JP2021100865A - Laminate having polyolefin resin layer and packaged product having the same - Google Patents

Abstract

To provide a laminate having a polyester resin layer comprising a polyester derived form conventional fossil fuel and a laminate having a polyester resin layer comprising a biomass polyester which is not inferior in physical properties such as mechanical characteristics.SOLUTION: There is provided a laminate having at least a paper base material layer, a polyester resin layer and a thermoplastic resin layer in this order, wherein the polyester resin layer contains a biomass polyester containing ethylene glycol derived from biomass as a diol unit and dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit and the biomass degree in the polyester resin layer is 5% or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminate provided with a polyester resin layer containing a biomass polyester, and more specifically, at least a paper substrate layer and a biomass-derived ethylene glycol are used as diol units, and a fossil fuel-derived dicarboxylic acid is a dicarboxylic acid. The present invention relates to a laminate including a polyester resin layer containing a biomass polyester as a unit and a thermoplastic resin layer. Furthermore, the present invention relates to a packaging product and a paper cup provided with the laminate.

Polyester is widely used in various industrial applications because it has excellent mechanical properties, chemical stability, heat resistance, transparency, etc., and is inexpensive. Polyester is obtained by polycondensing a diol unit and a dicarboxylic acid unit. For example, polyethylene terephthalate (hereinafter, may be abbreviated as PET) is obtained by subjecting ethylene glycol and terephthalic acid as raw materials to an esterification reaction. After that, it is produced by polycondensation reaction. These raw materials are produced from the fossil resource petroleum, for example, ethylene glycol is industrially produced from ethylene and terephthalic acid is industrially produced from xylene.

In recent years, with the growing demand for the construction of a sound material-cycle society, it is desired to break away from fossil fuels in the material field as well as energy, and the use of biomass is drawing attention. Biomass is an organic compound photosynthesized from carbon dioxide and water, and by utilizing it, it becomes carbon dioxide and water again, so-called carbon-neutral renewable energy. In recent years, the practical use of biomass plastics made from these biomass raw materials is rapidly advancing, and attempts are being made to produce polyester, which is a general-purpose polymer material, 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 the biomass raw materials, has been proposed (Patent Document 1).

In addition, biomass ethanol obtained by fermenting starch 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 Patent Publication No. 2002-512304

The present inventors have focused on ethylene glycol, which is a raw material for polyester, and instead of ethylene glycol obtained from conventional fossil fuels, biomass polyester using ethylene glycol derived from biomass as a raw material (hereinafter, simply "biomass polyester"). A paper cup having a laminate having a polyester resin layer containing (sometimes referred to as) is sometimes referred to as a polyester manufactured using ethylene glycol obtained from a conventional fossil fuel (hereinafter, simply referred to as "polyester derived from fossil fuel"). It was found that a paper cup having a laminate having a polyester resin layer made of) and a paper cup having physical properties such as mechanical properties can be obtained. The present invention is based on such findings.

Therefore, an object of the present invention is a laminate having a polyester resin layer containing a biomass polyester, which is comparable in physical properties such as mechanical properties to a paper cup having a laminate having a polyester resin layer made of polyester derived from a conventional fossil fuel. Is to provide a paper cup with.

In aspects of the invention
A paper cup comprising a laminate including at least a paper base material layer, an adhesive resin layer, a polyester resin layer having a barrier layer, and a first thermoplastic resin layer in this order.
The innermost layer of the laminate is the first thermoplastic resin layer.
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 (however, the polyester resin layer does not contain mechanical recycled polyester).
The first thermoplastic resin layer is low density polyethylene.
The degree of biomass in the polyester resin layer is 5% or more, and the degree of biomass is 5% or more.
A paper cup is provided in which the adhesive resin layer is in contact with the paper base material layer and the polyester resin layer having the barrier layer.
In the aspect of the present invention, it is preferable that the dicarboxylic acid is terephthalic acid.
In the aspect of the present invention, it is preferable that the barrier layer is made of an inorganic substance and / or an inorganic oxide.
In the aspect of the present invention, it is preferable that the barrier layer is made of a vapor-deposited film or a metal foil.
In the aspect of the present invention, the laminate comprises a second thermoplastic resin layer.
It is preferable that the outermost layer of the laminate is the second thermoplastic resin layer.
In the aspect of the present invention, it is preferable that the adhesive resin layer contains polyethylene derived from biomass.
In another aspect of the present invention, there is a method for producing a laminate used for the paper cup.
Provided is a method for manufacturing a paper cup in which a polyester resin layer having the barrier layer is laminated via the adhesive resin layer formed by melt extrusion.

In the paper cup provided with the laminate according to the present invention, the laminate includes at least a paper base material layer, a polyester resin layer containing biomass polyester, and a thermoplastic resin layer, so that the amount of fossil fuel used is compared to the conventional one. Can be reduced and the environmental load can be reduced. Further, the paper cup provided with the laminate according to the present invention is not inferior to the paper cup provided with the laminate provided with the polyester resin layer derived from the conventional fossil fuel in terms of physical properties such as mechanical properties, and therefore is derived from the conventional fossil fuel. A paper cup with a laminate with a polyester resin layer can be substituted.

It is a schematic cross-sectional view which shows an example of the laminated body by this invention. It is a schematic cross-sectional view which shows an example of the laminated body by this invention. It is a schematic cross-sectional view which shows an example of the laminated body by this invention. A perspective view in which a part of a paper cup is cut off. A partially cutaway front view showing another embodiment of a paper cup.

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

<Laminated body>
The laminate according to the present invention includes a paper base material layer, a polyester resin layer containing biomass polyester, and a thermoplastic resin layer in this order. Hereinafter, when the term "thermoplastic resin layer" is used, it means the first thermoplastic resin layer. By providing the laminate with a polyester resin layer containing biomass polyester, the amount of fossil fuel used can be reduced as compared with the conventional one, and the environmental load can be reduced. Further, the laminate according to the present invention is provided with the conventional fossil fuel-derived polyester resin layer because it is comparable in physical properties such as mechanical properties to the laminate having the conventional fossil fuel-derived polyester resin layer. The laminate can be replaced.

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

The laminate according to the present invention will be described with reference to the drawings. Examples of schematic cross-sectional views of the laminated body according to the present invention are shown in FIGS.
The laminate 10 shown in FIG. 1 includes a paper base material layer 11, a polyester resin layer 12 formed on the paper base material layer 11, and a thermoplastic resin layer 13 directly formed on the polyester resin layer 12. To prepare. In the case of a paper cup including the laminate 10, the thermoplastic resin layer 13 is located inside the paper cup. Here, the polyester resin layer 12 is a polyester resin layer containing biomass polyester.
The laminate 20 shown in FIG. 2 has an adhesive layer 14, a polyester resin layer 12, an adhesive layer 14, and a thermoplastic resin layer 13 on one surface of the paper base layer 11 and the paper base layer 11. And are prepared in this order. In the case of a paper cup including the laminate 20, the thermoplastic resin layer 13 is located inside the paper cup.
The laminate 30 shown in FIG. 3 has an adhesive layer 14, a barrier layer 15, a polyester resin layer 12, and an adhesive layer 14 on one surface of the paper base layer 11 and the paper base layer 11. The thermoplastic resin layer 13 is provided in this order. In the case of a paper cup including the laminate 30, the thermoplastic resin layer 13 is located inside the paper cup.
In any laminated body, a printing layer or a second thermoplastic resin layer may be laminated on the other surface of the paper base material layer 11. When laminating the printing layer and the second thermoplastic resin layer, the second thermoplastic resin layer may be laminated so as to be the outermost surface.
Hereinafter, each layer constituting the laminated body will be described.

(Paper substrate layer)
In the present invention, the paper base material layer functions as a base material layer for holding the polyester resin layer, and it is preferable that the laminate can be imparted with strength as a packaged product. The paper used as the paper substrate 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, and more preferably 200 g / m ² or more and 500 g / m ^{2 or less.} Have. As the paper base material layer, white paperboard in general is targeted, but from the viewpoint of safety, it is particularly preferable to use ivory paper, milk carton base paper, cup base paper, etc. using natural pulp.

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

(Polyester resin layer)
In the present invention, the polyester resin layer contains biomass polyester having ethylene glycol derived from biomass as a diol unit and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit. The polyester resin layer may further contain a fossil fuel-derived polyester having ethylene glycol derived from fossil fuel as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. It suffices if the following biomass degree can be realized as the entire polyester resin layer. In the present invention, since the polyester resin layer contains biomass polyester, the amount of fossil fuel-derived polyester can be reduced and the environmental load can be reduced as compared with the conventional case.

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

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

In the present invention, the degree of biomass in the polyester resin layer is 5% or more, preferably 10% or more, and more preferably 15% or more. When the biomass content in the polyester resin layer is 5% or more, the amount of fossil fuel-derived polyester can be reduced and the environmental load can be reduced as compared with the conventional case.

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

The polyester resin layer is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the polyester resin layer film extruded onto the cooling drum as described above is subsequently heated by roll heating, infrared heating, or the like, and stretched in the vertical direction to obtain a vertically stretched film. This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls. The longitudinal stretching is usually carried out in a temperature range of 50 ° C. or higher and 100 ° C. or lower. Further, the magnification of longitudinal stretching depends on the required characteristics of the film application, but is preferably 2.5 times or more and 4.2 times or less. When the draw ratio is less than 2.5 times, the thickness unevenness of the film becomes large and it is difficult to obtain a good film.

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

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

The 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, and further preferably 8 μm or more and 16 μm or less.
If the thickness of the polyester resin layer is in the above range, molding processing is easy.

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

Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained from biomass ethanol by a method of producing ethylene glycol via ethylene oxide by a conventionally known method. Further, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol Co., Ltd. can be preferably used.

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

Specific examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid, which usually have 2 or more and 40 or less carbon atoms. Examples thereof include chain-type or alicyclic dicarboxylic acids. Further, as a derivative of the aliphatic dicarboxylic acid, a lower alkyl ester such as a methyl ester, an ethyl ester, a propyl ester and a butyl ester of the aliphatic dicarboxylic acid, or a cyclic acid anhydride of the aliphatic dicarboxylic acid such as succinic anhydride can be used. Can be mentioned. Among these, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable, and succinic acid as a main component is particularly preferable. As the derivative of the aliphatic dicarboxylic acid, a methyl ester of adipic acid and succinic acid, or a mixture thereof is more preferable.

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

The biomass polyester may be a copolymerized polyester in which a copolymerization component is added as a third component in addition to the above-mentioned diol component and dicarboxylic acid component. Specific examples of the copolymerization component include a bifunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol for forming a crosslinked structure, a trifunctional or higher polyvalent carboxylic acid and / or an anhydride thereof, and 3 Included are at least one polyfunctional compound selected from the group consisting of more functional oxycarboxylic acids. Among these copolymerization components, a bifunctional and / or trifunctional or higher oxycarboxylic acid is particularly preferably used because a copolymerized polyester having a high degree of polymerization tends to be easily produced. Among them, the use of a trifunctional or higher functional oxycarboxylic acid is most preferable because a polyester having a high degree of polymerization can be easily produced in a very small amount without using a chain extender described later.

Further, the biomass polyester may be a high molecular weight polyester obtained by chain-extending (coupling) these copolymerized polyesters. As the chain extender, a chain extender such as a carbonate compound or a diisocyanate compound can be used, but the amount thereof is usually 100 mol% of all the monomer units constituting the polyester, and the carbonate bond and the urethane bond are formed. It is usually 10 mol% or less, preferably 5 mol% or less, and more preferably 3 mol% or less.

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

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

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

The amount of diol used in producing the biomass polyester is substantially equimolar to 100 mol of the dicarboxylic acid or its derivative, but is generally an 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 distillate inside.

Further, the polycondensation reaction is preferably carried out in the presence of a polymerization catalyst. The timing of adding the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added at the time of raw material preparation or at the start of reduced pressure.

Examples of the polymerization catalyst generally include compounds containing Group 1 to Group 14 metal elements excluding hydrogen and carbon in the periodic table. Specifically, at least one or more metals selected from the group consisting of titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium and potassium. Examples thereof include compounds containing organic groups such as carboxylates, alkoxy salts, organic sulfonates or β-diketonate salts, and inorganic compounds such as metal oxides and halides described above, and mixtures thereof. Among these, metal compounds containing titanium, zirconium, germanium, zinc, aluminum, magnesium and calcium, and mixtures thereof are preferable, and titanium compounds, zirconium compounds and germanium compounds are particularly preferable. Further, the catalyst is preferably a liquid at the time of polymerization, or a compound that is soluble in an ester low polymer or polyester, because the polymerization rate increases when the catalyst is melted or dissolved at the time of 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, and tetra. Benzyl titanates and mixed titanates thereof can be mentioned. In addition, titanium (oxy) acetylacetone, titanium tetraacetylacetone, titanium (diisoproxide) acetylacetonate, titanium bis (ammonium lactate) dihydroxydo, titanium bis (ethylacetacetate) diisopropoxide, titanium (triethanolamineate). ) Isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolaminate, butyl titanate dimer and the like are also preferably used. Further, titanium oxide and a composite oxide containing titanium and silicon are also preferably used. Among these, tetra-n-propyl titanate, tetraisopropyl titanate and tetra-n-butyl titanate, titanium (oxy) acetylacetonate, titaniumtetraacetylacetonate, titaniumbis (ammonium lactate) dihydroxyde, polyhydroxytitanium stearate. , Titanium Lactate, Butyl Titanium Dimer, Titanium Oxide, Titania / Silica Composite Oxide (eg, Product Name: C-94 from Acordis Industrial Fibers) , Titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium / silica composite oxide (for example, product name: C-94 manufactured by Acordis Industrial Fibers) is preferable.

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

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

When a metal compound is used as the polymerization catalyst, the lower limit of the amount of metal with respect to the produced polyester is usually 5 ppm or more, preferably 10 ppm or more, and the upper limit is usually 30,000 ppm or less, preferably 1000 ppm or less. It is more preferably 250 ppm or less, and particularly preferably 130 ppm or less. If the amount of catalyst used is too large, not only is it economically disadvantageous, but also the thermal stability of the polymer is low, whereas if it is too small, the polymerization activity is low, and the polymer is decomposed during polymer production. Is more likely to be triggered. As the amount of catalyst used here, the amount of terminal carboxyl groups of the polyester produced is reduced as the amount of catalyst used is reduced, so a method of reducing the amount of catalyst used is a preferred embodiment.

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

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

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

After solidification, the obtained polyester may be subjected to solid phase polymerization, if necessary, in order to further increase the degree of polymerization and 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. It is carried out by heating at the temperature of 1 hour or more and several tens of hours or less under the flow of an inert gas or under reduced pressure.

The intrinsic viscosity of the polyester obtained as described above (measured at 35 ° C. with an orthochlorophenol 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. It is preferably / g or less, and more preferably 0.6 dl / g or more and 1.2 dl / g or less.

Various additives may be added in the production process of the biomass polyester or to the produced biomass polyester as long as its characteristics are not impaired, for example, a plasticizer, an ultraviolet stabilizer, a color retardant, and a gloss. Erasing agents, deodorants, flame retardants, weather resistant agents, antistatic agents, thread friction reducing agents, mold release agents, antioxidants, ion exchangers, coloring pigments and the like can be added. These additives are added in a range of 5% by mass or more and 50% by mass or less, preferably 5% by mass or more and 20% by mass or less, based on the entire resin composition containing the biomass polyester.

(Thermoplastic resin layer)
The thermoplastic resin layer can be formed by using a conventionally known thermoplastic resin. By further providing the laminate with a thermoplastic resin layer, the same heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties as those of the conventional laminate are imparted. be able to.

Examples of the thermoplastic resin include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer. Combined, ethylene-methacrylic acid copolymer, ethylene-methylacrylate copolymer, ethylene-ethylacrylate copolymer, ethylene-methylmethacrylate copolymer, ionomer resin, polyester resin, polyvinyl chloride resin, polystyrene resin, nylon, etc. Examples thereof include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and ethylene-methacrylic acid copolymers.

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

When the thermoplastic resin layer contains biomass polyolefin, the biomass polyolefin preferably used is 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%), low-density polyethylene derived from polyolefin manufactured by Braskem (trade name: SPB681, density: 0.922 g / cm ³ , MFR: 3.8 g / 10 minutes, biomass degree 95%) And so on.

Further, as described above, the second thermoplastic resin layer may be provided on the surface of the paper base material layer opposite to the polyester resin layer. As the second thermoplastic resin layer, the same resin as the thermoplastic resin layer (first thermoplastic resin layer) can be used.

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

(Barrier layer)
The barrier layer is made of an inorganic substance and / or an inorganic oxide, and is preferably made of a vapor-deposited film of an inorganic substance or an inorganic oxide or a metal foil. The vapor-deposited film can be formed by a conventionally known method using a conventionally known inorganic substance or an inorganic oxide, and the composition and the forming method thereof are not particularly limited. When the laminate further has a barrier layer, it is possible to impart or improve a gas barrier property that blocks the permeation of oxygen gas, water vapor, and the like, and a light-shielding property that blocks the permeation of visible light, ultraviolet rays, and the like. The laminated body may have two or more barrier layers. When two or more barrier layers are provided, they may have the same composition or different compositions.

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

Representation of the inorganic oxide, for _example, SiO X, as such AlO _X MO _X (In the formula, M represents an inorganic element, the value of X, varies each of an inorganic element range.) In expressed. The range of X values is 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1 for magnesium (Mg), and 0 to 1 for calcium (Ca). Potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1, 5, and titanium (Ti). Can take a value in the range of 0 to 2, lead (Pb) can take a value in the range of 0 to 1, zirconium (Zr) can take a value in the range of 0 to 2, and yttrium (Y) can take a value in the range of 0 to 1.5. In the above, when X = 0, it is a completely inorganic simple substance (pure substance) and is not transparent, and the upper limit of the range of X is a completely oxidized value. Silicon (Si) and aluminum (Al) are preferably used as the packaging material, with silicon (Si) in the range of 1.0 to 2.0 and aluminum (Al) in the range of 0.5 to 1.5. You can use the one with the value of.

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

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

Further, according to another aspect, the barrier layer may be a metal foil obtained by rolling a metal. As the metal foil, a conventionally known metal foil can be used. Aluminum foil is preferable from the viewpoint of gas barrier property that blocks the transmission of oxygen gas, water vapor, and the like, and light-shielding property that blocks the transmission of visible light, ultraviolet rays, and the like.

(Plastic film)
In the present invention, various plastic films may be used as other layers. For example, one or more of a stretched nylon film, a stretched polypropylene film, a nylon 6 / metaxylylene diamine nylon 6 co-pressed co-stretched film, a polypropylene / ethylene-vinyl alcohol copolymer co-pressed co-stretched film, and the like. It may be a composite film in which films are laminated. The plastic film may be coated with polyvinyl alcohol or the like.

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

(Adhesive layer)
The adhesive layer can be an adhesive layer formed by applying an adhesive to the surface of the layer to be laminated and drying it when the two layers are bonded by the dry laminating method.
Examples of the adhesive include one-component or two-component curable or non-curable vinyl type, (meth) acrylic type, polyamide type, polyester type, polyether type, polyurethane type, epoxy type, rubber type, and others. Such solvent type, water-based type, or emulsion type adhesives can be used. As a coating method of the above-mentioned adhesive for laminating, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a fonten method, a transfer roll coating method, or other methods are used to form a laminate. It can be applied to the coated surface of the layer. The coating amount is preferably 0.1 g / m ² or more and 10 g / m ² or less (dry state), and more preferably 1 g / m ² or more and 5 g / m ² or less (dry state).

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 it when laminating a thermoplastic resin layer or the like by a melt extrusion laminating method. You may. Examples of the anchor coating agent include an anchor coating agent made of any resin having a heat resistant temperature of 135 ° C. or higher, for example, a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, or the like. An anchor coating agent composed of a polyacrylic or polymethacrylic resin having a hydroxyl group and an isocyanate compound as a curing agent can be preferably used. Further, a silane coupling agent may be used in combination with this as an additive, or nitric acid cotton may be used in combination to increase heat resistance.

Further, the adhesive layer may be an adhesive resin layer used when two layers are bonded by a sand laminating method or a melt extrusion laminating method. Examples of the thermoplastic resin that can be used for the adhesive resin layer include polyethylene-based resins, polypropylene-based resins, or cyclic polyolefin-based resins, or copolymer resins containing these resins as main components, modified resins, or mixtures (including alloys). ) Can be used. Examples of the polyolefin resin include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene (PP), and metallocene catalyst. Ethylene-α / olefin copolymer, random or block copolymer of ethylene / polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene / Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-maleic acid copolymer, ionomer resin, and adhesion between layers. It is possible to use an acid-modified polyolefin-based resin obtained by modifying the above-mentioned polyolefin-based resin with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. it can. Further, as the polyolefin resin, an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, a resin obtained by graft-polymerizing or copolymerizing an ester monomer and the like can be used. These materials can be used alone or in combination of two or more. As the cyclic polyolefin resin, for example, cyclic polyolefins such as ethylene-propylene copolymer, polymethylpentene, polybutene, and polynorbonene can be used. These resins can be used alone or in combination of two or more. Needless to say, as the above-mentioned polyethylene-based resin, one using the above-mentioned biomass-derived ethylene as a monomer unit can be used.

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

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

(Manufacturing method of laminated body)
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 a dry laminating method, a melt extrusion laminating method, and a sand laminating method. In the present invention, the polyester resin layer can be laminated via the adhesive resin layer formed by melt extrusion using the sand laminating method.

The thickness of the laminate obtained as described above is arbitrary depending on the intended 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 provided with chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubrication functions, optical functions, thermal functions, surface functions such as biocompatibility, and the like. It is also possible to perform secondary processing for the purpose. 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, etc.) Coating, etc.) and the like. Further, the laminated body according to the present invention may be subjected to laminating processing (dry laminating or extrusion laminating), bag making processing, and other post-treatment processing to produce a molded product.

(Use)
The laminate according to the present invention can be used for packaging products such as paper cups, liquid paper containers, label materials, and lid materials.

(Paper cup)
The laminate according to the present invention can be particularly preferably used for paper cups. A case where a paper cup is formed by using the laminate according to the present invention will be described. FIG. 4 is a perspective view in which a part of the paper cup is cut off. As shown in FIG. 4, the paper cup 40 is provided at a cylindrical body portion 42 having a flange portion 41 at the upper portion and gradually expanding in diameter toward the opening, and a lower end (one end) of the body portion 42. It is provided with a bottom 43. The body portion 42 is provided with a flange portion 41 whose upper end is rounded outward. The paper cup 40 may be sealed by attaching a lid material (not shown) along the flange portion 41 of the body portion 42 after storing the contents. The lid material preferably has a gas barrier property.

Further, as shown in FIG. 5, the paper cup 40 may be provided with an exterior body 44 on the outer periphery of the body portion 42. As the exterior body 44, for example, paper can be used. A convex portion 45 is formed on the body portion 42. The convex portion 45 is formed to provide a gap 46 in the air layer between the body portion 42 and the exterior body 44. One or more convex portions 45 are provided in the horizontal direction, and for example, two convex portions 45 can be provided as shown in FIG.

(Other aspects)
The present inventors have focused on ethylene glycol, which is a raw material for polyester, and instead of ethylene glycol obtained from conventional fossil fuels, biomass polyester using ethylene glycol derived from biomass as a raw material (hereinafter, simply "biomass polyester"). The laminate including the polyester resin layer containing (may be referred to as) is made of polyester produced using ethylene glycol obtained from conventional fossil fuels (hereinafter, may be simply referred to as "polyester derived from fossil fuels"). It was found that a laminate having a polyester resin layer and a laminate having physical properties such as mechanical properties can be obtained. Another aspect of the invention is based on such findings.
Therefore, an object of another aspect of the present invention is a laminate having a polyester resin layer containing a polyester resin derived from a biomass polyester, which is comparable in physical properties such as mechanical properties to a laminate having a polyester resin layer made of polyester derived from a conventional fossil fuel. To provide the body.
In another aspect of the invention
A laminate including at least a paper base material layer, a polyester resin layer, and a thermoplastic resin layer in this order.
The polyester resin layer contains biomass polyester having ethylene glycol derived from biomass as a diol unit and dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit.
A laminate having a biomass content of 5% or more in the polyester resin layer is provided.
In another aspect of the present invention, it is preferable that the dicarboxylic acid is terephthalic acid.
In another aspect of the invention, the thermoplastic resin layer comprises a resin material selected from the group consisting of low density polyethylene, linear low density polyethylene, medium density polyethylene, and ethylene-methacrylic acid copolymers. Is preferable.
In another aspect of the invention, a packaged product comprising the laminate is provided.
In another aspect of the present invention, the paper cup provided with the laminate is provided.
A paper cup is provided in which the innermost layer of the paper cup is the thermoplastic resin layer.
The laminate according to another aspect of the present invention includes at least a paper base material layer, a polyester resin layer containing biomass polyester, and a thermoplastic resin layer, thereby reducing the amount of fossil fuel used as compared with the conventional one. It can reduce the environmental load. Further, since the laminate according to another aspect of the present invention is comparable in physical properties such as mechanical properties to the laminate provided with the polyester resin layer derived from the conventional fossil fuel, the polyester resin derived from the conventional fossil fuel A laminate with layers can be substituted.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

<Measurement / conditions>
In the following Reference Examples, Reference Comparative Examples, Examples, and Comparative Examples, the biomass degree is a value of carbon concentration derived from biomass as measured by radiocarbon (C14).

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

[Example 1]
<Preparation of laminated body 1>
A biaxially stretched polyester film 1 (biomass degree: 20%, manufactured by Toyobo Co., Ltd., DE038, thickness 12 μm) formed by using terephthalic acid derived from fossil fuel and ethylene glycol derived from biomass (biomass polyester) was prepared. .. An acid-resistant coated cup (manufactured by Chuetsu Pulp & Paper Co., Ltd., basis weight 270 g / m ² ) is prepared as a paper substrate layer, and after corona treatment is applied to one surface, an anchor coating agent (Matsumoto Fine Chemical Co., Ltd.) is applied to the corona treated surface. , WS-700) was applied and dried to form an anchor coat layer. Subsequently, low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Corporation, LC520, density: 0.923 ^{g / cm 3} , MFR: 3.6 g / 10 minutes, biomass degree: 0%) was placed on the anchor coat layer at 320 ° C. A second thermoplastic resin layer (biomass degree: 0%, thickness 20 μm) was formed by melt-extruding and laminating at a resin temperature of 100 m / min and a line speed of 100 m / min. Next, the surface of the paper substrate layer opposite to the second thermoplastic resin layer is subjected to corona treatment, and then the corona-treated surface is subjected to a sand laminate method to use low-density polyethylene derived from fossil fuel (Japan). Made of polyethylene, LC520, density: 0.923 ^{g / cm 3} , MFR: 3.6 g / 10 minutes, biomass degree: 0%) while extruding this adhesive resin layer (biomass degree: 0%, thickness 15 μm). The corona-treated surfaces of the corona-treated polyester film 1 (polyester resin layer) were bonded to each other. Subsequently, an anchor coating agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the polyester film 1 to form an anchor coating layer. After that, low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 ^{g / cm 3} , MFR: 3.6 g / 10 minutes, biomass degree: 0%) was placed on the anchor coat layer at 320 ° C. A thermoplastic resin layer (biomass degree: 0%, thickness 40 μm) is formed by melt-extruding and laminating at a resin temperature and a line speed of 100 m / min, and a second thermoplastic resin layer, an anchor coat layer, and a paper base material are formed. A laminated body 1 in which a layer, an adhesive resin layer, a polyester resin layer, an anchor coat layer, and a thermoplastic resin layer were laminated in this order was obtained.

[Example 2]
<Preparation of laminated body 2>
An acid-resistant coated cup (manufactured by Chuetsu Pulp & Paper Co., Ltd., basis weight 270 g / m ² ) is prepared as a paper substrate layer, and after corona treatment is applied to one surface, an anchor coating agent (Matsumoto Fine Chemical Co., Ltd.) is applied to the corona treated surface. , WS-700) was applied and dried to form an anchor coat layer. Subsequently, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, biomass degree: 95%) was placed on the anchor coat layer with a resin at 320 ° C. A second thermoplastic resin layer (biomass degree: 95%, thickness 20 μm) was formed by melt-extruding and laminating at a temperature and a line speed of 100 m / min.
Next, the surface of the paper substrate layer opposite to the second thermoplastic resin layer is subjected to corona treatment, and then the corona-treated surface is subjected to a sand-lamination method to produce low-density polyethylene derived from biomass (Brasschem). Made, SBC818, Density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, Biomass degree: 95%) Through this adhesive resin layer (Biomass degree: 95%, Thickness 15 μm) , The corona-treated surfaces of the corona-treated polyester film 1 (polyester resin layer) were bonded together. Subsequently, an anchor coating agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the polyester film 1 to form an anchor coating layer. Then, low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, biomass degree: 95%) was placed on the anchor coat layer at a resin temperature of 320 ° C. , Molten extruded and laminated at a line speed of 100 m / min to form a thermoplastic resin layer (biomass degree: 95%, thickness 40 μm), and formed a second thermoplastic resin layer, anchor coat layer, paper base material layer, A laminated body 2 in which an adhesive resin layer, a polyester resin layer, an anchor coat layer, and a thermoplastic resin layer were laminated in this order was obtained.

[Comparative Example 1]
<Preparation of laminated body 3>
Biaxially stretched polyester film 2 (biomass degree: 0%, manufactured by Toyobo Co., Ltd., T4100, thickness 12 μm) formed by using terephthalic acid derived from fossil fuel and ethylene glycol derived from fossil fuel (polyester derived from fossil fuel). Prepared. An acid-resistant coated cup (manufactured by Chuetsu Pulp & Paper Co., Ltd., basis weight 270 g / m ² ) is prepared as a paper substrate layer, and after corona treatment is applied to one surface, an anchor coating agent (Matsumoto Fine Chemical Co., Ltd.) is applied to the corona treated surface. , WS-700) was applied and dried to form an anchor coat layer. Subsequently, low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Corporation, LC520, density: 0.923 ^{g / cm 3} , MFR: 3.6 g / 10 minutes, biomass degree: 0%) was placed on the anchor coat layer at 320 ° C. A second thermoplastic resin layer (biomass degree: 0%, thickness 20 μm) was formed by melt-extruding and laminating at a resin temperature of 100 m / min and a line speed of 100 m / min. Next, the surface of the paper substrate layer opposite to the second thermoplastic resin layer is subjected to corona treatment, and then the corona-treated surface is subjected to a sand laminate method to obtain low-density polyethylene derived from fossil fuel (Japan). Made of polyethylene, LC520, density: 0.923 ^{g / cm 3} , MFR: 3.6 g / 10 minutes, biomass degree: 0%) while extruding this adhesive resin layer (biomass degree: 0%, thickness 15 μm). The corona-treated surfaces of the corona-treated polyester film 2 (resin layer) were bonded to each other. Subsequently, an anchor coating agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the polyester film 2 to form an anchor coating layer. After that, low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 ^{g / cm 3} , MFR: 3.6 g / 10 minutes, biomass degree: 0%) was placed on the anchor coat layer at 320 ° C. A thermoplastic resin layer (biomass degree: 0%, thickness 40 μm) is formed by melt-extruding and laminating at a resin temperature and a line speed of 100 m / min, and a second thermoplastic resin layer, an anchor coat layer, and a paper base material are formed. A laminated body 3 in which a layer, an adhesive resin layer, a resin layer, an anchor coat layer, and a thermoplastic resin layer were laminated in this order was obtained.

[Example 3]
<Preparation of laminated body 4>
A cup base paper (manufactured by Nippon Paper Co., Ltd., with a basis weight of 280 g / m ² ) is prepared as a paper substrate layer, one surface is corona-treated, and then the corona-treated surface is subjected to a fossil fuel by a sand laminating method. While extruding the derived low-density polyethylene (manufactured by Nippon Polyethylene, LC600A, density: 0.919 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass degree: 0%), this adhesive resin layer (biomass degree: 0). %, Thickness 15 μm), and the corona-treated surfaces of the corona-treated polyester film 1 were bonded together. Subsequently, an anchor coating agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the polyester film 1 to form an anchor coating layer. After that, low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC600A, density: 0.919 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass degree: 0%) was placed on the anchor coat layer at 320 ° C. A thermoplastic resin layer (biomass degree: 0%, thickness 40 μm) is formed by melt-extruding and laminating at a resin temperature and a line speed of 100 m / min, and a paper base material layer, an adhesive resin layer, a polyester resin layer, and an anchor coat are formed. A laminated body 4 in which a layer and a thermoplastic resin layer were laminated in this order was obtained.

[Example 4]
<Preparation of laminated body 5>
A cup base paper (manufactured by Nippon Paper Industries Co., Ltd., basis weight 280 g / m ² ) is prepared as a paper base layer, one surface is corona-treated, and then the corona-treated surface is derived from biomass by using a sand laminate method. Low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, biomass degree: 95%) while extruding this adhesive resin layer (biomass degree: 95%, The corona-treated surfaces of the corona-treated polyester film 1 were bonded together via a thickness of 15 μm). Subsequently, an anchor coating agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the polyester film 1 to form an anchor coating layer. Then, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, biomass degree: 95%) was placed on the anchor coat layer at a resin temperature of 320 ° C. , A thermoplastic resin layer (biomass degree: 95%, thickness 40 μm) is formed by melt-extruding and laminating at a line speed of 100 m / min, and a paper base material layer, an adhesive resin layer, a polyester resin layer, an anchor coat layer, A laminated body 5 in which thermoplastic resin layers were laminated in order was obtained.

[Comparative Example 2]
<Preparation of laminated body 6>
A cup base paper (manufactured by Nippon Paper Co., Ltd., with a basis weight of 280 g / m ² ) is prepared as a paper substrate layer, one surface is corona-treated, and then the corona-treated surface is subjected to a fossil fuel by a sand laminating method. While extruding the derived low-density polyethylene (manufactured by Nippon Polyethylene, LC600A, density: 0.919 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass degree: 0%), this adhesive resin layer (biomass degree: 0). %, Thickness 15 μm), and the corona-treated surfaces of the corona-treated polyester film 2 were bonded together. Subsequently, an anchor coating agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the polyester film 2 to form an anchor coating layer. After that, low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC600A, density: 0.919 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass degree: 0%) was placed on the anchor coat layer at 320 ° C. A thermoplastic resin layer (biomass degree: 0%, thickness 40 μm) is formed by melt-extruding and laminating at a resin temperature and a line speed of 100 m / min, and a paper base material layer, an adhesive resin layer, a resin layer, and an anchor coat layer are formed. , A laminated body 6 in which thermoplastic resin layers were laminated in order was obtained.

[Example 5]
<Preparation of laminated body 7>
A polyester film 1 is used, which is mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and then, under the conditions shown below, a 200 Å thick silicon oxide vapor deposition film is formed on the corona-treated surface of the above polyethylene terephthalate film. Was formed to obtain a silicon oxide-deposited polyester film 1.
(Evaporation conditions)
Deposited surface; Corona treated surface Introduced gas amount; Hexamethyldisiloxane: Oxygen gas: Helium = 1: 3: 3 (Unit: slm)
Degree of vacuum in the vacuum chamber; 2-6 x ^10-6 mBar
Vacuum degree in vapor deposition chamber; 2-5 x 10 ^-3 mBar
Cooling / electrode drum supply power; 10 kW
Line speed: 100m / min

A cup base paper (manufactured by Nippon Paper Co., Ltd., with a basis weight of 260 g / m ² ) is prepared as a paper substrate layer, one surface is corona-treated, and then the corona-treated surface is subjected to a fossil fuel by a sand laminating method. While extruding the derived low-density polyethylene (manufactured by Nippon Polyethylene, LC600A, density: 0.919 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass degree: 0%), this adhesive resin layer (biomass degree: 0). %, Thickness 15 μm), and the vapor-deposited surfaces of the above-mentioned silicon oxide-deposited polyester film 1 were bonded together. Subsequently, an anchor coating agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the silicon oxide-deposited polyester film 1 to form an anchor coating layer. After that, low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 ^{g / cm 3} , MFR: 3.6 g / 10 minutes, biomass degree: 0%) was placed on the anchor coat layer at 320 ° C. Extrusion molding at a resin temperature and a line speed of 100 m / min to form a thermoplastic resin layer (biomass degree: 0%, thickness 25 μm), and forming a paper base material layer, an adhesive resin layer, a barrier layer, a polyester resin layer, A laminated body 7 in which an anchor coat layer and a thermoplastic resin layer were laminated in this order was obtained.

[Example 6]
<Preparation of laminated body 8>
A cup base paper (manufactured by Nippon Paper Industries Co., Ltd., with a basis weight of 260 g / m ² ) is prepared as a paper base layer, and one surface is subjected to corona treatment, and then the corona treated surface is derived from biomass by using a sand laminate method. Low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, biomass degree: 95%) while extruding this adhesive resin layer (biomass degree: 95%, The vapor-deposited surfaces of the above-mentioned silicon oxide-deposited polyester film 1 were laminated via a thickness of 15 μm). Subsequently, an anchor coating agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the silicon oxide-deposited polyester film 1 to form an anchor coating layer. Then, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 ^{g / cm 3} , MFR: 8.1 g / 10 minutes, biomass degree: 95%) was placed on the anchor coat layer at a resin temperature of 320 ° C. , Extruded at a line speed of 100 m / min to form a thermoplastic resin layer (biomass degree: 95%, thickness 25 μm), and formed a paper base material layer, an adhesive resin layer, a barrier layer, a polyester resin layer, and an anchor coat. A laminated body 8 in which a layer and a thermoplastic resin layer were laminated in this order was obtained.

[Comparative Example 3]
<Preparation of laminated body 9>
A silicon oxide-deposited polyester film 2 was obtained in the same manner as in Example 3 except that the polyester film 2 was used.

A cup base paper (manufactured by Nippon Paper Co., Ltd., biomass 260 g / m ² ) is prepared as a paper base layer, and one surface is corona-treated, and then the corona-treated surface is subjected to a fossil fuel by a sand laminating method. While extruding the derived low-density polyethylene (manufactured by Nippon Polyethylene, LC600A, density: 0.919 ^{g / cm 3} , MFR: 7.0 g / 10 minutes, biomass degree: 0%), this adhesive resin layer (biomass degree: 0). %, Thickness 15 μm), and the vapor-deposited surfaces of the above-mentioned silicon oxide-deposited polyester film 2 (biomass degree: 0%) were bonded together. Subsequently, an anchor coating agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the silicon oxide-deposited polyester film 2 to form an anchor coating layer. After that, low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 ^{g / cm 3} , MFR: 3.6 g / 10 minutes, biomass degree: 0%) was placed on the anchor coat layer at 320 ° C. Extrusion molding at a resin temperature and a line speed of 100 m / min to form a thermoplastic resin layer (biomass degree: 0%, thickness 25 μm), and forming a paper base material layer, an adhesive resin layer, a barrier layer, a resin layer, and an anchor. A laminated body 9 in which a coat layer and a thermoplastic resin layer were laminated in this order was obtained.

[Manufacturing Examples 1 to 9]
<Making a paper cup>
A paper cup was manufactured by the following steps by combining the laminate for the body member and the laminate for the bottom member shown in Table 1 below. First, a conical trapezoidal blank plate for forming the body of a paper cup from the body member laminate was punched out. Next, the above blank plate was wound into a tubular shape, both ends thereof were partially overlapped, and the polymerized portion was subjected to hot air treatment to heat and melt the low density polyethylene resin layer existing in the polymerized portion. .. Subsequently, the body was pasted by pressing with a hot plate or the like to form a body seal portion, and a tubular cup body portion constituting a paper cup was manufactured.

On the other hand, the laminate for the bottom member is punched into a circular shape to manufacture a disk constituting the bottom portion, and then the outer peripheral portion of the disk is vertically formed into a tubular shape to form a bottom portion having the upright molded portion. Manufactured. Next, after inserting the bottom paper also manufactured in the upper part into the tubular cup body manufactured above, the tubular cup body and the bottom paper are blown with hot air or the like at the joint portion thereof. The resin layer existing at the joint was heated and melted. Subsequently, the tip of the tubular cup body is bent inward by the curl mold and covered with the upright molding portion constituting the bottom, and the tip and bottom of the tubular cup body are covered. By knurling the overlapping portion with the upright molded portion from the inner diameter side with a knurl, the tubular cup body and the bottom are closely adhered to form a joint, and the tubular cup body is formed. And the bottom of the paper cup.

After that, the short tip on the opposite side to the side where the joint is formed by tightly adhering the bottom of the tubular cup body is curled while being bent outward by a curl mold in the same manner as above, and the upper end is curled. An outward curl portion was formed to manufacture a paper cup having a full capacity of 382 cc.

<Performance evaluation test>
The following performance evaluation tests were conducted on the manufactured paper cups.

(Destructive inspection test)
The manufactured paper cup was destructively inspected, and the adhesive state was visually evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.
(Evaluation criteria)
◯: The phenomenon of paper peeling was confirmed or the material was destroyed, and there was no problem with the adhesive state.
X: There was a seal abnormality, and the adhesive state was poor.

(Liquid leak test)
Forty 40 paper cups were prepared, a neutral detergent (0.3% solution) was added to each paper cup, and the mixture was allowed to stand for 10 minutes, and then visually evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.
(Evaluation criteria)
◯: There was no liquid leakage, and the performance as a paper cup was good.
X: There was liquid leakage, and the performance as a paper cup was poor.

10, 20, 30 Laminated body 11 Paper base material layer 12 Polyester resin layer 13 Thermoplastic resin layer 14 Adhesive layer 15 Barrier layer 40 Paper cup 41 Flange part 42 Body part 43 Bottom part 44 Exterior body 45 Convex part 46 Gap

Claims (7)

A paper cup comprising a laminate including at least a paper base material layer, an adhesive resin layer, a polyester resin layer having a barrier layer, and a first thermoplastic resin layer in this order.
The innermost layer of the laminate is the first thermoplastic resin layer.
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 (however, the polyester resin layer does not contain mechanical recycled polyester).
The first thermoplastic resin layer is low density polyethylene.
The degree of biomass in the polyester resin layer is 5% or more, and the degree of biomass is 5% or more.
A paper cup in which the adhesive resin layer is in contact with the paper base material layer and the polyester resin layer having the barrier layer. The paper cup according to claim 1, wherein the dicarboxylic acid is terephthalic acid. The paper cup according to claim 1 or 2, wherein the barrier layer is made of an inorganic substance and / or an inorganic oxide. The paper cup according to claim 3, wherein the barrier layer is made of a thin-film film or a metal foil. The laminate comprises a second thermoplastic resin layer.
The paper cup according to any one of claims 1 to 4, wherein the outermost layer of the laminate is the second thermoplastic resin layer. The paper cup according to any one of claims 1 to 5, wherein the adhesive resin layer contains polyethylene derived from biomass. A method for producing a laminate used for a paper cup according to any one of claims 1 to 6.
A method for producing a paper cup, in which a polyester resin layer having the barrier layer is laminated via the adhesive resin layer formed by melt extrusion.

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