JP2020203409A - Laminate and packaging bag - Google Patents

Abstract

To provide a laminate which suppresses deformation of a laminate by heat seal while maintaining oxygen barrier property and water vapor barrier property of the laminate, and is excellent in recyclability.SOLUTION: A laminate 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, in which the adhesive layer is a cured product of a two-pack type curable adhesive containing polyester polyol and an isocyanate compound, the polyester polyol is polyester polyol obtained by polycondensation of a directed ortho polyvalent carboxylic acid or its anhydride and polyhydric alcohol, polyester polyol having a glycerol skeleton or polyester polyol having an isocyanuric ring, 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.SELECTED DRAWING: Figure 1

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. Further, since the packaging bag is required to have various functions such as oxygen barrier property and water vapor barrier property depending on the contents to be filled, a laminate composed of a plurality of resin films is widely used. For example, since a resin film made of a thermoplastic resin such as polypropylene or polyethylene alone cannot secure sufficient strength as a packaging bag, it is laminated with a resin film made of polyester such as polyethylene terephthalate. Further, for the purpose of improving oxygen barrier property and water vapor barrier property, lamination with a resin film made of polyamide, a metal foil, or the like, or formation of a vapor-deposited film on the resin film is performed (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2009-202519

Some packaging bags are provided with a zipper tape inside the packaging bag (hereinafter, also referred to as a zippered packaging bag). When manufacturing this zippered packaging bag, the laminate and the zipper tape are heated and heat-sealed (heat-sealed). This heat-sealing is on the side opposite to the side where the zipper tape is heat-sealed. This is done by heating from the surface of the laminate.

In general, the heat seal between the laminate and the zipper tape requires heating for a longer time than the heat seal between the laminates.
The above-mentioned laminate having improved strength and barrier properties is characterized by having a large number of layers and a large thickness because it includes a resin film made of polyester or polyamide, a metal foil, or the like. However, when heat-sealing the laminate and the zipper tape using such a laminate, it is necessary to heat the laminate at a temperature higher than usual for a long time, and the laminate, particularly the layer on the heated side, becomes There was a risk that it would melt and the surface would be deformed, spoiling the appearance.

In recent years, with the growing demand for the construction of a recycling-oriented society, attempts have been made to recycle and use packaging bags. However, when a plurality of different resin films are bonded together, it is difficult to separate the resin films from each other, which is not suitable for recycling, and there is a demand for using a packaging bag having a smaller environmental load.

The present inventors have a stretched polypropylene resin film, an adhesive layer made of a two-component curable urethane adhesive, an aluminum vapor-deposited film, and unstretched polypropylene for the purpose of suppressing deformation of the laminate due to the heat sealing and improving recycling suitability. An attempt was made to produce a packaging bag with a zipper using a laminate provided with a resin film and having a small number of layers.
However, the zippered packaging bag is molded by a former or the like provided in the packaging machine at the time of its production and filling of the contents, but since a large bending load is applied to the packaging bag by the molding process, the zippered packaging bag is used. It was found that the oxygen barrier property and the water vapor barrier property are lowered. It was also found that heating when heat-sealing the laminate and the zipper tape causes further deterioration of the oxygen barrier property and the water vapor barrier property of the zippered packaging bag.

The present invention has been made to solve the above problems, and the problem to be solved is to suppress deformation of the laminated body due to heat sealing while maintaining the oxygen barrier property and the water vapor barrier property of the laminated body. , And to provide a laminate having excellent recyclability.

Furthermore, an object 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 includes 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. The polyester polyol is a cured product of an adhesive, and the polyester polyol is a polyester polyol obtained by polycondensing an ortho-oriented polyvalent carboxylic acid or an anhydride thereof with a polyhydric alcohol, a polyester polyol having a glycerol skeleton, or an isocyanul ring. It is a polyester polyol that has
The base material is a stretched resin film, and the base material and the sealant layer are laminated bodies containing 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 laminated body according to the present invention, the thickness of the laminated body may be 10 μm or more and 130 μm or less.

In the laminated body according to the present invention, the thickness of the adhesive layer may be 0.5 μm or more and 6 μm or less.

In the laminated body according to the present invention, the film thickness of the vapor-deposited film may be 1 nm or more and 140 nm or less.

In the laminated body according to the present invention, the vapor-deposited film may be an aluminum-deposited film.

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

According to the present invention, it is possible to provide a laminate having excellent recyclability while suppressing deformation of the laminate due to heat sealing while maintaining the oxygen barrier property and the water vapor barrier property of the laminate.

Further, according to the present invention, it is possible to provide a packaging bag including the laminate and a zipper tape.

It is sectional drawing which shows one Embodiment of the laminated body of this invention. It is a front view which shows an example of the packaging bag which includes the laminate of this invention and a zipper tape. It is sectional drawing which shows the case where the packaging bag shown in FIG. 2 is seen along the line AA. It is a front perspective view which shows an example of the packaging bag which includes the laminated body of this invention and a zipper tape. It is a rear perspective view which shows an example of the packaging bag provided with the laminate of this invention and a zipper tape. It is a front view which shows an example of the packaging bag which includes the laminate of this invention and a zipper tape.

(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 thin-film deposition film 14 between the adhesive layer 12 and the sealant layer 13. ..

The base material provided in the laminate of the present invention and the sealant layer contain the same resin material, and the same resin material is polypropylene. This makes it possible to improve the recyclability of the packaging bag provided with the laminate.
In addition, in this invention, "the same resin material" and "the same resin material" mean that the resin classification is the same.

In the laminated body, the content of the same resin material is preferably 90% by mass or more, more preferably 92% by mass or more, and further preferably 94% by mass or more. Thereby, the recycling suitability can be further improved.
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 material in each layer constituting the laminate.

The laminated body 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, preferably 0.05 cc. It is preferably / 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 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 in an environment of 40 ° C. and 90% relative humidity, preferably 0.01 g. It is preferably / m ² / day / atm or more and 1.0 g / m ² / day / atm or less.
In the present invention, the 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, and more preferably 15 μm or more and 110 μm or less. As a result, deformation of the laminated body due to heat sealing can be further suppressed.

(Base material)
The substrate contains polypropylene. Polypropylene 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.

The base material is a stretched resin film. As a result, 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 composed of polypropylene may be used.

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

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

An image may be formed on the surface of the base material. Since it is possible to prevent the formed image from coming into contact with the outside air, it is preferable to form the image on the surface of the base material on the adhesive layer side.
The image to be formed is not particularly limited, and characters, patterns, symbols, combinations thereof, and the like are represented.
The image formation can be performed using a conventionally known ink, but it is preferably performed using a biomass-derived ink. As a result, it is possible to produce a packaging bag having a smaller environmental load by using the laminated body.
The method for forming the image is not particularly limited, and examples thereof include conventionally known printing methods such as a gravure printing method, an offset printing method, and a flexo printing method.

The base material is preferably surface-treated. Thereby, the adhesion with the adjacent layer can be improved. The surface treatment method is not particularly limited, and 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 thickness of the base material is preferably 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 40 μm or less. As a result, deformation of the laminated body due to heat sealing can be further suppressed. In addition, the mechanical strength and processability of the laminate can be improved.

(Adhesive layer)
The adhesive layer is a cured product of a two-component curable adhesive containing a polyester polyol and an isocyanate compound, and is a polyester obtained by polycondensing a polyester polyol with an ortho-oriented polyvalent carboxylic acid or an anhydride thereof and a polyhydric alcohol. It is a polyol, a polyester polyol having a glycerol skeleton, or a polyester polyol having an isocyanul ring. When the laminated body provided with the vapor-deposited film is applied to the packaging bag, 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 or the like. Since the adhesive layer is a cured product of the above-mentioned two-component curable adhesive, the oxygen barrier property and the water vapor barrier property of the laminated body can be maintained even when the vapor-deposited film is cracked. Further, this eliminates the need to use a resin film or metal foil made of polyester or polyamide, enables a laminated body having a small number of layers and a thin thickness, and a heat load due to heat sealing between the laminated body and the zipper tape. Can be reduced. Therefore, deformation of the laminated body due to heat sealing can be suppressed.

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

The two-component 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.
[Example] Polyester polyol obtained by polycondensing an ortho-oriented polyvalent carboxylic acid or its anhydride with a polyhydric alcohol [Example] Polyester polyol having a glycerol skeleton [Example] Having an isocyanul ring Polyester polyols Each polyester polyol will be described below.

The polyester polyol according to the first example is selected from the group consisting of a polyvalent carboxylic acid component containing at least one orthophthalic acid and an anhydride thereof, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. It is a polycondensate obtained by polycondensing with a polyhydric alcohol component containing at least one of these.
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.
Specifically, aliphatic polyvalent carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanediocarboxylic acid, unsaturated bond-containing polyvalent carboxylic acids such as maleic anhydride, maleic acid and fumaric acid, 1, Alicyclic polyvalent carboxylic 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 thereof include aromatic polyvalent carboxylic acids such as sex 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 preferable.
In addition, you may use 2 or more kinds of the above-mentioned other polyvalent carboxylic acids.

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-anthraquinonediyl group and a 2,3-anthracendyl 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, a methylpentylene group. 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. Anhydride, 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.

Further, examples of the polyhydric alcohol component include an alkylene diol 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 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-anthracendyl 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, a methylpentylene group. 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 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 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.

Further, examples of the polyhydric alcohol component include an alkylene diol 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 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.

Oxidation of the polyester polyol is preferably 20 mgKOH / g or more, and more preferably 50 mgKOH / g or more. Thereby, the oxygen barrier property and the water vapor barrier property of the laminated body can be further maintained.

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 compounds of the isocyanate compound include, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydride diphenylmethane diisocyanate, metaxylylene diisocyanate, hydrogenated xylylene 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.

The two-component curable adhesive used to form the adhesive layer may contain a phosphoric acid-modified compound. Thereby, the oxygen barrier property and the water vapor barrier property of the laminated body can be further maintained.
The phosphoric acid-modified compound 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 a (meth) acryloyl. It is a group selected from alkyl groups having 1 to 4 carbon atoms 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 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. It is 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 two-component 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 setting the content of the phosphoric acid-modified compound within the above numerical range, the oxygen barrier property and the water vapor barrier property of the laminate can be further maintained.

The two-component curable adhesive used for forming the adhesive layer preferably contains a plate-like inorganic compound, whereby the oxygen barrier property and the water vapor barrier property of the laminated body can be further maintained.
Plate-like inorganic compounds include, for example, kaolinite-serpentinite clay minerals (haloisite, kaolinite, enderite, dicite, nacrite, antigolite, chrysotile, etc.) and pyrophyllite-talc (pyrophilite, talc, etc.) Kerorai, etc.) and the like.

The two-component curable adhesive used to form the adhesive layer may contain a coupling agent.
Thereby, the oxygen barrier property and the water vapor barrier property of the laminated body can be further maintained.
Examples of the coupling agent include a silane-based coupling agent represented by the following general formula (7), a titanium-based coupling agent, and an aluminum-based coupling agent. In addition, these coupling agents may be used alone or in combination of two or more types.

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-isocyanuspropyltriethoxysilane, 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 (dioctyl phosphate), and aluminum. Examples thereof include -2-ethylhexanoate oxide trimmer, aluminum stearate oxide trimmer and alkylacetate aluminum oxide trimmer.

The two-component curable adhesive used to form the adhesive layer preferably contains cyclodextrin and / or a derivative thereof. Thereby, the oxygen barrier property and the water vapor barrier property of the laminated body can be further maintained.
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 resin composition, 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. Thereby, the oxygen barrier property and the water vapor barrier property can be further maintained.

The adhesive layer is applied and dried on a substrate 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

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

The sealant layer is preferably subjected to the above-mentioned 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, and more preferably 10 μm or more and 100 μm or less. As a result, deformation of the laminated body due to heat sealing can be suppressed. In addition, mechanical strength and processability can be improved. Further, it is possible to improve the processability and puncture resistance of the laminated body while maintaining the heat sealability of the sealant layer.

(Embedded film)
The laminate further comprises a thin-film film between the substrate and the adhesive layer, or between the adhesive layer and the sealant layer. Thereby, the laminated body can have oxygen barrier property and water vapor barrier property.

Examples of the thin-film film include a metal such as aluminum and an inorganic oxide such as aluminum oxide, silicon oxide, magsium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, and barium oxide.
Among these, an aluminum-deposited film is preferable from the viewpoint of oxygen barrier property and water vapor barrier property.

Conventionally known methods can be adopted as the vapor deposition film forming method, for example, physical vapor deposition methods (Physical Vapor Deposition method, PVD method) such as vacuum vapor deposition method, sputtering method and ion plating method, and plasma chemical vapor deposition. Examples thereof include chemical vapor deposition methods (Chemical Vapor Deposition methods, CVD methods) such as a growth method, a thermochemical vapor deposition method, and a photochemical vapor deposition method.

The film thickness of the vapor-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 further preferably 5 nm or more and 40 nm or less. By setting the thickness of the thin-film deposition film within the above numerical range, it is possible to prevent the occurrence of cracks and the like in the thin-film deposition film.
When the vapor-deposited film is an aluminum-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 further preferably 10 nm or more and 40 nm or less.
When the vapor-deposited film is a silicon oxide or aluminum oxide vapor-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 further preferably 5 nm or more and 20 nm or less. ..

Further, for example, both the physical vapor deposition method and the chemical vapor deposition method can be used in combination to form a composite film composed of two or more layers of thin-film deposition films of different kinds of inorganic oxides. The degree of vacuum deposition chamber, before introduction of ^oxygen, preferably about 10 ^-2 to 10 -8 mbar, in the after introduction of ^oxygen, preferably about 10 ^-1 ~10 -6 mbar. The amount of oxygen introduced differs depending on the size of the vapor deposition machine and the like. As the oxygen to be introduced, an inert gas such as argon gas, helium gas, or nitrogen gas may be used as the carrier gas within a range that does not hinder. The transport speed of the film is preferably about 10 to 800 m / min, particularly preferably about 50 to 600 m / min.

(Gas barrier layer)
The laminate may include a gas barrier layer between any layers, for example, the adhesive layer and the vapor deposition film. Thereby, the oxygen barrier property and the water vapor barrier property of the laminated body can be improved.

In one embodiment, the gas barrier layer is a hydrolyzate of a metal alkoxide 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. 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, 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.

Examples of the metal alkoxide 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 can be mentioned.

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, β- (3,4-epoxidecyclohexyl) ethyltrimethoxysilane, and the like. Be done.

Two or more kinds of the silane coupling agent as described above may be used, and the silane coupling agent is used within a range of about 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the alkoxide. Is preferable.

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 layer 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. Thereby, the oxygen barrier property, the water vapor barrier property and the 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, 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 effectively preventing the generation of cracks in the gas barrier layer.

In the gas barrier layer, a composition containing a higher-level material is applied onto a substrate by a conventionally known means such as a roll coat such as a gravure roll coater, a spray coat, a spin coat, a dipping, a brush, a barcode, and an applicator. The composition can be formed by polycondensation 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. Examples include amines. 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. As a result, the thickness of the formed gas barrier layer can be made uniform, and the catalytic effect can be further improved.

The composition may further contain an acid. The acid is used as a catalyst for the sol-gel method, mainly as a catalyst for 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 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 alkoxide and the silane coupling agent. As a result, the thickness of the formed gas barrier layer can be made uniform, and the catalytic effect can be further improved.

The composition may contain water in a proportion 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 alkoxide. preferable. As a result, the oxygen barrier property and the water vapor barrier property of the gas barrier layer can be improved, and the hydrolysis reaction can be carried out quickly.

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 layer 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 alkoxide and the water-soluble polymer (and the silane coupling agent if the composition contains a silane coupling agent) further proceeds, and a layer of the composite polymer is formed.
Finally, the 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.

(Manufacturing method of laminated body)
The method for producing the laminate according to the present invention is not particularly limited, and the laminate can be produced by using conventionally known methods such as a melt extrusion laminating method, a dry laminating method, and a sand laminating method.

The laminate according to the present invention is provided with chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubrication functions, optical functions, thermal functions, surface functions such as biocompatibility, and the like. It is also possible to perform secondary processing for the purpose. Examples of secondary processing include embossing, painting, adhesion, printing, metallizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, etc.) Coating, etc.) and the like. Further, the laminated body according to the present invention may be subjected to laminating processing (dry laminating or extruded laminating), bag making processing, and other post-treatment processing to produce a molded product.

(Packaging bag)
The packaging bag of the present invention includes the laminate and the zipper tape, and the zipper tape is located on the sealant layer. Further, the base material and the zipper tape provided in the packaging bag contain the same resin material, and the same resin material is polypropylene. Thereby, the recycling suitability can be improved. As the polypropylene contained in the zipper tape, the same polypropylene as the base material can be used. 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 material films (using the above laminated body) 21, 21', and a zipper tape 23, and has a through hole 22 in the upper part of the flat bag 20. The chuck tape is a member provided for resealing the packaging bag after opening the packaging bag.

FIG. 3 is a cross-sectional view showing a case where the packaging bag 20 shown in FIG. 2 is viewed along the 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'so as to face the male tape 24. 25 and. The male tape 24 and the female tape 25 are configured to be fitted to each other. In this case, by fitting the male tape 24 and the female tape 25, the package bag 20 after opening can be resealed. Further, the contents can be taken out again by removing the fitting between the male tape 24 and the female tape 25. 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 of manufacturing the flat bag 20 will be described with reference to FIG.
First, the body material films 21 and 21'are prepared and arranged so that the sealant layers of the body material films 21 and 21'face each other. Subsequently, the zipper tape 23 is inserted in the upper part between the body material films 21 and 21', and the respective body material films 21 and 21'and the zipper tape 23 are heat-sealed. Subsequently, the lower parts of the body material films 21 and 21'are heat-sealed. Using the point seal bar, the protrusions of the male tape 24 and the female tape 25 of the zipper tape 23 located at the heat seal portions on both sides of the body material films 21 and 21'are crushed. Subsequently, the side seal bars are used to heat seal the heat seal portions on both sides of the body material films 21 and 21'. Subsequently, the male tape 24 is removed from the female tape 25 of the zipper tape 23 to open the zipper tape 23, and the contents are filled from the upper opening. Subsequently, the male tape 24 and the female tape 25 are refitted to seal the opening, and the upper portions of the body material films 21 and 21'are heat-sealed. Finally, the flat bag 20 can be manufactured by forming the through hole 22. Here, the shaded portion in FIG. 2 represents the heat-sealed portion.
The flat bag 20 may be manufactured by heat-sealing the upper part of the body material films 21 and 21'first, filling the contents, and then heat-sealing the lower part of the body material films 21 and 21'.

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 (using the above-mentioned laminate) 31 and a zipper tape 33, and has a through hole 32 in the upper portion of the pillow bag 30. As the zipper tape 33, the same one as the zipper tape 23 described with reference to FIGS. 2 and 3 can be used.

Next, a method of manufacturing the pillow bag 30 will be described with reference to FIGS. 4 and 5.
First, the body material film 31 is prepared, and the zipper tape 33 is heat-sealed on the sealant layer of the body material film 31 toward the upper center. Subsequently, the 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 hold the sealant layers together. Subsequently, the inner surface of the tubular body material film 31 on the gassho portion side and the zipper tape 33 are heat-sealed. Subsequently, the lower part of the body material film 31 is heat-sealed. Subsequently, the male tape is removed from the female tape of the zipper tape 33 to open the zipper tape 33, and the contents are filled through the upper opening. Subsequently, the male tape and the female tape are refitted to seal the opening, and the upper part of the body material film 31 is heat-sealed. Finally, the pillow bag 30 can be manufactured by forming the through hole 32. Here, the shaded portion in FIGS. 4 and 5 represents the heat-sealed portion.
The pillow bag 30 may be manufactured by heat-sealing the upper part of the body material film 31 first, filling the contents, and then heat-sealing the lower part of the body material film 31.

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 a body material film (using the above laminate) 41, 41', a bottom material film (which may be the same as or different from the body material film) 44, and a zipper. It includes a tape 43 and has a through hole 32 at the top of the stand pouch 40. As the zipper tape 43, the same one as the zipper tape 23 described with reference to FIGS. 2 and 3 can be used.

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

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

Next, the present invention will be described 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 having a thickness of 30 μm was prepared as a base material, and a printing layer was formed on the biaxially stretched polypropylene resin film by gravure printing. The thickness of the print layer was 1 μm.

Subsequently, an unstretched polypropylene resin film (manufactured by Toray Processing Film Co., Ltd., trade name: VM-CPP 2703, thickness: 30 μm) having an aluminum vapor deposition film having a thickness of 50 nm on one surface was prepared and biaxially stretched. The printed surface of the polypropylene resin film and the vapor-deposited surface of the unstretched polypropylene resin film are separated by a two-component curable adhesive containing a polyester polyol and an isocyanate compound (manufactured by DIC Co., Ltd., trade name: PASLIM VM NSRD011 / NSRD006). And laminated. The thickness of the adhesive layer formed by the two-component curable 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.

Subsequently, using the laminate obtained in this example and a zipper tape containing polypropylene (manufactured by Takiron CI 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 material film (laminated body) was not deformed by the heat seal.

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

Subsequently, using the laminate obtained in this example and a zipper tape containing polypropylene (manufactured by Takiron CI 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 material film (laminated body) was not deformed by the heat seal.

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

Subsequently, an aluminum foil having a thickness of 7 μm was prepared, and the printed layer of the PET resin film and the aluminum foil were bonded to a two-component curable adhesive (manufactured by Rock Paint Co., Ltd., trade name: Adlock main agent: RU-77T, Hardener: Laminated via H-7). The thickness of the adhesive layer formed by the two-component curable adhesive was 3 μm.

Subsequently, a polyethylene resin film having a thickness of 60 μm was prepared, and the aluminum foil and the polyethylene resin film were bonded to a two-component curable adhesive (manufactured by Rock Paint Co., Ltd., trade name: Adlock main agent: RU-77T, curing agent). : Laminated via H-7). The thickness of the adhesive layer formed by the two-component curable adhesive was 3 μm.

The thickness of the laminate thus obtained was 86 μm.

Subsequently, using the laminate obtained in this comparative example and a zipper tape containing polypropylene (manufactured by Takiron Sea Eye Co., Ltd., trade name: zipper tape MX-13F, MX soft grade), as shown in FIG. A flat bag 20 was produced (processing conditions: sealing temperature 175 ° C., sealing time 0.45 seconds). The body material film (laminated body) was not deformed by the heat seal.

[Comparative Example 2]
The two-component curable adhesive of Example 1 (manufactured by DIC Corporation, trade name: PASLIM VM NSRD011 / NSRD006) and the two-component curable adhesive of Comparative Example 1 (manufactured by Rock Paint Co., Ltd., trade name: Adlock) A laminate was prepared in the same manner as in Example 1 except that the main agent was changed to RU-77T and the curing agent was changed to H-7). The thickness of the adhesive layer formed by the adhesive was 2.5 μm.

Subsequently, using the laminate obtained in this comparative example and a zipper tape containing polypropylene (manufactured by Takiron CI 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 material film (laminated body) was not deformed by the heat seal.

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

Subsequently, a PET resin film (thickness 12 μm) provided with an aluminum vapor deposition film is prepared, and the printing layer of the biaxially stretched polypropylene resin film and the PET resin film are bonded to a two-component curable adhesive (Rock Paint Co., Ltd.). ), Trade name: Adlock Main agent: RU-77T, Hardener: H-7). The thickness of the adhesive layer formed by the two-component curable adhesive was 3 μm.

Subsequently, an unstretched polypropylene resin film having 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 combined with a two-component curable adhesive (manufactured by Rock Paint Co., Ltd.). Product name: Adlock Main agent: RU-77T, hardener: H-7) and laminated. The thickness of the adhesive layer formed by the two-component curable adhesive was 3 μm.

The thickness of the laminate thus obtained was 79 μm.

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

<< Oxygen barrier test >>
The laminates obtained in the above Examples and Comparative Examples were cut into A4 size, and using OXTRAN2 / 20 manufactured by MOCON of the United States, oxygen permeability (cc / m ^{2) in} an environment of 23 ° C. and 90% relative humidity. / 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 using PERMATRAN 3/31 manufactured by MOCON, USA, the water vapor permeability (g) in an environment of 40 ° C. and 90% relative humidity. / 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 bending load (stroke: 155 mm, bending) in accordance with ASTM F 392 using Gelboflex Tetter (Tester Sangyo Co., Ltd., trade name: BE1006BE). Operation: 440 °) was given 5 times.
After applying the bending load, the oxygen permeability and the steam permeability were measured in the same manner as in the oxygen barrier property test and the water vapor barrier property test. The measurement results are summarized in Table 1.

10: Laminated body 11: Base material 12: Adhesive layer 13: Sealant layer 14: Vapor deposition 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 film 32: Through hole 33: Zipper tape 40: Stand pouch 41, 41': Body film 42: Through hole 43: Zipper tape 44: Bottom material film

Claims (8)

With a base material, an adhesive layer, and a sealant layer,
A thin-film film is further provided between the adhesive layer and the sealant layer.
The adhesive layer is a cured product of a two-component curable adhesive containing a polyester polyol and an isocyanate compound.
The polyester polyol is a polyester polyol obtained by polycondensing an ortho-oriented polyvalent carboxylic acid or an anhydride thereof with a polyhydric alcohol, a polyester polyol having a glycerol skeleton, or a polyester polyol having an isocyanul ring.
The base material is a stretched resin film.
The base material and the sealant layer contain the same resin material and contain 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 thickness of the laminate is 10 μm or more and 130 μm or less. The laminate according to any one of claims 1 to 4, wherein the thickness of the adhesive layer is 0.5 μm or more and 6 μm or less. The laminate according to any one of claims 1 to 5, wherein the film thickness of the vapor-deposited film is 1 nm or more and 140 nm or less. The laminate according to any one of claims 1 to 6, wherein the vapor-deposited film is an aluminum-deposited film. With the laminate according to any one of claims 1 to 7.
Including zipper tape,
The zipper tape is located on the sealant layer and
The base material, the sealant layer and the zipper tape contain the same resin material.
A packaging bag in which the same resin material is polypropylene.