m ² · day · atm to 0.5~0.7cc / m ² · day · atm was observed, the water vapor transmission Regarding the degree, a decrease from 0.3 to 0.4 g / m ² · day before retort to 0.7 to 1.2 g / m ² · day was observed. The oxygen permeability in Comparative Examples 2-5 to Re此, and 1.4~4.1cc / m ² · day · atm from retorting previous 0.3~0.4cc / m ² · day · atm There was a significant decline. Regarding also vapor permeability, from the retort before 0.4~1.1g / m ² · day, it decreased significantly and 1.8~5.6g / m ² · day after the retort was observed.

  The transparent barrier laminate film of the present invention has an ultraviolet transmittance, is excellent in barrier properties that prevent the transmission of oxygen gas, water vapor, and the like, and can also be used as a highly transparent barrier packaging material. . In addition, the retort pouch using the transparent barrier laminate film of the present invention maintains high barrier properties after retort treatment, and can be used as a material for a highly transparent retort pouch. is there.

1 is a schematic cross-sectional view of a transparent barrier laminate film of the present invention. It is a schematic block diagram of a winding-type vacuum evaporation apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent barrier laminated film 2 Transparent plastic base film 3 Deposition film 4 Barrier film 41 Rewind-type vacuum deposition apparatus 42 Vacuum chamber 43 Unwinding roll 44 Guide roll 45 Guide roll 46 Coating roll 47 Crucible 48 Deposition film 49 Oxygen gas Air outlet 50 Mask 51 Winding roll

Claims (3)

On the transparent plastic base film, an aluminum oxide vapor deposition film having an ultraviolet transmittance of 82 to 94% at 366 nm is formed,
And the thickness of the deposited film of the aluminum oxide is 200 to 300 mm,
Next, the general formula R ¹ nM (OR ² ) m (wherein R ¹ and R ² are organic groups having 1 to 8 carbon atoms, and M represents a metal atom) on the vapor-deposited film of aluminum oxide. , N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), at least one alkoxide represented by the following formula: polyvinyl alcohol resin and / or ethylene / vinyl alcohol A coating material comprising a copolymer and further comprising a barrier material composition obtained by polycondensation by a sol-gel method is applied, dried at a temperature of 140 ° C. or more to form a barrier film, and a transparent barrier laminate Producing films,
Next, the transparent barrier laminate film is subjected to an aging treatment at a temperature of 40 to 80 ° C. for 1 to 3 days to increase the ultraviolet transmittance of the transparent barrier laminate film, and the oxygen permeability and water vapor permeability. A method for producing a transparent barrier laminate film, characterized by lowering the thickness. An aluminum oxide vapor deposition film is formed by reacting aluminum vapor and oxygen in the gas phase and adjusting the reaction system to form an aluminum oxide vapor deposition film in which the ultraviolet transmittance at 366 nm is adjusted to a range of 82 to 94%. The method for producing a transparent barrier laminate film according to claim 1, wherein: 3. The transparent according to claim 1, wherein the aluminum oxide vapor deposition film forms the aluminum oxide vapor deposition film and forms a plasma-treated surface with oxygen gas on the aluminum oxide vapor deposition film. A method for producing a barrier laminate film.

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