JP7322426B2 - High interlayer adhesion gas barrier deposition film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a high interlayer adhesion gas barrier vapor-deposited film having a substrate layer and a gas barrier layer, and a gas barrier laminate, a gas barrier packaging material, and a gas barrier package produced using the high interlayer adhesion gas barrier vapor-deposited film. .
INDUSTRIAL APPLICABILITY The gas barrier vapor-deposited film with high interlayer adhesion according to the present invention can be applied to products in various fields that require high barrier properties, and can be particularly suitably used as packaging materials. For example, it can be used for applications such as pharmaceuticals, cosmetics, chemicals, and food and drink.

In packaging materials, barrier laminated films that can stably demonstrate higher barrier properties that are not affected by temperature, humidity, etc. are needed to prevent deterioration of contents and maintain their functions and properties. In response to this demand, a barrier laminated film having a multi-layer structure in which a barrier layer consisting of a thin film of deposited film of silicon oxide, aluminum oxide, or the like and a barrier coating layer are laminated on a resin base material has also been developed.
For example, Patent Document 1 discloses a substrate made of a plastic material, a first evaporated thin film layer provided on the substrate, and a water-soluble polymer provided on the first evaporated thin film layer. a laminate comprising a gas-barrier intermediate layer formed by applying a coating agent containing A gas barrier laminate having a primer layer composed of a polyol, an isocyanate compound and a silane coupling agent provided therebetween is disclosed.
Patent Document 2 discloses a base film made of a synthetic resin, a flattening layer laminated on at least one surface of the base film, and an inorganic oxide or A gas barrier layer formed from an inorganic nitride, and a planarizing layer formed by a sol-gel method using a composition containing another metal alkoxide and/or its hydrolyzate laminated on the outer surface of this gas barrier layer. A high barrier sheet is disclosed comprising:

However, the multi-layered barrier laminate film described above not only raises costs such as raw material costs and equipment operating costs because the number of processes increases in the manufacturing method, but also quality checks for each layer and quality control based on that. Complex work such as management correction and history management is required.
Therefore, there is a demand for a barrier film with excellent barrier properties that solves the above-described problems in production and does not cause a decrease in productivity.

WO2002/083408 JP 2005-324469 A

The present invention solves the above-mentioned problems, is excellent in manufacturing suitability, has a simple layer structure, has excellent gas barrier properties, and has excellent interlayer adhesion strength between the base material layer and the metal oxide deposition layer. An object of the present invention is to provide a gas barrier deposited film, and a laminate, packaging material, and package using the same.

As a result of various investigations, the present inventors have found that a base material layer made of a specific resin and layer structure and having a specific surface roughness and a metal oxide deposition layer laminated on the base layer in contact therewith. We have found that a vapor-deposited film having a specific layer configuration, including a gas barrier layer, achieves the above objectives.

That is, the present invention is characterized by the following points.
1. A high interlayer adhesion gas barrier deposition film having a substrate layer and a gas barrier layer,
The base layer has a layer made of a biaxially stretched resin film containing a polyolefin resin,
The gas barrier layer has a metal oxide deposition layer,
The metal oxide deposition layer is laminated on and in contact with the base material layer,
The surface roughness of the surface of the base material layer on which the gas barrier layer is laminated is
Ra is 7 nm or less,
characterized by a PV value of 50 nm or less,
High interlayer adhesion gas barrier deposition film.
2. The substrate layer further has a PVA-based resin layer on its surface,
The metal oxide deposition layer is laminated in contact with the PVA-based resin layer,
1. The high interlayer adhesion gas barrier deposition film according to 1 above.
3. 3. The high interlayer adhesion gas barrier deposition film according to 1 or 2 above, wherein the metal oxide deposition layer is a silicon oxide deposition layer deposited by a CVD method.
4. 3. The high interlayer adhesion gas barrier vapor-deposited film according to 1 or 2 above, wherein the metal oxide vapor-deposited layer is an aluminum oxide layer vapor-deposited by a PVD method.
5. The gas barrier layer further has a barrier protective layer,
The barrier protective layer is a layer formed from a resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin, and is laminated on and in contact with the metal oxide deposition layer,
5. The high interlayer adhesion gas barrier deposition film according to any one of 1 to 4 above.
6. 6. The high interlayer adhesion gas barrier deposition film according to any one of 1 to 5 above, wherein the polyolefin resin is a polypropylene resin.
7. A high interlayer adhesion gas barrier laminate having a layer composed of the high interlayer adhesion gas barrier vapor-deposited film according to any one of 1 to 6 above and a sealant layer containing a heat-sealing resin,
The sealant layer is laminated on the surface of the high interlayer adhesion gas barrier vapor-deposited film on the side opposite to the base layer,
High interlayer adhesion gas barrier laminate.
8. 8. The high interlayer adhesion gas barrier laminate according to 7 above, wherein the heat-sealing resin is a polypropylene resin.
9. 9. The high interlayer adhesion gas barrier laminate according to 7 or 8 above, wherein the sealant layer is a layer made of an unstretched polypropylene resin film.
10. The polyolefin-based resin and the heat-sealing resin contain resins having the same basic skeleton,
The content of the resin having the same basic skeleton in the gas barrier laminate is 50% by mass or more,
The high interlayer adhesion gas barrier laminate according to any one of 7 to 9 above.
11. 11. The high interlayer adhesion gas barrier laminate according to 10 above, wherein the resin having the same basic skeleton is a polypropylene-based resin.
12. A high interlayer adhesion gas barrier packaging material produced from the high interlayer adhesion gas barrier laminate according to any one of 7 to 11 above.
13. 13. A high interlayer adhesion gas barrier package produced from the high interlayer adhesion gas barrier packaging material described in 12 above.
14. 13. A high interlayer adhesion gas barrier packaging bag produced from the high interlayer adhesion gas barrier packaging material described in 12 above.

The high interlayer adhesion gas barrier vapor deposition film of the present invention is excellent in manufacturing suitability, has a simple layer structure, yet exhibits extremely excellent gas barrier properties, and has excellent interlayer adhesion between the base material layer and the metal oxide vapor deposition layer. It can demonstrate strength.
In addition, the laminate, packaging material, and package produced from the high interlayer adhesion gas barrier vapor deposition film of the present invention have a simple layer structure, and yet have excellent gas barrier properties derived from the high interlayer adhesion gas barrier vapor deposition film. The interlayer adhesion strength between the substrate layer and the metal oxide deposition layer can be exhibited.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the high interlayer adhesion gas barrier vapor-deposited film of the present invention. FIG. 3 is a schematic cross-sectional view showing an example of another embodiment of the layer structure of the high interlayer adhesion gas barrier vapor-deposited film of the present invention. FIG. 4 is a schematic cross-sectional view showing yet another example of the layer structure of the high interlayer adhesion gas barrier vapor-deposited film of the present invention. FIG. 4 is a schematic cross-sectional view showing an example of another embodiment of the layer structure of the high interlayer adhesion gas barrier laminate of the present invention.

In each drawing, the sizes and proportions of members may be changed or exaggerated for the sake of clarity. In addition, for the sake of clarity, parts that are not necessary for explanation and symbols that are repeated may be omitted.
Furthermore, in each drawing, the uneven portion is illustrated as a pattern having clear corners, but it may be a shape with rounded corners.

The high interlayer adhesion gas barrier vapor-deposited film, high interlayer adhesion gas barrier laminate, high interlayer adhesion gas barrier packaging material, high interlayer adhesion gas barrier package, and high interlayer adhesion gas barrier packaging bag of the present invention are described in more detail below. . The present invention will be described by showing a specific example, but the present invention is not limited to this.

<High interlayer adhesion gas barrier deposition film>
The high interlayer adhesion gas barrier deposition film of the present invention has at least a substrate layer and a gas barrier layer, as shown in FIG.

[Base material layer]
The substrate layer has at least a layer made of a biaxially stretched resin film containing a polyolefin resin, and the surface on which the gas barrier layer is laminated has a specific surface roughness.

A polyolefin resin is a polymer or copolymer using an olefin monomer raw material, and a biaxially oriented resin film can be used for the base layer of the high interlayer adhesion gas barrier vapor-deposited film of the present invention for use as a packaging material. well-known polyolefin-based resins can be used.
Examples of such polyolefin-based resins include (co)polymers of alkene monomers having 2 to 8 carbon atoms such as polyethylene-based resins and polypropylene-based resins, and cyclic polyolefin-based resins. It is preferable to use an α-positioned alkene having a carbon-carbon double bond as a terminal, and a polypropylene-based resin is more preferable.
Crystallinity, flexibility and toughness can be modified by using a compound having a long linear chain such as 1-hexene or 1-octene as an α-olefin as a raw material monomer for copolymerization.

The thickness of the layer composed of the biaxially stretched resin film containing the polyolefin resin is preferably 10 μm or more and 50 μm or less. If the thickness is less than the above range, the rigidity of the substrate layer may be insufficient.

Since the substrate layer has a surface with the specific surface roughness, it can further have a resin layer on the side on which the gas barrier layer is laminated to reduce and smoothen the surface roughness. . As the resin layer, a PVA (polyvinyl alcohol) resin layer is preferable.

The PVA-based resin is a resin composed of a polymer or copolymer having a repeating unit represented by the following formula: -CH ₂ CH(OH)- in the main skeleton, and the resin having the above-mentioned repeating unit in the main skeleton. There is no particular limitation as long as it has various functional groups.
For example, a polyvinyl alcohol obtained by saponifying polyvinyl acetate or an ethylene/vinyl alcohol copolymer obtained by saponifying a copolymer of ethylene and vinyl acetate can be used.
The saponification degree of the PVA-based resin is preferably 80 to 100 mol%, more preferably 85 to 100 mol%, and particularly preferably 90 to 100 mol%. The higher the degree of saponification, the higher the gas barrier properties tend to be.

The thickness of the PVA-based resin layer is preferably 0.3 μm or more and 1.5 μm or less. If it is thinner than the above range, the effect of providing the PVA-based resin layer is difficult to be exhibited, and if it is thicker than the above-mentioned range, it tends to be difficult to make the thickness of the PVA-based resin layer uniform, and the rigidity is high. If it becomes too thick, handling of the vapor-deposited gas barrier film tends to become difficult.

The PVA-based resin layer can be formed by a known method. In order to form a thin and uniform PVA-based resin layer, a resin composition for the PVA-based resin layer is applied to the surface of the substrate layer. , preferably by drying.

(Surface roughness of base material layer)
The surface roughness Ra of the surface of the substrate layer on which the gas barrier layer is laminated is preferably 1 nm or more and 7 nm or less, more preferably 1 nm or more and 5 nm or less. It is difficult to prepare a substrate layer having an Ra smaller than the above range, and even if it is realized, the cost becomes too high to be practical. It becomes weaker and the gas barrier property is likely to be deteriorated.

The PV value of the surface roughness of the surface of the substrate layer on which the gas barrier layer is laminated is preferably 10 nm or more and 50 nm or less, more preferably 10 nm or more and 40 nm or less. It is difficult to prepare a substrate layer having an Ra smaller than the above range, and even if it is realized, the cost becomes too high to be practical. It becomes weaker and the gas barrier property is likely to be deteriorated.

As for the surface roughness of the surface of the substrate layer on which the gas barrier layer is laminated, the Ra and/or the PV value are preferably within their respective specified ranges, and both may be within their respective specified ranges. more preferred.

(Ra)
Surface roughness Ra is the arithmetic mean roughness defined in JIS B 0601:2001. Specifically, the roughness curve of the substrate surface is measured, only the reference length L is extracted from the roughness curve in the direction of the average line, the direction of the average line of the extracted portion is the X axis, and the longitudinal magnification A line is drawn in the X-axis direction at the center of the roughness curve, and the total area on the curve obtained by the center line is divided by the length L, and the roughness curve is y = f (x) is obtained by the following formula. The unit is μm, nm, etc., according to the length unit used for measurement.

(PV value)
The PV value of the surface roughness is obtained by measuring the roughness curve of the substrate surface, extracting only the reference length L from the roughness curve in the direction of the average line, and It represents the difference between the highest point (Peak) and the lowest point (Valley) when the roughness curve is represented by y=f(x) with the X axis and Y axis representing the direction of longitudinal magnification. , given by the following formula: The unit is μm, nm, etc., according to the length unit used for measurement. Synonymous with Rz.
PV value = | f(x) _max - f(x) _min |

[Method for adjusting surface roughness of substrate layer]
A substrate layer with a small surface roughness can be obtained by a known method.
For example, when the substrate layer is produced, it is sandwiched between smooth rolls with a small surface roughness such as an ultra-mirror chill roll. A substrate layer with a small thickness can be produced. In this case, the surface roughness of the substrate layer can be adjusted by adjusting the surface roughness of the roll surface.
Alternatively, it can also be produced by applying a resin composition capable of forming a surface state with very uniform and low surface roughness on the surface of the substrate layer and drying. If necessary, a leveling agent or the like may be added to the resin composition.

As a specific example of the case of using a smooth roll, for example, in the case of producing by the extrusion method, the resin composition for the base material layer is heated and melted, and expanded and stretched in the necessary width direction with a T die. The surface roughness of the resin film can be reduced by extruding the resin film in a curtain shape, allowing the melt to flow down onto the surfaces of a pair of rolls, and sandwiching it between smooth rolls having a small surface roughness.
Alternatively, the resin composition constituting the surface resin layer of the base material layer is heated and melted, expanded and stretched in the necessary width direction with a T-die, and extruded in a curtain shape, and the melted product is placed on the surface of the resin film. The surface roughness of the surface resin layer can be reduced by allowing it to flow down and sandwiching it between smooth rolls having a small surface roughness.
Furthermore, a ready-made resin film or a ready-made resin film having a surface resin layer is softened by heating and sandwiched between smooth rolls having a small surface roughness, thereby reducing the surface roughness of the resin film or the surface layer. can be made smaller.
Even when the substrate layer has a surface resin layer, the surface roughness of the surface resin layer can be easily reduced by reducing the surface roughness of the underlying resin film.

[Gas barrier layer]
The gas barrier layer is a layer having at least a metal oxide deposition layer, and as shown in FIG. 2, can further have a barrier protective layer on the surface of the metal oxide deposition layer.

(Metal oxide deposition layer)
It is preferable that the metal oxide deposited layer is laminated on and in contact with the PVA-based resin layer of the substrate layer. By laminating the metal oxide deposition layer in contact with the PVA-based resin layer, the interlayer adhesion strength between the substrate layer and the metal oxide deposition layer can be increased, and the gas barrier property of the gas barrier deposition film can be enhanced. The same applies when the substrate layer has a smoothing resin layer such as a PVA-based resin layer.
The metal oxide vapor deposition layer can include a vapor deposition layer made of a known metal oxide by a known vapor deposition method used for packaging materials. Chemical Vapor Deposition method) or PVD method (Physical Vapor Deposition method) is preferable, and silicon oxide or aluminum oxide is preferable as the metal oxide.
Among others, it is preferable to include a silicon oxide deposition layer deposited by a CVD method and/or an aluminum oxide deposition layer deposited by a PVD method. These vapor-deposited metal oxide layers may be of a single layer or a multi-layer structure of two or more layers, or may be a multi-layer structure of two or more layers of two or more types.
The vapor deposition layer of silicon oxide and the vapor deposition layer of aluminum oxide mentioned above mean that they contain silicon oxide and aluminum oxide, respectively, as main components, and other metal components, metal oxide components, metal nitride components, metal A trace amount of carbide or the like may be contained.

Examples of CVD methods include plasma CVD, plasma polymerization, thermal CVD, photo CVD, and catalytic CVD. A plasma CVD method capable of forming is preferable, and even if the base material layer contains a polyolefin resin with relatively low heat resistance, the deterioration of the base material layer is suppressed to form a metal oxide deposition layer. can do.

Examples of the PVD method include a vacuum deposition method, a sputtering method, an ion plating method, an ion beam assist method, a cluster ion beam method, and the like, but the sputtering method is preferable because it facilitates vaporization of plasma raw materials.

(Barrier protective layer)
The barrier protective layer is a layer laminated on and in contact with the metal oxide vapor deposition layer, and physically and chemically protects and stabilizes the metal oxide vapor deposition layer, and also acts as a substrate layer/metal oxide vapor deposition layer. can stabilize the adhesion between layers and improve the barrier properties of the high interlayer adhesion gas barrier deposition film.
The barrier protective layer preferably has a chemical structure formed by a sol-gel hydrolytic condensation reaction of a barrier protective resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin. Moreover, the barrier protective resin composition may contain a solvent.
In the present invention, the hydrolysis reaction is a chemical reaction in which water molecules react with alkoxy groups, phenoxy groups, etc. of metal alkoxides to produce metal hydroxides, alcohols, phenols, and hydrogen molecules. is.
A condensation reaction is a chemical reaction in which metal hydroxides, including, in some cases, a hydroxyl-containing water-soluble resin, are combined by a dehydration reaction to form a polymer.
The hydrolysis-condensation reaction is a chemical reaction in which the above hydrolysis and condensation proceed continuously.

The barrier protective layer is formed by applying a barrier protective resin composition to the metal oxide deposition layer, drying by heating, and further aging by heating as necessary.
The main purpose of drying here is to remove the solvent in the barrier-protecting resin composition, and the barrier-protecting resin composition can be dried at a low temperature in a short period of time. The drying temperature is preferably 70° C. or higher and 120° C. or lower, more preferably 80° C. or higher and 110° C. or lower, since the solvent needs to be evaporated. If it is lower than the above range, the progress of drying is slow, and if it is higher than the above range, the barrier protective layer tends to become brittle. Although the drying time depends on the composition of the barrier protective resin composition, it is preferably 5 seconds or more and 30 minutes or less, more preferably 10 seconds or more and 10 minutes or less, within the above temperature range.

Furthermore, the aging (firing) is intended to promote the above hydrolysis-condensation reaction.
There are no particular restrictions on the aging conditions, and using a general coating machine and simple heating equipment, aging at 60 ° C. or less is possible. is possible.
The aging temperature is preferably 20°C or higher and 200°C or lower, more preferably 30°C or higher and 180°C or lower, and particularly preferably 40°C or higher and 120°C or lower.
In the present invention, the substrate layer is a low heat-resistant material having a layer made of a biaxially stretched resin film containing a polyolefin resin and a PVA resin layer. ° C. or lower is particularly preferred.
If it is lower than the above range, the progress of aging is slow, and if it is higher than the above range, the barrier protective layer tends to become brittle. The aging time is preferably 1 day or more and 70 days or less, more preferably 1 day or more and 5 days or less. Also, water is produced as a by-product during aging, but the amount produced is small, so there is no problem.

The thickness of the barrier protective layer is preferably 0.01 μm or more and 1 μm or less, more preferably 0.05 μm or more and 0.7 μm or less, and particularly preferably 0.1 μm or more and 0.5 μm or less. If the thickness is less than the above range, the effect of forming the barrier protective layer tends to be difficult to be exhibited sufficiently, and if it is larger than the above range, the flexibility tends to be inferior.
In addition, the barrier protective layer may be a single layer or may be composed of a plurality of layers (two or more layers) having the same or different compositions. It is possible to balance the gas barrier properties of the

Formation of the barrier protective layer is preferably performed in-line so as not to be exposed to the outside air, continuously with the formation of the metal oxide deposited layer. By continuously performing in-line, contamination and deterioration of the surface of the metal oxide vapor deposition layer are suppressed, the interlayer adhesion between the metal oxide vapor deposition layer and the barrier protective layer is strengthened, and the protective effect of the barrier protective layer is enhanced. can be done.

(solvent)
The solvent contained in the barrier-protecting resin composition may be any solvent capable of uniformly dissolving or dispersing the metal alkoxide, its hydrolyzate, hydrolyzed condensate oligomer, and hydroxyl group-containing water-soluble resin, and may be water or an organic solvent. A solvent may be used, and one kind or a mixture of two or more kinds may be used.
Further, the solvent is preferably water-soluble and preferably has an octanol/water partition coefficient Log _Pow of 0.5 or less.
Specific solvents include water, methanol (Log P _ow : -0.77), ethanol (Log P _ow : -0.30), 1-propanol (Log P _ow : 0.25), 2-propanol ( Log P _ow : 0.05), and mixtures thereof.

(metal alkoxide)
In the present invention, the metal alkoxide is a compound having a metal atom and an alkoxy group bonded to the metal atom, capable of producing a metal hydroxide after hydrolysis, and having two or more hydroxyl groups. is preferred, and may be a monomer or an oligomer. Moreover, it may be one that already has a hydroxyl group.
By having two or more hydroxyl groups, a continuous hydrolytic condensate can be formed by a sol-gel method to form a barrier protective layer.

Specific metal elements include silicon, aluminum, titanium, zirconium, tin, lead, borane, and the like, with silicon being particularly preferred. These metal elements can be used singly or in combination of two or more.

Specific alkoxy groups include aliphatic alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and 3-(meth)acryloxy; Among them, aliphatic alkoxy groups are preferred, and methoxy and ethoxy groups are more preferred. These alkoxy groups can be used singly or in combination of two or more.
The metal alkoxide may further have various functional groups, and specific functional groups include epoxy group, (meth)acrylic group, amino group, vinyl group and the like.

Specific metal alkoxides include trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, and methyltriethoxysilane. , methyltripropoxysilane, methyltributoxysilane, methyltriphenoxysilane, phenylphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltri Ethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, trifluoromethyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, γ-glycidoxypropyltrimethoxysilane, γ-glycid xypropylmethyldimethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylethoxysilane, or β Examples include various alkoxysilanes such as -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and phenoxysilanes. Among these, tetraethoxysilane and γ-glycidoxypropyltrimethoxysilane are preferred. The above metal alkoxides may be used singly or in combination of two or more.

The content of the metal atoms derived from the metal alkoxide in the barrier protective layer is preferably 20% by mass or more and 50% by mass or less, particularly preferably 25% by mass or more and 45% by mass or less, and 30% by mass or more and 40% by mass. Most preferred are: If the content is larger than the above range, the barrier protective layer tends to become brittle and the protective effect tends to be insufficient, and if the content is smaller than the above range, gas barrier properties tend to decrease. easy to become
In addition, the content of metal atoms derived from metal alkoxide in all non-solvent components in the barrier protective resin composition before hydrolysis is preferably 70% by mass or more and 99% by mass or less, and 80% by mass or more. , 97% by mass or less is particularly preferable, and 85% by mass or more and 95% by mass or less is most preferable. When the content is larger than the above range, the coating properties of the barrier protective resin composition tend to be poor, and the barrier protective layer tends to become brittle. is weakened, and the gas barrier property tends to be lowered.

(Hydroxyl group-containing water-soluble resin)
The hydroxyl-containing water-soluble resin provides excellent coatability to the barrier protective resin composition.
It makes it difficult for cracks to occur in the barrier protective layer and stabilizes the gas barrier properties.
Hydroxyl group-containing water-soluble resins are excellent in water solubility and have good affinity with metal alkoxides because they have hydroxyl groups. An excellent and homogeneous barrier protective layer can be obtained.
The hydroxyl group of the hydroxyl-containing water-soluble resin may be either a phenolic hydroxyl group or an alcoholic hydroxyl group, but an alcoholic hydroxyl group is preferred. The main chain structure of the molecular skeleton of the hydroxyl-containing water-soluble resin may be either an aromatic main chain or an aliphatic main chain, but the aliphatic main chain is preferable because of its excellent flexibility.

The content of the hydroxyl group-containing water-soluble resin in the barrier protective layer is preferably 5% by mass or more and 35% by mass or less, more preferably 10% by mass or more and 30% by mass or less, and 15% by mass or more and 25% by mass or less. Most preferred.
When the amount is less than the above range, the barrier protective layer tends to become brittle, and when the amount is more than the above range, the gas barrier properties tend to deteriorate.
In addition, the content of the hydroxyl group-containing water-soluble resin in all non-solvent components in the barrier protective resin composition before hydrolysis is preferably 1% by mass or more and 30% by mass or less, 3% by mass or more, 20% by mass or less is more preferable, and 5% by mass or more and 15% by mass or less is most preferable.
When the amount is less than the above range, the coating properties of the barrier protective resin composition tend to be poor, and the resulting barrier protective layer tends to be brittle. tend to be easy.

The degree of polymerization of the hydroxyl group-containing water-soluble resin is preferably 500 or more and 5000 or less, more preferably 1000 or more and 4000 or less, and particularly preferably 1500 or more and 3000 or less. The molecular weight of the hydroxyl group-containing water-soluble resin is preferably 20,000 or more and 230,000 or less, more preferably 40,000 or more and 180,000 or less, and particularly preferably 60,000 or more and 140,000 or less.
When the degree of polymerization and/or molecular weight of the hydroxyl group-containing water-soluble resin is within the above range, the coating properties of the barrier protective resin composition are likely to be favorable, the barrier protective layer is likely to obtain appropriate flexibility, and the protective effect is high. easy to become

The average number of hydroxyl groups in one molecule of the hydroxyl-containing water-soluble resin is preferably 2 or more, more preferably 400 or more and 5000 or less.
Specific compounds of the hydroxyl-containing water-soluble resin include polyacrylic acid, polyacrylamide, polyvinyl alcohol, poly-2-hydroxymethyl methacrylate, poly-2-hydroxyethyl methacrylate, polyethylene glycol, and the like. Here, these are the names of polymers of a single monomer, but copolymers in which other monomers are used together for modification may also be used.
Further examples include linear polymers in which two or more components are polymerized, such as a polymer of a bifunctional phenol compound and a bifunctional epoxy compound, and an ethylene-vinyl alcohol copolymer. These may be used alone or in combination of two or more.

Among these, polyvinyl alcohol and ethylene-vinyl alcohol copolymer are preferred because of their excellent flexibility and affinity, and those having a saponification degree of 90 mol% or more and 100 mol% or less are particularly preferred, and 95 mol. % or more and 100 mol % or less is more preferable, and 99 mol % or more and 100 mol % or less is most preferable. If the degree of saponification is smaller than the above range. The hardness of the barrier coating layer tends to decrease.
Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate, and ethylene/vinyl alcohol copolymer can be obtained by saponifying ethylene/vinyl acetate copolymer.

<High interlayer adhesion gas barrier laminate>
The high interlayer adhesion gas barrier laminate of the present invention is a laminate having a layer comprising the high interlayer adhesion gas barrier vapor-deposited film of the present invention and a sealant layer containing a heat-sealing resin.
The sealant layer is laminated on the surface of the high interlayer adhesion gas barrier vapor-deposited film on the side opposite to the substrate layer.

[Sealant layer]
As the heat-sealing resin contained in the sealant layer, known thermoplastic resins used for the sealant layer of packaging materials can be used.
Specific examples of heat-sealable resins include polyethylene-based resins such as LLDPE and LDPE; polypropylene-based resins; and polypropylene-based resins are preferred.
Polypropylene-based resins are copolymers such as random copolymers and block copolymers obtained by copolymerizing propylene with ethylene or butene monomers, even if they are propylene homopolymers obtained by polymerizing propylene monomers alone. or a mixture thereof.
Propylene homopolymers are excellent in rigidity, heat resistance, oil resistance, etc., random copolymers can have a lower melting point than homopolymers and are excellent in low-temperature sealing properties, and block copolymers are excellent in impact strength at low temperatures.
Polypropylene-based resins are excellent in heat-sealing properties, have higher heat resistance than ethylene-based resins, and have high resistance to retort treatment. Also, the polypropylene film for the sealant layer is preferably a non-stretched film.

The sealant layer may be a layer laminated by extrusion coating the above heat-sealing resin on another layer, and the heat-sealing resin once formed into a resin film is removed from the adhesive layer or the like. It may be a layer formed by laminating through layers, but it is preferably a layer formed after being formed into a non-stretched resin film.
That is, the sealant layer is more preferably a layer formed from a heat-sealable non-stretched polypropylene resin film.

The thickness of the sealant layer is preferably 20 µm or more and 150 µm or less, more preferably 30 µm or more and 100 µm or less, and particularly preferably 30 µm or more and 80 µm or less. If it is thinner than the above range, the heat-sealing property tends to be inferior, and if it is thicker than the above range, the flexibility tends to be inferior.
In addition, the sealant layer can be composed of two or more layers with the same or different compositions, and by sharing the intended action, it is possible to balance barrier properties against various gases and various properties. can take

The heat-sealing resin contained in the sealant layer is preferably a resin having the same basic skeleton as the polyolefin resin contained in the biaxially stretched resin film layer constituting the base layer. For example, it is preferable that the heat-sealable resin contained in the sealant layer and the polyolefin resin contained in the biaxially stretched resin film layer constituting the base material layer contain a polypropylene resin.

Furthermore, it is more preferable that the content of the resin having the same basic skeleton in the high interlayer adhesion gas barrier laminate is 50% by mass or more. There is no particular upper limit, and ideally it is 100% by mass. By containing the resin having the same basic skeleton in the above range, it is possible to obtain the effect of facilitating recycling of the high interlayer adhesiveness gas barrier laminate and the packaging materials and packages produced therefrom.
Here, the resin having the same basic skeleton refers to a resin obtained by (co)polymerizing the same raw material monomer as the main component. They may be different, and the lamination methods may be different.
For example, the biaxially stretched resin film constituting the base layer is a non-heat-sealable biaxially stretched polypropylene resin film, and the sealant layer is a layer formed from a heat-sealable non-stretched polypropylene resin film, Alternatively, it may be a heat-sealable layer formed by laminating a polypropylene-based resin by extrusion coating or the like.

<High interlayer adhesion gas barrier packaging material>
The high interlayer adhesion gas barrier packaging material of the present invention is a packaging material produced from the high interlayer adhesion gas barrier laminate of the present invention.
Intermediate layers having various functions can be laminated between the substrate layer and the sealant layer or outside the substrate layer, if necessary, in the gas barrier packaging material with high interlayer adhesion.

<High interlayer adhesion gas barrier package>
The high interlayer adhesion gas barrier package of the present invention is a package produced from the high interlayer adhesion gas barrier packaging material of the present invention.
For example, by heat-sealing such as heat-sealing the sealant layer of a gas-barrier packaging material with high interlayer adhesion made of a multi-layer film, a pillow packaging bag, a three-side seal, a four-side seal, a gusset type gas-barrier package, etc. can be produced. can.

<High interlayer adhesion gas barrier packaging bag>
The high interlayer adhesion gas barrier packaging bag of the present invention is one aspect of the high interlayer adhesion gas barrier packaging material, and is a packaging bag made from the high interlayer adhesion gas barrier packaging material of the present invention.

<Raw materials>
Main raw materials used in this example are as follows.
- Base resin film 1: Biaxially oriented polypropylene film A-OP-BH with a PVA-based resin layer (about 0.7 μm thick) on one side, manufactured by Mitsui Chemicals Tohcello, Inc. 20 μm thick. Ra of PVA-based resin layer surface: 3.9 μm, PV value: 38 nm.
Base resin film 2: Biaxially oriented resin polypropylene film, U-1, manufactured by Mitsui Chemicals Tohcello, Inc., 20 μm thick, underside corona treated. Ra of the corona-treated surface is 8.7 nm, PV value is 250 nm.
- Sealant resin film 1: Unstretched polypropylene film, ZK-207, manufactured by Toray Advanced Film Co., Ltd., 70 μm thick.
DL Adhesive 1: RU-77T/H-7 dry laminate adhesive manufactured by Rock Paint Co., Ltd.
- Hydroxyl group-containing water-soluble resin 1: Polyvinyl alcohol having a degree of polymerization of 2400 and a degree of saponification of 99 mol% or more.

[Preparation of Base Resin Film 3]
The PVA-based resin layer side surface of the base resin film 1 is pressed against and sandwiched between rolls having a quasi-mirror surface, so that the surface of the PVA-based resin layer side has an Ra of 7 nm and a PV value of 50 nm. A resin film 3 was obtained.

[Preparation of Base Resin Film 4]
By pressing the PVA-based resin layer side surface of the base resin film 1 against a roll having a non-mirror surface and sandwiching it, a base material having an Ra of the PVA-based resin layer side surface of 8 nm and a PV value of 55 nm was obtained. A resin film 3 was obtained.

[Preparation of barrier protective resin composition 1]
A solvent consisting of 300 g of water and 146 g of isopropyl alcohol was mixed with 7.3 g of 0.5N hydrochloric acid as a hydrolysis accelerator to adjust the pH to 2.2. 9.2 g of methoxysilane were mixed while cooling to 10° C. to prepare a solution A.
Next, a solution B was prepared by mixing the following raw materials.
Hydroxyl group-containing water-soluble resin 1 4.7 parts by mass Water 324 parts by mass Isopropyl alcohol 17 parts by mass Then, liquid A and liquid B were mixed so that the mass ratio was 3.5:6.5 to form a barrier protective resin composition. Got item 1.

[Example 1]
On the surface of the PVA-based resin layer of the base resin film 1 as a base layer, a silicon oxide vapor deposition layer (20 nm thick) was formed as a gas barrier layer by a CVD method under the following conditions to obtain a high interlayer adhesion gas barrier vapor deposition film. Obtained.
Silicon oxide deposited layer forming conditions/cooling/power supplied to electrode drum: 10 kW
・Degree of vacuum: 5×10 ⁻¹ Pa
・Conveyance speed: 100m/min
・Supply gas: hexamethyldisiloxane/oxygen gas/helium Next, the DL adhesive 1 is applied to the above gas barrier layer, dried, and the sealant resin film 1 is laminated to form a high interlayer adhesion gas barrier laminate. It was produced and various evaluations were carried out.
A similar evaluation was carried out.

[Example 2]
The barrier protective resin composition 1 was applied to the surface of the silicon oxide deposition layer, dried at 80°C at a conveying speed of 100 m/min, and aged at 55°C for 3 days to form a barrier protective layer (0.3 µm thick). A high interlayer adhesion gas barrier vapor-deposited film and a high interlayer adhesion gas barrier laminate were produced in the same manner as in Example 1 except that the evaluation was carried out in the same manner.

[Example 3]
The procedure of Example 2 was repeated except that the silicon oxide deposited layer by the CVD method was replaced with an aluminum oxide deposited layer (20 nm) by the PVD method prepared under the following conditions to obtain a high interlayer adhesion gas barrier deposited film, A gas barrier laminate with high interlayer adhesion was produced and evaluated in the same manner.
Aluminum oxide deposition layer formation conditions Heating means for vacuum deposition method: Reactive resistance heating system Degree of vacuum: 8.1×10 ⁻² Pa
・Conveyance speed: 400m/min
・Oxygen gas supply amount: 8000 sccm

[Example 4]
A high interlayer adhesion gas barrier deposition film and a high interlayer adhesion gas barrier laminate were produced in the same manner as in Example 2 except that the base resin film 1 was replaced with the base resin film 3, and evaluated in the same manner. carried out.

[Comparative Example 1]
Except for changing the base resin film 1 to the base resin film 2, the same operation as in Example 2 was carried out to obtain a gas barrier vapor-deposited film and a high interlayer adhesion gas barrier laminate, which were evaluated in the same manner.

[Comparative Example 2]
Except for changing the base resin film 1 to the base resin film 4, the same operation as in Example 2 was carried out to obtain a gas barrier vapor-deposited film and a high interlayer adhesion gas barrier laminate, which were evaluated in the same manner.

<Summary of results>
Examples 1 to 4, in which the Ra and PV values of the substrate layer surface satisfy the provisions of the present invention, exhibited good gas barrier properties and high interlayer adhesion strength, but Comparative Example 1, which did not satisfy the provisions, was inferior. The gas barrier property and the interlayer adhesion strength were inferior.

<Evaluation method>
[Surface roughness]
The surface roughness of the side of the substrate layer on which the gas barrier layer is laminated was measured using an AFM manufactured by SII Nanotechnology Co., Ltd., and the Ra and PV value were calculated.

[Oxygen permeability]
Using an oxygen transmission rate measuring device (OX-TRAN2/22, manufactured by MOCON), the test piece was set so that the base layer surface of the test piece was on the oxygen supply side, and measured at 23 ° C. and relative humidity in accordance with JIS K 7126. Oxygen permeability was measured in a 90% RH environment.

[Water vapor permeability]
Using a water vapor transmission rate measuring device (manufactured by MOCON, PERMATRAN-W3-34G), the test piece was set so that the base layer surface of the test piece was on the water vapor supply side. The water vapor transmission rate was measured under a humidity of 90% RH environment.

[Interlayer adhesion strength]
The laminate was cut into strips with a width of 15 mm, and the interlaminar adhesion strength (N/15 mm) between the deposited film/sealant was measured using a tensile tester under the following conditions.
Tensile test conditions Tensile speed: 50 mm/min
Peeling angle: 90°

[Heat sealability]
Cut the laminate into 10 cm × 10 cm pieces, fold in half, overlap the sealant surfaces, and use a heat seal tester (manufactured by Tester Sangyo Co., Ltd.: TP-701-A) to divide the ends into two without heat sealing. A region of 1 cm×10 cm was heat-sealed under the following conditions so as to remain in the state of being held, and further cut into strips with a width of 15 mm to prepare test pieces.
Then, each bifurcated end of the test piece was attached to a tensile tester, the tensile strength (N/15 mm) was measured under the following conditions, and evaluated according to the following pass/fail criteria.
Heat sealing conditions Temperature: 180°C
Pressure: 1 kgf/ ^cm2
Time: 1 second Tensile strength test conditions: 100N
Pass/fail judgment ◯: Tensile strength is 25 N/15 mm or more, passing.
x: Tensile strength is less than 25 N/15 mm, failing.

[Bag-making properties]
A pouch bag having a size of 150 mm×210 mm was produced from the laminate by four-sided sealing with a sealing width of 10 mm under the following conditions, and evaluated according to the following pass/fail criteria.
Heat sealing conditions Temperature: 180°C
Pressure: 1 kgf/ ^cm2
Time: 1 second Pass/fail judgment ◯: The bag was made without any problems.
x: The bag could not be made.

1 High interlayer adhesion gas barrier deposition film 2 Base material layer 2a Biaxially stretched resin film layer 2b PVA-based resin layer 3 Gas barrier layer 3a Metal oxide deposition layer 3b Barrier protection layer 4 Interlayer adhesion gas barrier laminate, interlayer adhesion gas barrier packaging Material 5 Sealant layer

Claims (12)

A high interlayer adhesion gas barrier deposition film having a substrate layer and a gas barrier layer,
The base layer has a layer made of a biaxially stretched resin film containing a polyolefin resin,
The gas barrier layer has a metal oxide deposition layer,
The metal oxide deposition layer is laminated on and in contact with the base material layer,
The substrate layer is a PVA-based resin made of polyvinyl alcohol obtained by saponifying polyvinyl acetate or an ethylene-vinyl alcohol copolymer obtained by saponifying a copolymer of ethylene and vinyl acetate. having a layer on the surface,
The metal oxide deposition layer is laminated on and in contact with the PVA-based resin layer,
The polyolefin-based resin is a polypropylene-based resin,
The surface roughness of the surface of the substrate layer on which the gas barrier layer is laminated has an Ra of 7 nm or less and a PV value of 50 nm or less,
The interlayer adhesion strength between the metal oxide deposition layer and the PVA-based resin layer is 3 N/15 mm or more,
High interlayer adhesion gas barrier deposition film. wherein the metal oxide deposition layer is a silicon oxide deposition layer deposited by a CVD method,
The high interlayer adhesion gas barrier deposition film according to claim 1. wherein the metal oxide deposition layer is an aluminum oxide layer deposited by a PVD method,
The high interlayer adhesion gas barrier deposition film according to claim 1 or 2. The gas barrier layer further has a barrier protective layer,
The barrier protective layer is a layer formed from a resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin, and is laminated on and in contact with the metal oxide deposition layer,
The high interlayer adhesion gas barrier deposition film according to any one of claims 1 to 3. A high interlayer adhesion gas barrier laminate comprising a layer composed of the high interlayer adhesion gas barrier vapor-deposited film according to any one of claims 1 to 4 and a sealant layer containing a heat-sealing resin,
The sealant layer is laminated on the surface of the high interlayer adhesion gas barrier vapor-deposited film on the side opposite to the base layer,
High interlayer adhesion gas barrier laminate. The heat-sealable resin is a polypropylene resin,
The high interlayer adhesion gas barrier laminate according to claim 5 . The sealant layer is a layer made of an unstretched polypropylene resin film,
The high interlayer adhesion gas barrier laminate according to claim 5 or 6. the polyolefin-based resin and the heat-sealable resin contain resins having the same basic skeleton,
The content of the resin having the same basic skeleton in the gas barrier laminate is 50% by mass or more,
The high interlayer adhesion gas barrier laminate according to any one of claims 5 to 7. The resin having the same basic skeleton is a polypropylene-based resin,
The high interlayer adhesion gas barrier laminate according to claim 8 . A high interlayer adhesion gas barrier packaging material produced from the high interlayer adhesion gas barrier laminate according to any one of claims 5 to 9. A high interlayer adhesion gas barrier package produced from the high interlayer adhesion gas barrier packaging material according to claim 10 . A high interlayer adhesion gas barrier packaging bag produced from the high interlayer adhesion gas barrier packaging material according to claim 10 .

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