JP2021142689A - Laminate and package - Google Patents

Abstract

To provide a laminate having high recyclability, gas barrier properties and UV barrier properties.SOLUTION: A laminate includes a substrate, a printed layer, a barrier adhesive layer and a sealant layer, and further includes: a vapor-deposited film at least in one of an interlayer between the substrate and the barrier adhesive layer and an interlayer between the barrier adhesive layer and the sealant layer. The barrier 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 printed layer includes an ultraviolet scattering particle. The substrate and the sealant layer contain the same polyolefin, and transmittance in wavelength 280 nm to 320 nm is 1% or less.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a laminate and a package composed of the laminate.

Conventionally, a resin film made of a resin material has been used as a constituent material of a packaging body.
For example, a laminate composed of different types of resin films, which comprises a polyethylene terephthalate film as a base material and a polyethylene film as a sealant layer, is used for producing a package.

Further, the package is required to have various functions such as gas barrier property (oxygen barrier property and water vapor barrier property) depending on the contents to be filled. In such a case, a polyamide film or the like is further provided as an intermediate layer of the above-mentioned laminate.

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 the packaging. However, it is difficult to separate a package made of a laminated film obtained by laminating a plurality of different resin films into each layer, and the package collected after use is not suitable for recycling and has a higher environmental load. There was a request to use a packaging with less recycling.

Here, as a laminate used for producing a package 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-deposited film, and an unstretched polypropylene film is widely used. Are known. Such a laminated body does not need to separate each layer and can be recycled as it is.

We have found a new problem that the package made of the above-mentioned laminate does not have sufficient barrier property against ultraviolet rays and causes deterioration of quality, taste and aroma depending on the contents to be filled.

The present disclosure has been made in view of the above problems, and the problem to be solved is to provide a laminate having high recyclability, gas barrier property, and ultraviolet barrier property.
Another object of the present disclosure to be solved is to provide a package made of the laminate.

The laminate of the present disclosure comprises a base material, a printing layer, a barrier adhesive layer, and a sealant layer.
A thin-film deposition film is further provided between the base material and the barrier adhesive layer, and between at least one layer between the barrier adhesive layer and the sealant layer.
The barrier 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 printed layer contains ultraviolet scattering particles and contains
The base material and the sealant layer contain the same polyolefin, and the base material and the sealant layer contain the same polyolefin.
It is characterized in that the transmittance at a wavelength of 280 nm to 320 nm is 1% or less.

In one embodiment, the same polyolefin contained in the substrate and the sealant layer is polyethylene or polypropylene.

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

In one embodiment, the printing layer is formed on the entire surface of the substrate.

In one embodiment, the ultraviolet scattering particles contained in the printing layer are titanium oxide or zinc oxide.

In one embodiment, the primary average particle size of the ultraviolet scattering particles contained in the printing layer is 100 nm or more and 600 nm or less.

In one embodiment, the content of the ultraviolet scattering particles in the printing layer is 15% by mass or more and 60% by mass or less.

In one embodiment, the thickness of the print layer is 0.5 μm or more and 5 μm or less.

In one embodiment, the laminate further comprises an ultraviolet barrier layer at any location.

In one embodiment, the UV barrier layer comprises UV scattering particles.

In one embodiment, the primary particle size of the ultraviolet scattering particles contained in the ultraviolet barrier layer is 5 nm or more and 50 nm or less.

In one embodiment, the UV barrier layer comprises an organic UV absorber.

In one embodiment, the ultraviolet barrier layer is formed on the surface of the printing layer on the barrier adhesive layer side.

In one embodiment, the thickness of the ultraviolet barrier layer is 0.3 μm or more and 5 μm or less.

In one embodiment, the vapor-deposited film is a transparent vapor-deposited film composed of an inorganic oxide and is provided between the printing layer and the barrier adhesive layer.

In one embodiment, the vapor-deposited film is made of metal and is provided between the barrier adhesive layer and the sealant layer.

The package of the present disclosure is characterized by being composed of the above-mentioned laminate.

In one embodiment, the packaging is a pillow bag.

According to the present disclosure, it is possible to provide a laminate having high recyclability, gas barrier property, and ultraviolet barrier property.
Further, according to the present disclosure, it is possible to provide a package made of the laminated body.

It is sectional drawing which shows one Embodiment of the laminated body of this disclosure. It is a front view which shows one Embodiment of the package (pillow bag) produced using the laminated body of this disclosure. It is a front view which shows one Embodiment of the package (pillow bag) produced using the laminated body of this disclosure. It is sectional drawing to explain the structure of the zipper tape. It is a perspective view which shows one Embodiment of the package (stand pouch) produced using the laminated body of this disclosure. It is a figure which shows the transmittance of the laminated body obtained in an Example and a comparative example at a wavelength of 280 nm to 320 nm.

As shown in FIG. 1, the laminate 10 of the present disclosure includes a base material 11, a printing layer 12, a barrier adhesive layer 13, and a sealant layer 14.
A thin-film deposition film 15 (in FIG. 1, the barrier adhesive layer 13 and the sealant layer) is located between the printing layer 12 and the barrier adhesive layer 13 and between at least one of the barrier adhesive layer 13 and the sealant layer 14. Between 14) and
To be equipped.

In one embodiment, the laminate 10 further includes an ultraviolet barrier layer 16 at any location, as shown in FIG.
The ultraviolet barrier layer 16 can be formed at any position, for example, the outermost surface of the base material 11 (the side opposite to the barrier adhesive layer side), the surface of the base material 11 on the print layer 12 side, and the print layer 12. It can be formed on the surface of the barrier adhesive layer 13 side of the above.

In a preferred embodiment, the ultraviolet barrier layer 16 is provided on the surface of the printing layer 12 on the barrier adhesive layer 13 side, as shown in FIG.

Further, in one embodiment, the laminated body 10 may be provided with a gas barrier layer between arbitrary layers (not shown).

The base material provided in the laminate of the present disclosure and the sealant layer contain the same polyolefin, which can improve the recyclability of the package produced by using the laminate of the present disclosure.
In the present disclosure, the “same polyolefin” refers to one in which the monomers mainly constituting the polyolefin are the same.
Further, in the present disclosure, the "monomer mainly composed of polyolefin" refers to a monomer having a content of 50 mol% or more in polyolefin, and more preferably 60 mol% or more from the viewpoint of recyclability. It is more preferably 80 mol% or more, and particularly preferably 90 mol% or more.
Ethylene or propylene is preferable as the main constituent monomer.

In the laminate of the present disclosure, the content of the same polyolefin 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 even more preferable.

The laminate of the present disclosure has a transmittance of 1% or less, preferably 0.5% or less, and more preferably 0.1% or less at a wavelength of 280 nm to 320 nm. This makes it possible to improve the storage stability of the contents of the packaging bag produced by using the laminate of the present disclosure. ..
In the present disclosure, the transmittance of the laminate at wavelengths of 280 nm to 320 nm is based on JIS K7361-1, and a visible ultraviolet absorptiometer with an integrating sphere (JASCO V-660 Spectrometer) or a measuring device having similar performance is used. Use to measure.

The laminate of the present disclosure, 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 this disclosure, the oxygen permeability is measured in accordance with JIS K 7126.

The laminate of the present disclosure 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 disclosure, the oxygen permeability is measured in accordance with JIS K 7129.

(Base material)
The base material contains the same polyolefin as the polyolefin contained in the sealant layer (hereinafter, referred to as the same polyolefin in some cases). Thereby, the recycling suitability of the laminated body can be improved.
Examples of the polyolefin include polymers of olefin monomers such as ethylene, propylene, 1-butene, 4-methyl-1pentene and hexene, and polymers of olefin monomers and other monomers.
Specifically, polyethylene, polyproprene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-4-methyl-1pentene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl ( Examples thereof include meta) acrylate copolymers and ionomer resins.
Among these, polyethylene and polypropylene are preferable.
Moreover, the base material may contain two or more kinds of the same polyolefin.

The content of the same polyolefin in the base material is preferably 80% by mass or less, and more preferably 90% by mass or less. Thereby, the recyclability of the laminate of the present disclosure can be further improved.

To the extent that the properties of the present disclosure are not impaired, the base material contains a resin material other than the same polyolefin (hereinafter, referred to as other resin material in some cases), and for example, a polyolefin different from the polyolefin contained in the sealant layer, polyethylene terephthalate. (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), 1,4-polycyclohexylene methylene terephthalate, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer and other polyesters, nylon 6 and nylon 6 , 6 etc. polyamide, polyvinyl chloride, polyvinyl alcohol (PVA), polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, vinyl resin such as polyvinyl butyral and polyvinylpyrrolidone (PVP), polyacrylate, polymethacrylate and poly (Meta) acrylic resins such as methyl methacrylate, cellophane, cellulose acetate, nitrocellulose, cellulose resins such as cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB), styrene resins such as polystyrene (PS), and these. Chlorinated resin and the like.

In the present disclosure, "(meth) acrylic" means to include both "acrylic" and "methacryl". Further, "(meth) acrylate" means to include both "acrate" and "metaaclate".

The content of the other resin material in the base material is not particularly limited, but from the viewpoint of the above-mentioned recycling suitability, it is preferably 10% by mass or less, more preferably 5% by mass or less. It is more preferably 3% by mass or less.

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 disclosure 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 wet lamination method, an extraction method, or the like.

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.

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 disclosure are not impaired.

(Print layer)
The print layer contains UV scattering particles. Thereby, the ultraviolet barrier property of the laminated body can be further improved. The print layer having such a structure is preferably formed on the entire surface of the base material.

Examples of the ultraviolet scattering particles include titanium oxide, zinc oxide, octyltrimethoxysilane-coated titanium oxide and cerium oxide, iron oxide, zirconium oxide, magnesium oxide and the like. Among these, titanium oxide and zinc oxide are preferable from the viewpoint of ultraviolet barrier property.

The primary particle size of the ultraviolet scattering particles is preferably 100 nm or more and 600 nm or less, and more preferably 200 nm or more and 400 nm or less. Thereby, the ultraviolet barrier property can be further improved.

The content of the ultraviolet scattering particles in the printing layer is preferably 15% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 50% by mass or less. Thereby, the ultraviolet barrier property can be further improved.

In one embodiment, the printing layer comprises at least one resin material. Examples of the resin material include polyolefin, polyester, polyamide, vinyl resin, cellulose resin, styrene resin and the like.

The thickness of the print layer containing the ultraviolet scattering particles is preferably 0.5 μm or more and 5 μm or less, and more preferably 0.8 μm or more and 3 μm or less. As a result, the ultraviolet barrier property can be further improved while maintaining the recyclability of the laminated body.

The method for forming the print layer is not particularly limited, and examples thereof include conventionally known printing methods such as a gravure printing method, an offset printing method, and a flexographic printing method. Among these, the flexographic printing method is preferable from the viewpoint of environmental load.

(Barrier adhesive layer)
The barrier adhesive layer is a layer composed of an adhesive having a gas barrier property that suppresses the permeation of oxygen and water vapor.
The barrier adhesive layer is a layer provided for suppressing the passage of oxygen and water vapor laminates, which cannot be completely suppressed by the thin-film deposition film. More specifically, since the surface of the thin-film deposition film is formed with fine uneven shapes, the thickness of the thin-film deposition film is not completely uniform, and the barrier property of the relatively thinned portion becomes low. It ends up. By providing the barrier adhesive layer adjacent to the vapor-deposited film, the uneven shape of the vapor-deposited film can be flattened and the barrier property can be made uniform.

The barrier adhesive layer is 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 (polyisocyanate). Consists of.

The polyol resin preferably has, for example, a polyester structure, a polyester polyurethane structure, or a polyester polyurethane structure as the main skeleton.

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 resin obtained by polycondensing polyvalent carboxylic acid or its anhydride with polyhydric alcohol [2nd example] Polyester resin having a glycerol skeleton [3rd example] Polyester resin having an isocyanul ring Hereinafter, each polyester polyol will be described.

Hereinafter, the first example 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.

As the isocyanate compound, an aromatic isocyanate compound is preferable from the viewpoint of oxygen barrier property, and an isocyanate compound having a metaxylene skeleton is more preferable.
Specifically, examples of the isocyanate compound include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydride diphenylmethane diisocyanate, metaxylylene diisocyanate, hydride hydride diisocyanate, isophorone diisocyanate, and these isocyanate compounds. Examples thereof include a trimer, 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。 In one embodiment, the cured product of the resin composition constituting the barrier adhesive layer can contain a phosphoric acid-modified compound. Thereby, the adhesive strength can be 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 cured product of the resin composition constituting the barrier adhesive layer can contain a plate-like inorganic compound. Thereby, the adhesive strength and the gas barrier property 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, and one or more of these can be used.

The cured product of the resin composition constituting the barrier adhesive layer may contain a coupling agent.
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 cured product of the resin composition constituting the barrier adhesive layer can contain cyclodextrin and / or a derivative thereof.
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 barrier adhesive layer is preferably 0.5 μm or more and 8 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 gas barrier property can be further improved. In addition, bending resistance can be improved, and deterioration of gas barrier property after bending can be suppressed.

The resin composition constituting the barrier adhesive layer may or may not contain a solvent.

The barrier adhesive layer provided in the laminate of the present disclosure can also be formed by using a commercially available adhesive.
As the adhesive containing a solvent, PASLIM VM001 / 108CP sold by DIC Corporation can be used.
As the solvent-free adhesive (non-solvent adhesive), PASLIM NS-680A / HA-680B sold by DIC Corporation can be used.
Further, the present invention is not limited to these, and for example, the non-bisphenol A-based polyepoxy resin disclosed in JP-A-2003-300271 and JP-A-2010-012769 is used as a main agent, and polyamine is used as a curing agent. As an adhesive, "Maxive (registered trademark)" marketed by Mitsubishi Gas Chemical Company, Inc. can be used.

(Sealant layer)
The sealant layer contains the same polyolefin as described above, and the content thereof is preferably 80% by mass or more, and more preferably 90% by mass or less. Thereby, the recyclability of the laminate of the present disclosure can be further improved.
Further, the sealant layer may contain two or more kinds of the same polyolefin.

The sealant layer may contain the above-mentioned other resin materials as long as the characteristics of the present disclosure are not impaired. The content of the other resin material in the sealant layer is not particularly limited, but from the viewpoint of the above-mentioned recycling suitability, it is preferably 10% by mass or less, more preferably 5% by mass or less. It is more preferably 3% by mass or less.

The sealant layer 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 disclosure are not impaired. ..

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

The thickness of the sealant 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 puncture resistance of the laminate of the present disclosure while maintaining the heat sealability of the sealant layer.

(Embedded film)
The laminate of the present disclosure includes a thin-film deposition film between the printing layer and the barrier adhesive layer, and at least one between the barrier adhesive layer and the sealant layer.

The vapor deposition film is composed of metals such as aluminum, magnesium, zinc and tin, and inorganic oxides such as aluminum oxide, silicon oxide, magsium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide and barium oxide. Examples include a vapor-deposited film.
When the vapor-deposited film is provided between the base material and the barrier adhesive layer, the vapor-deposited film is preferably a transparent vapor-deposited film composed of an inorganic oxide.
When the vapor-deposited film is provided between the barrier adhesive layer and the sealant layer, the vapor-deposited film is preferably made of metal.

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.

(UV barrier layer)
In one embodiment, the laminate of the present disclosure comprises an ultraviolet barrier layer at any location. Thereby, the ultraviolet barrier property of the laminated body can be further improved.
In a preferred embodiment, the UV barrier layer is provided on the barrier adhesive layer side surface of the print layer.

In one embodiment, the UV barrier layer comprises UV scattering particles. Examples of the ultraviolet scattering particles include titanium oxide, zinc oxide, octyltrimethoxysilane-coated titanium oxide and cerium oxide, iron oxide, zirconium oxide, magnesium oxide and the like.
Among these, titanium oxide and zinc oxide are preferable from the viewpoint of ultraviolet barrier property.

The primary particle size of the ultraviolet scattering particles is preferably 5 nm or more and 50 nm or less, and more preferably 8 nm or more and 40 nm or less. Thereby, the ultraviolet barrier property can be further improved.

The content of the ultraviolet scattering particles in the ultraviolet barrier layer is preferably 3% by mass or more and 35% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. Thereby, the ultraviolet barrier property can be further improved.

In one embodiment, the UV barrier layer comprises an organic UV absorber. Organic UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV, benzoate UV absorbers, benzoxadinone UV absorbers, cyanoacrylate UV absorbers, and benzoxazole UV absorbers. Examples thereof include agents, merocyanine-based ultraviolet absorbers, salicylate-based ultraviolet rays, formamidine-based ultraviolet rays, and oxanilide-based ultraviolet rays.

In one embodiment, the UV barrier layer comprises at least one resin material. Examples of the resin material include polyolefin, polyester, polyamide, vinyl resin, cellulose resin, styrene resin and the like.

To the extent that the properties of the present disclosure are not impaired, the UV barrier layer may contain additives such as fillers, plasticizers, antistatic agents, UV absorbers, inorganic particles, organic particles, mold release agents and dispersants. good.

The thickness of the ultraviolet barrier layer is preferably 0.3 μm or more and 5 μm or less, more preferably 0.4 μm or more and 4 μm or less, and further preferably 0.5 μm or more and 3 μm or less. As a result, it is possible to improve the ultraviolet barrier property of the laminated body while maintaining the recyclability of the laminated body.

In the ultraviolet barrier layer, the above-mentioned material is dispersed in water or a suitable solvent, or the above-mentioned material is dissolved in water or a suitable solvent to prepare a coating liquid, which is applied onto a base material or the like to form a coating film. Can be formed by forming the above and drying it. As the coating means, known means such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method or a rod coating method can be used.

Further, a commercially available ink may be used for forming the ultraviolet barrier layer, and for example, a Ramic F220UV reducer manufactured by Dainichiseika Kogyo Co., Ltd. or an NB300UV reducer (NT) can be used.

(Gas barrier layer)
The laminate of the present disclosure may be provided with a gas barrier layer between arbitrary layers. Thereby, the oxygen barrier property and the water vapor barrier property of the laminate of the present disclosure can be further improved.

In one embodiment, the gas barrier layer is a polyamide such as ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyacrylonitrile, nylon 6, nylon 6,6 and polymethoxylylen adipamide (MXD6), polyester, polyurethane. , And a gas barrier resin such as (meth) acrylic resin.

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

The gas barrier layer may contain additives as long as the properties of the present disclosure are not impaired. Examples of the additive include a cross-linking agent, an antioxidant, an anti-blocking agent, a slip agent, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a compatibilizer, a pigment and the like. Be done.

The thickness of the gas barrier layer is preferably 0.01 μm or more and 10 μm or less, and more preferably 0.1 μm or more and 5 μm or less.
By setting the thickness of the gas barrier layer to 0.01 μm or more, the oxygen barrier property and the water vapor barrier property of the laminated body can be further improved. By setting the thickness of the gas barrier layer to 10 μm or less, the recyclability of the laminated body can be improved.

The gas barrier layer can be formed by dissolving or dispersing the above-mentioned material in water or a suitable solvent, applying the material on a substrate or the like, and drying the material.

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.
By providing the gas barrier layer of this form adjacent to the vapor-deposited film made of an inorganic oxide, it is possible to effectively prevent the occurrence of cracks in the vapor-deposited film.

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

As the metal atom M, for example, silicon, zirconium, titanium, aluminum, 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 body)
The package of the present disclosure is characterized by being composed of the above-mentioned laminated body.
The shape of the package is not particularly limited and may be a bag shape.
For example, pillow bag (gassho sticker type bag), standing pouch, two-way seal type bag, three-way seal type bag, four-way seal type bag, side seal type bag, envelope sticker type bag, foldable seal type bag, flat bottom seal Examples include a mold bag, a square bottom seal mold bag, and a bag with a gusset.

As shown in FIG. 2, the package 100 of the present disclosure is a pillow bag made of the above-mentioned laminate.
For the pillow bag, one of the above laminated bodies is prepared, both ends thereof are heat-sealed so that the sealant layer is on the inside, and a back seal portion 101 is formed to form a tubular shape, and the upper and lower openings are formed. It can be manufactured by heat-sealing and forming the upper seal portion 102 and the lower seal portion 103. The heat seal at one end is performed after filling the contents.

In one embodiment, the packaging can be provided with zipper tape 104, as shown in FIG.
As shown in FIG. 4, the zipper tape 104 includes a male mold 105 attached to one inner surface of the package and a female mold 106 attached to the other inner surface of the package so as to face the male mold 105. , Equipped with.
The male type 105 and the female type 106 are configured to be fitted to each other. In this case, by fitting the male mold 105 and the female mold 106, the package 100 after opening can be resealed. Further, by removing the fitting between the male mold 105 and the female mold 106, the contents can be taken out again.

In one embodiment, the package is provided with through holes 107 at any location in the heat seal portion. This makes it possible to hang and sell a product in which the contents are filled in the package.

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. 5, the package has a stand pouch-like shape including a body portion and a bottom portion.
The stand pouch-shaped package has a body formed by heat-sealing the laminate so that the sealant layer of the laminate is on the inside, and then the sealant layer is inside the other laminate. The bottom portion can be formed and manufactured by folding it into a V shape, sandwiching it from one end of the body portion, and heat-sealing it.

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

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

Example 1
As a base material, a 25 μm-thick biaxially stretched polypropylene (PP) film (manufactured by Futamura Chemical Co., Ltd., trade name: FOR) having one surface treated with corona was prepared.
A printing layer was formed on the corona-treated surface of the base material by a gravure printing method using Ramic FB (containing titanium oxide particles having a primary particle diameter of 200 to 400 nm (25 to 35% by mass)) manufactured by Dainichiseika Co., Ltd. Formed.
The printed layer was formed on the entire surface of the substrate, and its thickness was 1 μm.

Ultraviolet cut ink A (manufactured by Dainichi Seika Kogyo Co., Ltd., Ramic F220 UV reducer, containing titanium oxide particles with a primary particle diameter of 15 nm (5 to 10% by mass)) is applied to the printing layer forming surface of the base material by a gravure printing method. , Applied and dried to form an ultraviolet barrier layer having a thickness of 1 μm.

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 ultraviolet barrier layer and the vapor-deposited surface of the unstretched PP film were laminated via a two-component curable adhesive (manufactured by DIC Corporation, trade name: PASLIM NS-680A / HA-680B). The thickness of the barrier adhesive layer formed by the two-component curable adhesive was 2 μm. After the lamination, it was aged at 40 ° C. for 2 days to obtain a laminate. The proportion of PP in the laminate thus obtained was 92% by mass.

Example 2
Except for changing the UV cut ink A used to form the UV barrier layer to UV cut ink B (manufactured by Dainichi Seika Kogyo Co., Ltd., NB300 UV reducer (NT), containing zinc oxide particles with a primary particle diameter of 25 nm). , A laminated body was obtained in the same manner as in Example 1.

Example 3
Implemented except that the UV cut ink A used to form the UV barrier layer was changed to UV cut ink C (manufactured by Dainichiseika Kogyo Co., Ltd., containing SP-V AP-UV coating agent and organic UV absorber). A laminate was obtained in the same manner as in Example 1.

Comparative Example 1
A laminate was produced in the same manner as in Example 1 except that the ultraviolet barrier layer and the printing layer were not provided.

<< Measurement of transmittance at wavelengths of 280 nm to 320 nm >>
The transmittance of the laminate obtained in the above examples and the wavelengths of 280 nm to 320 nm was measured using a visible ultraviolet absorptiometer with an integrating sphere (JASCO V-660 Spectrometer) in accordance with JIS K7361-1. The measurement results are shown in FIG. As shown in FIG. 6, it can be seen that the transmittance of the laminate of the present invention at wavelengths of 280 nm to 320 nm is 1% or less.

<< 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 laminate obtained in the above example was cut into A4 size, and PERMATRAN 3/31 manufactured by MOCON of the United States was used, and the water vapor transmission rate (g / m ² · day) in an environment of 40 ° C. and 90% relative humidity. Was measured. The measurement results are summarized in Table 1.

10: Laminated body, 11: Base material, 12: Printing layer, 13: Barrier adhesive layer, 14: Sealant layer, 15: Thin film, 16: Ultraviolet barrier layer, 100: Package, 101: Back seal part, 102: Upper seal part, 103: Lower seal part, 104: Zipper tape, 105: Male type, 106: Female type, 107: Through hole

Claims (18)

A laminate including a base material, a printing layer, a barrier adhesive layer, and a sealant layer.
A thin-film deposition film is further provided between the base material and the barrier adhesive layer, and between at least one layer between the barrier adhesive layer and the sealant layer.
The barrier 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 printed layer contains ultraviolet scattering particles and contains
The base material and the sealant layer contain the same polyolefin, and the base material and the sealant layer contain the same polyolefin.
A laminate having a transmittance of 1% or less at a wavelength of 280 nm to 320 nm. The laminate according to claim 1, wherein the same polyolefin contained in the base material and the sealant layer is polyethylene or polypropylene. The laminate according to claim 1 or 2, wherein the content of the same polyolefin in the laminate is 90% by mass or more. The laminate according to any one of claims 1 to 3, wherein the printing layer is formed on the entire surface of the base material. The laminate according to any one of claims 1 to 4, wherein the ultraviolet scattering particles contained in the printing layer are titanium oxide or zinc oxide. The laminate according to any one of claims 1 to 5, wherein the primary average particle size of the ultraviolet scattering particles contained in the printing layer is 100 nm or more and 600 nm or less. The laminate according to any one of claims 1 to 6, wherein the content of the ultraviolet scattering particles in the printing layer is 15% by mass or more and 60% by mass or less. The laminate according to any one of claims 1 to 7, wherein the thickness of the printed layer is 0.5 μm or more and 5 μm or less. The laminate according to any one of claims 1 to 8, further comprising an ultraviolet barrier layer at an arbitrary position. The laminate according to claim 9, wherein the ultraviolet barrier layer contains ultraviolet scattering particles. The laminate according to claim 10, wherein the primary particle size of the ultraviolet scattering particles contained in the ultraviolet barrier layer is 5 nm or more and 50 nm or less. The laminate according to claim 9, wherein the ultraviolet barrier layer contains an organic ultraviolet absorber. The laminate according to any one of claims 9 to 12, wherein the ultraviolet barrier layer is formed on the surface of the printing layer on the barrier adhesive layer side. The laminate according to any one of claims 9 to 13, wherein the thickness of the ultraviolet barrier layer is 0.3 μm or more and 5 μm or less. The laminate according to any one of claims 1 to 14, wherein the thin-film vapor-deposited film is a transparent thin-film film made of an inorganic oxide and is provided between the printing layer and the barrier adhesive layer. .. The laminate according to any one of claims 1 to 14, wherein the vapor-deposited film is made of a metal and is provided between the barrier adhesive layer and the sealant layer. A package body composed of the laminate according to any one of claims 1 to 16. The package according to claim 17, which is a pillow bag.

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