JP2018001611A - Laminate equipped with polyester resin layer and packing product equipped with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate equipped with a polyester resin layer including a polyester derived from a conventional fossil fuel and a laminate equipped with a polyester resin layer including a biomass polyester by no means inferior with regard to physical properties such as mechanical characteristics.SOLUTION: A laminate at least includes a first thermoplastic resin layer, a paper substrate layer, a polyester resin layer and a second thermoplastic resin layer in this order. The polyester resin layer includes a biomass polyester having ethylene glycol derived from biomass as a diol unit and a dicarboxylic acid derived from a fossil fuel as a dicarboxylic acid unit. A biomass degree in the polyester resin layer is 5% or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate including a polyester resin layer containing biomass polyester, and more specifically, at least a paper base layer and biomass-derived ethylene glycol as diol units, and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid. The present invention relates to a laminate including a polyester resin layer containing biomass polyester as a unit and a thermoplastic resin layer. Furthermore, the present invention relates to a packaged product and a liquid paper container provided with the laminate.

  Polyesters are widely used in various industrial applications 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 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, with the growing demand for the establishment of a recycling-oriented society, the use of biomass has been attracting attention in the materials field, as it is desired to move away from fossil fuels as well as energy. Biomass is an organic compound photo-synthesized from carbon dioxide and water, and by using it, it is so-called carbon neutral renewable energy that becomes carbon dioxide and water again. In recent years, biomass plastics using these biomass as raw materials have been rapidly put into practical use, and attempts have been made to produce polyester, which is a general-purpose polymer material, from these biomass raw materials.

  For example, as a polyester using a biomass material, a polyester composed of isosorbide, terephthalic acid and ethylene glycol, which is one of biomass materials, has been proposed (Patent Document 1).

  Biomass ethanol obtained by fermenting starch and saccharides obtained from plants such as corn and sugarcane with microorganisms has been put into practical use, and ethylene glycol is industrially produced from this biomass ethanol via ethylene. Has also succeeded.

Special table 2002-512304 gazette

  The present inventors paid attention to ethylene glycol which is a raw material of polyester, and instead of ethylene glycol obtained from a conventional fossil fuel, biomass polyester (hereinafter simply referred to as “biomass polyester”) using ethylene glycol derived from biomass as its raw material. The laminate including a polyester resin layer containing a polyester resin layer (which may be referred to as “a”) is made of a polyester manufactured using ethylene glycol obtained from a conventional fossil fuel (hereinafter, sometimes simply referred to as “polyester derived from fossil fuel”). The present inventors have found that a laminate having a polyester resin layer and a product that is inferior in physical properties such as mechanical properties can be obtained. The present invention is based on this finding.

  Accordingly, an object of the present invention is to provide a laminate comprising a polyester resin layer comprising a polyester resin layer comprising biomass polyester, which is inferior in terms of physical properties such as mechanical properties and a laminate comprising a conventional polyester resin layer made of polyester derived from fossil fuel. That is.

In an embodiment of the present invention,
At least a laminate comprising a first thermoplastic resin layer, a paper base material layer, a polyester resin layer, and a second thermoplastic resin layer in this order,
The polyester resin layer includes biomass polyester having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit,
There is provided a laminate in which the degree of biomass in the polyester resin layer is 5% or more.

  In the embodiment of the present invention, the dicarboxylic acid is preferably terephthalic acid.

  In the embodiment of the present invention, the first or second thermoplastic resin layer is selected from the group consisting of low density polyethylene, linear low density polyethylene, medium density polyethylene, and ethylene-methacrylic acid copolymer. It is preferable to include a resin material.

  In another aspect of the present invention, a packaged product comprising the laminate is provided.

In another aspect of the present invention, a liquid paper container comprising the laminate,
A liquid paper container is provided in which the innermost layer of the liquid paper container is the second thermoplastic resin layer.

  The laminate according to the present invention includes at least a paper base material layer, a polyester resin layer containing biomass polyester, and a thermoplastic resin layer, so that the amount of fossil fuel used can be reduced compared to the conventional one. Environmental load can be reduced. In addition, the laminate according to the present invention is not inferior in terms of physical properties such as mechanical properties as compared with a laminate including a conventional fossil fuel-derived polyester resin layer, and thus a laminate including a conventional fossil fuel-derived polyester resin layer. The body can be replaced.

It is a schematic cross section which shows an example of the laminated body by this invention. It is a schematic cross section which shows an example of the laminated body by this invention. It is a schematic cross section which shows an example of the laminated body by this invention. It is a perspective view which shows an example of a liquid paper container.

  In the present invention, “biomass polyester” and “polyester resin layer containing biomass polyester” are those using at least a part of biomass-derived raw materials as raw materials, and all of the raw materials are derived from biomass. Does not mean.

<Laminated body>
The laminate according to the present invention comprises a first thermoplastic resin layer, a paper base material layer, a polyester resin layer containing biomass polyester, and a second thermoplastic resin layer in this order. When a liquid paper container is manufactured using a laminate, the layer of the laminate located outside the liquid paper container is the first thermoplastic resin layer, and the layer of the laminate located inside the liquid paper container is the first layer. No. 2 thermoplastic resin layer. Since the laminate includes a polyester resin layer containing biomass polyester, the amount of fossil fuel used can be reduced as compared with the conventional one, and the environmental load can be reduced. In addition, the laminate according to the present invention has a polyester resin layer derived from a conventional fossil fuel because it is not inferior in terms of physical properties such as mechanical properties as compared with a laminate including a polyester resin layer derived from a conventional fossil fuel. Laminates can be substituted.

  In addition to the above layers, the laminate according to the present invention may further include at least one other layer such as a printing layer, a barrier layer, a plastic film, and an adhesive layer. When two or more other layers are included, each may have the same composition or a different composition.

The laminate according to the present invention will be described with reference to the drawings. Examples of schematic cross-sectional views of the laminate according to the present invention are shown in FIGS.
A laminate 10 shown in FIG. 1 includes a first thermoplastic resin layer 11, a paper base layer 12, a polyester resin layer 13, and a second thermoplastic resin layer 14. In the case of a liquid paper container provided with the laminate 10, the first thermoplastic resin layer 11 is located outside the liquid paper container, and the second thermoplastic resin layer 14 is located inside the liquid paper container.
The laminate 20 shown in FIG. 2 includes a first thermoplastic resin layer 11, a paper base layer 12, an adhesive layer 15, a polyester resin layer 13, an adhesive layer 15, and a second thermoplastic resin layer. 14 in this order. In the case of a liquid paper container including the laminate 20, the first thermoplastic resin layer 11 is located outside the liquid paper container, and the second thermoplastic resin layer 14 is located inside the liquid paper container.
The laminate 30 shown in FIG. 3 includes a first thermoplastic resin layer 11, a paper base material layer 12, an adhesive layer 15, a barrier layer 16, a polyester resin layer 13, an adhesive layer 15, and a second layer. The thermoplastic resin layer 14 is provided in this order. In the case of a liquid paper container including the laminate 30, the first thermoplastic resin layer 11 is located outside the liquid paper container, and the second thermoplastic resin layer 14 is located inside the liquid paper container.
In any laminate, a printed layer or a thermoplastic resin layer may be further laminated.
Hereinafter, each layer which comprises a laminated body is demonstrated.

(Paper base material layer)
In the present invention, the paper base material layer functions as a base material layer for holding the polyester resin layer, and is preferably one capable of imparting strength as a packaged product to the laminate. The paper used as the paper base layer has a basis weight of 100 g / m ² or more and 700 g / m ² or less, preferably 150 g / m ² or more and 600 g / m ² or less, more preferably 200 g / m ² or more and 500 g / m ² or less. I have it. As the paper base layer, white paperboard in general is targeted, but ivory paper using natural pulp, milk carton base paper, cup base paper and the like are particularly preferable from the viewpoint of safety.

  Further, the paperboard used in the present invention may use neutral rosin, alkyl ketene dimer, alkenyl succinic anhydride as a sizing agent, and use cationic polyacrylamide or cationic starch as a fixing agent. Also good. It is also possible to make paper in a neutral region of pH 6 or more and pH 9 or less using a sulfuric acid band. In addition to the above sizing agents, as well as fixing agents, various papermaking fillers, yield improvers, dry paper strength enhancers, wet paper strength enhancers, binders, dispersants, flocculants, plastics An agent and an adhesive may be appropriately contained.

(Polyester resin layer)
In the present invention, the polyester resin layer contains biomass polyester having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. The polyester resin layer may further include a fossil fuel-derived polyester having a fossil fuel-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. The following biomass degree should just be implement | achieved as the whole polyester resin layer. In the present invention, since the polyester resin layer contains biomass polyester, it is possible to reduce the amount of polyester derived from fossil fuel and to reduce the environmental load compared to the conventional case.

In the present invention, “biomass degree” (biomass-derived carbon concentration) in the polyester resin layer is a value obtained by measuring the content of carbon derived from biomass by measurement of radioactive carbon (C14). Since carbon dioxide in the atmosphere contains C14 at a constant ratio (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 the carbon atoms in the polyester. In the present invention, in the case where the content of C14 in the polyester was P _C14, the content P _{bio Bio} carbon from biomass, can be obtained as follows.
P _bio (%) = P _C14 /105.5×100

Taking polyethylene terephthalate as an example, polyethylene terephthalate is a polymer obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1: 1. Is used, the content P _bio of carbon derived from biomass in the polyester is 20%. In the present invention, the content of biomass-derived carbon by radiocarbon (C14) measurement is preferably 10% or more and 20% or less, and preferably 10% or more and 19% or less, based on the total carbon in the biomass polyester. There may be. When the content of carbon derived from biomass in the biomass polyester is 10% or more, it is suitable as a carbon offset material. In addition, the biomass-derived carbon content in the fossil fuel-derived polyester produced using fossil fuel-derived ethylene glycol and the fossil fuel-derived dicarboxylic acid is 0%, and the biomass degree of the fossil fuel-derived polyester is 0%. Becomes 0%.

  In the present invention, the degree of biomass in the polyester resin layer is 5% or more, preferably 10% or more, more preferably 15% or more. If the degree of biomass in the polyester resin layer is 5% or more, it is possible to reduce the amount of polyester derived from fossil fuels and reduce the environmental burden compared to the conventional case.

  A polyester resin layer can be formed by, for example, forming a film by a T-die method using a biomass polyester resin composition or a resin composition containing biomass polyester and a fossil fuel-derived polyester. Specifically, after drying the resin composition described above, the resin composition is supplied to a melt extruder heated to a temperature of the melting point Tm or higher of the resin composition to a temperature of Tm + 70 ° C. to melt the resin composition, for example, A film of a polyester resin layer can be formed by extruding into a sheet form from a die such as a T-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, or the like can be used depending on the purpose.

  The polyester resin layer is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the polyester resin layer 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 ° C. or more and 100 ° C. or less. 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 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 ° C. or more and 100 ° C. or less. 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.

Breaking strength of the film of the polyester resin layer is a MD direction 5 kg / mm ² or more 40 kg / mm ² or less, at 35 kg / mm ² or less 5 kg / mm ² or more in the TD direction, elongation at break in the MD direction 50% or more and 350% or less, and 50% or more and 300% or less in the TD direction. Further, 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 polyester resin layer preferably has a thickness of 5 μm to 38 μm, more preferably 5 μm to 25 μm, and still more preferably 8 μm to 16 μm. If the thickness of the polyester resin layer is about the above range, the molding process is easy.

(Biomass polyester)
Biomass polyester consists of a diol unit and a dicarboxylic acid unit, and is obtained by a polycondensation reaction using biomass-derived ethylene glycol as the diol unit and fossil fuel-derived dicarboxylic acid as the dicarboxylic acid unit.

  Biomass-derived ethylene glycol uses ethanol (biomass ethanol) produced from biomass as a raw material. For example, 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 commercially available biomass ethylene glycol, for example, the biomass ethylene glycol marketed from India Glycol can be used conveniently.

  The dicarboxylic acid unit of biomass polyester uses a dicarboxylic acid derived from fossil fuel. As the dicarboxylic acid, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and derivatives thereof can be used without limitation. Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the aromatic dicarboxylic acid derivative include lower alkyl esters of aromatic dicarboxylic acid, specifically methyl ester, ethyl ester, propyl ester, and butyl. Examples include esters. Among these, terephthalic acid is preferable, and dimethyl terephthalate is preferable as an aromatic dicarboxylic acid derivative.

  Specific examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid. And a chain or alicyclic dicarboxylic acid. Examples of the aliphatic dicarboxylic acid derivative include lower alkyl esters such as methyl ester, ethyl ester, propyl ester and butyl ester of aliphatic dicarboxylic acid, and cyclic acid anhydrides of aliphatic dicarboxylic acid such as succinic anhydride. Can be mentioned. Among these, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable, and succinic acid as the main component is particularly preferable. As the derivative of the aliphatic dicarboxylic acid, methyl esters of adipic acid and succinic acid, or a mixture thereof are more preferable.

  These dicarboxylic acids can be used alone or in combination of two or more.

  The biomass polyester may be a copolymer polyester obtained by adding a copolymer component as a third component in addition to the diol component and the dicarboxylic acid component. Specific examples of the copolymer component include a bifunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol, a trifunctional or higher polyvalent carboxylic acid and / or an anhydride thereof, and 3 Examples include at least one polyfunctional compound selected from the group consisting of functional or higher oxycarboxylic acids. Among these copolymer components, a bifunctional and / or trifunctional or higher functional oxycarboxylic acid is particularly preferably used because a copolymer polyester having a high degree of polymerization tends to be easily produced. Among them, the use of a tri- or higher functional oxycarboxylic acid is most preferable because a polyester having a high degree of polymerization can be easily produced with a very small amount without using a chain extender described later.

  The biomass polyester may be a high molecular weight polyester obtained by chain extending (coupling) these copolymer polyesters. As the chain extender, a chain extender such as a carbonate compound or a diisocyanate compound can also be used. However, the amount of the chain extender is usually 100% by mole of all monomer units constituting the polyester, and a carbonate bond and a urethane bond. Usually, it is 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less.

  Specific examples of the carbonate compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, diamyl carbonate, and dicyclohexyl. Examples include carbonate. In addition, carbonate compounds composed of the same or different hydroxy compounds derived from hydroxy compounds such as phenols and alcohols can be used.

  Specific examples of the diisocyanate compound include 2,4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, and xylylene. Known diisocyanates such as range isocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate can be used.

  Biomass polyester can be obtained by a conventionally known method in which the above-described diol unit and dicarboxylic acid unit are polycondensed. Specifically, after performing the esterification reaction and / or transesterification reaction of the dicarboxylic acid component and the diol component, a general method of melt polymerization such as a polycondensation reaction 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 used when producing the biomass polyester is substantially equimolar with respect to 100 mol of the dicarboxylic acid or derivative thereof. Generally, however, esterification and / or transesterification and / or polycondensation reactions are performed. It is preferable to use an excess amount of 0.1 mol% or more and 20 mol% or less because of the distillation in the inside.

  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.

  Examples of the polymerization catalyst include compounds containing a Group 1 to Group 14 metal element excluding hydrogen and carbon in the periodic table. Specifically, at least one metal selected from the group consisting of titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium, and potassium. And compounds containing an organic group such as carboxylate, alkoxy salt, organic sulfonate, or β-diketonate salt, and inorganic compounds such as metal oxides and halides described above, and mixtures thereof. Of these, metal compounds containing titanium, zirconium, germanium, zinc, aluminum, magnesium and calcium, and mixtures thereof are preferred, and titanium compounds, zirconium compounds and germanium compounds are particularly preferred. In addition, the catalyst is preferably a compound that is liquid at the time of polymerization or that dissolves in an ester low polymer or polyester because the polymerization rate increases when it is melted or dissolved at the time of polymerization.

  The titanium compound is preferably a tetraalkyl titanate, specifically, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetra Examples include benzyl titanate and mixed titanates thereof. In addition, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium (diisoproxide) acetylacetonate, titanium bis (ammonium lactate) dihydroxide, titanium bis (ethylacetoacetate) diisopropoxide, titanium (triethanolaminate) ) Isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolamate, butyl titanate dimer and the like are also preferably used. Furthermore, titanium oxide and composite oxides containing titanium and silicon are also preferably used. Among these, tetra-n-propyl titanate, tetraisopropyl titanate and tetra-n-butyl titanate, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium bis (ammonium lactate) dihydroxide, polyhydroxytitanium stearate , Titanium lactate, butyl titanate dimer, titanium oxide, titania / silica composite oxide (for example, product name: C-94 manufactured by Acordis Industrial Fibers), particularly tetra-n-butyl titanate, polyhydroxy titanium stearate , Titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titania / silica composite oxide (for example, Acordis Industrial Fiber) The product name manufactured by s company: C-94) is preferable.

  Specific examples of the zirconium compound include zirconium tetraacetate, zirconium acetylate hydroxide, zirconium tris (butoxy) stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium potassium oxalate, and polyhydroxyzirconium. Examples include stearate, zirconium ethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium tributoxyacetylacetonate and mixtures thereof. Further, zirconium oxide or a complex oxide containing, for example, zirconium and silicon may be used. Among these, zirconyl diacetate, zirconium tris (butoxy) stearate, zirconium tetraacetate, zirconium acetate acetate, zirconium ammonium oxalate, potassium potassium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n-propoxy Zirconium tetraisopropoxide, zirconium tetra-n-butoxide, and zirconium tetra-t-butoxide are preferred.

  Specific examples of the germanium compound include inorganic germanium compounds such as germanium oxide and germanium chloride, and organic germanium compounds such as tetraalkoxygermanium. In view of price and availability, germanium oxide, tetraethoxygermanium, tetrabutoxygermanium, and the like are preferable, and germanium oxide is particularly preferable.

  The amount of the catalyst used in the case of using a metal compound as these polymerization catalysts, the lower limit is usually 5 ppm or more, preferably 10 ppm or more, and the upper limit is usually 30000 ppm or less, preferably 1000 ppm or less, as the amount of metal relative to the produced polyester. More preferably, it is 250 ppm or less, Especially preferably, it is 130 ppm or less. If too much catalyst is used, it is not only economically disadvantageous but also lowers the thermal stability of the polymer. Conversely, if it is too little, the polymerization activity is lowered, and as a result, the polymer decomposes during polymer production. Is more likely to be triggered. The amount of catalyst used here is a preferred embodiment because the amount of terminal carboxyl groups of the polyester produced is reduced as the amount used is reduced.

  The reaction temperature of the esterification reaction and / or transesterification reaction between the dicarboxylic acid component and the diol component is usually in the range of 150 ° C. to 260 ° C., and the reaction atmosphere is usually an inert gas atmosphere such as nitrogen or argon. It is. Further, the reaction pressure is usually from normal pressure to 10 kPa. The reaction time is usually 1 hour or more and 10 hours or less.

  In the production process described above, a chain extender (coupling agent) may be added to the reaction system. After the completion of polycondensation, the chain extender is added to the reaction system without solvent in a uniform molten state and reacted with the polyester obtained by polycondensation.

  High molecular weight polyesters using these chain extenders (coupling agents) can be produced using known techniques. After the completion of polycondensation, the chain extender is added to the reaction system without solvent in a uniform molten state and reacted with the polyester obtained by polycondensation. Specifically, a polyester obtained by catalyzing a diol and a dicarboxylic acid and having a terminal group substantially having a hydroxyl group and a weight average molecular weight (Mw) of 20,000 or more, preferably 40,000 or more. By reacting the chain extender with the prepolymer, a polyester resin having a higher molecular weight can be obtained. If the prepolymer has a mass average molecular weight of 20,000 or more, the use of a small amount of a coupling agent does not affect the remaining catalyst even under severe conditions such as a molten state, so that no gel is formed during the reaction. High molecular weight polyester can be produced.

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

  The intrinsic viscosity (measured at 35 ° C. with an orthochlorophenol solution) of the polyester obtained as described above is 0.5 dl / g or more and 1.5 dl from the viewpoint of productivity in the raw material production process and the film formation process. / G or less, more preferably 0.6 dl / g or more and 1.2 dl / g or less.

  Various additives may be added to the biomass polyester in the manufacturing process of the biomass polyester or the manufactured biomass polyester as long as the characteristics are not impaired. For example, plasticizer, UV stabilizer, anti-coloring agent, gloss Detergents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, mold release agents, antioxidants, ion exchange agents, color pigments, and the like can be added. These additives are 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, with respect to the entire resin composition containing biomass polyester.

(Thermoplastic resin layer)
The thermoplastic resin layer can be formed using a conventionally known thermoplastic resin. As described above, when a liquid paper container is produced using a laminated body, the layer of the laminated body located outside the liquid paper container is used as the first thermoplastic resin layer, and the laminated body located inside the liquid paper container. This layer is the second thermoplastic resin layer. The laminate further includes a thermoplastic resin layer to provide the same heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties as those of the conventional laminate. be able to.

  Examples of the first or second thermoplastic resin include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, Ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin, polyester resin, polyvinyl chloride resin , Polystyrene resin, nylon and the like, and low density polyethylene, linear low density polyethylene, medium density polyethylene, and ethylene-methacrylic acid copolymer are preferable. The type of the first or second thermoplastic resin may be the same or different.

  The 1st or 2nd thermoplastic resin layer may contain the material derived from biomass, and may contain the material derived from a fossil fuel. When the thermoplastic resin layer contains a biomass-derived material, it may contain biomass polyolefin, which is a polymer of monomers containing biomass-derived ethylene.

When the first or second thermoplastic resin layer contains biomass polyolefin, the biomass polyolefin preferably used is low density polyethylene derived from biomass (trade name: SBC818, density: 0.918 g / cm, manufactured by Braskem). ³ , MFR: 8.1 g / 10 minutes, biomass degree 95%), low density polyethylene derived from biomass manufactured by Braskem (trade name: SPB681, density: 0.922 g / cm ³ , MFR: 3.8 g / 10 minutes) , Biomass degree 95%) and the like.

(Print layer)
The printed layer can be used to display decorations, contents, display of the best-before period, display of manufacturers, sellers, etc., and display of other characters and letters, numbers, pictures, figures, symbols, patterns, etc. It is a layer for forming a desired arbitrary printed pattern. A printing layer can be provided as needed, for example, can be provided in the surface on the opposite side to the polyester resin layer of a paper base material layer. The printing layer may be provided on the entire surface of the paper base material layer, or may be provided on a part thereof. A printing layer can be formed using a conventionally well-known pigment and dye, The formation method is not specifically limited.

(Barrier layer)
The barrier layer is made of an inorganic substance and / or an inorganic oxide, and is preferably made of a vapor deposited film of an inorganic substance or an inorganic oxide or a metal foil. A vapor deposition film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and its composition and formation method are not particularly limited. When the laminate further includes a barrier layer, gas barrier properties that prevent transmission of oxygen gas, water vapor, and the like, and light shielding properties that prevent transmission of visible light, ultraviolet light, and the like can be imparted or improved. Note that the laminate may have two or more barrier layers. When two or more barrier layers are provided, each may have the same composition or a different composition.

  Examples of the deposited film include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium (Ti). ), Lead (Pb), zirconium (Zr), yttrium (Y) and other inorganic or inorganic oxide vapor deposition films can be used. In particular, an aluminum metal vapor-deposited film or a silicon oxide or aluminum metal or aluminum oxide vapor-deposited film is preferably used as a packaging material (bag) or the like.

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. As a range of the value of X, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, 0 to 0.5 for potassium (K), 0 to 2 for tin (Sn), 0 to 0.5 for sodium (Na), 0 to 1,5 for boron (B), titanium (Ti) Can take values in the range of 0 to 2, lead (Pb) in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5. In the above, when X = 0, it is a complete 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 suitably used for the packaging material, silicon (Si) is in the range of 1.0 to 2.0, and aluminum (Al) is in the range of 0.5 to 1.5. Can be used.

  In the present invention, the film thickness of the inorganic or inorganic oxide vapor-deposited film as described above varies depending on the type of inorganic or inorganic oxide used, but is, for example, 50 to 2000 mm, preferably 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, the film thickness is preferably 50 to 600 mm, more preferably 100 to 450 mm, and in the case of an aluminum oxide or silicon oxide deposited film, The film thickness is from 50 to 500 mm, more preferably from 100 to 300 mm.

  The deposited film can be formed on the polyester resin layer or the following plastic film by using the following forming method. As a method for forming a vapor deposition film, for example, a physical vapor deposition method (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, a thermochemical method, or the like. 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.

  According to another aspect, the barrier layer may be a metal foil obtained by rolling a metal. A conventionally known metal foil can be used as the metal foil. Aluminum foil is preferred from the viewpoints of gas barrier properties that prevent transmission of oxygen gas, water vapor, and the like, and light shielding properties that prevent transmission of visible light, ultraviolet light, and the like.

(Gas barrier coating film)
A gas barrier coating film may be provided on the vapor deposition film as necessary. The gas barrier coating film is a layer that functions as a layer that suppresses permeation of oxygen gas, water vapor, and the like. The gas barrier coating film has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group 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 the polyvinyl alcohol system as described above It is obtained by a gas barrier composition containing a resin and / or an ethylene / vinyl alcohol copolymer and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , at least one kind of a partial hydrolyzate of alkoxide and a condensate of hydrolysis of alkoxide can be used. Moreover, as a partial hydrolyzate of said alkoxide, all the alkoxy groups do not need to be hydrolyzed, The thing by which 1 or more was hydrolyzed, and its mixture may be sufficient. As a condensate of hydrolysis of alkoxide, a dimer or more of partially hydrolyzed alkoxide, specifically, a 2 to 6 mer is used.

In the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , as the metal atom represented by M, silicon, zirconium, titanium, aluminum, and the like can be used. In the present embodiment, examples of preferable metals include silicon and titanium. In the present invention, alkoxides may be used alone or in combination of two or more different metal atom alkoxides in the same solution.

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, i Examples thereof include 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. In the alkoxide represented by the 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, i -Propyl group, n-butyl group, sec-butyl group, and the like. These alkyl groups in the same molecule may be the same or different.

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

(Plastic film)
In the present invention, various plastic films may be used as other layers. For example, any of a stretched polyethylene terephthalate film, a stretched nylon film, a stretched polypropylene film, a nylon 6 / metaxylylenediamine nylon 6 co-extrusion co-stretch film, a polypropylene / ethylene-vinyl alcohol copolymer co-extrusion co-stretch film, or the like, or The composite film which laminated | stacked these two or more films may be sufficient. The plastic film may be coated with polyvinyl alcohol or the like.

  The plastic film may contain a biomass-derived material or a fossil fuel-derived material. When the plastic film includes a biomass-derived material, the same material as the polyester resin layer can be used.

(Adhesive layer)
The adhesive layer can be an adhesive layer formed by applying an adhesive to the surface of the layer to be laminated and drying it when two layers are adhered by a dry laminating method. 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 is preferably 0.1 g / m ² or more and 10 g / m ² or less (dry state), and more preferably 1 g / m ² or more and 5 g / m ² or less (dry state).

  The adhesive layer is an anchor coat layer formed by applying an anchor coating agent to the surface of the layer to be laminated and drying it when laminating a thermoplastic resin layer or the like by a melt extrusion lamination method. May be. Examples of the anchor coating agent include any resin having a heat-resistant temperature of 135 ° C. or higher, such as a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, and the like. An anchor coating agent comprising a polyacrylic or polymethacrylic resin having a hydroxyl group 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.

  Further, the adhesive layer may be an adhesive resin layer used when two layers are bonded by the sand lamination method or used in the melt extrusion lamination method. 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 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.

  The adhesive resin layer may contain a material derived from biomass or a material derived from fossil fuel. When the adhesive resin layer contains a biomass-derived material, it may contain biomass polyolefin, which is a polymer of monomers containing biomass-derived ethylene.

When the adhesive resin layer contains biomass polyolefin, the biomass polyolefin preferably used is low density polyethylene derived from biomass (trade name: SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g) manufactured by Braskem. / 10 min, biomass degree 95%), low density polyethylene derived from biomass (trade name: SPB681, density: 0.922 g / cm ³ , MFR: 3.8 g / 10 min, biomass degree 95%), etc. Is mentioned.

  In one aspect of the present invention, when the resin layer between the plastic film provided with a metal foil or a vapor deposition film and the paper base material layer is polyethylene derived from biomass, the thickness of the resin layer may be 50 μm or more. preferable. By this, even if it does not use EMAA, since a plastic film provided with metal foil or a vapor deposition film and a paper base material layer can be bonded together, biomass degree can be raised.

(Resin layer)
As other layers, a resin layer may be provided. The thermoplastic resin that can be used for the resin layer is a polyethylene resin, a polypropylene resin, or a cyclic polyolefin resin, or a copolymer resin, a modified resin, or a mixture containing these resins as a main component (including alloys). 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 An ethyl acrylate copolymer (EEA), an ethylene-methacrylic acid copolymer (EMAA), an ethylene-methyl methacrylate copolymer (EMMA), an ethylene / maleic acid copolymer, an ionomer resin, and the above-described polyolefin resin , Acrylic acid, methacrylic acid, malein It can be used maleic acid 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.

  The resin layer may include a biomass-derived material or a fossil fuel-derived material. When the adhesive resin layer contains a biomass-derived material, it may contain biomass polyolefin, which is a polymer of monomers containing biomass-derived ethylene.

When the resin layer contains biomass polyolefin, the biomass polyolefin that is suitably used includes biomass-derived low density polyethylene (trade name: SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree 95%), low density polyethylene derived from biomass (trade name: SPB681, density: 0.922 g / cm ³ , MFR: 3.8 g / 10 minutes, biomass degree 95%) manufactured by Braskem, etc. Can be mentioned.

(Laminate manufacturing method)
The manufacturing method of the laminated body by this invention is not specifically limited, It can manufacture by conventionally well-known methods, such as the dry lamination method, the melt extrusion lamination method, and the sand lamination method. In the present invention, a polyester resin layer can be laminated through an adhesive resin layer formed by melt extrusion using a sand laminating method.

  The thickness of the laminate obtained as described above is arbitrary depending on the application, but is usually 5 μm or more and 500 μm or less, preferably 20 μm or more and 300 μm or less.

  The laminate according to the present invention is provided with chemical functions, electrical functions, magnetic functions, mechanical functions, friction / abrasion / lubrication functions, optical functions, thermal functions, surface functions such as biocompatibility, etc. For the purpose, it is also possible to perform secondary processing. Examples of secondary processing include embossing, painting, adhesion, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, Coating, etc.). Further, the laminate according to the present invention can be subjected to laminating processing (dry laminating or extrusion laminating), bag making processing, and other post-processing processing to produce a molded product.

(Use)
The laminated body by this invention can be used for packaging products, such as a paper cup, a liquid paper container, a label material, and a cover material.

(Liquid paper container)
Since the liquid paper container according to the present invention has excellent barrier properties, alcohol such as sake, shochu and wine, milk beverages such as milk, foods such as soft drinks such as orange juice and tea, car wax, shampoo and detergent, etc. It can be suitably used as a packaging paper container for all liquids such as chemical products. The case where a paper container is formed using the laminated body by this invention is demonstrated. For example, the liquid paper container 40 shown in FIG. 4 can be formed after the ruled line processing is performed on the laminated body shown in FIGS.

  As shown in FIG. 4, the liquid paper container 40 has a quadrangular cylindrical body portion 41 including a side surface, a square plate-like bottom portion 42, and an upper portion 43. Yes. The upper portion 43 includes a pair of opposed inclined plates 44 and a pair of folding portions 45 that are positioned between the pair of 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. Note that a spout may be attached to one of the pair of inclined plates 44 and the spout may be sealed with a cap. Further, a flat top type container may be formed.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

<Measurement and conditions>
In the following reference examples, reference comparative examples, examples, and comparative examples, the biomass degree is the value of the biomass-derived carbon concentration as measured by radioactive carbon (C14).

The conditions of the extrusion film forming machine used below were as follows.
Screw diameter: 90mm
Screw type: Full flight L / D: 28
T die: 11S type straight manifold T die effective opening length: 560mm

[Example 1]
<Preparation of laminated body 1>
A biaxially stretched polyester film 1 (biomass degree: 20%, manufactured by Toyobo, DE024, thickness 12 μm) formed using fossil fuel-derived terephthalic acid and biomass-derived ethylene glycol (biomass polyester) was prepared. . Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / min) on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first thermoplastic resin layer (biomass degree: 0%) , A thickness of 20 μm). Next, on the surface opposite to the first thermoplastic resin layer of the paper base material layer, a low-density polyethylene derived from fossil fuel (LC520, manufactured by Nippon Polyethylene Co., Ltd., density: 0.923 g / min) is used by a sand lamination method. While extruding cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%, through this adhesive resin layer (biomass degree: 0%, thickness 15 μm), polyester film 1 (polyester resin layer, thickness 12 μm). Subsequently, an anchor coat agent (manufactured by Toyo Morton Co., Ltd., EL540 / CAT-RT32) was applied and dried on the polyester film 1 to form an anchor coat layer. Thereafter, fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is 320 ° C. on the anchor coat layer. A thermoplastic resin layer (biomass degree: 0%, thickness 55 μm) is formed by melt extrusion lamination at a resin temperature and a line speed of 100 m / min to form a first thermoplastic resin layer, a paper base material layer, and an adhesive resin. A laminate 1 in which a layer, a polyester resin layer, an anchor coat layer, and a second thermoplastic resin layer were sequentially laminated was obtained.

[Example 2]
<Preparation of laminated body 2>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and biomass-derived low-density polyethylene (Brasschem, SBC818, density: 0.918 g / cm ^{3) on one side.} MFR: 8.1 g / 10 min, biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first thermoplastic resin layer (biomass degree: 95%, thickness) 20 μm) was formed. Next, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 g / cm ³⁾ on the surface of the paper base material layer opposite to the first thermoplastic resin layer using a sand lamination method. , MFR: 8.1 g / 10 min, biomass degree: 95%), while extruding this adhesive resin layer (biomass degree: 95%, thickness 15 μm), polyester film 1 (polyester resin layer, biomass degree: 20% and a thickness of 12 μm). Subsequently, an anchor coat agent (manufactured by Toyo Morton Co., Ltd., EL540 / CAT-RT32) was applied and dried on the polyester film 1 to form an anchor coat layer. Thereafter, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) on the anchor coat layer is a resin temperature of 320 ° C. , Melt extrusion extrusion at a line speed of 100 m / min to form a thermoplastic resin layer (biomass degree: 95%, thickness 55 μm), a first thermoplastic resin layer, a paper base material layer, an adhesive resin layer, A laminate 2 was obtained in which a polyester resin layer, an anchor coat layer, and a second thermoplastic resin layer were sequentially laminated.

[Comparative Example 1]
<Preparation of laminate 3>
Biaxially stretched polyester film 2 formed using terephthalic acid derived from fossil fuel and ethylene glycol derived from fossil fuel (polyester derived from fossil fuel) (biomass degree: 0%, manufactured by Toyobo Co., Ltd., E5100, thickness 12 μm) Prepared. Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene, LC520, density: 0.923 g / min) on one side cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first thermoplastic resin layer (biomass degree: 0%) , A thickness of 20 μm). Next, on the surface opposite to the first thermoplastic resin layer of the paper base material layer, a low-density polyethylene derived from fossil fuel (LC520, manufactured by Nippon Polyethylene Co., Ltd., density: 0.923 g / min) is used by a sand lamination method. While extruding cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%, through this adhesive resin layer (biomass degree: 0%, thickness 15 μm), polyester film 2 (resin layer, biomass degree) : 0%, thickness 12 μm). Subsequently, an anchor coat agent (manufactured by Toyo Morton, EL540 / CAT-RT32) was applied and dried on the polyester film 2 to form an anchor coat layer. Thereafter, fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is 320 ° C. on the anchor coat layer. Melt extrusion lamination at a resin temperature and a line speed of 100 m / min to form a second thermoplastic resin layer (biomass degree: 0%, thickness 55 μm), a first thermoplastic resin layer, a paper base material layer Thus, a laminate 3 was obtained in which an adhesive resin layer, a plastic film, an anchor coat layer, and a second thermoplastic resin layer were sequentially laminated.

[Example 3]
<Preparation of laminate 4>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / min) on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) was melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first thermoplastic resin layer (biomass degree: 0 %, Thickness 20 μm). Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface of the paper base material layer opposite to the first thermoplastic resin layer using a sand lamination method. ) Through the adhesive resin layer (biomass degree 0%, thickness 20 μm), and aluminum foil (Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and polyester film 1 (polyester resin layer, biomass degree: 20) %, Thickness 12 μm) and a two-component curable adhesive (manufactured by DIC Graphics: main ingredient LX-703A / curing agent KR-90) were laminated together on the aluminum foil surface of a dry laminate film. Subsequently, a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) was coated on one surface of the polyester film of the dry laminate film to form an anchor coat layer. Thereafter, fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is 320 ° C. on the anchor coat layer. Melt extrusion lamination at a resin temperature and a line speed of 100 m / min to form a second thermoplastic resin layer (biomass degree: 0%, thickness 55 μm), a first thermoplastic resin layer, a paper base material layer Thus, a laminate 4 was obtained in which an adhesive resin layer, a barrier layer, an adhesive layer, a polyester resin layer, an anchor coat layer, and a second thermoplastic resin layer were sequentially laminated.

[Example 4]
<Preparation of laminated body 5>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and biomass-derived low-density polyethylene (Brasschem, SBC818, density: 0.918 g / cm ^{3) on one side.} , MFR: 8.1 g / 10 min, biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first thermoplastic resin layer (biomass degree: 95%, A thickness of 20 μm) was formed. Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface of the paper base material layer opposite to the first thermoplastic resin layer using a sand lamination method. ) Through the adhesive resin layer (biomass degree 0%, thickness 20 μm), and aluminum foil (Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and polyester film 1 (polyester resin layer, biomass degree: 20) %, Thickness 12 μm) and a two-component curable adhesive (manufactured by DIC Graphics: main ingredient LX-703A / curing agent KR-90) were laminated together on the aluminum foil surface of a dry laminate film. Subsequently, a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) was coated on one surface of the polyester film of the dry laminate film to form an anchor coat layer. Thereafter, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) on the anchor coat layer is a resin temperature of 320 ° C. , Melt extrusion lamination at a line speed of 100 m / min to form a second thermoplastic resin layer (biomass degree: 95%, thickness 55 μm), first thermoplastic resin layer, paper base material layer, adhesion A laminate 5 was obtained in which a resin layer, a barrier layer, an adhesive layer, a polyester resin layer, an anchor coat layer, and a second thermoplastic resin layer were sequentially laminated.

[Comparative Example 2]
<Preparation of laminate 6>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / min) on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) was melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first thermoplastic resin layer (biomass degree: 0 %, Thickness 20 μm). Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface of the paper base material layer opposite to the first thermoplastic resin layer using a sand lamination method. ) Through this adhesive resin layer (biomass degree 0%, thickness 20 μm) and aluminum foil (Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and polyester film 2 (resin layer, biomass degree: 0%) The aluminum foil surface of a dry laminate film obtained by dry lamination using a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) was bonded together. Subsequently, a two-component curable anchor agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075) was coated on the polyester film 2 side of the dry laminate film to form an anchor coat layer. Thereafter, fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is 320 ° C. on the anchor coat layer. Melt extrusion lamination at a resin temperature and a line speed of 100 m / min to form a second thermoplastic resin layer (biomass degree: 0%, thickness 55 μm), a first thermoplastic resin layer, a paper base material layer A laminate 4 was obtained in which an adhesive resin layer, a barrier layer, a plastic film, an anchor coat layer, and a second thermoplastic resin layer were sequentially laminated.

[Example 5]
<Preparation of laminate 7>
As the barrier film 1, a polyester film (biomass degree: 20%, manufactured by Saiichi Kogyo Co., Ltd., thickness 12 μm) on which an aluminum vapor deposition film was formed was prepared.

Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene, LC520, density: 0.923 g / min) on one side cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) was melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first thermoplastic resin layer (biomass degree: 0 %, Thickness 20 μm). Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface of the paper base material layer opposite to the first thermoplastic resin layer using a sand lamination method. The vapor deposition surface of the barrier film 1 was bonded through this adhesive resin layer (biomass degree 0%, thickness 20 μm). Subsequently, on the polyester film surface of the barrier film 1, a two-component curable anchor agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075) was coated to form an anchor coat layer. Then, using a sand lamination method, low density polyethylene derived from fossil fuel (LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree on the anchor coat layer: 0%), through this adhesive resin layer (biomass degree 0%, thickness 20 μm), fossil fuel-derived linear low density polyethylene film (Dai Nippon Printing Co., Ltd .: DYS-01N, thickness 40 μm) ) To form a second thermoplastic resin layer (biomass degree: 0%, thickness 55 μm), and the first thermoplastic resin layer, paper substrate layer, adhesive resin layer, barrier layer, polyester A laminate 7 was obtained in which a resin layer, an anchor coat layer, an adhesive resin layer, and a second thermoplastic resin layer were sequentially laminated.

[Example 6]
<Preparation of laminated body 8>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and biomass-derived low-density polyethylene (Brasschem, SBC818, density: 0.918 g / cm ^{3) on one side.} , MFR: 8.1 g / 10 min, biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first thermoplastic resin layer (biomass degree: 95%, A thickness of 20 μm) was formed. Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface of the paper base material layer opposite to the first thermoplastic resin layer using a sand lamination method. The vapor deposition surface of the barrier film 1 was bonded through this adhesive resin layer (biomass degree 0%, thickness 20 μm). Subsequently, on the polyester film surface of the barrier film 1, a two-component curable anchor agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075) was coated to form an anchor coat layer. Then, using a sand laminate method, low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95% on the anchor coat layer. ) While extruding, through this adhesive resin layer (biomass degree 95%, thickness 20 μm), a low-density polyethylene film derived from biomass (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g) / 10 minutes, degree of biomass: 95%, thickness 40 μm), the first thermoplastic resin layer, paper base material layer, adhesive resin layer, barrier layer, polyester resin layer, anchor coat layer, adhesive resin layer A laminate 8 in which the second thermoplastic resin layers were sequentially laminated was obtained.

[Comparative Example 3]
<Preparation of laminated body 9>
As the barrier film 2, a polyester film (biomass degree: 0%, manufactured by Saiichi Kogyo Co., Ltd., thickness 12 μm) on which an aluminum vapor deposition film was formed was prepared.

Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / min) on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) was melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first thermoplastic resin layer (biomass degree: 0 %, Thickness 20 μm). Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface of the paper base material layer opposite to the first thermoplastic resin layer using a sand lamination method. The vapor deposition surface of the barrier film 2 was bonded through this adhesive resin layer (biomass degree 0%, thickness 20 μm). Subsequently, a two-component curable anchor agent (Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the polyester film surface of the barrier film 2 to form an anchor coat layer. Then, using a sand lamination method, low density polyethylene derived from fossil fuel (LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree on the anchor coat layer: 0%), through this adhesive resin layer (biomass degree 0%, thickness 20 μm), fossil fuel-derived linear low density polyethylene film (Dai Nippon Printing Co., Ltd .: DYS-01N, thickness 40 μm) ) To form a second thermoplastic resin layer (biomass degree: 0%, thickness 55 μm), and the first thermoplastic resin layer, paper base material layer, adhesive resin layer, barrier layer, plastic film Thus, a laminate 9 was obtained in which the anchor coat layer, the adhesive resin layer, and the second thermoplastic resin layer were laminated in this order.

[Example 7]
<Preparation of Laminate 10>
Polyester film 1 (biomass degree: 20%, manufactured by Toyobo Co., Ltd., DE024, thickness 12 μm) was prepared. Next, a vapor deposition layer of silicon oxide having a thickness of 120 mm was formed on one surface of the polyester film 1 using the plasma chemical vapor deposition method under the following vapor deposition conditions.
(Deposition conditions)
Raw material: Hexamethyldisiloxane Introduced gas amount: Hexamethyldisiloxane: Oxygen gas: Helium = 1.0: 1.5: 1.0 (unit: slm)

  Next, a barrier coating solution prepared as described below is coated on the vapor deposition layer and then heat-treated to form a gas barrier coating film having a thickness of 0.3 μm (in a dry operation state). Film 3 was produced.

The barrier coating liquid described above was prepared according to the following composition table, mixed with a composition a consisting of polyvinyl alcohol, isopropyl alcohol, and ion-exchanged water, composition b, ethyl silicate, silane coupling agent, isopropyl alcohol. Then, a hydrolyzed solution composed of hydrochloric acid and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
(Composition table)

Next, using a dry laminating method, the surface of the gas barrier coating film of the barrier film 3 and the biomass origin through a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) A laminated film 1 was formed by laminating a low density polyethylene film (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%, thickness 60 μm). .

Next, a milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g /) on one side. cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first thermoplastic resin layer (biomass degree: 95%) , A thickness of 20 μm), and a laminated film 2 was formed.

Next, the surface of the polyester film 1 of the laminated film 1 is coated with a two-component curable anchor agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075) to form an anchor coat layer, and then the biomass is obtained using a sand lamination method. While extruding low-density polyethylene derived from Braskem (SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%), this adhesive resin layer (95% biomass degree, The surface of the polyester film 1 of the laminated film 1 and the surface of the paper base material layer of the laminated film 2 are bonded together via a thickness of 50 μm), and the first thermoplastic resin layer, paper base material layer, adhesive resin layer A laminate 10 was obtained in which an anchor coat layer, a polyester resin layer, a barrier layer, an adhesive layer, and a second thermoplastic resin layer were laminated in this order.

[Comparative Example 4]
<Preparation of Laminate 11>
A polyester film 2 (biomass degree: 0%, manufactured by Toyobo Co., Ltd., E5100, thickness 12 μm) was prepared. Next, a silicon oxide vapor deposition layer having a thickness of 120 mm was formed on one surface of the polyester film 2 in the same manner as in Example 7, and then a gas barrier having a thickness of 0.3 μm (in a dry operation state) was formed on the vapor deposition layer. The barrier film 4 was manufactured by forming a conductive coating film.

  Next, the surface of the gas barrier coating film of the barrier film 4 and the fossil fuel through a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) using a dry laminating method. A polyethylene film derived from Dainippon Printing Co., Ltd. (biomass degree: 0%, thickness: 60 μm) was laminated to form a laminated film 3.

Next, a milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) was prepared as a paper base layer, and fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene, LC520, density: 0.00) on one side. 923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) was melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first thermoplastic resin layer (biomass degree: 0%, thickness 20 μm) was formed, and the laminated film 4 was formed.

Next, the surface of the polyester film 2 of the laminated film 3 is coated with a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) to form an anchor coat layer, and then a fossil is used using a sand laminating method. While extruding low density polyethylene derived from fuel (manufactured by Nippon Polyethylene, LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%), this adhesive resin layer (biomass degree 0 The surface of the polyester film 2 of the laminated film 3 and the surface of the paper base material layer of the laminated film 4 are bonded to each other via the first thermoplastic resin layer, the paper base material layer, and the adhesive. A laminate 11 was obtained in which a resin layer, an anchor coat layer, a plastic film, a barrier layer, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Example 8]
<Preparation of laminated body 12>
The surface of the polyester film 1 of the barrier film 3 is coated with a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) to form an anchor coat layer, and then a biomass-derived low-density polyethylene (Braskem) SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and a resin layer ( The degree of biomass was 95% and the thickness was 20 μm), and the laminated film 5 was formed.

Next, using a dry laminating method, the surface of the gas barrier coating film of the laminated film 5 and the biomass-derived material are passed through a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90). A laminated film 6 was formed by laminating a low-density polyethylene film (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95%, thickness 60 μm).

Next, a milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0) using a sand laminating method. .918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%), while extruding the adhesive resin layer (biomass degree 95%, thickness 50 μm) of the resin layer of the laminated film 6 The laminated film 7 was formed by laminating the surface and one surface of the paper base material layer.

Next, on the other side of the paper base layer of the laminated film 7, biomass-derived low density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 95%, thickness 20 μm). A laminate 12 was obtained in which a layer, a paper base layer, an adhesive resin layer, a resin layer, an anchor coat layer, a polyester resin layer, a barrier layer, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Comparative Example 5]
<Preparation of Laminate 13>
The surface of the polyester film 2 of the barrier film 4 is coated with a two-component curable anchor agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075) to form an anchor coat layer, and then low density polyethylene derived from fossil fuel (Japan) Polyethylene, LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the resin A layer (biomass degree: 0%, thickness 20 μm) was formed, and a laminated film 8 was formed.

  Next, the surface of the gas barrier coating film of the barrier film 4 and the fossil fuel through a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) using a dry laminating method. A laminated film 9 was formed by pasting together a polyethylene film derived from Dai Nippon Printing Co., Ltd. (biomass degree: 0%, thickness 60 μm).

Next, a milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) was prepared as a paper base layer, and a low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density) : 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%), while extruding the adhesive resin layer (biomass degree 0%, thickness 50 μm) through the resin of the laminated film 9 The laminated film 10 was formed by bonding the surface of the layer and one surface of the paper base material layer.

Next, fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass on the other surface of the paper base layer of the laminated film 10 Degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0%, thickness 20 μm). A laminate 13 was obtained in which a plastic resin layer, a paper base layer, an adhesive resin layer, a resin layer, an anchor coat layer, a plastic film, a barrier layer, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Example 9]
<Preparation of laminated body 14>
Polyester film 1 (biomass degree: 20%, manufactured by Toyobo Co., Ltd., DE024, thickness 12 μm) was prepared. Next, an aluminum oxide vapor deposition layer having a thickness of 80 mm was formed under the following vapor deposition conditions by a PVD method using an electron beam (EB) heating method.
(Deposition conditions)
Degree of vacuum in the deposition chamber: 2 × 10 ⁻⁴ mbar
Electron beam power: 25kW

  Next, after coating the barrier coating liquid used in Example 7 on the vapor deposition layer, the film is subjected to heat treatment to form a gas barrier coating film having a thickness of 0.3 μm (in a dry operation state). Film 5 was produced.

Next, using the dry laminating method, the surface of the gas barrier coating film of the barrier film 5 and the biomass origin through a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) A low-density polyethylene film (Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%, thickness 60 μm) was laminated to form a laminated film 11 .

Next, the surface of the polyester film 1 of the laminated film 11 is coated with a two-component curable anchor agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075) to form an anchor coat layer, and then the biomass is obtained using a sand lamination method. While extruding low-density polyethylene derived from Braskem (SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%), this adhesive resin layer (95% biomass degree, The surface of the polyester film 1 of the laminated film 11 and the surface of the paper base material layer of the laminated film 2 are bonded together via a thickness of 50 μm), and the first thermoplastic resin layer, paper base material layer, adhesive resin layer A laminate 14 was obtained in which an anchor coat layer, a polyester resin layer, a barrier layer, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Comparative Example 6]
<Preparation of laminated body 15>
A polyester film 2 (biomass degree: 0%, manufactured by Toyobo Co., Ltd., E5100, thickness 12 μm) was prepared. Next, an aluminum oxide vapor deposition layer having a thickness of 80 mm was formed on one surface of the polyester film 2 in the same manner as in Example 9, and then a gas barrier having a thickness of 0.3 μm (in a dry operation state) was formed on the vapor deposition layer. The barrier film 6 was manufactured by forming a conductive coating film.

  Next, the surface of the gas barrier coating film of the barrier film 6 and the fossil fuel through a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) using a dry laminating method. A polyethylene film derived from Dainippon Printing Co., Ltd. (biomass degree: 0%, thickness: 60 μm) was laminated to form a laminated film 12.

Next, the surface of the polyester film 2 of the laminated film 12 is coated with a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) to form an anchor coat layer, and then a fossil is used by using a sand laminating method. While extruding low density polyethylene derived from fuel (manufactured by Nippon Polyethylene, LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%), this adhesive resin layer (biomass degree 0 The surface of the polyester film 1 of the laminated film 12 and the surface of the paper base material layer of the laminated film 4 are bonded to each other through the first thermoplastic resin layer, the paper base material layer, and the adhesive. A laminate 15 was obtained in which a resin layer, an anchor coat layer, a plastic film, a barrier layer, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Example 10]
<Preparation of Laminate 16>
The surface of the polyester film 1 of the barrier film 5 is coated with a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) to form an anchor coat layer, and then a biomass-derived low-density polyethylene (Braskem) SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and a resin layer ( Biomass degree: 95%, thickness 20 μm) was formed, and the laminated film 13 was formed.

Next, using a dry laminating method, the surface of the gas barrier coating film of the laminated film 13 and the biomass-derived material are passed through a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90). A low-density polyethylene film (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%, thickness 60 μm) was bonded to form a laminated film 14.

Next, a milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0) using a sand laminating method. .918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%), while extruding the adhesive resin layer (biomass degree 95%, thickness 50 μm) of the resin layer of the laminated film 14 The laminated film 15 was formed by laminating the surface and one surface of the paper base material layer.

Next, on the other surface of the paper base layer of the laminated film 15, biomass-derived low density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 95%, thickness 20 μm). A laminate 16 was obtained in which a layer, a paper base layer, an adhesive resin layer, a resin layer, an anchor coat layer, a polyester resin layer, a barrier layer, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Comparative Example 7]
<Preparation of Laminate 17>
The surface of the polyester film 2 of the barrier film 6 is coated with a two-component curable anchor agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075) to form an anchor coat layer, and then low density polyethylene derived from fossil fuel (Japan) Polyethylene, LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the resin A layer (biomass degree: 0%, thickness 20 μm) was formed, and a laminated film 16 was formed.

  Next, the surface of the gas barrier coating film of the barrier film 4 and the fossil fuel through a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) using a dry laminating method. A laminated film 17 was formed by pasting together a polyethylene film derived from Dainippon Printing Co., Ltd. (biomass degree: 0%, thickness 60 μm).

Next, a milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) was prepared as a paper base layer, and a low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density) using a sand laminating method. : 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%), while extruding the adhesive resin layer (biomass degree 0%, thickness 50 μm) through the resin of the laminated film 17 The surface of the layer and one surface of the paper substrate layer were bonded together to form a laminated film 18.

Next, on the other surface of the paper base layer of the laminated film 18, fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass Degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0%, thickness 20 μm). A laminate 13 was obtained in which a plastic resin layer, a paper base layer, an adhesive resin layer, a resin layer, an anchor coat layer, a plastic film, a barrier layer, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Example 11]
<Preparation of laminated body 18>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / min) on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) was melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first thermoplastic resin layer (biomass degree: 0 %, Thickness 20 μm). Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface of the paper base material layer opposite to the first thermoplastic resin layer using a sand lamination method. ) Through the adhesive resin layer (biomass degree 0%, thickness 20 μm), and aluminum foil (Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and polyester film 1 (polyester resin layer, biomass degree: 20) %, Thickness of 12 μm) was laminated using a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90), and the surface of polyester film 1 of a dry laminate film was laminated. . Subsequently, this adhesive resin layer was extruded while extruding an fossil fuel-derived ethylene-methacrylic acid copolymer (Mitsui DuPont Polychemical Nucrel N0908C) onto the aluminum foil surface of the dry laminate film using a sand laminate method. A fossil fuel-derived polyethylene film (manufactured by Dai Nippon Printing Co., Ltd .: SKL, thickness 40 μm) is bonded through (the biomass degree 0%, thickness 20 μm), and the first thermoplastic resin layer, paper base layer A laminate 18 was obtained in which an adhesive resin layer, a polyester resin layer, an adhesive layer, a barrier layer, an adhesive resin layer, and a second thermoplastic resin layer were sequentially laminated.

[Comparative Example 8]
<Preparation of Laminate 19>
Milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and low-density polyethylene derived from fossil fuels (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / min) on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) was melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the first thermoplastic resin layer (biomass degree: 0 %, Thickness 20 μm). Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N0908C) is formed on the surface of the paper base material layer opposite to the first thermoplastic resin layer using a sand lamination method. ) Through this adhesive resin layer (biomass degree 0%, thickness 20 μm) and aluminum foil (Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and polyester film 2 (resin layer, biomass degree: 0%) The surface of the polyester film 2 of a dry laminate film obtained by dry lamination using a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) was bonded together. Subsequently, this adhesive resin layer was extruded while extruding an fossil fuel-derived ethylene-methacrylic acid copolymer (Mitsui DuPont Polychemical Nucrel N0908C) onto the aluminum foil surface of the dry laminate film using a sand laminate method. A fossil fuel-derived polyethylene film (manufactured by Dai Nippon Printing Co., Ltd .: SKL, thickness 40 μm) is bonded through (the biomass degree 0%, thickness 20 μm), and the first thermoplastic resin layer, paper base layer Thus, a laminate 19 was obtained in which an adhesive resin layer, a plastic film, an adhesive layer, a barrier layer, an adhesive resin layer, and a second thermoplastic resin layer were sequentially laminated.

[Example 12]
<Preparation of Laminate 20>
Using the dry laminating method, low density derived from biomass and the surface of the polyester film 1 of the barrier film 3 through a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) A laminated film 19 was formed by laminating a polyethylene film (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%, thickness 60 μm).

Next, a two-component curable anchor agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) is coated on the surface of the gas barrier coating film of the laminated film 19 to form an anchor coat layer, and then using a sand lamination method, While extruding biomass-derived low density polyethylene (Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%), this adhesive resin layer (biomass degree 95% The surface of the polyester film 1 of the laminated film 19 and the surface of the paper base material layer of the laminated film 2 are bonded together through a thickness of 50 μm), and the first thermoplastic resin layer, paper base material layer, adhesive resin A laminate 20 was obtained in which a layer, an anchor coat layer, a barrier layer, a polyester resin layer, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Comparative Example 9]
<Preparation of Laminate 21>
Polyethylene derived from fossil fuel and the surface of the polyester film 2 of the barrier film 4 through a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) using a dry laminating method. A laminated film 20 was formed by laminating films (manufactured by Dai Nippon Printing Co., Ltd .: biomass degree: 0%, thickness 60 μm).

Next, a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) is coated on the surface of the gas barrier coating film of the laminated film 20 to form an anchor coat layer, and then a sand lamination method is used. While extruding low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene, LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%), this adhesive resin layer (biomass degree) The surface of the polyester film 2 of the laminated film 20 and the surface of the paper base material layer of the laminated film 4 are bonded to each other through the first thermoplastic resin layer, the paper base material layer, A laminate 21 was obtained in which an adhesive resin layer, an anchor coat layer, a barrier layer, a plastic film, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Example 13]
<Preparation of laminated body 22>
The surface of the gas barrier coating film of the barrier film 3 is coated with a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) to form an anchor coat layer, and then a biomass-derived low-density polyethylene (Braskem) SBC 818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) manufactured by the company, melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the resin layer (Biomass degree: 95%, thickness 20 μm) was formed, and the laminated film 21 was formed.

Next, using a dry laminating method, the surface of the polyester film 1 of the laminated film 21 and the low biomass-derived low-temperature adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) are used. A laminated film 22 was formed by bonding a density polyethylene film (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%, thickness 60 μm).

Next, a milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0) using a sand laminating method. .918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%), while extruding the adhesive resin layer (biomass degree 95%, thickness 50 μm) of the resin layer of the laminated film 22 The laminated film 23 was formed by laminating the surface and one surface of the paper base material layer.

Next, on the other surface of the paper base layer of the laminated film 23, a biomass-derived low density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 95%, thickness 20 μm). A laminate 22 was obtained in which a resin layer, a paper base layer, an adhesive resin layer, a resin layer, an anchor coat layer, a barrier layer, a polyester resin layer, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Comparative Example 10]
<Preparation of Laminate 23>
The surface of the gas barrier coating film of the barrier film 4 is coated with a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) to form an anchor coat layer, and then a low density polyethylene derived from fossil fuel ( Manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) were melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min. A resin layer (biomass degree: 0%, thickness 20 μm) was formed, and a laminated film 24 was formed.

  Next, using the dry laminating method, the surface of the polyester film 2 of the laminated film 24 and the fossil fuel-derived adhesive through a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90). A laminated film 25 was formed by laminating a polyethylene film (Dai Nippon Printing Co., Ltd., biomass degree: 0%, thickness 60 μm).

Next, a milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) was prepared as a paper base layer, and a low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density) using a sand laminating method. : 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%), while extruding the adhesive resin layer (biomass degree: 0%, thickness 50 μm) of the laminated film 25 The laminated film 26 was formed by bonding the surface of the resin layer and one surface of the paper base layer.

Next, on the other surface of the paper base layer of the laminated film 26, low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass Degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0%, thickness 20 μm). A laminate 23 was obtained in which a thermoplastic resin layer, a paper base layer, an adhesive resin layer, a resin layer, an anchor coat layer, a barrier layer, a plastic film, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Example 14]
<Preparation of Laminate 24>
Low density derived from biomass and the surface of the polyester film 1 of the barrier film 5 through a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) using a dry laminating method A laminated film 27 was formed by laminating a polyethylene film (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%, thickness 60 μm).

Next, a two-component curable anchor agent (Mitsui Chemicals Co., Ltd .: A3210 / A3075) is coated on the surface of the gas barrier coating film of the laminated film 27 to form an anchor coat layer, and then a sand lamination method is used. While extruding biomass-derived low density polyethylene (Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%), this adhesive resin layer (biomass degree 95% The surface of the polyester film 1 of the laminated film 27 and the surface of the paper base material layer of the laminated film 2 are bonded together through a thickness of 50 μm), and the first thermoplastic resin layer, paper base material layer, adhesive resin A laminate 20 was obtained in which a layer, an anchor coat layer, a barrier layer, a polyester resin layer, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Comparative Example 11]
<Preparation of Laminate 25>
Polyethylene derived from fossil fuel and the surface of the polyester film 2 of the barrier film 6 through a two-layer curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90) using a dry laminating method. A laminated film 28 was formed by laminating films (manufactured by Dai Nippon Printing Co., Ltd .: degree of biomass: 0%, thickness 60 μm).

Next, a two-component curable anchor agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) is coated on the surface of the gas barrier coating film of the laminated film 28 to form an anchor coat layer, and then a sand lamination method is used. While extruding low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene, LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%), this adhesive resin layer (biomass degree) 0%, thickness 50 μm), the surface of the polyester film 2 of the laminated film 28 and the surface of the paper base material layer of the laminated film 4 are bonded together, the first thermoplastic resin layer, the paper base material layer, A laminate 21 was obtained in which an adhesive resin layer, an anchor coat layer, a barrier layer, a plastic film, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Example 15]
<Preparation of Laminate 26>
The surface of the gas barrier coating film of the barrier film 5 is coated with a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) to form an anchor coat layer, and then a biomass-derived low density polyethylene (Braskem) SBC 818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) manufactured by the company, melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and the resin layer (Biomass degree: 95%, thickness 20 μm) was formed, and a laminated film 29 was formed.

Next, using the dry laminating method, the surface of the polyester film 1 of the laminated film 29 and the biomass-derived low-temperature adhesive are obtained via a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90). A laminated film 30 was formed by bonding a density polyethylene film (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%, thickness 60 μm).

Next, a milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) is prepared as a paper base layer, and a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0) using a sand laminating method. .918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%), while extruding the adhesive resin layer (biomass degree 95%, thickness 50 μm) of the resin layer of the laminated film 30 The laminated film 31 was formed by laminating the surface and one surface of the paper base material layer.

Next, on the other surface of the paper base layer of the laminated film 31, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) is melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 95%, thickness 20 μm). A laminate 22 was obtained in which a resin layer, a paper base layer, an adhesive resin layer, a resin layer, an anchor coat layer, a barrier layer, a polyester resin layer, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Comparative Example 12]
<Preparation of Laminate 27>
The surface of the gas barrier coating film of the barrier film 6 is coated with a two-component curable anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) to form an anchor coat layer, and then low density polyethylene derived from fossil fuel ( Manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) were melt extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min. A resin layer (biomass degree: 0%, thickness 20 μm) was formed, and a laminated film 32 was formed.

  Next, using the dry laminating method, the surface of the polyester film 2 of the laminated film 32 and the fossil fuel-derived adhesive through a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90). A laminated film 33 was formed by laminating a polyethylene film (Dai Nippon Printing Co., Ltd., biomass degree: 0%, thickness 60 μm).

Next, a milk carton base paper (manufactured by Clearwater, basis weight 400 g / m ² ) was prepared as a paper base layer, and a low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density) using a sand laminating method. : 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%), while extruding the adhesive resin layer (biomass degree: 0%, thickness 50 μm) of the laminated film 33 The laminated film 34 was formed by bonding the surface of the resin layer and one surface of the paper base layer.

Next, on the other surface of the paper base layer of the laminated film 34, low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass Degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0%, thickness 20 μm). A laminate 23 was obtained in which a thermoplastic resin layer, a paper base layer, an adhesive resin layer, a resin layer, an anchor coat layer, a barrier layer, a plastic film, an adhesive layer, and a second thermoplastic resin layer were sequentially laminated.

[Production Examples 1 to 27]
<Production of liquid paper container>
The laminates 1 to 27 were pressed with a male mold and a female mold to perform ruled line processing and punched into a blank for a paper container. Thereafter, with the liquid paper container filling machine “DR-10”, the center value of the seal temperature condition is set to the top heater temperature of 320 ° C. and the bottom heater temperature of 340 ° C. 27 was produced.

(Liquid leak test)
After the top and bottom of the liquid paper containers 1 to 27 produced above are cut off, a test solution (Microcheck penetration solution (manufactured by Taiho Kozai)) is injected into the top and bottom, left at room temperature for 30 minutes, and then microchecked. Washing was performed with a washing solution (manufactured by Taiho Kozai). Thereafter, the top and bottom portions were opened in a flat plate shape by heating with hot air, and liquid leakage and pinholes were visually evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2.
(Evaluation criteria for liquid leakage)
◯: There was no liquid leakage from the top seal part and the bottom seal part, and the performance as a liquid paper container was good.
X: There was liquid leakage from the top seal part and the bottom seal part, and the performance as a liquid paper container was poor.
(Pinhole evaluation criteria)
A: There were no pinholes at the top and bottom, and the performance as a liquid paper container was good.
X: There were pinholes at the top and bottom, and the performance as a liquid paper container was poor.

10, 20, 30 Laminated body 11 First thermoplastic resin layer 12 Paper base material layer 13 Polyester resin layer 14 Second thermoplastic resin layer 15 Adhesive layer 16 Barrier layer 40 Liquid paper container 41 Trunk part 42 Bottom part 43 Upper part 44 Inclined plate 45 Folding part 46 Margin

Claims (5)

At least a laminate comprising a first thermoplastic resin layer, a paper base material layer, a polyester resin layer, and a second thermoplastic resin layer in this order,
The polyester resin layer includes biomass polyester having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit,
The laminated body whose biomass degree in the said polyester resin layer is 5% or more.   The laminate according to claim 1, wherein the dicarboxylic acid is terephthalic acid.   The said 1st or 2nd thermoplastic resin layer contains the resin material selected from the group which consists of a low density polyethylene, a linear low density polyethylene, a medium density polyethylene, and an ethylene-methacrylic acid copolymer. The laminate according to 1 or 2.   Packaged product provided with the laminated body as described in any one of Claims 1-3. A liquid paper container comprising the laminate according to any one of claims 1 to 3,
A liquid paper container, wherein the innermost layer of the liquid paper container is the second thermoplastic resin layer.

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