JP3505546B1 - Gas barrier film for packaging material and method for producing the same - Google Patents

Abstract

[PROBLEMS] To provide a conventional gas barrier film having transparency, in particular, having flexibility, reducing the occurrence of cracks and the like, and capable of forming a coating film capable of high-speed processing. I will provide a. In a plastic film in which an inorganic oxide vapor deposition film is laminated on at least one surface, a protective layer is formed by applying at least a vapor deposition film protective coating material on the inorganic oxide vapor deposition film. It is obtained by laminating a deposited film protective layer through the process, between the plastic film and the inorganic oxide deposited film,
An anchor coat layer was provided by an anchor coat layer forming step, and the gas barrier film was determined to be a layer having a thermosetting property.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas barrier film, and particularly used for packaging materials such as foods and pharmaceuticals, which has improved water resistance, barrier property after boil, and excellent crack resistance. Gas barrier film for packaging, and a method for manufacturing a gas barrier film for packaging material.

[0002]

2. Description of the Related Art Conventionally, various materials have been developed and proposed as a packaging material having a so-called gas barrier property having a barrier property against oxygen, water vapor and the like. For example, packaging materials using gas barrier films using aluminum foil, etc. are widely known and used, but recently, in addition to this, transparent plastic films are used for inorganic oxide vapor deposition films such as silicon oxide and aluminum oxide. Gas barrier films having a structure provided with are widely used. This is because, as compared with a gas barrier film using an aluminum foil, it has excellent transparency and visibility, and is less likely to cause environmental problems at the time of disposal.

However, the above-mentioned gas barrier film has a problem that the barrier performance against oxygen, water vapor, etc. is deteriorated as compared with the gas barrier film provided with the aluminum foil. Therefore, a method of increasing the layer thickness of the inorganic oxide vapor deposition film in order to improve the barrier performance while securing the transparency and visibility is conceivable, but this causes another problem such that cracks easily occur. .

Therefore, there has been proposed a gas barrier film which is intended to solve these problems by further applying a gas barrier coating to the gas barrier film provided with the above-mentioned inorganic oxide vapor deposition film.

As a coating agent for applying the gas barrier coating, a vinylidene chloride coating material, a polyvinyl alcohol (PVA) coating material, an ethylene vinyl alcohol coating material (EVOH), etc. are used. In addition, a silane-based solution may be used (for example, see Patent Document 1).

[0006] By the way, in Patent Document 1, a packaging material which is superior in transparency and has a high barrier property to a packaging laminated material using an aluminum foil, and in order to improve impact resistance, a plastic material is used. The invention relates to a film in which an inorganic oxide thin film is provided on one surface of a substrate, and a transparent barrier film in which a thin film of a silane-based solution is further provided on the inorganic oxide thin film.

[0007]

[Patent Document 1] Japanese Unexamined Patent Publication No. 10-156998 (Claim 1, FIG. 1)

[0008]

As described above, instead of an attempt to improve the gas barrier property by increasing the film thickness of the inorganic oxide vapor deposition film itself, a gas barrier film provided with the inorganic oxide vapor deposition film is provided. It has been tried to obtain a film having high flexibility and high barrier property while securing transparency and visibility by applying a barrier coating to the film, but it has not been obtained yet. It was

For example, when a vinylidene chloride-based coating material is used as a coating agent, an attempt to incinerate the coating material causes environmental problems. Therefore, the coating material is currently not used, that is, it is not practical and is a problem. is there. When a polyvinyl alcohol (PVA) coating material, an ethylene vinyl alcohol coating material (EVOH), etc. are used, it is difficult to obtain sufficient water resistance with these coating materials, that is, these coating materials are used. In this case, if the content is water, there is a problem that it cannot withstand actual use. Further, if only a silane-based solution is laminated as seen in Patent Document 1, a flexible gas barrier laminate while ensuring transparency and visibility, which is the object of Patent Document 1, may be obtained. However, since the reaction speed of the silane-based solution itself is extremely slow, the method described in Patent Document 1 cannot be used for high-speed processing by roll-to-roll processing, that is, there is a problem in productivity. It is not suitable for actual production.

The present invention has been made in view of the above problems, and an object thereof is a conventional gas barrier film having transparency, which has flexibility, cracks, and the like. (EN) A gas barrier film for a packaging material, which can reduce the occurrence of a gas, and can form a coating film that can be processed at high speed, and a method for producing the gas barrier film for a packaging material.

[0011]

In order to solve the above problems, the gas barrier film for a packaging material according to claim 1 of the present invention is a plastic film having an inorganic oxide vapor deposition film laminated on at least one surface thereof. The vapor-deposited film protective layer is formed by coating a vapor-deposited film protective coating material on the inorganic oxide vapor-deposited film, and is formed by laminating a vapor-deposited film protective layer that protects the inorganic oxide vapor-deposited film. It has a thermosetting property, and the curing reaction is accelerated by the epoxy ring-opening polymerization and the condensation reaction, and the film thickness is 0.03μ.
In the layer having a thickness of m to 3 μm, the vapor deposition film protective coating material forming the vapor deposition film protective layer is a first silane compound, and pure water is 50 parts by weight with respect to 100 parts by weight of the first silane compound. The above is mixed to prepare a mixed solution, and then either one of hydrochloric acid or acetic acid is added to the mixed solution so that the pH of the mixed solution becomes 3 to 5 to prepare a main agent, and then, 1 part by weight or more and 10 parts by weight or less of a curing catalyst for accelerating the curing of the first silane compound is prepared by diluting the base material to prepare a diluent. Adding to the diluent,
Which is a coating material obtained by
-Glycidoxypropyltrimethoxysilane, or γ-
Glycidoxypropyltriethoxysilane, which is a mixture of either or both of the curing catalyst,
Iron acetylacetonate, zinc acetylacetonate,
It is any one of aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonatotitanium, and dihydroxybislactatotitanium.

The gas barrier film for a packaging material according to claim 2 of the present invention has at least one surface,
In a plastic film in which an inorganic oxide vapor deposition film is laminated via an anchor coat layer, the inorganic oxide vapor deposition film is formed by applying a vapor deposition film protective coating material on the inorganic oxide vapor deposition film to protect the inorganic oxide vapor deposition film. The vapor-deposited film protective layer is laminated, and the vapor-deposited film protective layer has a thermosetting property, and the curing reaction is promoted by the epoxy ring-opening polymerization and the condensation reaction. In the layer having a thickness of 3 μm, the vapor deposition film protective coating material for forming the vapor deposition film protective layer contains 50 parts by weight or more of pure silane compound and pure water in 100 parts by weight of the first silane compound. A mixed solution is prepared by mixing, and then either hydrochloric acid or acetic acid is added to the mixed solution so that the mixed solution has a pH of 3 to 5 to prepare a main agent. To dilute the And then adding a curing catalyst for accelerating the curing of the first silane compound to the diluent in an amount of 1 part by weight to 10 parts by weight per 100 parts by weight of the first silane compound. In the coating material obtained in, the first silane compound is a mixture of either or both of γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane, The curing catalyst is any one of iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonatotitanium, and dihydroxybislactatotitanium. .

The gas barrier film for a packaging material according to claim 3 of the present invention is a plastic film in which an inorganic oxide vapor deposition film is laminated on at least one surface with an anchor coat layer, and the inorganic oxide vapor deposition film is formed. On top of which a gas barrier layer formed by applying a coating agent is laminated, the gas barrier layer is a layer having thermosetting property, and the coating agent is an olefin polymer dissolved in an aqueous solvent. And a second silane-based compound, and further, iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonato titanium, dihydroxybislactato titanium. , Which is added as a curing catalyst. The mixing ratio of the the system polymer second silane compound, the second silane compound relative to the 100 parts by weight of the olefin polymer is 5 parts by weight or more 10
0 parts by weight or less, and the second silane compound is tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, or a mixture of two or more selected from these, Is characterized by.

The gas barrier film for a packaging material according to claim 4 of the present invention is a plastic film in which an inorganic oxide vapor deposition film is laminated on at least one surface via an anchor coat layer, wherein the inorganic oxide vapor deposition film is formed. On the above, at least a vapor deposition film protective layer formed by applying a vapor deposition film protective coating material, and a gas barrier layer formed by applying a coating agent are laminated in this order, The vapor deposition film protective coating material for forming the film protective layer is formed by adding pure water to the first silane compound.
50 parts by weight or more is mixed with 100 parts by weight of the silane-based compound to prepare a mixed solution, and then either hydrochloric acid or acetic acid is added to the mixed solution, and the pH of the mixed solution is 3 to 3.
5 to prepare a base material, then dilute the base material to prepare a diluent, and then add a curing catalyst for promoting curing of the first silane compound to the first silane. 1 part by weight or more based on 100 parts by weight of the base compound 10
In the coating material obtained by adding to the diluent below, by weight, the first silane compound is γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane. Either one or both are mixed, and the curing catalyst is iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonato titanium, dihydroxybislactato titanium. And the gas barrier layer is a layer having thermosetting property, and the coating agent is a mixture of an olefin polymer dissolved in an aqueous solvent and a second silane compound, In addition, iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate , Tin tetrachloride, diisopropoxybisacetylacetonato titanium, or dihydroxybislactato titanium is added as a curing catalyst, and the mixing ratio of the olefin polymer and the second silane compound is 5 parts by weight or more of the second silane-based compound with respect to 100 parts by weight of the olefin-based polymer 10
0 parts by weight or less, and the second silane compound is tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, or a mixture of two or more selected from these, Is characterized by.

According to a fifth aspect of the present invention, there is provided a method for producing a gas barrier film for a packaging material, wherein a plastic film having an inorganic oxide vapor deposition film laminated on at least one surface thereof is provided on the inorganic oxide vapor deposition film. In addition, the first silane compound having thermosetting property is mixed with pure water in an amount of 50 parts by weight or more based on 100 parts by weight of the first silane compound to prepare a mixed liquid, and then the mixed liquid. , Either hydrochloric acid or acetic acid is added so that the pH of the mixed solution is 3 to 5 to prepare a main agent, and then the main agent is diluted to prepare a diluted solution, and then the first solution is prepared. 1. A vapor deposition film protection obtained by adding a curing catalyst for accelerating the curing of a silane compound to the diluent in an amount of 1 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the first silane compound. Apply coating material , By which the thermal curing,
Further, by the curing catalyst, by epoxy ring-opening polymerization and condensation reaction, by promoting the curing of the vapor deposition film protective coating material, to form a vapor deposition film protective layer for protecting the inorganic oxide vapor deposition film, Characteristically, the first silane-based compound is γ-glycidoxypropyltrimethoxysilane,
Or γ-glycidoxypropyltriethoxysilane, which is a mixture of either or both, and the curing catalyst is iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, It is any one of diisopropoxybis acetylacetonato titanium and dihydroxybislactato titanium.

According to a sixth aspect of the present invention, there is provided a method for producing a gas barrier film for a packaging material, the method comprising: On the inorganic oxide vapor-deposited film, a mixture having a thermosetting property and a first silane compound is mixed with pure water in an amount of 50 parts by weight or more based on 100 parts by weight of the first silane compound. Then, either hydrochloric acid or acetic acid is added to the mixed solution so that the mixed solution has a pH of 3 to 5 to prepare a main agent, and then the main agent is diluted to prepare a diluted solution. And then adding a curing catalyst for accelerating the curing of the first silane compound to the diluent in an amount of 1 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the first silane compound. Obtained with That is coated with a vapor-deposited film protective coating material,
A vapor deposition film that protects the inorganic oxide vapor deposition film by thermally curing this and by promoting curing of the vapor deposition film protective coating material by epoxy ring-opening polymerization and condensation reaction by the curing catalyst. Forming a protective layer, wherein the first silane-based compound is a mixture of either or both of γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane. And the curing catalyst is any one of iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonatotitanium, and dihydroxybislactatotitanium. , Is included.

According to a seventh aspect of the present invention, there is provided a method for producing a gas barrier film for a packaging material, the method comprising: A mixture of an olefin polymer dissolved in an aqueous solvent and a second silane compound on the inorganic oxide vapor deposition film, and further iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, Tin chloride,
One of titanium diisopropoxybisacetylacetonato and titanium dihydroxybislactato is added as a curing catalyst, and the mixing ratio of the olefin polymer and the second silane compound is the olefin polymer 100. The second silane compound is 5 parts by weight or more and 100 parts by weight or less with respect to parts by weight, and the second silane compound is tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, or methyl. Trimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyl Trimethoxysilane, γ-a Nopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, or a coating agent that is a mixture of a plurality of these selected, It has a step of laminating a gas barrier layer having thermosetting property, which is formed by coating.

The method for producing a gas barrier film for a packaging material according to claim 8 of the present invention is a plastic film in which an inorganic oxide vapor deposition film is laminated on at least one surface through an anchor coat layer, and the inorganic oxide is used. A step of stacking at least a vapor deposition film protective layer formed by applying a vapor deposition film protective coating material and a gas barrier layer formed by applying a coating agent on the physical vapor deposition film in this order. Specifically, first, in the step of laminating the vapor deposition film protective layer, the first silane compound has a thermosetting property on the inorganic oxide vapor deposition film, and pure water is added to the first silane compound. A mixed solution is prepared by mixing 50 parts by weight or more with 100 parts by weight of the silane-based compound, and then either hydrochloric acid or acetic acid is added to the mixed solution to adjust the pH of the mixed solution to 3 to 5. To prepare a base material, then dilute the base material to prepare a diluent, and then add a curing catalyst for promoting the curing of the first silane-based compound to the first silane-based compound. 1 to 10 parts by weight per 100 parts by weight should be added to the diluent.
The application of the vapor-deposited film protective coating material obtained in the above step, and heat curing of the vapor-deposited film protective coating material, and the curing catalyst promotes curing of the vapor-deposited film protective coating material by epoxy ring-opening polymerization and condensation reaction. And a step of forming a vapor deposition film protective layer for protecting the inorganic oxide vapor deposition film, wherein the first silane compound is γ-glycidoxypropyltrimethoxysilane, or γ-glycid. Xypropyltriethoxysilane, or a mixture of either or both, and the curing catalyst is iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetyl. The step is to be either acetonato titanium or dihydroxybislactato titanium, which is then performed. In the step of laminating the gas barrier layer, a mixture of an olefin polymer dissolved in an aqueous solvent and a second silane compound is further added, and further, iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride. , Diisopropoxybisacetylacetonato titanium, or dihydroxybislactoto titanium is added as a curing catalyst, and the mixing ratio of the olefin polymer and the second silane compound is the olefin polymer. 5 parts by weight or more of the second silane-based compound with respect to 100 parts by weight 10
0 parts by weight or less, and the second silane compound is tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane,
Any one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, or a mixture of two or more selected from these coating agents. Is a step of laminating a gas barrier layer having thermosetting property, which is formed by applying.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. The embodiment shown here is merely an example, and the embodiment is not necessarily limited to this embodiment. (Embodiment 1) A gas barrier film for a packaging material according to the present invention will be described as a first embodiment. Although not described in detail here, it is possible to manufacture the gas barrier film for a packaging material according to the present embodiment by sequentially performing the method referred to in the following description, that is, it is the present invention. This is a method for producing such a gas barrier film for packaging material. This manufacturing method is the same in the other embodiments.

The gas barrier film for a packaging material according to the present embodiment is a plastic film in which an inorganic oxide vapor deposition film is laminated on at least one surface, and at least the vapor deposition film protective film is provided on the inorganic oxide vapor deposition film. A vapor deposition film protective layer is laminated through a protective layer forming step which is formed by applying a coating material.

An anchor coat layer may be provided between the plastic film and the inorganic oxide vapor deposition film in the anchor coat layer forming step.

Further, it is desirable that the vapor deposition film protective layer is a layer having a thermosetting property and a layer in which the curing reaction is promoted by the epoxy ring-opening polymerization and the condensation reaction, the reason for which will be described later.

Each part will be described below in order. The type of plastic film used as the base material is not particularly limited, and is versatile, such as polyethylene terephthalate film (PET film).
Any material can be used as long as it can be suitably used in consideration of distribution and the like.

Next, the anchor coat layer may be provided by a known method, for example, wet coating, sputtering, vapor deposition or the like. Although it is possible to omit this anchor coat layer, provision of the anchor coat layer further increases the interlayer adhesion between the base film and the inorganic oxide vapor deposition film. .

Next, an inorganic oxide vapor deposition film may be used, as long as it is a vapor deposition film having a known gas barrier property. For example, a vapor deposition film using silicon oxide, aluminum oxide or the like as a vapor deposition source may be used for sputtering or the like. It may be formed on the surface of the base material via the anchor coat layer by a known method described above, or directly formed on the surface of the base material.

Next, the vapor deposition film protective layer will be described. This vapor-deposited film protective layer acts as a layer for protecting the above-mentioned inorganic oxide vapor-deposited film, a so-called top coat, but by forming this layer on the surface of the inorganic oxide vapor-deposited film, the inorganic oxide vapor-deposited film is cracked, for example. Not only can it be protected from scratches, stains, etc., but at the same time, if the vapor-deposited film protective layer is provided with a gas barrier property, the gas barrier property of the inorganic oxide vapor-deposited film can be further complemented. That is,
When only the inorganic oxide vapor deposition film is provided, if the film thickness is increased to improve the gas barrier property, there are problems such as lack of flexibility and easy occurrence of cracks. Cracks caused by increasing the thickness of the inorganic oxide vapor deposition film by providing a vapor deposition film protective layer having gas barrier properties on top of that provided, that is, while keeping the thickness of the inorganic oxide vapor deposition film unchanged. It is possible to avoid the occurrence, and as a result, it is possible to improve the gas barrier property while ensuring flexibility.

Further, it is desirable that the vapor deposition film protective layer is a layer having thermosetting property, and further, the curing reaction is promoted by the epoxy ring-opening polymerization and the condensation reaction by the curing catalyst. Having such properties, that is, in addition to the usual condensation, improves the reaction rate by causing an addition reaction between a silanol group and an epoxy group, and also an inorganic oxide vapor deposition of an oxide anion in a ring-opening reaction of an epoxy group. Since the coordination to the dangling bond (oxygen defect) of the film occurs,
As a result, it is possible to protect the inorganic acid vapor deposition film and to complement the gas barrier properties of the inorganic oxide vapor deposition film.

Then, the vapor deposition film protective coating material for forming the vapor deposition film protective layer in the gas barrier film in the present embodiment, which is a vapor deposition film protective layer satisfying the above conditions, will be described. In addition, the silane-based compound in the following description of the present embodiment is referred to as a first silane-based compound. This is to avoid confusion with the silane compound in the second embodiment, but the first silane compound and the second silane compound may be the same silane compound or different silane compounds. I don't mind.

This vapor deposition film protective coating material is manufactured as follows. That is, 50 parts by weight or more of pure water is mixed with 100 parts by weight of the first silane compound to prepare a mixed solution, and then either the hydrochloric acid or acetic acid is added to the mixed solution. The pH of the mixed solution is 3 to
5 to prepare a base material, then dilute the base material to prepare a diluent, and then add a curing catalyst for promoting curing of the first silane compound to the first silane. 1 part by weight or more based on 100 parts by weight of the base compound 10
It can be obtained by adding not more than part by weight to the diluent.

The hydrochloric acid used in the above method is
For example, 1N hydrochloric acid is preferable. Further, the main component is diluted with a diluting liquid, and a solution or solvent capable of improving the film-forming property and dissolving the curing catalyst described later may be used for this.

More specifically, the first silane compound having an epoxy group is 100 parts by weight, and pure water is 100 parts by weight per 100 parts by weight of the first silane compound.
While mixing and stirring 1 part by weight, 1N hydrochloric acid or acetic acid is added thereto in an amount of 1 part by weight or more and 4 parts by weight or less based on 100 parts by weight of the first silane compound.
Added to promote hydrolysis, the main agent thus obtained is stirred for 1 hour, and then the main agent is diluted with a diluting solution for improving the film forming property of the vapor deposition film protective coating material, Then, a curing catalyst for accelerating the curing of the vapor deposition film protective coating material is added thereto.
It is obtained by adding 1 part by weight or more and 10 parts by weight or less with respect to parts by weight.

Either 1N hydrochloric acid or acetic acid is added to 1 part of 100 parts by weight of the first silane compound.
An amount of 4 parts by weight or more is added, but by setting this value to 1.5 parts by weight, a more preferable pH can be obtained, so that the workability becomes suitable and the hydrolyzability is excellent. It can be something.

Further, the main ingredient is diluted with a dilute solution for improving the film forming property of the vapor deposition film protective coating material, but the dilute solution is not particularly limited as long as it is a known solution. In the present embodiment, it is possible to obtain preferable results by using an isopropyl alcohol / n-butanol = 1/1 solution. The mixing ratio of isopropyl alcohol / n-butanol is not necessarily limited to 1/1, but by setting this ratio, the concentration of the main agent becomes a concentration that facilitates film formation. That is, it becomes easy to make the appearance of the vapor deposition film protective layer excellent, the leveling is good, and the concentration is suitable for forming a layer in which cracks are less likely to occur, and the film wettability is also excellent. is there.

Further, the curing catalyst for promoting the curing of the vapor deposition film protective coating material is added in an amount of 1 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the first silane compound. When this amount is 2 parts by weight or more and 8 parts by weight or less, preferable results are obtained, and when it is 4 parts by weight, further preferable results are obtained. That is, the curing is effectively promoted. Then, the curing catalyst used here is preferably, for example, a metal complex, and specifically, iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, diisopropoxybisacetylacetonato titanium, dihydroxybislacta. It is preferable to use titanium, especially aluminum acetylacetonate. Other than these, it is also suitable to use tin tetrachloride or the like. Then, by adding 4 parts by weight of aluminum acetylacetonate to 100 parts by weight of the first silane-based compound in the main component, the added aluminum acetylacetonate acts as a reaction catalyst. At the same time, the addition reaction between the silanol group and the epoxy group and the ring opening reaction of the epoxy group are promoted, and as a result, the formation of the vapor deposition film protective layer can be accelerated.

This point will be described in more detail. By coating the vapor deposition film protective coating material, a vapor deposition film protective layer mainly containing a silane-based compound is formed, but at this time, if the silane-based compound alone is used, the condensation reaction rate is extremely slow, so curing The reaction process is time consuming and therefore not suitable for practical high speed machining operations. However, if a curing catalyst is added to the vapor deposition film protective coating material mainly composed of silane-based compounds, the curing catalyst functions to accelerate the reaction. When the material is applied, not only the condensation reaction of the silane-based compound but also the addition reaction of the epoxy group and the silanol group and the ring-opening reaction of the epoxy group will be added, which accelerates the curing reaction process accordingly. As a result, the gas barrier film according to the present embodiment can be used for high-speed processing such as roll-to-roll processing. Further, since the chemical bond with the vapor deposition film becomes strong, the protection of the inorganic oxide vapor deposition film and the effect of complementing the gas barrier property of the inorganic oxide vapor deposition film can be improved.

Since the vapor deposition film protective layer formed as a result has an organic functional group in the polysiloxane skeleton, the gas barrier film according to the present embodiment can ensure flexibility. Further, since the gas barrier property can be ensured by having a polysiloxane skeleton, the gas barrier property of the original inorganic oxide vapor deposition film can be complemented, and the scratch resistance and the stain resistance are more excellent. I can. Although aluminum acetylacetonate is used as the curing catalyst in the present embodiment as described above, an aluminum complex other than this may be used, or any other known curing catalyst may be used.

Here, the first silane compound is γ-
Glycidoxypropyltrimethoxysilane, or γ-glycidoxypropyltriethoxysilane, which is a mixture of either or both, and more preferably the above state, that is, the vapor deposition film protective coating material. The curing process is facilitated. Further, by selecting these, cracks are less likely to occur, and the wettability to the film can be made more suitable. Further, by selecting these, the effect that the adhesive strength is improved by the chemical bond of the unreacted functional group with the sealant adhesive is also obtained. And, the effect of further improving the crack resistance and the like is obtained as initially intended.

The method of applying the vapor deposition film protective coating material thus obtained to the inorganic oxide vapor deposition film may be a conventionally known method. That is, a gravure method, a dipping method, a bar coater method and the like. After the coating, the vapor-deposited film protective layer is formed by drying it by a conventionally known method. The film thickness of the vapor deposition film protective layer is preferably 0.03 to 3 μm, and more preferably 0.05 to 0.1 μm. As described above, since the vapor deposition film protective layer is provided in place of increasing the thickness of the inorganic oxide vapor deposition film, increasing the thickness of the vapor deposition film protective layer can prevent cracks from occurring, which is the original purpose. This is because it becomes difficult to secure performance such as flexibility.
In addition, it is for reducing the volume contraction stress due to heat of the vapor deposition film protective layer, and because the vapor deposition film protective layer is intended to protect the inorganic oxide vapor deposition film and complement the gas barrier property of it. , Never be thicker than necessary.

With the gas barrier film according to the present embodiment formed as described above, the performance deterioration of the inorganic oxide vapor deposition film can be prevented by providing the vapor deposition film protective layer, and the result is obtained. The gas barrier film is superior in water resistance and barrier property after boiling compared with the conventional one, and also has flexibility because it has some organic functional groups, that is, a gas barrier film having excellent crack resistance. To get.

(Embodiment 2) Next, as a second embodiment, a gas barrier film according to the present invention, which is different from the first embodiment, will be described.

The gas barrier film according to the present embodiment is a plastic film having an inorganic oxide vapor deposition film laminated on at least one surface thereof, and at least a coating agent is applied onto the inorganic oxide vapor deposition film. A gas barrier layer is laminated through a gas barrier layer forming step of forming a gas barrier layer.

Here, similarly to the first embodiment, it is possible to provide an anchor coat layer between the plastic film and the inorganic oxide vapor deposition film through an anchor coat layer forming step. Further, the gas barrier layer may be a thermosetting layer.

Therefore, in the gas barrier film according to the present embodiment, an inorganic oxide vapor deposition film is formed on one surface of a plastic film via an anchor coat layer, and a coating agent is further applied thereon to laminate the gas barrier layer. It is assumed that Each part will be described below. The plastic film, the anchor coat layer, and the inorganic oxide vapor deposition film used as the base material are the same as those in the first embodiment, and therefore their explanations are omitted here.

The coating agent for forming the gas barrier layer in the present embodiment is preferably an organic-inorganic hybrid polymer. More specifically, this organic-inorganic hybrid polymer is preferably a mixture of an olefin polymer and a second silane compound. In addition, in order to avoid confusion with the silane-based compound in the first embodiment, the silane-based compound used in this embodiment is referred to as a second silane-based compound.

It is also possible to add a curing catalyst to this organic-inorganic hybrid polymer. This is because the addition of the curing catalyst promotes crosslinking of the applied coating agent and improves the performance of the gas barrier layer. The curing catalyst to be added is, for example, iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonato titanium, or dihydroxybislactato titanium.

The mixing ratio of the olefin polymer and the second silane compound is such that the olefin polymer 1 is
It is preferable that the amount of the second silane compound is 5 parts by weight or more and 100 parts by weight or less with respect to 00 parts by weight.

As the second silane compound used in the second embodiment described above, for example, tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane. , Dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-
Glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, It is preferable to use any one of the above or a mixture of a plurality of these. By selecting these, the pot life of the coating agent and the appearance at the time of application can be made suitable, the degree of freedom in the addition amount of the second silane compound can be easily obtained, and good gas barrier properties can be obtained. Will be able to get.

Thus, the olefin polymer and the second
By forming an organic-inorganic hybrid polymer mixed with a silane compound, the hydrophilic hydroxyl group of the olefin polymer and the reactive functional group of the silane compound are condensed and crosslinked,
A network structure is formed, and as a result, water resistance and heat resistance can be improved, and also gas barrier properties can be improved.

As described above, in the gas barrier film according to the second embodiment, by applying the coating agent, the gas barrier film of a different kind from the inorganic oxide vapor deposition film can be obtained without increasing the thickness of the inorganic oxide vapor deposition film. By stacking the gas barrier layer, it is possible to improve the gas barrier property, and because the gas barrier layer in the present embodiment is derived from a silane compound, the obtained gas barrier film has excellent crack resistance, It becomes possible to have flexibility.

(Third Embodiment) Next, a gas barrier film according to the present invention, which is different from any of the above-described embodiments, will be described as a third embodiment.

The gas barrier film according to the present embodiment is a plastic film having an inorganic oxide vapor deposition film laminated on at least one surface thereof, and at least the vapor deposition film protective coating material is provided on the inorganic oxide vapor deposition film. The vapor deposition film protective layer formed by coating and the gas barrier layer formed by coating a coating agent are laminated in this order. That is, the vapor barrier layer described in the first embodiment is further provided with the gas barrier layer described in the second embodiment on the surface thereof. The vapor deposition film protective layer and the gas barrier layer are the same as those described in the first embodiment and the second embodiment, respectively.

By stacking these two layers, the performance of the inorganic oxide vapor deposition film is prevented from deteriorating by the action of the vapor deposition film protective layer without increasing the thickness of the inorganic oxide vapor deposition film, and further, the inorganic barrier layer is used. The gas barrier property of the oxide vapor deposition film can be complemented.

[0053]

As described above, according to the gas barrier film of the present invention, by positively utilizing the ring-opening polymerization and the condensation reaction in the silane compound to be thermally cured,
A film having a polysiloxane skeleton is formed, and as a result,
In particular, it becomes possible to obtain a gas barrier film which has flexibility, reduces the occurrence of cracks, etc., and can form a coating film which can be processed at high speed.

Claims (8)

(57) [Claims] 1. A plastic film having an inorganic oxide vapor deposition film laminated on at least one surface thereof, wherein the inorganic film is formed by applying a vapor deposition film protective coating on the inorganic oxide vapor deposition film. A vapor-deposited film protective layer for protecting an oxide vapor-deposited film is laminated, and the vapor-deposited film protective layer has thermosetting property, and the curing reaction is promoted by epoxy ring-opening polymerization and condensation reaction, and the film is further formed. A layer having a thickness of 0.03 μm to 3 μm, wherein the vapor deposition film protective coating material forming the vapor deposition film protective layer is a first silane compound, and pure water is 100 parts by weight of the first silane compound. To 50
By mixing more than one part by weight to prepare a mixed solution, and then either hydrochloric acid or acetic acid is added to the mixed solution so that the pH of the mixed solution becomes 3 to 5 to prepare a main agent, Next, the base material is diluted to prepare a diluent, and then a curing catalyst for promoting the curing of the first silane compound is added in an amount of 1 part by weight or more and 10 parts by weight or more with respect to 100 parts by weight of the first silane compound. Parts below, the coating material obtained by adding to the diluent, wherein the first silane compound is γ-glycidoxypropyltrimethoxysilane, or γ
-Glycidoxypropyltriethoxysilane, which is a mixture of either or both, wherein the curing catalyst is iron acetylacetonate, zinc acetylacetonate,
A gas barrier film for packaging material, which is any one of aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonato titanium, and dihydroxybislactato titanium. 2. A plastic film in which an inorganic oxide vapor deposition film is laminated on at least one surface via an anchor coat layer, wherein a vapor deposition film protective coating material is applied onto the inorganic oxide vapor deposition film. Formed by laminating a vapor deposition film protective layer for protecting the inorganic oxide vapor deposition film, wherein the vapor deposition film protective layer has a thermosetting property and a curing reaction by an epoxy ring-opening polymerization and a condensation reaction. Is further promoted, and the film thickness is 0.03 μm to 3 μm, and the vapor deposition film protective coating material forming the vapor deposition film protective layer comprises a first silane compound, pure water and the first pure silane compound. 50 to 100 parts by weight of silane compound
By mixing more than one part by weight to prepare a mixed solution, and then either hydrochloric acid or acetic acid is added to the mixed solution so that the pH of the mixed solution becomes 3 to 5 to prepare a main agent, Next, the base material is diluted to prepare a diluent, and then a curing catalyst for promoting the curing of the first silane compound is added in an amount of 1 part by weight or more and 10 parts by weight or more with respect to 100 parts by weight of the first silane compound. Parts below, the coating material obtained by adding to the diluent, wherein the first silane compound is γ-glycidoxypropyltrimethoxysilane, or γ
-Glycidoxypropyltriethoxysilane, which is a mixture of either or both, wherein the curing catalyst is iron acetylacetonate, zinc acetylacetonate,
A gas barrier film for packaging material, which is any one of aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonato titanium, and dihydroxybislactato titanium. 3. A plastic film having an inorganic oxide vapor deposition film laminated on at least one surface thereof via an anchor coat layer, which is formed by applying a coating agent on the inorganic oxide vapor deposition film. A gas barrier layer is laminated, the gas barrier layer is a layer having a thermosetting property, and the coating agent is a mixture of an olefin polymer dissolved in an aqueous solvent and a second silane compound. In addition, any one of iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybis acetylacetonato titanium, and dihydroxybislactato titanium is added as a curing catalyst. The mixing ratio of the olefin-based polymer and the second silane-based compound is The amount of the second silane compound is 5 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the olefin polymer, and the second silane compound is tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, or vinyl. Triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, or any of these It is a mixture of several, characterized by a gas barrier film for packaging materials. 4. A plastic film having an inorganic oxide vapor deposition film laminated on at least one surface thereof via an anchor coat layer, wherein at least the vapor deposition film protective coating material is applied onto the inorganic oxide vapor deposition film. And a gas barrier layer formed by applying a coating agent are laminated in this order, and the vapor deposition film protective coating material forming the vapor deposition film protective layer is 50 parts of the first silane-based compound and 50 parts of pure water based on 100 parts by weight of the first silane-based compound.
By mixing more than one part by weight to prepare a mixed solution, and then either hydrochloric acid or acetic acid is added to the mixed solution so that the pH of the mixed solution becomes 3 to 5 to prepare a main agent, Next, the base material is diluted to prepare a diluent, and then a curing catalyst for promoting the curing of the first silane compound is added in an amount of 1 part by weight or more and 10 parts by weight or more with respect to 100 parts by weight of the first silane compound. Parts below, the coating material obtained by adding to the diluent, wherein the first silane compound is γ-glycidoxypropyltrimethoxysilane, or γ
-Glycidoxypropyltriethoxysilane, which is a mixture of either or both, wherein the curing catalyst is iron acetylacetonate, zinc acetylacetonate,
Aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonato titanium, or dihydroxybislactato titanium, the gas barrier layer is a layer having a thermosetting property, the coating agent, A mixture of an olefin polymer dissolved in an aqueous solvent and a second silane compound is further mixed with iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetate. Any one of nato titanium and dihydroxybislactato titanium is added as a curing catalyst, and the mixing ratio of the olefin polymer and the second silane compound is 100 parts by weight of the olefin polymer. 5 parts by weight or more of the second silane compound 100 And the second silane compound is tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, γ-glyce. Sidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltrisilane A gas barrier film for a packaging material, which is one of ethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, or a mixture of two or more thereof. 5. A plastic film having an inorganic oxide vapor deposition film laminated on at least one surface thereof, wherein a thermosetting and first silane-based compound is formed on the inorganic oxide vapor deposition film. 50 parts of pure water based on 100 parts by weight of the first silane compound
By mixing more than one part by weight to prepare a mixed solution, and then either hydrochloric acid or acetic acid is added to the mixed solution so that the pH of the mixed solution becomes 3 to 5 to prepare a main agent, Next, the base material is diluted to prepare a diluent, and then a curing catalyst for promoting the curing of the first silane compound is added in an amount of 1 part by weight or more and 10 parts by weight or more with respect to 100 parts by weight of the first silane compound. Part below, by adding to the diluent, by applying a vapor deposition film protective coating material obtained by, and thermally curing this, by the curing catalyst, by epoxy ring-opening polymerization and condensation reaction, the vapor deposition By forming a vapor deposition film protective layer that protects the inorganic oxide vapor deposition film by accelerating the curing of the film protective coating material, the first silane-based compound is γ-glycidoxypropyltriene. Methoxy Run, or γ
-Glycidoxypropyltriethoxysilane, which is a mixture of either or both of the above, and wherein the curing catalyst is iron acetylacetonate, zinc acetylacetonate,
It is any one of aluminum acetylacetonate, tin tetrachloride, diisopropoxy bis acetyl acetonato titanium, and dihydroxy bis lactoto titanium, The manufacturing method of the gas barrier film for packaging materials which has a process characterized by the above-mentioned. 6. A plastic film having an inorganic oxide vapor deposition film laminated on at least one surface thereof via an anchor coat layer, and having a thermosetting property on the inorganic oxide vapor deposition film, Further, the first silane compound is added to pure water in an amount of 50 parts by weight based on 100 parts by weight of the first silane compound.
By mixing more than one part by weight to prepare a mixed solution, and then either hydrochloric acid or acetic acid is added to the mixed solution so that the pH of the mixed solution becomes 3 to 5 to prepare a main agent, Next, the base material is diluted to prepare a diluent, and then a curing catalyst for promoting the curing of the first silane compound is added in an amount of 1 part by weight or more and 10 parts by weight or more with respect to 100 parts by weight of the first silane compound. Part below, by adding to the diluent, by applying a vapor deposition film protective coating material obtained by, and thermally curing this, by the curing catalyst, by epoxy ring-opening polymerization and condensation reaction, the vapor deposition By forming a vapor deposition film protective layer that protects the inorganic oxide vapor deposition film by accelerating the curing of the film protective coating material, the first silane-based compound is γ-glycidoxypropyltriene. Methoxy Run, or γ
-Glycidoxypropyltriethoxysilane, which is a mixture of either or both of the above, and wherein the curing catalyst is iron acetylacetonate, zinc acetylacetonate,
It is any one of aluminum acetylacetonate, tin tetrachloride, diisopropoxy bis acetyl acetonato titanium, and dihydroxy bis lactoto titanium, The manufacturing method of the gas barrier film for packaging materials which has a process characterized by the above-mentioned. 7. A plastic film having an inorganic oxide vapor deposition film laminated on at least one surface thereof via an anchor coat layer, and an olefin dissolved in an aqueous solvent on the inorganic oxide vapor deposition film. In addition to a mixture of a base polymer and a second silane compound, iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonato titanium, dihydroxybislacta Titanium is added as a curing catalyst, and the mixing ratio of the olefin polymer and the second silane compound is such that the second silane compound is 100 parts by weight of the olefin polymer. 5 parts by weight or more and 100 parts by weight or less, wherein the second silane-based compound is tetrameth Sisilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane , Γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltri Ethoxysilane, or a coating agent that is a mixture of two or more selected from these, and a step of laminating a gas barrier layer having thermosetting property, which is formed by applying the coating agent. To method of manufacturing a packaging material for a gas barrier film. 8. A plastic film having an inorganic oxide vapor deposition film laminated on at least one surface thereof via an anchor coat layer, wherein at least the vapor deposition film protective coating material is applied onto the inorganic oxide vapor deposition film. And a gas barrier layer formed by applying a coating agent are laminated in this order. Specifically, first, the vapor deposition film protective layer is laminated. A step of forming a first silane-based compound having a thermosetting property on the inorganic oxide deposited film, and adding pure water to 100 parts by weight of the first silane-based compound;
By mixing more than one part by weight to prepare a mixed solution, and then either hydrochloric acid or acetic acid is added to the mixed solution so that the pH of the mixed solution becomes 3 to 5 to prepare a main agent, Next, the base material is diluted to prepare a diluent, and then a curing catalyst for promoting the curing of the first silane compound is added in an amount of 1 part by weight or more and 10 parts by weight or more with respect to 100 parts by weight of the first silane compound. Part below, by adding to the diluent, by applying a vapor deposition film protective coating material obtained by, and thermally curing this, by the curing catalyst, by epoxy ring-opening polymerization and condensation reaction, the vapor deposition A step of forming a vapor deposition film protective layer that protects the inorganic oxide vapor deposition film by accelerating the curing of the film protective coating material, wherein the first silane compound is γ-glycid Xypropylt Limethoxysilane, or γ
-Glycidoxypropyltriethoxysilane, which is a mixture of either or both of the above, and wherein the curing catalyst is iron acetylacetonate, zinc acetylacetonate,
Aluminum acetylacetonate, tin tetrachloride, titanium diisopropoxybisacetylacetonato, or titanium dihydroxybislactato, which is the process of forming a gas barrier layer and then dissolving it in an aqueous solvent. In addition to the mixture of the olefin polymer and the second silane compound, iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonato titanium, dihydroxy. Any one of bislactotitanium is added as a curing catalyst, and the mixing ratio of the olefin polymer and the second silane compound is 100 parts by weight of the olefin polymer. 5 parts by weight or more and 100 parts by weight of the compound And the second silane compound is tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, γ-glycidoxy. Propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane , Γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, or a coating agent that is a mixture of two or more selected from these, having a thermosetting property. Moth A method of manufacturing a gas barrier film for packaging material, which comprises a step of laminating a barrier layer.