JP7129031B2 - Laminate provided with polyester resin layer and packaging product provided with the same - Google Patents

Description

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

Polyesters are widely used in various industrial applications because they are excellent in mechanical properties, chemical stability, heat resistance, transparency, etc., and are inexpensive. Polyester is obtained by polycondensation of diol units and dicarboxylic acid units. For example, polyethylene terephthalate (hereinafter sometimes abbreviated as PET) is obtained by esterifying ethylene glycol and terephthalic acid as raw materials. It is produced by a polycondensation reaction after These raw materials are produced from petroleum, which is a fossil resource. For example, ethylene glycol is industrially produced from ethylene, and terephthalic acid is industrially produced from xylene.

In recent years, along with the increasing demand for building a recycling-based society, the use of biomass has been attracting attention in the field of materials as well as the use of fossil fuels, as is the case with energy. Biomass is an organic compound that is photosynthesised from carbon dioxide and water, and is a so-called carbon-neutral renewable energy that is regenerated into carbon dioxide and water by using it. In recent years, the practical use of biomass plastics using these biomass as raw materials has progressed rapidly, and attempts have been made to produce polyesters, which are general-purpose polymer materials, from these biomass raw materials.

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

In addition, biomass ethanol obtained by fermenting starches and sugars obtained from plants such as corn and sugar cane with microorganisms has been put into practical use, and ethylene glycol is industrially produced from this biomass ethanol via ethylene. has also been successful.

Japanese translation of PCT publication No. 2002-512304

The present inventors focused on ethylene glycol, which is a raw material of polyester, and instead of ethylene glycol obtained from conventional fossil fuels, biomass polyester using biomass-derived ethylene glycol as its raw material (hereinafter simply "biomass polyester" A liquid paper container comprising a laminate comprising a polyester resin layer containing a polyester resin layer containing conventional fossil fuel-derived polyester (hereinafter simply referred to as "fossil fuel-derived polyester") It has been found that a paper container for liquid comprising a laminate comprising a polyester resin layer composed of (a) can be obtained in terms of physical properties such as mechanical properties that are comparable. The present invention is based on such findings.

Therefore, an object of the present invention is to provide a polyester resin layer containing biomass polyester that is comparable in physical properties such as mechanical properties to a paper container for liquid that includes a laminate having a polyester resin layer made of a conventional fossil fuel-derived polyester. An object of the present invention is to provide a paper container for liquid comprising a laminate.

In aspects of the invention,
At least a first thermoplastic resin layer, a paper base layer, a second adhesive resin layer, a polyester resin layer to which a metal foil is bonded or a polyester resin layer to which a vapor deposition film is formed, and a first adhesive A liquid paper container comprising a laminate comprising a resin layer and a second thermoplastic resin layer in this order,
The polyester resin layer contains a biomass polyester having biomass-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit,
The biomass degree in the polyester resin layer is 5% or more,
The first adhesive resin layer is in contact with the second thermoplastic resin layer,
The innermost layer of the laminate is the second thermoplastic resin layer,
A paper container for liquid is provided, wherein the first adhesive resin layer is polyethylene.
In aspects of the present invention, the dicarboxylic acid is preferably terephthalic acid.
In the aspect of the present invention, the first adhesive resin layer preferably contains biomass polyethylene, which is a polymer of monomers containing biomass-derived ethylene.
In an aspect of the present invention, the biomass polyethylene is preferably biomass-derived low-density polyethylene.
In the aspect of the present invention, the first adhesive resin layer is composed only of biomass-derived low-density polyethylene, or is a mixed resin of biomass-derived low-density polyethylene and fossil fuel-derived low-density polyethylene. preferably configured.
In the aspect of this invention, it is preferable that the said 2nd thermoplastic resin layer contains polyethylene derived from biomass.
In another aspect of the present invention, there is provided a method for manufacturing a laminate used for the liquid paper container,
A method for producing a laminate is provided, comprising laminating the second thermoplastic resin layer via the melt-extruded first adhesive resin layer.

A paper container for liquid comprising a laminate according to the present invention includes at least a paper base layer, a polyester resin layer containing biomass polyester, and a thermoplastic resin layer, thereby reducing the amount of fossil fuel used compared to the past. can reduce environmental impact. In addition, the liquid paper container comprising the laminate according to the present invention is comparable in physical properties such as mechanical properties to a laminate comprising a conventional fossil fuel-derived polyester resin layer. A liquid carton container comprising a laminate comprising a resin layer can be substituted.

1 is a schematic cross-sectional view showing an example of a laminate according to the present invention; FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention; FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention; FIG. It is a perspective view showing an example of a liquid paper container.

In the present invention, "biomass polyester" and "polyester resin layer containing biomass polyester" are those using biomass-derived raw materials as raw materials at least in part, and all raw materials are derived from biomass. does not mean

<Laminate>
A laminate according to the present invention comprises a first thermoplastic resin layer, a paper base layer, a polyester resin layer containing biomass polyester, and a second thermoplastic resin layer in this order.
When a paper container for liquid is produced using a laminate, the layer of the laminate positioned outside the paper container for liquid is defined as the first thermoplastic resin layer, and the layer of the laminate positioned inside the paper container for liquid is defined as the first thermoplastic resin layer. 2 thermoplastic resin layers. Since the laminate includes a polyester resin layer containing biomass polyester, it is possible to reduce the amount of fossil fuel used compared to conventional laminates, thereby reducing the environmental load. In addition, since the laminate according to the present invention is comparable in physical properties such as mechanical properties to laminates provided with conventional fossil fuel-derived polyester resin layers, it is provided with a conventional fossil fuel-derived polyester resin layer. Laminates can be substituted.

The laminate according to the present invention may further have at least one other layer such as a print layer, a barrier layer, a plastic film, an adhesive layer, etc., in addition to the above layers. When two or more other layers are provided, they may have the same composition or may have different compositions.

A laminate according to the present invention will be described with reference to the drawings. Examples of schematic cross-sectional views of laminates according to the present invention are shown in FIGS.
The laminate 10 shown in FIG. 1 comprises a first thermoplastic resin layer 11, a paper substrate layer 12, a polyester resin layer 13, and a second thermoplastic resin layer . In the case of a liquid carton with laminate 10, the first thermoplastic layer 11 is located on the outside of the liquid carton and the second thermoplastic layer 14 is located on the inside of the liquid carton.
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 carton with laminate 20, the first thermoplastic layer 11 is located on the outside of the liquid carton and the second thermoplastic layer 14 is located on the inside of the liquid carton.
The laminate 30 shown in FIG. 3 includes a first thermoplastic resin layer 11, a paper base layer 12, an adhesive layer 15, a barrier layer 16, a polyester resin layer 13, an adhesive layer 15, a second and a thermoplastic resin layer 14 in this order. In the case of a liquid carton with laminate 30, the first thermoplastic layer 11 is located on the outside of the liquid carton and the second thermoplastic layer 14 is located on the inside of the liquid carton.
In any laminate, a printed layer, a thermoplastic resin layer, or the like may be further laminated.
Each layer constituting the laminate will be described below.

(Paper base layer)
In the present invention, the paper base layer functions as a base layer for holding the polyester resin layer, and is preferably capable of imparting strength to the laminate as a packaging product. 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. have. As the paper substrate layer, white paperboard in general is used, but ivory paper, milk carton base paper, cup base paper, etc. using natural pulp are particularly preferable from the viewpoint of safety.

The paperboard used in the present invention may use neutral rosin, alkylketene dimer, alkenyl succinic anhydride as a sizing agent, and cationic polyacrylamide, cationic starch, etc. as a fixing agent. good too. Moreover, it is also possible to make paper in a neutral range of pH 6 or more and pH 9 or less using aluminum sulfate. In addition to the above sizing agents as necessary, fixing agents, various fillers for papermaking, retention improvers, dry strength enhancers, wet strength enhancers, binders, dispersants, flocculants, plasticizers Agents and adhesives may be contained as appropriate.

(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 contain 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. It suffices if the polyester resin layer as a whole can achieve the following biomass degree. In the present invention, by including biomass polyester in the polyester resin layer, it is possible to reduce the amount of polyester derived from fossil fuels and reduce the environmental load compared to the prior art.

In the present invention, the "biomass degree" (biomass-derived carbon concentration) in the polyester resin layer is a value obtained by measuring the content of biomass-derived carbon by radioactive carbon (C14) measurement. Since carbon dioxide in the atmosphere contains a certain proportion of C14 (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the ratio of C14 contained in the total carbon atoms in the polyester, the ratio of biomass-derived carbon can be calculated. In the present invention, the biomass-derived carbon content _{Pbio can be determined as follows, where Pc14} is the content of _C14 in the polyester.
P _bio (%) = P _C14 /105.5 x 100

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

In the present invention, the biomass content in the polyester resin layer is 5% or more, preferably 10% or more, more preferably 15% or more. If the biomass degree 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 conventional methods.

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

The polyester resin layer is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the film of the polyester resin layer 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 form a longitudinally stretched film. This stretching is preferably carried out using a difference in circumferential speed between two or more rolls. Longitudinal stretching is usually performed in a temperature range of 50°C or higher and 100°C or lower. Further, the longitudinal stretching ratio is preferably 2.5 times or more and 4.2 times or less, although it depends on the properties required for the film application. If the draw ratio is less than 2.5 times, the thickness unevenness of the film becomes large, making it difficult to obtain a good film.

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

The film breaking strength of the polyester resin layer is 5 kg/mm ² or more and 40 kg/mm ^{2 or less in the MD direction, and 5 kg/mm 2 or more and 35 kg/mm 2 or less} in the TD direction. It is 50% or more and 350% or less, and 50% or more and 300% or less in the TD direction. Moreover, the shrinkage rate when left in a temperature environment of 150° C. for 30 minutes is 0.1% or more and 5% or less.

The polyester resin layer preferably has a thickness of 5 μm or more and 38 μm or less, more preferably 5 μm or more and 25 μm or less, still more preferably 8 μm or more and 16 μm or less.
When the thickness of the polyester resin layer is within the above range, molding is easy.

(biomass polyester)
A 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 is produced from biomass-derived ethanol (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained by a method in which biomass ethanol is converted into ethylene glycol via ethylene oxide by a conventionally known method. Also, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol can be preferably used.

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

Further, as the aliphatic dicarboxylic acid, specifically, oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, etc., usually having 2 to 40 carbon atoms. chain or alicyclic dicarboxylic acids. In addition, as derivatives of aliphatic dicarboxylic acids, lower alkyl esters such as methyl esters, ethyl esters, propyl esters and butyl esters of the above aliphatic dicarboxylic acids and cyclic acid anhydrides of the above aliphatic dicarboxylic acids such as succinic anhydride are used. mentioned. Among these, adipic acid, succinic acid, dimer acid, or mixtures thereof are preferred, and those containing succinic acid as a main component are particularly preferred. More preferred derivatives of aliphatic dicarboxylic acids are methyl esters of adipic acid and succinic acid, or mixtures thereof.

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

The biomass polyester may be a copolymerized polyester obtained by adding a copolymerized component as a third component in addition to the above diol component and dicarboxylic acid component. Specific examples of copolymer components include bifunctional oxycarboxylic acids, trifunctional or higher polyhydric alcohols for forming a crosslinked structure, trifunctional or higher polycarboxylic acids and/or their anhydrides, and 3 At least one polyfunctional compound selected from the group consisting of functional or higher oxycarboxylic acids is included. Among these copolymerization components, a bifunctional and/or trifunctional or higher oxycarboxylic acid is particularly preferably used because a copolyester 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 with a high degree of polymerization can be easily produced with a very small amount without using a chain extender to be described later.

The biomass polyester may also be a high-molecular-weight polyester obtained by chain-extending (coupling) these copolyesters. A chain extender such as a carbonate compound or a diisocyanate compound can be used as the chain extender. It is usually 10 mol % or less, preferably 5 mol % or less, more preferably 3 mol % or less.

Specific examples of carbonate compounds 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. Carbonate etc. are illustrated. 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 diisocyanate compounds include 2,4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, xyloxy Known diisocyanates such as diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate can be used.

A biomass polyester can be obtained by a conventionally known method of polycondensing the above-described diol units and dicarboxylic acid units. 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 performing a polycondensation reaction under reduced pressure, or an organic solvent can be produced by a known solution heating dehydration condensation method using

The amount of diol used in the production of biomass polyester is substantially equimolar with respect to 100 mol of dicarboxylic acid or derivative thereof, but generally esterification and / or transesterification reaction and / or polycondensation reaction It is preferable to use an excess amount of 0.1 mol % or more and 20 mol % or less because there is a distillate in the middle.

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

Polymerization catalysts generally include compounds containing Group 1 to Group 14 metal elements in the periodic table, excluding hydrogen and carbon. 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 carboxylates, alkoxy salts, organic sulfonates or β-diketonate salts, inorganic compounds such as oxides and halides of the above metals, and mixtures thereof. Among 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 in a liquid state during polymerization or dissolves in the ester low polymer or polyester because the polymerization rate increases if it is in a molten or dissolved state during polymerization.

As the titanium compound, tetraalkyl titanate is preferable, and specifically, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetra Benzyl titanates and mixed titanates thereof. Also, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium (diisoproxide) acetylacetonate, titanium bis (ammonium lactate) dihydroxide, titanium bis (ethylacetoacetate) diisopropoxide, titanium (triethanolamine) ) isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolamine, 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 (eg, product name: C-94 manufactured by Acordis Industrial Fibers), particularly tetra-n-butyl titanate, polyhydroxytitanium stearate. , titanium (oxy)acetylacetonate, titanium tetraacetylacetonate, titania/silica composite oxide (for example, product name: C-94 manufactured by Acordis Industrial Fibers).

Specific examples of zirconium compounds include zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris(butoxy) stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium zirconium oxalate, and polyhydroxyzirconium. Stearate, zirconium ethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium tributoxy acetylacetonate and mixtures thereof. Alternatively, zirconium oxide or a composite oxide containing, for example, zirconium and silicon may be used. Among these, zirconyl diacetate, zirconium tris(butoxy)stearate, zirconium tetraacetate, zirconium acetate hydroxide, ammonium zirconium oxalate, potassium zirconium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n-propoxy zirconium tetraisopropoxide, zirconium tetra-n-butoxide and zirconium tetra-t-butoxide are preferred.

Specific examples of germanium compounds include inorganic germanium compounds such as germanium oxide and germanium chloride, and organic germanium compounds such as tetraalkoxygermanium. Germanium oxide, tetraethoxygermanium, tetrabutoxygermanium, and the like are preferred from the viewpoint of price and availability, and germanium oxide is particularly preferred.

In the case of using a metal compound as the polymerization catalyst, the amount of catalyst used is such that 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 with respect to the polyester to be produced. More preferably 250 ppm or less, particularly preferably 130 ppm or less. If the amount of catalyst used is too high, it is not only economically disadvantageous, but also the thermal stability of the polymer is low, whereas if it is too low, the polymerization activity is low, and the resulting degradation of the polymer during the production of the polymer. are more likely to be induced. As for the amount of the catalyst used here, since the amount of terminal carboxyl groups of the polyester produced is reduced as the amount used is reduced, the method of reducing the amount of the catalyst used is a preferred embodiment.

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

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

High-molecular-weight polyesters using these chain extenders (coupling agents) can be produced using known techniques. After completion of the polycondensation, the chain extender is added to the reaction system in a uniform molten state without a solvent, and reacted with the polyester obtained by the polycondensation. Specifically, a polyester obtained by catalytically reacting a diol and a dicarboxylic acid and having a terminal group substantially having a hydroxyl group and having a weight average molecular weight (Mw) of 20,000 or more, preferably 40,000 or more By reacting the prepolymer with the chain extender, 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, even under severe conditions such as a molten state, even with the use of a small amount of a coupling agent, it is not affected by the residual catalyst, so gel does not occur during the reaction. , can produce high molecular weight polyesters.

After solidifying the obtained polyester, if necessary, solid state polymerization may be carried out in order to further increase the degree of polymerization or 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 about 1 hour or longer and 8 hours or lower, and then 190° C. or higher and 230° C. or lower. at a temperature of 1 hour or more and several tens of hours or less under inert gas flow or under reduced pressure.

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

Various additives may be added in the biomass polyester manufacturing process or to the manufactured biomass polyester as long as the properties are not impaired. Erasers, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, release agents, antioxidants, ion exchange agents, color pigments, and the like can be added. These additives are added in an amount 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 the biomass polyester.

(Thermoplastic resin layer)
The thermoplastic resin layer can be formed using a conventionally known thermoplastic resin. As described above, when a paper container for liquid is produced using a laminate, the layer of the laminate positioned outside the paper container for liquid is the first thermoplastic resin layer, and the laminate positioned inside the paper container for liquid is used as the first thermoplastic resin layer. is used as a second thermoplastic resin layer. By further comprising a thermoplastic resin layer, the laminate has heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties similar to those of conventional laminates. 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, etc., and low density polyethylene, linear low density polyethylene, medium density polyethylene, and ethylene-methacrylic acid copolymer are preferred. The types of the first and second thermoplastic resins may be the same or different.

The first or second thermoplastic resin layer may contain a biomass-derived material, or may contain a fossil fuel-derived material. When the thermoplastic resin layer contains a biomass-derived material, it may contain a biomass polyolefin that is a polymer of a biomass-derived ethylene-containing monomer.

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

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

(barrier layer)
The barrier layer is composed of an inorganic substance and/or an inorganic oxide, preferably a deposited film of an inorganic substance or an inorganic oxide, or a metal foil. The deposited film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and the composition and formation method are not particularly limited. By further including a barrier layer in the laminate, it is possible to impart or improve a gas barrier property that prevents permeation of oxygen gas and water vapor, and a light shielding property that prevents permeation of visible light, ultraviolet light, and the like. Note that the laminate may have two or more barrier layers. When there are two or more barrier layers, they may have the same composition or different compositions.

Examples of deposited films include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti ), lead (Pb), zirconium (Zr), yttrium (Y), or the like, or a deposited film of an inorganic oxide. In particular, as materials suitable for packaging materials (bags) and the like, vapor-deposited films of aluminum metal, or vapor-deposited films of silicon oxide, aluminum metal, or aluminum oxide are preferably used.

Inorganic oxides are represented by MO _X such as SiO _X and AlO _X (wherein M represents an inorganic element, and the value of X varies depending on the inorganic element). expressed. The range of values of X is 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1 for magnesium (Mg), 0 to 1 for calcium (Ca), Potassium (K) is 0 to 0.5, Tin (Sn) is 0 to 2, Sodium (Na) is 0 to 0.5, Boron (B) is 0 to 1,5, Titanium (Ti) can range from 0 to 2, lead (Pb) from 0 to 1, zirconium (Zr) from 0 to 2, and yttrium (Y) from 0 to 1.5. In the above, when X=0, it is a completely inorganic substance (pure substance) and not transparent, and the upper limit of the range of X is the fully oxidized value. Silicon (Si) and aluminum (Al) are preferably used for packaging materials, with silicon (Si) in the range of 1.0 to 2.0 and aluminum (Al) in the range of 0.5 to 1.5. values can be used.

In the present invention, the film thickness of the vapor-deposited film of the inorganic substance or inorganic oxide as described above varies depending on the type of the inorganic substance or inorganic oxide used. It is desirable to select and form arbitrarily within the range of. More specifically, in the case of a vapor deposited film of aluminum, the film thickness is desirably 50 Å or more and 600 Å or less, more preferably 100 Å or more and 450 Å or less. The film thickness is desirably 50 Å or more and 500 Å or less, more preferably 100 Å or more and 300 Å or less.

The vapor deposition film can be formed on a polyester resin layer or the following plastic film using the following forming method. Examples of methods for forming a deposited film include physical vapor deposition methods such as vacuum deposition, sputtering, and ion plating (physical vapor deposition, PVD), plasma chemical vapor deposition, thermochemical vapor deposition, and the like. A chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a chemical vapor deposition method and a photochemical vapor deposition method can be used.

Also, 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 preferable from the viewpoint of gas barrier properties that prevent permeation of oxygen gas and water vapor, and light shielding properties that prevent permeation of visible light, ultraviolet rays, and the like.

(Gas barrier coating film)
If necessary, a gas barrier coating film may be provided on the deposited film. The gas barrier coating film is a layer that functions as a layer that suppresses permeation of oxygen gas and water vapor. The gas barrier coating film has the 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, n represents an integer of 0 or more, m represents an integer of 1 or more, and n+m represents the valence of M.) and at least one or more alkoxides represented by the above polyvinyl alcohol-based It contains a resin and/or an ethylene-vinyl alcohol copolymer, and is obtained by polycondensation by a sol-gel method in the presence of a sol-gel catalyst, acid, water and an organic solvent.

As the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , at least one of partial hydrolyzate of alkoxide and condensate of hydrolysis of alkoxide can be used. The partial hydrolyzate of the above alkoxide does not need to have all of the alkoxy groups hydrolyzed, and may be those in which one or more alkoxy groups are hydrolyzed, or a mixture thereof. As the condensate obtained by hydrolysis of alkoxide, a partially hydrolyzed alkoxide dimer or higher, specifically a dimer to hexamer, is used.

In the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , the metal atom represented by M can be silicon, zirconium, titanium, aluminum, or the like. In this embodiment, preferred metals include, for example, silicon and titanium. In the present invention, alkoxides can be used either singly or as a mixture of alkoxides of two or more different metal atoms in the same solution.

Further, in the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , specific examples of the organic group represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, i -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group, and the like. Further, 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 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 may be the same or different in the same molecule.

For example, a silane coupling agent may be added when preparing the gas barrier composition. Known organic reactive group-containing organoalkoxysilanes can be used as the silane coupling agent. In this embodiment, an organoalkoxysilane having an epoxy group is particularly preferably used. Specifically, examples include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or , β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like can be used. The above silane coupling agents may be used singly or in combination of two or more.

(plastic film)
In the present invention, various plastic films may be used as other layers. For example, an oriented polyethylene terephthalate film, an oriented nylon film, an oriented polypropylene film, a nylon 6/meta-xylylenediamine nylon 6 coextruded and coextended film, or a polypropylene/ethylene-vinyl alcohol copolymer coextruded and coextended film, or the like, or A composite film obtained by laminating two or more of these films may be used. The plastic film may be coated with polyvinyl alcohol or the like.

The plastic film may contain materials derived from biomass or may contain materials derived from fossil fuels. If the plastic film contains biomass-derived material, the same material as the polyester resin layer can be used.

(adhesion 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 lamination method.
Examples of adhesives include one-component or two-component curing or non-curing vinyl, (meth)acrylic, polyamide, polyester, polyether, polyurethane, epoxy, rubber, and others. A solvent-type, water-based, or emulsion-type adhesive can be used. Examples of coating methods for the lamination adhesive include direct gravure roll coating, gravure roll coating, kiss coating, reverse roll coating, fonten method, transfer roll coating, and other methods to form a laminate. It can be applied to the coated side of the layer. The coating amount is preferably 0.1 g/m ² or more and 10 g/m ² or less (dry state), more preferably 1 g/m ² or more and 5 g/m ² or less (dry state).

Further, 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 the layer when a thermoplastic resin layer or the like is laminated by a melt extrusion lamination method. may The anchor coating agent includes any resin having a heat resistance temperature of 135° C. or higher, such as an anchor coating agent made of a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, or 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. In addition, a silane coupling agent may be used together as an additive, and nitrocellulose may be used together to improve heat resistance.

Also, the adhesive layer may be an adhesive resin layer used for bonding two layers by a sand lamination method or a melt extrusion lamination method. Thermoplastic resins that can be used for the adhesive resin layer include polyethylene-based resins, polypropylene-based resins, cyclic polyolefin-based resins, or copolymer resins, modified resins, or mixtures (including alloys) containing these resins as main components. ) can be used. Polyolefin resins include, for example, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), metallocene catalyst Ethylene-α-olefin copolymer, ethylene-polypropylene random or block copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-α-olefin copolymer polymerized using Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-maleic acid copolymer, ionomer resin, adhesion between layers In order to improve the above, it is possible to use an acid-modified polyolefin resin obtained by modifying the above polyolefin resin with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, or itaconic acid. can. 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 singly or in combination of two or more. Cyclic polyolefins such as ethylene-propylene copolymers, polymethylpentene, polybutene, and polynorbonene can be used as cyclic polyolefin resins. These resins can be used singly or in combination. Needless to say, as the above-described polyethylene-based resin, one using the above-described biomass-derived ethylene as a monomer unit can be used.

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

When the adhesive resin layer contains biomass polyolefin, the biomass polyolefin that is suitably used includes low-density polyethylene derived from biomass manufactured by Braskem (trade name: SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g /10 min, biomass degree 95%), biomass-derived low-density polyethylene manufactured by Braskem (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 the metal foil or vapor deposition film and the paper base layer is made of biomass-derived polyethylene, the thickness of the resin layer can be 50 μm or more. preferable. As a result, the plastic film provided with the metal foil or vapor-deposited film and the paper substrate layer can be laminated together without using EMAA, so that the degree of biomass can be increased.

(resin layer)
A resin layer may be provided as another layer. Thermoplastic resins that can be used for the resin layer include polyethylene-based resins, polypropylene-based resins, cyclic polyolefin-based resins, copolymer resins, modified resins, and mixtures (including alloys) containing these resins as main components. can be used. Polyolefin resins include, for example, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), metallocene catalyst Ethylene-α-olefin copolymer, ethylene-polypropylene random or block copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-α-olefin copolymer polymerized using Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-maleic acid copolymer, ionomer resin, the above polyolefin resin , acid-modified polyolefin resins modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid and 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 singly or in combination of two or more. Cyclic polyolefins such as ethylene-propylene copolymers, polymethylpentene, polybutene, and polynorbonene can be used as cyclic polyolefin resins. These resins can be used singly or in combination. Needless to say, as the above-described polyethylene-based resin, one using the above-described biomass-derived ethylene as a monomer unit can be used.

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

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

(Laminate manufacturing method)
The method for producing the laminate according to the present invention is not particularly limited, and the laminate can be produced by using conventionally known methods such as dry lamination, melt extrusion lamination, and sand lamination. In the present invention, a sand lamination method can be used to laminate a polyester resin layer via an adhesive resin layer formed by melt extrusion.

The thickness of the laminate obtained as described above is arbitrary according to its use, 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 imparted with chemical functions, electrical functions, magnetic functions, mechanical functions, friction/wear/lubricating functions, optical functions, thermal functions, surface functions such as biocompatibility, and the like. For the purpose, it is also possible to apply secondary processing. Examples of secondary processing include embossing, painting, adhesion, printing, metallizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.). Also, the laminate according to the present invention can be subjected to lamination (dry lamination or extrusion lamination), bag making, and other post-treatments to produce a molded product.

(Application)
Laminates according to the present invention can be used for packaging products such as paper cups, paper containers for liquids, label materials, lids and the like.

(liquid paper container)
Since the liquid paper container according to the present invention has excellent barrier properties, it can be used for food such as alcohols such as sake, shochu and wine, milk drinks such as milk, soft drinks such as orange juice and tea, car wax, shampoo and detergents. It can be suitably used as a wrapping paper container for general liquids such as chemical products. A case where a paper container is formed using the laminate according to the present invention will be described. For example, the liquid paper container 40 shown in FIG. 4 can be formed after the laminate shown in FIGS. 1 to 3 is creased.

As shown in FIG. 4, the paper container for liquid 40 has a rectangular cylindrical body portion 41 including side surfaces, a rectangular plate-like bottom portion 42, and an upper portion 43, and is a so-called gobel-top type container. there is The upper portion 43 has a pair of opposing inclined plates 44 and a pair of folding portions 45 positioned between the pair of inclined plates 44 and folded between the inclined plates 44 . Also, the pair of inclined plates 44 are adhered to each other by glue margins 46 provided at their upper ends. Alternatively, one of the pair of inclined plates 44 may be fitted with a spout and the spout may be sealed with a cap. A flat-top container may also be formed.

(Other aspects)
The present inventors focused on ethylene glycol, which is a raw material of polyester, and instead of ethylene glycol obtained from conventional fossil fuels, biomass polyester using biomass-derived ethylene glycol as its raw material (hereinafter simply "biomass polyester" A laminate comprising a polyester resin layer containing a polyester resin layer containing a conventional fossil fuel is made of polyester produced using ethylene glycol obtained from conventional fossil fuel (hereinafter sometimes simply referred to as "fossil fuel-derived polyester"). The inventors have found that a laminate having a polyester resin layer can be obtained that is comparable in physical properties such as mechanical properties. Another aspect of the present invention is based on such findings.
Therefore, an object of another aspect of the present invention is to provide a laminate comprising a polyester resin layer containing a biomass polyester, which is comparable in physical properties such as mechanical properties to a laminate comprising a polyester resin layer made of a conventional fossil fuel-derived polyester. It is to provide the body.
In another aspect of the invention,
A laminate comprising at least a first thermoplastic resin layer, a paper base layer, a polyester resin layer, and a second thermoplastic resin layer in this order,
The polyester resin layer contains a biomass polyester having biomass-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit,
A laminate is provided in which the polyester resin layer has a biomass content of 5% or more.
In another aspect of the invention, it is preferred that the dicarboxylic acid is terephthalic acid.
In another aspect 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 that the resin material is included.
In another aspect of the invention, a packaged product is provided comprising the laminate.
In another aspect of the present invention, a liquid paper container comprising the laminate,
A paper container for liquid is provided, wherein the innermost layer of the paper container for liquid is the second thermoplastic resin layer.
A laminate according to another aspect of the present invention includes at least a paper base layer, a polyester resin layer containing biomass polyester, and a thermoplastic resin layer, thereby reducing the amount of fossil fuel used compared to the conventional one. can reduce environmental impact. In addition, since the laminate according to another aspect of the present invention is comparable in physical properties such as mechanical properties to a laminate comprising a conventional fossil fuel-derived polyester resin layer, the conventional fossil fuel-derived polyester resin A laminate comprising layers can be substituted.

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

<Measurements/Conditions>
In the following reference examples, reference comparative examples, examples, and comparative examples, the degree of biomass is the value of biomass-derived carbon concentration 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]
<Production of Laminate 1>
A biaxially stretched polyester film 1 (biomass degree: 20%, DE024 manufactured by Toyobo Co., Ltd., thickness 12 μm) formed using fossil fuel-derived terephthalic acid and biomass-derived ethylene glycol (biomass polyester) was prepared. . A milk carton base paper (manufactured by Clearwater Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and one surface was coated with a fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC520, density: 0.923 g/ cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%) is melt extrusion 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). Next, on the surface opposite to the first thermoplastic resin layer of the paper base layer, a low-density polyethylene derived from fossil fuel (LC520 manufactured by Japan Polyethylene Co., Ltd., density: 0.923 g/ cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%), polyester film 1 (polyester resin layer, thickness 12 μm) were laminated together. Subsequently, an anchor coat agent (EL540/CAT-RT32 manufactured by Toyo-Morton Co., Ltd.) was applied on the polyester film 1 and dried to form an anchor coat layer. After that, a fossil fuel-derived low-density polyethylene (LC520, manufactured by Japan Polyethylene Co., Ltd., density: 0.923 g/cm ³ , MFR: 3.6 g/10 minutes, biomass degree: 0%) was applied on the anchor coat layer at 320 ° C. Melt extrusion lamination is performed at a resin temperature and a line speed of 100 m / min to form a thermoplastic resin layer (biomass degree: 0%, thickness 55 μm), a first thermoplastic resin layer, a paper base layer, an adhesive resin A laminate 1 was obtained in which a layer, a polyester resin layer, an anchor coat layer, and a second thermoplastic resin layer were laminated in this order.

[Example 2]
<Production of laminate 2>
Milk carton base paper (manufactured by Clearwater Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ ) was coated on one side. , MFR: 8.1 g / 10 min, biomass degree: 95%) is melt extrusion laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form the first thermoplastic resin layer (biomass degree: 95%, thickness 20 μm) was formed. Next, a biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95%), polyester film 1 (polyester resin layer, biomass degree: 20%, thickness 12 μm). Subsequently, an anchor coat agent (EL540/CAT-RT32 manufactured by Toyo-Morton Co., Ltd.) was applied on the polyester film 1 and dried to form an anchor coat layer. After that, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, degree of biomass: 95%) was applied on the anchor coat layer at a resin temperature of 320°C. , Melt extrusion lamination 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 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 laminated in this order.

[Comparative Example 1]
<Production of Laminate 3>
Biaxially stretched polyester film 2 (biomass degree: 0%, manufactured by Toyobo Co., Ltd., E5100, thickness 12 μm) formed using fossil fuel-derived terephthalic acid and fossil fuel-derived ethylene glycol (fossil fuel-derived polyester) prepared. A milk carton base paper (manufactured by Clearwater Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and one surface was coated with a fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC520, density: 0.923 g/ cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%) is melt extrusion 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). Next, on the surface opposite to the first thermoplastic resin layer of the paper base layer, a low-density polyethylene derived from fossil fuel (LC520 manufactured by Japan Polyethylene Co., Ltd., density: 0.923 g/ cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%), polyester film 2 (resin layer, biomass degree: 0%) is passed through this adhesive resin layer (biomass degree: 0%, thickness 15 μm) : 0%, thickness 12 μm). Subsequently, an anchor coating agent (EL540/CAT-RT32 manufactured by Toyo-Morton Co., Ltd.) was applied on the polyester film 2 and dried to form an anchor coating layer. After that, a fossil fuel-derived low-density polyethylene (LC520, manufactured by Japan Polyethylene Co., Ltd., density: 0.923 g/cm ³ , MFR: 3.6 g/10 minutes, biomass degree: 0%) was applied on the anchor coat layer at 320 ° C. Melt extrusion lamination is performed 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 layer , an adhesive resin layer, a plastic film, an anchor coat layer, and a second thermoplastic resin layer were laminated in this order to obtain a laminate 3 .

[Example 3]
<Production of Laminate 4>
A milk carton base paper (manufactured by Clearwater Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and one surface was coated with a fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC520, density: 0.923 g/ cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%) is melt extrusion 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). Next, on the surface opposite to the first thermoplastic resin layer of the paper base layer, a sand lamination method is used to apply a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemicals, Nuclell N0908C ), aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and polyester film 1 (polyester resin layer, biomass degree: 20 %, thickness 12 μm) was dry-laminated using a two-component curing adhesive (manufactured by DIC Graphics: main agent LX-703A/curing agent KR-90), and the aluminum foil surface of the dry laminate film was laminated. Subsequently, one surface of the polyester film of the dry laminate film was coated with a two-liquid curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. After that, a fossil fuel-derived low-density polyethylene (LC520, manufactured by Japan Polyethylene Co., Ltd., density: 0.923 g/cm ³ , MFR: 3.6 g/10 minutes, biomass degree: 0%) was applied on the anchor coat layer at 320 ° C. Melt extrusion lamination is performed 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 layer , 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 laminated in this order to obtain a laminate 4 .

[Example 4]
<Production of laminate 5>
Milk carton base paper (manufactured by Clearwater Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ ) was coated on one side. , MFR: 8.1 g / 10 minutes, biomass degree: 95%) is melt extrusion 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%, 20 μm thick). Next, on the surface opposite to the first thermoplastic resin layer of the paper base layer, a sand lamination method is used to apply a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemicals, Nuclell N0908C ), aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and polyester film 1 (polyester resin layer, biomass degree: 20 %, thickness 12 μm) was dry-laminated using a two-component curing adhesive (manufactured by DIC Graphics: main agent LX-703A/curing agent KR-90), and the aluminum foil surface of the dry laminate film was laminated. Subsequently, one surface of the polyester film of the dry laminate film was coated with a two-liquid curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer.
After that, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, degree of biomass: 95%) was applied on the anchor coat layer at 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 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 laminated in this order.

[Comparative Example 2]
<Production of laminate 6>
A milk carton base paper (manufactured by Clearwater Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and one surface was coated with a fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC520, density: 0.923 g/ cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%) is melt extrusion 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). Next, on the surface opposite to the first thermoplastic resin layer of the paper base layer, a sand lamination method is used to apply a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemicals, Nuclell N0908C ), aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and polyester film 2 (resin layer, biomass degree: 0%) are extruded through this adhesive resin layer (biomass degree 0%, thickness 20 μm). , thickness 12 μm) were dry-laminated using a two-liquid curing adhesive (manufactured by DIC Graphics: main agent LX-703A/curing agent KR-90), and the aluminum foil surface of the dry laminate film was laminated. Subsequently, two sides of the polyester film of the dry laminate film were coated with a two-liquid curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. After that, a fossil fuel-derived low-density polyethylene (LC520, manufactured by Japan Polyethylene Co., Ltd., density: 0.923 g/cm ³ , MFR: 3.6 g/10 minutes, biomass degree: 0%) was applied on the anchor coat layer at 320 ° C. Melt extrusion lamination is performed 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 layer , an adhesive resin layer, a barrier layer, a plastic film, an anchor coat layer, and a second thermoplastic resin layer were laminated in this order to obtain a laminate 4 .

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

A milk carton base paper (manufactured by Clearwater Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and one surface was coated with a fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC520, density: 0.923 g/ cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%) is melt extrusion 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). Next, on the surface opposite to the first thermoplastic resin layer of the paper base layer, a sand lamination method is used to apply a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemicals, Nuclell N0908C ) was extruded, the vapor-deposited surface of the barrier film 1 was bonded via this adhesive resin layer (biomass degree 0%, thickness 20 μm). Subsequently, the polyester film surface of the barrier film 1 was coated with a two-liquid curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. After that, using a sand lamination method, a fossil fuel-derived low-density polyethylene (LC520 manufactured by Japan Polyethylene Co., Ltd., density: 0.923 g/cm ³ , MFR: 3.6 g/10 minutes, biomass degree: 3.6 g/10 minutes, biomass degree: 0%), a fossil fuel-derived linear low-density polyethylene film (manufactured by Dai Nippon Printing Co., Ltd.: DYS-01N, thickness 40 μm) is passed through this adhesive resin layer (biomass degree 0%, thickness 20 μm). ) to form a second thermoplastic resin layer (biomass degree: 0%, thickness 55 μm), first thermoplastic resin layer, paper base 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 laminated in this order.

[Example 6]
<Production of laminate 8>
Milk carton base paper (manufactured by Clearwater Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ ) was coated on one side. , MFR: 8.1 g / 10 minutes, biomass degree: 95%) is melt extrusion 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%, 20 μm thick). Next, on the surface opposite to the first thermoplastic resin layer of the paper base layer, a sand lamination method is used to apply a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemicals, Nuclell N0908C ) was extruded, the vapor-deposited surface of the barrier film 1 was bonded via this adhesive resin layer (biomass degree 0%, thickness 20 μm). Subsequently, the polyester film surface of the barrier film 1 was coated with a two-liquid curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. After that, using a sand lamination method, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, biomass degree: 95%) was applied onto the anchor coat layer. ) While extruding, a biomass-derived low-density polyethylene film (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95%, thickness 40 μm), first thermoplastic resin layer, paper base layer, adhesive resin layer, barrier layer, polyester resin layer, anchor coat layer, adhesive resin layer , to obtain a laminate 8 in which the second thermoplastic resin layers are sequentially laminated.

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

A milk carton base paper (manufactured by Clearwater Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and one surface was coated with a fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC520, density: 0.923 g/ cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%) is melt extrusion 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). Next, on the surface opposite to the first thermoplastic resin layer of the paper base layer, a sand lamination method is used to apply a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemicals, Nuclell N0908C ) was extruded, the vapor-deposited surface of the barrier film 2 was bonded via this adhesive resin layer (biomass degree 0%, thickness 20 μm). Subsequently, the polyester film surface of the barrier film 2 was coated with a two-liquid curing anchoring agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. After that, using a sand lamination method, a fossil fuel-derived low-density polyethylene (LC520 manufactured by Japan Polyethylene Co., Ltd., density: 0.923 g/cm ³ , MFR: 3.6 g/10 minutes, biomass degree: 3.6 g/10 minutes, biomass degree: 0%), a fossil fuel-derived linear low-density polyethylene film (manufactured by Dai Nippon Printing Co., Ltd.: DYS-01N, thickness 40 μm) is passed through this adhesive resin layer (biomass degree 0%, thickness 20 μm). ) to form a second thermoplastic resin layer (biomass degree: 0%, thickness 55 μm), first thermoplastic resin layer, paper base layer, adhesive resin layer, barrier layer, plastic film , an anchor coat layer, an adhesive resin layer, and a second thermoplastic resin layer were laminated in this order to obtain a laminate 9 .

[Example 7]
<Production of laminate 10>
A polyester film 1 (biomass degree: 20%, manufactured by Toyobo Co., Ltd., DE024, thickness: 12 μm) was prepared. Then, a vapor deposition layer of silicon oxide having a film thickness of 120 Å was formed on one surface of the polyester film 1 using the plasma chemical vapor deposition method under the following vapor deposition conditions.
(Vapor deposition conditions)
Raw material: Hexamethyldisiloxane Amount of introduced gas: Hexamethyldisiloxane: Oxygen gas: Helium = 1.0:1.5:1.0 (unit: slm)

Next, after coating the vapor deposition layer with a barrier coating liquid prepared in the following manner, it is heat-treated to form a gas barrier coating film having a thickness of 0.3 μm (in a dry state). A flexible film 3 was produced.

The above-mentioned barrier coating liquid was prepared according to the following composition table, and was prepared by adding ethyl silicate, silane coupling agent, , hydrochloric acid, and ion-exchanged water were added and stirred to obtain a colorless and transparent barrier coating liquid.
(Composition table)

Next, using a dry lamination method, the surface of the gas barrier coating film of the barrier film 3 and the biomass-derived 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 Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and one surface was coated with 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 extrusion 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) to form a laminated film 2.

Next, the surface of the polyester film 1 of the laminated film 1 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. While extruding the derived low-density polyethylene (manufactured by 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 1 and the surface of the paper base layer of the laminated film 2 are laminated together with a thickness of 50 μm) to form a first thermoplastic resin layer, a paper base layer, and an adhesive resin layer. , 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 to obtain a laminate 10 .

[Comparative Example 4]
<Production of laminate 11>
A polyester film 2 (biomass content: 0%, manufactured by Toyobo Co., Ltd., E5100, thickness: 12 μm) was prepared. Then, in the same manner as in Example 7, a vapor deposition layer of silicon oxide having a film thickness of 120 Å was formed on one surface of the polyester film 2, and then a gas barrier film having a thickness of 0.3 μm (dry state) was placed on the vapor deposition layer. A barrier film 4 was produced by forming a protective coating film.

Next, using a dry lamination method, the surface of the gas barrier coating film of the barrier film 4 and the fossil fuel are bonded via a two-component curing adhesive (manufactured by DIC Graphics: main agent LX-703A/curing agent KR-90). A laminated film 3 was formed by laminating a polyethylene film (manufactured by Dai Nippon Printing Co., Ltd., biomass degree: 0%, thickness: 60 μm).

Next, a milk carton base paper (manufactured by Clearwater Co., basis weight: 400 g/m ² ) was prepared as a paper base layer, and a low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Co., Ltd., LC520, density: 0.2) was coated on one side. 923 g/cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%) is melt extrusion 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) to form a laminated film 4.

Next, the surface of the polyester film 2 of the laminated film 3 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) to form an anchor coat layer. While extruding fuel-derived low-density polyethylene (LC520, density: 0.923 g/cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%) derived from fuel, this adhesive resin layer (biomass degree: 0 %, thickness 50 μm), the surface of the polyester film 2 of the laminated film 3 and the surface of the paper base layer of the laminated film 4 are laminated together, and the first thermoplastic resin layer, the paper base layer, 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 laminated in this order.

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

Next, using a dry lamination method, the surface of the gas barrier coating film of the laminated film 5 and the biomass-derived A laminate 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 min, biomass degree: 95%, thickness: 60 μm).

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

Next, on the other side of the paper base layer of the laminate film 7, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, biomass degree: 95%) is melt extrusion 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), and the first thermoplastic resin A layer, a paper substrate 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 laminated in this order to obtain a laminate 12 .

[Comparative Example 5]
<Production of laminate 13>
The surface of the polyester film 2 of the barrier film 4 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. 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. A layer (biomass degree: 0%, thickness: 20 μm) was formed to form a laminated film 8 .

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

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

Next, on the other side of the paper base layer of the laminated film 10, low-density polyethylene derived from fossil fuel (LC520 manufactured by Japan Polyethylene Co., Ltd., density: 0.923 g/cm ³ , MFR: 3.6 g/10 minutes, biomass degree: 0%) is melt-extrusion 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 substrate 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 laminated in this order.

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

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

Next, using a dry lamination method, the surface of the gas barrier coating film of the barrier film 5 and the biomass-derived A laminated film 11 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, the surface of the polyester film 1 of the laminated film 11 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. While extruding the derived low-density polyethylene (manufactured by 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 11 and the surface of the paper base layer of the laminated film 2 are pasted together with a thickness of 50 μm) to form a first thermoplastic resin layer, a paper base layer, and an adhesive resin layer. , 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 to obtain a laminate 14 .

[Comparative Example 6]
<Production of laminate 15>
A polyester film 2 (biomass content: 0%, manufactured by Toyobo Co., Ltd., E5100, thickness: 12 μm) was prepared. Next, in the same manner as in Example 9, after forming a vapor deposition layer of aluminum oxide having a film thickness of 80 Å on one surface of the polyester film 2, a gas barrier film having a thickness of 0.3 μm (dried state) was formed on the vapor deposition layer. A barrier film 6 was produced by forming a protective coating film.

Next, using a dry lamination method, the surface of the gas barrier coating film of the barrier film 6 and the fossil fuel are bonded via a two-component curing adhesive (manufactured by DIC Graphics: main agent LX-703A/curing agent KR-90). A laminated film 12 was formed by laminating a polyethylene film (manufactured by Dai Nippon Printing Co., Ltd., biomass degree: 0%, thickness: 60 μm).

Next, the surface of the polyester film 2 of the laminated film 12 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210 / A3075) to form an anchor coat layer. While extruding fuel-derived low-density polyethylene (LC520, density: 0.923 g/cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%) derived from fuel, this adhesive resin layer (biomass degree: 0 %, thickness 50 μm), the surface of the polyester film 1 of the laminated film 12 and the surface of the paper base layer of the laminated film 4 are laminated together, and the first thermoplastic resin layer, the paper base layer, 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 laminated in this order.

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

Next, using a dry lamination method, the surface of the gas barrier coating film of the laminated film 13 and the biomass-derived A laminated film 14 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 Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0) was prepared using a sand lamination method. .918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: 95%), the resin layer of the laminated film 14 is extruded through this adhesive resin layer (biomass degree: 95%, thickness: 50 μm). A laminated film 15 was formed by laminating the face and one face of the paper base layer.

Next, on the other side of the paper base layer of the laminate film 15, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, biomass degree: 95%) is melt extrusion 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), and the first thermoplastic resin A layer, a paper substrate 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 laminated in this order to obtain a laminate 16 .

[Comparative Example 7]
<Production of Laminate 17>
The surface of the polyester film 2 of the barrier film 6 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. 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. A layer (biomass degree: 0%, thickness: 20 μm) was formed to form a laminate film 16 .

Next, using a dry lamination method, the surface of the gas barrier coating film of the barrier film 4 and the fossil fuel are bonded via a two-component curing adhesive (manufactured by DIC Graphics: main agent LX-703A/curing agent KR-90). A laminated film 17 was formed by laminating a polyethylene film (manufactured by Dai Nippon Printing Co., Ltd.: biomass content: 0%, thickness: 60 μm).

Next, a milk carton base paper (manufactured by Clearwater Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and a low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Co., Ltd., LC520, density : 0.923 g/cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%), the resin of the laminated film 17 is extruded through this adhesive resin layer (biomass degree: 0%, thickness: 50 μm) A laminated film 18 was formed by laminating the surface of the layer and one surface of the paper base layer.

Next, on the other side of the paper base layer of the laminated film 18, a fossil fuel-derived low-density polyethylene (LC520 manufactured by Japan Polyethylene Co., Ltd., density: 0.923 g/cm ³ , MFR: 3.6 g/10 minutes, biomass degree: 0%) is melt-extrusion 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 substrate 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 laminated in this order.

[Example 11]
<Production of Laminate 18>
A milk carton base paper (manufactured by Clearwater Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and one surface was coated with a fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC520, density: 0.923 g/ cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%) is melt extrusion 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). Next, on the surface opposite to the first thermoplastic resin layer of the paper base layer, a sand lamination method is used to apply a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemicals, Nuclell N0908C ), aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and polyester film 1 (polyester resin layer, biomass degree: 20 %, thickness 12 μm) and a dry laminate film obtained by dry laminating using a two-component curing adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90). The surface of the polyester film 1 was bonded. . Subsequently, on the surface of the aluminum foil of the dry laminated film, using a sand lamination method, a fossil fuel-derived ethylene-methacrylic acid copolymer (Nucrel N0908C, manufactured by Mitsui DuPont Polychemicals Co., Ltd.) is extruded while this adhesive resin layer. (Biomass degree 0%, thickness 20 μm), a fossil fuel-derived polyethylene film (manufactured by Dai Nippon Printing Co., Ltd.: SKL, thickness 40 μm) is pasted together to form a first thermoplastic resin layer and a paper base layer. , an adhesive resin layer, a polyester resin layer, an adhesive layer, a barrier layer, an adhesive resin layer, and a second thermoplastic resin layer in this order.

[Comparative Example 8]
<Production of laminate 19>
A milk carton base paper (manufactured by Clearwater Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and one surface was coated with a fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC520, density: 0.923 g/ cm ³ , MFR: 3.6 g/10 min, biomass degree: 0%) is melt extrusion 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). Next, on the surface opposite to the first thermoplastic resin layer of the paper base layer, a sand lamination method is used to apply a fossil fuel-derived ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemicals, Nuclell N0908C ), aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and polyester film 2 (resin layer, biomass degree: 0%) are extruded through this adhesive resin layer (biomass degree 0%, thickness 20 μm). , thickness 12 μm) was dry-laminated using a two-component curing adhesive (manufactured by DIC Graphics: main agent LX-703A/curing agent KR-90), and the surface of the polyester film 2 of the dry laminate film was laminated. Subsequently, on the surface of the aluminum foil of the dry laminated film, using a sand lamination method, a fossil fuel-derived ethylene-methacrylic acid copolymer (Nucrel N0908C, manufactured by Mitsui DuPont Polychemicals Co., Ltd.) is extruded while this adhesive resin layer. (Biomass degree 0%, thickness 20 μm), a fossil fuel-derived polyethylene film (manufactured by Dai Nippon Printing Co., Ltd.: SKL, thickness 40 μm) is pasted together to form a first thermoplastic resin layer and a paper base layer. , an adhesive resin layer, a plastic film, an adhesive layer, a barrier layer, an adhesive resin layer, and a second thermoplastic resin layer in this order.

[Example 12]
<Production of laminate 20>
Using a dry lamination method, the surface of the polyester film 1 of the barrier film 3 and the biomass-derived low-density A laminated film 19 was formed by laminating polyethylene films (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, biomass degree: 95%, thickness: 60 μm).

Next, the surface of the gas barrier coating film of the laminate film 19 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. While extruding biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, biomass degree: 95%), this adhesive resin layer (biomass degree: 95% , thickness 50 μm), the surface of the polyester film 1 of the laminated film 19 and the surface of the paper base layer of the laminated film 2 are bonded together, and the first thermoplastic resin layer, the paper base layer, the adhesive resin A layer, an anchor coat layer, a barrier layer, a polyester resin layer, an adhesive layer, and a second thermoplastic resin layer were laminated in this order to obtain a laminate 20 .

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

Next, the surface of the gas barrier coating film of the laminate film 20 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. This adhesive resin layer ⁽ biomass degree 0%, thickness 50 μm), the surface of the polyester film 2 of the laminated film 20 and the surface of the paper base layer of the laminated film 4 are laminated together to form the first thermoplastic resin layer, the paper base 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 laminated in this order.

[Example 13]
<Production of laminate 22>
The surface of the gas barrier coating film of the barrier film 3 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. Co., Ltd., SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: 95%) was melt-extrusion laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a resin layer. (biomass degree: 95%, thickness: 20 μm) to form a laminated film 21 .

Next, using a dry lamination method, the polyester film 1 surface of the laminated film 21 and the biomass-derived low-temperature A laminated film 22 was formed by laminating 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 Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0) was prepared using a sand lamination method. .918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: 95%), the resin layer of the laminated film 22 is extruded through this adhesive resin layer (biomass degree: 95%, thickness: 50 μm). A laminated film 23 was formed by laminating the face and one face of the paper base layer.

Next, a biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, biomass degree: 8.1 g/10 minutes, biomass degree: 95%) is melt extrusion 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), the first thermoplastic 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 laminated in this order.

[Comparative Example 10]
<Production of laminate 23>
The surface of the gas barrier coating film of the barrier film 4 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. Japan Polyethylene Co., Ltd., LC520, density: 0.923 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. A resin layer (biomass content: 0%, thickness: 20 μm) was formed to form a laminated film 24 .

Next, using a dry lamination method, the surface of the polyester film 2 of the laminated film 24 and the surface of the fossil fuel-derived A laminated film 25 was formed by laminating a polyethylene film (manufactured by Dai Nippon Printing Co., Ltd., biomass content: 0%, thickness: 60 μm).

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

Next, on the other side of the paper base layer of the laminated film 26, a fossil fuel-derived low-density polyethylene (LC520 manufactured by Japan Polyethylene Co., Ltd., density: 0.923 g/cm ³ , MFR: 3.6 g/10 minutes, biomass degree: 0%) is melt extrusion 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), and the first A laminate 23 was obtained in which a thermoplastic resin layer, a paper substrate 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 laminated in this order.

[Example 14]
<Production of laminate 24>
Using a dry lamination method, the surface of the polyester film 1 of the barrier film 5 and the low-density biomass-derived low-density 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) was laminated to form a laminate film 27 .

Next, the surface of the gas barrier coating film of the laminate film 27 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. While extruding biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, biomass degree: 95%), this adhesive resin layer (biomass degree: 95% , thickness 50 μm), the surface of the polyester film 1 of the laminated film 27 and the surface of the paper base layer of the laminated film 2 are bonded together, and the first thermoplastic resin layer, the paper base layer, the adhesive resin A layer, an anchor coat layer, a barrier layer, a polyester resin layer, an adhesive layer, and a second thermoplastic resin layer were laminated in this order to obtain a laminate 20 .

[Comparative Example 11]
<Production of Laminate 25>
Using a dry lamination method, the surface of the polyester film 2 of the barrier film 6 and the polyethylene derived from fossil fuel are bonded via a two-component curing adhesive (manufactured by DIC Graphics: main agent LX-703A/curing agent KR-90). A laminated film 28 was formed by laminating films (manufactured by Dai Nippon Printing Co., Ltd.: biomass content: 0%, thickness: 60 μm).

Next, the surface of the gas barrier coating film of the laminated film 28 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. 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 layer of the laminated film 4 are laminated together to form the first thermoplastic resin layer, the paper base 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 laminated in this order.

[Example 15]
<Production of Laminate 26>
The surface of the gas barrier coating film of the barrier film 5 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. Co., Ltd., SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: 95%) was melt-extrusion laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a resin layer. (biomass degree: 95%, thickness: 20 μm) to form a laminate film 29 .

Next, using a dry lamination method, the polyester film 1 surface of the laminated film 29 and the biomass-derived low-temperature A laminate film 30 was formed by laminating 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 Co., basis weight 400 g/m ² ) was prepared as a paper base layer, and a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0) was prepared using a sand lamination method. .918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: 95%), the resin layer of the laminated film 30 is extruded through this adhesive resin layer (biomass degree: 95%, thickness: 50 μm). A laminated film 31 was formed by laminating the surface and one surface of the paper base layer.

Next, a biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, biomass degree: 95%) is melt extrusion 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), the first thermoplastic 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 laminated in this order.

[Comparative Example 12]
<Production of Laminate 27>
The surface of the gas barrier coating film of the barrier film 6 is coated with a two-component curing anchor agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. Japan Polyethylene Co., Ltd., LC520, density: 0.923 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. A resin layer (biomass degree: 0%, thickness: 20 μm) was formed to form a laminate film 32 .

Next, using a dry lamination method, the surface of the polyester film 2 of the laminated film 32 and the surface of the fossil fuel-derived A laminated film 33 was formed by laminating a polyethylene film (manufactured by Dai Nippon Printing Co., Ltd., biomass content: 0%, thickness: 60 μm).

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

Next, on the other side of the paper base layer of the laminated film 34, a fossil fuel-derived low-density polyethylene (LC520 manufactured by Japan Polyethylene Co., Ltd., density: 0.923 g/cm ³ , MFR: 3.6 g/10 minutes, biomass degree: 0%) is melt extrusion 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), and the first A laminate 23 was obtained in which a thermoplastic resin layer, a paper substrate 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 laminated in this order.

[Production Examples 1 to 27]
<Production of liquid paper container>
By pressing the laminates 1 to 27 with a male die and a female die, a creasing process was applied and blanks for paper containers were punched out. After that, using a liquid paper container filling machine "DR-10", the center value of the sealing temperature conditions is set to 320 ° C. for the top heater temperature and 340 ° C. for the bottom heater temperature, and the blank is made into a paper container 1 to the form shown in FIG. 27 was made.

(liquid leakage test)
After cutting off the top and bottom of liquid paper containers 1 to 27 prepared above, the test liquid (Microcheck penetrating liquid (manufactured by Taiho Kozai)) is injected into the top and bottom, left at room temperature for 30 minutes, and then Microcheck. Washing was performed with a washing liquid (manufactured by Taiho Kozai Co., Ltd.). Thereafter, the container was heated with hot air, the top and bottom portions were opened into a flat plate, and liquid leakage and pinholes were visually evaluated according to the following evaluation criteria. Table 2 shows the evaluation results.
(Evaluation criteria for liquid leakage)
◯: There was no liquid leakage from the top seal portion and the bottom seal portion, and the performance as a paper container for liquid was good.
x: There was liquid leakage from the top seal portion and the bottom seal portion, and the performance as a paper container for liquid was unsatisfactory.
(Evaluation criteria for pinholes)
◯: No pinholes were found in the top and bottom portions, and the performance as a paper container for liquid was good.
x: There were pinholes in the top and bottom parts, and the performance as a paper container for liquid was poor.

Reference Signs List 10, 20, 30 laminate 11 first thermoplastic resin layer 12 paper substrate layer 13 polyester resin layer 14 second thermoplastic resin layer 15 adhesive layer 16 barrier layer 40 paper container for liquid 41 body 42 bottom 43 top 44 Inclined plate 45 Folding portion 46 Overlap margin

Claims (7)

At least a first thermoplastic resin layer, a paper base layer, a second adhesive resin layer, a polyester resin layer to which a metal foil is bonded or a polyester resin layer to which a vapor deposition film is formed, and a first adhesive A liquid paper container comprising a laminate comprising a resin layer and a second thermoplastic resin layer in this order,
The polyester resin layer contains a biomass polyester having biomass-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit,
The biomass degree in the polyester resin layer is 5% or more,
The first adhesive resin layer is in contact with the second thermoplastic resin layer,
The innermost layer of the laminate is the second thermoplastic resin layer,
The first adhesive resin layer is polyethylene,
A paper container for liquids, wherein the second thermoplastic resin layer does not contain a low-crystalline rubber component . A liquid carton container according to claim 1, wherein said dicarboxylic acid is terephthalic acid. The paper container for liquid according to claim 1 or 2, wherein the first adhesive resin layer contains biomass polyethylene, which is a polymer of a monomer containing biomass-derived ethylene. 4. A paper container for liquids according to claim 3, wherein said biomass polyethylene is biomass-derived low density polyethylene. 3. The first adhesive resin layer is composed only of biomass-derived low-density polyethylene, or composed of a mixed resin of biomass-derived low-density polyethylene and fossil fuel-derived low-density polyethylene. A liquid carton according to . A paper container for liquids according to any one of claims 1 to 5, wherein the second thermoplastic resin layer comprises biomass-derived polyethylene. A method for producing a laminate used for the liquid paper container according to any one of claims 1 to 6,
A method for producing a laminate, comprising laminating the second thermoplastic resin layer via the melt-extruded first adhesive resin layer.

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