JP6944656B2 - Laminate - Google Patents

Description

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

Plastics, which are fossil fuel-derived materials, are mainly used in the manufacture of packaging materials for filling products such as pharmaceuticals, cosmetics, and foods from the viewpoint of ease of molding and cost. Polyester-based resins, polyolefin-based resins, polyamide-based resins, and the like are used as plastic materials that are 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 polycondensing a diol unit and a dicarboxylic acid unit. For example, polyethylene terephthalate (hereinafter, may be 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 movement year by year to reduce the use of fossil fuels for various purposes in consideration of the environment and to reduce CO _{2 emissions.} As an attempt to reduce the use of such 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 (recycled). For example, see Patent Documents 1 and 2). _{In Patent Documents 1 and 2, CO 2} emissions are reduced by using polyester formed from fossil fuel-derived polyester as a part of the packaging material so that the used product can be recovered and reused. It is proposed to try.

Japanese Unexamined Patent Publication No. 2011-256328 Japanese Unexamined Patent Publication No. 2012-41463

However, packaging materials using recycled PET recycled by mechanical recycling, in which recovered PET bottles and other polyester resin products are crushed, washed, and reused, are contaminated due to foreign matter adhering to the recycled PET. There is an impression that nations may have occurred. 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 obtain the trust of consumers.

An object of the present invention is to provide a laminate capable of effectively solving such a problem.

The present invention is a laminate including at least a base material layer, an adhesive layer, a barrier layer, and a sealant layer in this order. The base material layer contains ethylene glycol as a diol unit, and terephthalic acid and isophthalic acid. The barrier layer is a laminated body containing polyethylene terephthalate having an acid as a dicarboxylic acid unit, and the barrier layer including a vapor-deposited layer provided on the sealant layer.

In the laminated body according to the present invention, the vapor-deposited layer may be a metal-deposited layer.

The present invention is a laminate including at least a base material layer, a barrier layer, an adhesive layer, and a sealant layer in this order. The base material layer contains ethylene glycol as a diol unit, and terephthalic acid and isophthalic acid. The barrier layer is a laminated body containing polyethylene terephthalate having an acid as a dicarboxylic acid unit, and the barrier layer including a vapor-deposited layer provided on the base material layer.

In the laminated body according to the present invention, the thin-film deposition layer may be a transparent thin-film deposition layer.

In the laminated body according to the present invention, the barrier layer may further include a gas barrier coating film provided on the surface of the transparent vapor deposition layer.

In the laminate according to the present invention, the adhesive layer may have a cured product of a polyester polyol and an aliphatic isocyanate compound.

In the laminate according to the present invention, the polyester polyol has two or more hydroxyl groups in one molecule as a functional group, and the isocyanate compound has two or more isocyanate groups in one molecule as a functional group. The polyol may be a polycondensate of an ortho-oriented polyvalent carboxylic acid or an anhydride thereof and a polyhydric alcohol.

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）で表される化合物であってもよい。

In the laminate according to the present invention, the polyester polyol has two or more hydroxyl groups in one molecule as a functional group, and the isocyanate compound has two or more isocyanate groups in one molecule as a functional group. The polyol is a compound represented by the following general formula (1), and is a compound represented by the following general formula (1).

In the general formula (1), R ₁ , R ₂ , and R ₃ may be independently H (hydrogen atom) or a compound represented by the following general formula (2).

In the laminate according to the present invention, the polyester polyol has two or more hydroxyl groups in one molecule as a functional group, and the isocyanate compound has two or more isocyanate groups in one molecule as a functional group, and the polyester The polyol may have an isocyanate ring.

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

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

According to the present invention, it is possible to provide a laminate having an excellent _{CO 2} reduction effect and excellent hygiene as compared with a laminate made of non-recycled polyethylene terephthalate.

It is a schematic cross-sectional view which shows an example of the laminated body by this embodiment. It is a schematic cross-sectional view which shows an example of the laminated body by this embodiment. It is a schematic cross-sectional view which shows an example of a base material layer.

<Laminated body>
The laminate according to the present embodiment includes at least a base material layer, a barrier layer, and a sealant layer in this order. The laminate may further include an adhesive layer, a printing layer, another layer, and the like.

The laminated body according to the present embodiment will be described with reference to the drawings. Examples of schematic cross-sectional views of the laminated body according to the present embodiment are shown in FIGS. 1 and 2.

The laminate 10 shown in FIG. 1 includes a base material layer 11, an adhesive layer 14, a barrier layer 12, and a sealant layer 13 in this order. As shown in FIG. 1, the barrier layer 12 includes a thin-film deposition layer 121 provided on the sealant layer 13. Although not shown, the laminate 10 may further include a printing layer provided on the base material layer 11. In the packaging bag including the laminated body 10 shown in FIG. 1, the sealant layer 13 constitutes the inner surface of the packaging bag.

The laminate 10 shown in FIG. 2 includes a base material layer 11, a barrier layer 12, an adhesive layer 14, and a sealant layer 13 in this order. As shown in FIG. 2, the barrier layer 12 includes at least a thin-film deposition layer 121 provided on the base material layer 11. The barrier layer 12 may further include a gas barrier coating film 122 provided on the surface of the vapor deposition layer 121. Although not shown, the laminate 10 may further include a printing layer located between the barrier layer 12 and the adhesive layer 14. Also in the packaging bag including the laminated body 10 shown in FIG. 2, the sealant layer 13 constitutes the inner surface of the packaging bag.

Hereinafter, each layer constituting the laminated body will be described.

[Base 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 in which PET bottles are recycled by mechanical recycling, and the PET contains ethylene glycol as a diol unit and terephthalic acid and isophthalic acid as dicarboxylic acid units. Here, mechanical recycling generally refers to crushing a recovered polyethylene terephthalate resin product such as a PET bottle, cleaning it with an alkali to remove stains and foreign substances on the surface of the PET resin product, and then drying it at a high temperature and under reduced pressure for a certain period of time. This is a method in which the pollutants remaining inside the PET resin are diffused and decontaminated to remove stains on the resin product made of the PET resin, and the resin product is returned to the PET resin again. Hereinafter, in the present specification, polyethylene terephthalate obtained by recycling PET bottles is referred to as "recycled polyethylene terephthalate (hereinafter, also referred to as recycled PET)", and non-recycled polyethylene terephthalate is referred to as "virgin polyethylene terephthalate (hereinafter, also referred to as virgin PET)". ) ”.

Of 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, preferably 1.0 mol%, based on the total dicarboxylic acid units constituting the PET. More preferably, it is 2.5 mol% or more. If the content of isophthalic acid is less than 0.5 mol%, the flexibility may not be improved, while if it exceeds 5 mol%, the melting point of PET may be lowered and the heat resistance may be insufficient. The PET may be a biomass PET in addition to a PET derived from ordinary fossil fuels. The "biomass PET" contains ethylene glycol derived from biomass as a diol unit, and contains a dicarboxylic acid derived from fossil fuel 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 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.

The PET used in the PET bottle can be obtained by a conventionally known method of polycondensing the above-mentioned diol unit and dicarboxylic acid unit. Specifically, a general method of melt polymerization such as performing an esterification reaction and / or a transesterification reaction between the above diol unit and a dicarboxylic acid unit and then performing a polycondensation reaction under reduced pressure, or an organic solvent. It can be produced by a known solution heating dehydration condensation method or the like using the above.

The amount of the diol unit used in producing the PET is substantially equimolar with respect to 100 mol of the dicarboxylic acid or its derivative, but generally, esterification and / or transesterification reaction and / or condensation polymerization. Since there is distillation during the reaction, it is used in excess of 0.1 mol% or more and 20 mol% or less.

Further, 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 raw material preparation or at the start of reduced pressure.

PET bottles made from recycled PET bottles are polymerized and solidified as described above, and then solid-phase polymerization is performed as necessary in order to further increase the degree of polymerization and remove oligomers such as cyclic trimers. You may go. Specifically, in solid phase polymerization, the 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 lower for 1 hour to several tens of hours under an inert gas atmosphere or under reduced pressure.

The ultimate 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 ultimate viscosity is less than 0.58 dl / g, the mechanical properties required for the PET film as a base material may be insufficient. On the other hand, if the ultimate viscosity exceeds 0.80 dl / g, the productivity in the film forming process may be impaired. The ultimate viscosity is measured with an orthochlorophenol solution at 35 ° C.

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

Specific examples of the aliphatic dicarboxylic acid include chains having 2 to 40 carbon atoms, such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid and cyclohexanedicarboxylic acid. The shape or alicyclic dicarboxylic acid can be mentioned. Examples of the derivative of the aliphatic dicarboxylic acid include lower alkyl esters such as methyl ester, ethyl ester, propyl ester and butyl ester of the aliphatic dicarboxylic acid, and cyclic acid anhydride of the aliphatic dicarboxylic acid such as succinic anhydride. .. Among these, as the aliphatic dicarboxylic acid, adipic acid, succinic acid, dimeric acid or a mixture thereof is preferable, and one containing succinic acid as a main component is particularly preferable. As the derivative of the aliphatic dicarboxylic acid, a methyl ester of adipic acid and succinic acid, or a mixture thereof is more preferable.

The base material layer composed of such PET may be a single layer or a multi-layered structure. As shown in FIG. 3, when the recycled PET as described above is used as the base material layer, the base material layer may be provided with three layers of the first layer 31, the second layer 32, and the third layer 33. In this case, in the laminated body, the third layer 33 of the base material layer is located on the sealant layer side. Further, in this case, the second layer 32 is a layer composed of only recycled PET or a mixed layer of recycled PET and virgin PET, and the first layer 31 and the third layer 33 are a layer composed of only virgin PET. It is preferable to do so. As described above, by using only virgin PET for the first layer 31 and the third layer 33, it is possible to prevent the recycled PET from being exposed from the front surface or the back surface of the base material layer. Therefore, the hygiene of the laminated body can be ensured. Further, the base material layer may be a base material layer having two layers of the second layer 32 and the third layer 33 without providing the first layer 31 shown in FIG. Further, the base material layer may be a base material layer having two layers of the first layer 31 and the second layer 32 without providing the third layer 33 shown in FIG. Even in these cases, the second layer 32 is a layer composed of only 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 of only virgin PET. Is preferable.

When one layer is formed by mixing recycled PET and virgin PET, there are a method of separately supplying to a molding machine, a method of supplying after mixing with a dry blend or the like. Above all, the method of mixing by dry blend is preferable from the viewpoint of easy operation.

Various additives can be added to the PET constituting the base material layer in the manufacturing process thereof or after the manufacturing thereof as long as the characteristics are not impaired. Additives include, for example, plasticizers, UV stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, mold release agents, antioxidants, ions. Examples include replacement agents and coloring pigments. The additive is preferably added in the range of 5% by mass or more and 50% by mass or less, preferably 5% by mass or more and 20% by mass or less, based on the entire resin composition containing PET.

The base material layer can be formed by, for example, forming a film by the T-die method using the above-mentioned PET. Specifically, after the above-mentioned PET is dried, it is supplied to a melt extruder heated to a temperature (Tm) to Tm + 70 ° C. above the melting point of the PET to melt the resin composition, for example, a T die. A film can be formed by extruding a sheet-like material from a die such as a die and quenching and solidifying the extruded sheet-like material 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 and 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 vertical direction to obtain a vertically stretched film. This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls. The longitudinal stretching is usually carried out in a temperature range of 50 ° C. or higher and 100 ° C. or lower. Further, the magnification of longitudinal stretching depends on the required characteristics of the film application, but is preferably 2.5 times or more and 4.2 times or less. When the draw ratio is less than 2.5 times, the thickness unevenness of the PET film becomes large and it is difficult to obtain a good film.

The vertically stretched film is subsequently subjected to each of the treatment steps of transverse stretching, heat fixing, and heat relaxation to obtain a biaxially stretched film. The transverse stretching is usually carried out in a temperature range of 50 ° C. or higher and 100 ° C. or lower. The lateral stretching ratio depends on the required characteristics of this application, but is preferably 2.5 times or more and 5.0 times or less. If it is less than 2.5 times, the thickness unevenness of the film becomes large and it is difficult to obtain a good film, and if it exceeds 5.0 times, breakage is likely to occur during film formation.

After the transverse stretching, a heat-fixing treatment is subsequently performed, and a preferable temperature range for heat-fixing is Tg + 70 to Tm-10 ° C. of PET. The heat fixing time is preferably 1 second or more and 60 seconds or less. Further, for applications that require a reduction in the heat shrinkage rate, heat relaxation treatment may be performed as necessary.

The thickness of the PET film obtained as described above is arbitrary depending on the intended use, but is usually about 5 μm or more and 100 μm or less, and preferably 5 μm or more and 25 μm or less. Further, the breaking strength of the PET film in the MD direction 5 kg / mm ² or more 40 kg / mm ² or less, in TD direction 5 kg / mm ² or more 35 kg / mm ² or less, also elongation at break 50 in the MD direction % Or more and 350% or less, and 50% or more and 300% or less in the TD direction. The shrinkage rate when left in a temperature environment of 150 ° C. for 30 minutes is 0.1% or more and 5% or less.

The virgin PET may be fossil fuel polyethylene terephthalate (hereinafter, also referred to as fossil fuel PET) or biomass PET. Here, the "fossil fuel PET" is a fossil fuel-derived diol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. Further, the recycled PET may be obtained by recycling a PET resin product formed by using fossil fuel PET, or may be obtained by recycling a PET resin product formed by using biomass PET. There may be.

[Barrier layer]
Next, the barrier layer will be described. The barrier layer is a layer for suppressing a defect that the foreign matter appears on the sealant layer side of the barrier layer even if the foreign matter adheres to the recycled PET used for the base material layer. As a result, in the packaging bag constructed by using the laminated body, it is possible to suppress the problem that foreign matter is exposed to the inner surface side of the barrier layer, so that the hygiene of the contents can be ensured.

(Embedded layer)
Next, the vapor deposition layer of the barrier layer will be described. The thin-film deposition layer is a layer made of a thin-film deposition film that can be formed by a conventionally known method. By providing the thin-film deposition layer, it is possible to impart or improve the gas barrier property that prevents the permeation of oxygen gas, water vapor and the like. The thin-film film constituting the barrier layer may include two or more thin-film deposition layers. When two or more thin-film deposition layers are provided, they may have the same composition or different compositions.

The thin-film deposition film may be a metal-deposited layer made of a metal-deposited film, or may be a transparent-deposited layer made of an inorganic oxide-deposited film.

When the barrier layer includes a metal-deposited layer, in addition to the above-mentioned gas barrier property, it is possible to impart or improve a light-shielding property that blocks the transmission of visible light, ultraviolet rays, and the like. Further, since the packaging bag can be given a metallic luster, the design can be improved.
When the barrier layer includes a transparent thin-film deposition layer, it is possible to impart or improve gas barrier properties that prevent the permeation of oxygen gas, water vapor, etc., while maintaining the permeability of the contents.

In the laminate 10 shown in FIG. 1, the print layer can be provided on the base material layer 11 located on the outer surface side of the barrier layer 12. Therefore, the barrier layer 12 may have a light-shielding property. Therefore, in the laminated body 10 shown in FIG. 1, it is preferable that the vapor deposition layer 121 is a metal vapor deposition layer.

Examples of the metal vapor deposition layer include aluminum (Al), magnesium (Mg), tin (Sn), sodium (Na), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), and gold ( A metal vapor deposition layer such as Au) or chromium (Cr) can be used. In particular, for packaging bags, it is preferable to provide an aluminum vapor deposition layer.

The film thickness of the metal vapor deposition layer varies depending on the type of metal used and the like, but for example, it is desirable to arbitrarily select and form the film within the range of 50 Å or more and 2000 Å or less, preferably 100 Å or more and 1000 Å or less. More specifically, in the case of a thin-film aluminum film, the film thickness is preferably 50 Å or more and 600 Å or less, more preferably 100 Å or more and 450 Å or less.

When the thin-film vapor deposition layer of the barrier layer is a transparent thin-film deposition layer, the print layer can be visually recognized from the outer surface side even when the print layer is located closer to the sealant layer than the barrier layer. Therefore, as shown in FIG. 2, when the barrier layer 12 is provided on the base material layer 11, it is preferable that the vapor deposition layer 121 of the barrier layer 12 is a transparent vapor deposition layer.

Examples of the transparent thin-film deposition layer include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium ( A thin-film deposition layer of oxides such as Ti), lead (Pb), zirconium (Zr), and yttrium (Y) can be used. In particular, for packaging bags, it is preferable to provide a vapor-deposited layer of aluminum oxide or silicon oxide.

Representation of the inorganic oxide, for _example, SiO X, as such AlO _X MO _X (In the formula, M represents an inorganic element, the value of X, varies each of an inorganic element range.) In expressed. The range of the value of X is 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1 for magnesium (Mg), and 0 to 1 for calcium (Ca). Potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1.5, and titanium (Ti). Can take a value in the range of 0 to 2, lead (Pb) can take a value in the range of 0 to 2, zirconium (Zr) can take a value in the range of 0 to 2, and yttrium (Y) can take a value in the range of 0 to 1.5. In the above, when X = 0, it is a completely inorganic simple substance (pure substance) and is not transparent, and the upper limit of the range of X is a completely oxidized value. Silicon (Si) and aluminum (Al) are preferably used as the packaging material, with silicon (Si) in the range of 1.0 to 2.0 and aluminum (Al) in the range of 0.5 to 1.5. You can use the one with the value of.

The film thickness of the transparent thin-film deposition layer varies depending on the type of inorganic oxide used and the like, but for example, it is desirable to arbitrarily select and form the film thickness within the range of 50 Å or more and 2000 Å or less, preferably 100 Å or more and 1000 Å or less. For example, in the case of a vapor-deposited layer of aluminum oxide or silicon oxide, a film thickness of 50 Å or more and 500 Å or less, more preferably 100 Å or more and 300 Å or less is desirable.

The vapor-deposited layer can be formed on the base material layer or the sealant layer by the following forming method. Examples of the method for forming the vapor deposition layer include a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method and thermochemistry. Examples thereof include a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a vapor phase growth method and a photochemical vapor deposition method.

(Gas barrier coating film)
The gas barrier coating film is provided on the surface of the vapor deposition layer as needed. In particular, when the vapor deposition layer is a transparent vapor deposition layer, it is preferable that a gas barrier coating film is provided on the surface of the transparent vapor deposition layer.

The gas barrier coating film is a coating film that functions as a layer that suppresses the permeation of oxygen gas, water vapor, and the like. The gas barrier coating film is of the general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² represent organic groups having 1 to 8 carbon atoms, M represents a metal atom, and n. Represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M), and at least one alkoxide, a polyvinyl alcohol-based resin and / or It is obtained by a gas barrier composition containing an ethylene / vinyl alcohol copolymer and further polycondensing by the solgel method in the presence of a solgel method catalyst, acid, water, and an organic solvent.

As the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , at least one or more of a partial hydrolyzate of the alkoxide and a condensate of the hydrolysis of the alkoxide can be used. Further, the partial hydrolyzate of the alkoxide may be one in which all of the alkoxy groups are hydrolyzed, one or more in which one or more are hydrolyzed, and a mixture thereof. As the condensate of hydrolysis of the alkoxide, one having a dimer or more of the partially hydrolyzed alkoxide, specifically, one having a dimer of 2 to 6 is used.

In the above-mentioned ^{alkoxide represented by the general formula R 1} _n M (OR ² ) _m , silicon, zirconium, titanium, aluminum, or the like can be used as the metal atom represented by M. In the present embodiment, preferred metals include, for example, silicon and titanium. Further, in the present embodiment, the alkoxide may be used alone or by mixing alkoxides of two or more different metal atoms in the same solution.

Further, in the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m ^{, specific examples of the organic group represented by R 1} include, for example, a methyl group, an ethyl group, an n-propyl group, and i. Alkyl groups such as −propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and others can be mentioned. Further, in the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m ^{, specific examples of the organic group represented by R 2} include, for example, a methyl group, an ethyl group, an n-propyl group, and i. -Propyl group, n-butyl group, sec-butyl group, etc. can be mentioned. In addition, these alkyl groups may be the same or different in the same molecule.

When preparing the above gas barrier composition, for example, a silane coupling agent or the like may be added. As the above-mentioned silane coupling agent, known organic reactive group-containing organoalkoxysilanes can be used. In this embodiment, an organoalkoxysilane having an epoxy group is particularly preferably used. Specifically, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β − (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be used. The above-mentioned silane coupling agent may be used alone or in combination of two or more.

[Sealant layer]
The sealant layer is on the innermost layer side when it is used as a package. The sealant layer is a layer formed of a thermoplastic resin that can be fused to each other 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 fused to each other by heat, and specifically, for example, low-density polyethylene (LDPE), medium-density polyethylene (MDPE), and high density polymer. Density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), ethylene-α / olefin copolymer polymerized using 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-sealing ethylene / vinyl alcohol resins, or polyolefins such as methylpentene resins, ethylene-propylene copolymers, methylpentene polymers, polybutene polymers, polyethylene, polypropylene or cyclic olefin copolymers. Acid-modified polyolefin resin, polyvinyl acetate resin, poly (meth) acrylic obtained by modifying based resin and polyolefin resin with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. Examples thereof include based resins, polyvinyl chloride-based 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, a coating film thereof, or the like.

When polyethylene is used as the resin material for forming the sealant layer, a polymer obtained by polymerizing biomass-derived ethylene may be used as the raw material in addition to ethylene obtained from fossil fuel. As the biomass-derived ethylene, specifically, for example, those described in JP-A-2012-251006 can be used. By using polyethylene obtained by polymerizing biomass-derived ethylene as a material constituting the sealant layer, it can be formed with a layer made of a carbon-neutral material. The amount of fuel used can be reduced and the environmental load can be reduced.

As the biomass-derived ethylene, a commercially available polyethylene may be used. For example, a sugar cane-derived linear chain of "C4LL-LL118 (d = 0.916, MFR = 1.0 g / 10 minutes)" manufactured by Braskem Co., Ltd. A low-density polyethylene-based resin or a sugarcane-derived low-density polyethylene-based resin of "SBC118 (d = 0.918, MFR = 8.1 g / 10 minutes)" can be used.

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

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

[Adhesive layer]
The adhesive layer is a layer formed by applying an adhesive to the surface of the film on the side to be laminated among the film containing the base material layer 11 and the film containing the sealant layer 13 and drying the film. Examples of the adhesive include one-component or two-component cured or uncured vinyl type, (meth) acrylic type, polyamide type, polyester type, polyether type, polyurethane type, epoxy type, rubber type, and others. Such solvent type, water-based type, or emulsion type adhesives can be used. As the two-component curable adhesive, a cured product of a polyol and an isocyanate compound can be used. As the coating method of the above-mentioned adhesive for laminating, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a fonten method, a transfer roll coating method, or other methods can be applied. ..

The adhesive layer may be configured to reinforce the barrier properties of the barrier layer. In the following description, among the adhesive layers containing the cured product of the polyol and the isocyanate compound, the adhesive layer configured to reinforce the barrier property of the barrier layer is also referred to as a barrier adhesive layer in particular. Hereinafter, the barrier adhesive layer will be described.

(Barrier adhesive layer)
The barrier adhesive layer has a gas barrier property, particularly an oxygen and water vapor barrier property. 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 property tends 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 property after bending.

The barrier adhesive layer contains a cured product of a polyester polyol and an isocyanate compound. The polyester polyol has two or more hydroxyl groups in one molecule as a functional group. Further, the isocyanate compound has two or more isocyanate groups in one molecule as a functional group. The polyester polyol has, for example, a polyester structure or a polyester polyurethane structure as a main skeleton.

The resin composition for forming a cured product of the polyester polyol and the isocyanate compound may further contain a plate-like inorganic compound, a phosphoric acid-modified compound, a coupling agent, cyclodextrin and / or a derivative thereof, and the like. ..

The glass transition temperature of the cured coating film of the resin composition for an adhesive is preferably in the range of −30 ° C. or higher and 80 ° C. or lower. More preferably, it is 0 ° C. or higher and 70 ° C. or lower. More preferably, it is 25 ° C. or higher and 70 ° C. or lower. When the glass transition temperature is higher than 80 ° C., the flexibility of the cured coating film near room temperature is lowered, so that the adhesion to the film is deteriorated and the adhesive strength may be lowered. On the other hand, if the temperature is lower than -30 ° C, there is a risk that sufficient oxygen barrier properties will not be obtained due to the vigorous molecular motion of the cured coating film near room temperature, and there is a risk that the adhesive strength will be reduced due to insufficient cohesive force.

As a specific example of the resin composition containing a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound, a series of oxygen barrier adhesive PASLIM sold by DIC Co., Ltd. can be used, and in particular, mainly PASLIM VM001 / VM102CP, which is a compound having a polyester-based skeleton and a curing agent having two or more isocyanate groups, is preferably used.

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

[1st Example] Polypolypolypoly obtained by polycondensing an ortho-oriented polyvalent carboxylic acid or its anhydride with a polyhydric alcohol The polyester polyol according to the 1st example contains at least one orthophthalic acid and its anhydride. Polycondensation obtained by polycondensing the containing polyvalent carboxylic acid component and the polyhydric alcohol component containing at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. It may be a body. In particular, a polyester polyol in which the content of the orthophthalic acid and its anhydride with respect to all the components of the polyvalent carboxylic acid is 70 to 100% by mass is preferable.

The polyester polyol according to the first example requires the orthophthalic acid and its anhydride as the polyvalent carboxylic acid component, but copolymerizes other polyvalent carboxylic acid components as long as the effects of the present embodiment are not impaired. You may let me. Specifically, the aliphatic polyvalent carboxylic acid includes succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid and the like, and the unsaturated bond-containing polyvalent carboxylic acid includes maleic anhydride and maleic acid. Fumaric acid and the like, 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid as alicyclic polyvalent carboxylic acids, and terephthalic acid, isophthalic acid and pyromerit as aromatic polyvalent carboxylic 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. It can be used alone or in admixture of two or more. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, and isophthalic acid are preferable.

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

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）で表される化合物である。

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

In the general formula (1), R ₁ , R ₂ , and R ₃ are independently H (hydrogen atom) or a compound 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).

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

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 as a substituent. Represents an allylene group that may have. 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 methylpenti. 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) requires 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. Obtained by reacting as an ingredient.

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.

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 isocyanul ring The polyester polyol according to the third example is a polyester polyol having an isocyanul ring represented by the following general formula (3).

In the general formula (3), R ₁ , R ₂ , and R ₃ are independently "-(CH ₂ ) n1-OH (where n1 represents an integer of 2 to 4)" or the general formula (4). ) Represents the structure.

In the general formula (4), n2 represents an integer of 2 to 4, n3 represents an integer of 1 to 5, X represents a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, It represents an arylene group selected from the group consisting of a 2,3-anthraquinonediyl group and a 2,3-anthracendyl group and may have a substituent, and Y represents an alkylene group having 2 to 6 carbon atoms. ) Represents a group. 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 or 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 or a phenyl group, preferably a hydroxyl group, a phenoxy group, a cyano group, a nitro group or a phthalimide group. , A 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 methylpenti. 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). Above _{all, it is preferable that all of R 1} , R ₂ , and R ₃ are groups represented by the general formula (4).

Further, _{any one of R 1} , R ₂ , and R ₃ is a compound represented by the general formula (4), and _{any two of R 1} , R 2, and R ₃ are the general formula (4). A mixture of two or more compounds of the compound represented by the group represented by and the compound represented by the general formula (4) in which all of _{R 1} , R ₂ , and R _{3 are represented by the above general formula (4).} May be good.

The polyester polyol having an isocyanul ring represented by the general formula (3) is 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. Is obtained by reacting with as an essential component.

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

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. Therefore, the entire system can be made highly polar, and the crosslink density can be increased. 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.

It is presumed that the reason why the adhesive having an isocyanul ring can ensure the oxygen barrier property and the dry laminate adhesive property is as follows.

The isocyanul ring is highly polar and does not form hydrogen bonds. Generally, as a method for improving adhesiveness, a method of blending highly polar functional groups such as hydroxyl groups, urethane bonds, ureido bonds, and amide bonds is known, but resins having these bonds form intermolecular hydrogen bonds. It is easy and may impair the solubility in ethyl acetate, 2-butanone solvent, which is often used for dry laminate adhesives, but the polyester resin having an isocyanul ring does not impair the solubility, so that it can be easily diluted. Is.

Further, since the isocyanul ring is trifunctional, a polyester polyol compound having the isocyanul ring as the center of the resin skeleton and a polyester skeleton having a specific structure in the branched chain can obtain a high crosslink density. It is presumed that by increasing the crosslink density, the gap through which a gas such as oxygen passes can be reduced. As described above, it is presumed that the isocyanul ring has high polarity and a high crosslink density without forming an intermolecular hydrogen bond, so that oxygen barrier property and dry laminate adhesiveness can be ensured.

(Isocyanate compound)
The isocyanate compound has two or more isocyanate groups in the molecule and 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 (K) may be a blocked isocyanate compound obtained by subjecting it to an 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 preferable from the viewpoint of imparting oxygen barrier properties, and in particular, isocyanate compounds containing a metaxylene skeleton are urethane-based. It is preferable because the oxygen barrier property can be improved not only by hydrogen bonding but also by π-π stacking between aromatic rings.

Specific examples of the isocyanate compound include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydride diphenylmethane diisocyanate, metaxylylene diisocyanate, hydride xylylene diisocyanate, isophorone diisocyanate, and these isocyanate compounds. Trimeric 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, metaxylylene diamine and other low molecular weight active hydrogen compounds and their alkylene oxide adducts, various polyester resins, polyether polyols, polyamide polymers Examples thereof include an adduct-form, a burette-form, and an allophanate-form obtained by reacting with an active hydrogen compound and the like.

(Plate-shaped inorganic compound)
The plate-shaped inorganic compound has an effect of improving the laminating strength and gas barrier property of the barrier adhesive layer formed by curing the resin composition for adhesive.
Specific examples of the plate-like inorganic compound include kaolinite-kaolinite clay minerals (haloysite, kaolinite, enderite, deckite, nacrite, etc., antigolite, chrysotile, etc.), pyrophyllite-talc (pyrophyllite, etc.). Wright, talc, kaolin, etc.), etc., and one or more of these can be used.

(Phosphate-modified compound)
The 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 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 (meth) acryloyl. It is a group selected from alkyl groups having 1 to 4 carbon atoms having an oxy group, but at least one 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 have a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth) acryloyl group, a phenyl group which may have a substituent, and a (meth) acryloyloxy group. It is a group selected from alkyl groups of ~ 4, n represents an integer of 1 to 4, x represents an integer of 0 to 30, y represents an integer of 0 to 30, except when x and y are both 0. ..

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

More specifically, phosphoric acid, pyrophosphate, triphosphate, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxy. Ethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphoric acid and the like can be mentioned, and one or more of these can be used.

The content of the phosphoric acid-modified compound 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 it is more than 10% by mass or less, the barrier property may be deteriorated.

(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 vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxytrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacry Loxypropylmethyldiethoxysilane, 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 Examples thereof include propyltrimethoxysilane, 3-isocyanuppropyltriethoxysilane, 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, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, and tetraoctyl. Bis (didodecylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctainoltitanate, isopropyldimethacrylisostearoyl Examples thereof include titanate, isopropylisostearoyl 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, andisopropoxyaluminum alkylacetate mono (dioctyl phosphate). Examples thereof include aluminum-2-ethylhexanoate oxide trimmer, aluminum stearate oxide trimmer, and alkylacetoacetate aluminum oxide trimmer.

(Cyclodextrin and / or its derivative)
The cyclodextrin and / or its derivative is a preferable component for obtaining 1) excellent adhesion to a film having an inorganic layer, and 2) excellent enhancement of an oxygen barrier. Specifically, for example, in addition to cyclodextrin, cyclodextrins such as 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 are used. be able to. A branched cyclic dextrin can also be used. The cyclodextrin skeleton of cyclodextrin and cyclodextrin derivatives includes α-cyclodextrin consisting of 6 glucose units, β-cyclodextrin consisting of 7 glucose units, and γ-cyclodextrin consisting of 8 glucose units. Any of these can be used. 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 for an adhesive, 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. ..

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 its derivative is not particularly limited, but from the viewpoint of compatibility with resins, solvents and isocyanate compounds, improvement of adhesive strength, and improvement of barrier, 0. The range is preferably 01 parts by mass or more and 20 parts by mass or less, more preferably 0.05 parts by mass or more and 10 parts by mass or less, and further preferably 0.1 parts by mass or more and 5 parts by mass or less.

When the resin composition for an adhesive contains cyclodextrin and / or a derivative thereof, the cyclic and regularly arranged hydroxyl groups and ether groups of the cyclodextrin and / or its derivative have a plurality of interaction points with the inorganic surface. By having it as a coordination bond or a hydrogen bond, it is assumed that it can be an adhesive with strong adhesive strength when various films with an inorganic layer, especially metal foil, metal vapor deposition film, and transparent vapor deposition film are laminated. doing. It is also assumed that a large number of hydroxyl groups of cyclodextrin and / or its derivatives interact with each other to narrow the free volume pores through which gas permeates, thereby improving the barrier function.

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

[Print layer]
The printing layer is used for decoration, display of contents, display of expiration date, display of manufacturers, sellers, etc., and for display of other things and giving aesthetics, such as letters, numbers, patterns, figures, symbols, patterns, etc. A layer that forms any desired print pattern. The printing layer can be provided as needed, and can be provided, for example, between the base material layer and the barrier layer, or between the barrier layer and the sealant layer. The printing layer may be provided on the entire surface of the base material layer or may be provided on a part of the base material layer. The printed layer can be formed by using a conventionally known pigment or dye, and the forming method thereof is not particularly limited.

The printed 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, and further preferably 1 μm or more and 3 μm or less.

An example of the layer structure of the laminated body formed by combining the above-mentioned layers is as follows.
Configuration Example 1: Base material layer / adhesive layer / metal vapor deposition layer / sealant layer Configuration example 2: Base material layer / barrier adhesive layer / metal vapor deposition layer / sealant layer Configuration example 3: Base material layer / transparent vapor deposition layer / Adhesive layer / sealant layer configuration example 4: Base material layer / transparent vapor deposition layer / barrier adhesive layer / sealant layer configuration example 5: Base material layer / transparent vapor deposition layer / gas barrier coating film / adhesive layer / sealant layer configuration Example 6: Base material layer / transparent vapor deposition layer / gas barrier coating film / barrier adhesive layer / sealant layer “/” represents a layer-to-layer boundary.

As described above, the base material layer contains recycled PET in a proportion of, for example, 50% by weight or more and 95% by weight or less. According to the present embodiment, since the base material layer contains recycled PET, it is possible to provide a laminated body having a superior _{CO 2 reduction effect as compared with a laminated body not containing recycled PET.} Further, according to the present embodiment, when the laminated body includes the above-mentioned barrier layer, it is possible to provide a laminated body having excellent hygiene.

<Manufacturing method of laminated body>
The method for producing the laminate according to the present embodiment is not particularly limited, and the laminate can be produced by using a conventionally known method such as a dry laminate method.

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

The laminate can be used, for example, in a packaging bag for filling a product such as food. For example, the above laminate is used and folded in half, or two laminates are prepared, the surfaces of the sealants are opposed to each other and overlapped, and the peripheral end thereof is, for example, a side seal type. , Two-way seal type, three-way seal type, four-sided seal type, envelope-attached seal type, gassho-attached seal type (pillow seal type), fold-attached seal type, flat-bottom seal type, square-bottom seal type, gusset type, etc. Can be heat-sealed to produce various forms of packaging bags.

In the above, as the heat sealing method, 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.

Since the packaging bag has excellent hygiene while reducing the environmental load, it can be particularly suitably used as a packaging bag for sealing and packaging foods and the like.

10 Laminated body 11 Base material layer 12 Barrier layer 121 Deposited layer 122 Gas barrier coating film 13 Sealant layer 14 Adhesive layer

Claims (11)

At least a base material layer (however, the following base material layer A is excluded) , an adhesive layer (however, the following adhesive layer A and the following adhesive layer B are excluded) , a barrier layer, and a sealant layer. In this order, it is a laminated body
The base material layer contains recycled polyethylene terephthalate having ethylene glycol as a diol unit and terephthalic acid and isophthalic acid as a dicarboxylic acid unit.
The barrier layer is seen including a deposition layer disposed on the sealant layer,
The base material layer A contains a biomass polyester resin having ethylene glycol derived from biomass as a diol unit and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit.
The adhesive layer A is a resin composition for a gas barrier adhesive, which comprises a resin (A) having two or more hydroxyl groups in one molecule and a polyisocyanate (B) having two or more isocyanate groups. A mixture of a trivalent or higher valent polyisocyanate compound (b1) in which the polyisocyanate (B) has an aromatic ring in the molecule and a polyisocyanate compound (b2) in which the polyisocyanate (B) does not have an aromatic ring in the molecule. Consists of a resin composition for a gas barrier adhesive, which is
The adhesive layer B is a polyester polyol (A) containing a reaction product of an acid component containing an ortho-oriented aromatic dicarboxylic acid or an acid anhydride thereof as an essential component and a polyhydric alcohol, and the polyhydric alcohol is contained. Polypolyol (A) containing dihydric alcohol and trihydric alcohol, the polyester polyol (A) having a glass transition point of 5 to 40 ° C. and a hydroxyl value of 150 to 300 mgKOH / g, and poly. A resin composition containing a reaction product with the isocyanate compound (B).
Laminated body. The laminate according to claim 1, wherein the vapor-deposited layer is a metal-deposited layer. A laminate including at least a base material layer (excluding the base material layer A below) , a barrier layer, an adhesive layer, and a sealant layer in this order.
The base material layer contains recycled polyethylene terephthalate having ethylene glycol as a diol unit and terephthalic acid and isophthalic acid as a dicarboxylic acid unit.
The barrier layer is seen containing a transparent vapor deposited layer provided on the base layer, and a gas barrier coating film provided on a surface of the transparent deposition layer,
The base material layer A contains a biomass polyester resin having ethylene glycol derived from biomass as a diol unit and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit.
Laminated body. The laminate according to claim 3, wherein the transparent vapor deposition layer is a vapor deposition layer of aluminum oxide or silicon oxide. The gas barrier coating film has a general formula of R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent organic groups having 1 to 8 carbon atoms, and M represents a metal atom. n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M), and at least one alkoxide, a polyvinyl alcohol-based resin, and /. The laminate according to claim 4, further comprising an ethylene / vinyl alcohol copolymer. The laminate according to any one of claims 1 to 5, wherein the adhesive layer has a cured product of a polyester polyol and an aliphatic isocyanate compound. The polyester polyol has two or more hydroxyl groups in one molecule as a functional group.
The isocyanate compound is perforated at least two isocyanate groups in one molecule as a functional group, laminate of claim 6. The polyester polyol has two or more hydroxyl groups in one molecule as a functional group.
The isocyanate compound has two or more isocyanate groups in one molecule as a functional group.
The polyester polyol is a compound represented by the following general formula (1).

In the general formula _{(1), R 1, R} 2, R 3 are each independently, Ri compound der represented by H or 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. Represents an arylene group selected from the group consisting of a 3-anthraquinonediyl group and a 2,3-anthracendyl group, where Y represents an alkylene group having 2 to 6 carbon atoms), where R1 is used. , R2, R3 represent a group represented by the general formula (2).
The laminate according to claim 6. The polyester polyol has two or more hydroxyl groups in one molecule as a functional group.
The isocyanate compound has two or more isocyanate groups in one molecule as a functional group.
The laminate according to claim 6, wherein the polyester polyol has an isocyanul ring. The item according to any one of claims 1 to 9, wherein the content of the isophthalic acid is 0.5 mol% or more and 5.0 mol% or less with respect to all the dicarboxylic acid units constituting the polyethylene terephthalate. Laminated body. The laminate according to any one of claims 1 to 10, wherein the ultimate viscosity of the polyethylene terephthalate is 0.58 dl / g or more and 0.80 dl / g or less.

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