JP6773249B1 - Laminates with a polyolefin resin layer and packaging products with them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate having a polyolefin resin layer made of a conventional fossil fuel-derived polyolefin and a laminate having a polyolefin resin layer containing biomass polyolefin which is comparable in physical properties such as mechanical properties. SOLUTION: The laminate according to the present invention includes at least a paper base material layer and a polyolefin resin layer, and the polyolefin resin layer contains biomass polyolefin which is a polymer of a monomer containing ethylene derived from biomass. The degree of biomass in the polyolefin resin layer is 5% or more, and the biomass polyolefin has a density of 0.91 g / cm3 or more and 0.93 g / cm3 or less. [Selection diagram] Fig. 1

Description

The present invention relates to a laminate having a polyolefin resin layer containing biomass polyolefin, and more specifically, at least a paper base material layer and a polyolefin resin layer containing biomass polyolefin, which is a polymer of a monomer containing ethylene derived from biomass. With respect to a laminate comprising. Furthermore, the present invention relates to a packaging product and a paper cup provided with the laminate.

In recent years, with the growing demand for the construction of a recycling-oriented society, there is a desire 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 using 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 progressing, and attempts are being made to produce various resins from the biomass raw materials.

As a resin derived from biomass, polylactic acid (PLA), which is produced via lactic acid fermentation, started commercial production in advance, but its biodegradable performance and the current performance as a plastic are general-purpose plastics. Because it is very different from the above, there are limits to the product applications and product manufacturing methods, and it has not been widely used. In addition, a life cycle assessment (LCA) evaluation is being conducted for PLA, and discussions are being held on energy consumption during PLA manufacturing and equivalence when replacing general-purpose plastics.

Here, as the general-purpose plastic, various types such as polyethylene, polypropylene, polyvinyl chloride, and polystyrene are used. In particular, polyethylene is molded into films, sheets, bottles and the like, and is used for various purposes such as packaging materials, and is widely used all over the world. Therefore, the use of conventional fossil fuel-derived polyethylene has a large environmental load.

Therefore, it is desired to reduce the amount of fossil fuel used by using a raw material derived from biomass in the production of polyethylene. For example, to date, research has been conducted on producing ethylene and butylene, which are raw materials for polyolefin resins, from renewable natural raw materials (see, for example, Patent Document 1).

Japanese Patent Publication No. 2011-506628

The present inventors have focused on ethylene, which is a raw material for polyolefin resins, and instead of ethylene obtained from conventional fossil fuels, biomass polyolefins using ethylene derived from biomass as a raw material (hereinafter, simply referred to as "biomass polyolefin"). The laminate including the polyolefin resin layer containing (there is) is a polyolefin resin layer made of a polyolefin produced using ethylene obtained from a conventional fossil fuel (hereinafter, may be simply referred to as “polyolefin derived from fossil fuel”). It was found that a laminate having the above-mentioned material can be obtained in terms of physical properties such as mechanical properties. The present invention is based on such findings.

Therefore, an object of the present invention is a laminate for a paper cup having a polyolefin resin layer made of a polyolefin derived from a conventional fossil fuel, and a laminate for a paper cup having a polyolefin resin layer containing a biomass polyolefin, which is comparable in physical properties such as mechanical properties. To provide the body.

In aspects of the invention
A laminate for a paper cup including at least a thermoplastic resin layer, a paper base material layer, and a polyolefin resin layer in this order.
In a laminated body for a paper cup, which is used as a body portion of a paper cup and is used so that a body portion seal portion is formed by adhering the thermoplastic resin layer and the polyolefin resin layer.
The polyolefin resin layer contains low-density polyethylene derived from biomass, which is a polymer of a monomer containing ethylene derived from biomass.
The degree of biomass in the polyolefin resin layer is 5% or more,
The thermoplastic resin layer is low-density polyethylene derived from fossil fuel.
Provided is a laminate for paper cups, wherein the innermost layer of the laminate for paper cups is the polyolefin resin layer.
In the aspect of the present invention, it is preferable that the laminate for paper cups further has a barrier layer.
In the aspect of the present invention, it is preferable that the laminate for paper cups further has a printing layer.
In another aspect of the invention
A paper cup with a torso and a bottom
The laminate constituting the body includes at least a thermoplastic resin layer, a paper base material layer, and a polyolefin resin layer in this order.
The polyolefin resin layer contains low-density polyethylene derived from biomass, which is a polymer of a monomer containing ethylene derived from biomass.
The degree of biomass in the polyolefin resin layer is 5% or more,
The thermoplastic resin layer is low-density polyethylene derived from fossil fuel.
The innermost layer of the laminate for paper cups is the polyolefin resin layer.
A paper cup is provided in which a body seal portion of the paper cup is formed by adhering the thermoplastic resin layer and the polyolefin resin layer.
In another aspect of the present invention, it is preferable that the laminate constituting the body portion further has a barrier layer.
In another aspect of the present invention, it is preferable that the laminate constituting the body portion further has a printing layer.

By providing at least a thermoplastic resin layer, a paper base material layer, and a polyolefin resin layer containing biomass polyolefin, the laminate for a paper cup according to the present invention can reduce the amount of fossil fuel used as compared with the conventional one. It can reduce the environmental load. Further, since the laminate for paper cups according to the present invention is comparable in physical properties such as mechanical properties to the laminate for paper cups of polyolefin resin derived from conventional fossil fuels, the paper cups made of polyolefin resin derived from conventional fossil fuels. Can replace the laminated body.

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 of a part of a paper cup cut off. A partially cutaway front view showing another embodiment of a paper cup.

In the present invention, the "biomass polyolefin" and the "polyolefin resin layer containing biomass polyolefin" 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 and a polyolefin resin layer containing biomass polyolefin. The polyolefin resin layer is a layer that becomes the innermost layer when a packaging container is formed by using a laminated body. By providing the polyolefin resin layer containing biomass polyolefin, the laminate can reduce the amount of fossil fuel used as compared with the conventional one, and can reduce the environmental load. Further, the laminate according to the present invention is not inferior to the laminate of polyolefin resin produced from the raw material obtained from the conventional fossil fuel in terms of physical properties such as mechanical properties, and therefore the laminate of conventional polyolefin resin. Can be substituted.

In addition to the above layers, the laminate according to the present invention may further have at least one other layer such as a thermoplastic resin layer, a printing layer, a barrier layer, a plastic film, and an adhesive 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 and a polyolefin resin layer 12 formed on the paper base material layer 11. In the case of a paper cup including the laminate 10, the polyolefin resin layer 12 is located inside the paper cup. Here, the polyolefin resin layer 12 is a polyolefin resin layer containing biomass polyolefin.
The laminate 20 shown in FIG. 2 includes an adhesive layer 13, a barrier layer 14, and a polyolefin resin layer 12 in this order on one surface of the paper base layer 11 and the paper base layer 11. is there. In the case of a paper cup including the laminate 20, the polyolefin resin layer 12 is located inside the paper cup.
The laminate 30 shown in FIG. 3 has an adhesive layer 13, a plastic film 15, an adhesive layer 13, and a polyolefin resin layer 12 on one surface of the paper base layer 11 and the paper base layer 11. It prepares in order. In the case of a paper cup including the laminate 30, the polyolefin resin layer 12 is located inside the paper cup.
In any of the laminated bodies, a printing layer or a thermoplastic resin layer may be laminated on the other surface of the paper base material layer 11. When laminating the printing layer and the thermoplastic resin layer, the 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 polyolefin 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. To 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 sulfuric acid band to make paper in a neutral region of pH 6 or more and pH 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.

(Polyolefin resin layer)
In the present invention, the polyolefin resin layer contains biomass polyolefin, which is a polymer of a monomer containing ethylene derived from biomass, and may further contain polyolefin derived from fossil fuel. The polyolefin resin layer may contain 5% by mass or more and 100% by mass or less of biomass polyolefin and 0% by mass or more and 95% by mass or less of fossil fuel-derived polyolefin with respect to the entire polyolefin resin layer. It may contain less than mass% of biomass polyolefin and less than 0% by mass of 95% by mass or less of fossil fuel-derived polyolefin, 25% by mass or more and 75% by mass or less of biomass polyolefin and 25% by mass or more and 75% by mass% by mass. The following fossil fuel-derived polyolefins may be included. It suffices if the following biomass degree can be realized as the entire polyolefin resin layer. In the present invention, since the polyolefin resin layer contains biomass polyolefin, the amount of fossil fuel-derived polyolefin can be reduced and the environmental load can be reduced as compared with the conventional case.

In the present invention, the "biomass degree" (biomass-derived carbon concentration in the biomass polyolefin) in the polyolefin resin layer is a value obtained by measuring the content of biomass-derived carbon by radiocarbon (C14) measurement. 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 polyolefin. In the present invention, in the case where the content of C14 in the polyolefin was P _C14, the content P _{bio Bio} carbon from biomass, can be obtained as follows.
_{P bio (%) = P C14} /105.5×100

In the present invention, theoretically, if all biomass-derived ethylene is used as the raw material for the polyolefin, the biomass degree is 100%, and the biomass degree of the biomass-derived polyolefin is 100%. Further, the carbon concentration derived from biomass in the polyolefin derived from fossil fuel produced only from the raw material derived from fossil fuel is 0%, and the biomass degree of the polyolefin derived from fossil fuel is 0%.

In the present invention, the biomass degree in the polyolefin resin layer is 5% or more, preferably 10% or more, more preferably 15% or more, still more preferably 20% or more. The degree of biomass in the polyolefin resin layer does not have to be 100%. This is because if a raw material derived from biomass is used even in a part of the laminate, the purpose of the present invention is to reduce the amount of fossil fuel used as compared with the conventional case. When the biomass content in the polyolefin resin layer is 5% or more, the amount of fossil fuel-derived polyolefin can be reduced and the environmental load can be reduced as compared with the conventional case.

Polyolefin resin layer is preferably from 0.91 g / cm ³ or more 0.93 g / cm ³ or less, more preferably 0.911 g / cm ³ or more 0.928 g / cm ³ or less, more preferably 0.915 g / cm ³ or more It has a density of 0.925 g / cm ³ or less. The density of the polyolefin resin layer is a value measured according to the method specified in the method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1980. If the density of the polyolefin resin layer is 0.91 g / cm ³ or more 0.93 g / cm ³ or less, it is possible to facilitate processing and molding.

The polyolefin resin layer has a thickness of 5 μm or more and 100 μm or less, preferably 10 μm or more and 60 μm or less, and more preferably 15 μm or more and 40 μm or less. When the thickness of the polyolefin resin layer is about the above range, the function as a sealing layer of the packaging container can be sufficiently fulfilled.

(Biomass polyolefin)
In the present invention, the biomass polyolefin is a polymer of a monomer containing ethylene derived from biomass. As the biomass-derived ethylene, it is preferable to use the ethylene obtained by the production method described later. Since ethylene derived from biomass is used as the monomer as a raw material, the polymerized polyolefin is derived from biomass. The raw material monomer of polyolefin does not have to contain 100% by mass of ethylene derived from biomass.

The monomer that is the raw material of the biomass polyolefin may further contain a fossil fuel-derived ethylene monomer and / or a fossil fuel-derived α-olefin monomer, or may further contain a biomass-derived α-olefin monomer.

The above-mentioned α-olefin has no particular limitation on the number of carbon atoms, but usually one having 3 to 20 carbon atoms can be used, and it is preferably butylene, hexene, or octene. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a raw material derived from biomass. Further, by including such an α-olefin, the polymerized biomass polyolefin has an alkyl group as a branched structure, so that it can be made more flexible than a simple linear one.

As the biomass polyolefin, polyethylene or a copolymer of ethylene and α-olefin may be used alone, or two or more kinds thereof may be mixed and used. In particular, the biomass polyolefin is preferably polyethylene. This is because by using ethylene, which is a raw material derived from biomass, it is theoretically possible to produce with 100% biomass-derived components.

The biomass polyolefin may contain two or more kinds of biomass polyolefins having different biomass degrees, and the biomass degree of the entire polyolefin resin layer may be within the above range.

Biomass polyolefin, preferably 0.91 g / cm ³ or more 0.93 g / cm ³ or less, more preferably 0.912 g / cm ³ or more 0.928 g / cm ³ or less, more preferably 0.915 g / cm ³ or more 0 It has a density of .925 g / cm ³ or less.
The density of the biomass polyolefin is a value measured according to the method specified in the method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1980. When the density of the biomass polyolefin is 0.91 g / cm ³ or more, the rigidity of the polyolefin resin layer containing the biomass polyolefin can be increased, and it can be suitably used as the inner layer of the packaged product. Further, when the density of the biomass polyolefin is 0.93 g / cm ³ or less, the transparency and mechanical strength of the polyolefin resin layer containing the biomass polyolefin can be enhanced, and it can be suitably used as the inner layer of the packaged product.

The biomass polyolefin has a melt flow of 0.1 g / 10 minutes or more and 10 g / 10 minutes or less, preferably 0.2 g / 10 minutes or more and 9 g / 10 minutes or less, and more preferably 1 g / 10 minutes or more and 8.5 g / 10 minutes or less. It has a rate (MFR). The melt flow rate is a value measured by the method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method specified in JIS K7210-1995. When the MFR of the biomass polyolefin is 0.1 g / 10 minutes or more, the extrusion load during the molding process can be reduced. Further, when the MFR of the biomass polyolefin is 10 g / 10 minutes or less, the mechanical strength of the polyolefin resin layer containing the biomass polyolefin can be increased.

As the biomass polyolefin preferably used in the present invention, 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 biomass manufactured by Braskem (trade name: SPB681, density: 0.922 g / cm ³ , MFR: 3.8 g / 10 minutes, biomass degree 95%) and the like.

(Biomass-derived ethylene production method)
In the present invention, the method for producing biomass-derived ethylene, which is a raw material for biomass polyolefin, is not particularly limited and can be obtained by a conventionally known method. Hereinafter, an example of a method for producing ethylene-derived ethylene will be described.

Biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. In particular, it is preferable to use fermented ethanol derived from biomass obtained from plant raw materials. The plant material is not particularly limited, and conventionally known plants can be used. For example, corn, sugar cane, beets, and manioc can be mentioned.

In the present invention, the fermented ethanol derived from biomass refers to ethanol purified by contacting a culture solution containing a carbon source obtained from a plant raw material with a microorganism that produces ethanol or a product derived from a crushed product thereof. Conventionally known methods such as distillation, membrane separation, and extraction can be applied to the purification of ethanol from the culture broth. For example, a method of adding benzene, cyclohexane or the like and azeotropically boiling the mixture, or removing water by membrane separation or the like can be mentioned.

In order to obtain the ethylene of the present invention, advanced purification such as reducing the total amount of impurities in ethanol to 1 ppm or less may be further performed at this stage.

A catalyst is usually used when ethylene is obtained by a dehydration reaction of ethanol, but the catalyst is not particularly limited, and a conventionally known catalyst can be used. Advantageous in the process is a fixed bed flow reaction in which the catalyst and the product can be easily separated, and for example, γ-alumina is preferable.

Since this dehydration reaction is an endothermic reaction, it is usually carried out under heating conditions. As long as the reaction proceeds at a commercially useful reaction rate, the heating temperature is not limited, but a temperature of 100 ° C. or higher, more preferably 250 ° C. or higher, still more preferably 300 ° C. or higher is suitable. The upper limit is not particularly limited, but is preferably 500 ° C. or lower, more preferably 400 ° C. or lower, from the viewpoint of energy balance and equipment.

The reaction pressure is also not particularly limited, but a pressure higher than normal pressure is preferable in order to facilitate subsequent gas-liquid separation. Industrially, a fixed bed flow reaction in which the catalyst can be easily separated is preferable, but a liquid phase suspension bed, a fluidized bed, or the like may also be used.

In the dehydration reaction of ethanol, the yield of the reaction depends on the amount of water contained in the ethanol supplied as a raw material. Generally, when a dehydration reaction is carried out, it is preferable that there is no water in consideration of the efficiency of removing water. However, in the case of the dehydration reaction of ethanol using a solid catalyst, it was found that the amount of other olefins, especially butene, tends to increase in the absence of water. It is presumed that it is not possible to suppress ethylene dimerization after dehydration without the presence of a small amount of water. The lower limit of the allowable water content needs to be 0.1% or more, preferably 0.5% or more. The upper limit is not particularly limited, but from the viewpoint of mass balance and heat balance, it is preferably 50% by mass or less, more preferably 30% or less, still more preferably 20% or less.

By performing the ethanol dehydration reaction in this way, a mixed portion of ethylene, water and a small amount of unreacted ethanol can be obtained, but since ethylene is a gas at about 5 MPa or less at room temperature, it is separated from these mixed portions by gas-liquid separation. Ethylene can be obtained except for water and ethanol. This method may be performed by a known method.

Ethylene obtained by gas-liquid separation is further distilled, and the distillation method, operating temperature, residence time, and the like are not particularly limited except that the operating pressure at this time is normal pressure or higher.

When the raw material is ethanol derived from ammonia, the obtained ethylene contains carbonyl compounds such as ketones, aldehydes, and esters, which are impurities mixed in the ethanol fermentation process, carbon dioxide gas, which is a decomposition product thereof, and decomposition products of enzymes. It contains a very small amount of nitrogen-containing compounds such as amines and amino acids, which are impurities, and ammonia, which is a decomposition product thereof. Depending on the use of ethylene, these trace amounts of impurities may cause a problem, and may be removed by purification. The purification method is not particularly limited, and can be performed by a conventionally known method. As a suitable purification operation, for example, an adsorption purification method can be mentioned. The adsorbent used is not particularly limited, and conventionally known adsorbents can be used. For example, a material having a high surface area is preferable, and the type of adsorbent is selected according to the type and amount of impurities in ethylene obtained by the dehydration reaction of ethanol derived from biomass.

In addition, caustic water treatment may be used in combination as a method for purifying impurities in ethylene. When caustic water treatment is performed, it is desirable to perform it before adsorption purification. In that case, it is necessary to perform a water removal treatment after the caustic treatment and before the adsorption purification.

(Manufacturing method of biomass polyolefin)
In the present invention, the method for polymerizing a monomer containing ethylene derived from biomass is not particularly limited, and a conventionally known method can be used. The polymerization temperature and the polymerization pressure may be appropriately adjusted according to the polymerization method and the polymerization apparatus. The polymerization apparatus is not particularly limited, and conventionally known apparatus can be used. Hereinafter, an example of a method for polymerizing a monomer containing ethylene will be described.

The method for polymerizing a polyolefin, particularly an ethylene polymer or a copolymer of ethylene and α-olefin, is a method of polymerizing a target type of polyethylene, for example, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE). ), And linear low-density polyethylene (LLDPE) or the like, which can be appropriately selected depending on the difference in density and branching. For example, a multisite catalyst such as a Ziegler-Natta catalyst or a single site catalyst such as a metallocene catalyst is used as a polymerization catalyst by any of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ion polymerization. It is preferable to carry out in one stage or in multiple stages of two or more stages.

The above-mentioned single-site catalyst is a catalyst capable of forming a uniform active species, and is usually prepared by contacting a metallocene-based transition metal compound or a non-metallocene-based transition metal compound with an activation co-catalyst. .. Compared with the multisite catalyst, the single-site catalyst is preferable because it has a uniform active site structure and can polymerize a polymer having a high molecular weight and a high uniformity structure. As the single-site catalyst, it is particularly preferable to use a metallocene-based catalyst. The metallocene-based catalyst is a catalyst containing a transition metal compound of Group IV of the Periodic Table, which contains a ligand having a cyclopentadienyl skeleton, a cocatalyst, an organometallic compound if necessary, and each catalyst component of the carrier. is there.

In the transition metal compound of Group IV of the Periodic Table containing the ligand having the cyclopentadienyl skeleton, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group or the like. .. The substituted cyclopentadienyl group includes a hydrocarbon group having 1 to 30 carbon atoms, a silyl group, a silyl substituted alkyl group, a silyl substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group, a halogen group, a haloalkyl group, and a halosilyl. It has at least one substituent selected from the groups and the like. The substituted cyclopentadienyl group may have two or more substituents, and the substituents are bonded to each other to form a ring to form an indenyl ring, a fluorenyl ring, an azulenyl ring, a hydrogenated product thereof, or the like. It may be formed. Rings formed by bonding substituents to each other may further have substituents to each other.

In the transition metal compound of Group IV of the Periodic Table containing a ligand having a cyclopentadienyl skeleton, examples of the transition metal include zirconium, titanium and hafnium, and zirconium and hafnium are particularly preferable. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and the ligands having each cyclopentadienyl skeleton are preferably bonded to each other by a cross-linking group. Examples of the cross-linking group include a substituted silylene group such as an alkylene group having 1 to 4 carbon atoms, a silylene group, a dialkyl silylene group and a diaryl silylene group, and a substituted gel millene group such as a dialkyl gel millene group and a diaryl gel millene group. It is preferably a substituted silylene group.

In the transition metal compound of Group IV of the periodic table, typical ligands other than the ligand having a cyclopentadienyl skeleton are hydrogen and a hydrocarbon group having 1 to 20 carbon atoms (alkyl group). , Alkenyl group, aryl group, alkylaryl group, aralkyl group, polyenyl group, etc.), halogen, metaalkyl group, metaaryl group and the like.

The above-mentioned transition metal compound of Group IV of the Periodic Table containing a ligand having a cyclopentadienyl skeleton can have one or a mixture of two or more as a catalyst component.

The co-catalyst is one in which the transition metal compound of Group IV of the periodic table can be effectively used as a polymerization catalyst, or the ionic charge in a catalytically activated state can be equalized. As co-catalysts, benzene-soluble organoxane of organoaluminum oxy compounds, benzene-insoluble organoaluminum oxy compounds, ion-exchange layered silicates, boron compounds, cations containing or not containing active hydrogen groups and non-coordinating anions are used. Examples thereof include ionic compounds, lanthanoid salts such as lanthanum oxide, tin oxide, and phenoxy compounds containing a fluoro group.

The transition metal compound of Group IV of the Periodic Table, which contains a ligand having a cyclopentadienyl skeleton, may be used by supporting it on a carrier of an inorganic or organic compound. The carrier is preferably an inorganic or organic compound porous oxide, and specifically, an ion-exchangeable layered silicate such as montmorillonite, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O. ₃ , CaO, ZnO, BaO, ThO _2, etc. or a mixture thereof can be mentioned.

Further, examples of the organometallic compound used as necessary include organoaluminum compounds, organomagnesium compounds, and organozinc compounds. Of these, organoaluminum is preferably used.

In addition to the polyolefin as the main component, various additives may be added to the biomass polyolefin as long as its properties are not impaired. Additives include, for example, plasticizers, UV stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weatherproofing agents, antistatic agents, thread friction reducing agents, slip agents, mold release agents, anti-flammable agents. Excipients, ion exchangers, coloring pigments and the like can be added. These additives are preferably added in the range of 1% by mass or more and 20% by mass or less, preferably 1% by mass or more and 10% by mass or less, based on the total biomass polyolefin.

(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, similarly to the polyolefin resin layer.

(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 substrate layer opposite to the polyolefin 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 an inorganic substance or a vapor-deposited film of 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, etc., 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) of 0 to 1, zirconium (Zr) of 0 to 2, and yttrium (Y) 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. The value of can be used.

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. The film thickness is preferably about 50 to 500 Å, more preferably about 100 to 300 Å.

The vapor-deposited film can be formed on a plastic film such as polyethylene terephthalate or nylon by the following forming method. Examples of the method for forming the vapor-deposited 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 and water vapor, and light-shielding property that blocks the transmission of visible light and ultraviolet rays.

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

(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 formed by applying an anchor coating agent to the surface of the layer to be laminated and drying it when laminating a polyolefin resin layer, a thermoplastic resin layer, or the like by a melt extrusion laminating method. It may be a coat layer. 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, and in particular, two or more in the structure. 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 resin, polypropylene-based resin, or cyclic polyolefin-based resin, or a copolymer resin containing these resins as a main component, a modified resin, or a mixture (including an alloy). ) 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 copolymers polymerized using, random or block copolymers of ethylene / polypropylene, ethylene-vinyl acetate copolymers (EVA), ethylene-acrylic acid copolymers (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. In order to improve the above-mentioned polyolefin resin, it is possible to use an acid-modified polyolefin resin obtained by modifying the above-mentioned polyolefin 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 may contain 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 a monomer containing biomass-derived ethylene, similarly to the polyolefin resin layer.

(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, it is preferable to form a polyolefin resin layer on the surface of the layer to be laminated by using the melt extrusion laminating method. Further, the polyolefin resin layer and another layer may be laminated by a coextrusion method.

For example, the resin composition for forming the polyolefin resin layer by supplying it to a melt extruder heated to a temperature of Tm or higher and Tm + 70 ° C. of the resin composition for forming the polyolefin resin layer by the following method. The polyolefin resin layer is laminated by melting the material, extruding it into a sheet from a die such as a T die, and quenching and solidifying the extruded sheet with a rotating cooling drum or the like on the surface of the layer to be laminated. can do. 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 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 extruded 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 also has 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.

(Another aspect)
Another object of the present invention is to provide a laminate having a polyolefin resin layer made of a conventional fossil fuel-derived polyolefin and a laminate having a polyolefin resin layer containing a biomass polyolefin, which is comparable in physical properties such as mechanical properties. That is.
In another aspect of the invention
A laminate including at least a paper base material layer and a polyolefin resin layer.
The polyolefin resin layer contains biomass polyolefin, which is a polymer of a monomer containing ethylene derived from biomass.
The degree of biomass in the polyolefin resin layer is 5% or more,
The biomass polyolefin has a density of 0.91 g / cm ³ or more 0.93 g / cm ³ or less, laminate is provided.
In the aspect of the present invention, it is preferable that the polyolefin resin layer further contains a fossil fuel-derived polyolefin.
In the aspect of the present invention, it is preferable that the polyolefin resin layer contains 5% by mass or more and 100% by mass or less of the biomass polyolefin and 0% by mass or more and 95% by mass or less of the polyolefin derived from the fossil fuel.
In the aspect of the present invention, it is preferable that the polyolefin resin layer contains polyethylene.
In another aspect of the present invention, a packaged product comprising the laminate is provided.
In another aspect of the present invention, the paper cup provided with the laminate
A paper cup is provided in which the innermost layer of the paper cup is the polyolefin resin layer.
By providing at least a paper base material layer and a polyolefin resin layer containing biomass polyolefin, the laminate according to another aspect of the present invention can reduce the amount of fossil fuel used as compared with the conventional one, and has an environmental load. Can be reduced. Further, since the laminate according to another aspect of the present invention is not inferior to the conventional fossil fuel-derived polyolefin resin laminate in terms of physical properties such as mechanical properties, the conventional fossil fuel-derived polyolefin resin laminate Can replace the body.

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 extrusion film forming machine 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 laminate 1>
An acid-resistant coated cup (manufactured by Chuetsu Pulp Industry Co., Ltd., basis weight 270 g / m ² ) is prepared as a paper substrate layer, one surface is corona-treated, and then the corona-treated surface is made of low-density polyethylene derived from biomass ( Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a polyolefin. A resin layer (biomass degree: 95%, thickness 40 μm) was formed to obtain a laminate 1 in which a paper base material layer and a polyolefin resin layer were laminated in this order.

[Example 2]
<Preparation of laminated body 2>
An acid-resistant coated cup (manufactured by Chuetsu Pulp Industry Co., Ltd., basis weight 270 g / m ² ) is prepared as a paper substrate layer, one surface is corona-treated, and then the corona-treated surface is made of low-density polyethylene derived from biomass. (Brackem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95%) 70 parts by mass and low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene, LC520, Density: 0.923 g / cm ³ , MFR: 3.6 g / 10 min, Biomass degree: 0%) A mixed resin dry-blended with 30 parts by mass is melt-extruded at a resin temperature of 320 ° C. and a line speed of 100 m / min. By laminating, a polyolefin resin layer (biomass degree: 67%, thickness 40 μm) was formed, and a laminated body 2 in which a paper base material layer and a polyolefin resin layer were laminated in this order was obtained.

[Comparative Example 1]
<Preparation of laminated body 3>
An acid-resistant coated cup (manufactured by Chuetsu Pulp Industry Co., Ltd., basis weight 270 g / m ² ) is prepared as a paper base material layer, and one surface is corona-treated, and then the corona-treated surface is fossil fuel-derived low-density polyethylene. (Manufactured by Japan Polyethylene Corporation, LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min. , A resin layer (biomass degree: 0%, thickness 40 μm) was formed, and a laminated body 3 in which a paper base material layer and a resin layer were laminated in this order was obtained.

[Example 3]
<Preparation of laminated body 4>
An acid-resistant coated cup (manufactured by Chuetsu Pulp Industry Co., Ltd., basis weight 270 g / m ² ) is prepared as a paper substrate layer, one surface is corona-treated, and then the corona-treated surface is fossil fuel-derived low-density polyethylene. (Manufactured by Japan Polyethylene Corporation, LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min. , A thermoplastic resin layer (biomass degree: 0%, thickness 20 μm) was formed. Next, the surface of the paper substrate layer opposite to the thermoplastic resin layer is subjected to corona treatment, and then the corona-treated surface is subjected to low-density polyethylene derived from biomass (Brackem, SBC818, density: 0.918 g / cm. ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95%) 70 parts by mass and low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene, LC520, density: 0.923 g / cm ³ , MFR: 3.6 g A mixed resin dry-blended with 30 parts by mass (10 minutes, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and a polyolefin resin layer (biomass degree: 67%, thickness) is laminated. 40 μm) was formed to obtain a laminate 4 in which a thermoplastic resin layer, a paper base material layer, and a polyolefin resin layer were laminated in this order.

[Example 4]
<Preparation of laminated body 5>
An acid-resistant coated cup (manufactured by Chuetsu Pulp Industry Co., Ltd., basis weight 270 g / m2) is prepared as a paper base material layer, and after corona treatment is applied to one surface, a biomass-derived low-density polyethylene (Braskem) is applied to the corona-treated surface. SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min, and is thermoplastic. A resin layer (biomass degree: 95%, thickness 20 μm) was formed. Next, the surface of the paper substrate layer opposite to the thermoplastic resin layer is subjected to corona treatment, and then the corona-treated surface is subjected to low-density polyethylene derived from biomass (Brackem, SBC818, density: 0.918 g / cm. ^3. MFR: 8.1 g / 10 min, biomass degree: 95%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a polyolefin resin layer (biomass degree: 95%, thickness 40 μm). Was formed to obtain a laminate 5 in which a thermoplastic resin layer, a paper base material layer, and a polyolefin resin layer were laminated in this order.

[Comparative Example 2]
<Preparation of laminated body 6>
An acid-resistant coated cup (manufactured by Chuetsu Pulp Industry Co., Ltd., basis weight 270 g / m2) is prepared as a paper substrate layer, and one surface is subjected to corona treatment, and then the corona-treated surface is subjected to fossil fuel-derived low-density polyethylene ( Made by Japan Polyethylene Corporation, LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min. A thermoplastic resin layer (biomass degree: 0%, thickness 20 μm) was formed. Next, the surface of the paper substrate layer opposite to the thermoplastic resin layer is subjected to corona treatment, and then the corona-treated surface is made of low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g). / Cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is extruded at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a resin layer (biomass degree: 0%, thickness 40 μm). Was formed to obtain a laminate 6 in which a thermoplastic resin layer, a paper base material layer, and a resin layer were laminated in this order.

[Example 5]
<Preparation of laminated body 7>
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, 70 parts by mass of biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95%) and fossils were placed on the anchor coat layer. A mixed resin obtained by dry blending 30 parts by mass of fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%). A thermoplastic resin layer (biomass degree: 67%, thickness 20 μm) was formed by melt-extruding and laminating at a resin temperature of 320 ° C. and a line speed of 100 m / min. Next, the surface of the paper substrate layer opposite to the thermoplastic resin layer is subjected to corona treatment, and then the corona-treated surface is subjected to a fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd.) using a sand lamination method. , LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%) while extruding through this adhesive resin layer (biomass degree: 0%, thickness 15 μm). A corona-treated surface of a fossil fuel-derived polyethylene terephthalate film (manufactured by Toyo Boseki Co., Ltd., T4100, thickness 12 μm) that had been subjected to corona treatment was bonded. Subsequently, an anchor coating agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the polyethylene terephthalate film to form an anchor coating layer. After that, 70 parts by mass of 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%) and fossil fuel were placed on the anchor coat layer. A mixed resin obtained by dry blending 30 parts by mass of a low-density polyethylene derived from (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%) at 320 ° C. Polyolefin resin layer (biomass degree: 67%, thickness 40 μm) is formed by melt-extruding and laminating at the resin temperature and line speed of 100 m / min, and the thermoplastic resin layer, anchor coat layer, paper base material layer, and adhesion are formed. A laminated body 7 in which a resin layer, a plastic film, an anchor coat layer, and a polyolefin resin layer were laminated in this order was obtained.

[Comparative Example 3]
<Preparation of laminated body 8>
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 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 thermoplastic resin layer is subjected to corona treatment, and then the corona-treated surface is subjected to a fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd.) using a sand lamination method. , LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%) while extruding through this adhesive resin layer (biomass degree: 0%, thickness 15 μm). A corona-treated surface of a fossil fuel-derived polyethylene terephthalate film (manufactured by Toyo Boseki Co., Ltd., T4100, thickness 12 μm) that had been subjected to corona treatment was bonded. Subsequently, an anchor coating agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the polyethylene terephthalate film to form an anchor coating layer. After that, a low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%) was placed on the anchor coat layer at 320 ° C. A 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 to form a thermoplastic resin layer, an anchor coat layer, a paper base material layer, and an adhesive resin layer. , A laminated body 8 in which a plastic film, an anchor coat layer, and a resin layer were laminated in this order was obtained.

[Example 6]
<Preparation of laminated body 9>
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 laminate 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 surface of a fossil fuel-derived polyethylene terephthalate film (manufactured by Toyo Boseki Co., Ltd., T4100, thickness 12 μm) subjected to corona treatment was bonded. Subsequently, an anchor coating agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the polyethylene terephthalate film 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, degree of biomass: 95%) was placed on the anchor coat layer at a resin temperature of 320 ° C. , Polyolefin resin layer (biomass degree: 95%, thickness 40 μm) is formed by melt extrusion laminating at a line speed of 100 m / min, and a paper base material layer, an adhesive resin layer, a plastic film, an anchor coat layer, and a polyolefin resin. A laminated body 9 in which the layers were laminated in order was obtained.

[Comparative Example 4]
<Preparation of laminated body 10>
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 surface of a fossil fuel-derived polyethylene terephthalate film (manufactured by Toyo Boseki Co., Ltd., T4100, thickness 12 μm) subjected to corona treatment was bonded. Subsequently, an anchor coating agent (EL540 / CAT-RT32 manufactured by Toyo Morton Co., Ltd.) was applied and dried on the polyethylene terephthalate film to form an anchor coating layer. Then, low-density polyethylene derived from fossil fuel similar to the above is melt-extruded and laminated on the anchor coat layer at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a resin layer (biomass degree: 0%, thickness 40 μm). Was formed to obtain a laminate 10 in which a paper base material layer, an adhesive resin layer, a plastic film, an anchor coat layer, and a resin layer were laminated in this order.

[Example 7]
<Preparation of laminated body 11>
A polyethylene terephthalate film derived from fossil fuel (manufactured by Toyobo Co., Ltd., T4100, thickness 12 μm) was used, and this was attached to a delivery roll of a plasma chemical vapor deposition apparatus. A 200 Å thick thin-film silicon oxide film was formed on the corona-treated surface to obtain a silicon oxide-deposited polyethylene terephthalate 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, LC520, density: 0.923 g / cm ³ , MFR: 3.6 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 polyethylene terephthalate 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 polyethylene terephthalate film to form an anchor coating layer. Then, on the anchor coat layer, 70 parts by mass of low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 g / cm3, MFR: 8.1 g / 10 minutes, degree of biomass: 95%) and derived from fossil fuel. Low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm3, MFR: 3.6 g / 10 minutes, biomass degree: 0%) 30 parts by mass of a mixed resin dry-blended with a resin at 320 ° C. A polyolefin resin layer (biomass degree: 67%, thickness 25 μm) is formed by melt-extruding and laminating at a temperature and a line speed of 100 m / min, and a paper base material layer, an adhesive resin layer, a barrier layer, a plastic film, and an anchor coat are formed. A laminated body 11 in which a layer and a polyolefin resin layer were laminated in this order was obtained.

[Comparative Example 5]
<Preparation of laminated body 12>
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, LC520, density: 0.923 g / cm ³ , MFR: 3.6 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 polyethylene terephthalate 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 polyethylene terephthalate film to form an anchor coating layer. After that, 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 resin layer (biomass degree: 0%, thickness 25 μm) is formed by melt-extruding and laminating at a resin temperature and a line speed of 100 m / min to form a paper base material layer, an adhesive resin layer, a barrier layer, a plastic film, and an anchor coat. A laminated body 12 in which a layer and a resin layer were laminated in this order was obtained.

[Example 8]
<Preparation of laminated body 13>
Single-sided coated paper (manufactured by Mitsubishi Paper Co., Ltd., DMSC, biomass 260 g / m ² ) is prepared as the paper substrate layer, one surface is corona-treated, and then the sand-laminated method is used on the corona-treated surface. Then, while extruding low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene, LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%), this adhesive resin layer ( An aluminum foil (thickness 7 μm) was laminated via a biomass degree (95%, thickness 15 μm). Subsequently, a fossil fuel-derived ethylene-methacrylic acid copolymer (Nucrel N0908C, manufactured by Mitsui DuPont Polychemical Co., Ltd.) was melt-extruded and laminated on the aluminum foil to form a resin layer (thickness 12 μm). Further, on this resin layer, 70 parts by mass of low density polyethylene derived from polyolefin (manufactured by Braskem, SBC818, density: 0.918 g / cm3, MFR: 8.1 g / 10 minutes, degree of biomass: 95%) and derived from fossil fuel. Low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g / cm3, MFR: 3.6 g / 10 minutes, biomass degree: 0%) 30 parts by mass of a mixed resin dry-blended with a resin at 320 ° C. A polyolefin resin layer (biomass degree: 95%, thickness 28 μm) is formed by melt-extruding and laminating at a temperature and a line speed of 100 m / min to form a paper base material layer, an adhesive resin layer, a barrier layer, a resin layer, and a polyolefin resin. A laminated body 13 in which the layers were laminated in order was obtained.

[Comparative Example 6]
<Preparation of laminated body 14>
Single-sided coated paper (manufactured by Mitsubishi Paper Co., Ltd., DMSC, biomass 260 g / m ² ) is prepared as the paper substrate layer, one surface is corona-treated, and then the sand-laminated method is used on the corona-treated surface. Then, while extruding low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene, LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%), this adhesive resin layer ( An aluminum foil (thickness 7 μm) was laminated via a biomass degree: 0%, thickness 15 μm). Subsequently, a fossil fuel-derived ethylene-methacrylic acid copolymer (Nucrel N0908C, manufactured by Mitsui DuPont Polychemical Co., Ltd.) was melt-extruded and laminated on the aluminum foil to form a resin layer (thickness 12 μm). Further, 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%) is placed on this resin layer at 320 ° C. A resin layer (biomass degree: 0%, thickness 28 μm) is formed by melt-extruding and laminating at a resin temperature and a line speed of 100 m / min to form a paper base material layer, an adhesive resin layer, a barrier layer, a resin layer, and a resin layer. Was obtained in order to obtain a laminated body 14.

[Manufacturing Examples 1 to 14]
<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, and then the outer peripheral portion of the disk is vertically formed into a tubular shape to form a bottom having the upright formed 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 produce a paper cup having a full capacity of 382 cc.

<Performance evaluation test>
The following performance evaluation test was conducted on the manufactured paper cup.

(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 Polyolefin resin layer 13 Adhesive layer 14 Barrier layer 15 Plastic film 40 Paper cup 41 Flange part 42 Body part 43 Bottom part 44 Exterior body 45 Convex part 46 Gap

Claims (6)

A laminate for a paper cup including at least a thermoplastic resin layer, a paper base material layer, and a polyolefin resin layer in this order.
In a laminate for a paper cup, which is used as a body of a paper cup and is used so that a body seal portion is formed by adhering the thermoplastic resin layer and the polyolefin resin layer.
The polyolefin resin layer contains low-density polyethylene derived from biomass, which is a polymer of a monomer containing ethylene derived from biomass.
The degree of biomass in the polyolefin resin layer is 5% or more,
The thermoplastic resin layer is low-density polyethylene derived from fossil fuel.
A laminate for paper cups, wherein the innermost layer of the laminate for paper cups is the polyolefin resin layer. The laminate for paper cups according to claim 1, wherein the laminate for paper cups further has a barrier layer. The laminate for paper cups according to claim 1 or 2, wherein the laminate for paper cups further has a printing layer. A paper cup with a torso and a bottom
The laminate constituting the body includes at least a thermoplastic resin layer, a paper base material layer, and a polyolefin resin layer in this order.
The polyolefin resin layer contains low-density polyethylene derived from biomass, which is a polymer of a monomer containing ethylene derived from biomass.
The degree of biomass in the polyolefin resin layer is 5% or more,
The thermoplastic resin layer is low-density polyethylene derived from fossil fuel.
The innermost layer of the laminate for paper cups is the polyolefin resin layer.
A paper cup in which a body seal portion of the paper cup is formed by adhering the thermoplastic resin layer and the polyolefin resin layer. The paper cup according to claim 4, wherein the laminate constituting the body portion further has a barrier layer. The paper cup according to claim 4 or 5, wherein the laminate constituting the body portion further has a printing layer.

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