JP2022008362A - Packaging product having laminate including biomass-derived resin layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging product having a laminate including a paper board substrate and a polyolefin resin layer composed of a biomass polyolefin resin composition containing a polyethylene using a biomass-derived ethylene.

SOLUTION: A packaging product includes a laminate 10. The laminate includes a paper board substrate 11 and a biomass polyolefin resin layer 12 positioned on one side of the paper board substrate and composed of a biomass polyolefin resin composition containing a biomass-derived polyethylene obtained by polymerizing monomers including a biomass-derived ethylene and a fossil fuel-derived polyolefin. The paper board substrate is positioned at an outermost surface of the laminate. The packaging product is a laminate tube.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a packaging product including a laminate having a resin layer derived from biomass. More specifically, the present invention comprises a paperboard base material and a biomass derived from biomass obtained by polymerizing a monomer containing ethylene derived from biomass. The present invention relates to a packaging product comprising a laminate, which comprises a biomass polyolefin resin layer made of a polyolefin resin composition.

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 resin derived from biomass, polylactic acid (PLA), which is produced via lactic acid fermentation, started commercial production in advance, but its biodegradable and other plastic performance is currently a general-purpose plastic. 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, 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, 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 focused on ethylene, which is a raw material of a polyolefin laminate, and instead of ethylene obtained from a conventional fossil fuel, a laminate having a polyolefin polyolefin resin layer made of biomass-derived ethylene as a raw material. It has been found that the packaging products provided include packaging products having a laminate having a polyolefin resin layer manufactured using ethylene obtained from conventional fossil fuels, and those having physical properties such as mechanical properties. Obtained. The present invention is based on such findings.

Therefore, an object of the present invention is to provide a packaging product comprising a laminate having a paperboard base material and a biomass polyolefin resin layer composed of a biomass polyolefin resin composition containing carbon-neutral polyethylene using biomass-derived ethylene. To provide, a packaging product having a laminate having a resin layer manufactured from a raw material obtained from a conventional fossil fuel and a laminate having a biomass polyolefin resin layer comparable in physical properties such as mechanical properties are provided. To provide packaged products.

That is, according to one aspect of the present invention.
A packaged product provided with a laminate (excluding the raw fabric A for the laminate tube below).
The laminated body is
Paperboard base material and
Biomass composed of a biomass polyolefin resin composition, which is located on one surface side of the paperboard substrate and contains polyethylene derived from biomass obtained by polymerizing a monomer containing ethylene derived from biomass and polyolefin derived from fossil fuel. With a polyolefin resin layer,
The paperboard substrate is located on the outermost surface of the laminate,
A packaged product is provided in which the packaged product is a laminated tube.
(Raw cloth A for laminated tube: A metal foil, a low-density polyethylene film or linear low-density polyethylene film bonded to one side surface of the metal foil, and low-density polyethylene bonded to the other side surface of the metal foil, both sides thereof. A raw fabric for a laminated tube provided with a paper on which a film or a linear low-density polyethylene film is arranged and a vertically uniaxially rolled multilayer film laminated on the paper.)
In another aspect of the invention
A packaging product with a laminate,
The laminated body is
Paperboard base material and
Biomass composed of a biomass polyolefin resin composition, which is located on one surface side of the paperboard substrate and contains polyethylene derived from biomass obtained by polymerizing a monomer containing ethylene derived from biomass and polyolefin derived from fossil fuel. With a polyolefin resin layer,
The biomass polyolefin resin layer is located on the outermost surface of the laminate,
A packaged product is provided in which the packaged product is a lid material (however, the following lid material B is excluded).
(Cover material B: A lid material for a food container, which is composed of a laminated sheet having two waterproof layers and a base material layer made of paper arranged between the two waterproof layers, and is one of the two waterproof layers. A lid material for food containers, wherein at least one of the waterproof layers is an aluminum layer made of aluminum foil.)
In the aspect of the present invention, it is preferable that the biomass polyolefin resin layer contains low-density polyethylene derived from biomass and / and linear low-density polyethylene derived from biomass.
In the aspect of the present invention, it is preferable that the biomass polyolefin resin layer contains ethylene derived from the biomass in an amount of 5% by mass or more with respect to the entire biomass polyolefin resin layer.
In the aspect of the present invention, it is preferable to further have a barrier layer containing an inorganic substance.
In the aspect of the present invention, it is preferable to have a polyethylene resin layer located on the other surface side of the paperboard base material.

The packaging product according to the present invention comprises a laminate having a paperboard base material and a biomass polyolefin resin layer composed of a biomass polyolefin resin composition containing polyethylene derived from biomass obtained by polymerizing a monomer containing ethylene derived from biomass. This makes it possible to realize a packaged product including a laminate having a carbon-neutral polyolefin resin layer. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the conventional case, and the environmental load can be reduced. Further, the packaged product according to the present invention is not inferior to the packaged product having a laminate having a polyolefin resin layer produced from a raw material obtained from a conventional fossil fuel in terms of physical properties such as mechanical properties. It is possible to substitute a packaged product having a laminate having a polyolefin resin layer of the above.

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.

In the present invention, the "biomass polyolefin resin composition" and the "biomass polyolefin resin layer" 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 laminated body according to the present invention comprises a paperboard base material and a biomass polyolefin resin layer. By having the biomass polyolefin resin layer in the laminate, a carbon-neutral polyolefin resin laminate can be realized. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the conventional case, and the environmental load can be reduced. 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.

A schematic cross-sectional view of an example of the laminated body according to the present invention is shown in FIGS. 1 and 2. The laminate 10 shown in FIG. 1 includes a paperboard base material 11 and a biomass polyolefin resin layer 12 formed on the paperboard base material 11. The laminate 20 shown in FIG. 2 has a paperboard base material 21, a first biomass polyolefin resin layer 22 formed on the paperboard base material 21, and a second biomass polyolefin resin layer 22 formed on the first biomass polyolefin resin layer 22. The biomass polyolefin resin layer 23 is provided in this order. Hereinafter, each layer constituting the laminated body will be described.

Paperboard base material In the present invention, the paperboard base material functions as a base material layer, and is required to have strength to withstand the step of laminating a biomass polyolefin resin layer by extrusion molding. The paper used as the paperboard base material has a basis weight of 100 to 700 g / m ² , preferably 150 to 600 g / m ² , and more preferably 200 to 500 g / m ² . As the paperboard base material, 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 sulfate band to make paper in the neutral region of pH 6-9. In addition to the above sizing agents as needed, in addition to fixing agents, various paper-making 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.

Biomass Polyolefin Resin Layer In the present invention, the biomass polyolefin resin layer contains the following biomass-derived ethylene in an amount of preferably 5% by mass or more, more preferably 5 to 95% by mass, and further preferably 25 to 25% by mass based on the entire biomass polyolefin resin layer. It contains 75% by mass. The biomass polyolefin resin layer may be composed of at least two layers or more, and includes, for example, a first biomass polyolefin resin layer and a second biomass polyolefin resin layer in order from the paperboard substrate side. Both the seal layer and the core layer of the laminate may be a biomass polyolefin resin layer, or only one of them may be a biomass polyolefin resin layer.

First Biomass Polyolefin Resin Layer In the present invention, the first biomass polyolefin resin layer may function as a core layer of the laminate. By having the core layer, the laminated body does not break and can exhibit excellent flexibility.

The first biomass polyolefin resin layer contains ethylene derived from biomass in an amount of preferably 5% by mass or more, more preferably 5 to 95% by mass, still more preferably 25 to 75% by mass, based on the entire first biomass polyolefin resin layer. Most preferably, it contains 40 to 75%. If the concentration of biomass-derived ethylene in the first biomass polyolefin resin layer is 5% by mass or more, the amount of fossil fuel used can be reduced as compared with the conventional case, and a carbon-neutral polyolefin resin laminate can be realized. can.

The first biomass polyolefin resin layer is preferably 0.915 to 0.96 g / cm ³ , more preferably 0.92 to 0.955 g / cm ³ , and even more preferably 0.93 to 0.955 g / cm ³ . It has a density. The density of the first biomass 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 first biomass polyolefin resin layer is 0.915 g / cm ³ or more, the rigidity of the first biomass polyolefin resin layer can be increased. Further, when the density of the first biomass polyolefin resin layer is 0.96 g / cm ³ or less, the transparency and mechanical strength of the first biomass polyolefin resin layer can be enhanced.

The first biomass polyolefin resin layer has a melt flow rate (MFR) of 1 to 30 g / 10 minutes, preferably 3 to 25 g / 10 minutes, and more preferably 4 to 20 g / 10 minutes. 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 first biomass polyolefin resin layer is 1 g / 10 minutes or more, the extrusion load during the molding process can be reduced. Further, when the MFR of the biomass polyolefin resin composition is 30 g / 10 minutes or less, the mechanical strength of the first biomass polyolefin resin layer can be increased.

The first biomass polyolefin resin layer has a thickness of 10 to 100 μm, preferably 10 to 50 μm, and more preferably 15 to 30 μm.

Second Biomass Polyolefin Resin Layer In the present invention, the second biomass polyolefin resin layer may function as a sealing layer of the laminate. Since the laminate has a heat seal layer, it can be firmly adhered without using an adhesive or the like when laminating on another resin film.

The second biomass polyolefin resin layer contains ethylene derived from biomass in an amount of preferably 5% by mass or more, more preferably 5 to 95% by mass, still more preferably 25 to 75% by mass, based on the entire second biomass polyolefin resin layer. It consists of. When the concentration of biomass-derived ethylene in the second biomass polyolefin resin layer is 5% by mass or more, the amount of fossil fuel used can be reduced as compared with the conventional case, and a carbon-neutral polyolefin laminate can be realized.

The second biomass polyolefin resin layer has a density of 0.90 to 0.925 g / cm ³ , preferably 0.905 to 0.925 g / cm ³ . The density of the second biomass 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 second biomass polyolefin resin layer is 0.90 g / cm ³ or more, the rigidity of the second biomass polyolefin resin layer can be increased. Further, when the density of the second biomass polyolefin resin layer is 0.925 g / cm ³ or less, the transparency and mechanical strength of the second biomass polyolefin resin layer can be enhanced.

The second biomass polyolefin resin layer has a melt flow rate (MFR) of 1 to 30 g / 10 minutes, preferably 3 to 25 g / 10 minutes, and more preferably 4 to 20 g / 10 minutes. 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 second biomass polyolefin resin layer is 1 g / 10 minutes or more, the extrusion load during the molding process can be reduced. Further, when the MFR of the biomass polyolefin resin composition is 30 g / 10 minutes or less, the mechanical strength of the second biomass polyolefin resin layer can be increased.

The second biomass polyolefin resin layer has a thickness of 1 to 50 μm, preferably 1 to 20 μm, and more preferably 1 to 10 μm.

In the present invention, the first biomass polyolefin resin layer and the second biomass polyolefin resin layer satisfy the following specific relationships regarding density, thickness, MFR, and biomass degree (ethylene concentration derived from biomass). It is preferable to have.

In the present invention, it is preferable that the density d ₁ of the first biomass polyolefin resin layer and the density d ₂ of the second biomass polyolefin resin layer satisfy d ₁ > d ₂ . This is because the first biomass polyolefin resin layer functions as a core layer, so that rigidity is required, and the second biomass polyolefin resin layer functions as a heat seal layer, so that flexibility is required.

In the present invention, it is preferable that the thickness t ₁ of the first biomass polyolefin resin layer and the thickness t ₂ of the second biomass polyolefin resin layer satisfy t ₁ > t ₂ . This is because the first biomass polyolefin resin layer functions as a core layer and therefore requires a thickness, and the second biomass polyolefin resin layer functions as a heat seal layer and therefore does not need to be as thick as the core layer.

In the present invention, it is preferable that the MFR ₁ of the first biomass polyolefin resin layer and the MFR ₂ of the second biomass polyolefin resin layer satisfy MFR ₁ > MFR ₂ . This is because the first biomass polyolefin resin layer functions as a core layer, so that rigidity is required, and the second biomass polyolefin resin layer functions as a heat seal layer, so that flexibility is required.

In the present invention, it is preferable that the biomass-derived ethylene concentration C ₁ of the first biomass polyolefin resin layer and the biomass-derived ethylene concentration C ₂ of the second biomass polyolefin resin layer satisfy C ₁ > C ₂ . Since the first biomass polyolefin resin layer functions as a core layer, it is thick and uses a large amount of ethylene. Therefore, by increasing the biomass degree of the first biomass polyolefin resin layer, the amount of fossil fuel used can be further reduced. Is.

Biomass-Derived Ethylene In the present invention, the method for producing biomass-derived ethylene, which is a raw material for biomass-derived 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, beets, and manioc can be mentioned.

In the present invention, the fermented ethanol derived from biomass refers to ethanol obtained 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, producing the product, and then purifying the ethanol. 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, 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 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.

Biomass Polyolefin In the present invention, the biomass-derived polyolefin is obtained by polymerizing a monomer containing biomass-derived ethylene. As the biomass-derived ethylene, it is preferable to use the one obtained by the above-mentioned production method. 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 which is a raw material of the biomass-derived polyolefin may further contain ethylene and / or α-olefin derived from fossil fuel, and may further contain α-olefin 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.

The above 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-derived ethylene concentration in the above-mentioned polyolefin (hereinafter, may be referred to as “biomass degree”) 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 all biomass-derived ethylene is used as a raw material for the polyolefin, the biomass-derived ethylene concentration is 100%, and the biomass degree of the biomass-derived polyolefin is 100%. Further, the biomass-derived ethylene concentration 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-derived polyolefin and the biomass-derived resin layer do not have to have a biomass degree of 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.

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 bridging 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.

Further, as the polyolefin, a polymer of ethylene or a copolymer of ethylene and α-olefin may be used alone or in combination of two or more.

Biomass Polyolefin Resin Composition In the present invention, the biomass polyolefin resin composition contains the above-mentioned polyolefin as a main component. The biomass polyolefin resin composition contains ethylene derived from biomass in an amount of preferably 5% by mass or more, more preferably 5 to 95% by mass, still more preferably 25 to 75% by mass, based on the entire biomass polyolefin resin composition. be. When the concentration of ethylene derived from biomass in the biomass polyolefin resin composition is 5% by mass or more, the amount of fossil fuel used can be reduced as compared with the conventional case, and a carbon-neutral polyolefin laminate can be realized.

The biomass polyolefin resin composition may contain two or more kinds of polyolefins having different biomass degrees, and the concentration of ethylene derived from biomass as a whole of the biomass polyolefin resin composition may be within the above range.

The biomass polyolefin resin composition may further contain a fossil fuel-derived polyolefin obtained by polymerizing a monomer containing ethylene derived from fossil fuel and ethylene and / or α-olefin derived from fossil fuel. That is, in the present invention, the biomass polyolefin resin composition may be a mixture of a biomass-derived polyolefin and a fossil fuel-derived polyolefin. The mixing method is not particularly limited, and conventionally known methods can be used for mixing. For example, it may be a dry blend or a melt blend.

According to the aspect of the present invention, the biomass polyolefin resin composition is preferably 5 to 90% by mass, more preferably 25 to 75% by mass of biomass-derived polyolefin, and preferably 10 to 95% by mass, more preferably 25. It contains ~ 75% by mass of fossil fuel-derived polyolefin. Even when the biomass polyolefin resin composition of such a mixture is used, the concentration of ethylene derived from biomass may be within the above range as a whole of the biomass polyolefin resin composition.

In the manufacturing process of the above-mentioned biomass polyolefin resin composition, or to the manufactured biomass polyolefin resin composition, various additives other than the polyolefin as the main component may be added as long as the characteristics are not impaired. good. 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 to 20% by mass, preferably 1 to 10% by mass, based on the entire biomass polyolefin resin composition.

Non-biomass polyolefin resin layer The laminate according to the present invention may further have a non-biomass polyolefin resin layer. The non-biomass polyolefin resin layer is a resin layer made of a resin material containing a raw material derived from fossil fuel, and has a biomass degree of 0%. When only one of the core layer and the seal layer of the laminate is the biomass polyolefin resin layer, the other may be the non-biomass polyolefin resin layer. The non-biomass polyolefin resin layer can be formed by using a conventionally known raw material, and the composition and the forming method thereof are not particularly limited. By further having the non-biomass polyolefin resin layer, the laminate can impart or improve heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties. The laminate may have two or more non-biomass polyolefin resin layers. When two or more non-biomass polyolefin resin layers are provided, they may have the same composition or different compositions.

Examples of the non-biomass polyolefin resin layer 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. Resins such as copolymers, polyethylene-methacrylic acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, polyethylene-methyl methacrylate copolymers or ionomers can be used. These resins may be formed by an extrusion laminating method, or may be laminated with a heat-resistant substrate layer by a dry laminating method, an extrusion laminating method, or the like as a film formed in advance by a T-die method, an inflation method, or the like. ..

Further, stretched polyethylene terephthalate film, silica vapor-deposited stretched polyethylene terephthalate film, alumina vapor-deposited stretched polyethylene terephthalate film, stretched nylon film, silica vapor-deposited stretched nylon film, alumina vapor-deposited stretched nylon film, stretched polypropylene film, polyvinyl alcohol-coated stretched polypropylene film, nylon 6 / Metaxylylene diamine Nylon 6 co-pressed co-stretched film or polypropylene / ethylene-vinyl alcohol copolymer co-pressed co-stretched film, etc., or a composite film in which two or more of these films are laminated may be used.

Barrier layer The laminate according to the present invention may further have a 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, about 50 to 2000 Å, preferably about 100 to 1000 Å. 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 about 50 to 600 Å, more preferably about 100 to 450 Å is desirable, and in the case of an aluminum oxide or silicon oxide film, it is desirable. The film thickness is preferably about 50 to 500 Å, more preferably about 100 to 300 Å.

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 or the like is preferable from the viewpoint of a gas barrier property that blocks the transmission of oxygen gas, water vapor, and the like, and a light-shielding property that blocks the transmission of visible light, ultraviolet rays, and the like.

Other Layers The laminate according to the present invention may have at least one other layer in addition to the above layers. When two or more other layers are provided, they may have the same composition or different compositions. The other layers can be formed on one or more of the above layers. Examples of other layers include a printing layer and an adhesive layer. The printed layer can be formed by using a conventionally known pigment or dye, and the forming method thereof is not particularly limited. Further, the adhesive layer is an adhesive layer or an adhesive resin layer formed for laminating any two layers. Examples of the adhesive for laminating 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, and rubber-based adhesives. Other solvent-type, water-based, or emulsion-type laminating adhesives can be used. As the coating method of the above-mentioned 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 other methods can be applied. The coating amount is preferably about 0.1 g / m ² to 10 g / m ² (dry state), more preferably about 1 g / m ² to 5 g / m ² (dry state).

Further, as the adhesive resin layer, a resin layer made of a thermoplastic resin layer is used. Specifically, as the material of the adhesive resin layer, a low-density polyethylene resin, a medium-density polyethylene resin, a high-density polyethylene resin, a linear low-density polyethylene resin, and an ethylene / α-olefin polymerized by using a metallocene catalyst are used. Copolymer resin, ethylene / polypropylene copolymer resin, ethylene / vinyl acetate copolymer resin, ethylene / acrylic acid copolymer resin, ethylene / ethyl acrylate copolymer resin, ethylene / methacrylic acid copolymer resin, Ethyl / methyl methacrylate copolymer resin, ethylene / maleic acid copolymer resin, ionomer resin, polyolefin resin graft-polymerized with unsaturated carboxylic acid, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, and ester monomer. Alternatively, a copolymerized resin, a resin obtained by graft-modifying maleic anhydride to a polyolefin resin, or the like can be used. These materials can be used in combination of one or more.

The method for producing the laminate according to the present invention is not particularly limited, and the laminate can be produced by a conventionally known method. In the present invention, it is preferable to form the biomass polyolefin resin layer on the paper substrate by extrusion molding, and it is more preferable that the biomass polyolefin resin layer is formed by coextrusion molding. It is more preferable that the coextrusion molding is performed by the T-die method or the inflation method.

For example, the laminate can be molded by extrusion molding by the following method. After the above-mentioned biomass polyolefin resin composition is dried, it is supplied to a melt extruder heated to a temperature (Tm) to Tm + 70 ° C. above the melting point of the polyolefin to melt the biomass polyolefin resin composition, and the paper base is used. A laminate can be formed by extruding a sheet-like material from a die such as a T-die onto the material and quenching and solidifying the extruded sheet-like material with a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder and the like can be used depending on the purpose.

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

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.

Applications The laminate according to the present invention includes various packaging products such as packaging containers and packaging bags, sheet molded products such as decorative sheets and trays, laminated films, optical films, resin plates, various label materials, lid materials, and laminated tubes. It can be suitably used for various purposes, and packaged products are particularly preferable.

<Other aspects>
According to another aspect of the invention.
A packaged product provided with a laminate (excluding the raw fabric A for the laminate tube below).
The laminated body is
Paperboard base material and
Biomass composed of a biomass polyolefin resin composition, which is located on one surface side of the paperboard substrate and contains polyethylene derived from biomass obtained by polymerizing a monomer containing ethylene derived from biomass and polyolefin derived from fossil fuel. With a polyolefin resin layer,
A packaged product is provided in which the packaged product is a laminated tube.
(Raw cloth A for laminated tube: A metal foil, a low-density polyethylene film or linear low-density polyethylene film bonded to one side surface of the metal foil, and low-density polyethylene bonded to the other side surface of the metal foil, both sides thereof. A raw fabric for a laminated tube provided with a paper on which a film or a linear low-density polyethylene film is arranged and a vertically uniaxially rolled multilayer film laminated on the paper.)
According to yet another aspect of the invention.
A packaging product with a laminate,
The laminated body is
Paperboard base material and
Biomass composed of a biomass polyolefin resin composition, which is located on one surface side of the paperboard substrate and contains polyethylene derived from biomass obtained by polymerizing a monomer containing ethylene derived from biomass and polyolefin derived from fossil fuel. With a polyolefin resin layer,
A packaged product is provided in which the packaged product is a lid material (however, the following lid material B is excluded).
(Cover material B: A lid material for a food container, which is composed of a laminated sheet having two waterproof layers and a base material layer made of paper arranged between the two waterproof layers, and is one of the two waterproof layers. A lid material for food containers, wherein at least one of the waterproof layers is an aluminum layer made of aluminum foil.)
In another aspect of the present invention, it is preferable that the biomass polyolefin resin layer contains low-density polyethylene derived from biomass and / and linear low-density polyethylene derived from biomass.
In another aspect of the present invention, it is preferable that the biomass polyolefin resin layer contains ethylene derived from the biomass in an amount of 5% by mass or more based on the entire biomass polyolefin resin layer.
In another aspect of the present invention, it is preferable to further have a barrier layer containing an inorganic substance.
In another aspect of the present invention, it is preferable to have a polyethylene resin layer located on the other surface side of the paperboard substrate.
The present invention provides a laminate comprising a paperboard base material and a biomass polyolefin resin layer composed of a biomass polyolefin resin composition containing a carbon-neutral polyolefin using biomass-derived ethylene. It is also an object of the present invention to provide a laminate having a resin layer produced from a raw material obtained from a fossil fuel of the above, and a laminate of a biomass polyolefin resin which is comparable in physical properties such as mechanical properties.
According to still another aspect of the invention.
A paperboard substrate having a basis weight of 100 to 700 g / m ² and
Provided is a laminate comprising a biomass polyolefin resin layer comprising a biomass polyolefin resin composition comprising a biomass-derived polyolefin obtained by polymerizing a biomass-derived ethylene-containing monomer.
In still another aspect of the present invention, it is preferable that the biomass polyolefin resin layer contains 5% by mass or more of ethylene derived from the biomass with respect to the entire biomass polyolefin resin layer.
In still another aspect of the present invention, the biomass polyolefin resin layer comprises a first biomass polyolefin resin layer and a second biomass polyolefin resin layer in order from the paperboard substrate side, wherein the first biomass polyolefin resin layer is provided. The biomass polyolefin resin layer contains 5% by mass or more of the biomass-derived ethylene with respect to the entire first biomass polyolefin resin layer, and the second biomass polyolefin resin layer contains the biomass-derived ethylene in the second biomass. It is preferably contained in an amount of 5% by mass or more based on the entire polyolefin resin layer.
In still another embodiment of the present invention, the biomass-derived ethylene concentration C ₁ in the first biomass polyolefin resin layer and the biomass-derived ethylene concentration C ₂ in the second biomass polyolefin resin layer are C ₁ > C. It is preferable to satisfy ₂ .
In yet another aspect of the invention, the monomer may further comprise fossil fuel-derived ethylene and / or α-olefin.
In yet another aspect of the invention, the monomer may further comprise a biomass-derived α-olefin.
In still another aspect of the invention, the biomass polyolefin resin composition is derived from a fossil fuel obtained by polymerizing a monomer containing ethylene derived from the fossil fuel and ethylene and / or α-olefin derived from the fossil fuel. Further polyolefin may be included.
In still another aspect of the invention, the biomass polyolefin resin composition may comprise 5 to 90% by weight of the biomass-derived polyolefin and 10 to 95% by weight of the fossil fuel-derived polyolefin.
In still other embodiments of the invention, the α-olefin is preferably butylene, hexene, or octene.
In still another aspect of the invention, the polyolefin is preferably polyethylene.
In still another aspect of the invention, the laminate may further have a non-biomass polyolefin resin layer made of a resin material containing fossil fuel-derived raw materials.
In still another aspect of the invention, the laminate may further have a barrier layer made of an inorganic substance and / or an inorganic oxide.
In still another aspect of the present invention, it is preferable that the biomass polyolefin resin layer is formed on the paperboard substrate by extrusion molding.
In still another aspect of the present invention, it is preferred that the biomass polyolefin resin layer is formed by coextrusion molding.
In still another aspect of the invention, the coextrusion molding is preferably carried out by the T-die method or the inflation method.
In yet another aspect of the invention, a packaged product comprising the laminate is provided.
The laminate according to still another aspect of the present invention comprises a paperboard substrate and a biomass polyolefin resin layer comprising a biomass-derived polyolefin obtained by polymerizing a monomer containing biomass-derived ethylene. By having the above, a carbon-neutral polyolefin resin laminate can be realized. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the conventional case, and the environmental load can be reduced. Further, the laminate according to still another aspect of the present invention is comparable to the polyolefin laminate produced from the raw material obtained from the conventional fossil fuel in terms of physical properties such as mechanical properties, and therefore the conventional polyolefin. The laminate can be replaced.

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 content derived from biomass as measured by radiocarbon (C14).

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

Example 1
As the body material and bottom material of the paper cup container, acid-resistant paper (made by Oji Special Paper: acid-resistant BYO-500, basis weight 320 g / m ² ) was used as the paperboard base material, and the back surface thereof was subjected to corona treatment. Next, as the core layer on the paperboard substrate side, low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene: LC701, MFR: 14, density: 0.919) and linear low-density polyethylene derived from biomass (Braskem). A resin prepared by dry-blending 50:50 with SLL3180, MFR: 2.7, density: 0.918, biomass degree: 87%) was prepared. Further, as a seal layer, a low-density polyethylene resin derived from fossil fuel (manufactured by Japan Polyethylene Corporation: Novatec LC520, MFR: 3.6, density: 0.923) was prepared. The above resin is co-pressed on the corona-treated surface of the paperboard base material at resin temperatures of 290 ° C and 320 ° C (core layer: 20 μm, seal layer: 20 μm), extruded and coated at a line speed of 100 m / min, and biomass is used. A polyethylene laminate was obtained. The biomass degree of the extruded layer was 22%.

Example 2
As the body material and bottom material of the paper cup container, cup base paper (manufactured by Nippon Paper Co., Ltd .: basis weight 220 g / m ² ) is used for the paperboard base material, and after corona treatment, the corona treated surface is low-density derived from fossil fuel. Density polyethylene (manufactured by Nippon Polyethylene: LC520 (MFR: 3.6, density: 0.923) 55 parts by mass and linear low density polyethylene derived from biomass (manufactured by Braskem: SLL318, MFR: 2.7, density: A resin obtained by dry-blending 45 parts by mass (0.918, biomass degree: 87%) is extruded (25 μm) at a resin temperature of 320 ° C. and extruded and coated at a line speed of 100 m / min to obtain a biomass polyethylene laminate. The degree of biomass of the extruded layer was 41%.

Comparative Example 1
As the body material and bottom material of the paper cup container, acid-resistant paper (made by Oji Special Paper: acid-resistant BYO-500, basis weight 320 g / m ² ) is used for the paperboard base material, and the back surface is subjected to corona treatment and then the corona. Low-density polyethylene resin derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: Novatec LC520, MFR: 3.6, density: 0.923) is extruded on the treated surface at a resin temperature of 320 ° C (40 μm) to a line speed of 100 m / min. And extruded to obtain a non-biomass polyethylene laminate. The biomass degree of the extruded layer was 0%.

Comparative Example 2
As the body material and bottom material of the paper cup container, cup base paper (manufactured by Nippon Paper Co., Ltd .: basis weight 220 g / m ² ) is used as the base material of the paperboard, and after corona treatment, the corona treated surface is low from fossil fuel. Density polyethylene (manufactured by Nippon Polyethylene Co., Ltd .: LC520 (MFR: 3.6, density: 0.923) is extruded at a resin temperature of 320 ° C. (25 μm), extruded and coated at a line speed of 100 m / min, and non-biomass polyethylene. A laminate was obtained. The biomass degree of the extruded layer was 0%.

Preparation of Paper Cup Next, using the laminate produced above, a conical trapezoidal blank plate for forming the body of the paper cup was punched from the laminate. Next, the above blank plate was wound into a cylindrical shape, both ends thereof were partially overlapped, and the polymerized portion was frame-treated, and the low-density polyethylene resin layer existing in the polymerized portion was heated and melted. 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, in the same manner as above, the laminate manufactured above is used and punched into a circular shape to manufacture a disk constituting the bottom, and then the outer peripheral portion of the disk is erected in a cylindrical shape. Molding was performed to produce a bottom having an upright molded portion. 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 to the joint portion thereof. The resin layer present 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 forming 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 above-mentioned tubular cup body and bottom are closely adhered to form a joint, and the steam tubular cup body is formed. And the bottom of the paper cup.

After that, the short end of the tip opposite to the side where the bottom of the tubular cup body is tightly adhered to form the joint is curled while being bent outward by a curl mold in the same manner as above, and the upper end is formed. An outward curl portion was formed to manufacture a paper cup having a full capacity of 353 cc.

In both Examples 1 and 2 and Comparative Examples 1 and 2, cup forming could be carried out without any problem. In addition, when these paper cups were destructively inspected and visually confirmed for any sealing abnormality, the phenomenon of paper peeling was confirmed in both cases, and it was confirmed that sufficient sealing strength was obtained.

Reference example 1
50 parts by mass of linear low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: NH745 (MFR: 8.0, density: 0.913)) on the PET film as a base material in the first layer of coextrusion. Two layers of a resin (20 μm) that is a dry blend of 50 parts by mass of a linear low-density polyethylene derived from biomass (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87%). Low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: LC520 (MFR: 3.6, density: 0.923, 20 μm) is extruded at a resin temperature of 320 ° C. (line speed 100 m / min), non- A biomass polyethylene laminate was obtained.

Reference example 2
A linear low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Corporation: NH745 (MFR: 8.0, density: 0.913, 20 μm) is applied to the PET film as a base material in the first layer of coextrusion. Low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Corporation: LC520 (MFR: 3.6, density: 0.923, 20 μm) is extruded at a resin temperature of 300 ° C. (line speed 100 m / min). A non-biomass polyethylene laminate was obtained.

Evaluation of film The PET film of the base material was peeled off from the laminates obtained in Reference Example 1 and Reference Example 2 to obtain film samples A and B, respectively. Each of the obtained film samples was cut into test pieces having a width of 15 mm and a length of 200 mm from the MD direction and the CD direction, respectively, and the temperature was 23 ° C. using a tensile tester (Tencilon RTC-125A, manufactured by Orientec). , The strength and elongation of the test piece was measured in an environment of 50 RH% humidity. In addition, each film sample is heat-sealed at a sealing temperature of 150 ° C., a sealing pressure of 30 N / cm ² , and a sealing time of 1 second, and a sealing strength (N /) is used using a tensile tester (Tencilon RTC-125A, manufactured by Orientec). 15 mm) was measured.

The above evaluation results are as shown in Table 1. No significant difference was found in the film samples A and B in all the endpoints. That is, the biomass resin film (A) was comparable to the non-biomass resin film (B) in terms of physical properties such as mechanical properties.

Example 3
For liquid paper container use, milk carton base paper (manufactured by Clearwater Co., Ltd .: basis weight 320 g / m ² ) is used as the paper base material, and the surface side is frame-treated, and then low-density polyethylene derived from fossil fuel (Japan). Made of polyethylene: LC520 (MFR: 3.6, density: 0.923) was extruded at a resin temperature of 320 ° C. (20 μm). Subsequently, the back surface side was also frame-treated, and then this frame-treated surface. On the back side, 50 parts by mass of linear low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Corporation: NH745 (MFR: 8.0, density: 0.913)) and biomass-derived in the first layer of coextrusion. A resin (20 μm) dry-blended with 50 parts by mass of linear low-density polyethylene (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87%) is fossilized in the second layer. Low-density polyethylene derived from fuel (manufactured by Japan Polyethylene Corporation: LC520 (MFR: 3.6, density: 0.923, 20 μm) is extruded at a resin temperature of 300 ° C. (line speed 100 m / min), biomass polyethylene laminate The total biomass of the laminate excluding the paper substrate was 15%.

Comparative Example 3
Milk carton base paper (manufactured by Clearwater: 320 g / m ² ) is used as the base paper for the paperboard, and after frame treatment is applied to the surface side of the base paper, low density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene: LC520 (manufactured by Japan Polyethylene)) MFR: 3.6, density: 0.923) was extruded at a resin temperature of 320 ° C. (20 μm). Subsequently, the back surface side was also frame-treated, and then the frame-processed surface (back surface side) was subjected to frame treatment. Linear low density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Corporation: NH745 (MFR: 8.0, density: 0.913, 20 μm) in the first layer of coextrusion, low density derived from fossil fuel in the second layer Density polyethylene (manufactured by Japan Polyethylene Corporation: LC520 (MFR: 3.6, density: 0.923, 20 μm) was extruded at a resin temperature of 300 ° C. (line speed 100 m / min) to obtain a non-biomass polyethylene laminate. ..

Example 4
Mainly for use in liquid paper containers that can be stored at room temperature for a long time, such as sake, frame treatment is applied to the non-laminated surface of the base paper (Clearwater 400 g / m ² printed surface with low density polyethylene 20 g / m ² extruded and laminated). went. An aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 7 μm) and a fossil fuel-derived PET film (manufactured by Toyobo Co., Ltd .: E5100, 12 μm) are dry-laminated on this frame-processed surface (manufactured by DIC: main agent LX-703A / curing agent KR-90). ) Was extruded and laminated with an ethylene-acrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd .: Nuclel N0908C, 20 μm) and laminated. Then, the PET surface of the dry laminate film is coated with a polyester polyol / isocyanate two-component curable anchor agent (Mitsui Takeda Polychemical Co., Ltd .: A3210 / AT3075), and then low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .:). LC520 (MFR: 3.6, density: 0.923) 50 parts by mass and linear low-density polyethylene derived from biomass (Brackem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87 %) 50 parts by mass is dry blended, extruded (20 μm) at a resin temperature of 320 ° C., and a low density polyethylene film (Dainippon Printing Co., Ltd .: SKL, density: 0.923) at a line speed of 100 m / min. , 40 μm) to obtain a biomass polyethylene laminate. The total biomass of the laminate excluding the paper substrate was 6%.

Example 5
Mainly for use in room temperature long-term storage type liquid paper containers such as sake, frame treatment is applied to the non-laminated surface of the base paper (Clearwater Co., Ltd. 400 g / m ² printed surface with low density polyethylene 20 g / m ² extruded and laminated). went. Aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 7 μm) and PET film derived from biomass (manufactured by Toyobo Co., Ltd .: DE024, 12 μm) are dry-laminated on this frame-processed surface (manufactured by DIC: main agent LX-703A / curing agent KR-90). The film was extruded and laminated with an ethylene-acrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd .: Nuclel N0908C, 20 μm) and laminated. Then, the PET surface of the dry laminate film is coated with a polyester polyol / isocyanate two-component curable anchor agent (Mitsui Takeda Polychemical Co., Ltd .: A3210 / AT3075), and then low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .:). LC520 (MFR: 3.6, density: 0.923) 50 parts by mass and linear low-density polyethylene derived from biomass (Brackem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87 %) 50 parts by mass is dry blended, extruded (20 μm) at a resin temperature of 320 ° C., and a low density polyethylene film (Dainippon Printing Co., Ltd .: SKL, density: 0.923) at a line speed of 100 m / min. , 40 μm) to obtain a biomass polyethylene laminate. The total biomass of the laminate excluding the paper substrate was 9%.

Comparative Example 4
Mainly for use in liquid paper containers that can be stored at room temperature for a long time, such as sake, frame treatment is applied to the non-laminated surface of the base paper (Clearwater 400 g / m ² printed surface with low density polyethylene 20 g / m ² extruded and laminated). went. An aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 7 μm) and a fossil fuel-derived PET film (manufactured by Toyobo Co., Ltd .: E5100, 12 μm) are dry-laminated on this frame-processed surface (manufactured by DIC: main agent LX-703A / curing agent KR-90). ) Was extruded and laminated with an ethylene-acrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd .: Nuclel N0908C, 20 μm) and laminated. Then, the PET surface of the dry laminate film is coated with a polyester polyol / isocyanate two-component curable anchor agent (Mitsui Takeda Polychemical Co., Ltd .: A3210 / AT3075), and then low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .:). LC520 (MFR: 3.6, density: 0.923) is extruded (20 μm) at a resin temperature of 320 ° C., and a low density polyethylene film (Dainippon Printing Co., Ltd .: SKL,) at a line speed of 100 m / min. The density was 0.923, 40 μm) to obtain a biomass polyethylene laminate. The total biomass of the laminate excluding the paper substrate was 0%.

Comparative Example 5
Mainly for use in room temperature long-term storage type liquid paper containers such as Japanese sake, polyethyleneimine is used on the non-laminated surface of the base paper of the paper base (Clearwater 400 g / m ² low density polyethylene 20 g / m ² extruded and laminated on the printed surface). Anchor coat was done. A film obtained by dry laminating an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 7 μm) and a biomass-derived PET film (manufactured by Toyobo Co., Ltd .: DE024, 12 μm) on this film (manufactured by DIC: main agent LX-703A / curing agent KR-90). Was extruded and laminated with an ethylene-acrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd .: Nuclel N0908C, 20 μm) and laminated. Then, the PET surface of the dry laminate film is coated with a polyester polyol / isocyanate two-component curable anchor agent (Mitsui Takeda Polychemical Co., Ltd .: A3210 / AT3075), and then low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .:). LC520 (MFR: 3.6, density: 0.923) is extruded (20 μm) at a resin temperature of 320 ° C., and a low density polyethylene film (Dainippon Printing Co., Ltd .: SKL,) at a line speed of 100 m / min. The density was 0.923, 40 μm) to obtain a biomass polyethylene laminate. The total biomass of the laminate excluding the paper substrate was 3%.

Strength evaluation of containers Using the cartons produced in Example 4 and Comparative Example 4, water filling and molding were performed with a liquid paper container filling machine (DR-10) manufactured by Dai Nippon Printing Co., Ltd., and then these measurement samples were vertically placed. The single unit compression strength was measured in two directions, horizontal (all sides of the mouth). As shown in Table 2, no significant difference was found between the biomass-derived product and the fossil fuel-derived product.

Sealability evaluation (filling machine verification)
Using the cartons produced in Example 4 and Comparative Example 4, the sealing properties of the top and bottom were compared after water filling and molding with a liquid paper container filling machine (DR-10) manufactured by Dai Nippon Printing Co., Ltd. .. The sealability was evaluated by enclosing the penetrant and visually according to the following criteria. As shown in Table 3, there was no significant difference between the biomass-derived product and the fossil fuel-derived product.
Sealability evaluation criteria
◯: It was good.
Δ: The seal did not come off, but it tended to come off.
X: The seal was confirmed to be missing.

10 Laminated 11 Paper base material 12 Biomass polyolefin resin layer 20 Laminated body 21 Sheet paper base material 22 First biomass polyolefin resin layer 23 Second biomass polyolefin resin layer

Claims (6)

A packaged product provided with a laminate (excluding the raw fabric A for the laminate tube below).
The laminated body is
Paperboard base material and
Biomass composed of a biomass polyolefin resin composition, which is located on one surface side of the paperboard substrate and contains polyethylene derived from biomass obtained by polymerizing a monomer containing ethylene derived from biomass and polyolefin derived from fossil fuel. With a polyolefin resin layer,
The paperboard substrate is located on the outermost surface of the laminate,
A packaged product in which the packaged product is a laminated tube.
(Raw cloth A for laminated tube: A metal foil, a low-density polyethylene film or linear low-density polyethylene film bonded to one side surface of the metal foil, and low-density polyethylene bonded to the other side surface of the metal foil, both sides thereof. A raw fabric for a laminated tube provided with a paper on which a film or a linear low-density polyethylene film is arranged and a vertically uniaxially rolled multilayer film laminated on the paper.) A packaging product with a laminate,
The laminated body is
Paperboard base material and
Biomass composed of a biomass polyolefin resin composition, which is located on one surface side of the paperboard substrate and contains polyethylene derived from biomass obtained by polymerizing a monomer containing ethylene derived from biomass and polyolefin derived from fossil fuel. With a polyolefin resin layer,
The biomass polyolefin resin layer is located on the outermost surface of the laminate,
A packaged product in which the packaged product is a lid material (excluding the lid material B below).
(Cover material B: A lid material for a food container, which is composed of a laminated sheet having two waterproof layers and a base material layer made of paper arranged between the two waterproof layers, and is one of the two waterproof layers. A lid material for food containers, wherein at least one of the waterproof layers is an aluminum layer made of aluminum foil.) The packaged product according to claim 1 or 2, wherein the biomass polyolefin resin layer comprises low-density polyethylene derived from biomass and / and linear low-density polyethylene derived from biomass. The packaged product according to any one of claims 1 to 3, wherein the biomass polyolefin resin layer contains 5% by mass or more of ethylene derived from the biomass with respect to the entire biomass polyolefin resin layer. The packaged product according to any one of claims 1 to 4, further comprising a barrier layer containing an inorganic substance. The packaged product according to any one of claims 1 to 5, which has a polyethylene resin layer located on the other side of the paperboard base material.

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