JP7141602B2 - laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate, and more particularly to a laminate using as a raw material a recycled polyester resin recovered from a packaging material or the like so as to be reused.

Plastics, which are materials derived from fossil fuels, are mainly used in the manufacture of packaging materials for filling products such as pharmaceuticals, cosmetics, and foods, from the viewpoints of ease of molding and cost. Polyester-based resins, polyolefin-based resins, polyamide-based resins, and the like are used as plastic materials widely used as materials for packaging containers. Among them, polyester-based resins are widely used in various industrial applications such as films, sheets, and packaging containers because they are excellent in mechanical properties, chemical stability, heat resistance, transparency, etc., and are inexpensive.

Polyester is obtained by polycondensation of diol units and dicarboxylic acid units. For example, polyethylene terephthalate (hereinafter sometimes abbreviated as PET) is produced by using ethylene glycol and terephthalic acid as raw materials and subjecting them to an esterification reaction and then a polycondensation reaction. These raw materials are produced from petroleum, which is a fossil resource. For example, ethylene glycol is industrially produced from ethylene, and terephthalic acid is industrially produced from xylene.

In recent years, with respect to such fossil fuel-derived materials, there has been an increasing trend year by year to reduce the use of fossil fuels in various applications and to reduce CO ₂ emissions in consideration of the environment. As an attempt to reduce the use of fossil fuels, a method has been proposed in which polyester resin recovered from used packaging materials such as PET bottles can be reused and recycled as recycled polyester for molding packaging materials ( For example, see Patent Documents 1 and 2). In Patent Documents 1 and 2, CO ₂ emissions are reduced by using polyester, which is made from polyester derived from fossil fuels and which has been recovered and made reusable, as part of the packaging material. It is proposed that

JP 2011-256328 A JP 2012-41463 A

However, packaging materials using recycled PET, which is mechanically recycled by pulverizing, washing, and reusing polyester resin products such as collected PET bottles, are contaminated due to foreign substances adhering to the recycled PET. There is an impression that there is a possibility that nations and the like are occurring. For this reason, packaging materials manufactured using a laminate made of recycled PET, particularly packaging materials for filling products such as foods, are in a situation where it is difficult to gain trust from consumers.

An object of the present invention is to provide a laminate that can effectively solve such problems.

The present invention is a laminate comprising at least a substrate layer, an adhesive layer, and a sealant layer in this order, wherein the substrate layer comprises a first layer, a second layer, and a third layer in this order. The first layer and the third layer are layers composed only of virgin polyethylene terephthalate, and the second layer is a layer composed only of recycled polyethylene terephthalate or a layer of recycled polyethylene terephthalate and virgin polyethylene terephthalate. It is a mixed layer, and the recycled polyethylene terephthalate is a laminate containing polyethylene terephthalate having ethylene glycol as a diol unit and terephthalic acid and isophthalic acid as dicarboxylic acid units.

In the laminate according to the present invention, the isophthalic acid content may be 0.5 mol % or more and 5.0 mol % or less with respect to all dicarboxylic acid units constituting the polyethylene terephthalate.

In the laminate according to the present invention, the intrinsic viscosity of the polyethylene terephthalate may be 0.58 dl/g or more and 0.80 dl/g or less.

Advantageous Effects of Invention According to the present invention, it is possible to provide a laminate that is superior in CO ₂ reduction effect to a laminate made of polyethylene terephthalate that is not recycled, and that is excellent in sanitation.

1 is a schematic cross-sectional view showing an example of a laminate according to this embodiment; FIG. It is a schematic cross section which shows an example of a base material layer.

<Laminate>
The laminate according to this embodiment comprises at least a substrate layer, a barrier adhesive layer, and a sealant layer in this order. The laminate may further comprise printed layers, other layers, and the like.

A laminate according to this embodiment will be described with reference to the drawings. FIG. 1 shows an example of a schematic cross-sectional view of a laminate according to this embodiment.

The laminate 10 shown in FIG. 1 includes a substrate layer 11, a barrier adhesive layer 12, and a sealant layer 13 in this order. Although not shown, the laminate 10 may further include a printed layer provided on the base material layer 11 . In the packaging bag comprising the laminate 10 shown in FIG. 1, the sealant layer 13 constitutes the inner surface of the packaging bag.

Each layer constituting the laminate will be described below.

[Base material layer]
The base material layer contains polyethylene terephthalate recycled by mechanical recycling (hereinafter polyethylene terephthalate is also referred to as PET). Specifically, the base material layer contains PET obtained by mechanically recycling PET bottles, and this PET contains ethylene glycol as the diol unit and terephthalic acid and isophthalic acid as the dicarboxylic acid unit. Here, mechanical recycling generally refers to the process of pulverizing collected PET bottles and other polyethylene terephthalate resin products, washing with alkali to remove dirt and foreign matter from the surface of the PET resin products, and then drying for a certain period of time under high temperature and reduced pressure. In this method, the contaminants remaining inside the PET resin are diffused and decontaminated, the dirt on the resin product made of the PET resin is removed, and the resin product is returned to the PET resin. Hereinafter, in this specification, polyethylene terephthalate obtained by recycling PET bottles is referred to as "recycled polyethylene terephthalate (hereinafter also referred to as recycled PET)", and polyethylene terephthalate that is not recycled is referred to as "virgin polyethylene terephthalate (hereinafter also referred to as virgin PET). )”.

Among the PET contained in the base material layer, the content of isophthalic acid is preferably 0.5 mol% or more and 5 mol% or less, and 1.0 mol%, based on the total dicarboxylic acid units constituting the PET. It is more preferable that the content is at least 2.5 mol % or less. When the content of isophthalic acid is less than 0.5 mol %, the flexibility may not be improved. PET may be biomass PET in addition to PET derived from ordinary fossil fuels. “Biomass PET” contains biomass-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. This biomass PET may be formed only of PET having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit, or may be formed from biomass-derived ethylene glycol and fossil fuel-derived diol. It may be formed of PET having a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

PET used for PET bottles can be obtained by a conventionally known method of polycondensing the diol units and dicarboxylic acid units described above. Specifically, a general method of melt polymerization such as conducting an esterification reaction and/or a transesterification reaction between the diol unit and the dicarboxylic acid unit and then conducting a polycondensation reaction under reduced pressure, or an organic solvent can be produced by a known solution heating dehydration condensation method using

The amount of the diol unit used in the production of the PET is substantially equimolar with respect to 100 mol of the dicarboxylic acid or derivative thereof. Since there is distillation during the reaction, it is used in excess of 0.1 mol % or more and 20 mol % or less.

Moreover, the polycondensation reaction is preferably carried out in the presence of a polymerization catalyst. The timing of adding the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added at the time of charging the raw materials or at the start of depressurization.

After the PET from recycled PET bottles is polymerized and solidified as described above, solid state polymerization is performed as necessary to further increase the degree of polymerization and remove oligomers such as cyclic trimers. you can go Specifically, in the solid state polymerization, PET is chipped and dried, and then heated at a temperature of 100° C. or higher and 180° C. or lower for about 1 to 8 hours to pre-crystallize the PET, followed by 190° C. It is carried out by heating at a temperature of 230° C. or less in an inert gas atmosphere or under reduced pressure for 1 hour to several tens of hours.

The intrinsic viscosity of PET contained in the base material layer is preferably 0.58 dl/g or more and 0.80 dl/g or less. If the intrinsic viscosity is less than 0.58 dl/g, the mechanical properties required for the PET film as the substrate may be insufficient. On the other hand, when the intrinsic viscosity exceeds 0.80 dl/g, the productivity in the film forming process may be impaired. In addition, the intrinsic viscosity is measured at 35° C. with an orthochlorophenol solution.

The base material layer preferably contains recycled PET at a ratio of 50% by weight or more and 95% by weight or less, and may contain virgin PET in addition to recycled PET. The virgin PET may be PET containing ethylene glycol as the diol unit and containing terephthalic acid and isophthalic acid as the dicarboxylic acid unit as described above, or PET containing no isophthalic acid as the dicarboxylic acid unit. good too. Moreover, the base material layer may contain polyester other than PET. For example, dicarboxylic acid units may include aliphatic dicarboxylic acids and the like in addition to aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid.

Specific examples of aliphatic dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid, which usually have 2 to 40 carbon atoms. cyclic or alicyclic dicarboxylic acids. Derivatives of aliphatic dicarboxylic acids include lower alkyl esters such as methyl esters, ethyl esters, propyl esters and butyl esters of the above aliphatic dicarboxylic acids, and cyclic acid anhydrides of the above aliphatic dicarboxylic acids such as succinic anhydride. . Among these, as the aliphatic dicarboxylic acid, adipic acid, succinic acid, dimer acid, or a mixture thereof is preferable, and those containing succinic acid as a main component are particularly preferable. More preferred derivatives of aliphatic dicarboxylic acids are methyl esters of adipic acid and succinic acid, or mixtures thereof.

The substrate layer composed of such PET may be a single layer or multiple layers. As shown in FIG. 2, when the recycled PET as described above is used for the base material layer, the base material layer may have three layers of a first layer 31, a second layer 32 and a third layer 33. FIG. In this case, in the laminate, the third layer 33 of the base material layers is located on the sealant layer side. In this case, the second layer 32 is a layer composed only of recycled PET or a mixed layer of recycled PET and virgin PET, and the first layer 31 and the third layer 33 are layers composed only of virgin PET. preferably. By using only virgin PET for the first layer 31 and the third layer 33 in this manner, it is possible to prevent the recycled PET from being exposed from the front surface or the rear surface of the base material layer. Therefore, the sanitation of the laminate can be ensured. Also, the base layer may be a base layer having two layers, the second layer 32 and the third layer 33, without providing the first layer 31 shown in FIG. Furthermore, the base layer may be a base layer having two layers, the first layer 31 and the second layer 32, without providing the third layer 33 shown in FIG. Also in these cases, the second layer 32 is a layer composed only of recycled PET or a mixed layer of recycled PET and virgin PET, and the first layer 31 and the third layer 33 are layers composed only of virgin PET. It is preferable to

When recycled PET and virgin PET are mixed and molded into one layer, there are a method of feeding them separately to a molding machine, a method of feeding them after mixing by dry blending, and the like. Among them, the method of mixing by dry blending is preferable from the viewpoint of simple operation.

Various additives can be added to the PET constituting the base material layer during the production process or after the production, as long as the properties are not impaired. Additives such as plasticizers, UV stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, release agents, antioxidants, ions exchange agents, color pigments, and the like. The additive is preferably added in a range of 5% by mass to 50% by mass, preferably 5% by mass to 20% by mass, based on the total resin composition containing PET.

The substrate layer can be formed by forming a film from the PET described above, for example, by a T-die method. Specifically, after drying the above PET, it is supplied to a melt extruder heated to a temperature (Tm) above the melting point of PET to Tm + 70 ° C. to melt the resin composition, for example, a T die A film can be formed by extruding a sheet from a die such as the above, and rapidly cooling and solidifying the extruded sheet with a rotating cooling drum or the like.
As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose.

The film obtained as described above is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the film extruded onto the cooling drum as described above is subsequently heated by roll heating, infrared heating, or the like, and stretched in the longitudinal direction to obtain a longitudinally stretched film. This stretching is preferably carried out using a difference in circumferential speed between two or more rolls.
Longitudinal stretching is usually performed in a temperature range of 50°C or higher and 100°C or lower. Further, the longitudinal stretching ratio is preferably 2.5 times or more and 4.2 times or less, although it depends on the properties required for the film application.
If the draw ratio is less than 2.5 times, the thickness unevenness of the PET film becomes large, making it difficult to obtain a good film.

The longitudinally stretched film is then successively subjected to transverse stretching, heat setting, and heat relaxation steps to obtain a biaxially stretched film. Lateral stretching is usually performed in a temperature range of 50°C or higher and 100°C or lower. The lateral stretching ratio is preferably 2.5 times or more and 5.0 times or less, although it depends on the properties required for the application. If it is less than 2.5 times, the thickness of the film becomes uneven, making it difficult to obtain a good film.

After the transverse stretching, heat setting treatment is carried out, and the preferable temperature range for heat setting is Tg+70 to Tm−10° C. of PET. Moreover, the heat setting time is preferably 1 second or more and 60 seconds or less. Furthermore, for applications that require a reduction in heat shrinkage, heat relaxation treatment may be performed as necessary.

The thickness of the PET film obtained as described above is arbitrary according to its use, but is usually about 5 μm to 100 μm, preferably 5 μm to 25 μm. The breaking strength of the PET film is 5 kg/mm ² or more and 40 kg/mm ^{2 or less in the MD direction, and 5 kg/mm 2 or more and 35 kg/mm 2 or less} in the TD direction. % or more and 350% or less, and 50% or more and 300% or less in the TD direction. Moreover, the shrinkage rate when left in a temperature environment of 150° C. for 30 minutes is 0.1% or more and 5% or less.

Virgin PET may be fossil fuel polyethylene terephthalate (hereinafter also referred to as fossil fuel PET) or biomass PET. As used herein, “fossil fuel PET” has a diol unit derived from a fossil fuel and a dicarboxylic acid derived from a fossil fuel as a dicarboxylic acid unit. Recycled PET may be obtained by recycling PET resin products formed using fossil fuel PET, or obtained by recycling PET resin products formed using biomass PET. There may be.

[Barrier adhesive layer]
The barrier adhesive layer is a layer provided for bonding the base material layer 11 and the sealant layer 13 together, and also has a function of imparting barrier properties to the laminate. By providing the barrier adhesive layer, even if foreign matter adheres to the recycled PET used for the base material layer, it is a layer for suppressing the problem that the foreign matter is exposed to the sealant layer side rather than the barrier layer. be. As a result, it is possible to prevent foreign matter from appearing on the inner surface side of the barrier layer in the packaging bag constructed using the laminate, so that the sanitation of the contents can be ensured.

The barrier adhesive layer is formed by applying an adhesive composition as described below to the surface of the laminated film of the film containing the substrate layer 11 and the film containing the sealant layer 13, and drying the composition. It is the layer where Examples of coating methods for the lamination adhesive include a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a Fontaine method, a transfer roll coating method, and other methods. .

The barrier adhesive layer has gas barrier properties, particularly oxygen and water vapor barrier properties. The thickness of the barrier adhesive layer is, for example, 0.5 μm or more and 6.0 μm or less, preferably 0.8 μm or more and 5.0 μm or less, and more preferably 1.0 μm or more and 4.5 μm or less. If it is thinner than the above range, the gas barrier properties tend to be insufficient, and if it is thicker than the above range, the bending resistance tends to be inferior, which tends to lead to a decrease in the gas barrier properties after bending.

The barrier adhesive layer is made of a cured adhesive composition containing a polyester polyol, an isocyanate compound, and a plate-like inorganic compound. A polyester polyol has two or more hydroxyl groups in one molecule as a functional group. Moreover, the isocyanate compound has two or more isocyanate groups in one molecule as functional groups. A polyester polyol has, for example, a polyester structure or a polyester polyurethane structure as a main skeleton.

The adhesive composition may further contain a phosphoric acid-modified compound, a coupling agent, cyclodextrin and/or its derivatives, and the like.

The glass transition temperature of the cured coating film of the adhesive composition is preferably in the range of -30°C or higher and 80°C or lower. More preferably, the temperature is 0°C or higher and 70°C or lower. More preferably, the temperature is 25°C or higher and 70°C or lower. If the glass transition temperature is higher than 80° C., the flexibility of the cured coating film at around room temperature may be low, resulting in poor adhesion to the film and reduced adhesive force. On the other hand, when the temperature is lower than −30° C., there is a risk that sufficient oxygen barrier properties may not be obtained due to vigorous molecular movement of the cured coating film near room temperature, and that adhesive strength may be reduced due to insufficient cohesive strength.

As a specific example of the adhesive composition containing a polyester polyol, an isocyanate compound, and a plate-like inorganic compound, a series of oxygen-barrier adhesives (PASLIM) sold by DIC Corporation can be used. PASLIM or the like is preferably used.

(polyester polyol)
As a polyester polyol having two or more hydroxyl groups in one molecule as a functional group, for example, the following [first example] to [first example] can be used.
[Example 1] Polyester polyol obtained by polycondensation of an ortho-oriented polycarboxylic acid or its anhydride with a polyhydric alcohol [Example 2] Polyester polyol having a glycerol skeleton [Example 3] Having an isocyanuric ring Polyester Polyol Each polyester polyol will be described below.

[Example 1] Polyester polyol obtained by polycondensation of ortho-oriented polyvalent carboxylic acid or its anhydride and polyhydric alcohol The polyester polyol according to Example 1 contains at least one kind of ortho-phthalic acid and its anhydride. Polycondensation obtained by polycondensation of a polyhydric carboxylic acid component containing ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and a polyhydric alcohol component containing at least one selected from the group consisting of cyclohexanedimethanol It can be a body. In particular, a polyester polyol having a content of 70 to 100% by mass of the orthophthalic acid and its anhydride relative to the total polyvalent carboxylic acid component is preferred.

The polyester polyol according to the first example essentially contains the orthophthalic acid and its anhydride as the polyvalent carboxylic acid component, but other polyvalent carboxylic acid components are copolymerized to the extent that the effects of the present embodiment are not impaired. You may let Specifically, aliphatic polycarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc., and unsaturated bond-containing polycarboxylic acids include maleic anhydride, maleic acid, Fumaric acid and the like, 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid as alicyclic polycarboxylic acids, and terephthalic acid, isophthalic acid, and pyromellitic acid as aromatic polycarboxylic acids acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p '-dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; polybasic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids They can be used singly or in mixtures of two or more. Among them, succinic acid, 1,3-cyclopentanedicarboxylic acid and isophthalic acid are preferred.

Examples of the polyhydric alcohol component and other components include those described above.

一般式（１）において、Ｒ_１、Ｒ_２、Ｒ_３は、各々独立に、Ｈ又は下記の一般式（２）で表される化合物である。

[Second Example] Polyester Polyol Having a Glycerol Skeleton As a polyester polyol according to the second example, a polyester polyol having a glycerol skeleton represented by the general formula (1) can be mentioned.

In general formula (1), R ₁ , R ₂ and R ₃ are each independently H or a compound represented by general formula (2) below.

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

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

Further, a compound in which any one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (2) and any two of R ₁ , R ₂ and R ₃ are represented by the general formula (2) and a compound in which all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (2), and any two or more compounds are a mixture. good too.

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-anthraquinonediyl group, and a 2,3-anthracenediyl group; represents an arylene group which may be present. When X is substituted by substituents, it may be substituted by one or more substituents, which are attached to any carbon atom on X that is different from the radical. The substituents include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, phthalimido group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, naphthyl group and the like.

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

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

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

Further, the polyhydric alcohol component includes alkylenediol having 2 to 6 carbon atoms. Diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol and dimethylbutanediol can be exemplified.

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

[Third Example] Polyester polyol having an isocyanuric ring The polyester polyol according to the third example is a polyester polyol having an isocyanuric ring represented by the following general formula (3).

In general formula (3), R ₁ , R ₂ and R ₃ are each independently “—(CH ₂ )n1-OH (n1 represents an integer of 2 to 4)” or general formula (4 ) represents the structure of

In 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, represents an optionally substituted arylene group selected from the group consisting of a 2,3-anthraquinonediyl group and a 2,3-anthracenediyl group, 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. n1 is preferably 2 or 3, and most preferably 2.

In the general formula (4), n2 represents an integer of 2-4, and n3 represents an integer of 1-5.
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-anthraquinonediyl group, and a 2,3-anthracenediyl group, and has a substituent; represents an arylene group which may be

When X is substituted by substituents, it may be substituted by one or more substituents, which are attached to any carbon atom on X that is different from the radical. The substituents include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, phthalimido group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, naphthyl group and the like.

Among the substituents of X, hydroxyl group, cyano group, nitro group, amino group, phthalimido group, carbamoyl group, N-ethylcarbamoyl group and phenyl group are preferable. , 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, methylpentylene. It represents an alkylene group having 2 to 6 carbon atoms such as a len group and a dimethylbutylene group. Among them, Y is preferably a propylene group or an ethylene group, and most preferably an ethylene group.

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). Among them, it is preferable that all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (4).

Further, a compound in which any one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (4), and any two of R ₁ , R ₂ and R ₃ are represented by the general formula (4) and a compound in which all of R ₁ , R ₂ , and R ₃ are groups represented by the general formula (4), and two or more compounds are a mixture. good too.

The polyester polyol having an isocyanuric ring represented by the general formula (3) includes a triol having an isocyanuric ring, an aromatic polycarboxylic acid in which the carboxylic acid is substituted at the ortho position or an anhydride thereof, and a polyhydric alcohol component. are reacted as essential components.

Examples of triols having an isocyanuric ring include alkylene oxide adducts of isocyanuric acid such as 1,3,5-tris(2-hydroxyethyl)isocyanuric acid and 1,3,5-tris(2-hydroxypropyl)isocyanuric acid. etc.

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

The substituents include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, phthalimido group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, naphthyl group and the like.

Further, the polyhydric alcohol component includes alkylenediol having 2 to 6 carbon atoms. 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.

Among them, 1,3,5-tris(2-hydroxyethyl)isocyanuric acid or 1,3,5-tris(2-hydroxypropyl)isocyanuric acid is used as a triol compound having an isocyanuric ring, and the carboxylic acid is at the ortho position. A polyester polyol compound with an isocyanuric ring that uses orthophthalic anhydride as the substituted aromatic polycarboxylic acid or its anhydride and ethylene glycol as the polyhydric alcohol has particularly excellent oxygen barrier properties and adhesion. preferable.

The isocyanuric ring is highly polar and trifunctional. Therefore, the whole system can be made highly polar and the crosslink density can be increased. From this point of view, it is preferable that the isocyanuric ring content is 5% by mass or more based on the total solid content of the adhesive resin.

The reason why an adhesive having an isocyanuric ring can ensure oxygen barrier properties and dry laminate adhesion is presumed as follows.

Isocyanuric rings are highly polar and do not form hydrogen bonds. In general, as a technique for improving adhesion, it is known to add highly polar functional groups such as hydroxyl groups, urethane bonds, ureido bonds, and amide bonds, but resins with these bonds do not form intermolecular hydrogen bonds. However, polyester resins with isocyanuric rings do not impair the solubility and can be easily diluted. is.

Further, since the isocyanuric ring is trifunctional, a polyester polyol compound having an isocyanuric ring as the center of the resin skeleton and a polyester skeleton having a specific structure in its branched chain can obtain a high crosslink density. It is presumed that the gaps through which gases such as oxygen pass can be reduced by increasing the crosslink density. Thus, the isocyanuric ring is highly polar without forming intermolecular hydrogen bonds and provides a high crosslink density, so it is presumed that oxygen barrier properties and dry laminate adhesiveness can be ensured.

(isocyanate compound)
The isocyanate compound has two or more isocyanate groups in the molecule, may be either aromatic or aliphatic, may be either a low-molecular-weight compound or a high-molecular-weight compound, and may be a diisocyanate compound having two or three isocyanate groups. Known compounds such as the above polyisocyanate compounds can be used. The isocyanate compound may be a blocked isocyanate compound obtained by addition reaction using a known isocyanate blocking agent by a known and commonly used appropriate method.

Among them, polyisocyanate compounds are preferred from the viewpoint of adhesiveness and retort resistance, and those having an aromatic ring are preferred from the viewpoint of imparting oxygen barrier properties. It is preferable because oxygen barrier properties can be improved not only by hydrogen bonding but also by π-π stacking between aromatic rings.

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

(Plate-like inorganic compound)
Since the plate-like inorganic compound has a plate-like shape, it is characterized in that the laminate strength and barrier properties of the barrier adhesive layer are particularly improved.
Specific examples of plate-like inorganic compounds include hydrous silicates (phyllosilicate minerals, etc.), kaolinite-serpentine clay minerals (halloysite, kaolinite, endelite, dickite, nacrite, etc., antigorite, chrysotile etc.), pyrophyllite-talc group (pyrophyllite, talc, kerorai, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite, etc.), vermiculite group clay minerals (vermiculite etc.), mica or mica group clay minerals (mica such as muscovite, phlogopite, etc., margarite, tetrasilylic mica, teniolite, etc.), chlorite group (cookieite, pseudoite, clinochlore, chamosite, nimite, etc.), hydrotal site, platy barium sulfate, boehmite, aluminum polyphosphate, etc., and one or more of these can be used.

The average particle size of the plate-like inorganic compound is not particularly limited, but is preferably 0.1 μm or more, more preferably 1 μm or more. If the average particle diameter is 0.1 μm or less, the short side length of the long side prevents the detour path of oxygen molecules from becoming long, causing a problem that it is difficult to improve the oxygen barrier property and the problem that it is difficult to improve the adhesive force. . The side with a larger average particle size is not particularly limited. If defects such as streaks occur on the coated surface due to the coating method of the adhesive composition, it is preferable to use a material having an average particle size of 100 μm or less, more preferably 20 μm or less.

The aspect ratio of the plate-like inorganic compound is preferably as high as possible in order to improve the barrier performance due to the labyrinthine effect of oxygen. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.

Although the content of the plate-like inorganic compound is not particularly limited, it is preferably 5% by mass or more and 50% by mass or less in the barrier adhesive layer. If it is less than 5% by mass, it is difficult to improve the barrier properties, and if it exceeds 50% by mass, the tackiness of the coated surface of the adhesive composition may decrease, making it difficult to laminate, or the adhesive strength may be insufficient. is.

The adhesive composition for forming the barrier adhesive layer may further contain a phosphoric acid-modified compound, a coupling agent, cyclodextrin, etc., in addition to the components described above.

(Phosphate modified compound)
A phosphoric acid-modified compound is, for example, a compound represented by the following general formula (5) or (6).

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、（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。

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

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

The above phosphoric acid-modified compound has an effect of improving the laminate strength to the inorganic member of the present embodiment, and a known and commonly used compound can be used.

More specifically, phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxy 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 is preferably 0.005% by mass or more and 10% by mass or less in the adhesive resin composition of the present embodiment. More preferably, it is 0.01% by mass or more and 1% by mass or less. If it is less than 0.005% by mass, good adhesion cannot be obtained. If the amount is more than 10% by mass, the barrier properties may deteriorate.

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

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxytrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxysilane oxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercapto propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) and the like.

Examples of the titanium-based coupling agent include isopropyltriisostearoyl titanate, isopropyltri(N-aminoethyl-aminoethyl)titanate, isopropyltridodecylbenzenesulfonyltitanate, isopropyltris(dioctylpyrophosphate)titanate, and tetraoctyl. Bis(didodecylphosphite) titanate, tetraoctylbis(ditridecylphosphite) titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyltrioctynortitanate, isopropyldimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, diisostearoyl ethylene titanate, isopropyl tri(dioctylphosphate) titanate, isopropyl tricumylphenyl titanate, dicumylphenyloxyacetate titanate and the like.

Specific examples of the aluminum-based coupling agent include acetoalkoxyaluminum diisopropylate, diisopropoxyaluminum ethylacetoacetate, diisopropoxyaluminum monomethacrylate, isopropoxyaluminum alkylacetoacetate mono(dioctylphosphate), aluminum-2-ethylhexanoate oxide trimer, aluminum stearate oxide trimer, alkylacetoacetate aluminum oxide trimer and the like.

(Cyclodextrin and/or its derivative)
Said cyclodextrin and/or its derivatives are preferred components for obtaining 1) excellent adhesion to films with inorganic layers and 2) excellent oxygen barrier enhancement. Specifically, for example, in addition to cyclodextrin, alkylated cyclodextrin, acetylated cyclodextrin, hydroxyalkylated cyclodextrin, etc., in which the hydrogen atom of the hydroxyl group of the glucose unit of cyclodextrin is substituted with another functional group, etc. are used. be able to. Branched cyclic dextrins can also be used. In addition, cyclodextrin skeletons in cyclodextrins and cyclodextrin derivatives include α-cyclodextrin consisting of 6 glucose units, β-cyclodextrin consisting of 7 glucose units, and γ-cyclodextrin consisting of 8 glucose units. can be used. These compounds may be used alone or in combination of two or more. Moreover, hereinafter, these cyclodextrins and/or derivatives thereof may be collectively referred to as dextrin compounds.

From the viewpoint of compatibility and dispersibility in the adhesive composition, it is preferable to use a cyclodextrin derivative as the cyclodextrin compound. The degree of substitution is preferably in the range of 0.1 to 14/glucose, more preferably in the range of 0.3 to 8/glucose, from the viewpoint of the polarity of the various resins. .

As the alkylated cyclodextrin, for example, methyl-α-cyclodextrin, methyl-β-cyclodextrin, methyl-γ-cyclodextrin and the like can be used. These compounds may be used alone or in combination of two or more.

As the acetylated cyclodextrin, for example, monoacetyl-α-cyclodextrin, monoacetyl-β-cyclodextrin, monoacetyl-γ-cyclodextrin and the like can be used. These compounds may be used alone or in combination of two or more.

As the hydroxyalkylated cyclodextrin, for example, hydroxypropyl-α-cyclodextrin, hydroxypropyl-β-cyclodextrin, hydroxypropyl-γ-cyclodextrin and the like can be used. These compounds may be used alone or in combination of two or more.

The content of the cyclodextrin and/or derivative thereof is not particularly limited, but from the viewpoints of compatibility with resins, solvents, and isocyanate compounds, improvement of adhesive strength, and improvement of barrier properties, the content of the cyclodextrin and/or derivative thereof is 0.00% in the barrier adhesive layer. It is preferably in the range of 01 to 20 parts by mass, more preferably in the range of 0.05 to 10 parts by mass, and even more preferably in the range of 0.1 to 5 parts by mass.

When the adhesive composition contains cyclodextrin and/or its derivative, the cyclic and regularly arranged hydroxyl groups and ether groups of the cyclodextrin and/or its derivative coordinate multiple interaction points with the inorganic surface. It is assumed that by having bonds and hydrogen bonds, it is possible to make adhesives with strong adhesive strength when laminating films with inorganic layers, especially various films such as metal foils, metal vapor deposition films, and transparent vapor deposition films. there is In addition, it is assumed that a large number of hydroxyl groups possessed by cyclodextrin and/or its derivatives interact intermolecularly to narrow the free volume pores through which gas permeates, thereby improving the barrier function.

(solvent)
If the polyester polyol and the isocyanate compound are dissolved, the phosphoric acid-modified compound, the plate-like inorganic compound, etc. can be uniformly dispersed, and the boiling point and volatility are appropriate from the viewpoint of the process of forming the barrier adhesive layer, There are no particular restrictions.

[Sealant layer]
The sealant layer is the innermost layer in the package. The sealant layer is a layer formed of a thermoplastic resin that can be fused together by heat. The sealant layer may contain a resin material derived from fossil fuel, or may contain a resin material derived from biomass.

The resin material forming the sealant layer is not particularly limited as long as it is a resin that can be mutually fused by heat. High-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), ethylene-α-olefin copolymer polymerized using a metallocene catalyst, random or block copolymer of ethylene-polypropylene, polypropylene, Ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate Copolymers (EMMA), ionomer resins, heat-sealable ethylene-vinyl alcohol resins, or polyolefins such as methylpentene-based resins, ethylene-propylene copolymers, methylpentene polymers, polybutene polymers, polyethylene, polypropylene or cyclic olefin copolymers acid-modified polyolefin resins, poly(vinyl acetate) resins, poly(meth)acryl resins, polyvinyl chloride resins, and other resins. These may be used alone or as a mixture of two or more. The sealant layer can be used as a resin film or sheet as described above, or as a coating film thereof.

When polyethylene is used as the resin material for forming the sealant layer, it may be obtained by polymerizing biomass-derived ethylene in addition to ethylene obtained from fossil fuels. As the biomass-derived ethylene, specifically, for example, one described in JP-A-2012-251006 can be used. By using polyethylene obtained by polymerizing biomass-derived ethylene as a material for forming the sealant layer, it is possible to form a layer made of a carbon-neutral material. can reduce the amount used and reduce the environmental load.

As the biomass-derived ethylene, commercially available ones may be used. For example, Braskem's "C4LL-SLL118 (d = 0.916, MFR = 1.0 g / 10 minutes)" sugarcane-derived linear A low-density polyethylene-based resin or a sugarcane-derived low-density polyethylene-based resin such as "SBC118 (d=0.918, MFR=8.1 g/10 min)" can be used.

In this embodiment, one sealant layer is provided, but two or more sealant layers may be provided. When there are two or more sealant layers, each layer may have the same composition or different compositions. For example, the sealant layer is composed of three layers in which a first layer, a second layer and a third layer are laminated in order, the first layer and the third layer are made of a fossil fuel-derived resin material, and the second layer is made of a resin material derived from fossil fuel. The layer may be made of a resin material containing a biomass-derived resin material. When the sealant layer is composed of two or more layers, they can be laminated using a co-extrusion method.

The thickness of the sealant layer is preferably 20 μm or more and 200 μm or less, more preferably 30 μm or more and 130 μm or less.

[Print layer]
The printed layer contains letters, numbers, patterns, figures, symbols, patterns, etc. It is a layer that forms any desired printed pattern. The printed layer can be provided as necessary, for example, it can be provided between the base material layer and the barrier layer or between the barrier layer and the sealant layer. The printed layer may be provided on the entire surface of the base material layer, or may be provided on a part thereof. The print layer can be formed using conventionally known pigments and dyes, and the formation method is not particularly limited.

The print layer preferably has a thickness of 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, still more preferably 1 μm or more and 3 μm or less.

As described above, the base material layer contains recycled PET at a ratio of, for example, 50% by weight or more and 95% by weight or less. According to this embodiment, since the base material layer contains recycled PET, it is possible to provide a laminate that is more effective in reducing CO ₂ than a laminate that does not contain recycled PET. In addition, according to the present embodiment, since the laminate includes the above-described barrier layer, it is possible to provide a laminate excellent in sanitation.

<Method for manufacturing laminate>
The method for manufacturing the laminate according to the present embodiment is not particularly limited, and it can be manufactured using a conventionally known method such as a dry lamination method.

The laminate according to this embodiment has chemical functions, electrical functions, magnetic functions, mechanical functions, friction/wear/lubricating functions, optical functions, thermal functions, surface functions such as biocompatibility, and the like. It is also possible to apply secondary processing for the purpose of imparting. Examples of secondary processing include embossing, painting, adhesion, printing, metallizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.). Further, the laminate according to the present embodiment can be subjected to lamination (dry lamination or extrusion lamination), bag making, and other post-treatments to produce a molded product.

The laminate can be used, for example, as a packaging bag filled with products such as food. For example, using the above laminate, folding it in two, or preparing two laminates, overlapping the sealant surfaces with each other, and further sealing the peripheral edge thereof, for example, a side seal type , 2-side seal type, 3-side seal type, 4-side seal type, envelope seal type, palm seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, gusset type, etc. By heat-sealing with, various forms of packaging bags can be produced.

In the above, the heat sealing can be carried out by known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing and ultrasonic sealing.

Since the packaging bag has excellent hygienic properties while reducing the burden on the environment, it can be suitably used as a packaging bag for hermetically packaging foods and the like.

で表される化合物であり、
一般式（１）において、Ｒ_１、Ｒ_２、Ｒ_３は、各々独立に、Ｈ又は下記の一般式（２）

で表される化合物であり、
式（２）において、ｎは１～５の整数を表し、Ｘは、置換基を有してもよい１，２－フェニレン基、１，２－ナフチレン基、２，３－ナフチレン基、２，３－アントラキノンジイル基、及び２，３－アントラセンジイル基から成る群から選ばれるアリーレン基を表し、Ｙは炭素原子数２～６のアルキレン基を表し、但し、Ｒ_１、Ｒ_２、Ｒ_３のうち少なくとも一つは、一般式（２）で表される基を表してもよい。
本発明の他の態様による積層体において、前記ポリエステルポリオールは、イソシアヌル環を有していてもよい。
本発明の他の態様による積層体において、前記イソフタル酸の含有量は、前記ポリエチレンテレフタレートを構成する全ジカルボン酸単位に対して、０．５モル％以上５．０モル％以下であってもよい。
本発明の他の態様による積層体において、前記ポリエチレンテレフタレートの極限粘度は、０．５８ｄｌ／ｇ以上０．８０ｄｌ／ｇ以下であってもよい。 (Other aspects)
Another aspect of the present invention is a laminate comprising at least a substrate layer, a barrier adhesive layer, and a sealant layer in this order, wherein the substrate layer contains ethylene glycol as a diol unit and terephthalic acid. and isophthalic acid as dicarboxylic acid units, and the barrier adhesive layer includes a polyester polyol having two or more hydroxyl groups in one molecule as a functional group, and an isocyanate group in one molecule as a functional group. A laminate comprising a cured product of an adhesive composition containing two or more isocyanate compounds and a plate-like inorganic compound.
In the laminate according to another aspect of the present invention, the polyester polyol may be a polycondensate of an ortho-oriented polyhydric carboxylic acid or its anhydride and a polyhydric alcohol.
In the laminate according to another aspect of the present invention, the polyester polyol has the following general formula (1)

is a compound represented by
In general formula (1), R ₁ , R ₂ and R ₃ are each independently H or the following general formula (2)

is a compound represented by
In formula (2), n represents an integer of 1 to 5, X is a 1,2-phenylene group which may have a substituent, a 1,2-naphthylene group, a 2,3-naphthylene group, 2, represents an arylene group selected from the group consisting of a 3-anthraquinonediyl group and a 2,3-anthracenediyl group, Y represents an alkylene group having 2 to 6 carbon atoms, provided that R ₁ , R ₂ and R ₃ At least one of them may represent a group represented by general formula (2).
In the laminate according to another aspect of the invention, the polyester polyol may have an isocyanuric ring.
In the laminate according to another aspect of the present invention, the isophthalic acid content may be 0.5 mol % or more and 5.0 mol % or less with respect to all dicarboxylic acid units constituting the polyethylene terephthalate. .
In the laminate according to another aspect of the present invention, the intrinsic viscosity of the polyethylene terephthalate may be 0.58 dl/g or more and 0.80 dl/g or less.

10 laminate 11 substrate layer 12 barrier adhesive layer 13 sealant layer

Claims (4)

A laminate comprising at least a substrate layer (excluding polyester film A below), an adhesive layer, and a sealant layer in this order,
The base material layer is biaxially stretched,
The base layer comprises a first layer, a second layer, and a third layer in this order,
The first layer and the third layer are layers composed only of virgin polyethylene terephthalate,
The virgin polyethylene terephthalate is fossil fuel polyethylene terephthalate,
The second layer is a layer composed only of recycled polyethylene terephthalate or a mixed layer of recycled polyethylene terephthalate and virgin polyethylene terephthalate,
The recycled polyethylene terephthalate is a laminate containing polyethylene terephthalate having ethylene glycol as a diol unit and terephthalic acid and isophthalic acid as dicarboxylic acid units.
Polyester film A:
A polyester film comprising at least two layers,
a first layer comprising a biomass polyester comprising biomass-derived ethylene glycol as diol units and a fossil fuel-derived dicarboxylic acid as dicarboxylic acid units;
The second containing a recycled polyester obtained by recycling a polyester resin product containing a fossil fuel-derived diol and/or biomass-derived ethylene glycol as a diol unit, and a polyester containing a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. layer and
polyester film, including 2. The laminate according to claim 1, wherein the content of said isophthalic acid is 0.5 mol % or more and 5.0 mol % or less with respect to all dicarboxylic acid units constituting said polyethylene terephthalate. The laminate according to claim 1 or 2, wherein the intrinsic viscosity of the polyethylene terephthalate is 0.58 dl/g or more and 0.80 dl/g or less. A packaging bag comprising the laminate according to any one of claims 1 to 3.

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