Laminate having a polyolefin resin layer and packaging product having the same

Abstract

To provide laminates with polyolefin resin layers containing a biomass-derived low-density polyethylene that are comparable to laminates with polyolefin resin layers consisting of a conventional fossil fuel-derived low-density polyethylene in terms of physical properties such as mechanical properties.SOLUTION: There is provided a laminate having at least a substrate layer, a polyolefin resin layer, a barrier layer, an anchor coat layer, and a thermoplastic resin layer, in that order. The substrate layer is a polyethylene film or polyamide film. The polyolefin resin layer comprises a biomass-derived low-density polyethylene, and a biomass degree in the polyolefin resin layer is 5% or more. The anchor coat layer is composed of vinyl modified resin, epoxy resin, urethane resin or polyester resin. The thermoplastic resin that constitutes the thermoplastic resin layer is made only of low-density polyethylene or linear low-density polyethylene. The substrate layer constitutes the outermost layer, and the thermoplastic resin layer constitutes the innermost layer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminate including a polyolefin resin layer containing biomass polyolefin, more specifically to a laminate including at least a substrate layer, a polyolefin resin layer including biomass polyolefin, which is a polymer of a monomer containing ethylene derived from biomass, and a thermoplastic resin layer, and further to a packaging product and flexible packaging including the laminate. [Background technology]

[0002] In recent years, with growing calls for the creation of a recycling-oriented society, there has been a desire to move away from fossil fuels in the materials field, just as there has been in energy, and the use of biomass has been attracting attention. Biomass is an organic compound formed by photosynthesis from carbon dioxide and water, and by using it, it can be converted back into carbon dioxide and water, making it a so-called carbon-neutral renewable energy source. Recently, the practical application of biomass plastics made from these biomass materials has progressed rapidly, and attempts are also being made to produce various resins from biomass materials.

[0003] Among biomass-derived resins, polylactic acid (PLA), which is produced via lactic acid fermentation, was the first to be commercially produced, but because its performance as a plastic, including its biodegradability, is significantly different from that of current general-purpose plastics, there are limitations to its product applications and manufacturing methods, and it has not yet become widely used.In addition, a life cycle assessment (LCA) is being conducted on PLA, and discussions are underway regarding the energy consumption during PLA production and its equivalence as a replacement for general-purpose plastics.

[0004] Various types of general-purpose plastics are used, including polyethylene, polypropylene, polyvinyl chloride, and polystyrene. In particular, polyethylene is molded into films, sheets, bottles, and the like and is used in a variety of applications, such as packaging materials, and is used in large quantities worldwide. Therefore, using conventional polyethylene derived from fossil fuels places a heavy burden on the environment.

[0005] Therefore, it is desirable to reduce the amount of fossil fuel used by using biomass-derived raw materials in the production of polyethylene. For example, research has been conducted to date on the production of ethylene and butylene, which are raw materials for polyolefin resins, from renewable natural raw materials (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Special Publication No. 2011-506628 Summary of the Invention [Problem to be solved by the invention]

[0007] The present inventors focused on ethylene, a raw material for polyolefin resins, and discovered that a laminate comprising a polyolefin resin layer containing low-density polyethylene made from biomass-derived ethylene as the raw material instead of conventional ethylene obtained from fossil fuels (hereinafter sometimes simply referred to as "biomass-derived low-density polyethylene") has physical properties, such as mechanical properties, comparable to those of a laminate comprising a polyolefin resin layer made from low-density polyethylene produced using conventional ethylene obtained from fossil fuels (hereinafter sometimes simply referred to as "fossil-fuel-derived low-density polyethylene"). The present invention is based on this discovery.

[0008] Therefore, an object of the present invention is to provide a laminate comprising a polyolefin resin layer containing biomass-derived low-density polyethylene, which is comparable in terms of physical properties such as mechanical properties to laminates comprising a polyolefin resin layer made of conventional fossil fuel-derived low-density polyethylene. [Means for solving the problem]

[0009] In an embodiment of the present invention, A laminate comprising at least a substrate layer, a polyolefin resin layer, a barrier layer, an anchor coat layer, and a thermoplastic resin layer in this order, the substrate layer is a polyethylene film or a polyamide film, the polyolefin resin layer contains biomass-derived low-density polyethylene, The polyolefin resin layer has a biomass content of 5% or more, the anchor coat layer is made of a vinyl-modified resin, an epoxy resin, a urethane resin, or a polyester resin, the thermoplastic resin constituting the thermoplastic resin layer is only low-density polyethylene or only linear low-density polyethylene, the substrate layer constitutes an outermost layer, A laminate (excluding the laminate A described below) is provided in which the thermoplastic resin layer constitutes the innermost layer. Laminate A: a biomass polyester resin layer comprising a biomass polyester resin composition containing, as a main component, a polyester composed of diol units and dicarboxylic acid units, wherein the diol units are ethylene glycol derived from biomass; a biomass polyolefin resin layer made of a biomass polyolefin resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing ethylene derived from biomass; A laminate comprising: In this aspect of the present invention, the laminate preferably includes a plastic film between the polyolefin resin layer and the thermoplastic resin layer. In an aspect of the present invention, there is provided a method for producing the laminate, comprising the steps of: There is also provided a method for producing a laminate, which comprises laminating the barrier layer or plastic film via the melt-extruded polyolefin resin layer by sand lamination. In an aspect of the present invention, a packaging product is provided comprising the laminate. In one aspect of the present invention, there is provided a flexible package comprising the laminate. In another aspect of the present invention, there is provided a packaging bag comprising the laminate. [Effects of the Invention]

[0010] The laminate according to the present invention comprises at least a substrate layer, a polyolefin resin layer containing biomass-derived low-density polyethylene, and a thermoplastic resin layer, thereby enabling a reduction in the amount of fossil fuel used compared to conventional laminates and reducing the environmental load. Furthermore, the laminate according to the present invention is comparable in terms of physical properties such as mechanical properties to laminates comprising a polyolefin resin layer containing conventional fossil-fuel-derived low-density polyethylene, and can therefore replace the conventional polyolefin resin layer containing fossil-fuel-derived low-density polyethylene. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention. [Figure 2] 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention. [Figure 3] 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention. [Figure 4] FIG. 1 is a simplified diagram showing an example of the configuration of a standing pouch. [Figure 5] FIG. 2 is a simplified diagram showing an example of the configuration of a laminate tube. DETAILED DESCRIPTION OF THE INVENTION

[0012] In the present invention, "biomass polyolefin" and "polyolefin resin layer containing biomass polyolefin" mean that at least a portion of the raw materials used are derived from biomass, but do not mean that all of the raw materials are derived from biomass.

[0013] <Laminate> The laminate according to the present invention comprises, in this order, a substrate layer, a polyolefin resin layer containing biomass polyolefin, and a thermoplastic resin layer. Hereinafter, the term "thermoplastic resin layer" refers to the first thermoplastic resin layer. By including the polyolefin resin layer containing biomass polyolefin, the laminate can reduce the amount of fossil fuel used compared to conventional laminates, thereby reducing the environmental burden. Furthermore, the laminate according to the present invention is comparable in terms of physical properties, such as mechanical properties, to conventional polyolefin resin laminates produced from raw materials obtained from fossil fuels, and can therefore replace conventional polyolefin resin laminates.

[0014] In addition to the above layers, the laminate according to the present invention may further include at least one other layer such as a printed layer, a barrier layer, a plastic film, an adhesive layer, a second thermoplastic resin layer, etc. When two or more other layers are included, they may have the same composition or different compositions.

[0015] The laminate according to the present invention will be described with reference to the drawings, in which examples of schematic cross-sectional views of the laminate according to the present invention are shown in Figures 1 to 3. 1 includes a base material layer 11, a polyolefin resin layer 12 formed on the base material layer 11, and a thermoplastic resin layer 13 formed directly on the polyolefin resin layer 12. In the case of flexible packaging including the laminate 10, the thermoplastic resin layer 13 is located on the inside of the flexible packaging. Here, the polyolefin resin layer 12 is a polyolefin resin layer containing biomass polyolefin. 2 includes a base material layer 11, and on one surface of the base material layer 11, a polyolefin resin layer 12, a barrier layer 14, and a thermoplastic resin layer 13, in this order. In the case of flexible packaging including the laminate 20, the thermoplastic resin layer 13 is located on the inside of the flexible packaging. 3 includes a base material layer 11, and on one surface of the base material layer 11, a polyolefin resin layer 12, a plastic film 15, an adhesive layer 16, and a thermoplastic resin layer 13, in this order. In the case of flexible packaging including the laminate 30, the thermoplastic resin layer 13 is located on the inside of the flexible packaging. Any of the laminates may further include a printed layer or a second thermoplastic resin layer. When the printed layer and the second thermoplastic resin layer are laminated, the second thermoplastic resin layer may be laminated as the outermost layer. Each layer constituting the laminate will now be described.

[0016] (base material layer) In the present invention, the substrate layer functions as a substrate layer that supports the polyolefin resin layer and is preferably capable of imparting strength to the laminate as a packaging product. The substrate layer can be a resin substrate, preferably a plastic film made of a resin material such as polyester (e.g., polyethylene terephthalate), polyolefin (e.g., polyethylene or polypropylene), or polyamide (e.g., nylon). These may be used alone or in combination of two or more. When two or more types are combined, lamination may be performed using a dry lamination method or a melt extrusion method. The thickness of the substrate layer can be 5 μm or more and 38 μm or less, preferably 5 μm or more and 25 μm or less, and more preferably 8 μm or more and 16 μm or less.

[0017] The substrate layer may include a material derived from biomass or a material derived from fossil fuels.

[0018] The substrate layer may contain a biomass polyester having ethylene glycol derived from biomass as a diol unit and a dicarboxylic acid derived from a fossil fuel as a dicarboxylic acid unit. The substrate layer may further contain a polyester derived from a fossil fuel having ethylene glycol derived from a fossil fuel as a diol unit and a dicarboxylic acid derived from a fossil fuel as a dicarboxylic acid unit.

[0019] The "biomass ratio" (biomass-derived carbon concentration) in the substrate layer is a value measured by radiocarbon (C14) measurement of the biomass-derived carbon content. Atmospheric carbon dioxide contains a certain proportion of C14 (105.5 pMC), and it is known that the C14 content in plants that grow by absorbing atmospheric carbon dioxide, such as corn, is also about 105.5 pMC. It is also known that fossil fuels contain very little C14. Therefore, the proportion of biomass-derived carbon can be calculated by measuring the proportion of C14 in the total carbon atoms in the polyester. In the present invention, when the C14 content in the polyester is defined as PC14, the biomass-derived carbon content Pbio can be determined as follows. Pbio(%) = PC14 / 105.5 × 100

[0020] Taking polyethylene terephthalate as an example, polyethylene terephthalate is produced by polymerizing ethylene glycol containing two carbon atoms and terephthalic acid containing eight carbon atoms in a 1:1 molar ratio. Therefore, if only biomass-derived ethylene glycol is used, the biomass-derived carbon content (Pbio) of the polyester will be 20%. In the present invention, the biomass-derived carbon content, as determined by radiocarbon (C14) measurement, relative to the total carbon in the biomass polyester is preferably 10% to 20%, and may be 10% to 19%. Biomass polyesters with a biomass-derived carbon content of 10% or more are suitable as carbon offset materials. Furthermore, the biomass-derived carbon content of fossil fuel-derived polyesters produced using fossil fuel-derived ethylene glycol and fossil fuel-derived dicarboxylic acids is 0%, and the biomass content of the fossil fuel-derived polyester is 0%.

[0021] The biomass content in the base layer is 5% or more, preferably 10% or more, and more preferably 15% or more. If the biomass content in the base layer is 5% or more, the amount of polyester derived from fossil fuels can be reduced compared to conventional methods, thereby reducing the environmental impact.

[0022] The base layer can be formed by forming a film using a resin composition of biomass polyester or a resin composition containing biomass polyester and a polyester derived from a fossil fuel, for example, by a T-die method.

[0023] (biomass polyester) Biomass polyester is composed of diol units and dicarboxylic acid units, and is obtained by a polycondensation reaction using ethylene glycol derived from biomass as the diol units and dicarboxylic acid derived from fossil fuels as the dicarboxylic acid units.

[0024] Biomass-derived ethylene glycol is produced from ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene oxide by a conventionally known method to produce ethylene glycol. Alternatively, commercially available biomass ethylene glycol may be used; for example, biomass ethylene glycol commercially available from India Glycoal Limited can be suitably used.

[0025] The dicarboxylic acid units of the biomass polyester use dicarboxylic acids derived from fossil fuels. As dicarboxylic acids, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation. Examples of aromatic dicarboxylic acids include terephthalic acid and isophthalic acid, and examples of derivatives of aromatic dicarboxylic acids include lower alkyl esters of aromatic dicarboxylic acids, specifically methyl esters, ethyl esters, propyl esters, and butyl esters. Among these, terephthalic acid is preferred, and dimethyl terephthalate is preferred as a derivative of aromatic dicarboxylic acid.

[0026] (Polyolefin resin layer) In the present invention, the polyolefin resin layer contains a biomass polyolefin, which is a polymer of a monomer containing ethylene derived from biomass, and may further contain a polyolefin derived from a fossil fuel. The polyolefin resin layer may contain 5% by mass to 100% by mass of a biomass polyolefin and 0% by mass to 95% by mass of a fossil fuel-derived polyolefin relative to the entire polyolefin resin layer, or 5% by mass to less than 100% by mass of a biomass polyolefin and more than 0% by mass to 95% by mass of a fossil fuel-derived polyolefin, or 25% by mass to 75% by mass of a biomass polyolefin and 25% by mass to 75% by mass of a fossil fuel-derived polyolefin. It is sufficient that the polyolefin resin layer as a whole achieves the following biomass degree. In the present invention, by including a biomass polyolefin in the polyolefin resin layer, the amount of fossil fuel-derived polyolefin can be reduced compared to conventional methods, thereby reducing the environmental impact.

[0027] In the present invention, the "biomass content" (concentration of biomass-derived carbon in biomass polyolefin) in the polyolefin resin layer is a value measured by measuring the content of biomass-derived carbon by radiocarbon (C14) measurement. Carbon dioxide in the atmosphere contains a certain proportion (105.5 pMC) of C14, and it is known that the C14 content in plants that grow by absorbing carbon dioxide from the atmosphere, such as corn, is also about 105.5 pMC. It is also known that fossil fuels contain almost no C14. Therefore, the proportion of biomass-derived carbon can be calculated by measuring the proportion of C14 in the total carbon atoms in the polyolefin. In the present invention, the C14 content in the polyolefin is determined as P C14 The content of biomass-derived carbon in this case is P bio can be calculated as follows: P bio (%)=P C14 / 105.5×100

[0028] In the present invention, theoretically, if all biomass-derived ethylene is used as a polyolefin raw material, the biomass content is 100%, and the biomass content of the biomass-derived polyolefin is 100%. Also, the biomass-derived carbon concentration in fossil fuel-derived polyolefins produced only from fossil fuel-derived raw materials is 0%, and the biomass content of the fossil fuel-derived polyolefin is 0%.

[0029] In the present invention, the biomass content in the polyolefin resin layer is 5% or more, preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. The biomass content in the polyolefin resin layer does not need to be 100%. This is because using biomass-derived raw materials in even a part of the laminate is in line with the purpose of the present invention, which is to reduce the amount of fossil fuel used compared to conventional methods. If the biomass content in the polyolefin resin layer is 5% or more, the amount of fossil fuel-derived polyolefin can be reduced compared to conventional methods, thereby reducing the environmental load.

[0030] The polyolefin resin layer preferably has a density of 0.91 g / cm 3 More than 0.93g / cm 3 or less, more preferably 0.911 g / cm 3 More than 0.928g / cm 3 or less, more preferably 0.915 g / cm 3 More than 0.925g / cm 3 The density of the polyolefin resin layer is a value measured according to the method specified in Method A of JIS K7112-1980 after annealing as specified in JIS K6760-1995. 3 More than 0.93g / cm 3 If the thickness is less than this, processing and molding can be facilitated.

[0031] The polyolefin resin layer has a thickness of 5 μm to 100 μm, preferably 10 μm to 60 μm, and more preferably 15 μm to 40 μm. If the thickness of the polyolefin resin layer is within the above range, it can sufficiently perform the function of adhering the two layers together.

[0032] (Biomass polyolefin) In the present invention, biomass polyolefin is a polymer of a monomer containing biomass-derived ethylene. It is preferable to use biomass-derived ethylene obtained by the production method described below. Since biomass-derived ethylene is used as the raw material monomer, the polymerized polyolefin is biomass-derived. Note that the raw material monomer for polyolefin does not have to contain 100% by mass of biomass-derived ethylene.

[0033] The monomers that are the raw material for biomass polyolefin may further include ethylene monomers derived from fossil fuels and / or α-olefin monomers derived from fossil fuels, or may further include α-olefin monomers derived from biomass.

[0034] The number of carbon atoms in the α-olefin is not particularly limited, but those having 3 to 20 carbon atoms can usually be used, and butylene, hexene, or octene is preferred. This is because butylene, hexene, or octene can be produced by polymerizing ethylene, a raw material derived from biomass. Furthermore, by including such an α-olefin, the polyolefin obtained by polymerization has alkyl groups as a branched structure, and can therefore be more flexible than a simple linear one.

[0035] As the biomass polyolefin, polyethylene or a copolymer of ethylene and an α-olefin may be used alone or in combination. In particular, polyethylene is preferred as the biomass polyolefin. This is because, by using ethylene, a raw material derived from biomass, it is theoretically possible to produce a polyolefin from 100% biomass-derived components.

[0036] The biomass polyolefin may contain two or more kinds of biomass polyolefins having different biomass degrees, and it is sufficient that the biomass degree of the entire polyolefin resin layer is within the above range.

[0037] The biomass polyolefin preferably has a viscosity of 0.91 g / cm 3 More than 0.93g / cm 3 or less, more preferably 0.912 g / cm 3 More than 0.928g / cm 3 or less, more preferably 0.915 g / cm 3 More than 0.925g / cm 3 The density of biomass polyolefin is a value measured according to the method specified in Method A of JIS K7112-1980 after annealing as specified in JIS K6760-1995. 3 If the density of the biomass polyolefin is 0.93 g / cm or more, the rigidity of the polyolefin resin layer containing the biomass polyolefin can be increased, and the polyolefin resin layer can be suitably used as an inner layer of a packaging product. 3 If the content is below this level, the transparency and mechanical strength of the polyolefin resin layer containing biomass polyolefin can be increased, and the polyolefin resin layer can be suitably used as an inner layer of a packaging product.

[0038] The biomass polyolefin has a melt flow rate (MFR) of 0.1 g / 10 min to 10 g / 10 min, preferably 0.2 g / 10 min to 9 g / 10 min, and more preferably 1 g / 10 min to 8.5 g / 10 min. The melt flow rate is a value measured by Method A under conditions of a temperature of 190°C and a load of 21.18 N in accordance with the method specified in JIS K7210-1995. If the MFR of the biomass polyolefin is 0.1 g / 10 min or more, the extrusion load during molding can be reduced. Furthermore, if the MFR of the biomass polyolefin is 10 g / 10 min or less, the mechanical strength of the polyolefin resin layer containing the biomass polyolefin can be increased.

[0039] In the present invention, a biomass polyolefin that can be suitably used is a biomass-derived low-density polyethylene manufactured by Braskem (trade name: SBC818, density: 0.918 g / cm 3 , MFR: 8.1 g / 10 min, biomass content: 95%), Braskem biomass-derived low-density polyethylene (trade name: SPB681, density: 0.922 g / cm 3 , MFR: 3.8 g / 10 min, biomass content 95%).

[0040] (Method for producing ethylene from biomass) In the present invention, the method for producing biomass-derived ethylene, which is a raw material for biomass polyolefin, is not particularly limited, and it can be obtained by a conventionally known method. An example of a method for producing biomass-derived ethylene will be described below.

[0041] Biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. In particular, it is preferable to use biomass-derived fermented ethanol obtained from plant raw materials. The plant raw material is not particularly limited, and conventionally known plants can be used. Examples include corn, sugarcane, beet, and manioc.

[0042] In the present invention, biomass-derived fermented ethanol refers to ethanol produced by contacting a culture solution containing a carbon source obtained from plant raw materials with an ethanol-producing microorganism or a product derived from its disruption, and then purifying the ethanol. Conventional methods such as distillation, membrane separation, and extraction can be used to purify ethanol from the culture solution. Examples of such methods include adding benzene, cyclohexane, or the like and removing water by azeotropy or membrane separation.

[0043] In order to obtain the ethylene of the present invention, further advanced purification may be carried out at this stage, such as reducing the total amount of impurities in the ethanol to 1 ppm or less.

[0044] A catalyst is usually used when obtaining ethylene by the dehydration reaction of ethanol, but the catalyst is not particularly limited and any conventionally known catalyst can be used. From the viewpoint of the process, a fixed-bed flow reaction is advantageous because it allows easy separation of the catalyst from the product, and for example, γ-alumina is preferred.

[0045] Since this dehydration reaction is an endothermic reaction, it is usually carried out under heating conditions. The heating temperature is not limited as long as the reaction proceeds at a commercially useful reaction rate, but is preferably 100°C or higher, more preferably 250°C or higher, and even more preferably 300°C or higher. There is no particular upper limit, but from the viewpoint of energy balance and equipment, it is preferably 500°C or lower, more preferably 400°C or lower.

[0046] The reaction pressure is not particularly limited, but a pressure equal to or higher than atmospheric pressure is preferred to facilitate subsequent gas-liquid separation. From an industrial perspective, a fixed-bed flow reaction is preferred because it facilitates catalyst separation, but a liquid-phase suspension bed, a fluidized bed, or the like may also be used.

[0047] 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 performing a dehydration reaction, it is preferable to eliminate water in order to improve the efficiency of water removal. However, in the case of ethanol dehydration using a solid catalyst, it has been found that the absence of water tends to increase the amount of other olefins, particularly butene, produced. This is presumably because the presence of a small amount of water is insufficient to suppress ethylene dimerization after dehydration. The lower limit of the allowable water content is 0.1% or more, preferably 0.5% or more. There are no particular limitations on the upper limit, but from the viewpoints of material balance and heat balance, it is preferably 50% by mass or less, more preferably 30% or less, and even more preferably 20% or less.

[0048] By carrying out the dehydration reaction of ethanol in this manner, a mixture of ethylene, water, and a small amount of unreacted ethanol is obtained, but since ethylene is in a gaseous state at room temperature and below about 5 MPa, water and ethanol can be removed from this mixture by gas-liquid separation to obtain ethylene. This method can be carried out by any known method.

[0049] The ethylene obtained by the gas-liquid separation is further distilled. The distillation method, operation temperature, residence time, etc. are not particularly limited, except that the operation pressure at this time must be atmospheric pressure or higher.

[0050] When biomass-derived ethanol is used as the raw material, the resulting ethylene contains trace amounts of impurities introduced during the ethanol fermentation process, such as carbonyl compounds (e.g., ketones, aldehydes, and esters) and their decomposition products (e.g., carbon dioxide), as well as nitrogen-containing compounds (e.g., amines and amino acids) and their decomposition products (e.g., ammonia), which are enzymatic decomposition products and contaminants. Depending on the intended use of ethylene, these trace amounts of impurities may be problematic, so they may be removed by purification. The purification method is not particularly limited, and conventionally known methods can be used. An example of a suitable purification procedure is adsorption purification. The adsorbent used is not particularly limited, and conventionally known adsorbents can be used. For example, a material with a high surface area is preferred, and the type of adsorbent is selected depending on the type and amount of impurities in the ethylene obtained by the dehydration reaction of biomass-derived ethanol.

[0051] A caustic water treatment may be used in combination as a method for purifying impurities in ethylene. When caustic water treatment is used, it is preferable to carry out the treatment before adsorption purification. In this case, it is necessary to carry out a water removal treatment after the caustic treatment and before adsorption purification.

[0052] (Production method of biomass polyolefin) In the present invention, the method for polymerizing a biomass-derived ethylene-containing monomer is not particularly limited, and can be carried out by a conventionally known method. The polymerization temperature and polymerization pressure are preferably adjusted appropriately depending on the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and a conventionally known apparatus can be used. An example of a method for polymerizing an ethylene-containing monomer will be described below.

[0053] The polymerization method for polyolefins, particularly ethylene polymers and copolymers of ethylene and α-olefins, can be appropriately selected depending on the type of polyethylene desired, such as differences in density and branching, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). For example, it is preferable to use a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as the polymerization catalyst, and to carry out the polymerization in one stage or two or more stages by any of gas-phase polymerization, slurry polymerization, solution polymerization, and high-pressure ionic polymerization.

[0054] The single-site catalyst is a catalyst capable of forming a uniform active species, and is usually prepared by contacting a metallocene transition metal compound or a non-metallocene transition metal compound with an activating co-catalyst. Single-site catalysts are preferred because they have a more uniform active site structure than multi-site catalysts, making it possible to polymerize polymers with high molecular weights and highly uniform structures. Metallocene catalysts are particularly preferred as single-site catalysts. Metallocene catalysts are catalysts containing the following catalytic components: a transition metal compound of Group IV of the periodic table containing a ligand with a cyclopentadienyl skeleton, a co-catalyst, and optionally an organometallic compound and a carrier.

[0055] In the above-mentioned transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group, or the like. The substituted cyclopentadienyl group has at least one substituent selected from 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, a halosilyl group, and the like. The substituted cyclopentadienyl group may have two or more substituents, and the substituents may be bonded to each other to form a ring, such as an indenyl ring, a fluorenyl ring, an azulenyl ring, or a hydrogenated product thereof. The rings formed by bonding the substituents to each other may further have substituents.

[0056] In a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, the transition metal may be zirconium, titanium, hafnium, or the like, with zirconium and hafnium being particularly preferred. The transition metal compound typically contains two ligands having a cyclopentadienyl skeleton, and the ligands having the cyclopentadienyl skeleton are preferably bonded to each other via a bridging group. Examples of the bridging group include alkylene groups having 1 to 4 carbon atoms, silylene groups, substituted silylene groups such as dialkylsilylene groups and diarylsilylene groups, and substituted germylene groups such as dialkylgermylene groups and diarylgermylene groups. A substituted silylene group is preferred.

[0057] In the transition metal compounds of Group IV of the periodic table, representative examples of the ligand other than the ligand having a cyclopentadienyl skeleton include hydrogen, hydrocarbon groups having 1 to 20 carbon atoms (such as alkyl groups, alkenyl groups, aryl groups, alkylaryl groups, aralkyl groups, and polyenyl groups), halogens, metaalkyl groups, and metaaryl groups.

[0058] The above-mentioned compounds of transition metals of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton can be used as a catalyst component either singly or in combination of two or more kinds.

[0059] The co-catalyst refers to a catalyst that can effectively use the above-mentioned transition metal compound of Group IV of the periodic table as a polymerization catalyst or that can balance the ionic charge in a catalytically activated state. Examples of the co-catalyst include benzene-soluble aluminoxanes of organoaluminum oxy compounds and benzene-insoluble organoaluminum oxy compounds, ion-exchangeable layered silicates, boron compounds, ionic compounds consisting of a cation with or without an active hydrogen group and a non-coordinating anion, lanthanoid salts such as lanthanum oxide, tin oxide, and phenoxy compounds containing a fluoro group.

[0060] The transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton may be used by being supported on an inorganic or organic support, preferably an inorganic or organic porous oxide, such as montmorillonite or other ion-exchangeable layered silicates, SiO2, Al2O3, MgO, ZrO2, TiO2, BO3, CaO, ZnO, BaO, ThO2, or mixtures thereof.

[0061] Furthermore, examples of organometallic compounds that may be used if necessary include organoaluminum compounds, organomagnesium compounds, organozinc compounds, etc. Of these, organoaluminum compounds are preferably used.

[0062] In addition to the polyolefin as the main component, various additives may be added to biomass polyolefin as long as the properties are not impaired. Examples of additives that can be added include plasticizers, UV stabilizers, color inhibitors, matting agents, deodorizers, flame retardants, weather resistance agents, antistatic agents, thread friction reducers, slip agents, mold release agents, antioxidants, ion exchange agents, and color pigments. These additives are added in an amount of preferably 1% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass, based on the total biomass polyolefin.

[0063] (thermoplastic resin layer) The thermoplastic resin layer can be formed using a conventionally known thermoplastic resin. By further including a thermoplastic resin layer in the laminate, it is possible to impart heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties similar to those of conventional laminates.

[0064] Examples of thermoplastic resins include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, 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, with low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and ethylene-methacrylic acid copolymer being preferred.

[0065] The thermoplastic resin layer may contain a biomass-derived material or a fossil fuel-derived material. When the thermoplastic resin layer contains a biomass-derived material, it may contain a biomass polyolefin, which is a polymer of a monomer containing ethylene derived from biomass, similar to the polyolefin resin layer.

[0066] As described above, a second thermoplastic resin layer may be provided on the surface of the base layer opposite the polyolefin resin layer. The second thermoplastic resin layer may be made of the same resin as the thermoplastic resin layer (first thermoplastic resin layer).

[0067] (Printing layer) The printing layer is a layer on which any desired printed pattern such as letters, numbers, pictures, figures, symbols, designs, etc. is formed for the purpose of decoration, indication of contents, indication of expiration date, indication of manufacturer, seller, etc., or for the purpose of imparting aesthetic appeal. The printing layer can be provided as needed, for example, on the base material layer. The printing layer may be provided on the entire surface of the base material layer, or on a part of it. The printing layer can be formed using conventionally known pigments or dyes, and the method of forming the printing layer is not particularly limited.

[0068] (barrier layer) The barrier layer is made of an inorganic substance and / or an inorganic oxide, and is preferably made of a vapor-deposited film of an inorganic substance or inorganic oxide or a metal foil. The vapor-deposited film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and its composition and formation method are not particularly limited. When the laminate further has a barrier layer, it can be provided with or improved gas barrier properties that prevent the transmission of oxygen gas, water vapor, etc., and light-blocking properties that prevent the transmission of visible light, ultraviolet light, etc. The laminate may have two or more barrier layers. When two or more barrier layers are included, the layers may have the same composition or different compositions.

[0069] Examples of the vapor-deposited film that can be used include vapor-deposited films of inorganic substances or inorganic oxides such as silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y). Particularly suitable for packaging materials (bags) and the like are vapor-deposited films of aluminum metal, or vapor-deposited films of silicon oxide, aluminum metal, or aluminum oxide.

[0070] Inorganic oxides are expressed as, for example, SiO X , AlO X MO etc. X(wherein, M represents an inorganic element, and the value of X varies depending on the inorganic element.) The value of X can range from 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1.5 for magnesium (Mg), 0 to 1 for calcium (Ca), 0 to 1 for potassium (K), 0 to 0.5 for tin (Sn), 0 to 2 for sodium (Na), 0 to 0.5 for boron (B), 0 to 1.5 for titanium (Ti), 0 to 2 for lead (Pb), 0 to 1 for zirconium (Zr), and 0 to 1.5 for yttrium (Y). In the above, when X=0, it is a completely inorganic element (pure substance) and is not transparent, and the upper limit of the range of X is the value when it is completely oxidized. Silicon (Si) and aluminum (Al) are preferably used for packaging materials, with silicon (Si) having a value in the range of 1.0 to 2.0 and aluminum (Al) having a value in the range of 0.5 to 1.5.

[0071] In the present invention, the thickness of the vapor-deposited film of the inorganic substance or inorganic oxide described above varies depending on the type of inorganic substance or inorganic oxide used, but is desirably selected from the range of, for example, 50 to 2000 Å, preferably 100 to 1000 Å. More specifically, in the case of a vapor-deposited aluminum film, the thickness is desirably 50 to 600 Å, more preferably 100 to 450 Å, and in the case of a vapor-deposited aluminum oxide or silicon oxide film, the thickness is desirably 50 to 500 Å, more preferably 100 to 300 Å.

[0072] Vapor deposition films can be formed on plastic films such as polyethylene terephthalate and nylon using the following methods: Examples of methods for forming vapor deposition films include physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, and ion plating, and chemical vapor deposition (CVD) methods such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition.

[0073] In another embodiment, the barrier layer may be a metal foil obtained by rolling a metal. Any conventionally known metal foil can be used as the metal foil. Aluminum foil is preferred from the viewpoints of gas barrier properties that prevent the transmission of oxygen gas, water vapor, and the like, and light-shielding properties that prevent the transmission of visible light, ultraviolet light, and the like.

[0074] (plastic film) In the present invention, various plastic films may be used as other layers. For example, they may be any of stretched polyethylene terephthalate film, stretched nylon film, stretched polypropylene film, nylon 6 / metaxylylenediamine nylon 6 co-extruded co-stretched film, and polypropylene / ethylene-vinyl alcohol copolymer co-extruded co-stretched film, or composite films formed by laminating two or more of these films. The plastic film may be coated with polyvinyl alcohol or the like.

[0075] The plastic film may contain a biomass-derived material or a fossil fuel-derived material. When the plastic film contains a biomass-derived material, it may further contain a fossil fuel-derived polyester having fossil fuel-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

[0076] (adhesive layer) The adhesive layer can be formed by applying an adhesive to the surface of the layer to be laminated and drying it when two layers are bonded together by dry lamination. Examples of adhesives that can be used include one-component or two-component curing or non-curing vinyl, (meth)acrylic, polyamide, polyester, polyether, polyurethane, epoxy, rubber, and other solvent-based, water-based, or emulsion-based adhesives. The laminating adhesive can be applied to the coating surface of the layers constituting the laminate by, for example, direct gravure roll coating, gravure roll coating, kiss coating, reverse roll coating, Fountain coating, transfer roll coating, or other methods. The coating amount is 0.1 g / m. 2 More than 10g / m 2 Preferably less than 1g / m (dry state) 2 More than 5g / m 2 The following (dry state) is more preferred:

[0077] The adhesive layer may also be an anchor coating layer formed by applying an anchor coating agent to the surface of a layer to be laminated, such as a polyolefin resin layer or a thermoplastic resin layer, and drying the applied agent when laminating the layer using melt extrusion lamination. Examples of anchor coating agents include anchor coating agents made of any resin with a heat resistance temperature of 135°C or higher, such as vinyl-modified resins, epoxy resins, urethane resins, and polyester resins. In particular, anchor coating agents made of a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in its structure and an isocyanate compound as a curing agent are preferred. A silane coupling agent may also be used as an additive, and soluble nitrocellulose may also be used to enhance heat resistance.

[0078] The adhesive layer may also be an adhesive resin layer used when bonding two layers together by sand lamination or melt extrusion lamination. Thermoplastic resins that can be used for the adhesive resin layer include polyethylene resins, polypropylene resins, cyclic polyolefin resins, copolymer resins, modified resins, and mixtures (including alloys) containing these resins as the main components. Examples of polyolefin resins include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), polypropylene (PP), ethylene-α-olefin copolymers polymerized using metallocene catalysts, random or block copolymers of ethylene and 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, and ionomer resins. To improve interlayer adhesion, acid-modified polyolefin resins can be used, which are modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. Furthermore, resins obtained by graft polymerization or copolymerization of unsaturated carboxylic acids, unsaturated carboxylic anhydrides, or ester monomers onto polyolefin resins can also be used. These materials can be used alone or in combination of two or more. Examples of cyclic polyolefin-based resins that can be used include cyclic polyolefins such as ethylene-propylene copolymers, polymethylpentene, polybutene, and polynorbornene. These resins can be used alone or in combination of two or more. It goes without saying that the polyethylene-based resins mentioned above can be those that use the above-mentioned biomass-derived ethylene as a monomer unit.

[0079] The adhesive resin layer may contain a material derived from biomass or a material derived from fossil fuels. When the adhesive resin layer contains a material derived from biomass, it may contain a biomass polyolefin, which is a polymer of a monomer containing ethylene derived from biomass, similar to the polyolefin resin layer.

[0080] (Method of manufacturing laminate) The method for producing the laminate according to the present invention is not particularly limited, and it can be produced by a conventionally known method such as dry lamination, melt extrusion lamination, or sand lamination. In the present invention, it is preferable to use the sand lamination method to laminate another layer via a melt-extruded polyolefin resin layer. Alternatively, the polyolefin resin layer and another layer may be laminated by a co-extrusion method.

[0081] The thickness of the laminate obtained as described above is optional depending on the application, but is usually 5 μm or more and 500 μm or less, preferably 20 μm or more and 300 μm or less.

[0082] The laminate of the present invention can also be subjected to secondary processing for the purpose of imparting surface functions such as chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubrication functions, optical functions, thermal functions, and biocompatibility. Examples of secondary processing include embossing, painting, bonding, printing, metallizing (plating, etc.), machining, and surface treatments (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.). Furthermore, the laminate of the present invention can also be subjected to lamination (dry lamination or extrusion lamination), bag-making, and other post-processing to produce molded products.

[0083] (Application) The laminate according to the present invention can be used in packaging products, and is preferably used for flexible packaging such as packaging bags, laminated tubes, and lids. Examples of packaging bags include standing pouches, side-sealed bags, two-sided sealed bags, three-sided sealed bags, four-sided sealed bags, envelope-sealed bags, palm-sealed bags (pillow-sealed bags), pleated sealed bags, flat-bottom sealed bags, square-bottom sealed bags, and gusseted bags. The thickness of the laminate in this case can be determined appropriately depending on the application, and it is used in the form of a film having a thickness of, for example, 30 μm to 300 μm, preferably 35 μm to 180 μm.

[0084] (Flexible packaging) The laminate according to the present invention can be suitably used for flexible packaging, particularly for packaging bags and laminated tubes. A packaging bag, as an example, a stand-up pouch, is formed using the laminate according to the present invention. FIG. 4 is a simplified diagram showing an example of the configuration of a stand-up pouch. As shown in FIG. 4, the stand-up pouch 40 is composed of two body portions (side sheets) 41 and a bottom portion (bottom sheet) 42. The side sheets 41 and bottom sheet 42 of the stand-up pouch 40 may be composed of the same material, or may be composed of different materials. The side sheets 41 and bottom sheet 42 of the stand-up pouch 40 can be formed using the laminate according to the present invention.

[0085] Next, a laminated tube formed using the laminate according to the present invention will be described. Fig. 5 is a simplified diagram showing an example of a laminated tube. As shown in Fig. 5, laminated tube 50 comprises head 51 and cylindrical body 32. Head 51 is integrally formed with hollow conical shoulder 53 and spout 54. Cylindrical body 52 is connected to shoulder 53 of head 51. Cylindrical body 52 can be formed using a laminate in which at least a second thermoplastic resin layer, a substrate layer, a polyolefin resin layer, and a first thermoplastic resin layer are laminated in this order.

[0086] (Another aspect) The present inventors focused on ethylene, a raw material for polyolefin resins, and discovered that a laminate comprising a polyolefin resin layer containing biomass polyolefin (sometimes simply referred to as "biomass polyolefin"), which uses biomass-derived ethylene as its raw material instead of conventional ethylene obtained from fossil fuels, has physical properties such as mechanical properties that are comparable to those of a laminate comprising a polyolefin resin layer made from polyolefin produced using conventional ethylene obtained from fossil fuels (sometimes simply referred to as "fossil fuel-derived polyolefin"). Another aspect of the present invention is based on this discovery. Therefore, an object of another aspect of the present invention is to provide a laminate having a polyolefin resin layer containing a biomass polyolefin, which is comparable in physical properties such as mechanical properties to laminates having a polyolefin resin layer made of conventional polyolefins derived from fossil fuels. In another aspect of the present invention, A laminate including at least a base layer, a polyolefin resin layer, and a thermoplastic resin layer in this order, the polyolefin resin layer contains a biomass polyolefin which is a polymer of a monomer containing ethylene derived from biomass, The laminate has a biomass content of 5% or more in the polyolefin resin layer. In another aspect of the present invention, it is preferable that the polyolefin resin layer further contains a polyolefin derived from a fossil fuel. In another aspect of the present invention, the polyolefin resin layer preferably 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 fossil fuel-derived polyolefin. In another aspect of the present invention, the polyolefin resin layer preferably contains polyethylene. In another aspect of the present invention, the thermoplastic resin layer preferably contains a resin material selected from the group consisting of low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and ethylene-methacrylic acid copolymer. In another aspect of the present invention, the substrate layer preferably contains a resin material selected from the group consisting of polyester, polyolefin, and polyamide. In another aspect of the present invention, there is provided a method for producing the laminate, comprising the steps of: There is provided a method for producing a laminate, in which the base material layer and the thermoplastic resin layer are bonded together via the melt-extruded polyolefin resin layer. In another aspect of the present invention, there is provided a packaging product comprising the laminate. In another aspect of the present invention, there is provided a flexible package comprising the laminate. A laminate according to another aspect of the present invention comprises at least a substrate layer, a polyolefin resin layer containing biomass polyolefin, and a thermoplastic resin layer, thereby enabling a reduction in the amount of fossil fuel used compared to conventional methods and reducing the environmental load. Furthermore, the laminate according to another aspect of the present invention is comparable to laminates made of conventional fossil fuel-derived polyolefin resins in terms of physical properties such as mechanical properties, and can therefore replace conventional laminates made of fossil fuel-derived polyolefin resins.

[0087] In yet another aspect of the present invention, A laminate comprising at least a base layer, a polyolefin resin layer, a plastic film having a barrier layer, and a thermoplastic resin layer in this order, the base layer comprises polypropylene, the polyolefin resin layer contains biomass-derived low-density polyethylene, The polyolefin resin layer has a biomass content of 5% or more, the substrate layer constitutes an outermost layer, A laminate is provided in which the thermoplastic resin layer constitutes the innermost layer. In yet another aspect of the present invention, the laminate preferably includes an adhesive resin layer between the plastic film having the barrier layer and the thermoplastic resin layer. In yet another aspect of the present invention, there is provided a method for producing the laminate, comprising the steps of: There is provided a method for producing a laminate, in which the base material layer and the plastic layer having the barrier layer are bonded together via the melt-extruded polyolefin resin layer. In yet another aspect of the present invention, there is provided a packaging product comprising the laminate. In yet another aspect of the present invention, there is provided a flexible package comprising the laminate. In yet another aspect of the present invention, there is provided a packaging bag comprising the laminate. A laminate according to another aspect of the present invention comprises at least a substrate layer, a polyolefin resin layer containing biomass-derived low-density polyethylene, a plastic film having a barrier layer, and a thermoplastic resin layer, thereby enabling a reduction in the amount of fossil fuel used compared to conventional laminates and reducing the environmental load. Furthermore, the laminate according to the present invention is comparable in physical properties such as mechanical properties to laminates comprising a polyolefin resin layer containing conventional fossil-fuel-derived low-density polyethylene, and can therefore replace the conventional polyolefin resin layer containing fossil-fuel-derived low-density polyethylene. [Example]

[0088] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention should not be construed as being limited to the following examples.

[0089] <Measurement conditions> In the following Reference Examples, Reference Comparative Examples, Examples, and Comparative Examples, the biomass degree is the value of the carbon concentration derived from biomass as determined by radiocarbon (C14) measurement.

[0090] The conditions of the extrusion film-forming machine used below were as follows. Screw diameter: 90mm Screw type: Full flight L / D:28 T-die: 11S type straight manifold T-die effective opening length: 560 mm

[0091] [Example 1] <Preparation of Laminate 1> A fossil fuel-derived polyethylene terephthalate film (Toyobo Co., Ltd.: E5100, thickness 12 μm) was prepared as the substrate layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (Mitsui Chemicals Co., Ltd.: A3210 / A3075, polyurethane-based) to form an anchor coating layer. Next, a biomass-derived low-density polyethylene (Braskem Co., Ltd.: SBC818, density: 0.918 g / cm) was laminated onto the anchor coating layer using the sand lamination method. 3 While extruding the polyolefin resin layer (biomass content: 95%, MFR: 8.1 g / 10 min, biomass content: 95%), the corona-treated surface of a fossil fuel-derived linear low-density polyethylene film (TUX FC-S, manufactured by Mitsui Chemicals Tohcello, thickness: 40 μm) was bonded to the polyolefin resin layer (biomass content: 95%, thickness: 15 μm) to obtain Laminate 1, in which a substrate layer, anchor coat layer, polyolefin resin layer, and thermoplastic resin layer were laminated in that order.

[0092] [Example 2] <Preparation of Laminate 2> A fossil fuel-derived polyethylene terephthalate film (Toyobo Co., Ltd.: E5100, thickness: 12 μm) was prepared as the substrate layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (Mitsui Chemicals Co., Ltd.: A3210 / A3075) to form an anchor coating layer. Next, a biomass-derived low-density polyethylene (Braskem Co., Ltd.: SBC818, density: 0.918 g / cm) was laminated onto the anchor coating layer using the sand lamination method. 3 , MFR: 8.1 g / 10 min, biomass content: 95%) and 50 parts by mass of fossil fuel-derived low-density polyethylene (Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g / cm 3While extruding a mixed resin obtained by dry-blending 50 parts by mass of a polyolefin resin layer (biomass content: 48%, MFR: 7.0 g / 10 min, biomass content: 0%) and a fossil fuel-derived linear low-density polyethylene film (TUX FC-S, manufactured by Mitsui Chemicals Tohcello, thickness: 40 μm) was laminated onto the corona-treated surface of the polyolefin resin layer (biomass content: 48%, thickness: 15 μm), thereby obtaining Laminate 2, in which a substrate layer, anchor coat layer, polyolefin resin layer, and thermoplastic resin layer were laminated in that order.

[0093] [Comparative Example 1] <Preparation of Laminate 3> A fossil fuel-derived polyethylene terephthalate film (Toyobo Co., Ltd.: E5100, thickness: 12 μm) was prepared as the substrate layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (Mitsui Chemicals Co., Ltd.: A3210 / A3075) to form an anchor coat layer. Next, a fossil fuel-derived low-density polyethylene (Japan Polyethylene Co., Ltd.: LC600A, density: 0.918 g / cm) was laminated onto the anchor coat layer using the sand lamination method. 3 While extruding the adhesive resin layer (biomass content: 0%, MFR: 7.0 g / 10 min, biomass content: 0%), the corona-treated surface of a fossil fuel-derived linear low-density polyethylene film (TUX FC-S, manufactured by Mitsui Chemicals Tohcello, thickness: 40 μm) was bonded to the adhesive resin layer (biomass content: 0%, thickness: 15 μm), thereby obtaining laminate 3, in which a substrate layer, anchor coat layer, adhesive resin layer, and thermoplastic resin layer were laminated in that order.

[0094] [Example 3] <Preparation of Laminate 4> A fossil fuel-derived polyethylene terephthalate film (Toyobo Co., Ltd.: E5100, thickness: 12 μm) was prepared as the substrate layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (Mitsui Chemicals Co., Ltd.: A3210 / A3075) to form an anchor coating layer. Next, a biomass-derived low-density polyethylene (Braskem Co., Ltd.: SBC818, density: 0.918 g / cm) was laminated onto the anchor coating layer using the sand lamination method. 3While extruding the polyolefin resin layer (biomass content: 95%, MFR: 8.1 g / 10 min, biomass content: 95%), an aluminum foil (1N30, 7 μm thick, manufactured by Toyo Aluminum Co., Ltd.) was bonded to the polyolefin resin layer (biomass content: 95%, thickness: 15 μm) via the polyolefin resin layer. Subsequently, a two-component curing anchor coating agent (A3210 / A3075, manufactured by Mitsui Chemicals, Inc.) was coated onto the aluminum foil to form an anchor coating layer. Subsequently, a fossil fuel-derived low-density polyethylene (LC600A, manufactured by Japan Polyethylene Co., Ltd., density: 0.918 g / cm ) was applied onto the anchor coating layer. 3 , MFR: 7.0 g / 10 min, biomass content: 0%) was melt extrusion laminated at a resin temperature of 320°C and a line speed of 100 m / min to form a thermoplastic resin layer (biomass content: 0%, thickness: 30 μm), thereby obtaining Laminate 4 in which a substrate layer, anchor coat layer, polyolefin resin layer, barrier layer, anchor coat layer, and thermoplastic resin layer were laminated in this order.

[0095] [Example 4] <Preparation of Laminate 5> A fossil fuel-derived polyethylene terephthalate film (Toyobo Co., Ltd.: E5100, thickness: 12 μm) was prepared as the substrate layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (Mitsui Chemicals Co., Ltd.: A3210 / A3075) to form an anchor coating layer. Next, a biomass-derived low-density polyethylene (Braskem Co., Ltd.: SBC818, density: 0.918 g / cm) was laminated onto the anchor coating layer using the sand lamination method. 3 , MFR: 8.1 g / 10 min, biomass content: 95%) and 50 parts by mass of fossil fuel-derived low-density polyethylene (Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g / cm 3While extruding a mixed resin obtained by dry-blending 50 parts by mass of a polyolefin resin layer (biomass content: 48%, thickness: 15 μm) with 100 parts by mass of ethylenediaminetetraacetic acid (Ethylenediaminetetraacetic acid), MFR: 7.0 g / 10 min, biomass content: 0%), an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness: 7 μm) was bonded to the polyolefin resin layer (biomass content: 48%, thickness: 15 μm). Next, a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210 / A3075) was coated onto the aluminum foil to form an anchor coat layer. Next, a fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g / cm) was applied onto the anchor coat layer. 3 The resulting mixture was melt-extruded and laminated at a resin temperature of 320°C and a line speed of 100 m / min (MFR: 7.0 g / 10 min, biomass content: 0%) to form a thermoplastic resin layer (biomass content: 0%, thickness: 30 μm), thereby obtaining Laminate 5 in which a substrate layer, anchor coat layer, polyolefin resin layer, barrier layer, anchor coat layer, and thermoplastic resin layer were laminated in this order.

[0096] Comparative Example 2 <Production of Laminate 6> A fossil fuel-derived polyethylene terephthalate film (Toyobo Co., Ltd.: E5100, thickness: 12 μm) was prepared as the substrate layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (Mitsui Chemicals Co., Ltd.: A3210 / A3075) to form an anchor coat layer. Next, a fossil fuel-derived low-density polyethylene (Japan Polyethylene Co., Ltd.: LC600A, density: 0.918 g / cm) was laminated onto the anchor coat layer using the sand lamination method. 3 While extruding the adhesive resin layer (biomass content: 0%, MFR: 7.0 g / 10 min, biomass content: 0%), an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness: 7 μm) was bonded via the adhesive resin layer (biomass content: 0%, thickness: 15 μm). Next, a two-component curing anchor coating agent (manufactured by Mitsui Chemicals, Inc.: A3210 / A3075) was coated on the aluminum foil to form an anchor coat layer. Next, a fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g / cm) was applied on the anchor coat layer. 3, MFR: 7.0 g / 10 min, biomass content: 0%) was melt extrusion laminated at a resin temperature of 320°C and a line speed of 100 m / min to form a thermoplastic resin layer (biomass content: 0%, thickness: 30 μm), thereby obtaining Laminate 6 in which a substrate layer, anchor coat layer, adhesive resin layer, barrier layer, anchor coat layer, and thermoplastic resin layer were laminated in this order.

[0097] [Example 5] <Production of Laminate 7> As the aluminum vapor-deposited polyethylene terephthalate film 1, a fossil fuel-derived polyethylene terephthalate film (manufactured by Toray Advanced Film Co., Ltd., 1310, thickness 12 μm) on which an aluminum vapor-deposited film was formed was prepared.

[0098] A biaxially oriented polypropylene film (Toyobo Co., Ltd.: P2161, thickness 20 μm) was prepared as a substrate layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (Mitsui Chemicals Co., Ltd.: A3210 / A3075) to form an anchor coating layer. Next, a biomass-derived low-density polyethylene (Braskem Co., Ltd.: SBC818, density: 0.918 g / cm) was laminated onto the anchor coating layer using the sand lamination method. 3 While extruding a polyolefin resin layer (biomass content: 95%, MFR: 8.1 g / 10 min, biomass content: 95%), the aluminum vapor-deposited surface of the aluminum vapor-deposited polyethylene terephthalate film 1 was bonded to the aluminum vapor-deposited surface of the aluminum vapor-deposited polyethylene terephthalate film 1 via this polyolefin resin layer (biomass content: 95%, thickness: 15 μm). Next, a two-component curing anchor coating agent (A3210 / A3075, manufactured by Mitsui Chemicals, Inc.) was coated on the polyethylene terephthalate film surface of the aluminum vapor-deposited polyethylene terephthalate film 1 to form an anchor coat layer. After that, a biomass-derived low-density polyethylene (SBC818, manufactured by Braskem, density: 0.918 g / cm) was laminated on the anchor coat layer using a sand lamination method. 3While extruding the plastic film (biomass content: 95%, MFR: 8.1 g / 10 min, biomass content: 95%), the corona-treated surface of a fossil fuel-derived linear low-density polyethylene film (TUX FC-S, manufactured by Mitsui Chemicals Tohcello, thickness: 40 μm) was bonded to the adhesive resin layer (biomass content: 95%, thickness: 15 μm) to obtain Laminate 7, which was laminated in order with a substrate layer, anchor coat layer, polyolefin resin layer, barrier layer, plastic film, anchor coat layer, adhesive resin layer, and thermoplastic resin layer.

[0099] [Example 6] <Production of Laminate 8> A biaxially oriented polypropylene film (Toyobo Co., Ltd.: P2161, thickness 20 μm) was prepared as a substrate layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (Mitsui Chemicals Co., Ltd.: A3210 / A3075) to form an anchor coating layer. Next, a biomass-derived low-density polyethylene (Braskem Co., Ltd.: SBC818, density: 0.918 g / cm) was laminated onto the anchor coating layer using the sand lamination method. 3 , MFR: 8.1 g / 10 min, biomass content: 95%) and 50 parts by mass of fossil fuel-derived low-density polyethylene (Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g / cm 3 While extruding a mixed resin obtained by dry-blending 50 parts by mass of a polyolefin resin layer (biomass content: 48%, thickness: 15 μm) with 50 parts by mass of aluminium-deposited polyethylene terephthalate film 1, the polyolefin resin layer (biomass content: 48%, thickness: 15 μm) was laminated to the aluminium-deposited surface of the aluminium-deposited polyethylene terephthalate film 1. Subsequently, a two-component curing anchor coating agent (A3210 / A3075 manufactured by Mitsui Chemicals, Inc.) was coated on the polyethylene terephthalate film surface of the aluminium-deposited polyethylene terephthalate film 1 to form an anchor coat layer. Then, a biomass-derived low-density polyethylene (SBC818 manufactured by Braskem, density: 0.918 g / cm) was laminated on the anchor coat layer using a sand lamination method. 3 , MFR: 8.1 g / 10 min, biomass content: 95%) and 50 parts by mass of fossil fuel-derived low-density polyethylene (Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g / cm3 While extruding a mixed resin prepared by dry-blending 50 parts by mass of a fossil fuel-derived linear low-density polyethylene film (TUX FC-S, manufactured by Mitsui Chemicals Tohcello, thickness 40 μm) with 50 parts by mass of a polyethylene terephthalate resin (MFR: 7.0 g / 10 min, biomass content: 0%), the adhesive resin layer (biomass content: 48%, thickness: 15 μm) was bonded to the corona-treated surface of the film, and laminate 8 was obtained, in which the substrate layer, anchor coat layer, polyolefin resin layer, barrier layer, plastic film, anchor coat layer, adhesive resin layer, and thermoplastic resin layer were laminated in that order.

[0100] Comparative Example 3 <Production of Laminate 9> A biaxially oriented polypropylene film (Toyobo Co., Ltd.: P2161, thickness 20 μm) was prepared as a substrate layer, and its corona-treated surface was coated with a two-component curing anchor coating agent (Mitsui Chemicals Co., Ltd.: A3210 / A3075) to form an anchor coating layer. Next, a fossil fuel-derived low-density polyethylene (Japan Polyethylene Co., Ltd.: LC600A, density: 0.918 g / cm) was laminated onto the anchor coating layer using the sand lamination method. 3 While extruding a 100% polyester resin (MFR: 7.0 g / 10 min, biomass content: 0%), the aluminum vapor-deposited surface of the aluminum vapor-deposited polyethylene terephthalate film 1 was bonded via this adhesive resin layer (biomass content: 0%, thickness: 15 μm). Next, a two-component curing anchor coating agent (A3210 / A3075 manufactured by Mitsui Chemicals, Inc.) was coated on the polyethylene terephthalate film surface of the aluminum vapor-deposited polyethylene terephthalate film 1 to form an anchor coat layer. After that, a fossil fuel-derived low-density polyethylene (LC600A manufactured by Japan Polyethylene Co., Ltd., density: 0.918 g / cm) was laminated on the anchor coat layer using a sand lamination method. 3While extruding the plastic film (biomass content: 0%, MFR: 7.0 g / 10 min, biomass content: 0%), the corona-treated surface of a fossil fuel-derived linear low-density polyethylene film (TUX FC-S, manufactured by Mitsui Chemicals Tohcello, thickness: 40 μm) was bonded to the adhesive resin layer (biomass content: 0%, thickness: 15 μm) to obtain Laminate 9, which was laminated in order with a substrate layer, anchor coat layer, adhesive resin layer, barrier layer, plastic film, anchor coat layer, adhesive resin layer, and thermoplastic resin layer.

[0101] [Example 7] <Production of Laminate 10> A biaxially stretched polyester film 1 (biomass content: 20%, Toyobo Co., Ltd., DE024, thickness: 12 μm) was prepared as the substrate layer, which was produced using fossil fuel-derived terephthalic acid and biomass-derived ethylene glycol (biomass polyester). Next, a two-component curing anchor coating agent (Mitsui Chemicals, Inc., A3210 / A3075, polyurethane-based) was coated on the corona-treated surface of the polyester film 1 to form an anchor coating layer. Subsequently, a biomass-derived low-density polyethylene (Braskem, SBC818, density: 0.918 g / cm) was laminated onto the anchor coating layer using the sand lamination method. 3 While extruding the polyolefin resin layer (biomass content: 95%, MFR: 8.1 g / 10 min, biomass content: 95%), the corona-treated surface of a fossil fuel-derived linear low-density polyethylene film (TUX FC-S, manufactured by Mitsui Chemicals Tohcello, thickness: 40 μm) was bonded to the polyolefin resin layer (biomass content: 95%, thickness: 15 μm) to obtain a laminate 10 in which a substrate layer, anchor coat layer, polyolefin resin layer, and thermoplastic resin layer were laminated in that order.

[0102] [Example 8] <Production of laminate 11> A biaxially stretched polyester film 1 (biomass content: 20%, Toyobo Co., Ltd., DE024, thickness: 12 μm) was prepared as the substrate layer, which was produced using fossil fuel-derived terephthalic acid and biomass-derived ethylene glycol (biomass polyester). Next, a two-component curing anchor coating agent (Mitsui Chemicals, Inc.: A3210 / A3075) was coated on the corona-treated surface of the polyester film 1 to form an anchor coat layer. Subsequently, a biomass-derived low-density polyethylene (Braskem, SBC818, density: 0.918 g / cm) was laminated onto the anchor coat layer using the sand lamination method. 3 , MFR: 8.1 g / 10 min, biomass content: 95%) and 50 parts by mass of fossil fuel-derived low-density polyethylene (Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g / cm 3 While extruding a mixed resin obtained by dry-blending 50 parts by mass of a polyolefin resin layer (biomass content: 48%, MFR: 7.0 g / 10 min, biomass content: 0%) and a fossil fuel-derived linear low-density polyethylene film (TUX FC-S, manufactured by Mitsui Chemicals Tohcello, thickness: 40 μm) was laminated onto the corona-treated surface of the polyolefin resin layer (biomass content: 48%, thickness: 15 μm) to obtain a laminate 11 in which a substrate layer, an anchor coat layer, a polyolefin resin layer, and a thermoplastic resin layer were laminated in that order.

[0103] [Manufacturing Examples 1 to 11] <Making packaging bags> Standing pouches were formed by combining the body member laminate (side sheet) and bottom member laminate (bottom sheet) shown in Table 1 below, using the following process: Specifically, two side sheets were stacked facing each other with the thermoplastic resin layer serving as the innermost layer, and a bottom sheet was inserted between the two side sheets, and the side sheet and bottom sheet were heat-sealed to produce standing pouches 1 to 11 having the configuration shown in Fig. 4.

[0104] (Leakage test) The standing pouches 1 to 11 prepared above were filled with a test liquid (Ageless Seal Check (manufactured by Mitsubishi Gas Chemical Company, Inc.)) and stored at room temperature and humidity for 1 hour, after which leakage was visually evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1. (Evaluation criteria) ◯: There was no liquid leakage from the heat-sealed portion, and the performance as a standing pouch was good. ×: There was liquid leakage from the heat-sealed portion, and the performance as a standing pouch was poor.

[0105] [Table 1] [Explanation of symbols]

[0106] 10, 20, 30 laminates 11 Base material layer 12 Polyolefin resin layer 13 Thermoplastic resin layer 14 Barrier Layer 15 Plastic Film 16 Adhesive layer 40 standing pouches 41 Torso 42 Bottom 50 Laminated Tube 51 Head 52 Cylindrical body 53 Shoulder 54 Spout part

Claims

1. A method for producing a laminate including at least a substrate layer, a polyolefin resin layer, a barrier layer, a plastic film, an anchor coat layer, and a thermoplastic resin layer in this order, the method comprising: the substrate layer is a polyethylene film or a polyamide film, the polyolefin resin layer contains biomass-derived low-density polyethylene, The polyolefin resin layer has a biomass content of 5% or more, the polyolefin resin layer has a thickness of 15 μm or more and 100 μm or less, the barrier layer is made of a vapor-deposited film of an inorganic substance or an inorganic oxide, the anchor coat layer is made of a vinyl-modified resin, an epoxy resin, a urethane resin, or a polyester resin, the thermoplastic resin constituting the thermoplastic resin layer is only low-density polyethylene or only linear low-density polyethylene, the substrate layer constitutes an outermost layer, the thermoplastic resin layer constitutes an innermost layer, A method for producing a laminate, comprising laminating the barrier layer via the melt-extruded polyolefin resin layer by sand lamination.

2. A method for producing a packaging product using the method for producing a laminate according to claim 1.

3. A method for producing flexible packaging using the method for producing a laminate according to claim 1.

4. A method for producing a packaging bag using the method for producing a laminate according to claim 1.

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