JP2021142688A - Laminate for packaging material and packaging material - Google Patents

Abstract

To provide a laminate for a packaging material having high recyclability, oxygen barrier properties and water vapor barrier properties, as well as high flexural load resistance.SOLUTION: A laminate for a packaging material includes a substrate 11, an adhesion layer 12 and a heat sealable resin layer 13, and further includes a vapor-deposited film 14 between the substrate and the adhesion layer or between the adhesion layer and the heat sealable resin layer. The adhesion layer is composed of a cured product of a resin composition containing a resin having two or more hydroxyl groups in one molecule, and an isocyanate compound having two or more isocyanate groups in one molecule. The substrate and the heat sealable resin layer contain a resin material of the same kind.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminate for packaging materials and a packaging material composed of the laminate.

Conventionally, a resin film made of a resin material has been used as a constituent material of a packaging material. Further, since the packaging material is required to have various functions such as oxygen barrier property and water vapor barrier property depending on the content 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 material, 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 thin-film deposition film on the resin film is performed.

By the way, in recent years, with the increasing demand for the construction of a sound material-cycle society, attempts have been made to recycle and use packaging materials. 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 material having a smaller environmental load.

Here, as a laminate used for producing a packaging material for filling snacks and the like, a laminate having a stretched polypropylene film, an adhesive layer made of a two-component curable urethane adhesive, an aluminum vapor deposition film, and an unstretched polypropylene film is widely known. Has been done. Such a laminated body does not need to separate each layer and can be recycled as it is.

Nowadays, the present inventors mold the laminate by a former or the like provided in the packaging machine at the time of preparing the packaging material and filling the contents, and the molding process applies a large bending load to the packaging material. , It was found that the oxygen barrier property and the water vapor barrier property of the packaging material are lowered.

The present invention has been made in view of the above findings, and the problem to be solved is to obtain a laminate for packaging materials, which has high recyclability, oxygen barrier property, water vapor barrier property, and high bending load resistance. To provide.
Another object to be solved by the present invention is to provide a packaging material composed of the laminate.

The laminate for packaging material of the present invention includes a base material, an adhesive layer, and a heat-sealable resin layer.
A thin-film deposition film is further provided between the base material and the adhesive layer, or between the adhesive layer and the heat-sealing resin layer.
The adhesive layer is composed of a cured product of a resin composition containing a resin having two or more hydroxyl groups in one molecule and an isocyanate compound having two or more isocyanate groups in one molecule.
The base material and the heat-sealable resin layer are characterized by containing the same type of resin material.

In one embodiment, the same type of resin material is polyolefin or polyester.

In one embodiment, the content of the same type of resin material in the laminate is 90% by mass or more.

In one embodiment, the thickness of the adhesive layer is 0.5 μm or more and 6 μm or less.

In one embodiment, the vapor deposition film is an aluminum vapor deposition film.

In one embodiment, the laminate for packaging material of the present invention has an oxygen permeability of 0.05 cc / m ² · day · atm or more and 2.0 cc / m ² · day · in an environment of 23 ° C. and 90% relative humidity. It is less than or equal to atm.

In one embodiment, the packaging material laminate of the present invention has a water vapor transmission rate of 0.01 g / m ² · day or more and 2.0 g / m ² · day or less in an environment of 0 ° C. and 90% relative humidity. ..

The packaging material of the present invention is characterized by being composed of the above-mentioned laminate.

According to the present invention, it is possible to provide a laminate for packaging materials, which has high recyclability, oxygen barrier property, water vapor barrier property, and high bending load resistance.

It is sectional drawing which shows one Embodiment of the laminated body of this invention. It is a perspective view which shows one Embodiment of the packaging material produced using the laminated body of this invention. It is a perspective view which shows one Embodiment of the packaging material produced using the laminated body of this invention.

As shown in FIG. 1, the packaging material laminate 10 of the present invention includes a base material 11, an adhesive layer 12, and a heat-sealable resin layer 13, and is located between the base material 11 and the adhesive layer 12. A thin-film deposition film 14 is further provided between the adhesive layer 12 and the heat-sealable resin layer 13.

The base material provided in the laminate for packaging material of the present invention and the heat-sealable resin layer contain the same type of resin material. This makes it possible to improve the recyclability of the packaging material produced by using the packaging material laminate of the present invention.
In the present invention, the "same type of resin material" means that the resin classifications of vinyl resin, polyolefin, cellulose resin, polyester and the like are the same.

In the laminate of the present invention, the content of the same type of resin material is preferably 90% by mass or more, more preferably 93% by mass or more, and 95% by mass or more from the viewpoint of recyclability. Is more preferable.
The content of the same type of resin material in the laminate means the ratio of the same type of resin material to the sum of the contents of the resin material in each layer constituting the laminate.

The laminate of the invention, 23 ° C., the oxygen permeability under a relative humidity of 90% environment is preferably not more than 0.05cc ^/ m 2 · day · atm or more ^{20cc / m 2 · day · atm} , 0. it is preferable 05cc ^/ m 2 · day · atm or less than ^{10cc / m 2 · day · atm} .
In the present invention, the oxygen permeability is measured in accordance with JIS K 7126.

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

(Base material)
The base material contains at least one resin material, and examples of the resin material include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and 1,4-polycyclohexylene methylene terephthalate. , Polyester such as terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyamide such as nylon 6 and nylon 6,6, polyolefin such as polyethylene (PE), polypropylene (PP) and polymethylpentene, polyvinyl chloride, polyvinyl Vinyl resins such as alcohol (PVA), polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral and polyvinylpyrrolidone (PVP), (meth) acrylic resins such as polyacrylate, polymethacrylate and polymethylmethacrylate, Examples thereof include cellulose resins such as cellophane, cellulose acetate, nitrocellulose, cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB), styrene resins such as polystyrene (PS), and chlorinated resins thereof.
Among these, polyolefins and polyesters are preferable, polyolefins are more preferable, PE, PP and PET are more preferable, and PP is particularly preferable, from the viewpoint of recyclability.
In the present invention, "(meth) acrylic" means to include both "acrylic" and "methacryl". Further, "(meth) acrylate" means to include both "acrate" and "metaaclate".

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

In one embodiment, the base material is a resin film containing the above resin material, and the resin film may be a stretched film or an unstretched film, but from the viewpoint of strength, it may be uniaxially or A stretched film stretched in the biaxial direction is preferable.

Further, the above-mentioned laminated body of the resin film can be used as a base material. The laminate of the resin film can be produced by using a dry lamination method, a non-solvent lamination method, a wet lamination method, an extraction method, or the like.

The base material may be provided with a vapor-deposited film described later on its surface.

Further, 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.
Further, an anchor coat layer may be formed on the surface of the base material by using a conventionally known anchor coat agent as long as the characteristics of the present invention are not impaired.

Further, the substrate may have an image formed on its surface. 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. This makes it possible to produce a packaging material having a smaller environmental load by using the laminate of the present invention.
The method for forming an 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 flexographic printing method. Among these, the flexographic printing method is preferable from the viewpoint of environmental load.

The thickness of the base material is preferably 5 μm or more and 300 μm or less, and more preferably 7 μm or more and 100 μm or less, from the viewpoint of mechanical strength and processability.

(Adhesive layer)
The adhesive layer is characterized by being composed of a cured product of a resin composition containing a resin having two or more hydroxyl groups in one molecule (polyol resin) and an isocyanate compound having two or more isocyanate groups in one molecule. And.
Thereby, the oxygen barrier property, the water vapor barrier property, and the bending load resistance of the laminate of the present invention can be remarkably improved. Further, by providing the adhesive layer having such a structure on the thin-film deposition film, it is possible to effectively prevent cracks from being generated in the thin-film deposition film. In particular, it is possible to remarkably prevent the occurrence of cracks in the aluminum vapor deposition film.

The glass transition temperature of the resin composition is preferably −30 ° C. or higher and 80 ° C. or lower, more preferably 0 ° C. or higher and 70 ° C. or lower, and further preferably 25 ° C. or higher and 70 ° C. or lower. Thereby, the oxygen barrier property, the water vapor barrier property, and the laminate strength of the laminate of the present invention can be further improved.
In the present invention, Tg is a value obtained by DSC (Differential Scanning Calorimetry) in accordance with JIS K 7121.

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

In the first example, the polyester portion of the main skeleton can be obtained by polycondensing a polyvalent carboxylic acid and a polyhydric alcohol by a conventional method in Hunai.

Examples of the polyvalent carboxylic acid include an aliphatic polyvalent carboxylic acid and an aromatic polyvalent carboxylic acid.
Examples of the aliphatic polyvalent carboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid.
Examples of the aromatic polyvalent carboxylic acid include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid and 2,3-naphthalenedicarboxylic acid. 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 , Anhydrous of these dicarboxylic acids; polybasic acids such as p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and the like.
Among the above-mentioned multivalent carboxylic acids, ortho-oriented aromatic dicarboxylic acids or anhydrides thereof are preferable. Specific examples thereof include orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid and anhydrides thereof.
Two or more kinds of polyvalent carboxylic acids may be used.

Examples of the polyhydric alcohol include an aliphatic polyhydric alcohol and an aromatic polyhydric alcohol.
Examples of the aliphatic polyhydric alcohol include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexane. Examples thereof include diols, methylpentanediols, dimethylbutanediols, butylethylpropanediols, diethylene glycols, triethylene glycols, tetraethylene glycols, dipropylene glycols and tripropylene glycols.
Examples of the aromatic polyhydric alcohol include hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, bisphenol F, tetramethylbiphenol, ethylene oxide extensions thereof, and water-added aliphatic compounds thereof.

The second example will be described below.

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

As the polyol resin 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. Anhydrous, anthraquinone 2,3-dicarboxylic acid or an anhydride thereof, 2,3-anthracenecarboxylic acid or an anhydride thereof and the like can be mentioned.
These compounds may have a substituent on any carbon atom of the aromatic ring. Examples of the substituent include a chloro group, a bromo group, a methyl group, an ethyl group, an i-propyl group, a hydroxyl group, a methoxy group, an ethoxy group, a phenoxy group, a methylthio group, a phenylthio group, a cyano group, a nitro group and an amino group. Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group and a naphthyl group.

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

Hereinafter, a third example will be described.

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

The polyol resin 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 a triol having an isocyanul ring, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position or an anhydride thereof, and a polyhydric alcohol component. Can be synthesized by reacting with

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

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

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

Moreover, as a polyhydric alcohol component, an alkylenediol having 2 to 6 carbon atoms can be mentioned. For example, diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol and dimethylbutanediol. Can be mentioned.
Among them, 1,3,5-tris (2-hydroxyethyl) isocyanuric acid or 1,3,5-tris (2-hydroxypropyl) isocyanuric acid is used as the triol compound having an isocyanul ring, and the carboxylic acid is in the ortho position. A polyester polyol compound having an isocyanul ring using orthophthalic anhydride as the aromatic polyvalent carboxylic acid substituted with or 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 polyol resin is preferably 20 mgKOH / g or more, and more preferably 50 mgKOH / g or more. Thereby, the oxygen barrier property, the water vapor barrier property, and the bending load resistance of the laminate of the present invention can be further improved.

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, water vapor barrier property and bending load resistance.

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

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

式中、Ｒ_４、Ｒ_５は、水素原子、炭素数１〜３０のアルキル基、（メタ）アクリロイル基、置換基を有してもよいフェニル基及び（メタ）アクリロイルオキシ基を有する炭素数１〜４のアルキル基から選ばれる基であり、ｎは１〜４の整数、ｘは０〜３０の整数、ｙは０〜３０の整数を表すが、ｘとｙが共に０である場合を除く。 The resin composition used for forming the adhesive layer can contain a phosphoric acid-modified compound. Thereby, the oxygen barrier property, the water vapor barrier property, and the bending load resistance of the laminate of the present invention can be further improved.
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. 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 resin composition 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, the water vapor barrier property and the bending load resistance of the laminate of the present invention can be further improved.

The resin composition used for forming the adhesive layer preferably contains a plate-like inorganic compound, whereby the oxygen barrier property, the water vapor barrier property and the bending load resistance of the laminate of the present invention can be further improved. ..
Plate-like inorganic compounds include, for example, kaolinite-kaolinite clay minerals (haloysite, kaolinite, enderite, deckite, nacrite, antigolite, chrysotile, etc.) and pyrophyllite-talc (pyrophyllite, talc, etc.). Kerorai, etc.) and the like.

The resin composition used for forming the adhesive layer may contain a coupling agent.
Thereby, the oxygen barrier property, the water vapor barrier property, and the bending load resistance of the laminate of the present invention can be further improved.
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. These coupling agents may be used alone or in combination of two or more.

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

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

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

The resin composition used to form the adhesive layer preferably contains cyclodextrin and / or a derivative thereof. Thereby, the oxygen barrier property, the water vapor barrier property, and the bending load resistance of the laminate of the present invention can be further improved.
Specifically, for example, a cyclodextrin such as cyclodextrin, alkylated cyclodextrin, acetylated cyclodextrin, and hydroxyalkylated cyclodextrin in which the hydrogen atom of the hydroxyl group of the glucose unit is replaced with another functional group can be used. can. 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, the water vapor barrier property, and the bending load resistance of the laminate of the present invention can be further improved. Further, it is possible to more effectively prevent the occurrence of cracks in the vapor-deposited film.

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

Further, a commercially available resin composition containing a resin having two or more hydroxyl groups in one molecule and an isocyanate compound having two or more isocyanate groups in one molecule may be used, for example, DIC stock. The PASLIM series sold by the company can be used.

(Heat sealable resin layer)
In one embodiment, the heat sealable resin layer comprises at least one resin material.
Examples of the resin material include polyester, vinyl resin, (meth) acrylic resin, (meth) acrylic resin, polyurethane, cellulose resin, polyamide, polyolefin, styrene resin, and chlorinated resins thereof. Among these, polyolefins and polyesters are preferable, polyolefins are more preferable, PE, PP and PET are more preferable, and PP is particularly preferable, from the viewpoint of recyclability and heat sealability. Further, by using polyolefin, a laminate having high recyclability can be obtained.

The heat-sealing resin layer may contain the above additives as long as the characteristics of the present invention are not impaired.

The heat-sealing resin layer is preferably subjected to the above-mentioned surface treatment. Thereby, the adhesion with the adjacent layer can be improved.

The thickness of the heat-sealing resin layer is preferably 15 μm or more and 500 μm or less, more preferably 20 μm or more and 250 μm or less, and further preferably 30 μm or more and 100 μm or less. This makes it possible to improve the processability and piercing resistance of the laminate of the present invention while maintaining the heat-sealing property of the heat-sealing resin layer.

The heat-sealable resin layer is formed by providing a vapor-deposited film on a resin film composed of the above-mentioned thermoplastic resin, for example, polyolefin, and laminating the vapor-deposited surface with a base material via a conventionally known adhesive. can do.

(Embedded film)
The laminate for packaging materials of the present invention includes a vapor-deposited film between the base material and the adhesive layer, or between the adhesive layer and the heat-sealable resin layer.

Examples of the vapor-deposited film include a metal-deposited film containing 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 such as vacuum vapor deposition, sputtering and ion plating (Physical Vapor Deposition method, PVD 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.

In the case of an aluminum vapor-deposited film, the film thickness of the vapor-deposited film is preferably 1 nm or more and 100 nm or less, more preferably 15 nm or more and 60 nm or less, and further preferably 10 nm or more and 40 nm or less.
In the case of a silicon oxide or aluminum oxide vapor-deposited film, it 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.
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 while maintaining the oxygen barrier property and the water vapor barrier property.

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 vapor-deposited 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 of the present invention may include a gas barrier layer between any layers, for example, a base material and an adhesive layer. Thereby, the oxygen barrier property and the water vapor barrier property of the laminate of the present invention can be further 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, or 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, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. 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 the 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. Thereby, 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. Thereby, the thickness of the formed gas barrier layer can be made uniform, and the catalytic effect can be further improved.

Further, the composition may contain water at a ratio of preferably 0.1 mol or more and 100 mol or less, more preferably 0.8 mol or more and 2 mol or less, based on 1 mol of the total molar amount of 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 substrate 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 to form a layer of the composite polymer.
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.

(Packaging material)
The packaging material of the present invention is characterized by being composed of the above-mentioned laminate.
The shape of the packaging material is not particularly limited, and may be a bag-like shape as shown in FIG.
In one embodiment, the bag-shaped packaging material is produced by folding and stacking the laminate of the present invention in half so that the heat-sealing resin layer is on the inside, and heat-sealing the end portion thereof. Can be done.
Further, in another embodiment, the bag-shaped packaging material can also be produced by stacking two laminates so that the heat-sealing resin layers face each other and heat-sealing the ends thereof.
In the figure, the shaded area represents the heat-sealed part.

The heat sealing method is not particularly limited, and for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

Further, in one embodiment, as shown in FIG. 3, the packaging material has a stand pouch-like shape including a body portion and a bottom portion.
The stand pouch-shaped packaging material forms a body by heat-sealing in a tubular shape so that the heat-sealing resin layer of the laminate is on the inside, and then heats another laminate. The bottom portion can be formed and manufactured by folding it in a V shape so that the sealing resin layer is on the inside, sandwiching it from one end of the body portion, and heat-sealing it.

The contents to be filled in the packaging material are not particularly limited, and the contents may be a liquid, a powder or a gel. Moreover, it may be food or non-food.
After filling the contents, the opening can be heat-sealed to form a package.

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
As a base material, a biaxially stretched polypropylene (PP) film A (manufactured by Toyobo Co., Ltd.) having a thickness of 15 μm and one side of which was corona-treated was prepared.

An unstretched PP film (manufactured by Toray Industries, Inc., trade name: 2703, thickness: 25 μm) having an aluminum vapor deposition film having a thickness of 40 nm on one surface was prepared.

The corona-treated surface of the biaxially stretched PP film A and the vapor-deposited surface of the unstretched PP film are a resin having two or more hydroxyl groups in one molecule and an isocyanate compound having two or more isocyanate groups in one molecule. Was laminated via a resin composition (manufactured by DIC Co., Ltd., trade name: PASLIM) containing the above. The thickness of the adhesive layer formed by the resin composition was 2 μm. After the lamination, it was aged at 40 ° C. for 2 days to obtain a laminate for packaging material.
The proportion of PP in the laminate thus obtained was 95.2% by mass.

Example 2
A laminate for packaging material was produced in the same manner as in Example 1 except that the biaxially stretched polypropylene (PP) film A was changed to a biaxially stretched PP film B having a thickness of 18 μm. The proportion of PP in the laminate thus obtained was 95.6% by mass.

Example 3
A laminate for packaging material was produced in the same manner as in Example 1 except that the biaxially stretched polypropylene (PP) film A was changed to the biaxially stretched PP film C having a thickness of 20 μm. The proportion of PP in the laminate thus obtained was 95.7% by mass.

Example 4
A laminate for packaging material was produced in the same manner as in Example 1 except that the biaxially stretched polypropylene (PP) film A was changed to a biaxially stretched PP film D having a thickness of 25 μm. The proportion of PP in the laminate thus obtained was 96.2% by mass.

Example 5
A laminate for packaging material was produced in the same manner as in Example 1 except that the biaxially stretched polypropylene (PP) film A was changed to a biaxially stretched PP film E having a thickness of 30 μm. The proportion of PP in the laminate thus obtained was 96.5% by mass.

Example 6
A laminate for packaging material was produced in the same manner as in Example 1 except that the biaxially stretched polypropylene (PP) film A was changed to a biaxially stretched PP film F having a thickness of 40 μm. The proportion of PP in the laminate thus obtained was 97.0% by mass.

Comparative Example 1
As a base material, a biaxially stretched PP film C having a thickness of 20 μm and one surface of which was corona-treated was prepared.

An unstretched PP film (manufactured by Toray Film Processing Co., Ltd., trade name: 2703, thickness: 25 μm) having an aluminum vapor deposition film having a thickness of 40 nm on one surface was prepared.

The corona-treated surface of the biaxially stretched PP film C and the vapor-deposited surface of the unstretched PP film are bonded to a two-component curable urethane adhesive (manufactured by Toyo Morton Co., Ltd., trade names: Tomoflex TM-340 and CAT- It was laminated via 29). The thickness of the adhesive layer formed by the two-component curable adhesive was 3 μm. After the lamination, it was aged at 25 ° C. for 1 day to obtain a laminate for packaging material. The proportion of PP in the laminate thus obtained was 93.8% by mass.

Comparative Example 2
As a base material, a biaxially stretched PP film C having one surface treated with corona was prepared.

A stretched polyethylene terephthalate (PET) film (manufactured by Toray Film Processing Co., Ltd., trade name: 1310, thickness: 25 μm) having an aluminum vapor deposition film having a thickness of 40 nm on one surface was prepared.

The corona-treated surface of the biaxially stretched PP film and the vapor-deposited surface of the stretched PET film are two-component curable urethane adhesive (manufactured by Toyo Morton Co., Ltd., trade names: Tomoflex TM-340 and CAT-29). Laminated through. The thickness of the adhesive layer formed by the liquid-curable adhesive was 3 μm.

An unstretched PP film having a thickness of 25 μm (manufactured by Toyobo Co., Ltd., trade name: P1128) having one surface treated with corona was prepared, and the corona-treated surface and the non-deposited surface of the stretched PET film were formed. Laminates were formed via a two-component curable urethane adhesive (manufactured by Toyo Morton Co., Ltd., trade names: Tomoflex TM-340 and CAT-29). The thickness of the adhesive layer formed by the two-component curable adhesive was 3 μm. After the lamination, it was aged at 25 ° C. for 1 day to obtain a laminate for packaging material. The proportion of PP in the laminate thus obtained was 43.7% by mass.

Comparative Example 3
As a base material, a biaxially stretched PP film C having one surface treated with corona was prepared. An anchor coating agent (manufactured by Mitsui Chemicals, Inc., trade name: A-3210 / A-3075) is applied to the corona-treated surface of the biaxially stretched PP film C and dried to form an anchor coating layer having a thickness of 1 μm. bottom.

A stretched polyethylene terephthalate (PET) film (manufactured by Toray Film Processing Co., Ltd., trade name: 1310, thickness: 25 μm) having an aluminum vapor deposition film having a thickness of 40 nm on one surface was prepared.

Low-density polyethylene (manufactured by Japan Polyethylene Corporation, trade name: LC600A) is melt-extruded onto the anchor coat layer to form an adhesive layer with a thickness of 7 μm, and the vapor-deposited surface of the stretched PET film is formed through the adhesive layer. Was laminated.

An unstretched PP film having a thickness of 18 μm (manufactured by Mitsui Chemicals Tohcello Corporation, trade name: TAF-513) was prepared.

Low-density polyethylene (manufactured by Japan Polyethylene Corporation, trade name: LC600A) is melt-extruded onto the non-evaporated surface of the stretched PET film to form an adhesive layer having a thickness of 7 μm, and the unstretched layer is formed through the adhesive layer. The PP film was laminated. After the lamination, it was aged at 25 ° C. for 1 day to obtain a laminate for packaging material. The proportion of PP in the laminate thus obtained was 18.9% by mass.

<< Oxygen barrier test >>
The laminates obtained in the above Examples and Comparative Examples were cut into A4 size, and using OXTRAN 2/20 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 the above Examples and Comparative Examples were cut into A4 size, and using PERMATRAN 3/31 manufactured by MOCON of the United States, the water vapor transmission rate (g / m ^{2) in an environment of 40 ° C. and 90% relative humidity.} -Day) 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 bent with a gelboflex tester (Tester Sangyo Co., Ltd., trade name: BE1006BE) in accordance with ASTM F 392 with a bending load (stroke: 155 mm, bending). Operation: 440 °) was given 5 times.
After applying the bending load, the oxygen permeability and the water vapor transmission rate 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.

<< Laminate strength test >>
The laminates obtained in the above Examples and Comparative Examples were cut to prepare test pieces having a length of 100 mm and a width of 15 mm.
The prepared test piece was subjected to a T-shaped peeling method (tensile speed 50 mm / min) in an environment of 25 ° C. and a relative humidity of 65% using a Tensilon tensile tester (manufactured by Orientec Co., Ltd., trade name: RTC-1310A). ), The lamination strength (N / 15 mm) was measured. The laminate strength was defined as the maximum load when peeled off. The measurement results are summarized in Table 1.

10: Laminate for packaging material, 11: Base material, 12: Adhesive layer, 13: Heat-sealable resin layer, 14: Vapor-deposited film

Claims (8)

A laminate for packaging materials, comprising a base material, an adhesive layer, and a heat-sealing resin layer.
A thin-film film is further provided between the base material and the adhesive layer, or between the adhesive layer and the heat-sealing resin layer.
The adhesive layer is composed of a cured product of a resin composition containing a resin having two or more hydroxyl groups in one molecule and an isocyanate compound having two or more isocyanate groups in one molecule.
A laminate, wherein the base material and the heat-sealable resin layer contain the same type of resin material. The laminate according to claim 1, wherein the resin material is polyolefin or polyester. The laminate according to claim 1, wherein the content of the same type of resin material in the laminate is 90% by mass or more. The laminate according to any one of claims 1 to 3, 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 4, wherein the vapor-deposited film is an aluminum-deposited film. Any one of claims 1 to 5, wherein the oxygen permeability in an environment of 23 ° C. and 90% relative humidity is 0.05 cc / m ² · day · atm or more and 2.0 cc / m ^{2 · day · atm or less.} The laminate described in. The laminate according to any one of claims 1 to 6, wherein the water vapor transmission rate in an environment of 40 ° C. and 90% relative humidity is 0.01 g / m ² · day or more and 2.0 g / m ^{2 · day or less.} body. A packaging material composed of the laminate according to any one of claims 1 to 7.

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