JP2017196779A - Laminate having polyolefin resin layer and packaged product having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: 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 including a polyester resin layer containing biomass polyester, and more specifically, at least a paper base layer and biomass-derived ethylene glycol as diol units, and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid. The present invention relates to a laminate including a polyester resin layer containing biomass polyester as a unit and a thermoplastic resin layer. Furthermore, it is related with the packaging product and paper cup provided with this laminated body.

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

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

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

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

Special table 2002-512304 gazette

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

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

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

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

  In an aspect of the present invention, the thermoplastic resin layer may include a resin material selected from the group consisting of low density polyethylene, linear low density polyethylene, medium density polyethylene, and an ethylene-methacrylic acid copolymer. preferable.

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

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

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

It is a schematic cross section which shows an example of the laminated body by this invention. It is a schematic cross section which shows an example of the laminated body by this invention. It is a schematic cross section which shows an example of the laminated body by this invention. The perspective view which excised a part of paper cup. The front view which fractured | ruptured a part which shows another embodiment of a paper cup.

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

<Laminated body>
The laminate according to the present invention comprises a paper base material layer, a polyester resin layer containing biomass polyester, and a thermoplastic resin layer in this order. Hereinafter, the expression “thermoplastic resin layer” refers to the first thermoplastic resin layer. Since the laminate includes a polyester resin layer containing biomass polyester, the amount of fossil fuel used can be reduced as compared with the conventional one, and the environmental load can be reduced. In addition, the laminate according to the present invention has a polyester resin layer derived from a conventional fossil fuel because it is not inferior in terms of physical properties such as mechanical properties as compared with a laminate including a polyester resin layer derived from a conventional fossil fuel. Laminates can be substituted.

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

The laminate according to the present invention will be described with reference to the drawings. Examples of schematic cross-sectional views of the laminate according to the present invention are shown in FIGS.
A laminate 10 shown in FIG. 1 includes a paper base layer 11, a polyester resin layer 12 formed on the paper base layer 11, and a thermoplastic resin layer 13 directly formed on the polyester resin layer 12. It is to be prepared. In the case of a paper cup provided with the laminated body 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.
A laminate 20 shown in FIG. 2 includes a paper base layer 11, 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. Are provided in this order. In the case of a paper cup provided with the laminated body 20, the thermoplastic resin layer 13 is located inside the paper cup.
The laminate 30 shown in FIG. 3 includes a paper base layer 11, an adhesive layer 14, a barrier layer 15, a polyester resin layer 12, an adhesive layer 14 on one surface of the paper base layer 11, The thermoplastic resin layer 13 is provided in this order. In the case of a paper cup provided with the laminated body 30, the thermoplastic resin layer 13 is located inside the paper cup.
In any laminate, a printed layer or a second thermoplastic resin layer may be laminated on the other surface of the paper base layer 11. When laminating the printing layer and the second thermoplastic resin layer, they may be laminated so that the second thermoplastic resin layer is the outermost surface.
Hereinafter, each layer which comprises a laminated body is demonstrated.

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

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

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

In the present invention, “biomass degree” (biomass-derived carbon concentration) in the polyester resin layer is a value obtained by measuring the content of carbon derived from biomass by measurement of radioactive carbon (C14). Since carbon dioxide in the atmosphere contains C14 at a constant rate (105.5 pMC), the C14 content in plants that grow by incorporating carbon dioxide in the atmosphere, for example, corn, is also about 105.5 pMC. It is known. It is also known that fossil fuel contains almost no C14. Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of C14 contained in all the carbon atoms in the polyester. In the present invention, in the case where the content of C14 in the polyester was P _C14, the content P _{bio Bio} carbon from biomass, can be obtained as follows.
P _bio (%) = P _C14 /105.5×100

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

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

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

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

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

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

  The polyester resin layer preferably has a thickness of 5 μm to 38 μm, more preferably 5 μm to 25 μm, and still more preferably 8 μm to 16 μm. If the thickness of the polyester resin layer is about the above range, the molding process is easy.

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

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

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

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

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

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

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

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

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

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

  The amount of diol used in producing the biomass polyester is substantially equimolar with respect to 100 mol of the dicarboxylic acid or derivative thereof. It is preferable to use an excess amount of 0.1 mol% or more and 20 mol% or less because of the distillation in the inside.

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

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

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

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

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

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

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

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

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

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

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

  Various additives may be added to the biomass polyester in the manufacturing process of the biomass polyester or the manufactured biomass polyester as long as the characteristics are not impaired. For example, plasticizer, UV stabilizer, anti-coloring agent, gloss Detergents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, mold release agents, antioxidants, ion exchange agents, color pigments, and the like can be added. These additives are added in the range of 5% by mass or more and 50% by mass or less, preferably 5% by mass or more and 20% by mass or less, with respect to the entire resin composition containing biomass polyester.

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

  Examples of the 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. 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. Low density polyethylene, linear low density polyethylene, medium density polyethylene, and ethylene-methacrylic acid copolymers are preferred.

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

When the thermoplastic resin layer contains biomass polyolefin, the biomass polyolefin that is preferably used is low density polyethylene derived from biomass (trade name: SBC818, density: 0.918 g / cm ³ , MFR: 8. 1 g / 10 min, biomass degree 95%), low density polyethylene derived from biomass manufactured by Braskem (trade name: SPB681, density: 0.922 g / cm ³ , MFR: 3.8 g / 10 min, biomass degree 95%) Etc.

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

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

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

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

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

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

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

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

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

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

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

  The adhesive layer is an anchor coat layer formed by applying an anchor coating agent to the surface of the layer to be laminated and drying it when laminating a thermoplastic resin layer or the like by a melt extrusion lamination method. May be. Examples of the anchor coating agent include any resin having a heat-resistant temperature of 135 ° C. or higher, such as a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, and the like. An anchor coating agent comprising a polyacrylic or polymethacrylic resin having a hydroxyl group and an isocyanate compound as a curing agent can be preferably used. Moreover, a silane coupling agent may be used in combination as an additive, and nitrified cotton may be used in combination in order to improve heat resistance.

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

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

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

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

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

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

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

(Paper cup)
The laminate according to the present invention can be suitably used particularly for paper cups. The case where a paper cup is formed using the laminated body by this invention is demonstrated. FIG. 4 is a perspective view with a part of the paper cup cut away. As shown in FIG. 4, the paper cup 40 has a flange portion 41 at the top and is provided at a cylindrical barrel portion 42 that gradually increases in diameter toward the opening, and a lower end (one end) of the barrel portion 42. And a bottom portion 43. The body portion 42 is provided with a flange portion 41 whose upper end is rounded outward. Note that the paper cup 40 may be sealed by adhering a lid (not shown) along the flange portion 41 of the body portion 42 after storing the contents. The lid member preferably has gas barrier properties.

  Further, as shown in FIG. 5, the paper cup 40 may include 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 an air layer gap 46 between the body portion 42 and the exterior body 44. One or more convex portions 45 are provided in the horizontal direction. For example, two convex portions 45 can be provided as shown in FIG.

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

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

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

[Example 1]
<Preparation of laminated body 1>
A biaxially stretched polyester film 1 (biomass degree: 20%, manufactured by Toyobo, DE038, thickness 12 μm) formed using fossil fuel-derived terephthalic acid and biomass-derived ethylene glycol (biomass polyester) was prepared. . An acid-resistant coated cup (manufactured by Chuetsu Pulp Co., Ltd., basis weight 270 g / m ² ) is prepared as a paper base material layer. Manufactured, WS-700) was applied and dried to form an anchor coat layer. Subsequently, fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is 320 ° C. on the anchor coat layer. A second thermoplastic resin layer (biomass degree: 0%, thickness 20 μm) was formed by melt extrusion lamination at a resin temperature of 100 m / min. Next, after corona treatment was applied to the surface of the paper base material layer opposite to the second thermoplastic resin layer, low-density polyethylene derived from fossil fuel (Japan) was applied to the corona-treated surface using a sand lamination method. While extruding LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) manufactured by Polyethylene, this adhesive resin layer (biomass degree: 0%, thickness: 15 μm) Then, the corona-treated surface of the polyester film 1 (polyester resin layer) subjected to the corona treatment was bonded. Subsequently, an anchor coat agent (manufactured by Toyo Morton Co., Ltd., EL540 / CAT-RT32) was applied and dried on the polyester film 1 to form an anchor coat layer. Thereafter, fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is 320 ° C. on the anchor coat layer. A thermoplastic resin layer (biomass degree: 0%, thickness 40 μm) is formed by melt extrusion lamination at a resin temperature and a line speed of 100 m / min, and a second thermoplastic resin layer, an anchor coat layer, a paper base material A laminate 1 was obtained in which a layer, an adhesive resin layer, a polyester resin layer, an anchor coat layer, and a thermoplastic resin layer were sequentially laminated.

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

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

[Example 3]
<Preparation of laminate 4>
A glass base paper (manufactured by Nippon Paper Industries Co., Ltd., basis weight 280 g / m ² ) is prepared as a paper base material layer. While extruding low-density polyethylene derived from Nippon Polyethylene (LC600A, density: 0.919 g / cm ³ , MFR: 7.0 g / 10 min, biomass degree: 0%), this adhesive resin layer (biomass degree: 0 % And a thickness of 15 μm), the corona-treated surface of the polyester film 1 subjected to the corona treatment was bonded. Subsequently, an anchor coat agent (manufactured by Toyo Morton Co., Ltd., EL540 / CAT-RT32) was applied and dried on the polyester film 1 to form an anchor coat layer. Thereafter, fossil fuel-derived low density polyethylene (LC600A, density: 0.919 g / cm ³ , MFR: 7.0 g / 10 min, biomass degree: 0%) at 320 ° C. on the anchor coat layer. A thermoplastic resin layer (biomass degree: 0%, thickness 40 μm) is formed by melt extrusion lamination at a resin temperature and a line speed of 100 m / min, and a paper base layer, an adhesive resin layer, a polyester resin layer, an anchor coat A laminate 4 was obtained in which a layer and a thermoplastic resin layer were sequentially laminated.

[Example 4]
<Preparation of laminated body 5>
A glass base paper (manufactured by Nippon Paper Industries Co., Ltd., basis weight 280 g / m ² ) is prepared as a paper base material layer, and after corona treatment is performed on one surface, the corona-treated surface is derived from biomass using a sand laminating method. While extruding a low-density polyethylene (Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%), this adhesive resin layer (biomass degree: 95%, The corona-treated surface of the polyester film 1 subjected to the corona treatment was pasted through a thickness of 15 μm). Subsequently, an anchor coat agent (manufactured by Toyo Morton Co., Ltd., EL540 / CAT-RT32) was applied and dried on the polyester film 1 to form an anchor coat layer. Thereafter, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) on the anchor coat layer is a resin temperature of 320 ° C. , Melt extrusion lamination at a line speed of 100 m / min to form a thermoplastic resin layer (biomass degree: 95%, thickness 40 μm), paper base layer, adhesive resin layer, polyester resin layer, anchor coat layer, The laminated body 5 in which the thermoplastic resin layers were sequentially laminated was obtained.

[Comparative Example 2]
<Preparation of laminate 6>
A glass base paper (manufactured by Nippon Paper Industries Co., Ltd., basis weight 280 g / m ² ) is prepared as a paper base material layer. While extruding low-density polyethylene derived from Nippon Polyethylene (LC600A, density: 0.919 g / cm ³ , MFR: 7.0 g / 10 min, biomass degree: 0%), this adhesive resin layer (biomass degree: 0 % And a thickness of 15 μm), the corona-treated surface of the polyester film 2 subjected to the corona treatment was bonded. Subsequently, an anchor coat agent (manufactured by Toyo Morton, EL540 / CAT-RT32) was applied and dried on the polyester film 2 to form an anchor coat layer. Thereafter, fossil fuel-derived low density polyethylene (LC600A, density: 0.919 g / cm ³ , MFR: 7.0 g / 10 min, biomass degree: 0%) at 320 ° C. on the anchor coat layer. A thermoplastic resin layer (biomass degree: 0%, thickness 40 μm) is formed by melt extrusion lamination at a resin temperature and a line speed of 100 m / min, and a paper base layer, an adhesive resin layer, a resin layer, an anchor coat layer Thus, a laminate 6 in which the thermoplastic resin layers were sequentially laminated was obtained.

[Example 5]
<Preparation of laminate 7>
A polyester film 1 is used, and this is attached to a delivery roll of a plasma chemical vapor deposition apparatus. Then, under the conditions shown below, a 200-nm-thick silicon oxide deposited film is formed on the corona-treated surface of the polyethylene terephthalate film. To obtain a silicon oxide-deposited polyester film 1.
(Deposition conditions)
Deposition surface; corona-treated surface Introduction gas amount; hexamethyldisiloxane: oxygen gas: helium = 1: 3: 3 (unit: slm)
Degree of vacuum in the vacuum chamber; 2-6 × 10 ⁻⁶ mBar
Degree of vacuum in the deposition chamber; 2-5 × 10 ⁻³ mBar
Cooling and electrode drum power supply: 10kW
Line speed: 100m / min

A glass base paper (manufactured by Nippon Paper Industries Co., Ltd., basis weight 260 g / m ² ) is prepared as a paper base material layer. While extruding low-density polyethylene derived from Nippon Polyethylene (LC600A, density: 0.919 g / cm ³ , MFR: 7.0 g / 10 min, biomass degree: 0%), this adhesive resin layer (biomass degree: 0 % And a thickness of 15 μm), the vapor-deposited surface of the silicon oxide vapor-deposited polyester film 1 was bonded. Subsequently, an anchor coat 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 coat layer. Thereafter, fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is 320 ° C. on the anchor coat layer. 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), a paper base layer, an adhesive resin layer, a barrier layer, a polyester resin layer, A laminate 7 was obtained in which an anchor coat layer and a thermoplastic resin layer were sequentially laminated.

[Example 6]
<Preparation of laminated body 8>
A glass base paper (manufactured by Nippon Paper Industries Co., Ltd., basis weight 260 g / m ² ) is prepared as a paper base layer, and after corona treatment is performed on one surface, the corona-treated surface is derived from biomass using a sand lamination method While extruding a low-density polyethylene (Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%), this adhesive resin layer (biomass degree: 95%, The vapor-deposited surface of the silicon oxide vapor-deposited polyester film 1 was bonded through a thickness of 15 μm). Subsequently, an anchor coat 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 coat layer. Thereafter, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree: 95%) on the anchor coat layer is a resin temperature of 320 ° C. , Extrusion molding at a line speed of 100 m / min to form a thermoplastic resin layer (biomass degree: 95%, thickness 25 μm), paper base layer, adhesive resin layer, barrier layer, polyester resin layer, anchor coat A laminate 8 was obtained in which the layers and the thermoplastic resin layer were sequentially laminated.

[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 glass base paper (manufactured by Nippon Paper Industries Co., Ltd., basis weight 260 g / m ² ) is prepared as a paper base material layer. While extruding low-density polyethylene derived from Nippon Polyethylene (LC600A, density: 0.919 g / cm ³ , MFR: 7.0 g / 10 min, biomass degree: 0%), this adhesive resin layer (biomass degree: 0 % And a thickness of 15 μm), the vapor-deposited surface of the silicon oxide vapor-deposited polyester film 2 (biomass degree: 0%) was bonded. Subsequently, an anchor coat 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 coat layer. Thereafter, fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is 320 ° C. on the anchor coat layer. Extrusion molding is performed at a resin temperature and a line speed of 100 m / min to form a thermoplastic resin layer (biomass degree: 0%, thickness 25 μm), a paper base layer, an adhesive resin layer, a barrier layer, a resin layer, an anchor A laminate 9 in which a coat layer and a thermoplastic resin layer were sequentially laminated was obtained.

[Production Examples 1 to 9]
<Preparation of paper cup>
The body cup laminate and the bottom member laminate shown in Table 1 below were combined to produce a paper cup in the following steps. First, a frustoconical blank plate for forming a body portion of a paper cup was punched from the body member laminate. Next, the blank plate is wound into a cylindrical shape, both end portions thereof are partially overlapped, hot air treatment is performed on the polymerization portion, and the low density polyethylene resin layer existing in the polymerization portion is heated and melted. . Then, it pressed with the hot plate etc. and performed cylinder sticking, the cylinder seal part was formed, and the cylindrical cup trunk part which comprises a paper cup was manufactured.

  On the other hand, the bottom member laminate is punched into a circular shape to produce a disk that constitutes the bottom, and then the outer periphery of the disk is erected in a cylindrical shape to form a bottom having the erection part. Manufactured. Next, after inserting the bottom paper manufactured in the same manner into the cylindrical cup body manufactured above, the cylindrical cup body and the bottom paper are blown with hot air or the like on the joint portion. The resin layer present at the joint was melted by heating. Subsequently, the tip of the cylindrical cup body is bent inward by a curling die and placed on the upright molding part constituting the bottom, so that the tip and the bottom of the cylindrical cup body are By knurling the overlapping portion with the upright molded portion from the inner diameter side by knurling, the cylindrical cup barrel portion and the bottom portion are closely bonded to form a joint portion, and the cylindrical cup barrel portion is formed. And a bottom of the paper cup was formed.

  After that, the bottom end of the cylindrical cup barrel is tightly bonded, and the tip short part opposite to the side where the joint is formed is curled outwardly by the curling die in the same manner as above, and the upper end An outward curl portion was formed to produce a paper cup with a full capacity of 382 cc.

<Performance evaluation test>
The manufactured paper cup was subjected to the following performance evaluation test.

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

(Liquid leak test)
Forty paper cups were prepared, neutral detergent (0.3% solution) was added to each paper cup, 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)
A: 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 Laminate 11 Paper base 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 Projection part 46 Gap

Claims (5)

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

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