JP2021054078A - Barrier laminate, and packaging container having the barrier laminate - Google Patents

Abstract

To provide a barrier laminate which has an intermediate layer excellent in adhesion between a vapor-deposited film and layers and has extremely high gas barrier property.SOLUTION: A barrier laminate has a base material 11, an adhesive layer 12, a vapor-deposited film 13, an intermediate layer 14 and a sealant layer 15. The intermediate layer 14 has at least a surface resin layer 16 and a polypropylene resin layer 17. The surface resin layer 16 contains a resin material having a melting point of 180°C or higher, the vapor-deposited film 13 is composed of an inorganic oxide, and the surface resin layer 16 and the polypropylene resin layer 17 are subjected to drawing treatment.SELECTED DRAWING: Figure 1

Description

The present invention relates to a barrier laminate and a packaging container including the barrier laminate.

Conventionally, a film made of polyester such as polyethylene terephthalate (hereinafter, also referred to as polyester film) is excellent in mechanical properties, chemical stability, heat resistance and transparency, and is inexpensive, so that it is used for manufacturing packaging containers. It is used as a base material or an intermediate layer that constitutes the laminated body.

Depending on the contents to be filled in the packaging container, the packaging container is required to have gas barrier properties such as high oxygen barrier property and water vapor barrier property. In order to meet these requirements, a vapor-deposited film containing alumina, silica, etc. is formed on the surface of the polyester film. It is widely used to form (Patent Document 1).

By the way, in recent years, a search for a resin material to replace a polyester film has been conducted, and it has been studied to apply a polyolefin film, particularly a polypropylene film having a vapor-deposited film formed on the surface, as an intermediate layer.

Japanese Unexamined Patent Publication No. 2005-053223

The present inventors have been studying the use of a polypropylene stretched film (hereinafter, also referred to as a stretched polypropylene film) instead of the conventional polyester film, and have formed a vapor-deposited film on the surface of the stretched polypropylene film. However, we found a new problem that we could not obtain a satisfactory gas barrier property.

Then, as a result of the study by the present inventors, the packaging container using the barrier-type laminate in which the vapor-deposited film is provided on the stretched polypropylene film is not found in the conventional barrier-type laminate using the polyester film. It was found that a peculiar phenomenon, that is, peeling occurred between the layers of the stretched polypropylene film and the vapor-deposited film, and it was found that the phenomenon makes the gas barrier property insufficient.

Then, the present inventors improve the adhesion of the vapor-deposited film formed on the surface resin layer by providing a surface resin layer containing a resin material having a melting point of 180 ° C. or higher on the surface of the stretched polypropylene film. At the same time, it was found that the gas barrier property is also improved.

Further, the present inventors also provide a coat layer containing a resin material having a polar group on the surface of the stretched polypropylene film to improve the adhesion of the vapor-deposited film formed on the coat layer and to provide a gas barrier. We obtained the finding that the sex is also improved.

The present invention has been made based on such findings, and the problem to be solved is to provide a barrier laminate having an intermediate layer having excellent adhesion between layers with a vapor-deposited film and having extremely high gas barrier properties. It is to be.

Another object to be solved by the present invention is to provide a packaging container provided with the barrier laminate.

In the first aspect, the barrier laminate of the present invention comprises a base material, an adhesive layer, a vapor-deposited film, an intermediate layer, and a sealant layer.
The intermediate layer includes at least a surface resin layer and a polypropylene resin layer.
The surface resin layer contains a resin material having a melting point of 180 ° C. or higher.
The vapor-deposited film is composed of an inorganic oxide.
The surface resin layer and the polypropylene resin layer are characterized by being stretched.

In one embodiment, the polypropylene resin layer, the base material and the sealant layer are made of the same material, and the same material is polypropylene.

In one embodiment, the adhesive layer is an adhesive layer containing a cured product of a composition containing a polyester polyol and an isocyanate compound.

In one embodiment, the melting point of the resin material is 265 ° C. or lower.

In one embodiment, the difference between the melting point of the resin material and the melting point of polypropylene contained in the polypropylene resin layer is 20 to 80 ° C.

In one embodiment, the resin material has a polar group.

In one embodiment, the resin material is one or more resin materials selected from ethylene vinyl alcohol copolymer, polyvinyl alcohol, nylon 6, nylon 6,6, MXD nylon and amorphous nylon.

In one embodiment, the resin material is polyamide.

In one embodiment, the resin material is ethylene vinyl alcohol.

In one embodiment, the ratio of the thickness of the surface resin layer to the total thickness of the intermediate layer is 1% or more and 10% or less.

In one embodiment, the intermediate layer is a co-press film.

In the second aspect, the barrier laminate of the present invention comprises a base material, an adhesive layer, a vapor-deposited film, an intermediate layer, and a sealant layer.
The intermediate layer includes a surface coat layer and a polypropylene resin layer.
The polypropylene resin layer has been stretched and has been stretched.
Moreover, the surface coating layer contains a resin material having a polar group, and the surface coating layer contains a resin material.
The vapor-deposited film is characterized by being composed of an inorganic oxide.

In one embodiment, the polypropylene resin layer, the base material and the sealant layer are made of the same material, and the same material is polypropylene.

In one embodiment, the adhesive layer is an adhesive layer containing a cured product of a composition of polyester polyol and isocyanate compound.

In one embodiment, the ratio of the thickness of the surface coat layer to the total thickness of the intermediate layer is 0.08% or more and 20% or less.

In one embodiment, the thickness of the surface coat layer is 0.02 μm or more and 10 μm or less.

In one embodiment, the resin material is ethylene vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyester, polyethyleneimine, hydroxyl group-containing (meth) acrylic resin, nylon 6, nylon 6,6, MXD nylon, amorphous. One or more resin materials selected from nylon and polyurethane.

In one embodiment, the surface coat layer is a layer formed using a water-based emulsion or a solvent-based emulsion.

In one embodiment, the barrier laminate of the present invention further comprises a barrier coat layer between the intermediate layer and the vapor-deposited film.

In one embodiment, the barrier laminate of the present invention is used for packaging container applications.

The packaging container of the present invention is characterized by comprising the above-mentioned barrier laminate.

According to the present invention, it is possible to provide a packaging container having an intermediate layer having excellent adhesion between layers with a vapor-deposited film and having high lamination strength, and to provide a barrier laminate having extremely high gas barrier property. Can be done.
Further, according to the present invention, it is possible to provide a packaging container provided with the barrier laminate.

It is a schematic cross-sectional view which shows one Embodiment of the barrier laminated body of this invention. It is a schematic cross-sectional view which shows one Embodiment of the barrier laminated body of this invention. It is a schematic cross-sectional view which shows one Embodiment of the barrier laminated body of this invention. It is a schematic cross-sectional view which shows one Embodiment of the barrier laminated body of this invention. It is the schematic sectional drawing which shows one Embodiment of a thin-film deposition apparatus. It is the schematic sectional drawing which shows one Embodiment of a thin-film deposition apparatus. It is the schematic sectional drawing which shows another embodiment of the vapor deposition apparatus. It is a schematic cross-sectional view which shows one Embodiment of the barrier laminated body of this invention. It is a schematic cross-sectional view which shows one Embodiment of the barrier laminated body of this invention. It is a front view which shows one Embodiment of the packaging container of this invention. It is a perspective view which shows one Embodiment of the packaging container of this invention. It is the schematic which shows an example of the measuring method of the laminate strength. It is the schematic which shows an example of the measuring method of the laminate strength. It is a figure which shows the change of the tensile stress with respect to the space between a pair of grippers pulling a base material side and a sealant layer side for measuring a laminate strength.

(Barrier laminate in the first aspect)
As shown in FIG. 1, the barrier laminate 10 of the present invention includes a base material 11, an adhesive layer 12, a vapor-deposited film 13, an intermediate layer 14, and a sealant layer 15. At least a surface resin layer 16 and a polypropylene resin layer 17 are provided.
In one embodiment, the barrier laminate 10 of the present invention further includes a barrier coat layer 18 between the adhesive layer 12 and the vapor deposition film 13, as shown in FIG.
In one embodiment, the intermediate layer 14 includes an adhesive resin layer 19 between the surface resin layer 16 and the polypropylene resin layer 17, as shown in FIG.
In one embodiment, as shown in FIG. 4, the barrier laminate 10 includes a base material 11, an adhesive layer 12, a barrier coat layer 18, a vapor-deposited film 13, an intermediate layer 14, and a sealant layer 15. Prepare in order. The intermediate layer 14 includes at least a surface resin layer 16 and a polypropylene resin layer 17, and the adhesive resin layer 19 is provided between the surface resin layer 16 and the polypropylene resin layer 17.

In the barrier laminate according to the first aspect, the lamination strength between the intermediate layer and the vapor-deposited film is preferably 3N or more, more preferably 4N or more, and further preferably 5.5N or more in a width of 15 mm. The upper limit of the laminate strength of the barrier laminate in the first aspect may be 20 N or less.
The method for measuring the laminate strength of the barrier laminate will be described in Examples described later.

Conventionally, a laminate in which a base material, an intermediate layer, and a sealant layer are made of different kinds of resin materials has been used for manufacturing a packaging container. However, after collecting the used packaging container, different kinds of resin materials are used. Since it is difficult to separate each layer composed of plastics, the current situation is that they are not actively recycled.
By forming the base material, the polypropylene resin layer provided in the intermediate layer, and the sealant layer with the same material, it is not necessary to separate each layer, and the recycling suitability thereof can be improved.
By composing the base material and the sealant from the same material as the polyproprene resin layer provided in the intermediate layer, that is, polypropylene, it is not necessary to separate the recovered packaging container for each layer, and the recycling suitability thereof is improved. Can be done.

When the base material and the sealant layer are composed of polypropylene, the content of polypropylene with respect to the total amount of the resin material contained in the barrier laminate of the present invention is preferably 80% by mass or more, preferably 85% by mass or more. Is more preferable, and 90% by mass or more is further preferable. Thereby, the recyclability of the packaging container produced by using the barrier laminate of the present invention can be further improved.

Hereinafter, each layer included in the barrier laminate of the present invention will be described.

(Base material)
The base material contains a resin material, and examples thereof include polyolefins, vinyl resins, (meth) acrylic resins, cellulose resins, polyamides, polyimides, polyesters, ionomer resins, and the like.
From the viewpoint of recycling suitability of the barrier laminate of the present invention, it is preferable that the base material is made of the same material as the polypropylene resin layer provided in the intermediate layer, that is, polypropylene.
Further, by forming the base material with polypropylene, the oil resistance of the packaging container produced by using the barrier laminate can be improved.

To the extent that the properties of the present invention are not impaired, the substrate may contain additives, such as cross-linking agents, antioxidants, anti-blocking agents, slip agents, UV absorbers, light stabilizers, fillings. Examples include agents, reinforcing agents, antistatic agents, pigments and modifying resins.

The base material may have a single-layer structure or may have a multi-layer structure.
Further, the base material may be one that has been stretched or not, but from the viewpoint of heat resistance and strength of the barrier laminate, the stretching treatment is performed. It is preferable that it has been applied.

The thickness of the base material is preferably 10 μm or more and 50 μm or less, and more preferably 20 μm or more and 40 μm or less.
By setting the thickness of the base material to 10 μm or more, the strength and heat resistance of the barrier laminate of the present invention can be improved.
Further, by setting the thickness of the base material to 50 μm or less, the film forming property and processability of the barrier laminate of the present invention can be further improved.

The base material may have a printing layer on its surface, and the image formed on the printing layer is not particularly limited, and characters, patterns, symbols, combinations thereof, and the like are represented.
The print layer can be formed on the substrate by using an ink derived from biomass. As a result, the environmental load can be reduced.
The method for forming the print layer is not particularly limited, and examples thereof include conventionally known printing methods such as a gravure printing method, an offset printing method, and a flexographic printing method.

(Adhesive layer)
The barrier laminate of the present invention includes an adhesive layer between the base material and the vapor-deposited film.

The adhesive layer contains at least one type of adhesive, and may be a one-component curable type, a two-component curable type, or a non-curable type. The adhesive may be a solvent-free adhesive or a solvent-type adhesive, but from the viewpoint of environmental load, a solvent-free adhesive can be preferably used.
Examples of the solvent-free adhesive include polyether adhesives, polyester adhesives, silicone adhesives, epoxy adhesives and urethane adhesives, and among these, two-component curable urethanes. A system adhesive can be preferably used.
Examples of the solvent-based adhesive include rubber-based adhesives, vinyl-based adhesives, silicone-based adhesives, epoxy-based adhesives, phenol-based adhesives, and olefin-based adhesives.

Further, the adhesive layer is preferably an adhesive layer containing a cured product of a composition containing a polyester polyol and an isocyanate compound.
By having such a structure of the adhesive layer, the oxygen barrier property and the water vapor barrier property of the barrier laminate of the present invention can be further improved.
Further, usually, when a laminated body provided with a vapor-deposited film is applied to a packaging container, a bending load is applied to the laminated body by a molding machine or the like, so that the thin-film film may be cracked. By using the gas barrier organic adhesive, the bending load resistance of the barrier laminate of the present invention can be improved, and the deterioration of the oxygen barrier property and the water vapor barrier property can be suppressed.

The glass transition temperature of the cured product of the composition containing the polyester polyol and the isocyanate compound is preferably −30 ° C. or higher and 80 ° C. or lower, more preferably 0 ° C. or higher and 70 ° C. or lower, and 25 ° C. or higher and 70 ° C. or lower. Is more preferable. Thereby, the oxygen barrier property, the water vapor barrier property, and the laminate strength of the barrier laminate can be further improved.
In this specification, Tg is a value obtained by differential scanning calorimetry (DSC) in accordance with JIS K 7121: 2012.

The polyester polyol has two or more hydroxyl groups in one molecule as a functional group. Further, the isocyanate compound has two or more isocyanate groups in one molecule as a functional group. The polyester polyol has, for example, a polyester structure or a polyester polyurethane structure as a main skeleton.

As a specific example of the composition (adhesive) containing the polyester polyol and the isocyanate compound, the PASLIM series sold by DIC Corporation can be used.

The composition containing the polyester polyol and the isocyanate compound may further contain a phosphoric acid ester, a plate-like inorganic compound, a coupling agent, cyclodextrin and / or a derivative thereof and the like.

As the polyester polyol having two or more hydroxyl groups in one molecule as a functional group, for example, the following [1st example] to [3rd example] can be used.
[1st example] Polyester polyol obtained by polycondensing an ortho-oriented polyvalent carboxylic acid or its anhydride with a polyhydric alcohol [2nd example] Polyester polyol having a glycerol skeleton [3rd example] Having an isocyanul ring Polyester polyols Each polyester polyol will be described below.

The polyester polyol according to the first example is a polycondensate obtained by polycondensing a polyhydric carboxylic acid component containing at least one or more of orthophthalic acid and its anhydride and a polyhydric alcohol component.
In particular, a polyester polyol in which the content of orthophthalic acid and its anhydride with respect to all the components of the polyvalent carboxylic acid is 70 to 100% by mass is preferable.

The polyester polyol according to the first example requires orthophthalic acid and its anhydride as the polyvalent carboxylic acid component, but other polyvalent carboxylic acid components are copolymerized as long as the effects of the present embodiment are not impaired. You may.
Other polyvalent carboxylic acid components include aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid, and unsaturated bond-containing polyvalents such as maleic anhydride, maleic acid and fumaric acid. Alicyclic polyvalent carboxylic acids such as valent carboxylic acids, 1,3-cyclopentanedicarboxylic acids and 1,4-cyclohexanedicarboxylic acids, terephthalic acids, isophthalic acids, pyromellitic acids, trimellitic acids, 1,4-naphthalenedicarboxylic acids. Acids, 2,5-naphthalenedicarboxylic acids, 2,6-naphthalenedicarboxylic acids, naphthalic acids, biphenyldicarboxylic acids, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acids, anhydrides of these dicarboxylic acids and Aromatic polyvalent carboxylic acids such as ester-forming derivatives of these dicarboxylic acids, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and polybasic acids such as ester-forming derivatives of these dihydroxycarboxylic acids and the like. Can be mentioned. Among these, succinic acid, 1,3-cyclopentanedicarboxylic acid, and isophthalic acid are preferable.
In addition, two or more kinds of the above-mentioned other polyvalent carboxylic acids may be used.

Examples of the polyhydric alcohol component include aliphatic polyhydric alcohols and aromatic polyhydric alcohols.
Examples of the aliphatic polyhydric alcohol include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexane. Examples thereof include diols, methylpentanediols, dimethylbutanediols, butylethylpropanediols, diethylene glycols, triethylene glycols, tetraethylene glycols, dipropylene glycols and tripropylene glycols.
Examples of the aromatic polyhydric alcohol include hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, bisphenol F, tetramethylbiphenol, ethylene oxide extensions thereof, and water-added aliphatic compounds thereof.
In one embodiment, the polyhydric alcohol component comprises at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol.

一般式（１）において、Ｒ_１、Ｒ_２、Ｒ_３は、各々独立に、Ｈ（水素原子）または下記の一般式（２）で表される基である。

As the polyester polyol according to the second example, a polyester polyol having a glycerol skeleton represented by the general formula (1) can be mentioned.

In the general formula (1), R ₁ , R ₂ , and R ₃ are independently H (hydrogen atom) or a group represented by the following general formula (2).

In the formula (2), n represents an integer of 1 to 5, and X is a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, 2, which may have a substituent. It represents an arylene group selected from the group consisting of a 3-anthraquinone diyl group and a 2,3-anthracene diyl group, and Y represents a group represented by an alkylene group having 2 to 6 carbon atoms).
However, _{at least one of R 1} , R ₂ , and R ₃ represents a group represented by the general formula (2).

In the general formula (1), _{at least one of R 1} , R ₂ , and R ₃ needs to be a group represented by the general formula (2). Above _{all, it is preferable that all of R 1} , R ₂ , and R ₃ are groups represented by the general formula (2).

_Also, tables in the compound R _1, R 2, one of _{R 3} is a group represented by the general formula _(2), R _1, R 2, either _{R 3} 2 two generally formula (2) Any two or more compounds of the compound which is the group to be used and the compound which is the group in which _{all of R 1} , R ₂ and R ₃ are represented by the general formula (2) may be a mixture.

X is selected from the group consisting of a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, a 2,3-anthraquinone diyl group and a 2,3-anthracene diyl group, and has a substituent. Represents an allylene group that may be present.
When X is substituted with a substituent, it may be substituted with one or more substituents, the substituent being attached to any carbon atom on X different from the free radical. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group and a naphthyl group.

In the general formula (2), Y is an ethylene group, a propylene group, a butylene group, a neopentylene group, a 1,5-pentylene group, a 3-methyl-1,5-pentylene group, a 1,6-hexylene group, or a methylpentylene. Represents an alkylene group having 2 to 6 carbon atoms such as a group and a dimethylbutylene group. Among Y, a propylene group and an ethylene group are preferable, and an ethylene group is most preferable.

The polyester resin compound having a glycerol skeleton represented by the general formula (1) contains glycerol, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position or an anhydride thereof, and a polyhydric alcohol component as essential components. It can be synthesized by reacting as.

The aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position or its anhydride includes orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, naphthalene 1,2-dicarboxylic acid or its anhydride. Anhydrous, anthraquinone 2,3-dicarboxylic acid or an anhydride thereof, 2,3-anthracenecarboxylic acid or an anhydride thereof and the like can be mentioned.
These compounds may have a substituent on any carbon atom of the aromatic ring. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group and a naphthyl group.

Moreover, as a polyhydric alcohol component, an alkylene diol having 2 to 6 carbon atoms can be mentioned. For example, diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol and dimethylbutanediol. Can be exemplified.

一般式（３）において、Ｒ_１、Ｒ_２、Ｒ_３は、各々独立に、「−（ＣＨ_２）ｎ１−ＯＨ（但しｎ１は２〜４の整数を表す）」、または、一般式（４）の構造を表す。

The polyester polyol according to the third example is a polyester polyol having an isocyanul ring represented by the following general formula (3).

In the general formula (3), R ₁ , R ₂ , and R ₃ are independently "-(CH ₂ ) n1-OH (where n1 represents an integer of 2 to 4)" or the general formula (4). ) Represents the structure.

In the general formula (4), n2 represents an integer of 2 to 4, n3 represents an integer of 1 to 5, X represents a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, It represents an arylene group selected from the group consisting of a 2,3-anthraquinonediyl group and a 2,3-anthracenediyl group and may have a substituent, and Y represents an alkylene group having 2 to 6 carbon atoms). Represents a group represented by. However _{, at least one of R 1} , R ₂ , and R ₃ is a group represented by the general formula (4).

In the general formula (3), the _{alkylene group represented by − (CH 2} ) n1- may be linear or branched. Of these, n1 is preferably 2 or 3, and most preferably 2.

In the general formula (4), n2 represents an integer of 2 to 4, and n3 represents an integer of 1 to 5.
X is selected from the group consisting of a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, a 2,3-anthraquinone diyl group, and a 2,3-anthracene diyl group, and has a substituent. Represents an allylene group that may be present.

When X is substituted with a substituent, it may be substituted with one or more substituents, the substituent being attached to any carbon atom on X different from the free radical. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group and a naphthyl group.
The substituent of X is preferably a hydroxyl group, a cyano group, a nitro group, an amino group, a phthalimide group, a carbamoyl group, an N-ethylcarbamoyl group and a phenyl group, preferably a hydroxyl group, a phenoxy group, a cyano group, a nitro group, a phthalimide group and The phenyl group is most preferred.

In the general formula (4), Y is an ethylene group, a propylene group, a butylene group, a neopentylene group, a 1,5-pentylene group, a 3-methyl-1,5-pentylene group, a 1,6-hexylene group, or a methylpentylene. Represents an alkylene group having 2 to 6 carbon atoms such as a group and a dimethylbutylene group. Among Y, a propylene group and an ethylene group are preferable, and an ethylene group is most preferable.

In the general formula (3), _{at least one of R 1} , R ₂ , and R ₃ is a group represented by the general formula (4). Above _{all, it is preferable that all of R 1} , R ₂ , and R ₃ are groups represented by the general formula (4).

_Also, tables in the compound R _1, R 2, one of _{R 3} is a group represented by the general formula _(4), R _1, R 2, either _{R 3} 2 two generally formula (4) Any two or more compounds of the compound which is the group to be used and the compound which is the group in which _{all of R 1} , R ₂ and R ₃ are represented by the general formula (4) may be a mixture.

The polyester polyol having an isocyanul ring represented by the general formula (3) includes a triol having an isocyanul ring, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position or an anhydride thereof, and a polyhydric alcohol component. Can be synthesized by reacting with

Triols having an isocyanuric ring include, for example, alkylene oxide adducts of isocyanuric acid such as 1,3,5-tris (2-hydroxyethyl) isocyanuric acid and 1,3,5-tris (2-hydroxypropyl) isocyanuric acid. And so on.

Examples of the aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position or its anhydride include orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, and naphthalene 1,2-dicarboxylic acid. Or an anhydride thereof, anthraquinone 2,3-dicarboxylic acid or an anhydride thereof, 2,3-anthracenecarboxylic acid or an anhydride thereof, and the like. These compounds may have a substituent on any carbon atom of the aromatic ring.

Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group and a naphthyl group.

Moreover, as a polyhydric alcohol component, an alkylene diol having 2 to 6 carbon atoms can be mentioned. For example, diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol and dimethylbutanediol. Can be mentioned.
Among them, 1,3,5-tris (2-hydroxyethyl) isocyanuric acid or 1,3,5-tris (2-hydroxypropyl) isocyanuric acid is used as the triol compound having an isocyanul ring, and the carboxylic acid is in the ortho position. A polyester polyol compound having an isocyanul ring using an aromatic polyvalent carboxylic acid substituted with or using orthophthalic anhydride as its anhydride and ethylene glycol as the polyhydric alcohol is particularly excellent in oxygen barrier property and adhesiveness. preferable.

The isocyanul ring is highly polar and trifunctional, and can increase the polarity of the entire system and increase the crosslink density. From this point of view, it is preferable that the isocyanul ring is contained in an amount of 5% by mass or more based on the total solid content of the adhesive resin.

The isocyanate compound has two or more isocyanate groups in the molecule.
Further, the isocyanate compound may be an aromatic compound, an aliphatic compound, a low molecular weight compound, or a high molecular weight compound.
Further, the isocyanate compound may be a blocked isocyanate compound obtained by an addition reaction using a known isocyanate blocking agent by a known and commonly used appropriate method.
Among them, a polyisocyanate compound having three or more isocyanate groups is preferable from the viewpoint of adhesiveness and retort resistance, and an aromatic compound is preferable from the viewpoint of oxygen barrier property and water vapor barrier property.

Specific examples of the isocyanate compound include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydride diphenylmethane diisocyanate, metaxylylene diisocyanate, hydride hydride diisocyanate, isophorone diisocyanate, and these isocyanate compounds. Examples thereof include an adduct, a burette, and an allophanate obtained by reacting these isocyanate compounds with a low molecular weight active hydrogen compound or an alkylene oxide adduct thereof, or a high molecular weight active hydrogen compound.
Examples of the low molecular weight active hydrogen compound include ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, and sorbitol. Examples thereof include ethylenediamine, monoethanolamine, diethanolamine, triethanolamine and metaxylylene diamine, and examples of the molecularly active hydrogen compound include various polyester resins, polyether polyols and high molecular weight active hydrogen compounds of polyamide.

一般式（５）において、Ｒ_１、Ｒ_２、Ｒ_３は、水素原子、炭素数１〜３０のアルキル基、（メタ）アクリロイル基、置換基を有してもよいフェニル基および（メタ）アクリロイルオキシ基を有する炭素数１〜４のアルキル基から選ばれる基であるが、少なくとも一つは水素原子であり、ｎは、１〜４の整数を表す。

式中、Ｒ_４、Ｒ_５は、水素原子、炭素数１〜３０のアルキル基、（メタ）アクリロイル基、置換基を有してもよいフェニル基および（メタ）アクリロイルオキシ基を有する炭素数１〜４のアルキル基から選ばれる基であり、ｎは１〜４の整数、ｘは０〜３０の整数、ｙは０〜３０の整数を表すが、ｘとｙが共に０である場合を除く。 The adhesive layer composed of the cured product of the composition containing the polyester polyol and the isocyanate compound can contain a phosphoric acid-modified compound, and is, for example, a compound represented by the following general formula (5) or (6). ..

In the general formula (5), R ₁ , R ₂ , and R ₃ are a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth) acryloyl group, a phenyl group which may have a substituent, and (meth) acryloyl. It is a group selected from alkyl groups having 1 to 4 carbon atoms having an oxy group, but at least one is a hydrogen atom, and n represents an integer of 1 to 4.

In the formula, R ₄ and R ₅ have a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth) acryloyl group, a phenyl group which may have a substituent, and a (meth) acryloyloxy group. A group selected from alkyl groups of ~ 4, n represents an integer of 1 to 4, x represents an integer of 0 to 30, y represents an integer of 0 to 30, except when x and y are both 0. ..

More specifically, phosphoric acid, pyrophosphate, triphosphate, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxy. Ethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphoric acid and the like can be mentioned, and one or more of these can be used.

The content of the phosphoric acid-modified compound in the adhesive layer containing the polyester polyol and the isocyanate compound is preferably 0.005% by mass or more and 10% by mass or less, and more preferably 0.01% by mass or more and 1% by mass or less.
By setting the content of the phosphoric acid-modified compound to 0.005% by mass or more, the oxygen barrier property and the water vapor barrier property can be improved. Further, by setting the content of the phosphoric acid-modified compound to 10% by mass or less, the adhesiveness of the adhesive layer can be improved.

The adhesive layer containing the polyester polyol and the isocyanate compound may contain a plate-like inorganic compound, whereby the oxygen barrier property, the water vapor barrier property, and the adhesiveness of the adhesive layer can be improved. In addition, the bending load resistance of the barrier laminate of the present invention can be improved.
Plate-like inorganic compounds include, for example, kaolinite-serpentinite clay minerals (halloysite, kaolinite, enderite, dicite, nacrite, antigolite, chrysotile, etc.) and pyrophyllite-talc (pyrophilite, talc, etc.). Kerorai, etc.).

Examples of the coupling agent include a silane-based coupling agent represented by the following general formula (7), a titanium-based coupling agent, an aluminum-based coupling agent, and the like. These coupling agents may be used alone or in combination of two or more.

Examples of the silane coupling agent include vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ. -Glysidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxytrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Propylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyl Examples thereof include trimethoxysilane, 3-isocyanoxide propyltriethoxysilane, 3-acryloxypropyltrimethoxysilane and 3-triethoxysilyl-N- (1,3-dimethyl-butylidene).

Examples of the titanium-based coupling agent include isopropyltriisostearoyl titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, and tetraoctylbis. (Didodecylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctainoltitanate, isopropyldimethacrylisostearoyl titanate , Isostatearoyl diacrylic titanate, diisostearoyl ethylene titanate, isopropyltri (dioctyl phosphate) titanate, isopropyltricylphenyl titanate, dicumylphenyloxyacetate titanate and the like.

Specific examples of the aluminum-based coupling agent include acetalkoxyaluminum diisopropyrate, diisopropoxyaluminum ethylacetate, diisopropoxyaluminum monomethacrylate, isopropoxyaluminum alkylacetate monomethacrylate, and aluminum. -2-Ethylhexanoate oxide trimmer, aluminum stearate oxide trimmer, alkylacetate acetate aluminum oxide trimmer and the like can be mentioned.

The adhesive adhesive layer composed of the composition containing the polyester polyol and the isocyanate compound can contain cyclodextrin and / or a derivative thereof, whereby the adhesiveness of the adhesive layer can be improved. Moreover, the bending load resistance can be further improved.
Specifically, for example, a cyclodextrin such as cyclodextrin, alkylated cyclodextrin, acetylated cyclodextrin, and hydroxyalkylated cyclodextrin in which the hydrogen atom of the hydroxyl group of the glucose unit is replaced with another functional group is used. Can be done. A branched cyclic dextrin can also be used.
The cyclodextrin skeleton of cyclodextrin and cyclodextrin derivatives is α-cyclodextrin consisting of 6 glucose units, β-cyclodextrin consisting of 7 glucose units, and γ-cyclodextrin consisting of 8 glucose units. It may be either.
These compounds may be used alone or in combination of two or more. In addition, these cyclodextrins and / or derivatives thereof may be collectively referred to as dextrin compounds hereafter.

From the viewpoint of compatibility and dispersibility in the adhesive layer containing the polyester polyol and the isocyanate compound, it is preferable to use a cyclodextrin derivative as the cyclodextrin compound.
From the viewpoint of the polarity of the various resins, the degree of substitution is preferably in the range of 0.1 or more and 14 or less / glucose, and more preferably in the range of 0.3 or more and 8 or less / glucose.

Examples of the alkylated cyclodextrin include methyl-α-cyclodextrin, methyl-β-cyclodextrin and methyl-γ-cyclodextrin. These compounds may be used alone or in combination of two or more.

Examples of the acetylated cyclodextrin include monoacetyl-α-cyclodextrin, monoacetyl-β-cyclodextrin and monoacetyl-γ-cyclodextrin. These compounds may be used alone or in combination of two or more.

Examples of the hydroxyalkylated cyclodextrin include hydroxypropyl-α-cyclodextrin, hydroxypropyl-β-cyclodextrin and hydroxypropyl-γ-cyclodextrin. These compounds may be used alone or in combination of two or more.

The thickness of the adhesive layer is preferably 0.5 μm or more and 6 μm or less, more preferably 0.8 μm or more and 5 μm or less, and further preferably 1 μm or more and 4.5 μm or less.
By setting the thickness of the adhesive layer to 0.5 μm or more, the adhesiveness of the adhesive layer can be improved. Further, when the adhesive layer is an adhesive layer containing a cured product of a composition containing a polyester polyol and an isocyanate compound, bending load resistance can be improved.
By setting the thickness of the adhesive layer to 6 μm or less, the processability of the barrier laminate can be improved. Further, it is possible to improve the recyclability of the packaging container produced by using the laminate provided with the base material composed of polypropylene and the sealant layer.

The adhesive layer is applied and dried on a vapor-deposited film or the like by a conventionally known method such as a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a fonten method and a transfer roll coating method. Can be formed by

(Embedded film)
The barrier laminate of the present invention includes a vapor-deposited film composed of an inorganic oxide on a surface resin layer. Thereby, the gas barrier property, specifically, the oxygen barrier property and the water vapor barrier property of the barrier laminated body can be improved. In addition, it is possible to suppress a decrease in the mass of the contents filled in the packaging container produced by using the barrier laminate of the present invention.

Examples of the inorganic oxide include aluminum oxide (alumina), silicon oxide (silica), magsium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, and silicon carbide (carbon-containing silicon oxide). And so on.
Among the above, silica, silicon carbide oxide and alumina are preferable.
Further, silica is particularly preferable because it does not require an aging treatment after forming the thin-film deposition film.

The thickness of the thin-film deposition film is preferably 1 nm or more and 150 nm or less, more preferably 5 nm or more and 60 nm or less, and further preferably 10 nm or more and 40 nm or less.
By setting the thickness of the thin-film deposition film to 1 nm or more, the oxygen barrier property and the water vapor barrier property of the laminated body can be further improved.
Further, by setting the thickness of the thin-film vapor film to 150 nm or less, it is possible to prevent the occurrence of cracks in the thin-film film. Further, it is possible to improve the recyclability of the packaging container produced by using the laminate provided with the base material composed of polypropylene and the sealant layer.

The vapor deposition film can be formed by using a conventionally known method, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method and an ion plating method, and a plasma. Examples thereof include chemical vapor deposition methods (Chemical Vapor Deposition methods, CVD methods) such as chemical vapor deposition methods, thermochemical vapor deposition methods, and photochemical vapor deposition methods.

The thin-film deposition film may be a single layer formed by one vapor deposition step or a multilayer formed by a plurality of thin-film deposition steps. When there are multiple layers, each layer may be the same material or a different material. Further, each layer may be formed by the same method or by a different method.

As an apparatus used in the method for forming a vapor-deposited film by the PVD method, a vacuum film forming apparatus with plasma assist can be used.
An embodiment of a method for forming a vapor-deposited film using a vacuum film forming apparatus with plasma assist is described below.
In one embodiment, as shown in FIGS. 5 and 6, the vacuum film forming apparatus includes a vacuum container A, an unwinding portion B, a film forming drum C, a winding portion D, a transport roll E, an evaporation source F, and a reaction gas. A supply unit G, a protective box H, a vapor deposition material I, and a plasma gun J are provided.
5 is a schematic cross-sectional view of the vacuum film forming apparatus in the XZ plane direction, and FIG. 6 is a schematic cross-sectional view of the vacuum film forming apparatus in the XY plane direction.
As shown in FIG. 4, an intermediate layer 14 wound by the film forming drum C method is arranged on the upper part of the vacuum vessel A with its surface resin layer surface facing downward, and is used for film formation in the vacuum vessel A. Below the drum C, an electrically grounded protective box H is arranged. The evaporation source F is arranged on the bottom surface of the protective box H. The film forming drum C is placed in the vacuum vessel A so that the surface resin layer surface of the intermediate layer 10 wound around the film forming drum C is located at a position facing the upper surface of the evaporation source F at a certain interval. Is placed.
Further, the transport roll E is arranged between the unwinding portion B and the film forming drum C, and between the film forming drum C and the winding portion D.
The vacuum container is connected to the vacuum pump (not shown).
The evaporation source F is for holding the vaporized material I and includes a heating device (not shown).
The reaction gas supply unit G is a portion that supplies a reaction gas (oxygen, nitrogen, helium, argon, a mixed gas thereof, or the like) that reacts with the evaporated vaporized material.
The vaporized vaporized material I heated and evaporated from the evaporation source F is irradiated toward the surface resin layer of the intermediate layer 14, and at the same time, plasma is also irradiated from the plasma gun J toward the surface resin layer for vaporization. The membrane is formed.
Details of this forming method are disclosed in Japanese Patent Application Laid-Open No. 2011-214089.

As the plasma generator used in the plasma chemical vapor deposition method, a generator such as a high frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Further, an apparatus having two or more film forming chambers may be used. It is preferable that the device is provided with a vacuum pump and can hold each film forming chamber in a vacuum.
The degree of vacuum in each film forming chamber is preferably ^{1 × 10 to 1 × 10-6 Pa.}
An embodiment of a method for forming a vapor-deposited film using a plasma generator will be described below.
First, the intermediate layer is sent out to the film forming chamber, and is conveyed onto the cooling / electrode drum at a predetermined speed via an auxiliary roll.
Next, a mixed gas composition containing a film-forming monomer gas containing an inorganic oxide, an oxygen gas, an inert gas, etc. is supplied from the gas supply device into the film-forming chamber, and plasma is generated on the surface resin layer by glow discharge. Is generated and irradiated with this to form a vapor-deposited film containing an inorganic oxide on the surface resin layer.
Details of this forming method are disclosed in Japanese Patent Application Laid-Open No. 2012-076292.

FIG. 7 is a schematic configuration diagram showing a plasma chemical vapor deposition apparatus used in the CVD method.

In one embodiment, as shown in FIG. 7, the plasma chemical vapor deposition apparatus unwinds the intermediate layer 14 from the unwinding portion B1 arranged in the vacuum vessel A1, and further transfers the intermediate layer 14 to the transport roll E1. It is cooled at a predetermined speed and conveyed onto the peripheral surface of the electrode drum C1. Oxygen, nitrogen, helium, argon and a mixed gas thereof are supplied from G1 to the reaction gas supply, and a monomer gas for film formation is supplied from the raw material gas supply unit I1 to prepare a mixed gas composition for vapor deposition composed of them. While introducing the mixed gas composition for vapor deposition into the vacuum vessel A1 through the raw material supply nozzle H1, and on the surface resin layer of the intermediate layer 14 conveyed on the peripheral surface of the cooling / electrode drum C1 described above. , Glow discharge plasma F1 generates plasma and irradiates it to form a vapor deposition film. At that time, a predetermined electric power is applied to the cooling / electrode drum C1 from the power supply K1 arranged outside the vacuum vessel A1, and a magnet J1 is arranged in the vicinity of the cooling / electrode drum C1 to generate plasma. Is promoting the outbreak of. Next, after forming the thin-film deposition film, the intermediate layer 14 is wound around the winding portion D1 via the transport roll E1 at a predetermined winding speed. In the figure, L1 represents a vacuum pump.

As an apparatus used for the method for forming a vapor-deposited film, a continuous vapor-deposited film deposition apparatus including a plasma pretreatment chamber and a film-forming chamber can be used.
An embodiment of a method for forming a vapor-deposited film using the apparatus is described below.
First, in the plasma pretreatment chamber, plasma is irradiated from the plasma supply nozzle to the surface resin layer included in the intermediate layer. Next, a thin-film deposition film is formed on the plasma-treated surface resin layer in the film-forming chamber.
Details of this forming method will be disclosed in the international publication WO2019 / 0879960 pamphlet.

The surface of the vapor-deposited film is preferably subjected to the above surface treatment. Thereby, the adhesion with the adjacent layer can be improved.

In the barrier laminate of the present invention, the vapor-deposited film is preferably a vapor-deposited film formed by a CVD method, and more preferably a carbon-containing silicon oxide vapor-deposited film formed by a CVD method. As a result, even if the barrier laminate is bent, the decrease in gas barrier can be suppressed.

The carbon-containing silicon oxide vapor deposition film contains silicon, oxygen, and carbon. In the carbon-containing silicon oxide vapor-deposited film, the ratio C of carbon is preferably 3% or more and 50% or less, preferably 5% or more and 40% or less, based on 100% of the total of the three elements of silicon, oxygen, and carbon. More preferably, it is more preferably 10% or more and 35% or less.
By setting the ratio C of carbon in the carbon-containing silicon oxide vapor-deposited film to the above range, it is possible to suppress a decrease in gas barrier property even if the barrier laminate is bent.
In addition, in this specification, the ratio of each element is based on a molar.

In one embodiment of the carbon-containing silicon oxide vapor-deposited film, the ratio Si of silicon is preferably 1% or more and 45% or less, preferably 3% or more, based on 100% of the total of the three elements of silicon, oxygen, and carbon. It is more preferably 38% or less, and further preferably 8% or more and 33% or less. The ratio O of oxygen is preferably 10% or more and 70% or less, more preferably 20% or more and 65% or less, and 25% with respect to 100% of the total of the three elements of silicon, oxygen, and carbon. It is more preferably 60% or more.
By setting the ratio Si of silicon and the ratio O of oxygen in the carbon-containing silicon oxide vapor-deposited film within the above ranges, it is possible to further suppress a decrease in gas barrier property even if the barrier laminate is bent.

In one embodiment of the carbon-containing silicon oxide vapor deposition film, the oxygen ratio O is preferably higher than the carbon ratio C, and the silicon ratio Si is preferably lower than the carbon ratio C. The ratio O of oxygen is preferably higher than the ratio Si of silicon, that is, each ratio is preferably lower in the order of ratio O, ratio C, and ratio Si. As a result, even if the barrier laminate is bent, the decrease in gas barrier can be further suppressed.

The proportion C, proportion Si and proportion O in the carbon-containing silicon oxide vapor-deposited film can be measured by narrow scan analysis under the following measurement conditions by X-ray photoelectron spectroscopy (XPS).
(Measurement condition)
Equipment used: "ESCA-3400" (manufactured by Kratos)
[1] Spectral sampling conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV)
X-ray output: 150W (10kV, 15mA)
X-ray scanning area (measurement area): Approximately 6 mmφ
Photoelectron uptake angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar ⁺
Acceleration voltage: 0.2 (kV)
Emission current: 20 (mA)
etching range: 10 mmφ
Ion sputtering time: Performed in 30 seconds and collected the spectrum

(Middle layer)
The intermediate layer includes at least a surface resin layer and a polypropylene resin layer. Further, the intermediate layer may be provided with an adhesive resin layer between the polypropylene resin layer and the surface resin layer.
In the present invention, the surface resin layer and the polypropylene resin layer (when the adhesive resin layer is provided, the surface resin layer, the polypropylene resin layer and the adhesive resin layer) constituting the intermediate layer are stretched. The stretching treatment may be uniaxial stretching or biaxial stretching.
The stretching ratio of the intermediate layer in the vertical direction (MD direction) and the horizontal direction (TD direction) is preferably 2 times or more and 15 times or less, and preferably 5 times or more and 13 times or less.
By setting the draw ratio to 2 times or more, the strength and heat resistance of the intermediate layer can be further improved. In addition, the printability on the intermediate layer can be improved.
Further, from the viewpoint of the breaking limit of the intermediate layer, the draw ratio is preferably 15 times or less.
Further, when the polypropylene resin layer provided in the intermediate layer has a heat-sealing property and is used as a packaging container (for example, a tube) manufactured by attaching an envelope, the draw ratio shall be 2 times or more and 10 times or less. Is more preferable, and more preferably 2.5 times or more and 7 times or less.

In one embodiment, it is preferable to perform the stretching treatment so that the tensile strength of the intermediate layer in the vertical direction (MD direction) is larger than the tensile strength in the horizontal direction (TD direction).
With such a configuration, it is possible to impart high tearability in one direction to the packaging container produced by the barrier laminate of the present invention.
The tensile strength of the intermediate layer in the vertical direction (MD direction) is preferably 1.05 times or more, more preferably 1.10 times or more, and 1.2 times larger than the tensile strength in the horizontal direction (TD direction). It is more preferable that the size is larger than that.
The tensile strength in the vertical direction (MD direction) can be, for example, 200 MPa or more and 300 MPa or less.
In the present specification, the tensile strength is measured according to JIS K7127: 1999. As the measuring instrument, a tensile tester STA-1150 manufactured by Orientec Co., Ltd. can be used.
As the test piece, a piece obtained by cutting out an intermediate layer into a rectangular film having a width of 15 mm and a length of 150 mm can be used. The distance at the start of measurement between the pair of chucks holding the test piece is 100 mm, and the tensile speed is 300 mm / min. In the present application, unless otherwise specified, the environment at the time of measuring the tensile strength is a temperature of 23 ° C. and a relative humidity of 50%.

Further, the surface resin layer included in the intermediate layer may be surface-treated. Thereby, the adhesion with the adjacent layer can be improved.
The surface treatment method is not particularly limited, for example, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and / or nitrogen gas, physical treatment such as glow discharge treatment, and oxidation using chemicals. Examples include chemical treatment such as treatment.

(Surface resin layer)
The intermediate layer is provided with a surface protective layer containing a resin material having a melting point of 180 ° C. or higher (hereinafter, also referred to as a high melting point resin material) on a polypropylene resin layer, and thin-film deposition having high adhesion is provided on the surface resin layer. A film can be formed and the gas barrier property can be improved.
Further, as will be described later, the packaging container produced by using the barrier laminate provided with the surface resin layer has high lamination strength.

The melting point of the high melting point resin material is more preferably 185 ° C. or higher, further preferably 190 ° C. or higher, and particularly preferably 205 ° C. or higher.
By setting the melting point of the high melting point resin material to 185 ° C. or higher, the adhesion of the vapor-deposited film can be further improved, and the gas barrier property can be further improved. In addition, the laminating strength of the packaging container can be further improved.
From the viewpoint of film forming property of the intermediate layer, the melting point of the high melting point resin material is preferably 260 ° C. or lower, more preferably 260 ° C. or lower, and further preferably 250 ° C. or lower.
In this specification, the melting point can be measured according to JIS K7121: 2012 (method for measuring the transition temperature of plastics). Specifically, a differential scanning calorimetry (DSC) device can be used to measure the DSC curve at a rate of temperature rise of 10 ° C./min to determine the melting point.

The difference between the melting point of the high melting point resin material contained in the surface resin layer and the melting point of polypropylene contained in the polypropylene resin layer is preferably 20 to 80 ° C, more preferably 20 to 60 ° C.
When the difference between the melting point of the high melting point resin material contained in the surface resin layer and the melting point of polypropylene contained in the polypropylene resin layer is 20 ° C. or higher, the adhesion of the vapor-deposited film can be further improved and the gas barrier property can be improved. Can be further improved. In addition, the laminating strength of the packaging container can be further improved.
Further, when the difference between the melting point of the high melting point resin material contained in the intermediate layer and the melting point of polypropylene contained in the polypropylene resin layer is 80 ° C. or less, the film forming property of the intermediate layer can be further improved.

The refractory resin material preferably has a polar group.
In the present invention, the polar group refers to a group containing one or more heteroatoms, for example, an ester group, an epoxy group, a hydroxyl group, an amino group, an amide group, a carboxyl group, a carbonyl group, a carboxylic acid anhydride group, and a sulfone group. , Thiol group and halogen group and the like.
Among these, from the viewpoint of gas barrier properties and laminate strength of the packaging container, a hydroxyl group, an ester group, an amino group, an amide group, a carboxyl group and a carbonyl group are preferable, and an amide group is more preferable.

The high melting point resin material can be used without particular limitation as long as the melting point is 180 ° C. or higher. For example, vinyl resin, polyamide, polyimide, polyester, (meth) acrylic resin, cellulose resin, polyolefin resin and ionomer. Examples include resin.

In the present invention, a resin material having a melting point of 180 ° C. or higher and having a polar group is particularly preferable, such as ethylene vinyl alcohol copolymer, polyvinyl alcohol, polyester, nylon 6, nylon 6,6, MXD nylon, and amorphous nylon. Polyamide is preferable, and nylon 6 is particularly preferable.
By using such a resin material, the adhesion of the thin-film deposition film formed on the surface resin layer can be remarkably improved, and the gas barrier property thereof can be effectively improved.

In one embodiment, the refractory resin material is more preferably an ethylene vinyl alcohol copolymer. By using an ethylene vinyl alcohol copolymer as the refractory resin material, it is possible to suppress a decrease in gas barrier property even if the barrier laminate is bent.

In one embodiment, the refractory resin material is preferably polyamide. By using polyamide as the refractory resin material, it is possible to suppress a decrease in gas barrier property even if the barrier laminate is bent, and when a packaged product is produced using the barrier laminate, heat sealing or the like can be achieved. It is possible to suppress the deterioration of the gas barrier property even if the heating is performed. Nylon 6 is more preferable as the refractory resin material.

The content of the refractory resin material in the surface resin layer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

The surface resin layer may contain a resin material other than the refractory resin material as long as the characteristics of the present invention are not impaired.
Further, the surface resin layer may contain an additive as long as the characteristics of the present invention are not impaired, and for example, a cross-linking agent, an antioxidant, an anti-blocking agent, a slip agent, an ultraviolet absorber, and a light stabilizer. Examples include agents, fillers, reinforcing agents, antistatic agents, pigments and modifying resins.

The ratio of the thickness of the surface resin layer to the total thickness of the intermediate layer is preferably 1% or more and 10% or less, and more preferably 1% or more and 5% or less.
By setting the ratio of the thickness of the surface resin layer to the total thickness of the intermediate layer to 1% or more, the adhesion of the thin-film deposition film can be further improved, and the gas barrier property can be further improved. In addition, the laminating strength of the packaging container can be further improved.
Further, by setting the ratio of the thickness of the surface resin layer to the total thickness of the intermediate layer to 10% or less, the film-forming property and processability of the intermediate layer can be further improved. Further, it is possible to improve the recyclability of the packaging container produced by using the laminate provided with the base material composed of polypropylene and the sealant layer.

The thickness of the surface resin layer is preferably 0.1 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 4 μm or less.
By setting the thickness of the surface resin layer to 0.1 μm or more, the adhesion of the thin-film deposition film can be further improved, and the gas barrier property can be further improved. In addition, the laminating strength of the packaging container can be further improved.
Further, by setting the thickness of the surface resin layer to 5 μm or less, the film-forming property and processability of the intermediate layer material can be further improved. In addition, it is possible to improve the recyclability of the packaging container produced by using the laminate provided with the base material composed of polypropylene and the sealant layer.

(Polypropylene resin layer)
The polypropylene resin layer is made of polypropylene and may have a single-layer structure or a multi-layer structure.
By providing the intermediate layer with a layer made of polypropylene, it is possible to improve the oil resistance of the packaging container produced by using the barrier laminate provided with the intermediate layer.

The polypropylene contained in the polypropylene resin layer may be a homopolymer, a random copolymer or a block copolymer.
The polypropylene homopolymer is a polymer containing only propylene, and the polypropylene random copolymer is a polymer of propylene and other α-olefins other than propylene (for example, ethylene, butene-1, 4-methyl-1-pentene, etc.). It is a random copolymer, and the polypropylene block copolymer is a polymer having a polymer block made of propylene and a polymer block made of α-olefin other than the above-mentioned propylene.
Among these polypropylenes, it is preferable to use a homopolymer or a random copolymer from the viewpoint of transparency. It is preferable to use a homopolymer when the rigidity and heat resistance of the packaging bag are important, and to use a random copolymer when the impact resistance and the like are important.
Biomass-derived polypropylene and mechanically or chemically recycled polypropylene can also be used.

The polypropylene content in the polypropylene resin layer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

As long as the characteristics of the present invention are not impaired, the polypropylene resin layer may contain a resin material other than polypropylene, for example, polyolefin such as polyethylene, (meth) acrylic resin, vinyl resin, cellulose resin, polyamide resin, polyester. And ionomer resin and the like.
Further, the polypropylene resin layer can contain an additive as long as the characteristics of the present invention are not impaired, and for example, a cross-linking agent, an antioxidant, an anti-blocking agent, a slip agent, an ultraviolet absorber, and a light stabilizer. Examples include agents, fillers, reinforcing agents, antistatic agents, pigments and modifying resins.

The thickness of the polypropylene resin layer is preferably 10 μm or more and 50 μm or less, and more preferably 10 μm or more and 40 μm or less.
By setting the thickness of the polypropylene resin layer to 10 μm or more, the strength and heat resistance of the intermediate layer can be further improved.
Further, by setting the thickness of the polypropylene resin layer to 50 μm or less, the film-forming property and processability of the intermediate layer can be further improved.

(Adhesive resin layer)
In one embodiment, the intermediate layer can be provided with an adhesive resin layer between the polypropylene resin layer and the surface resin layer, whereby the adhesion between these layers can be improved.

The adhesive resin layer can be formed by using an adhesive resin such as a polyether, a polyester, a silicone resin, an epoxy resin, a polyurethane, a vinyl resin, a phenol resin, a polyolefin, and an acid-modified product of a polyolefin.
Among the above, polyolefin and its acid-modified product are preferable from the viewpoint of recycling suitability of a packaging container made of a laminate having a base material and a sealant layer composed of polyproprene, and polypropylene and this acid-modified product are preferable. Acid-modified products are particularly preferable.
As the adhesive polypropylene, commercially available polypropylene can be used, and for example, Admer series manufactured by Mitsui Chemicals, Inc. can be used.

The thickness of the adhesive resin layer is not particularly limited, but can be, for example, 1 μm or more and 15 μm or less. By setting the thickness of the adhesive resin layer to 1 μm or more, the adhesion between the polypropylene resin layer and the surface resin layer can be further improved. By setting the thickness of the adhesive layer to 15 μm or less, the processability of the intermediate layer can be improved.

In one embodiment, the intermediate layer is a co-pressed film, which can be produced by forming a film by using a T-die method, an inflation method, or the like, forming a laminated film, and then stretching the film.
By forming a film by the inflation method, the laminated film can be stretched at the same time.

(Sealant layer)
In one embodiment, the sealant layer comprises a resin material that can be fused to each other by heat.
Resin materials that can be fused to each other by heat include, for example, polyolefins such as polyethylene, polypropylene, polybutene, methylpentene polymer and cyclic olefin copolymer. Specifically, low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear (linear) low-density polyethylene (LLDPE), and ethylene copolymerized using a metallocene catalyst. Examples thereof include α-olefin copolymers and polyethylene-propylene copolymers such as random or block copolymers of ethylene and propylene.
Examples of resin materials that can be fused to each other by heat include ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), and ethylene-ethyl acrylate copolymer (EEA). , Ethylene-Methylacrylate Copolymer (EMAA), Ethylene-Methyl Methacrylate Copolymer (EMMA), Ionomer Resin, Heat Sealable Ethylene-Vinyl Alcohol Resin, Polyethylene as Acrylic Acid, Methacrylate, Maleic Acid, Maleic anhydride , Acid-modified polyolefin modified with unsaturated carboxylic acids such as fumaric acid and itaconic acid, polyesters such as polyethylene terephthalate (PET), polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, etc. Be done.
Among the above-mentioned resin materials, the sealant layer is preferably made of polypropylene from the viewpoint of recycling suitability of the packaging container produced by using the barrier laminate of the present invention.
Further, by forming the sealant layer with polypropylene, the oil resistance of the packaging container produced by using the barrier laminate can be improved.

The sealant layer can contain a heat seal modifier. Thereby, the heat sealability can be improved. The heat seal modifier is not particularly limited as long as it has excellent compatibility with a resin material constituting the heat seal layer, for example, polypropylene, and examples thereof include an olefin copolymer.
In addition, the sealant layer may contain the above-mentioned additive as long as the characteristics of the present invention are not impaired.

The sealant layer may have a single-layer structure or may have a multi-layer structure.
Further, the sealant layer may be one that has been stretched or one that has not been stretched.

The thickness of the sealant layer is preferably 15 μm or more and 100 μm or less, and more preferably 20 μm or more and 70 μm or less.
By setting the thickness of the sealant layer to 15 μm or more, the laminate strength of the packaging container provided with the barrier laminate of the present invention can be further improved.
Further, by setting the thickness of the sealant layer to 100 μm or less, the processability of the barrier laminate of the present invention can be further improved.

In one embodiment, the sealant layer is made of a film made of the above resin material, and can be formed by laminating this with an intermediate layer via the above adhesive layer.
Further, in another embodiment, the sealant layer can be formed by applying and drying a heat sealant containing the above resin material on the intermediate layer.

(Barrier coat layer)
The barrier laminate of the present invention can further include a barrier coat layer between the adhesive layer and the vapor-deposited film. Thereby, the oxygen barrier property and the water vapor barrier property of the barrier laminated body can be improved.

In one embodiment, the barrier coat layer is a polyamide such as ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyacrylonitrile, nylon 6, nylon 6,6 and polymethoxylylen adipamide (MXD6). , Polyester, polyurethane, and gas barrier resins such as (meth) acrylic resins. Among these, polyvinyl alcohol is preferable from the viewpoint of oxygen barrier property and water vapor barrier property.
Further, by incorporating polyvinyl alcohol in the barrier coat layer, it is possible to effectively prevent the occurrence of cracks in the vapor-deposited film.

The content of the gas barrier resin in the barrier coat layer is preferably 50% by mass or more and 95% by mass or less, and more preferably 75% by mass or more and 90% by mass or less. By setting the content of the gas barrier resin in the barrier coat layer to 50% by mass or more, the oxygen barrier property and the water vapor barrier property can be further improved.

The barrier coat layer can contain the above additives as long as the characteristics of the present invention are not impaired.

The thickness of the barrier coat layer is preferably 0.01 μm or more and 10 μm or less, and more preferably 0.1 μm or more and 5 μm or less.
By setting the thickness of the barrier coat layer to 0.01 μm or more, the oxygen barrier property and the water vapor barrier property of the barrier laminate can be further improved. By setting the thickness of the barrier coat layer to 10 μm or less, the processability of the barrier laminate can be improved. In addition, it is possible to improve the recyclability of the packaging container produced by using the laminate provided with the base material composed of polypropylene and the sealant layer.

The barrier coat layer can be formed by dissolving or dispersing the gas barrier resin in water or a suitable solvent, applying the resin, and drying the resin. The barrier coat layer can also be formed by applying a commercially available barrier coat agent and drying it.

Further, in another embodiment, the barrier coat layer is obtained by polycondensing a mixture of a metal alkoxide and a water-soluble polymer by a sol-gel method in the presence of a sol-gel method catalyst, water, an organic solvent, or the like. It is a gas barrier coating film containing at least one resin composition such as a hydrolyzate of the above or a hydrolyzed condensate of a metal alkoxide.
By providing such a barrier coat layer on the thin-film deposition film, it is possible to effectively prevent the occurrence of cracks in the thin-film deposition film.

In one embodiment, the metal alkoxide is represented by the following general formula.
R ¹ _n M (OR ² ) _m
(However, in the formula, R ¹ and R ² each represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents an integer of 1 or more. , N + m represents the valence of M.)

As the metal atom M, for example, silicon, zirconium, titanium, aluminum and the like can be used.
Examples of the organic group represented by R ¹ and R ² include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group. Can be done.

The metal alkoxide satisfying the above general formula, for example, tetramethoxysilane _{(Si (OCH 3) 4)} , tetraethoxysilane _{(Si (OC 2 H 5)} 4), tetra propoxy silane _{(Si (OC 3 H 7)} 4 ), Tetrabutoxysilane (Si (OC ₄ H ₉ ) ₄ ) and the like.

Further, it is preferable to use a silane coupling agent together with the above metal alkoxide.
As the silane coupling agent, known organic reactive group-containing organoalkoxysilanes can be used, but organoalkoxysilanes having an epoxy group are particularly preferable. Examples of the organoalkoxysilane having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Be done.

Two or more kinds of the above-mentioned silane coupling agent may be used, and the silane coupling agent is used within the range of about 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the above metal alkoxide. It is preferable to do so.

As the water-soluble polymer, polyvinyl alcohol and ethylene-vinyl alcohol copolymer are preferable, and from the viewpoint of oxygen barrier property, water vapor barrier property, water resistance and weather resistance, it is preferable to use these in combination.

The content of the water-soluble polymer in the gas barrier coating film is preferably 5 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the metal alkoxide.
By setting the content of the water-soluble polymer in the gas barrier coating film to 5 parts by mass or more with respect to 100 parts by mass of the metal alkoxide, the oxygen barrier property and the water vapor barrier property of the barrier laminate can be further improved. .. Further, by setting the content of the water-soluble polymer in the gas barrier coating film to 500 parts by mass or less with respect to 100 parts by mass of the metal alkoxide, the film forming property of the gas barrier coating film can be improved.

In the gas barrier coating film, the ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) is preferably 4.5 or less, preferably 1.0 or more and 4.5 or less, based on the mass. More preferably, it is more preferably 1.7 or more and 3.5 or less.
By setting the ratio of the metal alkoxide to the water-soluble polymer to 4.5 or less, it is possible to suppress a decrease in gas barrier property even if the barrier laminate is bent.
By setting the ratio of the metal alkoxide to the water-soluble polymer to 1.0 or more, it is possible to suppress a decrease in gas barrier property even if heating such as heat sealing is performed when a packaged product is produced using the barrier laminate. ..
The above ratio is a solid content ratio.

On the surface of the gas barrier coating film, the ratio of silicon atoms to carbon atoms (Si / C) measured by X-ray photoelectron spectroscopy (XPS) is preferably 1.60 or less, and 0.50 or more. It is more preferably 60 or less, and further preferably 0.90 or more and 1.35 or less.
By setting the ratio of silicon atoms to carbon atoms to 1.60 or less, it is possible to suppress a decrease in gas barrier properties even if the barrier laminate is bent.
By setting the ratio of silicon atoms to carbon atoms to 0.50 or more, it is possible to suppress a decrease in gas barrier properties even when heating such as heat sealing is performed when a packaged product is produced using a barrier laminate.
The above range of the ratio of the silicon atom to the carbon atom can be achieved by appropriately adjusting the ratio of the metal alkoxide to the water-soluble polymer.
In this specification, the ratio of silicon atom to carbon atom is on a molar basis.

The ratio of silicon atoms to carbon atoms by X-ray photoelectron spectroscopy (XPS) can be measured by narrow scan analysis under the following measurement conditions.
(Measurement condition)
Equipment used: "ESCA-3400" (manufactured by Kratos)
[1] Spectral sampling conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV)
X-ray output: 150W (10kV, 15mA)
X-ray scanning area (measurement area): Approximately 6 mmφ
Photoelectron uptake angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar ⁺
Acceleration voltage: 0.2 (kV)
Emission current: 20 (mA)
etching range: 10 mmφ
Ion sputtering time: 30 seconds + 30 seconds + 60 seconds (total 120 seconds), and the spectrum was collected.

The thickness of the gas barrier coating film is preferably 0.01 μm or more and 100 μm or less, and more preferably 0.1 μm or more and 50 μm or less. Thereby, the oxygen barrier property and the water vapor barrier property can be further improved while maintaining the recyclability.
By setting the thickness of the gas barrier coating film to 0.01 μm or more, the oxygen barrier property and the water vapor barrier property of the barrier laminate can be improved. In addition, it is possible to prevent the occurrence of cracks in the thin-film deposition film.
By setting the thickness of the gas barrier coating film to 100 μm or less, it is possible to improve the recyclability of the packaging container produced by using the laminate of the barrier laminate of the present invention and the sealant layer made of polypropylene. ..

The gas barrier coating film is prepared by applying a composition containing the above materials by a conventionally known means such as a roll coating such as a gravure roll coater, a spray coating, a spin coating, dipping, a brush, a bar code, and an applicator, and the composition thereof. The product can be formed by polycondensing the product by the sol-gel method.
As the sol-gel method catalyst, an acid or amine compound is suitable. As the amine compound, a tertiary amine which is substantially insoluble in water and soluble in an organic solvent is preferable, and for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, and trypentyl are preferable. Amine and the like can be mentioned. Among these, N, N-dimethylbenzylamine is preferable.
The sol-gel method catalyst is preferably used in the range of 0.01 parts by mass or more and 1.0 parts by mass or less, and 0.03 parts by mass or more and 0.3 parts by mass or less per 100 parts by mass of the metal alkoxide. Is more preferable.
By setting the amount of the sol-gel method catalyst to be 0.01 part by mass or more per 100 parts by mass of the metal alkoxide, the catalytic effect can be improved. Further, by setting the amount of the sol-gel method catalyst to be 1.0 part by mass or less per 100 parts by mass of the metal alkoxide, the thickness of the formed gas barrier coating film can be made uniform.

The composition may further contain an acid. The acid is used as a catalyst for the sol-gel process, mainly as a catalyst for hydrolysis of metal alkoxides, silane coupling agents and the like.
As the acid, for example, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid are used. The amount of the acid used is preferably 0.001 mol or more and 0.05 mol or less with respect to the total molar amount of the alkoxide content (for example, the silicate portion) of the metal alkoxide and the silane coupling agent.
The catalytic effect can be improved by setting the amount of the acid to be 0.001 mol or more with respect to the total molar amount of the alkoxide content (for example, the silicate portion) of the metal alkoxide and the silane coupling agent. Further, the thickness of the gas barrier coating film formed by setting the amount of acid used to 0.05 mol or less with respect to the total molar amount of the alkoxide content (for example, the silicate portion) of the metal alkoxide and the silane coupling agent. Can be made uniform.

The composition also contains water at a ratio of preferably 0.1 mol or more and 100 mol or less, more preferably 0.8 mol or more and 2 mol or less, based on 1 mol of the total molar amount of the metal alkoxide. Is preferable.
By setting the water content to 0.1 mol or more with respect to 1 mol of the total molar amount of the metal alkoxide, the oxygen barrier property and the water vapor barrier property of the barrier laminate of the present invention can be improved. Further, by setting the water content to 100 mol or less with respect to 1 mol of the total molar amount of alkoxide, the hydrolysis reaction can be carried out rapidly.

Moreover, the said composition may contain an organic solvent. As the organic solvent, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used.

Hereinafter, an embodiment of a method for forming a gas barrier coating film will be described below.
First, a composition is prepared by mixing a metal alkoxide, a water-soluble polymer, a sol-gel method catalyst, water, an organic solvent and, if necessary, a silane coupling agent. The polycondensation reaction gradually proceeds in the composition.
Next, the composition is applied and dried on the thin-film deposition film by the above-mentioned conventionally known method. By this drying, the polycondensation reaction of the metal alkoxide and the water-soluble polymer (and the silane coupling agent if the composition contains a silane coupling agent) further proceeds to form a layer of the composite polymer.
Finally, the gas barrier coating film can be formed by heating the composition at a temperature of, for example, 20 to 250 ° C., preferably 50 to 220 ° C. for 1 second to 10 minutes.

A printing layer may be formed on the surface of the barrier coat layer. The method of forming the print layer and the like are as described above.

(Barrier laminate in the second aspect)
As shown in FIG. 8, the barrier laminate 20 of the present invention includes a base material 21, an adhesive layer 22, a vapor-deposited film 23, an intermediate layer 24, and a sealant layer 25, and the intermediate layer 24 includes a base material 21, an adhesive layer 22, a vapor deposition film 23, and a sealant layer 25. A coat layer 26 and a polypropylene resin layer 27 are provided.
In one embodiment, the barrier laminate 20 of the present invention further includes a barrier coat layer 28 between the adhesive layer 22 and the vapor deposition film 23, as shown in FIG.

In the barrier laminate according to the second aspect, the lamination strength between the intermediate layer and the vapor-deposited film is preferably 3N or more, more preferably 4N or more, and further preferably 5.5N or more in a width of 15 mm. The upper limit of the laminate strength of the barrier laminate in the second aspect may be 20 N or less.
The method for measuring the laminate strength of the barrier laminate will be described in Examples described later.

Similar to the first aspect, it is preferable that the base material and the sealant base material are made of the same material as the polyproprene resin layer provided in the intermediate layer, that is, polypropylene. Thereby, the recyclability of the packaging container produced by using the barrier laminate of the present invention can be improved.

When the base material and the sealant layer are composed of polypropylene, the content of polypropylene with respect to the total amount of the resin material contained in the barrier laminate of the present invention is preferably 80% by mass or more, preferably 95% by mass or more. Is more preferable. Thereby, the recyclability of the packaging container produced by using the barrier laminate of the present invention can be further improved.

Hereinafter, the intermediate layer provided in the barrier laminate of the present invention will be described. The layers other than the intermediate layer provided by the barrier laminate in the second aspect are the same as those in the barrier laminate in the first aspect, and thus the description thereof will be omitted here.

(Middle layer)
The intermediate layer includes a surface coat layer and a polypropylene resin layer.

(Surface coat layer)
The intermediate layer is provided with a surface coat layer containing a resin material having a polar group on a polypropylene resin layer, and a vapor-deposited film having high adhesion can be formed on the surface coat layer to improve gas barrier properties. be able to.
Further, as will be described later, the packaging container produced by using the barrier laminate provided with the surface coating layer has high lamination strength.

The surface coat layer contains a resin material having a polar group, and in the present invention, the polar group refers to a group containing one or more heteroatoms, for example, an ester group, an epoxy group, a hydroxyl group, an amino group, an amide group, and a carboxyl group. Examples thereof include a group, a carbonyl group, a carboxylic acid anhydride group, a sulfone group, a thiol group and a halogen group.
Among these, from the viewpoint of the laminate property of the packaging container, a carboxyl group, a carbonyl group, an ester group, a hydroxyl group and an amino group are preferable, and a carboxyl group and a hydroxyl group are more preferable.

Examples of the resin material having a polar group include ethylene vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyester, polyethyleneimine, hydroxyl group-containing (meth) acrylic resin, nylon 6, nylon 6,6, MXD nylon, and amorphous. Polyamides such as nylon and polyurethane are preferable, and polyamides, hydroxyl group-containing (meth) acrylic resins, ethylene vinyl alcohol copolymers and polyvinyl alcohols are particularly preferable.
By using such a resin material, the adhesion of the thin-film deposition film formed on the surface coat layer can be remarkably improved, and the gas barrier property thereof can be effectively improved.

In the present invention, the surface coat layer can be formed by using an aqueous emulsion or a solvent-based emulsion. Specific examples of the aqueous emulsion include polyamide-based emulsions, polyethylene-based emulsions, polyurethane-based emulsions, and the like, and specific examples of solvent-based emulsions include polyester-based emulsions and the like.

The content of the resin material having a polar group in the surface coat layer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

The surface coating layer may contain a resin material other than the resin material having a polar group as long as the characteristics of the present invention are not impaired.
Further, the surface coating layer can contain additives as long as the characteristics of the present invention are not impaired, and for example, a cross-linking agent, an antioxidant, an anti-blocking agent, a slip agent, an ultraviolet absorber, and a light stabilizer. Examples include agents, fillers, reinforcing agents, antistatic agents, pigments and modifying resins.

The ratio of the thickness of the surface coat layer to the total thickness of the intermediate layer is preferably 0.08% or more and 20% or less, more preferably 0.2% or more and 20% or less, and 1% or more. It is more preferably 20% or less, and even more preferably 3% or more and 10% or less.
By setting the ratio of the thickness of the surface coat layer to the total thickness of the intermediate layer to 0.08% or more, the adhesion of the thin-film deposition film can be further improved, and the gas barrier property can be further improved. .. In addition, the laminating strength of the packaging container can be further improved.
Further, by setting the ratio of the thickness of the surface coat layer to the total thickness of the intermediate layer to 20% or less, the processability of the intermediate layer can be further improved. In addition, it is possible to improve the recyclability of the packaging container produced by using the laminate provided with the base material composed of polypropylene and the sealant layer.

The thickness of the surface coat layer is preferably 0.02 μm or more and 10 μm or less, more preferably 0.05 μm or more and 10 μm or less, more preferably 0.1 μm or more and 10 μm or less, and 0.2 μm or more. It is more preferably 5 μm or less.
By setting the thickness of the surface coat layer to 0.02 μm or more, the adhesion of the thin-film deposition film can be further improved, and the gas barrier property can be further improved. In addition, the laminating strength of the packaging container can be further improved.
Further, by setting the thickness of the surface coat layer to 10 μm or less, the processability of the intermediate layer can be further improved. In addition, it is possible to improve the recyclability of the packaging container produced by using the laminate provided with the base material composed of polypropylene and the sealant layer.

(Polypropylene resin layer)
The polypropylene resin layer is made of polypropylene and may have a single-layer structure or a multi-layer structure.
By providing the intermediate layer with a layer made of polypropylene, it is possible to improve the oil resistance of the packaging container produced by using the barrier laminate provided with the intermediate layer.

The polypropylene resin layer is a film that has been stretched, and the stretching treatment may be uniaxial stretching or biaxial stretching.
The draw ratio of the polypropylene resin layer in the vertical direction (MD direction) and the horizontal direction (TD direction) is preferably 2 times or more and 15 times or less, and preferably 5 times or more and 13 times or less.
By setting the draw ratio to 2 times or more, the strength and heat resistance of the polypropylene resin layer can be further improved. In addition, the printability on the polypropylene resin layer can be improved.
Further, from the viewpoint of the breaking limit of the polypropylene resin layer, the draw ratio is preferably 15 times or less.

The polypropylene contained in the polypropylene resin layer may be a homopolymer, a random copolymer or a block copolymer.
The polypropylene homopolymer is a polymer containing only propylene, and the polypropylene random copolymer is a polymer of propylene and other α-olefins other than propylene (for example, ethylene, butene-1, 4-methyl-1-pentene, etc.). It is a random copolymer, and the polypropylene block copolymer is a polymer having a polymer block made of propylene and a polymer block made of α-olefin other than the above-mentioned propylene.
Among these polypropylenes, it is preferable to use a homopolymer or a random copolymer from the viewpoint of transparency. It is preferable to use a homopolymer when the rigidity and heat resistance of the packaging bag are important, and to use a random copolymer when the impact resistance and the like are important.
Biomass-derived polypropylene and mechanically or chemically recycled polypropylene can also be used.

The polypropylene content in the polypropylene resin layer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

As long as the characteristics of the present invention are not impaired, the polypropylene resin layer may contain a resin material other than polypropylene, for example, polyolefin such as polyethylene, (meth) acrylic resin, vinyl resin, cellulose resin, polyamide resin, polyester. And ionomer resin and the like.
Further, the polypropylene resin layer can contain an additive as long as the characteristics of the present invention are not impaired, and for example, a cross-linking agent, an antioxidant, an anti-blocking agent, a slip agent, an ultraviolet absorber, and a light stabilizer. Examples include agents, fillers, reinforcing agents, antistatic agents, pigments and modifying resins.

The thickness of the polypropylene resin layer is preferably 10 μm or more and 50 μm or less, and more preferably 10 μm or more and 40 μm or less.
By setting the thickness of the polypropylene resin layer to 10 μm or more, the strength and heat resistance of the intermediate layer can be further improved.
Further, by setting the thickness of the polypropylene resin layer to 50 μm or less, the film-forming property and processability of the intermediate layer can be further improved.

Further, the polypropylene resin layer may be surface-treated. Thereby, the adhesion with the surface coat layer can be improved.
The surface treatment method is not particularly limited, for example, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and / or nitrogen gas, physical treatment such as glow discharge treatment, and oxidation using chemicals. Examples include chemical treatment such as treatment.

The intermediate layer can be manufactured offline. Specifically, a resin composition containing polypropylene is formed into a film by using a T-die method, an inflation method, or the like to form a resin film, and then stretched to obtain the resin. It can be produced by applying a coating liquid for coating on a film and drying it.
The intermediate layer can also be manufactured in-line. Specifically, a resin composition containing polypropylene is formed into a film by using a T-die method, an inflation method, or the like to form a resin film, and then in the vertical direction (MD). It can be produced by stretching in the direction), applying a coating liquid for coating on the resin film, drying, and then stretching in the lateral direction (TD direction). It should be noted that the stretching in the lateral direction may be performed first.

(Packaging container)
The packaging container of the present invention is characterized by comprising the above-mentioned barrier laminate. Examples of the packaging container include a packaging product (packaging bag), a lid material, and a laminated tube.

As a packaging bag, for example, standing pouch type, side seal type, two-way seal type, three-way seal type, four-way seal type, envelope-attached seal type, gassho-attached seal type (pillow-seal type), fold-attached seal type, flat-bottom seal type. , Various types of packaging bags such as a square bottom seal type and a gusset type.

As shown in FIG. 10, the packaging container of the present invention is a packaging bag 30 in which two barrier laminates are bonded together (the shaded area is a heat-sealed portion).
When the tensile strength of the intermediate layer in the vertical direction (MD direction) is larger than the tensile strength in the horizontal direction (TD direction), the vertical direction (MD direction) of the intermediate layer is in the horizontal direction of the packaging bag 30. It is preferable to manufacture the packaging bag so that the horizontal direction (TD direction) of the package corresponds to the vertical direction of the packaging bag 30. With such a configuration, it becomes extremely easy to tear the packaging container in the lateral direction. The same applies to the packaging containers illustrated below.

As shown in FIG. 11, the packaging container of the present invention is a standing pouch 40.
FIG. 11 is a diagram briefly showing an example of the configuration of the standing pouch. As shown in FIG. 11, the standing pouch 40 is composed of a body portion (side sheet) 41 and a bottom portion (bottom sheet) 42.
At least one of the side sheet 41 and the bottom sheet 42 included in the standing pouch 40 is composed of the barrier laminate of the present invention.

In one embodiment, the body portion 41 included in the standing pouch 40 can be formed by making a bag so that the sealant layer included in the barrier laminate of the present invention is the innermost layer.
In another embodiment, for the side sheet 41, two barrier laminates of the present invention are prepared, these are laminated so that the sealant layers face each other, and the sealant layer is formed from both ends of the laminated barrier laminate. It can be formed by inserting two V-shaped laminated bodies and heat-sealing them so that the surface is on the outside. According to such a manufacturing method, a stand pouch having a body portion with a side gusset can be obtained.

Further, in one embodiment, the bottom sheet 42 included in the standing pouch 40 can be formed by inserting the barrier laminate of the present invention between the bag-made side sheets and heat-sealing. More specifically, the barrier laminate can be formed by folding it in a V shape so that the sealant layer is on the outside, inserting it between the bag-made side sheets, and heat-sealing it.

Further, as shown in FIG. 10, the packaging container may be provided with the easy-opening means 51.
Examples of the easy-opening means 51 include a notch portion 52 which is a starting point of tearing and a half-cut line 53 formed by laser processing or a cutter as a path for tearing, as shown in FIG.

Further, as shown in FIG. 11, the packaging container may be provided with the steam venting mechanism 60. When the steam pressure in the packaging container exceeds a predetermined value, the steam bleeding mechanism 60 communicates the inside and the outside of the packaging container to release the steam, and at the same time, the steam is released at a place other than the steam bleeding mechanism 60. It is configured to suppress.
The steam bleeding mechanism 50 includes a steam bleeding seal portion 60a protruding from the side seal portion toward the inside of the packaging container, and a non-seal portion 60b isolated from the contents accommodating portion by the steam bleeding seal portion 60a.
The non-seal portion 60b communicates with the outside for easy packaging. By heating the packaging container in which the contents are filled and the opening is heat-sealed by a microwave oven or the like, the internal pressure is increased and the steam-sealed portion 60a is peeled off. The steam passes through the peeled portion of the steam seal 60a and the non-sealed portion 60b and escapes to the outside of the packaging container.

As a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal can be used.

The contents to be filled in the packaging container are not particularly limited, and the contents may be a liquid, a powder or a gel. Moreover, it may be food or non-food.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1-1
Polyamide (manufactured by Ube Kosan Co., Ltd., polyamide 6, melting point: 220 ° C.), adhesive resin (manufactured by Mitsui Chemicals Co., Ltd., Admer QF500, maleic anhydride-modified polypropylene), and polypropylene (manufactured by Nippon Polypro Co., Ltd., Novatec FL203D, melting point: 160 ° C.) is co-extruded and then stretched 5 times in the vertical direction (MD direction) and 10 times in the horizontal direction (TD direction) by a sequential biaxial stretching device to form a surface resin made of polypropylene. An intermediate layer having a thickness of 21 μm was prepared, comprising a layer (19.6 μm), an adhesive resin layer made of an adhesive resin (1 μm), and a polypropylene resin layer made of polypropylene (0.4 μm). The ratio of the thickness of the surface resin layer made of polyamide to the layer thickness of the intermediate layer was 2%.

Carbon-containing oxidation with a thickness of 12 nm on the surface resin layer of the intermediate layer prepared as described above while applying tension to the intermediate layer by Roll to Roll using an actual low-temperature plasma chemical vapor deposition apparatus. A silicon vapor deposition film was formed (CVD method). The conditions for forming the vapor-deposited film were as follows.
(Formation conditions)
-Hexamethyldisiloxane: Oxygen gas: Helium = 1:10:10 (Unit: slm)
・ Cooling / electrode drum supply power: 22kW
・ Line speed: 100m / min

In the carbon-containing silicon oxide vapor deposition film, the ratio C of carbon, the ratio Si of silicon, and the ratio O of oxygen are 32.7% and 29, respectively, with respect to 100% of the total of the three elements of silicon, oxygen, and carbon. It was 8.8% and 37.5%. The proportion of each element was measured by X-ray photoelectron spectroscopy (XPS) by narrow scan analysis under the following measurement conditions.
(Measurement condition)
Equipment used: "ESCA-3400" (manufactured by Kratos)
[1] Spectral sampling conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV)
X-ray output: 150W (10kV, 15mA)
X-ray scanning area (measurement area): Approximately 6 mmφ
Photoelectron uptake angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar ⁺
Acceleration voltage: 0.2 (kV)
Emission current: 20 (mA)
etching range: 10 mmφ
Ion sputtering time: Performed in 30 seconds and collected the spectrum

385 g of water, 67 g of isopropyl alcohol and 9.1 g of 0.5N hydrochloric acid were mixed to obtain a prepared solution having a pH of 2.2. To this solution, 175 g of tetraethoxysilane as a metal alkoxide and 9.2 g of glycidoxypropyltrimethoxysilane as a silane coupling agent were mixed while cooling at 10 ° C. to obtain a solution A.
As a water-soluble polymer, 14.7 g of polyvinyl alcohol having a degree of polymerization of 99% or more and a degree of polymerization of 2400 and 17 g of 324 g of water and 17 g of isopropyl alcohol were mixed to obtain a solution B.
Solution A and Solution B were mixed so that the ratio was 6.5: 3.5 on a mass basis to obtain a barrier coating agent.

A barrier coating agent was coated on the vapor-deposited film formed on the intermediate layer by a spin coating method, and heat-treated in an oven at 80 ° C. for 60 seconds to form a barrier coating layer having a thickness of 300 nm.

On the barrier coat layer formed as described above, an adhesive containing a polyester polyol and an isocyanate compound (manufactured by DIC Corporation, trade name: PASLIM VM001 / VM102CP (blending ratio 1: 1)) has a thickness of 3 μm. An adhesive layer was formed, and a stretched polyproprene film (manufactured by Mitsui Chemicals Tohcello Corporation, U1) having a thickness of 20 μm was laminated as a base material through the adhesive layer.

A polyurethane adhesive (Mitsui Chemicals, Inc., Takelac A-969V / Takenate A-5 (blending ratio 3/1)) is used to form an adhesive layer with a thickness of 1 μm on the polyproprene resin layer of the intermediate layer. An unstretched polyproprene film (manufactured by Mitsui Chemicals Tohcello Co., Ltd., CPS) having a thickness of 30 μm was laminated as a sealant layer through this adhesive layer to obtain the barrier laminate of the present invention.
The polypropylene content in the barrier laminate was 92% by mass.

Example 1-2
A barrier laminate was produced in the same manner as in Example 1-1, except that the sealant layer was changed to a heat-sealable biaxially stretched polypropylene film (manufactured by Toyo Co., Ltd., P6181) having a thickness of 30 μm.
The polypropylene content in the barrier laminate was 9% by mass.

Example 1-3
Example 1-1 except that a polypropylene-based heat-sealing material (Arrow Base DA1010N manufactured by Unitika Ltd.) was applied onto the polyproprene resin layer of the intermediate layer and dried to form a sealant layer having a thickness of 3 μm. In the same manner as above, the barrier laminate of the present invention was obtained.
The polypropylene content in the barrier laminate was 82% by mass.

Example 1-4
Example 1-Except that the polyamide used for producing the intermediate layer was changed to polyvinyl alcohol (manufactured by Japan Vam & Poval Co., Ltd., Bhopal JC-33, melting point: 200 ° C.) to form a surface resin layer. A barrier laminate was produced in the same manner as in 1.

Example 2-1
A 20 μm-thick biaxially stretched polypropylene film (ME-1 manufactured by Mitsui Chemicals Tocello Co., Ltd.) having one surface treated with corona is coated with a solution for forming a surface coat layer having the following composition and dried. Then, a surface coat layer having a thickness of 0.5 μm was formed to prepare an intermediate layer.
(Composition of coating liquid for forming surface coat layer)
・ Polyvinyl alcohol 5% by mass
(Manufactured by Japan Vam & Poval Co., Ltd., VC-10, degree of polymerization 1000, degree of saponification 99.3 mol% or more)
・ Water 90% by mass
・ Isopropanol (IPA) 5% by mass

A barrier laminate was prepared in the same manner as in Example 1-1, except that the intermediate layer prepared in Example 1-1 was changed to the intermediate layer prepared as described above.
The polypropylene content in the barrier laminate was 93% by mass.

Example 2-2
A barrier laminate was produced in the same manner as in Example 2-1 except that the composition of the coating liquid for forming the surface coat layer was changed as follows.
The polypropylene content in the barrier laminate was 93% by mass.
(Composition of coating liquid for forming surface coat layer)
・ EVOH 75% by mass
(Made by Nissan Cima Co., Ltd., Eversolve # 10)
・ Water 12.5% by mass
1-propanol 12.5% by mass

Comparative Example 1-1
After extruding the above polypropylene (manufactured by Japan Polypropylene Corporation, Novatec FL203D, melting point: 160 ° C.), it is stretched 5 times in the vertical direction (MD direction) and 10 times in the horizontal direction (TD direction) by a sequential biaxial stretching device. Then, a propylene film having a thickness of 20 μm was prepared.
A barrier laminate was prepared in the same manner as in Example 1-1, except that the intermediate layer in Example 1-1 was changed to the polypropylene film prepared as described above.

<< Evaluation of gas barrier property >>
The barrier laminates obtained in the above Examples and Comparative Examples were cut out to obtain test pieces. Using this test piece, oxygen permeability (cc / m ² · day · atm) and water vapor permeability (g / m ² · day) were measured by the following methods, and the results are summarized in Table 1.

[Oxygen permeability]
Using an oxygen permeability measuring device (OX-TRAN2 / 20 manufactured by MOCON), set the test piece so that the base material side is the oxygen supply side, and conform to JIS K 7126, 23 ° C., relative humidity 90. Oxygen permeability under% RH environment was measured.
[Water vapor permeability]
Using a water vapor permeability measuring device (MOCON, PERMATRAN-w 3/33), set the test piece so that the base material side is the water vapor supply side, and in accordance with JIS K 7129, 40 ° C, relative The water vapor permeability in a humidity 90% RH environment was measured.

<< Laminate strength test >>
Using a tensile tester (manufactured by Orientec Co., Ltd., Tencilon universal material tester), a sample obtained by cutting the barrier laminates obtained in the above Examples and Comparative Examples into strips having a width of 15 mm was used in JIS K6854-. According to No. 2, the lamination strength (N / 15 mm) was measured using 90 ° peeling (T-shaped peeling method) at a peeling speed of 50 mm / min.
Specifically, first, a strip-shaped test piece 70 is prepared by cutting out a barrier laminate and peeling the base material side 71 and the sealant layer side 72 by 15 mm in the long side direction as shown in FIG. did. Then, as shown in FIG. 13, the already peeled portions of the base material side 71 and the sealant layer side 72 were gripped by the gripping tool 73 of the measuring instrument, respectively. The gripping tools 73 are pulled in opposite directions in the direction orthogonal to the surface direction of the portion where the base material side 71 and the sealant layer side 72 are still laminated at a speed of 50 mm / min, respectively, and a stable region (FIG. The average value of the tensile stress in (see 14) was measured. The distance S between the gripping tools 73 at the start of pulling was set to 30 mm, and the distance S between the gripping tools 73 at the end of pulling was set to 60 mm. FIG. 14 is a diagram showing changes in tensile stress with respect to the interval S between the gripping tools 73. As shown in FIG. 14, the change in tensile stress with respect to the interval S passes through the first region and enters the second region (stable region) where the rate of change is smaller than that of the first region.
For the five test pieces 70, the average value of the tensile stress in the stable region was measured, and the average value was taken as the lamination strength. The environment at the time of measurement was a temperature of 23 ° C. and a relative humidity of 50%. The measurement results are summarized in Table 1.

Reference example 1-1
Polyamide (manufactured by Ube Kosan Co., Ltd., polyamide 6, melting point: 220 ° C.), adhesive resin (manufactured by Mitsui Chemicals Co., Ltd., Admer QF500, maleic anhydride-modified polypropylene), and polypropylene (manufactured by Nippon Polypro Co., Ltd., Novatec FL203D, melting point: 160 ° C.) is co-extruded and then stretched 5 times in the vertical direction (MD direction) and 10 times in the horizontal direction (TD direction) by a sequential biaxial stretching device to form a surface resin made of polypropylene. A 21 μm-thick substrate comprising a layer (19.6 μm), an adhesive resin layer (1 μm) made of an adhesive resin, and a polypropylene resin layer (0.4 μm) made of polypropylene was prepared. The ratio of the thickness of the surface resin layer made of polyamide to the layer thickness of the base material was 2%.

Carbon-containing oxidation having a thickness of 12 nm on the surface resin layer of the base material prepared as described above while applying tension to the base material by Roll to Roll using an actual low-temperature plasma chemical vapor deposition apparatus. A silicon vapor deposition film was formed (CVD method). The conditions for forming the vapor-deposited film were as follows.
(Formation conditions)
-Hexamethyldisiloxane: Oxygen gas: Helium = 1:10:10 (Unit: slm)
・ Cooling / electrode drum supply power: 22kW
・ Line speed: 100m / min

In the carbon-containing silicon oxide vapor deposition film, the ratio C of carbon, the ratio Si of silicon, and the ratio O of oxygen are 32.7% and 29, respectively, with respect to 100% of the total of the three elements of silicon, oxygen, and carbon. It was 8.8% and 37.5%. The proportion of each element was measured by X-ray photoelectron spectroscopy (XPS) by narrow scan analysis under the following measurement conditions.
(Measurement condition)
Equipment used: "ESCA-3400" (manufactured by Kratos)
[1] Spectral sampling conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV)
X-ray output: 150W (10kV, 15mA)
X-ray scanning area (measurement area): Approximately 6 mmφ
Photoelectron uptake angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar ⁺
Acceleration voltage: 0.2 (kV)
Emission current: 20 (mA)
etching range: 10 mmφ
Ion sputtering time: Performed in 30 seconds and collected the spectrum

A barrier coat layer was formed on the vapor-deposited film so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 5.1 on a mass basis.

The ratio of Si element and C element present on the surface of the barrier coat layer was measured. The measurement was performed by X-ray photoelectron spectroscopy (XPS) by narrow scan analysis under the following measurement conditions. In the following reference examples, the ratio of Si element and C element present on the surface of the barrier coat layer was measured in the same manner.
(Measurement condition)
Equipment used: "ESCA-3400" (manufactured by Kratos)
[1] Spectral sampling conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1253.6 eV)
X-ray output: 150W (10kV, 15mA)
X-ray scanning area (measurement area): Approximately 6 mmφ
Photoelectron uptake angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar ⁺
Acceleration voltage: 0.2 (kV)
Emission current: 20 (mA)
etching range: 10 mmφ
Ion sputtering time: 30 seconds + 30 seconds + 60 seconds (total 120 seconds), and the spectrum was collected.

Next, an unstretched polypropylene film (manufactured by Toyobo Co., Ltd., P1128) having a thickness of 60 μm was dry-laminated on the barrier coat layer with a two-component curable polyurethane adhesive to form a sealant layer, thereby forming a barrier laminate. Obtained.

Reference example 1-2
Similar to Reference Example 1-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis. Then, a barrier laminate was produced.

Reference example 1-3
Similar to Reference Example 1-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis. Then, a barrier laminate was produced.

Reference example 1-4
Similar to Reference Example 1-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis. Then, a barrier laminate was produced.

Reference example 1-5
Similar to Reference Example 1-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis. Then, a barrier laminate was produced.

Reference example 1-6
Similar to Reference Example 1-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis. Then, a barrier laminate was produced.

Reference example 2-1
A barrier laminate was produced in the same manner as in Reference Example 1-1, except that the formation of the thin-film deposition film was changed as follows.
In the pretreatment section, Roll to Roll using a continuous vapor deposition film deposition apparatus that separates the pretreatment section in which the oxygen plasma pretreatment device is arranged and the film formation section, which is an actual machine, on the surface resin layer. Then, while applying tension to the base material, plasma was introduced from the plasma supply nozzle under the following conditions, oxygen plasma pretreatment was performed, and vacuum deposition was performed on the oxygen plasma treatment surface on the oxygen plasma treatment surface under the following conditions. A reactive resistance heating method was used as the heating means of the method to form an aluminum oxide (alumina) vapor-deposited film having a thickness of 12 nm (PVD method).
(Formation conditions)
(Oxygen plasma pretreatment conditions)
・ Plasma intensity: 200 W ・ sec / m ²
-Plasma forming gas ratio: Oxygen: Argon = 2: 1
・ Voltage applied between pretreatment drum and plasma supply nozzle: 340V
(Film formation conditions)
・ Transport speed: 400m / min
・ Oxygen gas supply: 20000 sccm

Reference example 2-2
Similar to Reference Example 2-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis. Then, a barrier laminate was produced.

Reference example 2-3
Similar to Reference Example 2-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis. Then, a barrier laminate was produced.

Reference example 2-4
Similar to Reference Example 2-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis. Then, a barrier laminate was produced.

Reference example 2-5
Similar to Reference Example 2-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis. Then, a barrier laminate was produced.

Reference example 2-6
Similar to Reference Example 2-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis. Then, a barrier laminate was produced.

Reference example 3-1
A barrier laminate was prepared in the same manner as in Reference Example 1-1, except that the polyamide was changed to ethylene vinyl alcohol (manufactured by Kuraray Co., Ltd., EVAL F171B, melting point: 183 ° C.) to form a surface resin layer. did.

Reference example 3-2
Similar to Reference Example 3-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis. Then, a barrier laminate was produced.

Reference example 3-3
Similar to Reference Example 3-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis. Then, a barrier laminate was produced.

Reference example 3-4
Similar to Reference Example 3-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis. Then, a barrier laminate was produced.

Reference example 3-5
Similar to Reference Example 3-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis. Then, a barrier laminate was produced.

Reference example 3-6
Similar to Reference Example 3-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis. Then, a barrier laminate was produced.

Reference example 4-1
A barrier laminate was prepared in the same manner as in Reference Example 2-1 except that the polyamide was changed to ethylene vinyl alcohol (manufactured by Kuraray Co., Ltd., EVAL F171B, melting point: 183 ° C.) to form a surface resin layer. did.

Reference example 4-2
Similar to Reference Example 4-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis. Then, a barrier laminate was produced.

Reference example 4-3
Similar to Reference Example 4-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis. Then, a barrier laminate was produced.

Reference example 4-4
Similar to Reference Example 4-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis. Then, a barrier laminate was produced.

Reference example 4-5
Similar to Reference Example 4-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis. Then, a barrier laminate was produced.

Reference example 4-6
Similar to Reference Example 4-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis. Then, a barrier laminate was produced.

Reference example 5-1
A coating for forming a surface coat layer prepared as follows on the corona-treated surface of a 20 μm-thick biaxially stretched polypropylene film (ME-1 manufactured by Mitsui Chemicals Tohcello Corporation) with one surface treated with corona. The working solution was applied and dried to form a surface coat layer having a thickness of 0.5 μm to prepare a base material.

A hydroxyl group-containing (meth) acrylic resin (number average molecular weight 25,000, glass transition temperature 99 ° C., hydroxyl value 80 mgKOHL / g) is used in a mixed solvent of methyl ketone and ethyl acetate (mixing ratio 1: 1) to increase the solid content concentration. The main agent was prepared by diluting to 10% by mass.
An ethyl acetate solution (solid content 75% by mass) containing tolylene diisocyanate was added as a curing agent to the main agent to obtain a coating liquid for forming a surface coat layer. The amount of the curing agent used was 10 parts by mass with respect to 100 parts by mass of the main agent.

Carbon-containing oxidation having a thickness of 12 nm on the surface coat layer of the base material prepared as described above while applying tension to the base material by Roll to Roll using an actual low-temperature plasma chemical vapor deposition apparatus. A silicon vapor deposition film was formed (CVD method). The conditions for forming the vapor-deposited film were as follows.
(Formation conditions)
-Hexamethyldisiloxane: Oxygen gas: Helium = 1:10:10 (Unit: slm)
・ Cooling / electrode drum supply power: 22kW
・ Line speed: 100m / min

Next, a barrier coat layer was formed on the vapor-deposited film so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 5.1 on a mass basis.

Next, an unstretched polypropylene film (manufactured by Toyobo Co., Ltd., P1128) having a thickness of 60 μm was dry-laminated on the barrier coat layer with a two-component curable polyurethane adhesive to form a sealant layer, thereby forming a barrier laminate. Obtained.

Reference example 5-2
Similar to Reference Example 5-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis. Then, a barrier laminate was produced.

Reference example 5-3
Similar to Reference Example 5-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis. Then, a barrier laminate was produced.

Reference example 5-4
Similar to Reference Example 5-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis. Then, a barrier laminate was produced.

Reference example 5-5
Similar to Reference Example 5-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis. Then, a barrier laminate was produced.

Reference example 5-6
Similar to Reference Example 5-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis. Then, a barrier laminate was produced.

Reference example 6-1
A first barrier laminate was produced in the same manner as in Reference Example 5-1 except that the formation of the thin-film deposition film was changed as follows.
A 20 nm-thick silicon oxide (silica) vapor-deposited film on the surface coat layer while applying tension to the multilayer base material by Roll to Roll using an induction heating type vacuum film deposition apparatus equipped with a plasma gun, which is an actual machine. Was formed (PVD method). The conditions for forming the vapor-deposited film were as follows.
(Formation conditions)
(Plasma irradiation conditions)
・ Line speed: 30 m / min ・ Vacuum degree: 1.7 × 10 ^-2 Pa
-Output: 5.7 kW
・ Acceleration voltage: 151V
-Ar gas flow rate: 7.5 sccm
(Film formation conditions)
・ Thin-film deposition material: SiO
・ Reaction gas: O ₂
・ Reaction gas flow rate: 100 sccm

Reference example 6-2
Similar to Reference Example 6-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis. Then, a barrier laminate was produced.

Reference example 6-3
Similar to Reference Example 6-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis. Then, a barrier laminate was produced.

Reference example 6-4
Similar to Reference Example 6-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis. Then, a barrier laminate was produced.

Reference example 6-5
Similar to Reference Example 6-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis. Then, a barrier laminate was produced.

Reference example 6-6
Similar to Reference Example 6-1 except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis. Then, a barrier laminate was produced.

Reference example 7-1
A barrier laminate was produced in the same manner as in Reference Example 5-1 except that the formation of the thin-film deposition film was changed as follows.

In the pretreatment section, Roll to Roll using a continuous vapor deposition film deposition apparatus that separates the pretreatment section in which the oxygen plasma pretreatment device is arranged and the film formation section, which is an actual machine, on the surface coat layer. Therefore, while applying tension to the multilayer substrate, plasma is introduced from the plasma supply nozzle under the following conditions, oxygen plasma pretreatment is performed, and in the film formation section that is continuously conveyed, a vacuum is applied to the oxygen plasma treatment surface under the following conditions. A reactive resistance heating method was used as the heating means of the vapor deposition method to form an aluminum oxide (alumina) vapor deposition film having a thickness of 12 nm (PVD method).
(Formation conditions)
(Oxygen plasma pretreatment conditions)
・ Plasma intensity: 200 W ・ sec / m ²
-Plasma forming gas ratio: Oxygen: Argon = 2: 1
・ Voltage applied between pretreatment drum and plasma supply nozzle: 340V
(Film formation conditions)
・ Transport speed: 400m / min
・ Oxygen gas supply: 20000 sccm

Reference example 7-2
Similar to Reference Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 4.1 on a mass basis. Then, a barrier laminate was produced.

Reference example 7-3
Similar to Reference Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 3.3 on a mass basis. Then, a barrier laminate was produced.

Reference example 7-4
Similar to Reference Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 2.7 on a mass basis. Then, a barrier laminate was produced.

Reference example 7-5
Similar to Reference Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.9 on a mass basis. Then, a barrier laminate was produced.

Reference example 7-6
Similar to Reference Example 7-1, except that the barrier coat layer was formed so that the solid content ratio of the metal alkoxide to the water-soluble polymer (metal alkoxide / water-soluble polymer) was 1.5 on a mass basis. Then, a barrier laminate was produced.

<< Gas barrier property evaluation (after lamination) >>
The barrier laminate obtained in the above reference example was cut out to obtain a test piece. Using this test piece, oxygen permeability (cc / m ² · day · atm) and water vapor permeability (g / m ² · day) were measured in the same manner as described above. The results are summarized in Tables 2-8. In Tables 2 to 8, the units of oxygen permeability and vapor permeability are omitted.

<< Gas barrier property evaluation (after Gelboflex test) >>
A tubular bag was prepared using the barrier layer obtained in the above reference example. Using this bag, the ASTM F392 compliant Gelboflex test was repeated 10 times.
Then, the barrier laminate was cut out from the bag to obtain a test piece. Using this test piece, oxygen permeability (cc / m ² · day · atm) and water vapor permeability (g / m ² · day) were measured in the same manner as described above. The results are summarized in Tables 2-8. In Tables 2 to 8, the units of oxygen permeability and vapor permeability are omitted.

10: Barrier laminate, 11: Base material, 12: Adhesive layer, 13: Vapor film, 14: Intermediate layer, 15: Sealant layer, 16: Surface resin layer, 17: Polypropylene resin layer, 18: Barrier coat layer, 19: Adhesive resin layer, 20: Barrier laminate, 21: Base material, 22: Adhesive layer, 23: Vapor film, 24: Intermediate layer, 25: Sealant layer, 26: Surface coat layer, 27: Polypropylene resin layer , 28: Barrier coat layer, 30: Packaging bag, 40: Standing pouch, 41: Body (side sheet), 42: Bottom (bottom sheet), 51: Easy opening means, 52: Notch, 53: Half-cut line , 60: Steam venting mechanism, 60a: Steam seal part, 60b: Non-seal part, 70: Test piece, 71: Base material side, 72: Sealant layer side, 73: Grab tool, A: Vacuum pump, B: Unwinding Part, C: film-forming drum, D: take-up part, E: transfer roll, F: evaporation source, G: reaction gas supply part, H: sealant box, I: vapor deposition material, J: plasma gun, A1: Vacuum container, B1: Unwinding part, C1: Cooling / electrode drum, D1: Winding part, E1: Conveying roll, F1: Glow discharge plasma, G1: Reaction gas supply part, H1: Raw material supply nozzle, I1: Raw material gas Supply unit, J1: magnet, K1: power supply, L1: vacuum pump

Claims (21)

A base material, an adhesive layer, a thin-film deposition film, an intermediate layer, and a sealant layer are provided.
The intermediate layer includes at least a surface resin layer and a polypropylene resin layer.
The surface resin layer contains a resin material having a melting point of 180 ° C. or higher.
The thin-film deposition film is composed of inorganic oxides.
A barrier laminate characterized in that the surface resin layer and the polypropylene resin layer are subjected to a stretching treatment. The polypropylene resin layer, the base material, and the sealant layer are made of the same material.
The barrier laminate according to claim 1, wherein the same material is polypropylene. The barrier laminate according to claim 1 or 2, wherein the adhesive layer is an adhesive layer containing a cured product of a composition containing a polyester polyol and an isocyanate compound. The barrier laminate according to any one of claims 1 to 3, wherein the resin material has a melting point of 265 ° C. or lower. The barrier laminate according to any one of claims 1 to 4, wherein the difference between the melting point of the resin material and the melting point of polypropylene contained in the polypropylene resin layer is 20 to 80 ° C. The barrier laminate according to any one of claims 1 to 5, wherein the resin material has a polar group. Any one of claims 1 to 6, wherein the resin material is one or more resin materials selected from ethylene vinyl alcohol copolymer, polyvinyl alcohol, nylon 6, nylon 6,6, MXD nylon and amorphous nylon. The barrier laminate according to. The barrier laminate according to any one of claims 1 to 6, wherein the resin material is polyamide. The barrier laminate according to any one of claims 1 to 6, wherein the resin base material is an ethylene vinyl alcohol copolymer. The barrier laminate according to any one of claims 1 to 9, wherein the ratio of the thickness of the surface resin layer to the total thickness of the intermediate layer is 1% or more and 10% or less. The barrier laminate according to any one of claims 1 to 10, wherein the intermediate layer is a co-pressed film. A base material, an adhesive layer, a thin-film deposition film, an intermediate layer, and a sealant layer are provided.
The intermediate layer includes a surface coat layer and a polypropylene resin layer.
The polypropylene resin layer has been stretched and has been stretched.
Moreover, the surface coating layer contains a resin material having a polar group, and the surface coating layer contains a resin material.
A barrier laminate, wherein the vapor-deposited film is composed of an inorganic oxide. The polypropylene resin layer, the base material, and the sealant layer are made of the same material.
The barrier laminate according to claim 12, wherein the same material is polypropylene. The barrier laminate according to claim 12 or 13, wherein the adhesive layer is a cured product adhesive layer of a composition containing a polyester polyol and an isocyanate compound. The barrier laminate according to any one of claims 12 to 14, wherein the ratio of the thickness of the surface coat layer to the total thickness of the intermediate layer is 0.08% or more and 20% or less. The barrier laminate according to any one of claims 12 to 15, wherein the surface coat layer has a thickness of 0.02 μm or more and 10 μm or less. The resin material is from ethylene vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyester, polyethyleneimine, hydroxyl group-containing (meth) acrylic resin, nylon 6, nylon 6,6, MXD nylon, amorphous nylon and polyurethane. The barrier laminate according to any one of claims 12 to 16, which is one or more selected resin materials. The barrier laminate according to any one of claims 12 to 17, wherein the surface coat layer is a layer formed by using an aqueous emulsion or a solvent-based emulsion. The barrier laminate according to any one of claims 1 to 18, further comprising a barrier coat layer between the intermediate layer and the vapor-deposited film. The barrier laminate according to any one of claims 1 to 19, which is used for packaging containers. A packaging container comprising the barrier laminate according to any one of claims 1 to 20.

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