JP2024012580A - Laminate and packaging bag - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate that maintains oxygen and water vapor barrier properties of the laminate, suppresses deformation of the laminate due to heat sealing, and has excellent recyclability.

SOLUTION: A laminate of the present invention includes a base material, an adhesive layer, and a sealant layer, and further includes a deposition film between the adhesive layer and the sealant layer. The adhesive layer is a cured product of a two-component curing adhesive containing a polyester polyol and an isocyanate compound. The polyester polyol has an isocyanuric ring. The thickness of the deposition film is 1 nm or more and 140 nm or less. The base material is a stretched resin film. The base material and the sealant layer contain the same resin material, which is polypropylene.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2024,JPO&INPIT

Description

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

Conventionally, a resin film made of a resin material has been used as a constituent material of a packaging bag. In addition, since packaging bags are required to have various functions such as oxygen barrier properties and water vapor barrier properties depending on the contents to be filled, laminates composed of a plurality of resin films are widely used. For example, since a resin film made of thermoplastic resin such as polypropylene or polyethylene alone cannot ensure sufficient strength as a packaging bag, it is laminated with a resin film made of polyester such as polyethylene terephthalate. In addition, for the purpose of improving oxygen barrier properties and water vapor barrier properties, lamination with a resin film or metal foil made of polyamide, or formation of a vapor-deposited film on the resin film has been performed (for example, Patent Document 1).

Japanese Patent Application Publication No. 2009-202519

Some packaging bags have a zipper tape on the inside of the packaging bag (hereinafter also referred to as a zippered packaging bag). When producing this zippered packaging bag, the laminate and the zipper tape are heated and heat-sealed. This is done by heating the laminate from its surface.

Generally, heat-sealing a laminate and a zipper tape requires heating for a longer time than heat-sealing laminates together.
The above-mentioned laminate with improved strength and barrier properties is characterized by having a large number of layers and being thick because it includes a resin film made of polyester or polyamide, metal foil, and the like. However, when heat-sealing the laminate and zipper tape using such a laminate, heating is required at a higher temperature than usual for a long time, and the laminate, especially the layer on the side to be heated, is damaged. There was a risk that the material would melt and its surface would be deformed, impairing its appearance.

Furthermore, in recent years, with increasing calls for building a recycling-oriented society, attempts have been made to recycle and use packaging bags. However, when a plurality of different resin films are pasted together, it is difficult to separate the resin films, making them unsuitable for recycling, and there has been a desire to use packaging bags with less environmental impact.

The present inventors have developed a stretched polypropylene resin film, an adhesive layer made of a two-component curable urethane adhesive, an aluminum vapor-deposited film, and an unstretched polypropylene resin film for the purpose of suppressing deformation of the laminate due to heat sealing and improving recyclability. We attempted to create a zippered packaging bag using a laminate with a resin film and a small number of layers.
However, zippered packaging bags are formed using a former included in a packaging machine when they are manufactured and filled with contents, but this forming process applies a large bending load to the packaging bag. It was found that this leads to a decrease in oxygen barrier properties and water vapor barrier properties. Furthermore, it has been found that heating during heat-sealing the laminate and the zipper tape results in further deterioration of the oxygen barrier properties and water vapor barrier properties of the zippered packaging bag.

The present invention has been made to solve the above problems, and the object to be solved is to suppress the deformation of the laminate due to heat sealing while maintaining the oxygen barrier properties and water vapor barrier properties of the laminate. It is an object of the present invention to provide a laminate having excellent recyclability.

Furthermore, the problem to be solved by the present invention is to provide a packaging bag including the laminate and a zipper tape.

The present invention includes a base material, an adhesive layer, and a sealant layer, further comprising a vapor deposited film between the adhesive layer and the sealant layer, and the adhesive layer is a two-component curing type containing a polyester polyol and an isocyanate compound. It is a cured product of an adhesive, the polyester polyol is a polyester polyol having an isocyanuric ring, and the thickness of the deposited film is 1 nm or more and 140 nm or less,
The laminate is characterized in that the base material is a stretched resin film, the base material and the sealant layer contain the same resin material, and the same resin material is polypropylene.

In the laminate according to the present invention, the sealant layer may be an unstretched resin film.

In the laminate according to the present invention, the content of the same resin material may be 90% by mass or more.

In the laminate according to the present invention, the thickness of the laminate may be 10 μm or more and 130 μm or less.

In the laminate according to the present invention, the adhesive layer may have a thickness of 0.5 μm or more and 6 μm or less.

In the laminate according to the present invention, the vapor deposited film may be an aluminum vapor deposited film.

The present invention includes the above laminate and a zipper tape, the zipper tape is located on the sealant layer, the base material, the sealant layer, and the zipper tape include the same resin material, The same resin material is the packaging bag, which is polypropylene.

According to the present invention, it is possible to provide a laminate that maintains the oxygen barrier properties and water vapor barrier properties of the laminate, suppresses deformation of the laminate due to heat sealing, and has excellent recyclability.

Furthermore, according to the present invention, a packaging bag including the laminate and a zipper tape can be provided.

1 is a schematic cross-sectional view showing one embodiment of a laminate of the present invention. FIG. 1 is a front view showing an example of a packaging bag including a laminate and a zipper tape of the present invention. FIG. 3 is a sectional view showing the packaging bag shown in FIG. 2 taken along line AA. FIG. 1 is a front perspective view showing an example of a packaging bag including a laminate and a zipper tape of the present invention. FIG. 2 is a rear perspective view showing an example of a packaging bag including the laminate and zipper tape of the present invention. FIG. 1 is a front view showing an example of a packaging bag including a laminate and a zipper tape of the present invention.

(laminate)
As shown in FIG. 1, the laminate 10 of the present invention includes a base material 11, an adhesive layer 12, and a sealant layer 13, and further includes a vapor deposited film 14 between the adhesive layer 12 and the sealant layer 13. .

The base material and the sealant layer of the laminate of the present invention are characterized in that they contain the same resin material, and the same resin material is polypropylene. Thereby, the recyclability of the packaging bag including the laminate can be improved.
In the present invention, "the same resin material" and "the same resin material" mean that the resin classification is the same.

In the laminate, the content of the same resin material is preferably 90% by mass or more, more preferably 92% by mass or more, and even more preferably 94% by mass or more. Thereby, recyclability can be further improved.
Note that the content of the same resin material in the laminate means the ratio of the same resin material to the sum of the contents of the resin materials in each layer constituting the laminate.

The laminate preferably has an oxygen permeability of 0.05 cc/m ² /day/atm or more and 2.0 cc/m ² /day/atm or less in an environment of 23° C. and 90% relative humidity, and 0.05 cc/m 2 /day/atm or less. /m ² /day/atm or more and 1.0 cc/m ² /day/atm or less.
In the present invention, the oxygen permeability is measured in accordance with JIS K 7126.

The laminate preferably has a water vapor permeability of 0.01 g/m ² /day/atm or more and 2.0 g/m 2 /day/atm or less, and 0.01 g/m ² /day/atm or less, in an environment of 40° C. and 90% relative humidity. /m ² /day/atm or more and 1.0 g/m ² /day/atm or less.
In the present invention, oxygen permeability is measured in accordance with JIS K 7129.

The thickness of the laminate is preferably 10 μm or more and 130 μm or less, more preferably 15 μm or more and 110 μm or less. Thereby, deformation of the laminate due to heat sealing can be further suppressed.

(Base material)
The base material includes polypropylene. Polypropylene may be a homopolymer, a random copolymer, or a block copolymer. A polypropylene homopolymer is a polymer of only propylene, and a 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 copolymer having a polymer block made of propylene and a polymer block made of other α-olefins other than the above-mentioned propylene.

The base material is a stretched resin film. Thereby, sufficient strength and heat resistance can be imparted to the packaging bag. The stretched resin film may be a uniaxially stretched resin film or a biaxially stretched resin film. Further, as the stretched resin film, a stretched polypropylene resin film made of polypropylene may be used.

The base material may be a laminate of two or more of the resin films described above. The resin film laminate can be produced using a dry lamination method, a wet lamination method, an extrusion method, or the like.

The base material may contain additives such as fillers, plasticizers, antistatic agents, ultraviolet absorbers, inorganic particles, organic particles, mold release agents, and dispersants, as long as the characteristics of the present invention are not impaired. .

The base material may have an image formed on its surface. It is preferable to form the image on the adhesive layer side surface of the base material because it is possible to prevent the formed image from coming into contact with the outside air.
Furthermore, the image formed is not particularly limited, and may include characters, patterns, symbols, combinations thereof, and the like.
Although the image can be formed using a conventionally known ink, it is preferably performed using an ink derived from biomass. Thereby, a packaging bag with less environmental load can be produced using the laminate.
The image forming method is not particularly limited, and conventionally known printing methods such as gravure printing, offset printing, and flexographic printing can be used.

The base material is preferably surface-treated. Thereby, adhesion between adjacent layers can be improved. The surface treatment method is not particularly limited, and examples include physical treatments such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and/or nitrogen gas, glow discharge treatment, and oxidation using chemicals. Examples include chemical treatments such as treatment.

The thickness of the base material is preferably 5 μm or more and 50 μm or less, more preferably 10 μm or more and 40 μm or less. Thereby, deformation of the laminate due to heat sealing can be further suppressed. Moreover, the mechanical strength and processability of the laminate can be improved.

(Adhesive layer)
The adhesive layer is a cured product of a two-part curable adhesive containing a polyester polyol and an isocyanate compound, and is a polyester obtained by polycondensing the polyester polyol with an ortho-oriented polycarboxylic acid or its anhydride, and a polyhydric alcohol. It is characterized by being a polyol, a polyester polyol having a glycerol skeleton, or a polyester polyol having an isocyanuric ring. When a laminate including a vapor-deposited film is applied to a packaging bag, a bending load is applied to the laminate by a molding machine or the like, which may cause cracks or the like to occur in the vapor-deposited film. Since the adhesive layer is a cured product of the above-mentioned two-part curable adhesive, the oxygen barrier properties and water vapor barrier properties of the laminate can be maintained even if cracks occur in the deposited film. In addition, this eliminates the need to use resin films or metal foils made of polyester or polyamide, making it possible to create a laminate with a small number of layers and a thin thickness, and the heat load caused by heat sealing between the laminate and the zipper tape. can be reduced. Therefore, deformation of the laminate due to heat sealing can be suppressed.

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. A polyester polyol has, for example, a polyester structure or a polyester polyurethane structure as a main skeleton.

As a specific example of a two-part curable adhesive containing a polyester polyol and an isocyanate compound, the PASLIM series sold by DIC Corporation can be used.

The two-part curable adhesive may further contain 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, the following [1st example] to [3rd example] can be used.
[First example] Polyester polyol obtained by polycondensation of ortho-oriented polycarboxylic acid or its anhydride and polyhydric alcohol [Second example] Polyester polyol having a glycerol skeleton [Third example] Having an isocyanuric ring Polyester Polyol Each polyester polyol will be explained below.

The polyester polyol according to the first example is selected from the group consisting of a polycarboxylic acid component containing at least one orthophthalic acid and its anhydride, and ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. It is a polycondensate obtained by polycondensation with a polyhydric alcohol component containing at least one type of alcohol.
Particularly preferred is a polyester polyol in which the content of orthophthalic acid and its anhydride is 70 to 100% by mass based on the total polyhydric carboxylic acid components.

The polyester polyol according to the first example essentially contains orthophthalic acid and its anhydride as a polycarboxylic acid component, but other polycarboxylic acid components may be copolymerized to the extent that the effects of this embodiment are not impaired. It's okay.
Specifically, aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid, unsaturated bond-containing polycarboxylic acids such as maleic anhydride, maleic acid and fumaric acid, 1, Alicyclic polycarboxylic acids such as 3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5- Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, anhydrides of these dicarboxylic acids, and ester formation of these dicarboxylic acids Examples include aromatic polycarboxylic acids such as dihydroxy derivatives, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and polybasic acids such as ester-forming derivatives of these dihydroxycarboxylic acids. Among these, succinic acid, 1,3-cyclopentanedicarboxylic acid, and isophthalic acid are preferred.
Note that two or more types of the other polyhydric carboxylic acids mentioned above may be used.

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 each independently H (hydrogen atom) or a group represented by the following general formula (2).

In 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, It represents an arylene group selected from the group consisting of a 3-anthraquinonediyl group and a 2,3-anthracenediyl group, and Y represents 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 general formula (2).

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

Further, a compound in which any one of R ₁ , R ₂ , and R ₃ is a group represented by general formula (2), and a compound in which any two of R ₁ , R ₂ , and R ₃ are represented by general formula (2) A mixture of two or more of a compound in which R ₁ , R ₂ , and R ₃ are all groups represented by general formula (2) may be used.

X is selected from the group consisting of 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3-anthraquinonediyl group and 2,3-anthracenediyl group, and has a substituent. represents an optionally substituted arylene group.
When X is substituted with a substituent, it may be substituted with one or more substituents, and the substituent is bonded to any carbon atom on X that is different from the 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, an amino group, Examples include phthalimide group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, and naphthyl group.

In 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, a methylpentylene group. group and an alkylene group having 2 to 6 carbon atoms such as dimethylbutylene group. Among these, Y is preferably a propylene group or an ethylene group, and most preferably an ethylene group.

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

Examples of the aromatic polycarboxylic acid or its anhydride in which carboxylic acid is substituted at the ortho position include orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, and naphthalene 1,2-dicarboxylic acid or its anhydride. Examples include anhydride, anthraquinone 2,3-dicarboxylic acid or its anhydride, and 2,3-anthracenecarboxylic acid or its anhydride.
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, an amino group, Examples include phthalimide group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, and naphthyl group.

Further, examples of the polyhydric alcohol component include alkylene diols having 2 to 6 carbon atoms. 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.

The polyester polyol according to the third example is a polyester polyol having an isocyanuric ring represented by the following general formula (3).
In the general formula (3), R ₁ , R ₂ , and R ₃ each independently represent "-(CH ₂ ) n1-OH (where n1 represents an integer of 2 to 4)" or the general formula (4 ) represents the structure of

In the general formula (4), n2 represents an integer of 2 to 4, n3 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, An arylene group selected from the group consisting of 2,3-anthraquinonediyl group and 2,3-anthracenediyl group, which 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 general formula (4).

In general formula (3), the alkylene group represented by -(CH ₂ )n1- may be linear or branched. Among them, 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 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3-anthraquinonediyl group, and 2,3-anthracenediyl group, and has a substituent. represents an optionally substituted arylene group.

When X is substituted with a substituent, it may be substituted with one or more substituents, and the substituent is bonded to any carbon atom on X that is different from the 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, an amino group, Examples include phthalimide group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, and naphthyl group.
Among the substituents of Most preferred is phenyl.

In 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, a methylpentylene group. group and an alkylene group having 2 to 6 carbon atoms such as dimethylbutylene group. Among these, Y is preferably a propylene group or an ethylene group, and most preferably an ethylene group.

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

Further, a compound in which any one of R ₁ , R ₂ , and R ₃ is a group represented by general formula (4), and a compound in which any two of R ₁ , R ₂ , and R ₃ are represented by general formula (4) A mixture of two or more of a compound in which R ₁ , R ₂ , and R ₃ are all groups represented by general formula (4) may be used.

The polyester polyol having an isocyanuric ring represented by the general formula (3) is composed of a triol having an isocyanuric ring, an aromatic polycarboxylic acid in which a carboxylic acid is substituted at the ortho position or its anhydride, and a polyhydric alcohol component. Can be synthesized by reacting with as an essential component

Examples of triols having an isocyanuric ring include 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. etc.

In addition, examples of the aromatic polycarboxylic acid or its anhydride in which carboxylic acid is substituted at the ortho position include orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, and naphthalene 1,2-dicarboxylic acid. or its anhydride, anthraquinone 2,3-dicarboxylic acid or its anhydride, and 2,3-anthracenecarboxylic acid or its anhydride. 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, an amino group, Examples include phthalimide group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, and naphthyl group.

Further, examples of the polyhydric alcohol component include alkylene diols having 2 to 6 carbon atoms. 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 a triol compound having an isocyanuric ring, and the carboxylic acid is in the ortho position. A polyester polyol compound having an isocyanuric ring, which uses orthophthalic anhydride as the substituted aromatic polycarboxylic acid or its anhydride and ethylene glycol as the polyhydric alcohol, has particularly excellent oxygen barrier properties and adhesive properties. preferable.

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

The oxidation of the polyester polyol is preferably 20 mgKOH/g or more, more preferably 50 mgKOH/g or more. Thereby, the oxygen barrier properties and water vapor barrier properties of the laminate can be better maintained.

The isocyanate compound has two or more isocyanate groups in the molecule.
Further, the isocyanate compound may be aromatic or aliphatic, and may be a low molecular compound or a high molecular compound.
Furthermore, the isocyanate compound may be a blocked isocyanate compound obtained by addition reaction using a known isocyanate blocking agent by a known and commonly used method.
Among these, from the viewpoint of adhesiveness and retort resistance, polyisocyanate compounds having three or more isocyanate groups are preferred, and from the viewpoints of oxygen barrier properties and water vapor barrier properties, aromatic compounds are preferred.

Specific isocyanate compounds include, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, metaxylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and these isocyanate compounds. and adducts, burettes, and allophanates obtained by reacting these isocyanate compounds with low-molecular active hydrogen compounds, alkylene oxide adducts thereof, or high-molecular active hydrogen compounds.
Examples of low-molecular active hydrogen compounds include ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, Examples of the molecularly active hydrogen compounds include ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, metaxylylenediamine, and the like, and examples of molecularly active hydrogen compounds include polymeric active hydrogen compounds of various polyester resins, polyether polyols, and polyamides.

The two-part curable adhesive used to form the adhesive layer may contain a phosphoric acid modified compound. Thereby, the oxygen barrier properties and water vapor barrier properties of the laminate can be better maintained.
The phosphoric acid modified compound is, for example, a compound represented by the following general formula (5) or (6).
In 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 that may have a substituent, and (meth)acryloyl The group is selected from alkyl groups having 1 to 4 carbon atoms and having an oxy group, at least one of which is a hydrogen atom, and n represents an integer of 1 to 4.
In the formula, R ₄ and R ₅ 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 a (meth)acryloyloxy group having 1 carbon number. A group selected from ~4 alkyl groups, where n is an integer of 1 to 4, x is an integer of 0 to 30, and y is an integer of 0 to 30, except when x and y are both 0. .

More specifically, phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxy Examples include ethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, and polyoxyethylene alkyl ether phosphate, and one or more of these can be used.

The content of the phosphoric acid modified compound in the two-part curable adhesive 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 controlling the content of the phosphoric acid-modified compound within the above numerical range, the oxygen barrier properties and water vapor barrier properties of the laminate can be better maintained.

The two-component curing adhesive used to form the adhesive layer preferably contains a plate-like inorganic compound, thereby making it possible to better maintain the oxygen barrier properties and water vapor barrier properties of the laminate.
Examples of platy inorganic compounds include kaolinite-serpentinite clay minerals (halloysite, kaolinite, endellite, dickite, nacrite, antigorite, chrysotile, etc.) and pyrophyllite-talc group (pyrophyllite, talc, Kerolai et al.).

The two-part curable adhesive used to form the adhesive layer may contain a coupling agent. Thereby, the oxygen barrier properties and water vapor barrier properties of the laminate can be better maintained.
Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent represented by the following general formula (7). Note that these coupling agents may be used alone or in combination of two or more.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. - Glycidoxypropylmethyldiethoxysilane, 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(aminoethyl)γ-aminopropyltrimethoxysilane, ethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyl Examples include trimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-triethoxysilyl-N-(1,3-dimethyl-butylidene).

Examples of titanium-based coupling agents include isopropyl triisostearoyl titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, and tetraoctyl bis (didodecyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate, isopropyltrioctaynortitanate, isopropyl dimethacrylic isostearoyl titanate , isopropyl isostearoyl diacryl titanate, diisostearoyl ethylene titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, and dicumylphenyloxyacetate titanate.

Specific examples of aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate, diisopropoxyaluminum ethyl acetoacetate, diisopropoxyaluminum monomethacrylate, isopropoxyaluminum alkyl acetoacetate mono(dioctyl phosphate), aluminum Examples include -2-ethylhexanoate oxide trimer, aluminum stearate oxide trimer, and alkyl acetoacetate aluminum oxide trimer.

The two-part curable adhesive used to form the adhesive layer preferably contains cyclodextrin and/or a derivative thereof. Thereby, the oxygen barrier properties and water vapor barrier properties of the laminate can be better maintained.
Specifically, for example, cyclodextrins such as cyclodextrin, alkylated cyclodextrin, acetylated cyclodextrin, and hydroxyalkylated cyclodextrin in which the hydrogen atom of the hydroxyl group of the glucose unit of the cyclodextrin is replaced with another functional group may be used. Can be done. Branched cyclic dextrins can also be used.
In addition, the cyclodextrin skeleton in cyclodextrin and cyclodextrin derivatives includes 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. Further, these cyclodextrins and/or their derivatives may be hereinafter collectively referred to as dextrin compounds.

From the viewpoint of compatibility and dispersibility in the resin composition, it is preferable to use a cyclodextrin derivative as the cyclodextrin compound.
From the viewpoint of the polarity of the above-mentioned various resins, the degree of substitution is preferably in the range of 0.1 to 14/glucose, and more preferably in the range of 0.3 to 8/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 even more preferably 1 μm or more and 4.5 μm or less. Thereby, oxygen barrier properties and water vapor barrier properties can be better maintained.

The adhesive layer can be applied onto the base material etc. and dried 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 Fontaine method, and a transfer roll coating method. It can be formed by

(Sealant layer)
The sealant layer includes polypropylene. The same polypropylene as the base material can be used. The sealant layer may be formed from an unstretched resin film or may be formed by melt extrusion of polypropylene.

The sealant layer is preferably subjected to the above-described surface treatment.

The sealant layer may contain the above-mentioned additives as long as the characteristics of the present invention are not impaired.

The thickness of the sealant layer is preferably 5 μm or more and 120 μm or less, more preferably 10 μm or more and 100 μm or less. Thereby, deformation of the laminate due to heat sealing can be suppressed. Moreover, mechanical strength and processing suitability can be improved. Furthermore, the processability and puncture resistance of the laminate can be improved while maintaining the heat sealability of the sealant layer.

(deposited film)
The laminate further includes a vapor deposited film between the base material and the adhesive layer or between the adhesive layer and the sealant layer. Thereby, the laminate can have oxygen barrier properties and water vapor barrier properties.

Examples of the deposited film include a deposited film containing a metal such as aluminum or an inorganic oxide such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, or barium oxide.
Among these, aluminum vapor-deposited films are preferred from the viewpoint of oxygen barrier properties and water vapor barrier properties.

As a method for forming a deposited film, conventionally known methods can be adopted, such as physical vapor deposition methods (PVD methods) such as vacuum evaporation methods, sputtering methods, and ion plating methods, and plasma chemical vapor deposition methods. Examples include chemical vapor deposition methods (CVD methods) such as growth methods, thermal chemical vapor deposition methods, and photochemical vapor deposition methods.

Further, the thickness of the deposited film is preferably 1 nm or more and 140 nm or less, more preferably 5 nm or more and 60 nm or less, and even more preferably 5 nm or more and 40 nm or less. By setting the thickness of the deposited film within the above numerical range, it is possible to prevent cracks and the like from occurring in the deposited film.
When the vapor deposited film is an aluminum vapor deposited film, the film thickness is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 60 nm or less, and even more preferably 10 nm or more and 40 nm or less.
When the deposited film is a silicon oxide or aluminum oxide deposited film, the film thickness is preferably 1 nm or more and 140 nm or less, more preferably 5 nm or more and 30 nm or less, and even more preferably 5 nm or more and 20 nm or less. .

Furthermore, for example, a composite film consisting of two or more layers of vapor-deposited films of different types of inorganic oxides can be formed and used by using both physical vapor deposition and chemical vapor deposition. The degree of vacuum in the deposition chamber is preferably about 10 ^-2 to 10 ^-8 mbar before introducing oxygen, and preferably about 10 ^-1 to 10 ^-6 mbar after introducing oxygen. Note that the amount of oxygen introduced varies depending on the size of the vapor deposition machine and other factors. For the oxygen to be introduced, an inert gas such as argon gas, helium gas, nitrogen gas, etc. may be used as a carrier gas within a range that does not cause any problem. The transport speed of the film is preferably about 10 to 800 m/min, particularly about 50 to 600 m/min.

(Gas barrier layer)
The laminate may include a gas barrier layer between arbitrary layers, for example, between the adhesive layer and the deposited film. Thereby, the oxygen barrier properties and water vapor barrier properties of the laminate can be improved.

In one embodiment, the gas barrier layer is a metal alkoxide hydrolyzate 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, etc. Alternatively, it contains at least one resin composition such as a hydrolyzed condensate of a metal alkoxide.

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, silicon, zirconium, titanium, aluminum, etc. can be used, for example.
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.

Examples of metal alkoxides satisfying the above general formula include tetramethoxysilane (Si(OCH ₃ ) ₄ ), tetraethoxysilane (mass%) Si(OC ₂ H ₅ ) ₄ ), and tetrapropoxysilane (Si(OC ₃ H ₇ ) ₄ ), tetrabutoxysilane (Si(OC ₄ H ₉ ) ₄ ), and the like.

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

Two or more types of silane coupling agents as described above may be used, and the silane coupling agents are used in an amount of about 1 to 20 parts by mass based on 100 parts by mass of the total amount of the alkoxides. It is preferable.

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

The content of the water-soluble polymer in the gas barrier layer is preferably 5 parts by mass or more and 500 parts by mass or less based on 100 parts by mass of the metal alkoxide. Thereby, the oxygen barrier properties, water vapor barrier properties, and strength of the gas barrier layer can be further improved.

The thickness of the gas barrier layer is preferably 0.01 μm or more and 100 μm or less, more preferably 0.1 μm or more and 50 μm or less. This makes it possible to effectively prevent the occurrence of cracks in the gas barrier layer while further improving its oxygen barrier properties and water vapor barrier properties.

The gas barrier layer is prepared by applying a composition containing the upper material onto the base material by conventionally known means such as roll coating with a gravure roll coater, spray coating, spin coating, dipping, brush, barcode, applicator, etc. It can be formed by polycondensing the composition using a sol-gel method.
As the sol-gel method catalyst, acid or amine compounds are suitable. As the amine compound, tertiary amines that are substantially insoluble in water and soluble in organic solvents are suitable, such as N,N-dimethylbenzylamine, tripropylamine, tributylamine, tripentyl Examples include amines and the like. Among these, N,N-dimethylbenzylamine is preferred.
The sol-gel method catalyst is preferably used in a 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 metal alkoxide. It is more preferable. Thereby, the thickness of the gas barrier layer formed can be made uniform, and the catalytic effect can be further improved.

The above composition may further contain an acid. Acids are used as catalysts in the sol-gel process, mainly for the hydrolysis of alkoxides, silane coupling agents, and the like.
As the acid, 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 acid to be used is preferably 0.001 mol or more and 0.05 mol or less based on the total molar amount of the alkoxide and the alkoxide portion (for example, silicate portion) of the silane coupling agent. Thereby, the thickness of the gas barrier layer formed can be made uniform, and the catalytic effect can be further improved.

Further, the above composition may contain water in a proportion of preferably 0.1 mol or more and 100 mols or less, more preferably 0.8 mol or more and 2 mols or less, per 1 mol of the total molar amount of the alkoxide. preferable. Thereby, the oxygen barrier properties and water vapor barrier properties of the gas barrier layer can be improved, and the hydrolysis reaction can be carried out quickly.

Further, the above composition may contain an organic solvent. As the organic solvent, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used.

An embodiment of a method for forming a gas barrier layer will be described below.
First, a metal alkoxide, a water-soluble polymer, a sol-gel catalyst, water, an organic solvent, and if necessary a silane coupling agent are mixed to prepare a composition. A polycondensation reaction gradually proceeds in the composition.
Next, the composition is applied onto the deposited film by the conventionally known method described above and dried.
By this drying, the polycondensation reaction of the alkoxide and the water-soluble polymer (and the silane coupling agent if the composition includes the silane coupling agent) further proceeds, and a composite polymer layer is formed.
Finally, a gas barrier layer can be formed by heating the composition at a temperature of 20 to 250°C, preferably 50 to 220°C, for 1 second to 10 minutes.

(Method for manufacturing laminate)
The method for manufacturing the laminate according to the present invention is not particularly limited, and it can be manufactured using conventionally known methods such as melt extrusion lamination, dry lamination, and sand lamination.

The laminate according to the present invention can be provided with surface functions such as chemical functions, electrical functions, magnetic functions, mechanical functions, friction/wear/lubrication functions, optical functions, thermal functions, and biocompatibility. It is also possible to perform secondary processing for this purpose. Examples of secondary processing include embossing, painting, adhesion, printing, metallization (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.). Moreover, a molded product can also be manufactured by subjecting the laminate according to the present invention to lamination processing (dry lamination or extrusion lamination), bag making processing, and other post-processing processing.

(packaging bag)
The packaging bag of the present invention includes the above-mentioned laminate and a zipper tape, and the zipper tape is located on the sealant layer. Further, the base material comprising the packaging bag and the zipper tape contain the same resin material, and the same resin material is polypropylene. Thereby, recyclability can be improved. The same polypropylene as the base material can be used for the zipper tape. An example of the packaging bag according to the present invention will be described with reference to the drawings.

FIG. 2 is a front view showing an example of the packaging bag of the present invention. The flat bag 20 shown in FIG. 2 includes body films 21 and 21' (using the above-mentioned laminate) and a zipper tape 23, and has a through hole 22 in the upper part of the flat bag 20. A zipper tape is a member provided to reseal a packaging bag after it has been opened.

FIG. 3 is a cross-sectional view of the packaging bag 20 shown in FIG. 2, taken along line AA. As shown in FIG. 3, the zipper tape 23 includes a male tape 24 attached to the inner surface of the body film 21 and a female tape attached to the inner surface of the body film 21' opposite to the male tape 24. Contains 25. The male tape 24 and the female tape 25 are configured to be able to fit into each other. In this case, by fitting the male tape 24 and the female tape 25 together, the packaging bag 20 can be resealed after being opened. Furthermore, by disengaging the male tape 24 and female tape 25, the contents can be taken out again. Although not shown, the male tape 24 may be attached to the body film 21', and the female tape 25 may be attached to the body film 21.

Next, a method for manufacturing the flat bag 20 will be described with reference to FIG. 2.
First, the shell films 21 and 21' are prepared and arranged so that the sealant layers of the shell films 21 and 21' face each other. Subsequently, the zipper tape 23 is inserted between the body films 21 and 21', and the zipper tape 23 and each body film 21 and 21' are heat-sealed. Subsequently, the lower portions of the body films 21 and 21' are heat-sealed. Using a point seal bar, the protrusions of the male tape 24 and female tape 25 of the zipper tape 23 located at the heat-sealed portions on both sides of the body films 21, 21' are crushed. Subsequently, the heat-sealed portions on both sides of the body films 21, 21' are heat-sealed using a side seal bar. Subsequently, the male tape 24 is removed from the female tape 25 of the zipper tape 23 to open it, and the contents are filled from the upper opening. Subsequently, the male tape 24 and the female tape 25 are fitted together again to seal the opening, and the upper portions of the body films 21 and 21' are heat-sealed. Finally, by forming the through holes 22, the flat bag 20 can be manufactured. Here, the shaded area in FIG. 2 represents the heat-sealed area.
Note that the flat bag 20 may be manufactured by heat-sealing the upper part of the trunk material films 21, 21' first, and then heat-sealing the lower part of the trunk material films 21, 21' after filling the contents.

4 and 5 are a front perspective view and a rear perspective view showing another example of the packaging bag of the present invention. The pillow bag 30 shown in FIGS. 4 and 5 includes a body film 31 (using the above-mentioned laminate) and a zipper tape 33, and has a through hole 32 in the upper part of the pillow bag 30. The zipper tape 33 can be the same as the zipper tape 23 described in FIGS. 2 and 3.

Next, a method for manufacturing the pillow bag 30 will be described with reference to FIGS. 4 and 5.
First, the body film 31 is prepared, and the zipper tape 33 is heat-sealed to the upper center of the sealant layer of the body film 31. Subsequently, both left and right ends of the body material film 31 are folded toward the center so that the zipper tape 33 is located inside, and the sealant layers are heat-sealed so as to press their palms together. Subsequently, the inner surface of the cylindrical body material film 31 on the palm-to-palm side and the zipper tape 33 are heat-sealed. Subsequently, the lower part of the body film 31 is heat-sealed. Subsequently, the male tape is removed from the female tape of the zipper tape 33 to open it, and the contents are filled from the upper opening. Subsequently, the male tape and the female tape are fitted together again to seal the opening, and the upper part of the body film 31 is heat-sealed. Finally, the pillow bag 30 can be manufactured by forming the through holes 32. Here, the shaded area in FIGS. 4 and 5 represents the heat-sealed area.
Note that the pillow bag 30 may be manufactured by first heat-sealing the upper part of the trunk material film 31 and then heat-sealing the lower part of the trunk material film 31 after filling the contents.

FIG. 6 is a front view showing another example of the packaging bag of the present invention. The stand pouch 40 shown in FIG. 6 includes trunk material films (using the above-mentioned laminate) 41, 41', a bottom material film 44 (which may be the same as or different from the trunk material film), and a zipper. The stand pouch 40 has a through hole 32 in the upper part thereof. The zipper tape 43 can be the same as the zipper tape 23 described in FIGS. 2 and 3.

Next, a method for manufacturing the stand pouch 40 will be described with reference to FIG.
First, the shell films 41 and 41' are prepared and arranged so that the sealant layers of the shell films 41 and 41' face each other. Subsequently, the bottom material film 44 is folded inward and inserted between the lower portions of the body material films 41, 41', and is formed to have a gusset portion, and the bottom portion of the boat bottom shape including the peripheral edge portion is heat-sealed. Next, the bottom film 42 is folded inward and inserted between the lower parts of the shell films 41, 41' so as to have a gusset part, and the shell films 41, 41' are sealed using a ship bottom-shaped heat-sealing hot plate. and the bottom material film 42 are heat-sealed. Using a point seal bar, the protrusions of the male and female tapes of the zipper tape 43 located at the heat-sealed portions on both sides of the body films 41, 41' are crushed. Subsequently, the heat-sealed portions on both sides of the body films 41, 41' are heat-sealed using a side seal bar. Subsequently, the male tape is removed from the female tape of the zipper tape 43 to open it, and the contents are filled from the upper opening. Subsequently, the male tape and the female tape are fitted together again to seal the opening, and the upper portions of the body films 41, 41' are heat-sealed. Finally, by forming the through hole 42, the stand pouch 40 can be manufactured. Here, the shaded area in FIG. 6 represents the heat-sealed area.
Note that the stand pouch 40 may be manufactured by heat-sealing the upper part of the trunk film 41 first, filling the contents, and then heat-sealing the lower part of the trunk film 31 and the bottom film 44.

The contents filled in the packaging bag are not particularly limited, and the contents may be liquids, powders, or gels in addition to solids. Moreover, it may be food or non-food.

(Other aspects)
Another aspect of the present invention includes a base material, an adhesive layer, and a sealant layer, and further includes a vapor-deposited film between the adhesive layer and the sealant layer, the adhesive layer containing a polyester polyol and an isocyanate compound. It is a cured product of a two-part curable adhesive, and the polyester polyol is a polyester polyol obtained by polycondensing an ortho-oriented polycarboxylic acid or its anhydride and a polyhydric alcohol, a polyester polyol having a glycerol skeleton, or a polyester polyol having an isocyanuric ring,
The laminate is characterized in that the base material is a stretched resin film, the base material and the sealant layer contain the same resin material, and the same resin material is polypropylene.
In the laminate according to another aspect of the present invention, the sealant layer may be an unstretched resin film.
In the laminate according to another aspect of the present invention, the content of the same resin material may be 90% by mass or more.
In the laminate according to another aspect of the present invention, the thickness of the laminate may be 10 μm or more and 130 μm or less.
In the laminate according to another aspect of the present invention, the adhesive layer may have a thickness of 0.5 μm or more and 6 μm or less.
In the laminate according to another aspect of the present invention, the thickness of the deposited film may be 1 nm or more and 140 nm or less.
In the laminate according to another aspect of the present invention, the vapor deposited film may be an aluminum vapor deposited film.
Another aspect of the present invention includes the above laminate and a zipper tape, the zipper tape is located on the sealant layer, and the base material, the sealant layer, and the zipper tape are made of the same resin material. and the same resin material is polypropylene.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Example 1]
A biaxially stretched polypropylene resin film with a thickness of 30 μm was prepared as a base material, and a printed layer was formed on the biaxially stretched polypropylene resin film by gravure printing. The thickness of the printed layer was 1 μm.

Next, an unstretched polypropylene resin film (manufactured by Toray Processed Film Co., Ltd., trade name: VM-CPP 2703, thickness: 30 μm) having an aluminum vapor-deposited film with a thickness of 50 nm on one side was prepared, and biaxially stretched. The printed surface of the polypropylene resin film and the vapor-deposited surface of the unstretched polypropylene resin film were bonded together using a two-component curing adhesive (manufactured by DIC Corporation, product name: PASLIM VM NSRD011/NSRD006) containing a polyester polyol and an isocyanate compound. Laminated. The thickness of the adhesive layer formed from the two-component curing adhesive was 2.5 μm.

The thickness of the laminate thus obtained was 63.5 μm, and the weight was 57.5 g/m ² . The proportion of polypropylene in the laminate was 93.9% by mass.

Next, using the laminate obtained in this example and a zipper tape containing polypropylene (manufactured by Takiron C.I. Co., Ltd., trade name: Zipper Tape MX-13F, MX general purpose grade), as shown in FIG. A flat bag 20 was produced (processing conditions: sealing temperature 175°C, sealing time 0.30 seconds). The body film (laminate) was not deformed by heat sealing.

[Example 2]
A laminate was produced in the same manner as in Example 1.

Next, using the laminate obtained in this example and a zipper tape containing polypropylene (manufactured by Takiron C.I. Co., Ltd., trade name: Zipper Tape MX-13FS, MX Soft Grade), as shown in FIG. A flat bag 20 was produced (processing conditions: sealing temperature 175°C, sealing time 0.30 seconds). The body film (laminate) was not deformed by heat sealing.

[Comparative example 1]
A polyethylene terephthalate (PET) resin film with a thickness of 12 μm was prepared as a base material, and a printed layer was formed on the PET resin film by gravure printing. The thickness of the printed layer was 1 μm.

Next, prepare an aluminum foil with a thickness of 7 μm, and glue the printed layer of PET resin film and the aluminum foil with a two-component curing adhesive (manufactured by Rock Paint Co., Ltd., product name: Adrock, main ingredient: RU-77T, Lamination was performed via a curing agent: H-7). The thickness of the adhesive layer formed from the two-component curing adhesive was 3 μm.

Next, a 60 μm thick polyethylene resin film was prepared, and aluminum foil and polyethylene resin film were glued together with a two-component curing adhesive (manufactured by Rock Paint Co., Ltd., product name: Adrock, main ingredient: RU-77T, curing agent). :H-7). The thickness of the adhesive layer formed from the two-component curing adhesive was 3 μm.

The thickness of the laminate thus obtained was 86 μm.

Next, using the laminate obtained in this comparative example and a zipper tape containing polypropylene (trade name: Zipper Tape MX-13F, MX Soft Grade, manufactured by Takiron C.I. Co., Ltd.), a film was prepared as shown in FIG. A flat bag 20 was produced (processing conditions: sealing temperature 175°C, sealing time 0.45 seconds). The body film (laminate) was not deformed by heat sealing.

[Comparative example 2]
The two-component curing adhesive of Example 1 (manufactured by DIC Corporation, trade name: PASLIM VM NSRD011/NSRD006) was replaced with the two-component curing adhesive of Comparative Example 1 (manufactured by Rock Paint Co., Ltd., trade name: ADROC). A laminate was produced in the same manner as in Example 1, except that the base material: RU-77T and the curing agent: H-7) were used. Note that the thickness of the adhesive layer formed from the adhesive was 2.5 μm.

Next, using the laminate obtained in this comparative example and a zipper tape containing polypropylene (manufactured by Takiron C.I. Co., Ltd., trade name: Zipper Tape MX-13F, MX general purpose grade), as shown in FIG. A flat bag 20 was produced (processing conditions: sealing temperature 175°C, sealing time 0.30 seconds). The body film (laminate) was not deformed by heat sealing.

[Comparative example 3]
A biaxially stretched polypropylene resin film with a thickness of 30 μm was prepared as a base material, and a printed layer was formed on the biaxially stretched polypropylene resin film by gravure printing. The thickness of the printed layer was 1 μm.

Next, a PET resin film (thickness: 12 μm) having an aluminum vapor-deposited film was prepared, and the printed layer of the biaxially stretched polypropylene resin film and the PET resin film were bonded together using a two-component curing adhesive (Rock Paint Co., Ltd.). ), product name: Adlock Base material: RU-77T, curing agent: H-7). The thickness of the adhesive layer formed from the two-component curing adhesive was 3 μm.

Next, an unstretched polypropylene resin film with a thickness of 30 μm was prepared, and the PET resin film of the biaxially stretched polypropylene resin film and the unstretched polypropylene resin film were bonded together using a two-component curing adhesive (manufactured by Rock Paint Co., Ltd., Product name: Adlock Base material: RU-77T, curing agent: H-7) Laminated through. The thickness of the adhesive layer formed from the two-component curing adhesive was 3 μm.

The thickness of the laminate thus obtained was 79 μm.

Next, using the laminate obtained in this comparative example and a zipper tape containing polypropylene (trade name: Zipper Tape MX-13F, MX Soft Grade, manufactured by Takiron C.I. Co., Ltd.), a film was prepared as shown in FIG. A flat bag 20 was produced (processing conditions: sealing temperature 175°C, sealing time 0.45 seconds). The body film (laminate) was deformed by heat sealing.

<<Oxygen barrier test>>
The laminates obtained in the above Examples and Comparative Examples were cut into A4 size, and oxygen permeability (cc/m ² /day/atm) was measured. The measurement results are summarized in Table 1.

<<Water vapor barrier test>>
The laminates obtained in Example 1 and Comparative Examples 1 to 3 were cut into A4 size, and the water vapor permeability (g /m ² /day/atm) was measured. The measurement results are summarized in Table 1.

<<Bending load resistance test>>
The laminates obtained in the above Examples and Comparative Examples were subjected to a bending load (stroke: 155 mm, bending Movement: 440°) was given 5 times.
After applying a bending load, the oxygen permeability and water vapor permeability were measured in the same manner as the oxygen barrier property test and water vapor barrier property test. The measurement results are summarized in Table 1.

10: Laminate 11: Base material 12: Adhesive layer 13: Sealant layer 14: Deposited film 20: Flat bag 21, 21': Body film 22: Through hole 23: Zipper tape 24: Male tape 25: Female tape 30: Pillow bag 31: Body material film 32: Through hole 33: Zipper tape 40: Stand pouch 41, 41': Body material film 42: Through hole 43: Zipper tape 44: Bottom material film

Claims (7)

A base material, an adhesive layer, a sealant layer,
Further comprising a vapor deposited film between the adhesive layer and the sealant layer,
The adhesive layer is a cured product of a two-part curable adhesive containing a polyester polyol and an isocyanate compound,
The polyester polyol is a polyester polyol having an isocyanuric ring,
The base material is a stretched resin film,
The thickness of the vapor deposited film is 1 nm or more and 140 nm or less,
the base material and the sealant layer include the same resin material,
A laminate, wherein the same resin material is polypropylene. The laminate according to claim 1, wherein the sealant layer is an unstretched resin film. The laminate according to claim 1 or 2, wherein the content of the same resin material is 90% by mass or more. The laminate according to any one of claims 1 to 3, wherein the laminate has a thickness of 10 μm or more and 130 μm or less. The laminate according to any one of claims 1 to 4, wherein the adhesive layer has a thickness of 0.5 μm or more and 6 μm or less. The laminate according to any one of claims 1 to 5, wherein the vapor-deposited film is an aluminum vapor-deposited film. The laminate according to any one of claims 1 to 6,
Includes zipper tape,
the zipper tape is located on the sealant layer;
the base material, the sealant layer and the zipper tape include the same resin material,
A packaging bag, wherein the same resin material is polypropylene.