JP2017056693A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate capable of suppressing development of cracks in a laminate in which a polyester resin layer comprising a biomass polyester and a thin film layer are laminated.MEANS: The laminate includes at least a polyester resin layer and a thin film layer comprising at least either an inorganic matter or an inorganic oxide laminated. The polyester resin layer comprises 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; and the dicarboxylic acid comprises terephthalic acid and isophthalic acid.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate, and more particularly to a laminate using a biomass polyester resin.

  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 viewpoint of ease of molding and cost, and these plastic materials are It is produced from petroleum, a fossil resource. As plastic materials widely used as materials for packaging containers, polyester resins, polyolefin resins, polyamide resins, and the like are used. Among these, polyester 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 and the like and are inexpensive.

  Polyester is obtained by polycondensation of a diol unit and a dicarboxylic acid unit. For example, polyethylene terephthalate (hereinafter sometimes abbreviated as PET) is obtained by esterifying both ethylene glycol and terephthalic acid as raw materials. After the polycondensation reaction. These raw materials are produced from petroleum which is a fossil resource, for example, ethylene glycol is produced industrially from ethylene and terephthalic acid is produced industrially from xylene.

In recent years, the use of alternative petroleum raw materials for various applications in consideration of the environment has been increasing year after year for such fossil fuel-derived materials, and in order to reduce CO ₂ emissions, we are moving away from fossil fuels. Is desired. As an attempt to reduce the use of fossil fuels, biomass plastics using biomass raw materials as part of various resin raw materials are being put into practical use as packaging materials. As an example, in polyester resins, those derived from biomass as ethylene glycol, which is a monomer component, have been put into practical use, and it is also proposed to apply polyester resins containing such biomass-derived raw materials to packaging materials. ing. For example, Patent Document 1 discloses a packaging film using a resin film containing a polyester (hereinafter, also referred to as biomass polyester) obtained using biomass-derived ethylene glycol and a fossil fuel-derived dicarboxylic acid. Etc. have been proposed. Moreover, even if it is a case where it is a case where it is a case where it uses as a film using the resin which contains biomass polyester in the ratio of 50-95 mass% in patent document 2, the physical property which is inferior to the film using the polyester resin derived from the conventional fossil fuel. It has also been proposed to be obtained.

JP 2012-96469 A JP 2012-97163 A

  By the way, the packaging film having a polyester resin or the like as a base material layer is provided with a sealant layer on the inner layer side, and heat-sealed from the outer layer side (base material layer side) to form a package. When sealing, the film may be pressed with a male mold and a female mold. The present inventors have noticed that cracks are generated in the film when biomass polyester resin is used as a base material layer when such sealing is performed or when the film is bent. And as a result of earnest examination, the knowledge that the generation | occurrence | production of a crack as mentioned above can be suppressed by containing isophthalic acid in addition to terephthalic acid as a dicarboxylic acid component which comprises biomass polyester was acquired. The present invention is based on such knowledge.

  Therefore, the objective of this invention is providing the laminated body which can improve a softness | flexibility in the laminated body by which the polyester resin layer containing biomass polyester and the thin film layer were laminated | stacked.

The laminate according to the present invention is a laminate in which at least a polyester resin layer and a thin film layer containing at least one of an inorganic substance and an inorganic oxide are laminated,
The polyester resin layer comprises biomass polyester resin having ethylene glycol derived from biomass as a diol unit and dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit,
The dicarboxylic acid contains terephthalic acid and isophthalic acid.

  In the present invention, a laminate in which at least the polyester resin layer, the thin film layer, and the barrier coat film are sequentially laminated may be used.

  In the present invention, a laminate in which paper layers are further laminated may be used.

  In the present invention, the first and / or second sealant layer includes a fossil fuel-derived or biomass-derived resin material, and the resin material is selected from the group consisting of polyethylene, polypropylene, and polylactic acid. Resin may be included.

  According to the present invention, in a laminate including a polyester resin layer containing a biomass polyester resin in which biomass-derived ethylene glycol is a diol unit and fossil fuel-derived dicarboxylic acid is a dicarboxylic acid unit, isophthalic acid is used as a dicarboxylic acid component. By including, the laminated body which can improve a softness | flexibility is realizable.

Sectional drawing which shows simply embodiment of the laminated constitution of the laminated body by this invention. Sectional drawing which shows other embodiment of the laminated constitution of the laminated body by this invention simply. The figure which shows an example of a structure of a standing pouch simply. Sectional drawing which shows simply embodiment of the laminated constitution of the laminated body which forms the side sheet | seat of a standing pouch. The fragmentary sectional view which shows an example of a tube container simply. Sectional drawing which shows simply embodiment of the laminated constitution of the laminated body which forms the cylindrical trunk | drum of a tube container. Sectional drawing which shows simply embodiment of the laminated constitution of the laminated body which forms a liquid paper container. The perspective view which shows an example of a liquid paper container. Sectional drawing which shows simply embodiment of the laminated constitution of the laminated body which forms a paper cup. The perspective view which excised a part of paper cup. The front view which fractured | ruptured a part which shows another embodiment of a paper cup.

[Definition]
In this specification,
“Polyester” means a polymer obtained by a polycondensation reaction between a diol unit and a dicarboxylic acid unit.
The “fossil fuel polyester” means a polymer having a diol derived from fossil fuel as a diol unit and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit.
“Biomass polyester” refers to a polymer having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

  DESCRIPTION OF EMBODIMENTS Hereinafter, modes for carrying out the present invention (hereinafter referred to as embodiments) will be described in detail with reference to the drawings. In addition, this invention is not limited by the following embodiment. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art and those that are substantially the same. Furthermore, the constituent elements disclosed in the following embodiments can be appropriately combined.

  The laminate according to the present invention will be described with reference to the drawings. As shown in FIG. 1, a laminate 10 according to the present invention is a laminate in which at least a polyester resin layer 1 and a thin film layer 2 are laminated. In the present invention, as shown in FIG. 2, the laminate 10 according to the present invention may be a laminate in which a polyester resin layer 1, a thin film layer 2, and a barrier coat film 3 are provided in this order. Hereinafter, each layer which comprises the laminated body by this invention is demonstrated.

[Polyester resin layer]
The polyester resin layer 1 constituting the laminate according to the present invention comprises a biomass polyester resin. As described above, the biomass polyester contains biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. The present invention is characterized by containing terephthalic acid and isophthalic acid as a dicarboxylic acid unit which is a copolymerization component of biomass polyester. The conventional biomass polyester was obtained by polycondensation of biomass-derived ethylene glycol and terephthalic acid. Therefore, in a laminate using a biomass polyester resin as a base material layer, a package using the laminate is used. In some cases, cracks may occur. This invention pays attention to this problem, and discovered that the softness | flexibility of a laminated body can be improved by containing isophthalic acid in addition to terephthalic acid as a dicarboxylic acid unit which is an acid component of biomass polyester. Hereinafter, the biomass polyester used in the present invention will be described.

  Biomass-derived ethylene glycol uses ethanol (biomass ethanol) produced from biomass as a raw material. Biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method, such as a method of producing ethylene glycol via ethylene oxide. Moreover, you may use the biomass ethylene glycol marketed, for example, the biomass ethylene glycol marketed by India Glycol company can be used conveniently.

  As the dicarboxylic acid unit, a dicarboxylic acid derived from fossil fuel is used. As the dicarboxylic acid derived from fossil fuel, terephthalic acid and isophthalic acid are included as essential components. In the present invention, by including isophthalic acid in addition to terephthalic acid as a dicarboxylic acid unit, the flexibility of the obtained biomass polyester is improved, and as a result, the crack resistance in the case of a laminate is improved. Conceivable. The content of isophthalic acid is preferably 0.5 to 2.5 mol%, and preferably 1.0 to 2.5 mol%, based on all dicarboxylic acid units constituting the biomass polyester. If it is less than 0.5 mol%, the flexibility may not be improved. On the other hand, if it exceeds 2.5 mol%, the melting point of the biomass polyester may be lowered and the heat resistance may be insufficient.

  Biomass polyester can be obtained by a conventionally known method in which the above-described diol unit and dicarboxylic acid unit are polycondensed. Specifically, a general method of melt polymerization in which an esterification reaction and / or a transesterification reaction between the diol unit and the dicarboxylic acid unit is performed, and then a polycondensation reaction is performed under reduced pressure, or an organic solvent It can be produced by a known solution heating dehydration condensation method using

  The amount of the diol unit used in producing the biomass polyester is substantially equimolar with respect to 100 mol of the dicarboxylic acid or derivative thereof. Generally, esterification and / or transesterification and / or polycondensation are performed. Since there is distillation during the reaction, it is used in an excess of 0.1 to 20 mol%.

  The polycondensation reaction is preferably performed in the presence of a polymerization catalyst. The addition timing of the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added when the raw materials are charged, or may be added at the start of pressure reduction.

  The obtained biomass polyester may be solidified after solidification, if necessary, in order to further increase the degree of polymerization and remove oligomers such as cyclic trimers. Specifically, after biomass polyester is chipped and dried, biomass polyester is pre-crystallized by heating at a temperature of 100 to 180 ° C for 1 to 8 hours, and subsequently at a temperature of 190 to 230 ° C. It is performed by heating for 1 hour to several tens of hours in an inert gas atmosphere or under reduced pressure.

  The inherent viscosity of the obtained biomass polyester is preferably 0.5 dl / g to 1.5 dl / g, more preferably 0.6 dl / g to 1.2 dl / g. When the intrinsic viscosity is less than 0.5 dl / g, mechanical properties required for a biomass polyester film as a transflective film substrate, including tear strength, may be insufficient. On the other hand, when the intrinsic viscosity exceeds 1.5 dl / g, productivity in the raw material manufacturing process and the film forming process is impaired. The intrinsic viscosity is measured at 35 ° C. with an orthochlorophenol solution.

The biomass polyester preferably contains 10 to 30% of the carbon derived from biomass as measured by radioactive carbon (C14) with respect to the total carbon in the biomass polyester. Since carbon dioxide in the atmosphere contains C14 at a constant rate (105.5 pMC), the C14 content in plants that grow by incorporating carbon dioxide in the atmosphere, for example, corn, is also about 105.5 pMC. It is known. It is also known that fossil fuel contains almost no C14. Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of C14 contained in all carbon atoms in the biomass polyester. In the present invention, the content P _bio of the carbon derived from biomass when the content of C14 in the biomass polyester is PC ₁₄ is defined as the following formula (1).
P _bio (%) = P _C14 /105.5×100 (1)

  The polyester resin layer 1 constituting the laminate of the present invention may contain other components. It is preferable that the polyester resin layer 1 contains 10 to 30% of the carbon derived from biomass as measured by radioactive carbon (C14) with respect to the total carbon in the polyester resin layer 1 and 15 to 25%. Is more preferable. The other component contained in the polyester resin layer 1 may be polyester such as fossil fuel-derived polyester or recycled polyester, and polyethylene such as polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polypropylene terephthalate. A polyester resin other than terephthalate may be contained.

  The polyester resin layer 1 can be formed by forming a film by, for example, the T-die method using the resin as described above. Specifically, after drying the resin composition described above, the resin composition is supplied to a melt extruder heated to a temperature equal to or higher than the melting point of the polyester (Tm) to Tm + 70 ° C. to melt the resin composition, for example, A film can be formed by extruding into a sheet form from a die such as a T die, and rapidly 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 performed by utilizing the difference in peripheral speed between two or more rolls. The longitudinal stretching is usually performed in a temperature range of 50 to 100 ° C. Further, the ratio of the longitudinal stretching is preferably 2.5 times or more and 4.2 times or less, although it depends on the required characteristics of the film application. When the draw ratio is less than 2.5, the thickness unevenness of the polyester film becomes large and it is difficult to obtain a good film.

  The longitudinally stretched film is successively subjected to the transverse stretching, heat setting, and thermal relaxation treatment steps to form a biaxially stretched film. The transverse stretching is usually performed in a temperature range of 50 to 100 ° C. The transverse stretching ratio is preferably 2.5 times or more and 5.0 times or less, although it depends on the required characteristics of this application. 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 tends to occur during film formation.

  A heat setting treatment is subsequently performed after the transverse stretching, and a preferable temperature range for heat setting is Tg + 70 to Tm-10 ° C. of polyester. The heat setting time is preferably 1 to 60 seconds. Furthermore, for applications that require a low thermal shrinkage rate, heat relaxation treatment may be performed as necessary.

The thickness of the stretched film of the resin film obtained as described above is arbitrary depending on the application, but is usually 5 to 100 μm, preferably 5 to 25 μm. Breaking strength of such a resin film is 5 to 35 kg / mm ² at 5~40kg / ^mm 2, TD direction MD direction, elongation at break from 50 to 350% in MD direction, the TD direction 50-300%. Further, the shrinkage rate when left in a temperature environment of 150 ° C. for 30 minutes is 0.1 to 5%.

[Thin film layer]
The thin film layer 2 is a thin film layer containing at least one of an inorganic substance and an inorganic oxide. By providing the laminated body with a thin film layer on at least one surface of the polyester resin layer 1, gas barrier properties that prevent permeation of oxygen gas, water vapor, and the like can be improved. Note that the laminate may include two or more thin film layers. When two or more thin film layers are provided, each may have the same composition or a different composition.

  As the thin film layer, for example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti) ), Lead (Pb), zirconium (Zr), yttrium (Y), or other inorganic materials or inorganic oxides can be used. In particular, as a material suitable for a package or the like, a silicon oxide or an aluminum metal or aluminum oxide vapor deposition film is preferably used.

  In the present invention, the film thickness of the inorganic material or inorganic oxide thin film layer as described above varies depending on the type of inorganic material or inorganic oxide used, but is, for example, about 50 to 2000 mm, preferably about 100 to 1000 mm. It is desirable to select and form arbitrarily within the range. More specifically, in the case of an aluminum deposited film, a film thickness of about 50 to 600 mm, more preferably about 100 to 450 mm, is desirable, and in the case of an aluminum oxide or silicon oxide deposited film, The film thickness is about 50 to 500 mm, more preferably about 100 to 300 mm.

  As a method for forming the thin film layer 2, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, and an ion plating method, a plasma chemical vapor deposition method, a thermal method, or the like. Examples include chemical vapor deposition and chemical vapor deposition (chemical vapor deposition, CVD) such as photochemical vapor deposition.

  In addition to the polyester resin layer 1 and the thin film layer 2 described above, the laminate according to the present invention includes an anchor coat layer, a barrier coat film, a first sealant layer, a second sealant layer, a support layer, a barrier layer, a paper layer, Other layers such as a printing layer may be provided. These other layers can be laminated together via an adhesive layer by a dry lamination method or via an adhesive resin layer by a melt extrusion lamination method. Hereinafter, each layer will be described.

[Surface modification of polyester resin layer by plasma]
Surface modification by plasma is performed by applying plasma generated in a vacuum environment to the surface of the polyester resin layer 1 using argon, oxygen, nitrogen, carbon dioxide gas, or a mixed gas thereof. it can. By performing the surface modification by the plasma on the polyester resin layer 1, the adhesion between the thin film layer 2 and the polyester resin layer 1 can be improved.

[Anchor coat layer]
The anchor coat layer may be provided between the polyester resin layer 1 and the thin film layer 2. Thereby, the adhesive strength of a polyester resin layer and a thin film layer can be improved, and generation | occurrence | production of the delamination after a hot-water sterilization process can be prevented.

  For such purposes, the anchor coating agent that can be used in the present invention is an anchor coating made of any resin having a heat-resistant temperature of 135 ° C. or higher, such as a vinyl-modified resin, an epoxy resin, a urethane resin, or a polyester resin. In particular, an anchor coating agent composed of a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in the structure and an isocyanate compound as a curing agent can be preferably used. Moreover, a silane coupling agent may be used in combination as an additive, and nitrified cotton may be used in combination in order to improve heat resistance.

  The anchor coat layer is coated with the above-described anchor coat agent by a known coating method such as roll coat, gravure coat, knife coat, dip coat, spray coat, etc., and the solvent, diluent, etc. are removed by drying and cured. Can be formed. The thickness of the anchor coat layer is preferably about 0.2 to 0.3 μm.

[Barrier coat film]
The barrier coat film 3 is preferably provided on the thin film layer 2. Thereby, gas barrier property can be improved further. As such a barrier coat, a composition containing at least one alkoxide represented by the general formula: R ¹ _n M (OR ² ) _m , polyvinyl alcohol and / or ethylene / vinyl alcohol is overlapped by a sol-gel method. A barrier coat composition obtained by condensation can be suitably used. Furthermore, a silane coupling agent can be added.

The alkoxide that can be suitably used for the barrier coat film is represented by the general formula: R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic groups having 1 to 8 carbon atoms, M is a metal atom, n Is an integer of 0 or more, m is an integer of 1 or more, and n + m represents the valence of M), and at least one kind of a partial hydrolyzate of this alkoxide or a hydrolysis condensate of alkoxide is included. Can be used. In addition, as a partial hydrolyzate of said alkoxide, all the alkoxy groups do not need to be hydrolyzed, The thing by which one or more was hydrolyzed, and its mixture may be sufficient. Moreover, the condensate of hydrolysis represents that the partially hydrolyzed alkoxide is a dimer or more, and a 2-6 mer is usually used.

  The barrier coat film 3 can be formed on the thin film layer 2 by applying the above-described barrier coat composition by a conventional method and drying it by a conventional method. As a method of applying the barrier coat film, for example, a coating method such as roll coating such as a gravure coater, spray coating, spin coating, dipping, brush, bar code, applicator, etc. is applied once or multiple times and dried. A barrier coat having a film thickness of 0.01 μm to 30 μm, preferably 0.1 μm to 10 μm can be formed. If necessary, a primer agent or the like can be applied on the thin film layer 2 in advance when the barrier coat film is applied.

  In the present invention, after the thin film layer 2 and the barrier coat film 3 are provided on the polyester resin layer 1, a thin film layer may be further provided, and the barrier coat film may be formed on the thin film layer in the same manner as described above. . Thus, by increasing the number of stacked layers, the gas barrier property can be further improved.

[First sealant layer]
The first sealant layer is the innermost layer side when a package is used. The sealant layer is a layer formed of a heat sealable resin that can be fused to each other by heat. The first sealant layer may contain a fossil fuel-derived resin material or a biomass-derived resin material.

  The resin material for forming the first sealant layer is not particularly limited as long as it is a resin that can be fused to each other by heat. Specifically, for example, low density polyethylene (LDPE), medium density polyethylene (MDPE) ), High-density polyethylene (HDPE), linear (linear) low-density polyethylene (LLDPE), ethylene-α-olefin copolymer polymerized using a metallocene catalyst, ethylene-polypropylene random or block copolymer , Polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene- Methyl methacrylate copolymer (EMMA), ionomer resin, heat sealable ethylene -Vinyl alcohol resin, or copolymerized resin methylpentene resin, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene, polypropylene or cyclic olefin copolymer, polyolefin resin such as acrylic acid, Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, etc. And the like. 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 a coating film thereof.

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

  Commercially available ethylene may be used as biomass-derived ethylene, for example, “C4LL-LL118 (d = 0.916, MFR = 1.0 g / 10 min)” made by Braschem Co. A low density polyethylene resin or a sugarcane-derived low density polyethylene resin of “SBC118 (d = 0.918, MFR = 8.1 g / 10 min)” can be used.

  In the present embodiment, the first sealant layer is a single layer, but two or more first sealant layers may be provided. When two or more first sealant layers are provided, each may have the same composition or a different composition. For example, the sealant layer 2 is composed of three layers in which a first layer, a second layer, and a third layer are laminated in order, and the first layer and the third layer are made of a fossil fuel-derived resin material, The two layers may be a resin material containing a biomass-derived resin material. In addition, when comprising the sealant layer 2 by two or more layers, it can laminate | stack using a coextrusion method.

  As thickness of a 1st sealant layer, 20-200 micrometers is preferable and 30-130 micrometers is more preferable.

  Examples of the method of laminating the first sealant layer on one surface (inner surface side) of the laminate include a dry lamination method and a melt extrusion lamination method. Moreover, when performing said lamination | stacking, pre-treatments, such as a corona treatment, an ozone treatment, a flame treatment, etc., can be given to a film as needed. Among these, the dry lamination method is more preferable because of excellent adhesive strength.

[Second sealant layer]
The second sealant layer is the outermost layer when formed into a package. The second sealant layer is a layer formed of a heat sealable resin that can be fused to each other by heat. The same material as the first sealant layer 3 can be used for the second sealant layer.

[Support layer]
The support layer is not particularly limited as long as it can support the laminate and improve the strength characteristics and impact resistance of the laminate. The support layer may include a fossil fuel-derived resin material or a biomass-derived resin material. Examples of the resin material for forming the support layer 3 include polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyamides such as polypropylene and nylon. The support layer is preferably stretched, and more preferably biaxially stretched. Moreover, a support body layer can use these layers individually or in combination of 2 or more layers.

  As the polyester that can be used as a material constituting the support layer, a biomass-derived polyester can be used in addition to a conventionally known fossil fuel-derived polyester. Further, the polyester may be a mixture of a resin material containing a conventional raw material derived from fossil fuel and a resin material containing a raw material derived from biomass.

  In order to improve the adhesion between the support layer and the first sealant layer, a layer made of a modified polyolefin resin made of a modified polyolefin may be provided between the support layer and the first sealant layer. . The modified polyolefin is modified by a method such as replacing a part of the main component polyolefin with another substance (monomer) by copolymerization or cocondensation, or reacting an appropriate substance (monomer) locally. Polyolefin resin. Specifically, for example, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), ethylene polymerized using a metallocene catalyst -Α-olefin copolymer, polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ionomer resin, ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), Polyolefin resins such as ethylene-methacrylic acid copolymer (EMAA), ethylene-propylene copolymer, methylpentene polymer, polyethylene, polyethylene resin, or polypropylene resin, acrylic acid, methacrylic acid, maleic anhydride, Modified with fumaric acid or other unsaturated carboxylic acid Acid-modified polyolefin-based resin and the like. In addition, it cannot be overemphasized that what uses the above-mentioned ethylene derived from biomass as a monomer unit can be used as above-mentioned polyethylene-type resin.

  A preferable modified polyolefin is a copolymer having a structure in which a polyolefin segment and a segment having a polarity other than olefin are bonded in a block shape and / or a graft shape and / or a random shape, such as a propylene-based polyolefin segment. A copolymer of ethylene and a segment containing lactic acid as a constituent component, a copolymer of an ethylene-based polyolefin segment and a segment containing an acrylic acid unit as a constituent component, a propylene-based polyolefin segment and a segment containing an acrylic acid unit as a constituent component A copolymer etc. are mentioned. Specifically, for example, ADMER SE800, SF740, SF731, and SF730 manufactured by Mitsui Chemicals, Inc. can be used as the maleic anhydride-modified polyolefin resin.

  Moreover, polylactic acid may be used as a biomass-derived resin material constituting the support layer, and for example, a polylactic acid film sold by Mitsui Chemicals, Inc., Cerro Toro may be suitably used.

  The thickness of the support layer is, for example, 5 to 100 μm, and may be appropriately adjusted depending on the use application of the laminate. For example, when the laminate is used as a packaging material for applications requiring rigidity, the support is used. The thickness of the layer may be increased.

  Moreover, a support body layer turns into a layer which consists of carbon neutral resin by forming a support body layer using the resin material containing the raw material derived from biomass. For this reason, by using together with the polyester resin layer 1, the usage-amount of a fossil fuel can be reduced further and an environmental load can be reduced.

  The support layer can be produced using, for example, an inflation method or a T-die method.

[Paper layer]
As the paper layer, any paper can be used depending on the desired rigidity, for example, high-quality paper, imitation paper, art paper, coated paper, pure white roll paper, kraft paper, label paper with improved water resistance Well-known paper such as paperboard such as cup base paper, card paper, ivory paper, and Manila ball, milk carton base paper, cup base paper, synthetic paper, and clay coat paper can be used.

  Before laminating other layers on the paper layer, the surface of the paper layer may be subjected to corona discharge treatment, flame treatment or the like. By performing these treatments, the adhesive strength between the layers can be improved. The corona discharge treatment can be performed by using a known corona discharge treatment device and passing the paper substrate through the generated corona atmosphere. The frame processing can be performed by using a known frame processing device and burning the surface of the paper substrate with fire.

The basis weight of the paper layer 1 is about 80 to 600 g / m ² , preferably about 150 to 450 g / m ² .

[Print layer]
A printing layer can be provided as needed, for example, can be provided in the surface by the side of the thin film layer 2 of the polyester resin layer 1, or the outer surface of a paper layer. The print layer can be any desired printed pattern such as characters, pictures, figures, symbols, patterns, etc. for decoration, content display, best-of-life display, manufacturer, seller display, etc. It is a layer which forms. The printing layer may be provided on the entire surface or may be provided on a part.

[Adhesive layer]
The adhesive layer provided when two layers are bonded by the dry lamination method can be formed by applying an adhesive layer on the surface of the layer to be laminated and drying it. Examples of the adhesive include one-part or two-part cured or non-cured vinyl, (meth) acrylic, polyamide, polyester, polyether, polyurethane, epoxy, rubber, etc. An adhesive such as a solvent type, an aqueous type, or an emulsion type can be used. Examples of the coating method for the laminating adhesive include a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a fountain method, a transfer roll coating method, and other methods to form a laminate. It can apply | coat to the application surface of a layer. The coating ^{amount, 0.1g / m 2 ~10g / m} 2 ( dry) are ^{preferred, 1g / m 2 ~5g / m} 2 ( dry) is more preferable.

  The adhesive layer provided when two layers are bonded by the melt extrusion lamination method is formed by the melt extrusion lamination method using an adhesive resin layer that is a thermoplastic resin. Examples of the thermoplastic resin that can be used for the adhesive resin layer include a polyethylene resin, a polypropylene resin, or a cyclic polyolefin resin, or a copolymer resin, a modified resin, or a mixture (including an alloy) containing these resins as a main component. ) Can be used. Examples of polyolefin resins include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene (PP), and metallocene catalysts. Ethylene-α / olefin copolymer, ethylene / polypropylene random or block copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene / maleic acid copolymer, ionomer resin, and interlayer adhesion In order to improve the , It can be used acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and an acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as itaconic acid. Further, a resin obtained by graft polymerization or copolymerization of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or an ester monomer can be used as the polyolefin resin. These materials can be used alone or in combination of two or more. As the cyclic polyolefin-based resin, for example, cyclic polyolefins such as ethylene-propylene copolymer, polymethylpentene, polybutene, and polynorbornene can be used. These resins can be used alone or in combination. In addition, it cannot be overemphasized that what uses the above-mentioned ethylene derived from biomass as a monomer unit can be used as above-mentioned polyethylene-type resin. For example, in a laminate in which a paper layer, an adhesive resin layer, a thin film layer 2, a polyester resin layer 1, and a first sealant layer are sequentially laminated, when the thin film layer 2 contains a metal, the adhesive resin layer is made of ethylene-methacrylic acid copolymer. By using a polymer (EMAA), the adhesion between the paper layer and the thin film layer 2 can be improved.

  The thickness of the adhesive resin layer can be appropriately set within a range of usually 5 to 800 μm, preferably 10 to 500 μm. If the thickness is less than this range, the moisture barrier property is insufficient, and if it is more than this range, the quality becomes excessive and the moldability also deteriorates. When the adhesive layer is laminated on the surface of the polyester resin layer by melt extrusion laminating using a polyolefin resin having a polar group such as the acid-modified polyolefin resin as described above, an anchor coat is used. The adhesive layer can be laminated without performing a surface treatment such as an agent.

  As described above, the laminate according to the present invention includes the polyester resin layer 1 and the thin film layer 2, and the polyester resin layer 1 is formed of a layer made of a carbon neutral material and contains isophthalic acid. Yes. For this reason, the usage-amount of a fossil fuel can be reduced significantly and an environmental load can be reduced. Moreover, it is more flexible than conventional biopolyesters containing only terephthalic acid. Therefore, the generation of cracks can be suppressed in the specification of the reference example described later.

[Usage]
The laminated body by this invention can be used conveniently for uses, such as a packaging bag, a paper container, a paper cup, various label materials, a cover material, a sheet molded product, a laminate tube. As packaging bags, for example, standing pouch type, side seal type, two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, joint-attached seal type (pillow seal type), pleated seal type, flat bottom seal type And various forms such as a square bottom seal type and a gusset type. The thickness of the laminated body in that case can be suitably determined according to the application, and is used in the form of a film having a thickness of 30 to 300 μm, preferably 35 to 180 μm, for example.

[Packaging bag]
The case where the laminated body by this invention is applied to a standing pouch is demonstrated. FIG. 3 is a diagram schematically illustrating an example of a configuration of a standing pouch. As shown in FIG. 3, the standing pouch 20 includes two body parts (side sheet) 21 and a bottom part (bottom sheet) 22. The standing pouch 20 includes a side sheet 21 and a bottom sheet 22 made of the same member. For example, as shown in FIG. 4, the side sheet 21 and the bottom sheet 22 of the standing pouch 20 are formed using a laminated body 10 </ b> A in which a polyester resin layer 1, a thin film layer 2, and a first sealant layer 4 are sequentially laminated. be able to. In the present embodiment, the standing pouch 20 includes the side sheet 21 and the bottom sheet 22 made of the same member, but is not limited thereto, and the side sheet 21 and the bottom sheet 22 are separate members. It may be comprised.

[Tube container]
Next, the case where a tube container is formed using the laminated body by this invention is demonstrated. FIG. 5 is a partial cross-sectional view schematically showing an example of a tube container. As shown in FIG. 5, the tube container 30 includes a head portion 31 and a cylindrical body portion 32. The head portion 31 includes a hollow conical shoulder portion 33 and a spout portion 34 and is integrally formed.

  The cylindrical body portion 32 is connected to the shoulder portion 33 of the head portion 31. The cylindrical trunk | drum 32 can be formed using the laminated body 10B. FIG. 6 shows a partial cross-sectional view of the laminate 10B that forms the cylindrical body of the tube container. As shown in FIG. 6, the laminated body 10 </ b> B forming the cylindrical body portion 32 is obtained by sequentially laminating the second sealant layer 5, the polyester resin layer 1, the thin film layer 2, and the first sealant layer 4. . The first sealant layer 4 is an innermost layer when a tube container is used, and the second sealant layer 5 is an outermost layer when a tube container is used.

[Paper container]
The case where a paper container is formed using the laminated body by this invention is demonstrated. For example, as shown in FIG. 7, the paper container uses a laminate 10C in which a second sealant layer 5, a paper layer 6, a thin film layer 2, a polyester resin layer 1, and a first sealant layer 4 are laminated in this order. Can be formed. The first sealant layer 4 is an innermost layer when a paper container is used, and the second sealant layer 5 is an outermost layer when a paper container is used. As shown in FIG. 8, the paper container 40 has a rectangular tubular body 41 including a side surface, a square plate-shaped bottom part 42, and an upper part 43, and is a so-called gobber top type container. .

  The upper portion 43 includes a pair of opposed inclined plates 44 and a pair of folding portions 45 that are positioned between the inclined plates 44 and are folded between the inclined plates 44. The pair of inclined plates 44 are bonded to each other by a margin 46 provided at each upper end. In addition, a spout may be attached to one inclined plate 44 of the pair of inclined plates 44, and the spout may be sealed with a cap. The paper container 40 can be used as a liquid paper container, for example. Moreover, you may form a flat top type container using the laminated body 10C.

[Paper cup]
The case where a paper cup is formed using the laminated body by this invention is demonstrated. For example, as shown in FIG. 9, the paper cup can be formed using a laminate 10D in which a paper layer 6, a thin film layer 2, a polyester resin layer 1, and a first sealant layer 4 are sequentially laminated. FIG. 10 is a perspective view in which a part of the paper cup is cut away. As shown in FIG. 10, the paper cup 50 has a flange portion 51 at the top and is provided at a cylindrical barrel portion 52 that gradually increases in diameter toward the opening, and a lower end (one end) of the barrel portion 52. The bottom part 53 is provided. The body portion 52 is provided with a flange portion 51 whose upper end is rounded outward. The paper cup 50 is sealed by attaching a lid (not shown) along the flange portion 51 of the trunk portion 52 after storing the contents. The lid member preferably has gas barrier properties.

  Further, the paper cup 50 may include an exterior body 54 on the outer periphery of the body portion 52 as shown in FIG. As the exterior body 54, for example, paper can be used. A convex portion 55 is formed on the body portion 52. The convex portion 55 is formed to provide an air layer gap 56 between the body portion 52 and the exterior body 54. One or more convex portions 55 are provided in the horizontal direction. For example, two convex portions 55 can be provided as shown in FIG.

[Evaluation of flexibility]
Here, the result of having evaluated the softness | flexibility using the laminated body provided with the polyester resin 1 is shown.

<Reference Example 1>
<Preparation of laminated body 1>
Fossil fuel-derived terephthalic acid, fossil fuel-derived isophthalic acid, biomass-derived ethylene glycol (biomass polyester), fossil fuel-derived terephthalic acid and fossil fuel-derived ethylene glycol (fossil fuel polyester) A biaxially stretched polyester film 1 having a thickness of 12 μm was prepared. Polyester film 1 had a biomass carbon content of 20% as measured by radioactive carbon (C14). Further, the content of isophthalic acid is 2.0 mol% with respect to all dicarboxylic acid units constituting the biomass polyester, and the content of isophthalic acid in the polyester film 1 is the total dicarboxylic acid constituting the polyester film 1. It was 1.33 mol% with respect to the unit.

One side of the polyester film 1 was subjected to corona treatment, and a printed layer (pattern) was formed on the corona-treated surface. Next, using the sand laminating method, the printing surface of the polyester film 1 and the aluminum foil (thickness 7 μm) are passed through low-density polyethylene (density 0.920 g / m ³ , thickness 15 μm) derived from fossil fuel. And pasted. Furthermore, using a sand laminate method, the aluminum foil and a low-density polyethylene film derived from fossil fuel (density 0.920 g / m ³ , thickness 40 μm) are combined with a low-density polyethylene derived from fossil fuel (density 0.920 g). / M ³ and a thickness of 15 μm) to obtain a laminate 1 in which a polyester film 1, a printing layer, a low density polyethylene, an aluminum foil, a low density polyethylene, and a low density polyethylene film are laminated in this order.

<Reference Example 2>
<Preparation of laminated body 2>
Biaxially formed with fossil fuel-derived terephthalic acid and biomass-derived ethylene glycol (biomass polyester), fossil fuel-derived terephthalic acid and fossil fuel-derived ethylene glycol (fossil fuel polyester) with a thickness of 12 μm A stretched polyester film 2 was prepared. Polyester film 2 had a biomass carbon content of 20% as measured by radioactive carbon (C14).

  A polyester film 1, a printed layer, a low density polyethylene, an aluminum foil, a low density polyethylene, and a low density polyethylene film are prepared in the same manner as in Reference Example 1 except that the polyester film 2 is used instead of the polyester film 1. The laminated body 2 laminated | stacked in order was obtained.

<Flexibility evaluation>
Using the laminates 1 and 2, the flexibility (loop stiffness) of the polyester films 1 and 2 was evaluated. The evaluation results are shown in Table 1. Here, MD direction points the conveyance direction of a biomass polyester film, and TD direction points out the direction orthogonal to MD direction. Flexibility was evaluated as follows. First, a sample was cut into a width of 15 mm and a length of 165 mm to obtain test pieces, respectively. And the waist strength value (mN / 15mm) of each laminated body was measured for this test piece using a loop stiffness tester (made by Tester Sangyo Co., Ltd.) with a loop length of 60 mm.

This result shows that the polyester film 1 is softer. From this result, it can be expected that the polyester film 1 is less likely to crack in the thin film layer than the polyester film 2.

[Evaluation of cracks]
Next, the result of having evaluated the generation | occurrence | production of a crack using the laminated body provided with the polyester resin 1 is shown.

<Reference Example 3>
<Preparation of laminate 3>
First, one surface of the polyester film 1 and a low-density polyethylene film derived from fossil fuel (density 0.920 g / m ³ , thickness 40 μm) are combined with a low-density polyethylene derived from fossil fuel using a sand lamination method. (Density 0.920 g / m ³ , thickness 15 μm). Next, the other surface of the polyester film 1 and an aluminum foil (thickness 7 μm) were bonded using a dry laminating method. Further, low-density polyethylene (density 0.920 g / m ³ , thickness 20 μm) derived from fossil fuel was laminated on one surface of paper (basis weight 400 g / m ² ) using an extrusion laminating method. Finally, the aluminum foil and the other surface of the paper (basis weight 400 g / m ² ) are bonded via fossil fuel-derived ethylene methacrylate (EMAA, thickness 20 μm) using a sand laminating method. Thus, a laminate 3 was obtained in which low-density polyethylene, paper, ethylene methacrylate, aluminum foil, polyester film 1, low-density polyethylene, and low-density polyethylene film were laminated in this order.

<Reference Example 4>
<Preparation of laminate 4>
A low density polyethylene, paper, ethylene methacrylate, aluminum foil, polyester film 2, low density polyethylene, low density polyethylene were prepared in the same manner as in Reference Example 3 except that the polyester film 2 was used instead of the polyester film 1. The laminated body 4 by which the film was laminated | stacked in order was obtained.

<Evaluation of crack>
By pressing with a male mold and a female mold, the laminated body 3 and the laminated body 4 were subjected to ruled line processing and punched into a blank for a paper container. Then, while accommodating an alcohol solution and making a blank in the paper container shown in FIG. 8 so that the surface of the low density polyethylene film becomes the inner surface, corrosion of the aluminum foil after one week was visually observed. In the laminate 3, corrosion of the aluminum foil was not observed. On the other hand, in the laminate 4 using the polyester film 2, corrosion of the aluminum foil was observed. This shows that as a result of cracks occurring in the polyester film 4 due to ruled line processing, the alcohol solution passed through the polyester film 4 and reached the aluminum foil from the surface of the low density polyethylene film. Also from this result, it can be expected that the polyester film 1 is less susceptible to cracking in the thin film layer than the polyester film 2.

<Example 1>
<Preparation of laminated body 5>
Fossil fuel-derived terephthalic acid, fossil fuel-derived isophthalic acid, biomass-derived ethylene glycol (biomass polyester), fossil fuel-derived terephthalic acid and fossil fuel-derived ethylene glycol (fossil fuel polyester) A biaxially stretched polyester film 1 having a thickness of 12 μm was prepared. Polyester film 1 had a biomass carbon content of 20% as measured by radioactive carbon (C14). Further, the content of isophthalic acid is 2.0 mol% with respect to all dicarboxylic acid units constituting the biomass polyester, and the content of isophthalic acid in the polyester film 1 is the total dicarboxylic acid constituting the polyester film 1. It was 1.33 mol% with respect to the unit.

The polyester film 1 was coated with an anchor coating agent and dried to form a 0.3 μm anchor coating layer. The anchor coating agent is composed of a main agent obtained by mixing and stirring 1 part by weight of nitrified cotton and 5 parts by weight of acrylic polyol in a dilute solvent of methyl ethyl ketone (MEK) / ethyl acetate 1: 1, and isophorone diisocyanate (IPDI). Here, the NCO group was prepared in an equivalent amount with respect to the OH group of the main agent. Next, after aging at 40 ° C. for 48 hours, an aluminum oxide thin film layer having a thickness of 200 mm was laminated by a vacuum vapor deposition method using an electron beam (EB) heating method under the following vapor deposition conditions. The cooling drum temperature at this time was −15 ° C.
(Deposition conditions)
・ Degree of vacuum in the deposition chamber: 2 × 10 ⁻⁴ mbar
・ Vacuum degree in the winding chamber: 2 × 10 ⁻² mbar
・ Electron beam power: 25 kW
Film transport speed: 480 m / min
・ Vapor deposition surface: Corona treatment

And the composition for barrier coat formation which has the following compositions was apply | coated by the gravure roll coat method on the formed vapor deposition film, then, heat-processed at 180 degreeC for 60 second, and thickness 0.3micrometer (dry) State) was formed, and a laminate 5 was obtained in which the polyester film 1, the thin film layer of aluminum oxide, and the barrier coat film were laminated in this order.

(Preparation method)
To the prepared mixture of polyvinyl alcohol of composition a, isopropyl alcohol and ion-exchanged water, add a hydrolyzed solution of ethyl silicate, silane coupling agent, hydrochloric acid, isopropyl alcohol and ion-exchanged water of composition b prepared in advance. And stirred to obtain a colorless and transparent composition for forming a barrier coat.

<Evaluation of barrier properties>
Using the laminate 5, the barrier property was evaluated as follows. The evaluation results are shown in Table 2. Each measurement was performed at four points of samples 1 to 4.
(Measurement of water vapor permeability)
Under conditions of a temperature of 40 ° C. and a humidity of 90% RH, the water vapor transmission rate was measured using a water vapor transmission meter (manufactured by PERMATRAN, MOCON). In addition, the case where water vapor permeability was 2.0 or less was evaluated as favorable.
(Measurement of oxygen permeability)
Under conditions of a temperature of 23 ° C. and a humidity of 90% RH, the oxygen permeability was measured using an oxygen permeability meter (manufactured by OX-TRAN, manufactured by MOCON). In addition, the case where oxygen permeability was 1.0 or less was evaluated as favorable.

<Example 2>
<Preparation of laminate 6>
Fossil fuel-derived low density polyethylene (density 0.920 g / m ³ , thickness 40 μm) is extruded at 320 ° C. on the surface of the laminate 5 on which the barrier coat film is provided to form a sealant layer, A laminate 6 was obtained in which a polyester film 1, an aluminum oxide thin film layer, a barrier coat film, and low-density polyethylene were laminated in this order. And the standing pouch shown in FIG. 3 was produced using the laminated body 6 as the side surface sheet 21 and the bottom sheet 22.

<Example 3>
<Preparation of laminate 7>
Instead of fossil fuel-derived low density polyethylene (density 0.920 g / m ³ , thickness 40 μm), biomass-derived low density polyethylene (Brasschem, SBC118, density 0.918 g / m ³ , thickness 40 μm) is used. Except for the above, it was produced in the same manner as in Example 2 to obtain a laminate 7 in which a polyester film 1, an aluminum oxide thin film layer, a barrier coat film, and a low-density polyethylene were laminated in this order. And the standing pouch shown in FIG. 3 was produced using the laminated body 7 as the side surface sheet 21 and the bottom sheet 22.

<Example 4>
<Preparation of laminated body 8>
Using a dry laminating method, the surface of the laminate 5 on which the barrier coat film is provided and a linear low-density polyethylene film (density 0.916 g / m ³ , thickness 130 μm) derived from fossil fuel are pasted. Combined. Next, using a dry laminating method, the side of the laminate that is not provided with the barrier coat film and a linear low density polyethylene film derived from fossil fuel (density 0.916 g / m ³ , thickness 130 μm) Were laminated to obtain a laminate 8 in which a linear low density polyethylene film, a barrier coat film, a thin film layer of aluminum oxide, a polyester film 1 and a linear low density polyethylene film were laminated in this order. And the tube container shown in FIG. 5 was produced using the laminated body 8 as the cylindrical trunk | drum 32 so that the linear low density polyethylene film adjacent to the polyester film 1 might become an inner surface.

<Example 5>
<Preparation of laminated body 9>
Instead of the linear low-density polyethylene film (density 0.916 g / m ³ , thickness 130 μm) derived from fossil fuel adjacent to the polyester film 1, the biomass-derived linear low-density polyethylene (Brasschem, SLL118, density) A linear low density polyethylene film, a barrier coat film, a thin film layer of aluminum oxide, a polyester film 1 and a straight film were prepared in the same manner as in Example 4 except that 0.916 g / m ³ and a thickness of 130 μm were used. A laminate 9 was obtained in which chain-like low density polyethylene films were sequentially laminated. And the tube container shown in FIG. 5 was produced using the laminated body 9 as the cylindrical trunk | drum 32 so that the linear low density polyethylene film adjacent to the polyester film 1 might become an inner surface.

<Example 6>
<Preparation of Laminate 10>
Using a sand laminating method, a fossil fuel-derived low-density polyethylene film (density 0.920 g / m ³ , thickness 40 μm) on the side of the laminate 5 on which the barrier coat film is not provided, Bonding was performed via low density polyethylene derived from fuel (density 0.920 g / m ³ , thickness 15 μm). Further, low-density polyethylene (density 0.920 g / m ³ , thickness 20 μm) derived from fossil fuel was laminated on one surface of paper (basis weight 400 g / m ² ) using an extrusion laminating method. Finally, by using a sand laminating method, the surface of the laminate 5 on which the barrier coat film is provided and the other surface of the paper (basis weight 400 g / m ² ) are combined with a low-density polyethylene derived from fossil fuel ( Low density polyethylene, paper, low density polyethylene, barrier coat film, thin film layer of aluminum oxide, polyester film 1, low density polyethylene, low density, with a density of 0.920 g / m ³ and a thickness of 15 μm) A laminate 10 in which polyethylene films were laminated in order was obtained. Then, the laminated body 10 is subjected to ruled line processing by pressing with a male mold and a female mold, and after punching into a blank for a paper container, the surface of the low density polyethylene film becomes the inner surface, as shown in FIG. A paper container was made.

<Example 7>
<Preparation of Laminate 11>
Instead of fossil fuel-derived low-density polyethylene film (density 0.920 g / m ³ , thickness 40 μm), biomass-derived low-density polyethylene (Brasschem, SBC118, density 0.918 g / m ³ , thickness 40 μm) Except that it was used, it was produced in the same manner as in Example 6, and low density polyethylene, paper, low density polyethylene, barrier coat film, aluminum oxide thin film layer, polyester film 1, low density polyethylene, and low density polyethylene film were laminated in this order. Thus obtained laminate 11 was obtained. Then, the laminate 11 is subjected to ruled line processing by pressing with a male mold and a female mold, and after punching into a blank for a paper container, the surface of the low-density polyethylene film becomes the inner surface, as shown in FIG. A paper container was made.

<Example 8>
<Preparation of laminated body 12>
Fossil fuel-derived low-density polyethylene (density 0.920 g / m ³ , thickness 40 μm) was laminated on the surface of the laminate 5 on which the barrier coat film was not provided, using an extrusion lamination method. Next, using a sand laminating method, paper (basis weight 270 g / m ² ) and the surface on the side of the laminate 5 on which the barrier coat film is provided are made of low-density polyethylene (density 0. 0) derived from fossil fuel. 920 g / m ³ , thickness 15 μm) to obtain a laminate 12 in which paper, low-density polyethylene, barrier coat film, aluminum oxide thin film layer, polyester film 1 and low-density polyethylene are laminated in this order. It was. Moreover, the printing layer was formed in paper (basis weight 250g / m < ² >). And after forming the trunk | drum 52 and the bottom part 53 using the laminated body 12, the paper cup shown in FIG. 11 is wound by winding the paper which provided the printing layer in the outer periphery of the trunk | drum 52 so that a printing layer may become an outer side. Produced.

<Example 9>
<Preparation of Laminate 13>
Instead of low density polyethylene (density 0.920 g / m ³ , thickness 40 μm) derived from fossil fuel in the innermost layer, low density polyethylene derived from biomass (BBCchem, SBC118, density 0.918 g / m ³ , thickness 40 μm) ) Was used in the same manner as in Example 8 to obtain a laminate 13 in which paper, low density polyethylene, barrier coat film, thin film layer of aluminum oxide, polyester film 1, and low density polyethylene were laminated in this order. It was. Moreover, the printing layer was formed in paper (basis weight 250g / m < ² >). And after forming the trunk | drum 52 and the bottom part 53 using the laminated body 13, the paper cup shown in FIG. 11 is wound by winding the paper which provided the printing layer in the outer periphery of the trunk | drum 52 so that a printing layer may become an outer side. Produced.

DESCRIPTION OF SYMBOLS 1 Polyester resin layer 2 Thin film layer 3 Barrier coat film 4 1st sealant layer 5 2nd sealant layer 6 Paper layer 10, 10A, 10B, 10C, 10D Laminate 20 Standing pouch 30 Tube container 40 Liquid paper container 50 Paper cup

Claims (6)

A laminate in which at least a polyester resin layer and a thin film layer containing at least one of an inorganic substance and an inorganic oxide are laminated,
The polyester resin layer comprises biomass polyester resin having ethylene glycol derived from biomass as a diol unit and dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit,
A laminate comprising the dicarboxylic acid containing terephthalic acid and isophthalic acid.   The laminate according to claim 1, wherein at least the polyester resin layer, the thin film layer, and the barrier coat film are sequentially laminated.   The laminate according to claim 1, wherein the polyester resin layer including the thin film layer on at least one of the surfaces and the first sealant layer are laminated.   Furthermore, the laminated body as described in any one of Claims 1-3 with which the paper layer was laminated | stacked.   The laminate according to claim 1, wherein at least the second sealant layer, the paper layer, the polyester resin layer including the thin film layer on one surface, and the first sealant layer are sequentially laminated.   The first and / or second sealant layer includes a resin material derived from fossil fuel or biomass, and the resin material includes a resin selected from the group consisting of polyethylene, polypropylene, and polylactic acid. Item 6. The laminate according to any one of Items 3 to 5.

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