JP7037774B2 - Laminates with a polyolefin resin layer and packaging products with them - Google Patents

Description

The present invention relates to a laminate having a polyolefin resin layer containing a biomass polyolefin, and more specifically, at least a paper substrate layer and a polyolefin resin layer containing a biomass polyolefin which is a polymer of a monomer containing ethylene derived from biomass. And a laminate including a thermoplastic resin layer. Further, the present invention relates to a packaging product and a liquid paper container provided with the laminate.

In recent years, with the growing demand for the construction of a sound material-cycle society, it is desired to break away from fossil fuels in the material field as well as energy, and the use of biomass is drawing attention. Biomass is an organic compound photosynthesized from carbon dioxide and water, and by 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 materials is rapidly advancing, and attempts are being made to manufacture various resins from biomass raw materials.

As a biomass-derived resin, polylactic acid (PLA), which is produced via lactic acid fermentation, has started commercial production in advance, but its biodegradable performance and current general-purpose plastic performance 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 has been conducted for PLA, and discussions have been made 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, using polyethylene derived from conventional fossil fuels has a large environmental load.

Therefore, it is desired to reduce the amount of fossil fuel used in the production of polyethylene by using a raw material derived from biomass. 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 biomass-derived ethylene as a raw material (hereinafter, simply referred to as "biomass polyolefin"). The liquid paper container provided with the laminate having the polyolefin resin layer containing (there is) is 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 liquid paper container having a laminate having a polyolefin resin layer made of a polyolefin resin layer and a liquid paper container having physical properties such as mechanical properties comparable to those can be obtained. The present invention is based on such findings.

Therefore, an object of the present invention is to provide a liquid paper container having a laminate having a polyolefin resin layer made of a conventional fossil fuel-derived polyolefin, and a polyolefin resin layer containing a biomass polyolefin, which is comparable in physical properties such as mechanical properties. It is to provide a liquid paper container provided with a laminate.

In aspects of the invention
A liquid paper container comprising a laminate including at least a first thermoplastic resin layer, a paper base material layer, a polyolefin resin layer, and a second thermoplastic resin layer in this order.
The polyolefin resin layer is composed of only low-density polyethylene derived from biomass, or a mixed resin of low-density polyethylene derived from biomass and low-density polyethylene derived from fossil fuel.
The degree of biomass in the polyolefin resin layer is 5% or more, and the degree of biomass is 5% or more.
The polyolefin resin layer is in contact with the second thermoplastic resin layer.
The innermost layer of the laminate is the second thermoplastic resin layer.
The outermost layer of the laminate is the first thermoplastic resin layer.
A liquid paper container is provided in which the second thermoplastic resin layer does not contain polybutene-1, poly (ethylene-butene), or poly (propylene-butene).
In the aspect of the present invention, it is preferable that the polyolefin resin layer contains 5% by mass or more of the low-density polyethylene derived from the biomass.
In the embodiment of the present invention, the first thermoplastic resin layer is made of low-density polyethylene derived from biomass, or is made of a mixed resin of low-density polyethylene derived from biomass and low-density polyethylene derived from fossil fuel. It is preferably configured.
In the aspect of the present invention, it is preferable that the second thermoplastic resin layer contains biomass polyolefin which is a polymer of a monomer containing ethylene derived from biomass.
In the aspect of the present invention, the method for producing a laminate used for the liquid paper container according to any one of claims 1 to 4.
Provided is a method for producing a laminated body, in which the second thermoplastic resin layer is bonded via the melt-extruded polyolefin resin layer.

The liquid paper container provided with the laminate according to the present invention is provided with at least a paper base material layer and a polyolefin resin layer containing biomass polyolefin, so that the amount of fossil fuel used can be reduced as compared with the conventional case, and the environment. The load can be reduced. Further, since the liquid paper container provided with the laminate according to the present invention is comparable in physical properties such as mechanical properties to the laminate of the conventional fossil fuel-derived polyolefin resin, the conventional fossil fuel-derived polyolefin resin is used. A liquid paper container provided with a laminate can be replaced.

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

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

<Laminated body>
The laminate according to the present invention comprises a first thermoplastic resin layer, a paper base material layer, a polyolefin resin layer containing biomass polyolefin, and a second thermoplastic resin layer in this order. When a liquid paper container is manufactured using the laminated body, the layer of the laminated body located on the outside of the liquid paper container is used as the first thermoplastic resin layer, and the layer of the laminated body located on the inner side of the liquid paper container is used as the first layer. The thermoplastic resin layer of No. 2 is used. 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 comparable 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 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 laminated body 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 first thermoplastic resin layer 11, a paper base material layer 12, a polyolefin resin layer 13, and a second thermoplastic resin layer 14 in this order. In the case of the liquid paper container provided with the laminate 10, the first thermoplastic resin layer 11 is located outside the liquid paper container, and the second thermoplastic resin layer 14 is located inside the liquid paper container.
The laminate 20 shown in FIG. 2 includes a first thermoplastic resin layer 11, a paper base material layer 12, an adhesive layer 15, a barrier layer 16, a polyolefin resin layer 13, and a second thermoplastic resin layer. 14 and 14 are provided in this order. In the case of the liquid paper container provided with the laminate 20, the first thermoplastic resin layer 11 is located outside the liquid paper container, and the second thermoplastic resin layer 14 is located inside the liquid paper container.
The laminate 30 shown in FIG. 3 includes a first thermoplastic resin layer 11, a paper base material layer 12, an adhesive layer 15, a plastic film 17, an adhesive layer 15, a polyolefin resin layer 13, and a second. The thermoplastic resin layer 14 of the above is provided in this order. In the case of the liquid paper container provided with the laminate 30, the first thermoplastic resin layer 11 is located outside the liquid paper container, and the second thermoplastic resin layer 14 is located inside the liquid paper container.
In any laminated body, a printed layer, a thermoplastic resin layer, or the like may be further laminated.
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 paper base material layer can impart strength as a packaged product to the laminate. The paper used as the paper substrate layer has a basis weight of 100 g / m ² or more and 700 g / m ² or less, preferably 150 g / m ² or more and 600 g / m ² or less, and more preferably 200 g / m ² or more and 500 g / m ² or less. Have. As the paper substrate 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 may be used as the fixing agent. May be good. It is also possible to use a aluminum sulfate band to make paper in a neutral region having a pH of 6 or more and a pH of 9 or less. In addition to the above sizing agents as needed, in addition to fixing agents, various papermaking fillers, yield improvers, dry paper strength enhancers, wet paper strength enhancers, binders, dispersants, flocculants, and plasticizers. It may contain an agent and an adhesive as appropriate.

(Polyolefin resin layer)
In the present invention, the polyolefin resin layer contains biomass polyolefin, which is a polymer of a monomer containing biomass 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 a fossil fuel-derived polyolefin with respect to the entire polyolefin resin layer. Biopolyolefins of less than mass% and polyolefins derived from fossil fuels in excess of 0% by mass and 95% by mass or less may be contained, and biomass polyolefins of 25% by mass or more and 75% by mass or less and fossil fuels of 25% by mass or more and 75% by mass or less. It may contain the polyolefin of origin. It suffices if the following biomass degree can be realized for the entire polyolefin resin layer. In the present invention, since the polyolefin resin layer contains biomass polyolefin, the amount of polyolefin derived from fossil fuel 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 measuring radioactive carbon (C14). Since carbon dioxide in the atmosphere contains C14 at a fixed ratio (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, the ratio of carbon derived from biomass can be calculated by measuring the ratio of C14 contained in all carbon atoms in the polyolefin. In the present invention, when the content of _C14 in the polyolefin is PC14, the carbon content P _bio derived from biomass can be determined as follows.
P _bio (%) = _PC14 / 105.5 × 100

In the present invention, theoretically, if ethylene derived from biomass is used as the raw material of the polyolefin, the biomass degree is 100%, and the biomass degree of the polyolefin derived from biomass is 100%. Further, the carbon concentration derived from biomass in the fossil fuel-derived polyolefin produced only from the fossil fuel-derived raw material is 0%, and the biomass degree of the fossil fuel-derived polyolefin 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 degree of biomass in the polyolefin resin layer is 5% or more, the amount of polyolefin derived from fossil fuel can be reduced and the environmental load can be reduced as compared with the conventional case.

The polyolefin resin layer is preferably 0.91 g / cm ³ or more and 0.93 g / cm ³ or less, more preferably 0.911 g / cm ³ or more and 0.928 g / cm ³ or less, and further 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. When the density of the polyolefin resin layer is 0.91 g / cm ³ or more and 0.93 g / cm ³ or less, processing and molding can be facilitated.

The polyolefin resin layer preferably has a thickness of 5 μm or more and 100 μm or less, more preferably 10 μm or more and 60 μm or less, and further 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 of adhering the two layers 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 an ethylene monomer derived from fossil fuel and / or an α-olefin monomer derived from fossil fuel, or may further contain an α-olefin monomer derived from biomass.

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 containing such an α-olefin, the polymerized 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.

The biomass polyolefin is preferably 0.91 g / cm ³ or more and 0.93 g / cm ³ or less, more preferably 0.912 g / cm ³ or more and 0.928 g / cm ³ or less, and further preferably 0.915 g / cm ³ or more and 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 is preferably 0.1 g / 10 minutes or more and 10 g / 10 minutes or less, more preferably 0.2 g / 10 minutes or more and 9 g / 10 minutes or less, and further preferably 1 g / 10 minutes or more and 8.5 g / 10 minutes or less. It has a melt flow rate (MFR) of. 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.

(Manufacturing method of ethylene derived from biomass)
In the present invention, the method for producing ethylene derived from biomass, 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 from biomass will be described.

Biomass-derived ethylene can be produced from 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, beet, 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 producing 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, or removing water by membrane separation or the like can be mentioned.

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

When ethylene is obtained by the dehydration reaction of ethanol, a catalyst is usually used, 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 and the like are 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 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 should be 0.1% or more, preferably 0.5% or more. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 30% or less, still more preferably 20% or less from the viewpoint of mass balance and heat balance.

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. However, 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 equal to or higher than normal pressure.

When the raw material is ethanol derived from biomass, the obtained ethylene contains carbonyl compounds such as ketones, aldehydes, and esters, which are impurities mixed in the ethanol fermentation process, carbonic acid 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 a conventionally known adsorbent 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 treating with caustic water, 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 polyethylene type, 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 Cheegler-Natta catalyst or a single site catalyst such as a metallocene-based 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. .. A single-site catalyst is preferable because it has a uniform active site structure as compared with a multi-site catalyst, 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 containing a ligand having a cyclopentadienyl skeleton, a cocatalyst, an organic metal compound if necessary, and each catalyst component of the carrier. be.

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, and an indenyl ring, a fluorenyl ring, an azulenyl ring, a hydrogenator thereof, etc. are formed. 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 dialkylsilylene group and a diallylsilylene group, a substituted gelmilene group such as a dialkylgelmylene group and a diarylgelmylene group and the like. It is preferably a substituted silylene group.

In the transition metal compound of Group IV of the periodic table, as typical ligands other than the ligand having a cyclopentadienyl skeleton, hydrogen and a hydrocarbon group having 1 to 20 carbon atoms (alkyl group) are typical. , Alkyl 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 catalytic component.

As the co-catalyst, 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 aluminoxane of organic aluminum oxy compounds, benzene-insoluble organic aluminum oxy compounds, ion-exchangeable layered silicates, boron compounds, cations containing or not containing active hydrogen groups and non-coordinating anions can be 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 containing a ligand having a cyclopentadienyl skeleton may be used by being carried on a carrier of an inorganic or organic compound. The carrier is preferably a porous oxide of an inorganic or organic compound, 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, organozinc compounds and the like. Of these, organoaluminum is preferably used.

Various additives may be added to the biomass polyolefin in addition to the polyolefin as the main component, as long as the characteristics are not impaired. Additives include, for example, plasticizers, UV stabilizers, anticoloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, slip agents, mold release agents, anti-inflammatory 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. As described above, when the liquid paper container is manufactured using the laminated body, the layer of the laminated body located on the outside of the liquid paper container is used as the first thermoplastic resin layer, and the laminated body located on the inner side of the liquid paper container. Is referred to as a second thermoplastic resin layer. 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 first or second thermoplastic resin include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, and ethylene-vinyl acetate copolymer. Ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin, polyester resin, polyvinyl chloride resin , Polystyrene resin, nylon and the like, and low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and ethylene-methacrylic acid copolymer are preferable. The types of the first and second thermoplastic resins may be the same or different, respectively.

The first or second 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 best-by date, display of manufacturers, sellers, etc., and for the purpose of giving a sense of beauty, such as letters, numbers, patterns, figures, symbols, and patterns. A layer that forms any desired print pattern. The print layer can be provided as needed, and is provided, for example, on the surface of the paper substrate layer opposite to the polyolefin resin layer or the surface of the first thermoplastic resin layer opposite to the paper substrate layer. be able to. The print 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 a vapor-deposited film of the inorganic substance or the inorganic oxide or a metal foil is preferable. The thin-film 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 laminated body further has a barrier layer, it is possible to impart or improve a gas barrier property that blocks the permeation of oxygen gas, water vapor, and the like, and a light-shielding property that blocks the permeation of visible light, ultraviolet rays, and the like. The laminated body may have two or more barrier layers. When having two or more barrier layers, each 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 suitable for packaging materials (bags) and the like, it is preferable to use a thin-film film of aluminum metal or a thin-film film of silicon oxide or aluminum metal or aluminum oxide.

The notation of the inorganic oxide is MO _X such as SiO _X , AlO _X , etc. (However, in the formula, M represents an inorganic element, and the value of X has a range different depending on the inorganic element). expressed. The range of the value of X 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, and 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. You can use the one with the value of.

In the present invention, the thickness of the vapor-filmed 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 50 Å or more and 500 Å or less, more preferably 100 Å or more and 300 Å or less.

The thin-film 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 deposition film include a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method and thermochemistry. Examples thereof include a vapor phase growth method, a chemical vapor deposition method such as a photochemical vapor deposition method, and a CVD method.

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

(Plastic film)
In the present invention, various plastic films may be used as another layer. 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 these two or more 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-based, (meth) acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, rubber-based, and others. An adhesive such as a solvent type, an aqueous type, or an emulsion type can be used. As a coating method of the above-mentioned laminating adhesive, 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 any other method is used to form a laminate. It can be applied to the coated surface of the layer. The coating amount is preferably 0.1 g / m ² or more and 10 g / m ² or less (dry state), and more preferably 1 g / m ² or more and 5 g / m ² or less (dry state).

Further, the adhesive layer is an anchor 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 nitrified cotton may be used in combination to enhance 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. The thermoplastic resin that can be used for the adhesive resin layer includes a polyethylene resin, a polypropylene resin, a cyclic polyolefin 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 catalysts. Ethylene-α / olefin copolymer polymerized using, random or block copolymer of ethylene / polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene / Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-maleic acid copolymer, ionomer resin, and adhesion between layers. It is possible to use an acid-modified polyolefin-based resin obtained by modifying the above-mentioned polyolefin-based resin with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. 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, a cyclic polyolefin such as an ethylene-propylene copolymer, polymethylpentene, polybutene, or polynorbonene can be used. These resins can be used alone or in combination of two or more. Needless to say, as the above-mentioned polyethylene-based resin, one using the above-mentioned biomass-derived ethylene as a monomer unit can be used.

The adhesive resin layer may contain a material derived from biomass or a material derived from fossil fuel. When the adhesive resin layer contains a material derived from biomass, it may contain biomass polyolefin which is a polymer of a monomer containing ethylene derived from biomass, 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 laminate another layer via the melt-extruded polyolefin resin layer by using the sand laminating method. Further, the polyolefin resin layer and another layer may be laminated by a co-extrusion method.

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

The laminate according to the present invention is provided with a chemical function, an electrical function, a magnetic function, a mechanical function, a friction / wear / lubrication function, an optical function, a thermal function, a surface function 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 liquid paper containers, paper cups, label materials, and lid materials.

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

As shown in FIG. 4, the liquid paper container 40 has a square cylinder-shaped body 41 including a side surface, a square plate-shaped bottom 42, and a top 43, and is a so-called gable top type container. There is. The upper portion 43 has a pair of inclined plates 44 facing each other and a pair of folding portions 45 located between the pair of inclined plates 44 and folded between the inclined plates 44. Further, the pair of inclined plates 44 are adhered to each other by a margin 46 provided at the upper end of each. A spout may be attached to one of the slanted plates 44 of the pair of slanted plates 44, and the spout may be sealed with a cap. Further, a flat top type container may be formed.

(Other aspects)
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 biomass-derived ethylene 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 structure and a laminate having the same physical properties such as mechanical properties can be obtained. Other aspects of the invention are based on such findings.
Therefore, an object of another aspect of the present invention is a laminate having a polyolefin resin layer containing a polyolefin resin derived from a conventional fossil fuel, and a laminate having a polyolefin resin layer containing a biomass polyolefin, which is comparable in physical properties such as mechanical properties. To provide the body.
In another aspect of the invention
A laminate including at least a first thermoplastic resin layer, a paper base material layer, a polyolefin resin layer, and a second thermoplastic resin layer in this order.
The polyolefin resin layer contains biomass polyolefin, which is a polymer of a monomer containing ethylene derived from biomass.
A laminate having a biomass degree of 5% or more in the polyolefin resin layer is provided.
In another aspect of the invention, it is preferred that the polyolefin resin layer further contains a fossil fuel-derived polyolefin.
In another 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 another aspect of the present invention, the polyolefin resin layer preferably contains polyethylene.
In another aspect of the invention, the first or second thermoplastic resin layer is selected from the group consisting of low density polyethylene, linear low density polyethylene, medium density polyethylene, and ethylene-methacrylic acid copolymer. It is preferable to include the resin material to be used.
In another aspect of the present invention, there is a method for producing the laminated body.
Provided is a method for producing a laminated body, in which the paper base material layer and the second thermoplastic resin layer are bonded together via the melt-extruded polyolefin resin layer.
In another aspect of the invention, a packaged product comprising the laminate is provided.
In another aspect of the present invention, the liquid paper container provided with the laminate is provided.
A liquid paper container is provided in which the innermost layer of the liquid paper container is the second thermoplastic resin layer.
The laminate according to another aspect of the present invention is provided with at least a paper base material layer and a polyolefin resin layer containing biomass polyolefin, so that the amount of fossil fuel used can be reduced as compared with the conventional case, and the environmental load can be reduced. 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 is not inferior. It 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 measured by radiocarbon (C14).

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

[Example 1]
<Manufacturing of laminated body 1>
Milk carton base paper (manufactured by Clearwater, 320 g / m 2) is prepared as the paper base layer, and low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene, LC520, density: 0.923 g / m ² ) is prepared on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0%). , 17 μm in thickness) was formed. Next, a low-density polyethylene derived from biomass (SBC818, manufactured by Braskem, density: 0.918 g / cm ³ ) was used on the surface of the paper substrate layer opposite to the first thermoplastic resin layer by a sand laminating method. , MFR: 8.1 g / 10 minutes, biomass degree: 95%), through this polyolefin resin layer (biomass degree: 95%, thickness 20 μm), a polyethylene film derived from fossil fuel (Dainippon Printing Co., Ltd.) Manufactured by: SKL, thickness 40 μm) was laminated to obtain a laminated body 1 in which a first thermoplastic resin layer, a paper base material layer, a polyethylene resin layer, and a second thermoplastic resin layer were laminated in this order.

[Example 2]
<Manufacturing of laminated body 2>
Milk carton base paper (manufactured by Clearwater, 320 g / m 2) is prepared as the paper base layer, and low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene, LC520, density: 0.923 g / m ² ) is prepared on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0). %, Thickness 17 μm) was formed. Next, on the surface of the paper substrate layer opposite to the first thermoplastic resin layer, a low-density polyethylene derived from biomass (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ ) was used by a sand laminating method. , MFR: 8.1 g / 10 minutes, biomass degree: 95%) 50 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 polyethylene film derived from fossil fuel (large) is passed through this polyolefin resin layer (biomass degree: 48%, thickness 20 μm) while extruding a mixed resin dry-blended with 50 parts by mass of biomass degree: 0% for 10 minutes. Nippon Printing Co., Ltd .: SKL, thickness 40 μm) was laminated to obtain a laminate 2 in which a first thermoplastic resin layer, a paper substrate layer, a polyethylene resin layer, and a second thermoplastic resin layer were laminated in this order. rice field.

[Comparative Example 1]
<Manufacturing of laminated body 3>
Milk carton base paper (manufactured by Clearwater, 320 g / m 2) is prepared as the paper base layer, and low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene, LC520, density: 0.923 g / m ² ) is prepared on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0%). , 17 μm in thickness) was formed. Next, the surface of the paper substrate layer opposite to the first thermoplastic resin layer is subjected to corona treatment, and then the corona-treated surface is subjected to a sand laminating method to use low-density polyethylene derived from fossil fuel (Japan). This adhesive resin layer (biomass degree: 0%, thickness 28 μm) is extruded while extruding polyethylene, LC520, density: 0.923 g / cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%). A polyethylene film derived from fossil fuel (manufactured by Dainippon Printing Co., Ltd .: SKL, thickness 40 μm) is bonded to the first thermoplastic resin layer, the paper base material layer, the adhesive resin layer, and the second thermoplastic resin. A laminated body 3 in which layers were laminated in order was obtained.

[Example 3]
<Preparation of laminated body 4>
Milk carton base paper (Clearwater, 400 g / m 2 basis weight) is prepared as the paper substrate layer, and low-density polyethylene derived from fossil fuel (Japan Polyethylene, LC520, density: 0.923 g / m ² ) is prepared on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0). %, Thickness 20 μm) was formed. Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (Nucrel N0908C, manufactured by Mitsui DuPont Polychemical Co., Ltd.) was used on the surface of the paper substrate layer opposite to the first thermoplastic resin layer by using a sand laminating method. ), And through this adhesive resin layer (biomass degree 0%, thickness 20 μm), aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and fossil fuel-derived polyethylene terephthalate film (manufactured by Toyo Spinning Co., Ltd .: The aluminum foil surface of the dry laminate film, which was dry-laminated with E5100 (thickness 12 μm) using a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90), was bonded. Subsequently, a two-component curable anchoring agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the surface of the polyethylene terephthalate film of the dry laminating film to form an anchor coat layer. Then, on the anchor coat layer, a low-density polyethylene derived from biomass (SBC818 manufactured by Brassem Co., Ltd., density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95) was used by a sand laminating method. %) While extruding, a polyethylene film derived from fossil fuel (manufactured by Dainippon Printing Co., Ltd .: SKL, thickness 40 μm) is bonded via this polyolefin resin layer (biomass degree: 95%, thickness 20 μm). A laminate 4 in which the thermoplastic resin layer, the paper base material layer, the adhesive resin layer, the barrier layer, the adhesive layer, the plastic film, the anchor coat layer, the polyolefin resin layer, and the second thermoplastic resin layer of 1 are laminated in this order. Obtained.

[Example 4]
<Preparation of laminated body 5>
Milk carton base paper (Clearwater, 400 g / m 2 basis weight) is prepared as the paper substrate layer, and low-density polyethylene derived from fossil fuel (Japan Polyethylene, LC520, density: 0.923 g / m ² ) is prepared on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0). %, Thickness 20 μm) was formed. Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (Nucrel N0908C, manufactured by Mitsui DuPont Polychemical Co., Ltd.) was used on the surface of the paper substrate layer opposite to the first thermoplastic resin layer by using a sand laminating method. ), And through this adhesive resin layer (biomass degree 0%, thickness 20 μm), aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and fossil fuel-derived polyethylene terephthalate film (manufactured by Toyo Spinning Co., Ltd .: The aluminum foil surface of the dry laminate film, which was dry-laminated with E5100 (thickness 12 μm) using a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90), was bonded. Subsequently, a two-component curable anchoring agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the surface of the polyethylene terephthalate film of the dry laminating film to form an anchor coat layer. Then, on the anchor coat layer, a low-density polyethylene derived from biomass (SBC818 manufactured by Brassem Co., Ltd., density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95) is used by a sand laminating method. %) 50 parts by mass and 50 parts by mass 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 minutes, biomass degree: 0%). While extruding the dry-blended mixed resin, a polyethylene film derived from fossil fuel (manufactured by Dainippon Printing Co., Ltd .: SKL, thickness 40 μm) is bonded via this polyolefin resin layer (biomass degree: 48%, thickness 20 μm). The first thermoplastic resin layer, the paper base material layer, the adhesive resin layer, the barrier layer, the adhesive layer, the plastic film, the anchor coat layer, the polyolefin resin layer, and the second thermoplastic resin layer are laminated in this order. I got body 5.

[Comparative Example 2]
<Preparation of laminated body 6>
Milk carton base paper (Clearwater, 400 g / m 2 basis weight) is prepared as the paper substrate layer, and low-density polyethylene derived from fossil fuel (Japan Polyethylene, LC520, density: 0.923 g / m ² ) is prepared on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0). %, Thickness 20 μm) was formed. Next, a fossil fuel-derived ethylene-methacrylic acid copolymer (Nucrel N0908C, manufactured by Mitsui DuPont Polychemical Co., Ltd.) was used on the surface of the paper substrate layer opposite to the first thermoplastic resin layer by using a sand laminating method. ), And through this adhesive resin layer (biomass degree 0%, thickness 20 μm), aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness 7 μm) and fossil fuel-derived polyethylene terephthalate film (manufactured by Toyo Spinning Co., Ltd .: The aluminum foil surface of the dry laminate film, which was dry-laminated with E5100 (thickness 12 μm) using a two-component curable adhesive (manufactured by DIC Graphics: main agent LX-703A / curing agent KR-90), was bonded. Subsequently, a two-component curable anchoring agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the surface of the polyethylene terephthalate film of the dry laminating film to form an anchor coat layer. Then, on the anchor coat layer, using the sand laminating method, 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%) is extruded, and a polyethylene film derived from fossil fuel (Dainippon Printing Co., Ltd .: SKL, thickness 40 μm) is bonded via this adhesive resin layer (biomass degree: 0%, thickness 20 μm). , A first thermoplastic resin layer, a paper base material layer, an adhesive resin layer, a barrier layer, an adhesive layer, a plastic film, an anchor coat layer, an adhesive resin layer, and a second thermoplastic resin layer in this order. 6 was obtained.

[Example 5]
<Manufacturing of laminated body 7>
As the aluminum-deposited polyethylene terephthalate film 1, a fossil fuel-derived polyethylene terephthalate film (MWR7, thickness 12 μm, manufactured by Saichi Kogyo Co., Ltd.) on which an aluminum-deposited film was formed was prepared.

Milk carton base paper (Clearwater, 400 g / m 2 basis weight) is prepared as the paper substrate layer, and low-density polyethylene derived from fossil fuel (Japan Polyethylene, LC520, density: 0.923 g / m ² ) is prepared on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0). %, Thickness 20 μm) was formed. Next, an ethylene-methacrylic acid copolymer derived from fossil fuel (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nuclel N0908C) was used on the surface of the paper substrate layer opposite to the first thermoplastic resin layer by a sand laminating method. ) Was extruded, and the vapor-deposited surface of the above-mentioned aluminum-deposited polyethylene terephthalate film 1 was bonded through the adhesive resin layer (biomass degree 0%, thickness 20 μm). Subsequently, a two-component curable anchoring agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the polyethylene terephthalate film surface of the aluminum-deposited polyethylene terephthalate film 1 to form an anchor coat layer. Then, on the anchor coat layer, a low-density polyethylene derived from biomass (SBC818 manufactured by Brassem Co., Ltd., density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95) was used by a sand laminating method. %) While extruding, through this polyolefin resin layer (biomass degree: 95%, thickness 20 μm), a linear low-density polyethylene film derived from fossil fuel (manufactured by Dainippon Printing Co., Ltd .: DYS-01N, thickness 40 μm). ) Are laminated, and the first thermoplastic resin layer, the paper base material layer, the adhesive resin layer, the barrier layer, the plastic film, the anchor coat layer, the polyolefin resin layer, and the second thermoplastic resin layer are laminated in this order. I got a body 7.

[Example 6]
<Preparation of laminated body 8>
Milk carton base paper (Clearwater, 400 g / m 2 basis weight) is prepared as the paper substrate layer, and low-density polyethylene derived from fossil fuel (Japan Polyethylene, LC520, density: 0.923 g / m ² ) is prepared on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 48). %, Thickness 20 μm) was formed. Next, an ethylene-methacrylic acid copolymer derived from fossil fuel (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nuclel N0908C) was used on the surface of the paper substrate layer opposite to the first thermoplastic resin layer by a sand laminating method. ) Was extruded, and the vapor-deposited surface of the above-mentioned aluminum-deposited polyethylene terephthalate film 1 was bonded through the adhesive resin layer (biomass degree 0%, thickness 20 μm). Subsequently, a two-component curable anchoring agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the polyethylene terephthalate film surface of the aluminum-deposited polyethylene terephthalate film 1 to form an anchor coat layer. Then, on the anchor coat layer, a low-density polyethylene derived from biomass (SBC818 manufactured by Brassem Co., Ltd., density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95) is used by a sand laminating method. %) 50 parts by mass and 50 parts by mass 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 minutes, biomass degree: 0%). While extruding the dry-blended mixed resin, a linear low-density polyethylene film derived from fossil fuel (manufactured by Dainippon Printing Co., Ltd .: DYS-01N,) is passed through this polyolefin resin layer (biomass degree: 48%, thickness 20 μm). A first thermoplastic resin layer, a paper base material layer, an adhesive resin layer, a barrier layer, a plastic film, an anchor coat layer, a polyolefin resin layer, and a second thermoplastic resin layer are laminated in this order by laminating (thickness 40 μm). The resulting laminated body 8 was obtained.

[Comparative Example 3]
<Preparation of laminated body 9>
Milk carton base paper (Clearwater, 400 g / m 2 basis weight) is prepared as the paper substrate layer, and low-density polyethylene derived from fossil fuel (Japan Polyethylene, LC520, density: 0.923 g / m ² ) is prepared on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0). %, Thickness 20 μm) was formed. Next, an ethylene-methacrylic acid copolymer derived from fossil fuel (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nuclel N0908C) was used on the surface of the paper substrate layer opposite to the first thermoplastic resin layer by a sand laminating method. ) Was extruded, and the vapor-deposited surface of the above-mentioned aluminum-deposited polyethylene terephthalate film 1 was bonded through the adhesive resin layer (biomass degree 0%, thickness 20 μm). Subsequently, a two-component curable anchoring agent (manufactured by Mitsui Chemicals, Inc .: A3210 / A3075) was coated on the polyethylene terephthalate film surface of the aluminum-deposited polyethylene terephthalate film 1 to form an anchor coat layer. Then, on the anchor coat layer, using the sand laminating method, 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%) while extruding, through this adhesive resin layer (biomass degree: 0%, thickness 20 μm), a linear low-density polyethylene film derived from fossil fuel (manufactured by Dainippon Printing Co., Ltd .: DYS-01N, thickness) The first thermoplastic resin layer, the paper base material layer, the adhesive resin layer, the barrier layer, the plastic film, the anchor coat layer, the adhesive resin layer, and the second thermoplastic resin layer are laminated in this order. The laminated body 9 was obtained.

[Example 7]
<Preparation of laminated body 10>
A milk carton base paper (Clearwater, 400 g / m ² basis weight) was prepared as the paper substrate layer, and low-density polyethylene derived from biomass (Brackem, SBC818, density: 0.918 g / cm ³ ) was prepared on one side. , MFR: 8.1 g / 10 min, biomass degree: 95%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 95%, A thickness of 20 μm) was formed. Next, a fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g /) was used on the surface of the paper substrate layer opposite to the first thermoplastic resin layer by using a sand laminating method. Fossil fuel-derived polyethylene terephthalate film (manufactured by Toyo Boseki Co., Ltd.) via an adhesive resin layer (biomass degree: 0%, thickness 15 μm) extruded from cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%). , T4100, thickness 12 μm) 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, a low-density polyethylene derived from biomass (SBC818 manufactured by Brassem Co., Ltd., density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95) was used by a sand laminating method. %) While extruding, a polyethylene film derived from fossil fuel (manufactured by Dainippon Printing Co., Ltd .: SKL, thickness 40 μm) is bonded via this polyolefin resin layer (biomass degree: 95%, thickness 20 μm). A laminate 10 in which the thermoplastic resin layer, the paper base material layer, the adhesive resin layer, the plastic film, the anchor coat layer, the polyolefin resin layer, and the second thermoplastic resin layer of No. 1 were laminated in this order was obtained.

[Example 8]
<Preparation of laminated body 11>
Milk carton base paper (Clearwater, 400 g / m ² basis weight) was prepared as the paper substrate layer, and low-density polyethylene derived from biomass (Brackem, SBC818, density: 0.918 g / cm ³ ) was prepared on one side. , MFR: 8.1 g / 10 minutes, biomass degree: 95%) 50 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 50 parts by mass (10 minutes, biomass degree: 0%) was melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0%). 48%, thickness 20 μm) was formed. Next, a fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g /) was used on the surface of the paper substrate layer opposite to the first thermoplastic resin layer by using a sand laminating method. Fossil fuel-derived polyethylene terephthalate film (manufactured by Toyo Boseki Co., Ltd.) via an adhesive resin layer (biomass degree: 0%, thickness 15 μm) extruded from cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%). , T4100, thickness 12 μm) 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, a low-density polyethylene derived from biomass (SBC818 manufactured by Brassem Co., Ltd., density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95) is used by a sand laminating method. %) 50 parts by mass and 50 parts by mass 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 minutes, biomass degree: 0%). While extruding the dry-blended mixed resin, a polyethylene film derived from fossil fuel (manufactured by Dainippon Printing Co., Ltd .: SKL, thickness 40 μm) is bonded via this polyolefin resin layer (biomass degree: 48%, thickness 20 μm). A laminate 11 in which a first thermoplastic resin layer, a paper base material layer, an adhesive resin layer, a plastic film, an anchor coat layer, a polyolefin resin layer, and a second thermoplastic resin layer were laminated in this order was obtained.

[Comparative Example 4]
<Preparation of laminated body 12>
Milk carton base paper (Clearwater, 400 g / m 2 basis weight) is prepared as the paper substrate layer, and low-density polyethylene derived from fossil fuel (Japan Polyethylene, LC520, density: 0.923 g / m ² ) is prepared on one side. cm ³ , MFR: 3.6 g / 10 min, biomass degree: 0%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0). %, Thickness 20 μm) was formed. Next, a fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC520, density: 0.923 g /) was used on the surface of the paper substrate layer opposite to the first thermoplastic resin layer by using a sand laminating method. Fossil fuel-derived polyethylene terephthalate film (manufactured by Toyo Boseki Co., Ltd.) via an adhesive resin layer (biomass degree: 0%, thickness 15 μm) extruded from cm ³ , MFR: 3.6 g / 10 minutes, biomass degree: 0%). , T4100, thickness 12 μm) 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, using the sand laminating method, 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%) is extruded, and a polyethylene film derived from fossil fuel (Dainippon Printing Co., Ltd .: SKL, thickness 40 μm) is bonded via this adhesive resin layer (biomass degree: 0%, thickness 20 μm). , A first thermoplastic resin layer, a paper base material layer, an adhesive resin layer, a plastic film, an anchor coat layer, an adhesive resin layer, and a second thermoplastic resin layer were laminated in this order to obtain a laminate 12.

[Example 9]
<Preparation of laminated body 13>
A milk carton base paper (Clearwater, 320 g / m ² ) is prepared as a paper base layer, and low-density polyethylene derived from biomass (Brackem, SBC818, density: 0.918 g / cm ³ ) is prepared on one side. , MFR: 8.1 g / 10 min, biomass degree: 95%) is melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 95%, thickness). 17 μm) was formed. Next, a low-density polyethylene derived from biomass (SBC818, manufactured by Braskem, density: 0.918 g / cm ³ ) was used on the surface of the paper substrate layer opposite to the first thermoplastic resin layer by a sand laminating method. , MFR: 8.1 g / 10 minutes, degree of biomass: 95%), and through this polyolefin resin layer (degree of biomass: 95%, thickness 20 μm), a low-density polyethylene film derived from biomass (manufactured by Braskem). , SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95%, thickness 40 μm), and the first thermoplastic resin layer, paper substrate layer, polyethylene A laminated body 13 in which a resin layer and a second thermoplastic resin layer were laminated in this order was obtained.

[Example 10]
<Preparation of laminated body 14>
Milk carton base paper (Clearwater, 320 g / m ² ) was prepared as the paper substrate layer, and low-density polyethylene derived from biomass (Brackem, SBC818, density: 0.918 g / cm ³ ) was prepared on one side. , MFR: 8.1 g / 10 minutes, biomass degree: 95%) 50 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 50 parts by mass (10 minutes, biomass degree: 0%) was melt-extruded and laminated at a resin temperature of 320 ° C. and a line speed of 100 m / min to form a first thermoplastic resin layer (biomass degree: 0%). 48%, thickness 17 μm) was formed. Next, a low-density polyethylene derived from biomass (SBC818, manufactured by Braskem, density: 0.918 g / cm ³ ) was used on the surface of the paper substrate layer opposite to the first thermoplastic resin layer by a sand laminating method. , MFR: 8.1 g / 10 minutes, biomass degree: 95%) 50 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 minutes, 50 parts by mass of biomass (degree of biomass: 0%) while extruding a mixed resin, through this polyolefin resin layer (degree of biomass: 48%, thickness 20 μm), a low-density polyethylene film derived from biomass (thickness 20 μm) (Brashchem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95%) 50 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 minutes, degree of biomass: 0%) Mixed resin dry-blended with 50 parts by mass, thickness 40 μm), and the first thermoplastic resin A laminated body 14 in which a layer, a paper base material layer, a polyolefin resin layer, and a second thermoplastic resin layer were laminated in this order was obtained.

[Manufacturing Examples 1 to 14]
<Making a liquid paper container>
By pressing the laminates 1 to 14 with a male mold and a female mold, ruled line processing was performed and a blank for a paper container was punched out. After that, in the liquid paper container filling machine "DR-10", the center values of the sealing temperature conditions are set to the top heater temperature of 320 ° C. and the bottom heeder temperature of 340 ° C. 14 was made.

(Leakage and pinhole test)
After cutting off the top and bottom of the liquid paper containers 1 to 14 prepared above, a test solution (Microcheck penetrant (manufactured by Taiho Kozai)) is injected into the top and bottom, left at room temperature for 30 minutes, and then microchecked. Cleaning was performed with a cleaning solution (manufactured by Taiho Kozai). After that, it was heated with hot air and the top and bottom were opened in a flat plate shape, and liquid leakage and pinholes were visually evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.
(Evaluation criteria for liquid leakage)
◯: There was no liquid leakage from the top seal part and the bottom seal part, and the performance as a liquid paper container was good.
X: There was liquid leakage from the top seal portion and the bottom seal portion, and the performance as a liquid paper container was poor.
(Pinhole evaluation criteria)
◯: There were no pinholes on the top and bottom, and the performance as a liquid paper container was good. X: There were pinholes at the top and bottom, and the performance as a liquid paper container was poor.

10, 20, 30 Laminated body 11 First thermoplastic resin layer 12 Paper substrate layer 13 Polyolefin resin layer 14 Second thermoplastic resin layer 15 Adhesive layer 16 Barrier layer 17 Plastic film 40 Liquid paper container 41 Body 42 Bottom 43 Upper part 44 Inclined plate 45 Folded part 46 Glue margin

Claims (5)

A liquid paper container comprising a laminate including at least a first thermoplastic resin layer, a paper base material layer, a polyolefin resin layer, and a second thermoplastic resin layer in this order.
The polyolefin resin layer is composed of only low-density polyethylene derived from biomass, or a mixed resin of low-density polyethylene derived from biomass and low-density polyethylene derived from fossil fuel.
The degree of biomass in the polyolefin resin layer is 5% or more, and the degree of biomass is 5% or more.
The polyolefin resin layer is in contact with the second thermoplastic resin layer.
The innermost layer of the laminate is the second thermoplastic resin layer.
The outermost layer of the laminate is the first thermoplastic resin layer.
A liquid paper container in which the second thermoplastic resin layer does not contain polybutene-1, poly (ethylene-butene), poly (propylene-butene) , or synthetic rubber . The liquid paper container according to claim 1, wherein the polyolefin resin layer contains 5% by mass or more of the low-density polyethylene derived from biomass. Claim 1 in which the first thermoplastic resin layer is composed of low-density polyethylene derived from biomass or a mixed resin of low-density polyethylene derived from biomass and low-density polyethylene derived from fossil fuel. Or the liquid paper container according to 2. The liquid paper container according to any one of claims 1 to 3, wherein the second thermoplastic resin layer contains biomass polyolefin, which is a polymer of a monomer containing ethylene derived from biomass. The method for manufacturing a laminate used for the liquid paper container according to any one of claims 1 to 4.
A method for producing a laminated body, in which the second thermoplastic resin layer is bonded via a melt-extruded polyolefin resin layer.

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