Packaging materials and products

Abstract

To provide a packaging material with an improved degree of biomass.SOLUTION: A packaging material at least has a surface protective layer, a printed layer, an outer thermoplastic resin layer, a paper substrate layer and an inner thermoplastic resin layer, which are laminated in this order. The outer thermoplastic resin layer has polyethylene. The surface protective layer has biomass-derived nitrocellulose.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to packaging materials that include biomass-derived components and packaged products that include the packaging materials. [Background technology]

[0002] Conventionally, various packaging materials have been developed and proposed as packaging materials for constituting packaged products in which various items such as food and beverages, medicines, chemicals, cosmetics, sanitary products, daily necessities, etc. are filled and packaged. The packaging materials are composed of a laminate including at least a base layer and a printing layer for forming a printed pattern.

[0003] In recent years, with the growing demand for the creation of a recycling-oriented society, there is a desire to move away from fossil fuels in the field of laminates that make up packaging materials, just as in the field of energy, and the use of biomass has attracted attention. Biomass is an organic compound that is photosynthesized from carbon dioxide and water, and by using it, it is converted back into carbon dioxide and water, making it a so-called carbon-neutral renewable energy. Recently, the practical application of biomass plastics made from these biomass raw materials has progressed rapidly, and attempts are being made to produce various resins from biomass raw materials.

[0004] As a biomass-derived resin, polylactic acid (PLA), which is produced via lactic acid fermentation, was the first to be commercially produced, but since its performance as a plastic differs significantly from current general-purpose plastics, including its biodegradability, 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 being held on the energy consumption during PLA production and its equivalence when replacing general-purpose plastics.

[0005] Here, various types of general-purpose plastics are used, such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, and polyester. In particular, polyethylene is molded into films, sheets, bottles, and the like, and is used in various applications such as packaging materials, and is used in large quantities around the world. Therefore, using conventional fossil fuel-derived polyethylene places a large burden on the environment. Therefore, it is desired to use biomass-derived raw materials in the production of polyethylene to reduce the amount of fossil fuel used. 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 Patent Document 1). In the field of soft packaging such as pouches, it has been proposed to apply such biomass-derived raw materials to packaging materials (see Patent Document 2). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Special Publication No. 2011-506628 [Patent Document 2] JP 2018-51788 A Summary of the Invention [Problem to be solved by the invention]

[0007] In the field of packaging materials that contain paper base layers, it is also desirable to use raw materials derived from biomass and reduce the amount of fossil fuel used.

[0008] The present invention has been made in consideration of these points, and an object of the present invention is to provide a packaging material including a paper base layer with an increased biomass content. [Means for solving the problem]

[0009] The present invention is a packaging material having at least a surface protective layer, a printed layer, an outer thermoplastic resin layer, a paper base layer, and an inner thermoplastic resin layer laminated in that order, wherein the outer thermoplastic resin layer contains polyethylene, and the surface protective layer contains biomass-derived nitrocellulose.

[0010] In the packaging material according to the present invention, the surface protective layer may further contain a cured product of a polyol and an isocyanate compound.

[0011] In the packaging material according to the present invention, at least one of the polyol and the isocyanate compound may contain a biomass-derived component.

[0012] The packaging material according to the present invention may further comprise a barrier layer between the paper base layer and the inner thermoplastic resin layer.

[0013] In the packaging material according to the present invention, the barrier layer may be a metal foil or a vapor-deposited film.

[0014] The present invention is a packaging product comprising the packaging material described above. Effect of the Invention

[0015] According to the present invention, it is possible to increase the biomass content of a packaging material that includes a paper base layer. [Brief description of the drawings]

[0016] [Figure 1] FIG. 1 is a cross-sectional view showing an example of a packaging material of the present invention. [Diagram 2] FIG. 1 is a cross-sectional view showing an example of a packaging material of the present invention. [Diagram 3] FIG. 1 is a cross-sectional view showing an example of a packaging material of the present invention. [Figure 4] FIG. 1 is a cross-sectional view showing an example of a packaging material of the present invention. [Diagram 5] FIG. 1 is a cross-sectional view showing an example of a packaging material of the present invention. [Figure 6]FIG. 1 is a cross-sectional view showing an example of a packaging material of the present invention. [Figure 7] FIG. 1 is a cross-sectional view showing an example of a packaging material of the present invention. [Figure 8] FIG. 1 is a cross-sectional view showing an example of a packaging material of the present invention. [Figure 9] FIG. 1 is a cross-sectional view showing an example of a packaging material of the present invention. [Figure 10] FIG. 1 is a cross-sectional view showing an example of a packaging material of the present invention. [Figure 11] FIG. 1 is a cross-sectional view showing an example of a packaging material of the present invention. [Figure 12] FIG. 1 is a diagram showing an example of a liquid paper container equipped with the packaging material of the present invention. [Figure 13] FIG. 2 is a diagram showing the layer structure of the packaging materials of Examples 1A to 19B. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The laminate constituting the packaging material according to the present invention comprises at least a surface protective layer, a printed layer, an outer thermoplastic resin layer, a paper base layer and an inner thermoplastic resin layer, which are laminated in this order from the outer surface side to the inner surface side. The inner surface is the surface located on the side of the contents contained in a packaging product formed from the packaging material. The outer surface is the surface located opposite the inner surface. In this application, the term "in this order" in descriptions such as "provided in this order" and "laminated in this order" refers to the order in the direction from the outer surface side to the inner surface side, unless otherwise specified.

[0018] In the present invention, the biomass ratio, which will be described below, of the entire laminate constituting the packaging material is preferably 40% or more, more preferably 80% or more and less than 100%. If the biomass ratio is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

[0019] 1 is a cross-sectional view showing an example of a packaging material 20 of the present invention. The packaging material 20 includes, in this order, a surface protective layer 11, a printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, and an inner thermoplastic resin layer 15. The surface protective layer 11 constitutes an outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes an inner surface 20x of the packaging material 20.

[0020] 2 is a cross-sectional view showing another example of a packaging material 20 of the present invention. The packaging material 20 includes, in this order, a surface protective layer 11, a printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, a barrier resin layer 21, an intermediate thermoplastic resin layer 22, and an inner thermoplastic resin layer 15. The surface protective layer 11 constitutes an outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes an inner surface 20x of the packaging material 20.

[0021] 3 is a cross-sectional view showing another example of a packaging material 20 of the present invention. The packaging material 20 includes, in this order, a surface protective layer 11, a printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, a polyolefin resin layer 23, an intermediate thermoplastic resin layer 22, a barrier resin layer 21, an intermediate thermoplastic resin layer 24, and an inner thermoplastic resin layer 15. The surface protective layer 11 constitutes an outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes an inner surface 20x of the packaging material 20.

[0022] 4 is a cross-sectional view showing another example of a packaging material 20 of the present invention. The packaging material 20 includes, in this order, a surface protective layer 11, a printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, a plastic film layer 28, an anchor coat layer 29, and an inner thermoplastic resin layer 15. The surface protective layer 11 constitutes an outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes an inner surface 20x of the packaging material 20.

[0023] 5 is a cross-sectional view showing another example of a packaging material 20 of the present invention. The packaging material 20 includes, in this order, a surface protective layer 11, a printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, a plastic film layer 28, an anchor coat layer 29, an adhesive resin layer 30, and an inner thermoplastic resin layer 15. The surface protective layer 11 constitutes an outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes an inner surface 20x of the packaging material 20.

[0024] 6 is a cross-sectional view showing another example of a packaging material 20 of the present invention. The packaging material 20 includes, in this order, a surface protective layer 11, a printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, a plastic film layer 28, an adhesive layer 31, and an inner thermoplastic resin layer 15. The surface protective layer 11 constitutes an outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes an inner surface 20x of the packaging material 20.

[0025] 7 is a cross-sectional view showing another example of a packaging material 20 of the present invention. The packaging material 20 includes, in this order, a surface protective layer 11, a printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, and an inner thermoplastic resin layer 15. The surface protective layer 11 constitutes an outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes an inner surface 20x of the packaging material 20.

[0026] 8 is a cross-sectional view showing another example of a packaging material 20 of the present invention. The packaging material 20 includes, in this order, a surface protective layer 11, a printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive resin layer 30, and an inner thermoplastic resin layer 15. The surface protective layer 11 constitutes an outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes an inner surface 20x of the packaging material 20.

[0027] 9 is a cross-sectional view showing another example of a packaging material 20 of the present invention. The packaging material 20 includes, in this order, a surface protective layer 11, a printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, and an inner thermoplastic resin layer 15. The surface protective layer 11 constitutes an outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes an inner surface 20x of the packaging material 20.

[0028] 10 is a cross-sectional view showing another example of a packaging material 20 of the present invention. The packaging material 20 includes, in this order, a surface protective layer 11, a printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a plastic film layer 28, an adhesive layer 27, a barrier layer 26, an intermediate thermoplastic resin layer 22, and an inner thermoplastic resin layer 15. The surface protective layer 11 constitutes an outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes an inner surface 20x of the packaging material 20.

[0029] 11 is a cross-sectional view showing another example of a packaging material 20 of the present invention. The packaging material 20 includes, in this order, a surface protective layer 11, a printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, a polyolefin resin layer 23, an adhesive resin layer 25, a barrier layer 26, an intermediate thermoplastic resin layer 22, and an inner thermoplastic resin layer 15. The surface protective layer 11 constitutes an outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes an inner surface 20x of the packaging material 20.

[0030] It is also possible to appropriately combine a plurality of layer structures of the packaging material 20 shown in the above-mentioned Figs. 1 to 11.

[0031] Each layer constituting the packaging material 20 will now be described.

[0032] (Paper base layer) The paper base layer 14 is a layer containing paper. The paper base layer 14 has a thickness of 100 g / m 2 More than 700g / m 2 Less than 150 g / m 2 More than 600g / m 2 Less than 200 g / m2 More than 500g / m 2 The paper base layer 14 may be any white paperboard, but from the standpoint of safety, it is preferable to use ivory paper, milk carton base paper, cup base paper, or the like, which uses natural pulp.

[0033] The paperboard may use neutral rosin, alkyl ketene dimer, or alkenyl succinic anhydride as a sizing agent, and cationic polyacrylamide, cationic starch, or the like as a fixing agent. It is also possible to use aluminum sulfate to make the paperboard in a neutral range of pH 6 to 9. In addition to the above sizing agents, the paperboard may also contain various papermaking fillers, retention aids, dry strength agents, wet strength agents, binders, dispersants, flocculants, plasticizers, and adhesives as appropriate, in addition to fixing agents.

[0034] (Printing layer) The printed layer 12 is a layer formed by printing for decoration, display of contents, display of expiration date, display of manufacturer, seller, etc., and for imparting aesthetics. The printed layer 12 includes a pattern layer that forms any desired pattern, such as a picture, photograph, letter, number, figure, symbol, pattern, etc. The printed layer may further include a background color layer formed by printing to make the pattern of the pattern layer stand out.

[0035] The printed layer 12 is formed by gravure printing. The printed layer 12 contains a colorant and a binder resin. The ink composition for forming the printed layer 12 contains a solvent suitable for gravure printing in addition to the colorant and the binder resin.

[0036] [Coloring Agent] The colorant is not particularly limited, and any conventionally known pigment or dye can be used.

[0037] [Binder resin] The binder resin includes nitrocellulose. Preferably, the binder resin includes a biomass-derived component. For example, the binder resin includes biomass-derived nitrocellulose.

[0038] <Nitrocellulose> Nitrocellulose is a nitro-substituted cellulose resin in which some of the hydroxyl groups in the cellulose skeleton are nitrated. The cellulose skeleton of the nitrocellulose resin is a biomass material. As the nitrocellulose, any ordinary nitrocellulose can be used without any problems, but it is particularly preferable to use nitrocellulose in which an average of 1.3 to 2.7 nitro groups are substituted per glucose unit constituting the cellulose skeleton.

[0039] Nitrocellulose is classified into two types according to molecular weight: L type and H type. From the viewpoint of solubility in organic solvents, it is preferable to use L type.

[0040] The printed layer 12 preferably has a biomass degree of 5% or more, more preferably 5% to 50%, and even more preferably 10% to 50%. If the biomass degree is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced. The weight of the printed layer 12 after drying is preferably 0.1 g / m 2 More than 10g / m 2 Less than 1 g / m, more preferably 2 More than 5g / m 2 More preferably, 1 g / m or less 2 More than 3g / m 2 The thickness of the printed layer 12 is preferably 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, and even more preferably 1 μm or more and 3 μm or less. Note that a plurality of printed layers 12 having such weights and thicknesses may be provided.

[0041] The "biomass content" may be expressed as a value obtained by measuring the amount of carbon derived from biomass using radiocarbon (C14) measurement, or may be expressed as a weight ratio of components derived from biomass.

[0042] When the value measured for the amount of carbon derived from biomass by radiocarbon (C14) measurement is indicated as the "biomass degree," the "biomass degree" can be calculated as follows. That is, atmospheric carbon dioxide contains a certain proportion of C14 (105.5 pMC), and it is known that the C14 content of 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 very little C14. Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of C14 contained in the total carbon atoms in the biomass-derived raw material. The C14 content in the printing layer 12 is expressed as P C14 The content of carbon derived from biomass, P bio It can be calculated as follows: P bio (%)=P C14 / 105.5×100

[0043] Furthermore, when expressing the "biomass degree" as the weight ratio of biomass-derived components, the "biomass degree" can be calculated as follows. For example, in the case of nitrocellulose, the number of hydroxyl groups contained in each glucose unit (formula weight = 172) constituting the cellulose skeleton, which is the starting material, is three, and one to three of these hydroxyl groups can be converted to nitrate esters (hydrogen is replaced by a nitro group (non-biomass material, formula weight = 46)). If the original cellulose skeleton is made up of 100% biomass material by weight, and the number of nitro groups replaced per glucose unit is n on average, then the proportion (weight %) of biomass material in the entire nitrocellulose molecule is (172-n) This can be calculated by ×100 / (172-n+46n). The proportion of biomass material in the entire nitrocellulose molecule is approximately 78.8% by weight when each glucose unit that constitutes the cellulose backbone is substituted with an average of one nitro group, approximately 64.9% by weight when each glucose unit is substituted with two nitro groups, and approximately 55.0% by weight when each glucose unit is substituted with three nitro groups (values ​​calculated using the above formula).

[0044] Hereinafter, unless otherwise specified, the term "biomass content" refers to the weight ratio of biomass-derived components.

[0045] The binder resin of the printed layer 12 may further contain a cured product of a polyol and an isocyanate compound. In this case, preferably, at least one of the polyol as the base material and the isocyanate compound as the curing agent is formed using a cured product containing a biomass-derived component. This can increase the biomass content of the packaging material 20. As the polyol, polyester polyol, which is a reaction product of a polyfunctional alcohol and a polyfunctional carboxylic acid, polyether polyol, which is a reaction product of a polyfunctional alcohol and a polyfunctional isocyanate, or polycarbonate polyol, which is a reaction product of a polyfunctional alcohol and a carbonate, can be used.

[0046] <Polyester polyol> When the polyester polyol contains a biomass-derived component, at least one of the polyfunctional alcohol and the polyfunctional carboxylic acid contains a biomass-derived component. The following are examples of polyester polyols containing a biomass-derived component. Reaction product of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid Reaction products of polyfunctional alcohols derived from fossil fuels and polyfunctional carboxylic acids derived from biomass Reaction products of biomass-derived polyfunctional alcohols and fossil fuel-derived polyfunctional carboxylic acids

[0047] As the biomass-derived polyfunctional alcohol, an aliphatic polyfunctional alcohol obtained from a plant raw material such as corn, sugarcane, cassava, or sago palm can be used. As the biomass-derived aliphatic polyfunctional alcohol, for example, polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butylene glycol (BG), hexamethylene glycol, etc., which are obtained from a plant raw material by the following method, can be used, and any of them can be used. These may be used alone or in combination.

[0048] Biomass-derived polypropylene glycol is produced by a fermentation method in which glucose is obtained by decomposing plant raw materials, via 3-hydroxypropylaldehyde (HPA) from glycerol. Compared with polypropylene glycol produced by the EO production method, polypropylene glycol produced by a biomethod such as the fermentation method is preferable in terms of safety, since useful by-products such as lactic acid can be obtained, and the production cost can be kept low. Biomass-derived butylene glycol can be produced by producing glycol from plant raw materials, fermenting the resulting succinic acid, and then hydrogenating the resulting succinic acid. Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

[0049] As the polyfunctional alcohol derived from fossil fuel, a compound having two or more, preferably two to eight hydroxyl groups in one molecule can be used. Specifically, as the polyfunctional alcohol derived from fossil fuel, there is no particular limitation and a conventionally known substance can be used. For example, polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butylene glycol (BG), hexamethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, 1,9-nonanediol, 3-methyl-1,5-pentanediol, polyether polyol, polycarbonate polyol, polyolefin polyol, acrylic polyol, etc. can be used. These may be used alone or in combination of two or more.

[0050] As the biomass-derived polyfunctional carboxylic acid, aliphatic polyfunctional carboxylic acids obtained from plant raw materials such as plant-derived oils that can be reproduced, such as soybean oil, linseed oil, tung oil, coconut oil, palm oil, castor oil, and the like, and regenerated oils obtained by recycling waste edible oils mainly composed of these can be used. As the biomass-derived aliphatic polyfunctional carboxylic acid, for example, sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, dimer acid, and the like can be mentioned. For example, sebacic acid is produced by subjecting ricinoleic acid obtained from castor oil to alkaline pyrolysis, with heptyl alcohol being a by-product. In the present invention, it is particularly preferable to use succinic acid derived from biomass or sebacic acid derived from biomass. These may be used alone or in combination of two or more kinds.

[0051] As the polyfunctional carboxylic acid derived from fossil fuel, an aliphatic polyfunctional carboxylic acid or an aromatic polyfunctional carboxylic acid can be used. As the aliphatic polyfunctional carboxylic acid derived from fossil fuel, there is no particular limitation and a conventionally known substance can be used, for example, adipic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, and dimer acid, as well as ester compounds thereof. As the aromatic polyfunctional carboxylic acid derived from fossil fuel, there is no particular limitation and a conventionally known substance can be used, for example, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid, as well as ester compounds thereof. These may be used alone or in combination of two or more.

[0052] <Polyether polyol> When the polyether polyol contains a biomass-derived component, at least one of the polyfunctional alcohol and the polyfunctional isocyanate contains a biomass-derived component. Examples of polyether polyols containing a biomass-derived component include the following. Reaction product of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional isocyanate Reaction product of polyfunctional alcohol derived from fossil fuels and polyfunctional isocyanate derived from biomass Reaction product of biomass-derived polyfunctional alcohol and fossil fuel-derived polyfunctional isocyanate

[0053] As the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol described above in relation to the polyester polyol can be used.

[0054] As the biomass-derived polyfunctional isocyanate, a product obtained by converting a plant-derived divalent carboxylic acid into a terminal amino group by acid amidation and reduction, and then reacting with phosgene to convert the amino group into an isocyanate group can be used. The biomass-derived polyfunctional isocyanate is, for example, a biomass-derived diisocyanate. Examples of the biomass-derived diisocyanate include dimer acid diisocyanate (DDI), octamethylene diisocyanate, and decamethylene diisocyanate. In addition, a plant-derived diisocyanate can also be obtained by using a plant-derived amino acid as a raw material and converting its amino group into an isocyanate group. For example, lysine diisocyanate (LDI) can be obtained by methyl esterifying the carboxyl group of lysine, and then converting the amino group into an isocyanate group. In addition, 1,5-pentamethylene diisocyanate can be obtained by decarboxylating the carboxyl group of lysine, and then converting the amino group into an isocyanate group.

[0055] Other methods for synthesizing 1,5-pentamethylene diisocyanate include the phosgenation method and the carbamate method. More specifically, the phosgenation method is a method in which 1,5-pentamethylene diamine or a salt thereof is directly reacted with phosgene, or a method in which pentamethylene diamine hydrochloride is suspended in an inert solvent and reacted with phosgene to synthesize 1,5-pentamethylene diisocyanate. In addition, the carbamate method is a method in which 1,5-pentamethylene diamine or a salt thereof is first carbamateized to generate pentamethylene dicarbamate (PDC), which is then thermally decomposed to synthesize 1,5-pentamethylene diisocyanate. In the present invention, a polyisocyanate that is preferably used is 1,5-pentamethylene diisocyanate-based polyisocyanate (trade name: STABIO (registered trademark)) manufactured by Mitsui Chemicals, Inc.

[0056] The fossil fuel-derived polyfunctional isocyanate is not particularly limited, and conventionally known substances can be used. For example, aromatic diisocyanates such as toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4'-methylenebis(phenylene isocyanate) (MDI), jurylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4'-diisocyanate dibenzyl can be mentioned. Other examples include aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; and alicyclic diisocyanates such as 1,4-cyclohexylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI. These may be used alone or in combination of two or more.

[0057] <Polycarbonate polyol> When the polycarbonate polyol contains a biomass-derived component, the polycarbonate polyol can be a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate derived from a fossil fuel. Examples of the carbonate include dimethyl carbonate, dipropyl carbonate, diethyl carbonate, diethylene carbonate, dibutyl carbonate, ethylene carbonate, and diphenyl carbonate. These can be used alone or in combination of two or more.

[0058] As the biomass-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol explained in the above-mentioned polyester polyol can be used.

[0059] <Isocyanate compounds> As the isocyanate compound containing a biomass-derived component, the biomass-derived polyfunctional isocyanate described in the polyether polyol can be used.

[0060] (Surface protective layer) The surface protective layer 11 is a layer that protects the printed layer 12. The surface protective layer 11 may be provided so as to be in contact with the printed layer 12. The surface protective layer 11 is formed by applying a paint containing solids and a solvent. The solids of the paint may be the same material as the binder resin of the printed layer 12. Therefore, the configuration of the surface protective layer 11 is the same as the configuration of the printed layer 12, except that it does not contain a colorant.

[0061] The surface protective layer 11 also contains biomass-derived nitrocellulose. As the biomass-derived nitrocellulose, the biomass-derived nitrocellulose described in relation to the printed layer 12 can be used.

[0062] The surface protection layer 11 may further contain a cured product of a polyol and an isocyanate compound. In this case, it is preferable that at least one of the polyol as the base agent and the isocyanate compound as the curing agent is formed using a cured product containing a biomass-derived component. As the cured product of the polyol and the isocyanate compound, the cured product of the polyol and the isocyanate compound described in the printing layer 12 can be used.

[0063] The surface protective layer 11 preferably has a biomass degree of 5% or more, more preferably 5% to 50%, and even more preferably 10% to 50%. If the biomass degree is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced. The weight of the surface protective layer 11 after drying is preferably 0.1 g / m 2 More than 10g / m 2 Less than 1 g / m, more preferably 2 More than 5g / m 2More preferably, 1 g / m or less 2 More than 3g / m 2 The surface protective layer 11 has a thickness of preferably 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, and further preferably 1 μm or more and 3 μm or less.

[0064] (Inner thermoplastic resin layer) The inner thermoplastic resin layer 15 can be formed using a conventionally known thermoplastic resin. The inner thermoplastic resin layer 15 is located on the inner side of the packaging material 20. By providing the inner thermoplastic resin layer 15, the packaging material 20 can be imparted with heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties.

[0065] The inner thermoplastic resin layer 15 may contain a biomass-derived component or may not contain a biomass-derived component. When the inner thermoplastic resin layer 15 is formed from a material containing a biomass-derived component, the inner thermoplastic resin layer 15 can be formed from the following biomass polyolefin. When the inner thermoplastic resin layer 15 is formed from a material not containing a biomass-derived component, the inner thermoplastic resin layer 15 can be formed from a conventionally known thermoplastic resin derived from fossil fuels.

[0066] Biomass polyolefin is a polymer of monomers containing olefins such as ethylene derived from biomass. Since biomass-derived olefins are used as the raw material monomers, the polyolefins obtained by polymerization are derived from biomass. Note that the raw material monomers for polyolefins do not have to contain 100% by mass of biomass-derived olefins.

[0067] For example, 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 a plant raw material. The plant raw material is not particularly limited, and any conventionally known plant can be used. Examples of the plant raw material include corn, sugarcane, beet, and manioc.

[0068] Fermented ethanol derived from biomass refers to ethanol produced by contacting a culture solution containing a carbon source obtained from a plant raw material with an ethanol-producing microorganism or a product derived from the crushed microorganism, and then purifying the ethanol. Conventionally known methods such as distillation, membrane separation, and extraction can be applied to purify ethanol from the culture solution. For example, there is a method of adding benzene, cyclohexane, etc., and removing water by azeotropy or membrane separation.

[0069] The monomers that are the raw material for the biomass polyolefin may further contain ethylene monomers derived from fossil fuels and / or α-olefin monomers derived from fossil fuels, or may further contain α-olefin monomers derived from biomass.

[0070] The number of carbon atoms of the above-mentioned α-olefin is not particularly limited, but one having 3 to 20 carbon atoms can usually be used, and butylene, hexene, or octene is preferable. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a raw material derived from biomass. In addition, by including such an α-olefin, the polyolefin obtained by polymerization has an alkyl group as a branched structure, and therefore can be more flexible than a simple linear one.

[0071] As the biomass polyolefin, polyethylene or a copolymer of ethylene and α-olefin may be used alone or in combination of two or more. In particular, the biomass polyolefin is preferably polyethylene. This is because the use of ethylene, which is a raw material derived from biomass, makes it theoretically possible to produce the polyolefin from 100% biomass-derived components.

[0072] 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 falls within the range described below.

[0073] The biomass polyolefin preferably has a viscosity of 0.91 g / cm 3 More than 0.93g / cm 3 Less than or equal to 0.912 g / cm 3 More than 0.928g / cm 3 More preferably, 0.915 g / cm 3 More than 0.925g / cm 3 The density of the biomass polyolefin is a value measured according to the method A of JIS K7112-1980 after annealing as described in JIS K6760-1995. The density of the biomass polyolefin is 0.91 g / cm 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.

[0074] 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, more preferably 1 g / 10 min to 8.5 g / 10 min. The melt flow rate is a value measured by the A method under the conditions of a temperature of 190° C. and a load of 21.18 N in 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. In addition, 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.

[0075] A suitable biomass polyolefin is a biomass-derived low-density polyethylene (product name: SBC818, density: 0.918 g / cm) manufactured by Braskem. 3, MFR: 8.1 g / 10 min, biomass content 95%), Braskem biomass-derived low-density polyethylene (product name: SPB681, density: 0.922 g / cm 3 , MFR: 3.8g / 10min, biomass content 95%), Braskem biomass-derived linear low-density polyethylene (product name: SLL118, density: 0.916g / cm 3 , MFR: 1.0 g / 10 min, biomass ratio 87%).

[0076] Examples of the thermoplastic resin derived from fossil fuels 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, and ionomer.

[0077] The inner thermoplastic resin layer 15 preferably has a biomass degree of 5% or more, more preferably 10% or more and 95% or less. If the biomass degree is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

[0078] The inner thermoplastic resin layer 15 may be a single layer or may be a multilayer. When the above-mentioned biomass polyolefin is used for the inner thermoplastic resin layer, the inner thermoplastic resin layer may have three layers, an inner layer, an intermediate layer, and an outer layer. In this case, it is preferable that the intermediate layer is a layer made of biomass polyolefin or a layer made of a mixture of biomass polyolefin and a conventionally known polyolefin derived from fossil fuel, and the inner layer and the outer layer are conventionally known polyolefin derived from fossil fuel.

[0079] The inner thermoplastic resin layer 15 has a thickness of preferably 10 μm or more and 300 μm or less, more preferably 20 μm or more and 200 μm or less, and further preferably 30 μm or more and 150 μm or less.

[0080] (Outer thermoplastic resin layer) The outer thermoplastic resin layer 13 is a layer containing polyethylene. The outer thermoplastic resin layer 13 is located between the printed layer 12 and the paper base layer 14. By providing the packaging material 20 with the outer thermoplastic resin layer 13, it is possible to impart waterproofing to the paper base layer and improve sealing properties.

[0081] Examples of the polyethylene of the outer thermoplastic resin layer 13 include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, etc. In addition to the above-mentioned polyethylene, the outer thermoplastic resin layer 13 may contain, for example, 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, etc.

[0082] The outer thermoplastic resin layer 13 may contain a material derived from biomass or a material derived from fossil fuels. When the outer thermoplastic 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 inner thermoplastic resin layer 15.

[0083] It has a thickness of 10 μm or more and 30 μm or less, more preferably 10 μm or more and 20 μm or less.

[0084] (Intermediate thermoplastic resin layer) The intermediate thermoplastic resin layer can be formed using a conventionally known thermoplastic resin. By providing the packaging material 20 with the intermediate thermoplastic resin layer, it is possible to provide adhesion between the layers.

[0085] Examples of the thermoplastic resin layer 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.

[0086] The intermediate thermoplastic resin layer may contain a material derived from biomass or a material derived from fossil fuels. When the intermediate thermoplastic resin layer contains a material derived from biomass, it may contain a biomass polyolefin, which is a polymer of a monomer including ethylene derived from biomass, like the inner thermoplastic resin layer.

[0087] The intermediate thermoplastic resin layer preferably has a thickness of 2 μm or more and 10 μm or less, more preferably 3 μm or more and 8 μm or less.

[0088] (Barrier resin layer) The barrier resin layer 21 is a layer that imparts or improves 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 rays, etc. The barrier resin layer 21 contains at least one type of barrier resin, and examples thereof include ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyacrylonitrile, polyamides such as nylon 6, nylon 6,6, and polymetaxylylene adipamide (MXD6), polyester, polyurethane, and (meth)acrylic resin, and among these, EVOH is preferred from the viewpoint of gas barrier properties that prevent the transmission of oxygen gas, water vapor, etc.

[0089] The barrier resin layer may contain additives within the range that does not impair the characteristics of the present invention, such as crosslinking agents, antioxidants, antiblocking agents, slip agents, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, compatibilizers, and pigments.

[0090] The thickness of the gas barrier resin layer is preferably 0.5 μm or more and 10 μm or less, and more preferably 1 μm or more and 7 μm or less.

[0091] (Polyolefin resin layer) The polyolefin resin layer 23 is a layer for enhancing adhesion between the paper base layer 14 and each of the other layers. Examples of polyolefins for the polyolefin resin layer 23 include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, and propylene-ethylene copolymers. From the viewpoint of adhesion to the paper base layer 14, the polyolefin resin layer 23 is preferably a polyethylene resin layer.

[0092] The polyolefin resin layer 23 has a thickness of preferably 10 μm or more and 30 μm or less, more preferably 12 μm or more and 25 μm or less, and further preferably 15 μm or more and 22 μm or less.

[0093] (Barrier layer) The barrier layer 26 is a layer that imparts or improves 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 rays, etc. The barrier layer is preferably a metal foil or a vapor-deposited film.

[0094] [Metal foil] The metal foil is a member obtained by rolling a metal. As the metal foil, a conventionally known metal foil can be used. From the viewpoints of 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., aluminum foil is preferred.

[0095] [Vapor-deposited film] The vapor-deposited film includes a substrate and a vapor-deposited film that is vapor-deposited on the substrate. The vapor-deposited film is located on the outer surface side of the substrate.

[0096] The substrate is a plastic film. As the material of the plastic film, various plastics such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyester, etc. can be used. The substrate may or may not contain a biomass-derived component.

[0097] When the substrate includes a biomass-derived component, the substrate can be formed using a biomass polyester or biomass polyethylene as described below.

[0098] The biomass polyester has ethylene glycol derived from biomass as a diol unit and dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit. In addition to the biomass polyester, the substrate may further contain a polyester derived from fossil fuel having ethylene glycol derived from fossil fuel as a diol unit and dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit.

[0099] When the substrate contains a biomass-derived component, the biomass ratio in the substrate is 5% or more, preferably 10% to 30%, and more preferably 15% to 25%. If the biomass ratio in the substrate is 5% or more, the amount of polyester derived from fossil fuels can be reduced compared to conventional methods, thereby reducing the environmental load.

[0100] Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained by a method of producing ethylene glycol from biomass ethanol via ethylene oxide using a conventionally known method. Commercially available biomass ethylene glycol may also be used, and for example, biomass ethylene glycol commercially available from India Glycoal Limited can be suitably used.

[0101] The dicarboxylic acid unit of the biomass polyester uses a dicarboxylic acid derived from a fossil fuel. As the dicarboxylic acid, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation. As the aromatic dicarboxylic acid, terephthalic acid and isophthalic acid can be mentioned, and as the derivative of the aromatic dicarboxylic acid, lower alkyl esters of aromatic dicarboxylic acids, specifically, methyl ester, ethyl ester, propyl ester, butyl ester, etc. can be mentioned. Among these, terephthalic acid is preferred, and as the derivative of the aromatic dicarboxylic acid, dimethyl terephthalate is preferred.

[0102] In addition, specific examples of the aliphatic dicarboxylic acid include linear or alicyclic dicarboxylic acids having 2 to 40 carbon atoms, such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid. In addition, examples of the derivatives of the aliphatic dicarboxylic acids include lower alkyl esters such as methyl esters, ethyl esters, propyl esters, and butyl esters of the above aliphatic dicarboxylic acids, and cyclic acid anhydrides of the above aliphatic dicarboxylic acids, such as succinic anhydride. Among these, adipic acid, succinic acid, dimer acid, or a mixture thereof is preferred, and those containing succinic acid as the main component are particularly preferred. Examples of the derivatives of the aliphatic dicarboxylic acid include methyl esters of adipic acid and succinic acid, or a mixture thereof. These dicarboxylic acids can be used alone or in combination of two or more.

[0103] The biomass polyester may be a copolymer polyester in which a copolymer component is added as a third component in addition to the above diol component and dicarboxylic acid component. Specific examples of the copolymer component include bifunctional oxycarboxylic acid, and at least one polyfunctional compound selected from the group consisting of trifunctional or more polyhydric alcohols, trifunctional or more polyvalent carboxylic acids and / or their anhydrides, and trifunctional or more oxycarboxylic acids to form a crosslinked structure. Among these copolymer components, bifunctional and / or trifunctional or more oxycarboxylic acids are particularly preferably used because they tend to easily produce copolymer polyesters with a high degree of polymerization. Among them, the use of trifunctional or more oxycarboxylic acids is most preferred because it allows easy production of polyesters with a high degree of polymerization with a very small amount without using a chain extender described later.

[0104] Biomass polyester can be obtained by a conventionally known method of polycondensing the above-mentioned diol unit and dicarboxylic acid unit. Specifically, it can be produced by a general melt polymerization method in which the above-mentioned dicarboxylic acid component and diol component are subjected to an esterification reaction and / or transesterification reaction, followed by a polycondensation reaction under reduced pressure, or a known solution heating dehydration condensation method using an organic solvent. The amount of diol used in producing biomass polyester is substantially equimolar to 100 moles of dicarboxylic acid or its derivative, but in general, it is preferable to use an excess amount of 0.1 mol% to 20 mol% because distillation occurs during the esterification and / or transesterification reaction and / or condensation polymerization reaction.

[0105] A resin composition of biomass polyester or a resin composition containing biomass polyester and a polyester derived from fossil fuel can be used to form a substrate by, for example, forming a film by a T-die method. Specifically, after drying the above-mentioned resin composition, the resin composition is supplied to a melt extruder heated to a temperature of Tm or higher to Tm+70°C to melt the resin composition, and extruded into a sheet from a die such as a T-die, and the extruded sheet is quenched and solidified by a rotating cooling drum, etc., to form a substrate. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder, etc. can be used depending on the purpose.

[0106] Biomass polyethylene is a monomer polymer containing ethylene derived from biomass. As the biomass-derived ethylene, the biomass-derived ethylene described in the inner thermoplastic resin layer 15 can be used.

[0107] When the substrate is formed from a material that does not contain biomass-derived components, the plastic film that constitutes the substrate can be, for example, a polyester film such as a polyethylene terephthalate film or a polybutylene terephthalate film, a polyolefin film such as a polyethylene film or a polypropylene film, a polypropylene / ethylene-vinyl alcohol copolymer co-extruded co-stretched film, or a composite film formed by laminating two or more of these films.

[0108] As the vapor-deposited film, for example, a vapor-deposited film of a metal such as aluminum (Al) or lead (Pb) can be used.

[0109] (Plastic film layer) In the present invention, various plastic films may be used as the plastic film layer 28. For example, it may be any one of a stretched polyethylene terephthalate film, a stretched nylon film, a stretched polypropylene film, a nylon 6 / metaxylylenediamine nylon 6 co-extruded co-stretched film, and a polypropylene / ethylene-vinyl alcohol copolymer co-extruded co-stretched film, or a composite film in which two or more of these films are laminated. The plastic film may be coated with polyvinyl alcohol or the like.

[0110] The plastic film layer 28 preferably has a thickness of 9 μm or more and 16 μm or less, and more preferably 9 μm or more and 12 μm or less.

[0111] (Anchor coat layer) The anchor coat layer 29 is a layer for enhancing adhesion between the plastic film layer 28 and the inner thermoplastic resin layer 15. Polyethyleneimine or the like can be used as a material for forming the anchor coat layer 29. The anchor coat layer 29 can be formed by applying a paint containing these materials and a solvent to the plastic film layer 28.

[0112] (Adhesive resin layer) The adhesive resin layer is a layer provided when any two layers are bonded together. The adhesive resin layer can be formed by a conventionally known method, such as a melt extrusion lamination method or a sand lamination method. As the thermoplastic resin that can be used for the adhesive resin layer, a polyethylene resin, a polypropylene resin, or a cyclic polyolefin resin, or a copolymer resin, modified resin, or mixture (including alloy) containing these resins as the main component can be used. 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 a metallocene catalyst, 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. In addition, to improve the adhesion between layers, acid-modified polyolefin resins obtained by modifying the above-mentioned polyolefin resins with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid can be used. In addition, resins obtained by graft-polymerizing or copolymerizing unsaturated carboxylic acids, unsaturated carboxylic anhydrides, and ester monomers with polyolefin resins can be used. These materials can be used alone or in combination of two or more. As the cyclic polyolefin-based resin, for example, cyclic polyolefins such as ethylene-propylene copolymer, polymethylpentene, polybutene, polynorbornene, etc. can be used. These resins can be used alone or in combination of two or more. In addition, as the above-mentioned polyethylene-based resin, the above-mentioned biomass-derived ethylene can be used as a monomer unit to further improve the biomass degree.

[0113] When the adhesive resin layer is laminated by the melt extrusion lamination method, an anchor coat layer may be provided on the surface of the layer to be laminated by applying and drying an anchor coat agent. The anchor coat agent may be any resin having a heat resistance of 135°C or higher, such as a vinyl modified resin, an epoxy resin, a urethane resin, a polyester resin, or a polyethyleneimine. In particular, an anchor coat agent that is a cured product of a polyacrylic or polymethacrylic resin (polyol) having two or more hydroxyl groups in the structure and an isocyanate compound as a curing agent is preferably used. In addition, a silane coupling agent may be used in combination with this as an additive, and nitrocellulose may be used in combination to increase heat resistance.

[0114] The anchor coat layer after drying has a thickness of 0.1 μm to 1 μm, preferably 0.3 μm to 0.5 μm. The adhesive resin layer after drying has a thickness of 1 μm to 10 μm, preferably 2 μm to 5 μm. The adhesive resin layer preferably has a thickness of 5 μm to 50 μm, preferably 10 μm to 30 μm.

[0115] (adhesive layer) The adhesive layer is a layer provided when any two layers are bonded together. The adhesive layer may contain a biomass-derived component. In the adhesive layer containing a biomass-derived component, at least one of a polyol and an isocyanate compound contains a biomass-derived component.

[0116] In the adhesive layer, the isocyanate compound containing a biomass-derived component can be the same isocyanate compound containing a biomass-derived component as in the above-mentioned printed layer 12. In addition, in the adhesive layer, the polyol containing a biomass-derived component can be the same polyol as in the above-mentioned printed layer 12. When both the printed layer 12 and the adhesive layer are formed using a cured product containing a biomass-derived component, the cured product in the printed layer 12 and the cured product in the adhesive layer may have the same composition or different compositions.

[0117] The adhesive layer preferably has a biomass ratio of 5% or more, more preferably 5% to 50%, and even more preferably 30% to 50%. If the biomass ratio is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

[0118] The dry weight of the adhesive layer is preferably 0.1 g / m 2 More than 10g / m 2 Less than 1 g / m, more preferably 2 More than 6g / m 2 Less than 2 g / m, more preferably 2 More than 5g / m 2 The following is the result.

[0119] The adhesive layer preferably has a thickness of 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 6 μm or less, and even more preferably 2 μm or more and 5 μm or less.

[0120] (Manufacturing method of packaging materials) Next, an example of a method for producing the laminate that constitutes the packaging material 20 will be described.

[0121] An example of a method for manufacturing the packaging material 20 shown in FIG. 1 will be described. First, the above-mentioned paper base layer 14 is prepared. Then, a molten resin is extruded onto the paper base layer 14 by melt extrusion lamination to form the outer thermoplastic resin layer 13. Then, a molten resin is extruded onto the surface of the paper base layer 14 opposite to the surface on which the outer thermoplastic resin layer 13 is formed by melt extrusion lamination to form the inner thermoplastic resin layer 15. Then, the above-mentioned ink composition is printed onto the outer thermoplastic resin layer 13 by gravure printing to form a printing layer 12 on the outer thermoplastic resin layer 13. Then, the above-mentioned paint containing solids and a solvent is applied onto the printing layer 12 to form a surface protective layer 11 on the printing layer 12. This makes it possible to obtain a packaging material 20 including the surface protective layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, and the inner thermoplastic resin layer 15. As a method for applying the paint, a gravure method, a roll coater method, or the like can be used.

[0122] After the inner thermoplastic resin layer 15 is formed on the paper base layer 14, the outer thermoplastic resin layer 13, the printing layer 12 and the surface protection layer 11 may be formed on the paper base layer 14.

[0123] An example of a method for producing the packaging material 20 shown in FIG. 2 will be described. First, the above-mentioned paper base layer 14 is prepared. Then, a molten resin is extruded onto the paper base layer 14 by melt extrusion lamination to form the outer thermoplastic resin layer 13. Then, a molten resin is extruded onto the surface of the paper base layer 14 opposite to the surface on which the outer thermoplastic resin layer 13 is formed by melt extrusion lamination to form the barrier resin layer 21, the intermediate thermoplastic resin layer 22, and the inner thermoplastic resin layer 15. Then, the above-mentioned ink composition is printed onto the outer thermoplastic resin layer 13 by gravure printing to form the printing layer 12 on the outer thermoplastic resin layer 13. Then, the above-mentioned paint containing solids and a solvent is applied onto the printing layer 12 to form the surface protective layer 11 on the printing layer 12. This makes it possible to obtain a packaging material 20 including the surface protective layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the barrier resin layer 21, the intermediate thermoplastic resin layer 22, and the inner thermoplastic resin layer 15.

[0124] In addition, after forming the barrier resin layer 21, the intermediate thermoplastic resin layer 22 and the inner thermoplastic resin layer 15 on the paper base layer 14, the outer thermoplastic resin layer 13, the printing layer 12 and the surface protection layer 11 may be formed on the paper base layer 14.

[0125] An example of a method for producing the packaging material 20 shown in FIG. 3 will be described. First, the above-mentioned paper base layer 14 is prepared. Then, a molten resin is extruded onto the paper base layer 14 by melt extrusion lamination to form the outer thermoplastic resin layer 13. Then, a molten resin is extruded onto the surface of the paper base layer 14 opposite to the surface on which the outer thermoplastic resin layer 13 is formed by melt extrusion lamination to form the polyolefin resin layer 23, the intermediate thermoplastic resin layer 22, the barrier resin layer 21, the intermediate thermoplastic resin layer 24, and the inner thermoplastic resin layer 15. Then, the above-mentioned ink composition is printed onto the outer thermoplastic resin layer 13 by gravure printing to form the printed layer 12 on the outer thermoplastic resin layer 13. Then, the above-mentioned paint containing a solid content and a solvent is applied onto the printed layer 12 to form the surface protective layer 11 on the printed layer 12. This allows for the production of a packaging material 20 comprising a surface protective layer 11, a printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, a polyolefin resin layer 23, an intermediate thermoplastic resin layer 22, a barrier resin layer 21, an intermediate thermoplastic resin layer 24 and an inner thermoplastic resin layer 15.

[0126] In addition, after forming the polyolefin resin layer 23, the intermediate thermoplastic resin layer 22, the barrier resin layer 21, the intermediate thermoplastic resin layer 24 and the inner thermoplastic resin layer 15 on the paper base layer 14, the outer thermoplastic resin layer 13, the printing layer 12 and the surface protection layer 11 may be formed on the paper base layer 14.

[0127] An example of a manufacturing method of the packaging material 20 shown in Fig. 4 will be described. First, the above-mentioned paper base layer 14 is prepared. Next, a molten resin is extruded onto the paper base layer 14 by melt extrusion lamination to form the outer thermoplastic resin layer 13. Next, a film constituting the barrier layer 26 and a film constituting the plastic film layer 28 are laminated separately via an adhesive layer 27 by dry lamination.

[0128] In the dry lamination method, first, an adhesive composition is applied to one of the two films to be laminated. Then, the applied adhesive composition is dried to volatilize the solvent. Then, the two films are laminated via the dried adhesive composition. Then, the two laminated films are wound up and aged, for example, in an environment of 20°C or higher for 24 hours or more.

[0129] Next, the paper base layer 14 on which the outer thermoplastic resin layer 13 has been formed and the barrier layer 26 to which the plastic film layer 28 has been attached are laminated via the adhesive resin layer 25 by a sandwich lamination method.

[0130] In the sand lamination method, first, an adhesive resin layer 25 is formed on one of the two films to be laminated, and a molten resin is extruded onto it. Then, the other film is laminated onto the resin extruded onto the one film.

[0131] Next, an anchor coat agent is applied onto the plastic film layer 28 and dried to form an anchor coat layer 29. Next, an inner thermoplastic resin layer 15 is formed on the anchor coat layer 29 by a melt extrusion lamination method. Next, the above-mentioned ink composition is printed onto the outer thermoplastic resin layer 13 by gravure printing to form a printed layer 12 on the outer thermoplastic resin layer 13. Next, the above-mentioned paint containing solids and a solvent is applied onto the printed layer 12 to form a surface protective layer 11 on the printed layer 12. In this way, a packaging material 20 including the surface protective layer 11, the printed layer 12, the outer thermoplastic resin layer 13, the paper substrate layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27, the plastic film layer 28, the anchor coat layer 29, and the inner thermoplastic resin layer 15 can be obtained.

[0132] In addition, after laminating the paper base layer 14 and the barrier layer 26 to which the plastic film layer 28 is bonded via the adhesive resin layer 25, an outer thermoplastic resin layer 13, a printing layer 12 and a surface protective layer 11 may be formed on the paper base layer 14.

[0133] An example of a manufacturing method of the packaging material 20 shown in FIG. 5 will be described. First, the above-mentioned paper base layer 14 is prepared. Then, a molten resin is extruded onto the paper base layer 14 by melt extrusion lamination to form the outer thermoplastic resin layer 13. Then, a film constituting the barrier layer 26 and a film constituting the plastic film layer 28 are laminated via an adhesive layer 27 by dry lamination. Then, the paper base layer 14 on which the outer thermoplastic resin layer 13 has been formed and the barrier layer 26 to which the plastic film layer 28 has been attached are laminated via an adhesive resin layer 25 by sand lamination. Then, an anchor coat agent is applied onto the plastic film layer 28 and dried to form an anchor coat layer 29. Then, the anchor coat layer 29 and a film constituting the inner thermoplastic resin layer 15 are laminated via an adhesive resin layer 30 by sand lamination. Then, the above-mentioned ink composition is printed on the outer thermoplastic resin layer 13 by gravure printing to form a printing layer 12 on the outer thermoplastic resin layer 13. Next, the above-mentioned paint containing solids and a solvent is applied onto the printed layer 12 to form a surface protective layer 11 on the printed layer 12. In this way, a packaging material 20 including the surface protective layer 11, the printed layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27, the plastic film layer 28, the anchor coat layer 29, the adhesive resin layer 30, and the inner thermoplastic resin layer 15 can be obtained.

[0134] In addition, after laminating the paper base layer 14 and the barrier layer 26 to which the plastic film layer 28 is bonded via the adhesive resin layer 25, an outer thermoplastic resin layer 13, a printing layer 12 and a surface protective layer 11 may be formed on the paper base layer 14.

[0135] An example of a manufacturing method of the packaging material 20 shown in FIG. 6 will be described. First, the above-mentioned paper base layer 14 is prepared. Then, a molten resin is extruded onto the paper base layer 14 by melt extrusion lamination to form the outer thermoplastic resin layer 13. Then, a film constituting the barrier layer 26 and a film constituting the plastic film layer 28 are laminated via an adhesive layer 27 by dry lamination. Then, the paper base layer 14 on which the outer thermoplastic resin layer 13 has been formed and the barrier layer 26 to which the plastic film layer 28 has been attached are laminated via an adhesive resin layer 25 by sand lamination. Then, the plastic film layer 28 and a film constituting the inner thermoplastic resin layer 15 are laminated via an adhesive layer 31 by dry lamination. Then, the above-mentioned ink composition is printed on the outer thermoplastic resin layer 13 by gravure printing to form a printed layer 12 on the outer thermoplastic resin layer 13. Then, the above-mentioned paint containing a solid content and a solvent is applied onto the printed layer 12 to form a surface protective layer 11 on the printed layer 12. This allows for the production of a packaging material 20 comprising a surface protective layer 11, a printing layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, a plastic film layer 28, an adhesive layer 31 and an inner thermoplastic resin layer 15.

[0136] In addition, after laminating the paper base layer 14 and the barrier layer 26 to which the plastic film layer 28 is bonded via the adhesive resin layer 25, an outer thermoplastic resin layer 13, a printing layer 12 and a surface protective layer 11 may be formed on the paper base layer 14.

[0137] An example of a manufacturing method of the packaging material 20 shown in FIG. 7 will be described. First, the above-mentioned paper base layer 14 is prepared. Then, a molten resin is extruded onto the paper base layer 14 by melt extrusion lamination to form the outer thermoplastic resin layer 13. Then, the paper base layer 14 on which the outer thermoplastic resin layer 13 has been formed and a film constituting the barrier layer 26 are laminated via the adhesive resin layer 25 by sand lamination. Then, the inner thermoplastic resin layer 15 is formed on the barrier layer 26 by melt extrusion lamination. Then, the above-mentioned ink composition is printed on the outer thermoplastic resin layer 13 by gravure printing to form the printing layer 12 on the outer thermoplastic resin layer 13. Then, the above-mentioned paint containing solids and a solvent is applied onto the printing layer 12 to form the surface protective layer 11 on the printing layer 12. As a result, a packaging material 20 including the surface protective layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, and the inner thermoplastic resin layer 15 can be obtained.

[0138] In addition, after laminating the paper base layer 14 and the film constituting the barrier layer 26 via the adhesive resin layer 25, an outer thermoplastic resin layer 13, a printing layer 12 and a surface protective layer 11 may be formed on the paper base layer 14.

[0139] An example of a manufacturing method of the packaging material 20 shown in FIG. 8 will be described. First, the above-mentioned paper base layer 14 is prepared. Then, a molten resin is extruded onto the paper base layer 14 by melt extrusion lamination to form the outer thermoplastic resin layer 13. Then, the paper base layer 14 on which the outer thermoplastic resin layer 13 has been formed and a film constituting the barrier layer 26 are laminated via an adhesive resin layer 25 by sand lamination. Then, the barrier layer 26 and a film constituting the inner thermoplastic resin layer 15 are laminated via an adhesive resin layer 30 by sand lamination. Then, the above-mentioned ink composition is printed on the outer thermoplastic resin layer 13 by gravure printing to form a printing layer 12 on the outer thermoplastic resin layer 13. Then, the above-mentioned paint containing a solid content and a solvent is applied onto the printing layer 12 to form a surface protection layer 11 on the printing layer 12. This allows for the production of a packaging material 20 having a surface protective layer 11, a printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive resin layer 30 and an inner thermoplastic resin layer 15.

[0140] In addition, after laminating the paper base layer 14 and the film constituting the barrier layer 26 via the adhesive resin layer 25, an outer thermoplastic resin layer 13, a printing layer 12 and a surface protective layer 11 may be formed on the paper base layer 14.

[0141] An example of a manufacturing method of the packaging material 20 shown in FIG. 9 will be described. First, the above-mentioned paper base layer 14 is prepared. Then, a molten resin is extruded onto the paper base layer 14 by melt extrusion lamination to form the outer thermoplastic resin layer 13. Then, the paper base layer 14 on which the outer thermoplastic resin layer 13 has been formed and a film constituting the barrier layer 26 are laminated via an adhesive resin layer 25 by sand lamination. Then, the barrier layer 26 and a film constituting the inner thermoplastic resin layer 15 are laminated via an adhesive layer 27 by dry lamination. Then, the above-mentioned ink composition is printed on the outer thermoplastic resin layer 13 by gravure printing to form a printing layer 12 on the outer thermoplastic resin layer 13. Then, the above-mentioned paint containing a solid content and a solvent is applied onto the printing layer 12 to form a surface protection layer 11 on the printing layer 12. This allows for the production of a packaging material 20 having a surface protective layer 11, a printing layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27 and an inner thermoplastic resin layer 15.

[0142] In addition, after laminating the paper base layer 14 and the film constituting the barrier layer 26 via the adhesive resin layer 25, an outer thermoplastic resin layer 13, a printing layer 12 and a surface protective layer 11 may be formed on the paper base layer 14.

[0143] An example of a manufacturing method of the packaging material 20 shown in FIG. 10 will be described. First, the above-mentioned paper base layer 14 is prepared. Then, a molten resin is extruded onto the paper base layer 14 by melt extrusion lamination to form the outer thermoplastic resin layer 13. Then, a film constituting the plastic film layer 28 and a film constituting the barrier layer 26 are laminated via an adhesive layer 27 by dry lamination. Then, the paper base layer 14 on which the outer thermoplastic resin layer 13 is formed and the plastic film layer 28 to which the barrier layer 26 is bonded are laminated via an adhesive resin layer 25 by sand lamination. Then, the intermediate thermoplastic resin layer 22 and the inner thermoplastic resin layer 15 are formed on the barrier layer 26 by melt extrusion lamination. Then, the above-mentioned ink composition is printed on the outer thermoplastic resin layer 13 by gravure printing to form the printed layer 12 on the outer thermoplastic resin layer 13. Then, the above-mentioned paint containing a solid content and a solvent is applied onto the printed layer 12 to form the surface protective layer 11 on the printed layer 12. This allows for the production of a packaging material 20 having a surface protective layer 11, a printing layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a plastic film layer 28, an adhesive layer 27, a barrier layer 26, an intermediate thermoplastic resin layer 22 and an inner thermoplastic resin layer 15.

[0144] In addition, after laminating the paper base layer 14 and the plastic film layer 28 to which the barrier layer 26 is bonded via the adhesive resin layer 25, an outer thermoplastic resin layer 13, a printing layer 12 and a surface protective layer 11 may be formed on the paper base layer 14.

[0145] An example of a manufacturing method of the packaging material 20 shown in FIG. 11 will be described. First, the above-mentioned paper base layer 14 is prepared. Then, by melt extrusion lamination, a molten resin is extruded onto the paper base layer 14 to form the outer thermoplastic resin layer 13. Then, by melt extrusion lamination, a molten resin is extruded onto the surface of the paper base layer 14 opposite to the surface on which the outer thermoplastic resin layer 13 is formed, to form a polyolefin resin layer 23. Then, by sand lamination, the above-mentioned polyolefin resin layer 23 and a film constituting the barrier layer 26 are laminated via an adhesive resin layer 25. Then, by melt extrusion lamination, the intermediate thermoplastic resin layer 22 and the inner thermoplastic resin layer 15 are formed on the barrier layer 26. Then, the above-mentioned ink composition is printed on the outer thermoplastic resin layer 13 by gravure printing to form a printing layer 12 on the outer thermoplastic resin layer 13. Then, the above-mentioned paint containing a solid content and a solvent is applied onto the printing layer 12 to form a surface protective layer 11 on the printing layer 12. This allows for the production of a packaging material 20 having a surface protective layer 11, a printing layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, a polyolefin resin layer 23, an adhesive resin layer 25, a barrier layer 26, an intermediate thermoplastic resin layer 22 and an inner thermoplastic resin layer 15.

[0146] After the polyolefin resin layer 23 is formed on the paper base layer 14, the outer thermoplastic resin layer 13, the printing layer 12 and the surface protective layer 11 may be formed on the paper base layer 14.

[0147] <Packaging products> An example of a packaging product formed by using the packaging material 20 will be described. Fig. 12 is a diagram showing a paper container for liquids 40, which is an example of the packaging product. Because the paper container for liquids has excellent barrier properties, it can be suitably used as a paper container for packaging all kinds of liquids, such as alcoholic beverages such as sake, shochu, and wine, dairy drinks such as milk, and soft drinks such as orange juice and tea, as well as car wax and chemical products such as shampoo and detergent.

[0148] As shown in Fig. 12, the paper container for liquid 40 has a rectangular cylindrical body 41 including sides, a rectangular plate-shaped bottom 42, and an upper portion 43, and is a so-called Gabeltop type container. The upper portion 43 has a pair of opposing inclined plates 44 and a pair of folded portions 45 located between the pair of inclined plates 44 and folded between the inclined plates 44. The pair of inclined plates 44 are bonded to each other by a glue tab 46 provided at each upper end. A spout may be attached to one of the pair of inclined plates 44, and the spout may be sealed with a cap. A flat-top type container may also be formed.

[0149] By constructing a packaged product using the packaging material 20 having the surface protective layer 11 containing a biomass-derived component, it is possible to reduce the amount of fossil fuel used compared to conventional methods, thereby reducing the environmental burden. EXAMPLES

[0150] Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples as long as it does not depart from the gist of the present invention.

[0151] [Example 1A] The paper base layer 14 is 320 g / m 2 A liquid container base paper having a basis weight of 100 g was prepared. Next, an outer thermoplastic resin layer 13 was formed on the paper base layer 14 by melt extrusion lamination. Fossil fuel-derived polyethylene was used as the outer thermoplastic resin layer 13. The thickness of the outer thermoplastic resin layer 13 was 17 μm.

[0152] Next, the inner thermoplastic resin layer 15 was formed on the paper base layer 14 by melt extrusion lamination. Fossil fuel-derived polyethylene was used as the inner thermoplastic resin layer 15. The thickness of the inner thermoplastic resin layer 15 was 28 μm.

[0153] Next, the printed layer 12 was formed on the outer thermoplastic resin layer 13. In the process of forming the printed layer 12, first, an ink composition containing a colorant, a binder resin, and a solvent was prepared. The binder resin used was one containing nitrocellulose. Next, the ink composition was applied in a predetermined pattern by gravure printing on the outer thermoplastic resin layer 13 to form the printed layer 12. The thickness of the printed layer 12 was 2 μm.

[0154] Next, the surface protective layer 11 was formed on the printed layer 12. In the process of forming the surface protective layer 11, first, a paint containing a binder resin and a solvent was prepared. The binder resin used was one containing nitrocellulose derived from biomass. Next, the paint was applied to the entire area of ​​the printed layer 12 by a gravure method to form the surface protective layer 11. The thickness of the surface protective layer 11 was 1 μm. In this manner, a packaging material 20 having the layer structure shown in FIG. 1 was produced.

[0155] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / print / external heat 17 / paper / internal heat (2) 28 The " / " indicates the boundary between layers. The leftmost layer is the layer that constitutes the outer surface of the packaging material, and the rightmost layer is the layer that constitutes the inner surface of the packaging material. "Bio-surface" means a surface protection layer derived from biomass. "Print" means a printing layer. "External heat" means external heat derived from fossil fuels. "Paper" means a paper base layer. "Internal heat (2)" means an inner thermoplastic resin layer derived from fossil fuels formed by melt extrusion lamination. The numbers indicate the thickness of the layer (unit: μm).

[0156] Next, a paper container 40 for liquids shown in Fig. 12 was produced using the packaging material 20. The paper container 40 for liquids can contain, for example, milk or juice.

[0157] [Example 1B] A packaging material 20 was produced in the same manner as in Example 1A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0158] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / Bio stamp / External heat 17 / Paper / Internal heat (2) 28 "Bio-print" refers to a printed layer derived from biomass.

[0159] [Example 1C] A packaging material 20 was produced in the same manner as in Example 1B, except that the polyethylene used for the outer thermoplastic resin layer 13 and the inner thermoplastic resin layer 15 contained a biomass-derived component.

[0160] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / Bio print / Bio external heat 17 / Paper / Bio internal heat (2) 28 "External biothermal" refers to an outer thermoplastic resin layer containing biomass-derived components. "Internal biothermal (2)" refers to an inner thermoplastic resin layer derived from biomass formed by melt extrusion lamination.

[0161] [Example 2A] In the same manner as in Example 1A, a paper substrate layer 14 was prepared, and an outer thermoplastic resin layer 13 was formed on the paper substrate layer 14. The thickness of the outer thermoplastic resin layer 13 was 20 μm. Then, a barrier resin layer 21, an intermediate thermoplastic resin layer 22, and an inner thermoplastic resin layer 15 were formed on the paper substrate layer 14 by melt extrusion lamination. EVOH was used as the barrier resin layer 21. The thickness of the barrier resin layer 21 was 5 μm. Fossil fuel-derived polyethylene was used as the intermediate thermoplastic resin layer 22. The thickness of the intermediate thermoplastic resin layer 22 was 5 μm. Fossil fuel-derived polyethylene was used as the inner thermoplastic resin layer 15. The thickness of the inner thermoplastic resin layer 15 was 20 μm. Then, a printing layer 12 and a surface protective layer 11 were formed on the outer thermoplastic resin layer 13 in the same manner as in Example 1A. In this manner, a packaging material 20 having a layer structure shown in FIG. 2 was produced.

[0162] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / EVOH5 / medium heat 5 / internal heat(2)20 "EVOH" means a barrier resin layer using EVOH. "Medium Heat" means an intermediate thermoplastic resin layer.

[0163] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can contain, for example, fruit juice or tea.

[0164] [Example 2B] A packaging material 20 was produced in the same manner as in Example 2A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0165] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / Bio print / External heat 20 / Paper / EVOH5 / Medium heat 5 / Internal heat(2)20

[0166] [Example 3A] A packaging material 20 was produced in the same manner as in Example 2A, except that polymetaxylylene adipamide was used as the barrier resin layer 21. The thickness of the barrier resin layer 21 was 5 μm.

[0167] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / print / external heat 20 / paper / MXD6 5 / medium heat 5 / internal heat (2) 20 "MXD6" means a barrier resin layer using polymetaxylylene adipamide.

[0168] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can contain, for example, fruit juice or tea.

[0169] [Example 3B] A packaging material 20 was produced in the same manner as in Example 3A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0170] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / Bio stamp / External heat 20 / Paper / MXD6 5 / Medium heat 5 / Internal heat (2) 20

[0171] [Example 4A] A packaging material 20 was produced in the same manner as in Example 2A, except that nylon 6 was used for the barrier resin layer 21. The thickness of the barrier resin layer 21 was 5 μm.

[0172] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / print / external heat 20 / paper / 6NY5 / medium heat 5 / internal heat (2) 20 "6NY" means a barrier resin layer using nylon 6.

[0173] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can contain, for example, fruit juice or tea.

[0174] [Example 4B] A packaging material 20 was produced in the same manner as in Example 4A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0175] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / Bio stamp / External heat 20 / Paper / 6NY5 / Medium heat 5 / Internal heat (2) 20

[0176] [Example 5A] In the same manner as in Example 1A, a paper base layer 14 was prepared, and an outer thermoplastic resin layer 13 was formed on the paper base layer 14. The thickness of the outer thermoplastic resin layer 13 was 20 μm. Next, a polyolefin resin layer 23, an intermediate thermoplastic resin layer 22, a barrier resin layer 21, an intermediate thermoplastic resin layer 24, and an inner thermoplastic resin layer 15 were formed on the paper base layer 14 by a melt extrusion lamination method. As the polyolefin resin layer 23, polyethylene derived from fossil fuel was used. The thickness of the polyolefin resin layer 23 was 20 μm. As the intermediate thermoplastic resin layer 22, polyethylene derived from fossil fuel was used. The thickness of the intermediate thermoplastic resin layer 22 was 5 μm. As the barrier resin layer 21, EVOH was used. The thickness of the barrier resin layer 21 was 5 μm. As the intermediate thermoplastic resin layer 24, polyethylene derived from fossil fuel was used. The thickness of the intermediate thermoplastic resin layer 24 was 5 μm. As the inner thermoplastic resin layer 15, polyethylene derived from fossil fuel was used. The thickness of the inner thermoplastic resin layer 15 was 20 μm. Then, in the same manner as in Example 1A, the printed layer 12 and the surface protective layer 11 were formed on the outer thermoplastic resin layer 13. In this manner, a packaging material 20 having the layer structure shown in FIG. 3 was produced.

[0177] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / PE20 / medium heat 5 / EVOH5 / medium heat 5 / internal heat(2)20 "PE" means a polyolefin resin layer using polyethylene.

[0178] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can contain, for example, fruit juice or tea.

[0179] [Example 5B] A packaging material 20 was produced in the same manner as in Example 5A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0180] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / Bio mark / External heat 20 / Paper / PE20 / Medium heat 5 / EVOH5 / Medium heat 5 / Internal heat(2)20

[0181] [Example 6A] A packaging material 20 was produced in the same manner as in Example 5A, except that polymetaxylylene adipamide was used as the barrier resin layer 21. The thickness of the barrier resin layer 21 was 5 μm.

[0182] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / PE20 / medium heat 5 / MXD6 5 / medium heat 5 / internal heat(2)20

[0183] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can contain, for example, fruit juice or tea.

[0184] [Example 6B] A packaging material 20 was produced in the same manner as in Example 6A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0185] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / Bio stamp / External heat 20 / Paper / PE20 / Medium heat 5 / MXD6 5 / Medium heat 5 / Internal heat (2) 20

[0186] [Example 7A] A packaging material 20 was produced in the same manner as in Example 5A, except that nylon 6 was used for the barrier resin layer 21. The thickness of the barrier resin layer 21 was 5 μm.

[0187] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / PE20 / medium heat 5 / 6NY5 / medium heat 5 / internal heat(2)20

[0188] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can contain, for example, fruit juice or tea.

[0189] [Example 7B] A packaging material 20 was produced in the same manner as in Example 7A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0190] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / Bio stamp / External heat 20 / Paper / PE20 / Medium heat 5 / 6NY5 / Medium heat 5 / Internal heat (2) 20

[0191] [Example 8A] In the same manner as in Example 1A, a paper base layer 14 was prepared, and an outer thermoplastic resin layer 13 was formed on the paper base layer 14. The thickness of the outer thermoplastic resin layer 13 was 20 μm.

[0192] Next, the film constituting the barrier layer 26 and the film constituting the plastic film layer 28 were bonded together by a dry lamination method via the adhesive layer 27. An aluminum foil (thickness 7 μm) was used as the barrier layer 26. A PET film (thickness 12 μm) containing fossil fuel-derived polyethylene terephthalate was used as the plastic film layer 28. In the dry lamination method, a polyester polyol, which is a reaction product of a fossil fuel-derived polyfunctional alcohol and a fossil fuel-derived polyfunctional carboxylic acid, was prepared as the main agent. In addition, an isocyanate compound derived from fossil fuel was prepared as the curing agent.

[0193] Next, the paper base layer 14 on which the outer thermoplastic resin layer 13 was formed and the barrier layer 26 attached to the plastic film layer 28 were bonded together by a sand lamination method via an adhesive resin layer 25. Fossil fuel-derived polyethylene was used as the adhesive resin layer 25. The adhesive resin layer 25 had a thickness of 20 μm.

[0194] Next, an anchor coat layer 29 was formed on the plastic film layer 28, and an inner thermoplastic resin layer 15 was formed on the anchor coat layer 29 by melt extrusion lamination. Fossil fuel-derived polyethylene was used as the inner thermoplastic resin layer 15. The thickness of the inner thermoplastic resin layer 15 was 50 μm.

[0195] Subsequently, in the same manner as in Example 1A, a printed layer 12 and a surface protective layer 11 were formed on the outer thermoplastic resin layer 13. In this manner, a packaging material 20 having the layer structure shown in FIG. 4 was produced.

[0196] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / adhesive resin 20 / AL foil 7 / adhesive / PET 12 / AC / internal heat (2) 50 "AL foil" means aluminum foil. "Adhesive" means adhesive layer. "PET" means PET film containing polyethylene terephthalate. "AC" means anchor coat layer.

[0197] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can store, for example, alcoholic beverages or soft drinks.

[0198] [Example 8B] A packaging material 20 was produced in the same manner as in Example 8A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0199] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / Bio mark / External heat 20 / Paper / Adhesive resin 20 / AL foil 7 / Adhesive / PET 12 / AC / Internal heat (2) 50

[0200] [Example 9A] In the same manner as in Example 1A, a paper base layer 14 was prepared, and an outer thermoplastic resin layer 13 was formed on the paper base layer 14. The thickness of the outer thermoplastic resin layer 13 was 20 μm.

[0201] Next, the film constituting the barrier layer 26 and the film constituting the plastic film layer 28 were bonded together by a dry lamination method via the adhesive layer 27. An aluminum foil (thickness 7 μm) was used as the barrier layer 26. A PET film (thickness 12 μm) containing fossil fuel-derived polyethylene terephthalate was used as the plastic film layer 28. In the dry lamination method, a polyester polyol, which is a reaction product of a fossil fuel-derived polyfunctional alcohol and a fossil fuel-derived polyfunctional carboxylic acid, was prepared as the main agent. In addition, an isocyanate compound derived from fossil fuel was prepared as the curing agent.

[0202] Next, the paper base layer 14 on which the outer thermoplastic resin layer 13 was formed and the barrier layer 26 attached to the plastic film layer 28 were bonded together by a sand lamination method via an adhesive resin layer 25. Fossil fuel-derived polyethylene was used as the adhesive resin layer 25. The adhesive resin layer 25 had a thickness of 20 μm.

[0203] Next, an anchor coat layer 29 was formed on the plastic film layer 28. Next, the anchor coat layer 29 and the inner thermoplastic resin layer 15 were bonded together by a sand lamination method via an adhesive resin layer 30. A polyethylene film (thickness 40 μm) derived from fossil fuels was used as the inner thermoplastic resin layer 15. A polyethylene derived from fossil fuels was used as the adhesive resin layer 30. The thickness of the adhesive resin layer 30 was 20 μm.

[0204] Subsequently, in the same manner as in Example 1A, a printed layer 12 and a surface protective layer 11 were formed on the outer thermoplastic resin layer 13. In this manner, a packaging material 20 having the layer structure shown in FIG. 5 was produced.

[0205] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / adhesive resin 20 / AL foil 7 / adhesive / PET 12 / AC / adhesive resin 20 / internal heat (1) 40 "Inner Heat (1)" means an inner thermoplastic film derived from fossil fuels.

[0206] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can store, for example, alcoholic beverages or soft drinks.

[0207] [Example 9B] A packaging material 20 was produced in the same manner as in Example 9A, except that the binder resin for the surface protective layer 11 was one containing nitrocellulose derived from biomass.

[0208] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / Bio mark / External heat 20 / Paper / Adhesive resin 20 / AL foil 7 / Adhesive / PET 12 / AC / Adhesive resin 20 / Internal heat (1) 40

[0209] [Example 10A] In the same manner as in Example 1A, a paper base layer 14 was prepared, and an outer thermoplastic resin layer 13 was formed on the paper base layer 14. The thickness of the outer thermoplastic resin layer 13 was 20 μm.

[0210] Next, the film constituting the barrier layer 26 and the film constituting the plastic film layer 28 were bonded together by a dry lamination method via the adhesive layer 27. An aluminum foil (thickness 7 μm) was used as the barrier layer 26. A PET film (thickness 12 μm) containing fossil fuel-derived polyethylene terephthalate was used as the plastic film layer 28. In the dry lamination method, a polyester polyol, which is a reaction product of a fossil fuel-derived polyfunctional alcohol and a fossil fuel-derived polyfunctional carboxylic acid, was prepared as the main agent. In addition, an isocyanate compound derived from fossil fuel was prepared as the curing agent.

[0211] Next, the paper base layer 14 on which the outer thermoplastic resin layer 13 was formed and the barrier layer 26 attached to the plastic film layer 28 were bonded together by a sand lamination method via an adhesive resin layer 25. Fossil fuel-derived polyethylene was used as the adhesive resin layer 25. The adhesive resin layer 25 had a thickness of 20 μm.

[0212] Next, the plastic film layer 28 and the inner thermoplastic resin layer 15 were bonded together by a dry lamination method via an adhesive layer 31. A polyethylene film (thickness 60 μm) derived from fossil fuels was used as the inner thermoplastic resin layer 15. In the dry lamination method, a polyester polyol, which is a reaction product of a polyfunctional alcohol derived from fossil fuels and a polyfunctional carboxylic acid derived from fossil fuels, was prepared as the main agent. In addition, an isocyanate compound derived from fossil fuels was prepared as the curing agent.

[0213] Subsequently, in the same manner as in Example 1A, a printed layer 12 and a surface protective layer 11 were formed on the outer thermoplastic resin layer 13. In this manner, a packaging material 20 having the layer structure shown in FIG. 6 was produced.

[0214] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / adhesive resin 20 / AL foil 7 / bonding / PET 12 / bonding / internal heat (1) 60

[0215] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can store, for example, alcoholic beverages or soft drinks.

[0216] [Example 10B] A packaging material 20 was produced in the same manner as in Example 10A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0217] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / Bio mark / External heat 20 / Paper / Adhesive resin 20 / AL foil 7 / Adhesive / PET 12 / Adhesive / Internal heat (1) 60

[0218] [Example 11A] In the same manner as in Example 1A, a paper base layer 14 was prepared, and an outer thermoplastic resin layer 13 was formed on the paper base layer 14. The thickness of the outer thermoplastic resin layer 13 was 20 μm.

[0219] Next, the paper base layer 14 on which the outer thermoplastic resin layer 13 was formed and the barrier layer 26 were bonded together by a sand lamination method via the adhesive resin layer 25. Aluminum foil (thickness 7 μm) was used as the barrier layer 26. Fossil fuel-derived polyethylene was used as the adhesive resin layer 25. The thickness of the adhesive resin layer 25 was 20 μm.

[0220] Next, the inner thermoplastic resin layer 15 was formed on the barrier layer 26 by melt extrusion lamination. Fossil fuel-derived polyethylene was used as the inner thermoplastic resin layer 15. The thickness of the inner thermoplastic resin layer 15 was 40 μm.

[0221] Subsequently, in the same manner as in Example 1A, a printed layer 12 and a surface protective layer 11 were formed on the outer thermoplastic resin layer 13. In this manner, a packaging material 20 having the layer structure shown in FIG. 7 was produced.

[0222] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / adhesive resin 20 / AL foil 7 / internal heat (2) 40

[0223] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can store, for example, alcoholic beverages or soft drinks.

[0224] [Example 11B] A packaging material 20 was produced in the same manner as in Example 11A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0225] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / Bio print / External heat 20 / Paper / Adhesive resin 20 / AL foil 7 / Internal heat (2) 40

[0226] [Example 12A] A packaging material 20 was produced in the same manner as in Example 11A, except that a vapor-deposited film (thickness: 12 μm) in which an aluminum vapor-deposited film was formed on a polyethylene terephthalate film was used as the barrier layer 26.

[0227] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / adhesive resin 20 / VM-PET12 / internal heat(2)40 "VM-PET" means vapor deposited film.

[0228] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can store, for example, alcoholic beverages or soft drinks.

[0229] [Example 12B] A packaging material 20 was produced in the same manner as in Example 12A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0230] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / Bio stamp / External heat 20 / Paper / Adhesive resin 20 / VM-PET12 / Internal heat (2)40

[0231] [Example 13A] In the same manner as in Example 1A, a paper base layer 14 was prepared, and an outer thermoplastic resin layer 13 was formed on the paper base layer 14. The thickness of the outer thermoplastic resin layer 13 was 20 μm.

[0232] Next, the paper base layer 14 on which the outer thermoplastic resin layer 13 was formed and the barrier layer 26 were bonded together by a sand lamination method via the adhesive resin layer 25. Aluminum foil (thickness 7 μm) was used as the barrier layer 26. Fossil fuel-derived polyethylene was used as the adhesive resin layer 25. The thickness of the adhesive resin layer 25 was 20 μm.

[0233] Next, the barrier layer 26 and the inner thermoplastic resin layer 15 were bonded together by a sand lamination method via an adhesive resin layer 30. A polyethylene film (thickness 40 μm) derived from fossil fuels was used as the inner thermoplastic resin layer 15. A polyethylene derived from fossil fuels was used as the adhesive resin layer 30. The thickness of the adhesive resin layer 30 was 20 μm.

[0234] Subsequently, in the same manner as in Example 1A, a printed layer 12 and a surface protective layer 11 were formed on the outer thermoplastic resin layer 13. In this manner, a packaging material 20 having the layer structure shown in FIG. 8 was produced.

[0235] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / adhesive resin 20 / AL foil 7 / adhesive resin 20 / internal heat (1) 40

[0236] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can store, for example, alcoholic beverages or soft drinks.

[0237] [Example 13B] A packaging material 20 was produced in the same manner as in Example 13A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0238] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / Bio stamp / External heat 20 / Paper / Adhesive resin 20 / AL foil 7 / Adhesive resin 20 / Internal heat (1) 40

[0239] [Example 14A] A packaging material 20 was produced in the same manner as in Example 13A, except that a vapor-deposited film (thickness: 12 μm) in which an aluminum vapor-deposited film was formed on a polyethylene terephthalate film was used as the barrier layer 26.

[0240] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / print / external heat 20 / paper / adhesive resin 20 / VM-PET12 / adhesive resin 20 / internal heat (1) 40

[0241] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can store, for example, alcoholic beverages or soft drinks.

[0242] [Example 14B] A packaging material 20 was produced in the same manner as in Example 14A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0243] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio table / Bio stamp / External heat 20 / Paper / Adhesive resin 20 / VM-PET12 / Adhesive resin 20 / Internal heat (1) 40

[0244] [Example 15A] In the same manner as in Example 1A, a paper base layer 14 was prepared, and an outer thermoplastic resin layer 13 was formed on the paper base layer 14. The thickness of the outer thermoplastic resin layer 13 was 20 μm.

[0245] Next, the paper base layer 14 on which the outer thermoplastic resin layer 13 was formed and the barrier layer 26 were bonded together by a sand lamination method via the adhesive resin layer 25. Aluminum foil (thickness 7 μm) was used as the barrier layer 26. Fossil fuel-derived polyethylene was used as the adhesive resin layer 25. The thickness of the adhesive resin layer 25 was 20 μm.

[0246] Next, the barrier layer 26 and the inner thermoplastic resin layer 15 were bonded together by a dry lamination method via an adhesive layer 27. A polyethylene film (thickness 60 μm) derived from fossil fuels was used as the inner thermoplastic resin layer 15. In the dry lamination method, a polyester polyol, which is a reaction product of a polyfunctional alcohol derived from fossil fuels and a polyfunctional carboxylic acid derived from fossil fuels, was prepared as the main agent. Also, an isocyanate compound derived from fossil fuels was prepared as the curing agent.

[0247] Subsequently, in the same manner as in Example 1A, a printed layer 12 and a surface protective layer 11 were formed on the outer thermoplastic resin layer 13. In this manner, a packaging material 20 having the layer structure shown in FIG. 9 was produced.

[0248] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / adhesive resin 20 / AL foil 7 / contact / internal heat (1) 60

[0249] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can store, for example, alcoholic beverages or soft drinks.

[0250] [Example 15B] A packaging material 20 was produced in the same manner as in Example 15A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0251] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / Bio mark / External heat 20 / Paper / Adhesive resin 20 / AL foil 7 / Adhesive / Internal heat (1) 60

[0252] [Example 16A] A packaging material 20 was produced in the same manner as in Example 15A, except that a vapor-deposited film (thickness: 12 μm) in which an aluminum vapor-deposited film was formed on a polyethylene terephthalate film was used as the barrier layer 26.

[0253] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / adhesive resin 20 / VM-PET12 / contact / internal heat(1)60

[0254] Next, a paper container for liquids 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquids 40 can store, for example, alcoholic beverages or soft drinks.

[0255] [Example 16B] A packaging material 20 was produced in the same manner as in Example 16A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0256] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / Bio mark / External heat 20 / Paper / Adhesive resin 20 / VM-PET12 / Adhesive / Internal heat(1)60

[0257] [Example 17A] In the same manner as in Example 1A, a paper base layer 14 was prepared, and an outer thermoplastic resin layer 13 was formed on the paper base layer 14. The thickness of the outer thermoplastic resin layer 13 was 20 μm.

[0258] Next, the film constituting the plastic film layer 28 and the film constituting the barrier layer 26 were bonded together by a dry lamination method via the adhesive layer 27. An aluminum foil (thickness 7 μm) was used as the barrier layer 26. A PET film (thickness 12 μm) containing fossil fuel-derived polyethylene terephthalate was used as the plastic film layer 28. In the dry lamination method, a polyester polyol, which is a reaction product of a fossil fuel-derived polyfunctional alcohol and a fossil fuel-derived polyfunctional carboxylic acid, was prepared as the main agent. In addition, an isocyanate compound derived from fossil fuel was prepared as the curing agent.

[0259] Next, the paper base layer 14 on which the outer thermoplastic resin layer 13 was formed and the plastic film layer 28 attached to the barrier layer 26 were bonded together by a sand lamination method via an adhesive resin layer 25. Fossil fuel-derived polyethylene was used as the adhesive resin layer 25. The adhesive resin layer 25 had a thickness of 20 μm.

[0260] Next, the intermediate thermoplastic resin layer 22 and the inner thermoplastic resin layer 15 were formed on the barrier layer 26 by melt extrusion lamination. Fossil fuel-derived polyethylene was used as the intermediate thermoplastic resin layer 22. The intermediate thermoplastic resin layer 22 had a thickness of 20 μm. Fossil fuel-derived polyethylene was used as the inner thermoplastic resin layer 15. The inner thermoplastic resin layer 15 had a thickness of 40 μm.

[0261] Subsequently, in the same manner as in Example 1A, a printed layer 12 and a surface protective layer 11 were formed on the outer thermoplastic resin layer 13. In this manner, a packaging material 20 having the layer structure shown in FIG. 10 was produced.

[0262] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / adhesive resin 20 / PET 12 / adhesive / AL foil 7 / medium heat 20 / internal heat (2) 40

[0263] Next, a paper container 40 for liquids shown in Fig. 12 was produced using the packaging material 20. The paper container 40 for liquids can contain, for example, detergents or chemical products.

[0264] [Example 17B] A packaging material 20 was produced in the same manner as in Example 17A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0265] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / Bio mark / External heat 20 / Paper / Adhesive resin 20 / PET 12 / Adhesive / AL foil 7 / Medium heat 20 / Internal heat (2) 40

[0266] [Example 18A] In the same manner as in Example 1A, a paper base layer 14 was prepared, and an outer thermoplastic resin layer 13 was formed on the paper base layer 14. The thickness of the outer thermoplastic resin layer 13 was 20 μm.

[0267] Next, a polyolefin resin layer 23 was formed on the paper base layer 14 by melt extrusion lamination. Fossil fuel-derived polyethylene was used as the polyolefin resin layer 23. The thickness of the polyolefin resin layer 23 was 20 μm.

[0268] Next, the polyolefin resin layer 23 and the barrier layer 26 were bonded together by a sand lamination method via the adhesive resin layer 25. An aluminum foil (thickness 7 μm) was used as the barrier layer 26. Fossil fuel-derived polyethylene was used as the adhesive resin layer 25. The thickness of the adhesive resin layer 25 was 5 μm.

[0269] Next, the intermediate thermoplastic resin layer 22 and the inner thermoplastic resin layer 15 were formed on the barrier layer 26 by melt extrusion lamination. Fossil fuel-derived polyethylene was used as the intermediate thermoplastic resin layer 22. The intermediate thermoplastic resin layer 22 had a thickness of 5 μm. Fossil fuel-derived polyethylene was used as the inner thermoplastic resin layer 15. The inner thermoplastic resin layer 15 had a thickness of 30 μm.

[0270] Subsequently, in the same manner as in Example 1A, a printed layer 12 and a surface protective layer 11 were formed on the outer thermoplastic resin layer 13. In this manner, a packaging material 20 having the layer structure shown in FIG. 11 was produced.

[0271] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / PE 20 / adhesive resin 5 / AL foil 7 / medium heat 5 / internal heat (2) 30

[0272] Next, a paper container for liquid 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquid 40 can contain, for example, a milk drink or a soft drink.

[0273] [Example 18B] A packaging material 20 was produced in the same manner as in Example 18A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0274] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / Bio print / External heat 20 / Paper / PE 20 / Adhesive resin 5 / AL foil 7 / Medium heat 5 / Internal heat (2) 30

[0275] [Example 19A] A packaging material 20 was produced in the same manner as in Example 18A, except that a vapor-deposited film (thickness: 12 μm) in which an aluminum vapor-deposited film was formed on a polyethylene terephthalate film was used as the barrier layer 26.

[0276] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / print / external heat 20 / paper / PE 20 / adhesive resin 5 / VM-PET 12 / medium heat 5 / internal heat (2) 30

[0277] Next, a paper container for liquid 40 shown in Fig. 12 was produced using the packaging material 20. The paper container for liquid 40 can contain, for example, a milk drink or a soft drink.

[0278] [Example 19B] A packaging material 20 was produced in the same manner as in Example 19A, except that the binder resin for the printed layer 12 was one containing nitrocellulose derived from biomass.

[0279] The layer structure of the packaging material 20 of this embodiment is expressed as follows. Bio surface / Bio mark / External heat 20 / Paper / PE 20 / Adhesive resin 5 / VM-PET 12 / Medium heat 5 / Internal heat (2) 30

[0280] FIG. 13 shows examples of the layer configurations and types of packaging containers of the packaging materials 20 of Examples 1A to 19B. [Explanation of symbols]

[0281] 11 Surface protective layer 12 printing layer 13 Outer thermoplastic resin layer 14 Paper base layer 15 Inner thermoplastic resin layer 20 Packaging materials 21 Barrier resin layer 22 Intermediate thermoplastic resin layer 23 Polyolefin resin layer 24 Middle thermoplastic resin layer 25 Adhesive resin layer 26 Barrier Layer 27 Adhesive layer 28 Plastic Film Layer 29 Anchor coat layer 30 Adhesive resin layer 31 Adhesive layer 40 Liquid cartons 41 Torso 42 Bottom 43 Top 44 Inclined plate 45 Folding section 46 Glue

Claims

1. A packaging material in which at least a surface protective layer, a printing layer, an outer thermoplastic resin layer, a paper base layer, and an inner thermoplastic resin layer are laminated in this order, the outer thermoplastic layer comprises polyethylene; The surface protective layer contains nitrocellulose derived from biomass, The surface protective layer further contains a cured product of a polyol and an isocyanate compound, The packaging material further comprises a barrier resin layer.

2. The packaging material according to claim 1 , wherein at least one of the polyol or the isocyanate compound contains a biomass-derived component.

3. The packaging material of claim 1 or 2, further comprising a barrier layer between the paper substrate layer and the inner thermoplastic resin layer.

4. The packaging material of claim 3 , wherein the barrier layer is a metal foil or a vapor-deposited film.

5. A packaging product comprising a packaging material according to any one of claims 1 to 4.

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