JP2020055161A - Packaging material and packaging product - Google Patents

Abstract

To provide a packaging material with an improved degree of biomass.SOLUTION: A packaging material at least has a surface resin layer, a printed layer, and a paper substrate layer, which are laminated in this order. The surface resin layer has polyethylene, polyethylene terephthalate or polypropylene. The printed layer has a colorant, nitrocellulose, and a cured product of a polyol and an isocyanate compound. At least one of the nitrocellulose, polyol, or isocyanate compound has a biomass-derived component.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a packaging material containing a biomass-derived component and a packaging product provided with the packaging material.

  2. Description of the Related Art Conventionally, various packaging materials have been developed and proposed as packaging materials for configuring packaging products for filling and packaging various articles such as food and drink, pharmaceuticals, chemicals, cosmetics, sanitary products, daily necessities, and the like. The packaging material is composed of a laminate including at least a base layer and a printed layer for forming a printed pattern.

  In recent years, with the growing demand for the establishment of a recycling-based society, in the field of laminates that constitute packaging materials, as in the field of energy, it has been desired to break away from fossil fuels, and the use of biomass has attracted attention. I have. Biomass is an organic compound that is photosynthesized from carbon dioxide and water, and is a so-called carbon-neutral renewable energy that is converted into carbon dioxide and water again by using it. Recently, biomass plastics using biomass as a raw material have been rapidly commercialized, and attempts have been made to produce various resins from biomass raw materials.

  As a biomass-derived resin, commercial production of polylactic acid (PLA), which is manufactured via lactic acid fermentation, has begun, but its performance as a plastic, including its biodegradability, is the current general-purpose plastic. Therefore, there is a limit in the product use and the method of manufacturing the product, and the product has not been widely used. In addition, a life cycle assessment (LCA) evaluation is performed on the PLA, and the energy consumption at the time of manufacturing the PLA and the equivalence at the time of replacing the general-purpose plastic are discussed.

  Here, as the general-purpose plastic, various types such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, and polyester are used. In particular, polyethylene is formed into films, sheets, bottles, and the like, and is used for various uses such as packaging materials, and is widely used worldwide. Therefore, using polyethylene derived from the conventional fossil fuel has a large environmental load. Therefore, it is desired to reduce the amount of fossil fuel used by using biomass-derived raw materials in the production of polyethylene. For example, to date, it has been studied to produce ethylene and butylene as 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).

JP 2011-506628 A JP 2018-51788 A

  Also in the field of packaging materials for paper containers including a paper base layer, it is desired to reduce the amount of fossil fuel used by using biomass-derived raw materials.

  The present invention has been made in view of such a point, and an object of the present invention is to provide a packaging material for a paper container with an increased degree of biomass.

  The present invention is a packaging material in which at least a surface resin layer, a printing layer, and a paper base layer are sequentially laminated, wherein the surface resin layer contains polyethylene, polyethylene terephthalate, or polypropylene, and the printing layer is colored. A packaging material comprising an agent, a nitrocellulose, and a cured product of a polyol and an isocyanate compound, wherein at least one of the nitrocellulose, the polyol or the isocyanate compound contains a biomass-derived component.

  In the packaging material according to the present invention, the nitrocellulose may include a biomass-derived component.

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

  In the packaging material according to the present invention, the printing layer may further include a polyamide resin.

  In the packaging material according to the present invention, the polyamide resin may include a biomass-derived component.

  In the packaging material according to the present invention, the surface resin layer may include polyethylene containing a biomass-derived component.

  The present invention is a packaged product provided with the packaging material described above.

  ADVANTAGE OF THE INVENTION According to this invention, the biomass degree of the packaging material containing a paper base material layer can be raised.

It is a sectional view showing an example of the packaging material by a 1st embodiment of the present invention. It is a sectional view showing an example of the packaging material by a 1st embodiment of the present invention. It is a sectional view showing an example of the packaging material by a 1st embodiment of the present invention. It is a sectional view showing an example of the packaging material by a 1st embodiment of the present invention. It is a sectional view showing an example of the packaging material by a 1st embodiment of the present invention. It is a sectional view showing an example of the packaging material by a 1st embodiment of the present invention. It is a sectional view showing an example of the packaging material by a 1st embodiment of the present invention. It is a sectional view showing an example of the packaging material by a 1st embodiment of the present invention. It is a sectional view showing an example of the packaging material by a 1st embodiment of the present invention. It is a sectional view showing an example of the packaging material by a 1st embodiment of the present invention. It is a sectional view showing an example of the packaging material by a 1st embodiment of the present invention. It is a sectional view showing an example of the packaging material by a 1st embodiment of the present invention. It is a figure showing an example of a packaging container provided with packaging material by a 1st embodiment of the present invention. It is a figure which shows another example of the packaging container provided with the packaging material by 2nd Embodiment of this invention. It is a figure which shows the layer constitution of the packaging material of Examples 1A-10. It is a figure which shows the layer structure of the packaging material of Example 1A, 1L, 1P, and 1Q. It is a figure which shows the layer structure of the packaging material of Example 1A and 2A-12.

  The laminate constituting the packaging material according to the present invention includes at least a surface resin layer, a print layer, and a paper base layer that are sequentially laminated from the outer surface side to the inner surface side. The inner surface is a surface located on the side of the content accommodated in the packaging product in the packaging product formed from the packaging material. The outer surface is a surface located on the opposite side of the inner surface. In the present application, the term “order” in descriptions such as “provide in this order” and “laminated in order” indicates the order in the direction from the outer surface side to the inner surface side, unless otherwise specified.

  In the present invention, the biomass degree described below is preferably 40% or more, more preferably 80% or more and less than 100%, in the entire laminate constituting the packaging material. When the biomass degree is in the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

First Embodiment FIG. 1 is a sectional view showing an example of a packaging material 20 according to a first embodiment of the present invention. The packaging material 20 includes a surface resin layer 11, a print layer 12, a paper base layer 14, and an inner thermoplastic resin layer 15 in this order. The surface resin layer 11 forms the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 forms the inner surface 20x of the packaging material 20.

  FIG. 2 is a cross-sectional view illustrating another example of the packaging material 20 according to the first embodiment of the present invention. The packaging material 20 includes a surface resin layer 11, a printing layer 12, a paper base layer 14, a barrier resin layer 21, an intermediate thermoplastic resin layer 22, and an inner thermoplastic resin layer 15 in this order. The surface resin layer 11 forms the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 forms the inner surface 20x of the packaging material 20.

  FIG. 3 is a sectional view showing another example of the packaging material 20 according to the first embodiment of the present invention. The packaging material 20 includes a surface resin layer 11, a print layer 12, a paper base layer 14, a paper base layer inner surface side thermoplastic 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 in this order. The surface resin layer 11 forms the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 forms the inner surface 20x of the packaging material 20.

  FIG. 4 is a sectional view showing another example of the packaging material 20 according to the first embodiment of the present invention. The packaging material 20 includes a surface resin layer 11, a print layer 12, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, a plastic film layer 28, and an anchor coat layer 29. And an inner thermoplastic resin layer 15 in this order. The surface resin layer 11 forms the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 forms the inner surface 20x of the packaging material 20.

  FIG. 5 is a sectional view showing another example of the packaging material 20 according to the first embodiment of the present invention. The packaging material 20 includes a surface resin layer 11, a print layer 12, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, a plastic film layer 28, and an anchor coat layer 29. And an adhesive resin layer 30 and an inner thermoplastic resin layer 15 in this order. The surface resin layer 11 forms the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 forms the inner surface 20x of the packaging material 20.

  FIG. 6 is a cross-sectional view illustrating another example of the packaging material 20 according to the first embodiment of the present invention. The packaging material 20 includes a surface resin layer 11, a printing layer 12, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, a plastic film layer 28, and an adhesive layer 31. , A polyethylene film layer 32, an anchor coat layer 29, and an inner thermoplastic resin layer 15 in this order. The surface resin layer 11 forms the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 forms the inner surface 20x of the packaging material 20.

  FIG. 7 is a sectional view showing another example of the packaging material 20 according to the first embodiment of the present invention. The packaging material 20 includes a surface resin layer 11, a printing layer 12, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, a plastic film layer 28, and an adhesive layer 31. , A polyethylene film layer 32, an anchor coat layer 29, an adhesive resin layer 30, and an inner thermoplastic resin layer 15 in this order. The surface resin layer 11 forms the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 forms the inner surface 20x of the packaging material 20.

  FIG. 8 is a sectional view showing another example of the packaging material 20 according to the first embodiment of the present invention. The packaging material 20 includes at least a surface resin layer 11, a print layer 12, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, and an inner thermoplastic resin layer 15 in this order. The surface resin layer 11 forms the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 forms the inner surface 20x of the packaging material 20.

  FIG. 9 is a sectional view showing another example of the packaging material 20 according to the first embodiment of the present invention. The packaging material 20 includes at least the surface resin layer 11, the printing layer 12, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive resin layer 30, and the inner thermoplastic resin layer 15. Prepare in this order. The surface resin layer 11 forms the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 forms the inner surface 20x of the packaging material 20.

  FIG. 10 is a sectional view showing another example of the packaging material 20 according to the first embodiment of the present invention. The packaging material 20 includes at least a surface resin layer 11, a printing layer 12, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, a polyethylene film layer 32, and an anchor coat. A layer 29 and an inner thermoplastic resin layer 15 are provided in this order. The surface resin layer 11 forms the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 forms the inner surface 20x of the packaging material 20.

  FIG. 11 is a cross-sectional view illustrating another example of the packaging material 20 according to the first embodiment of the present invention. The packaging material 20 includes at least a surface resin layer 11, a printing layer 12, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, a polyethylene film layer 32, and an anchor coat. A layer 29, an adhesive resin layer 30, and an inner thermoplastic resin layer 15 are provided in this order. The surface resin layer 11 forms the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 forms the inner surface 20x of the packaging material 20.

  The packaging material 20 shown in FIG. 12 is different only in that the inner thermoplastic resin layer 15 includes a plurality of layers, for example, two layers of a first layer 151 and a second layer 152. This is the same as the packaging material 20 shown in FIG. The first layer 151 of the inner thermoplastic resin layer 15 forms the inner surface 20x of the packaging material 20, and the second layer 152 is laminated on the outer surface 20y side of the first layer 151.

  In addition, it is also possible to appropriately combine a plurality of layer configurations of the packaging material 20 shown in FIGS. 1 to 12 described above. For example, the inner thermoplastic resin layer 15 of the packaging material 20 shown in FIGS. 2 to 11 may include a plurality of layers as in the case of the inner thermoplastic resin layer 15 of the packaging material 20 shown in FIG.

  Hereinafter, each layer constituting the packaging material 20 will be described.

(Paper base layer)
The paper base material layer 14 is a layer containing paper. The paper base layer 14 has a basis weight of 100 g / m ² or more and 700 g / m ² or less, preferably 150 g / m ² or more and 600 g / m ² or less, more preferably 200 g / m ² or more and 500 g / m ² or less. The paper substrate layer 14 is intended for white paperboard in general, but ivory paper using natural pulp, milk carton base paper, cup base paper, and the like are particularly preferable from the viewpoint of safety.

  The paperboard may use neutral rosin, alkyl ketene dimer, or alkenyl succinic anhydride as a sizing agent, or cationic polyacrylamide or cationic starch as a fixing agent. It is also possible to use a sulfuric acid band to make paper in a neutral region of pH 6 or more and pH 9 or less. In addition, if necessary, in addition to the above-mentioned sizing agent, other than the fixing agent, various fillers for papermaking, a retention enhancer, a dry paper strength enhancer, a wet paper strength enhancer, a binder, a dispersant, a flocculant, a plasticizer. Agents and adhesives may be appropriately contained.

(Print layer)
The printing layer 12 is a layer formed by printing to display decoration, display of contents, display of a best-before period, display of a manufacturer, a seller, and the like, and display and beauty. The printing layer 12 includes, for example, a picture layer that forms a desired arbitrary picture such as a picture, a photograph, a character, a number, a figure, a symbol, and a pattern. The printing layer may further include a ground color layer formed by printing so as to make the picture of the picture layer stand out.

  In the present embodiment, the print layer 12 is formed by gravure printing. The printing layer 12 contains a coloring agent and a binder resin. The ink composition for forming the print layer 12 contains a solvent suitable for gravure printing, in addition to the colorant and the binder resin.

(Coloring agent)
The colorant is not particularly limited, and conventionally known pigments and dyes can be used.

(Binder resin)
The binder resin contains a biomass-derived component. For example, the binder resin includes nitrocellulose and a cured product of a polyol and an isocyanate compound. The binder resin contains a biomass-derived component. For example, at least one of nitrocellulose, a polyol, and an isocyanate compound contains a biomass-derived component. For example, nitrocellulose contains a biomass-derived component. Alternatively, at least one of the polyol and the isocyanate compound contains a biomass-derived component.

<Nitrocellulose>
Nitrocellulose is a nitro group-substituted cellulosic resin in which a part of the hydroxyl groups of the cellulose skeleton has been esterified with nitric acid. When the nitrocellulose contains a biomass-derived component, the cellulose skeleton of the nitrocellulose resin is a biomass material. As nitrocellulose, general nitrocellulose can be used without any problem. In particular, nitrocellulose substituted with an average of 1.3 to 2.7 nitro groups per glucose unit constituting the cellulose skeleton is preferable. It is preferable to use it.

  When the nitrocellulose does not contain a biomass-derived component, the cellulose skeleton of the nitrocellulose resin may be, for example, from a fossil fuel.

  Nitrocellulose is classified into L type and H type according to the molecular weight. From the aspect of solubility in an organic solvent, it is preferable to use an L-type one.

<Cured product of polyol and isocyanate compound>
The cured product of the polyol and the isocyanate compound is preferably formed using a cured product in which at least one of the polyol as the main component and the isocyanate compound as the curing agent contains a biomass-derived component. As the polyol, a polyester polyol which is a reactant of a polyfunctional alcohol and a polyfunctional carboxylic acid, a polyether polyol which is a reactant of a polyfunctional alcohol and a polyfunctional isocyanate, or a reactant of a polyfunctional alcohol and a carbonate Certain polycarbonate polyols can be used.

<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 examples can be given as polyester polyols containing biomass-derived components.
・ Reacted product of polyfunctional alcohol derived from biomass and polyfunctional carboxylic acid derived from biomass ・ Reacted product of polyfunctional alcohol derived from fossil fuel and polyfunctional carboxylic acid derived from biomass ・ Polyfunctional alcohol derived from biomass and derived from fossil fuel With polyfunctional carboxylic acid

  As the polyfunctional alcohol derived from biomass, an aliphatic polyfunctional alcohol obtained from a plant material such as corn, sugar cane, cassava, and sago palm can be used. Examples of the aliphatic polyfunctional alcohols derived from biomass include, for example, polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), and butylene obtained from plant raw materials by the following method. Glycol (BG), hexamethylene glycol, etc., and any of them can be used. These may be used alone or in combination.

Biomass-derived polypropylene glycol is produced from glycerol via 3-hydroxypropyl aldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant materials. Compared with polypropylene glycol produced by the EO production method, polypropylene glycol produced by a bio-method such as the above fermentation method can provide useful by-products such as lactic acid from the viewpoint of safety, and can also keep production costs low. It is also preferred that it is possible.
Butylene glycol derived from biomass can be produced by producing succinic acid by producing and fermenting glycol from plant raw materials and hydrogenating it.
Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

  As the polyfunctional alcohol derived from fossil fuel, a compound having two or more, preferably 2 to 8 hydroxyl groups in one molecule can be used. Specifically, as the polyfunctional alcohol derived from fossil fuel, there is no particular limitation, and conventionally known ones 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 and the like can be used. These may be used alone or in combination of two or more.

  Biomass-derived polyfunctional carboxylic acids include recyclable plant-derived oils such as soybean oil, linseed oil, tung oil, coconut oil, palm oil, castor oil, and waste edible oil mainly composed of them. An aliphatic polyfunctional carboxylic acid obtained from a plant material such as oil can be used. Examples of the aliphatic polyfunctional carboxylic acid derived from biomass include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, dimer acid and the like. For example, sebacic acid is produced as a by-product of heptyl alcohol by subjecting ricinoleic acid obtained from castor oil to alkaline pyrolysis. 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.

  As the polyfunctional carboxylic acid derived from the 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 conventionally known ones can be used. Examples thereof include adipic acid, dodecane diacid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and maleic anhydride. Acids, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, and dimer acid, and ester compounds thereof. The aromatic polyfunctional carboxylic acid derived from fossil fuel is not particularly limited, and conventionally known ones can be used.For example, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, And pyromellitic acid, and ester compounds thereof. These may be used alone or in combination of two or more.

<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. The following examples can be given as polyether polyols containing components derived from biomass.
・ Reacted product of polyfunctional alcohol derived from biomass and polyfunctional isocyanate derived from biomass ・ Reacted product of polyfunctional alcohol derived from fossil fuel and polyfunctional isocyanate derived from biomass ・ Multifunctional alcohol derived from biomass and polyfunctional isocyanate Reactant with functional isocyanate

  As the polyfunctional alcohol derived from biomass and the polyfunctional alcohol derived from fossil fuel, the polyfunctional alcohol derived from biomass and the polyfunctional alcohol derived from fossil fuel described in the above polyester polyol can be used.

  As a biomass-derived polyfunctional isocyanate, a plant-derived divalent carboxylic acid is acid-amidated, converted to a terminal amino group by reduction, and further reacted with phosgene to convert the amino group to an isocyanate group. The obtained one 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. Alternatively, a plant-derived diisocyanate can be obtained by using a plant-derived amino acid as a raw material and converting the amino group into an isocyanate group. For example, lysine diisocyanate (LDI) is obtained by subjecting a carboxyl group of lysine to methyl esterification and then converting an amino group to an isocyanate group. In addition, 1,5-pentamethylene diisocyanate is obtained by decarboxylating a carboxyl group of lysine and then converting an amino group to an isocyanate group.

  Other methods for synthesizing 1,5-pentamethylene diisocyanate include a phosgenation method and a carbamate method. More specifically, the phosgenation method is a method in which 1,5-pentamethylenediamine or a salt thereof is directly reacted with phosgene or a method in which pentamethylenediamine hydrochloride is suspended in an inert solvent and reacted with phosgene. According to the method, 1,5-pentamethylene diisocyanate is synthesized. In the carbamate method, 1,5-pentamethylene diisocyanate or a salt thereof is first carbamate to produce pentamethylene dicarbamate (PDC), and then thermally decomposed to give 1,5-pentamethylene diisocyanate. It is to be synthesized. In the present invention, as a polyisocyanate suitably used, 1,5-pentamethylene diisocyanate-based polyisocyanate (trade name: Stabio (registered trademark)) manufactured by Mitsui Chemicals, Inc. may be mentioned.

  The polyfunctional isocyanate derived from fossil fuel is not particularly limited, and conventionally known ones can be used. For example, toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-isocyanate 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), Julilylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4'-diisocyanate diisocyanate Aromatic diisocyanate such as Njiru the like. Aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) ), 1,5-tetrahydronaphthalenediisocyanate, isophorone diisocyanate, alicyclic diisocyanates such as hydrogenated MDI and hydrogenated XDI. These may be used alone or in combination of two or more.

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

  As the polyfunctional alcohol derived from biomass, the polyfunctional alcohol derived from biomass described in the above polyester polyol can be used.

<Isocyanate compound>
As the isocyanate compound containing a biomass-derived component, the polyfunctional isocyanate derived from biomass described for the polyether polyol can be used.

The printing layer 12 has a biomass degree of preferably 5% or more, more preferably 5% or more and 50% or less, and still more preferably 10% or more and 50% or less. When the biomass degree is in 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 or more and 10 g / m ² or less, more preferably 1 g / m ² or more and 5 g / m ² or less, and still more preferably 1 g / m ² or more and 3 g / m ^{2. 2} or less. The printing layer 12 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 still more preferably 1 μm or more and 3 μm or less. Note that a plurality of printing layers 12 having such weight and thickness may be provided.

  The “degree of biomass” may be indicated by a value obtained by measuring the content of carbon derived from biomass by measuring radioactive carbon (C14), or may be indicated by a weight ratio of a biomass-derived component.

When the value obtained by measuring the content of carbon derived from biomass by radioactive carbon (C14) measurement is indicated as "biomass degree", the "biomass degree" can be obtained as follows. That is, since carbon dioxide in the atmosphere contains C14 at a constant rate (105.5 pMC), plants that take in carbon dioxide in the atmosphere and grow, for example, corn, also have a C14 content of about 105.5 pMC. It is known that It is also known that C14 is hardly contained in fossil fuels. Therefore, by measuring the ratio of C14 contained in all the carbon atoms in the polyester, the ratio of carbon derived from biomass can be calculated. When the content of C14 in the print layer 12 is defined as _PC14 , the content P _bio of carbon derived from biomass can be determined as follows.
P _bio (%) = P _C14 /105.5×100

When the “biomass degree” is represented by the weight ratio of the biomass-derived component, the “biomass degree” can be determined as follows. For example, in the case of nitrocellulose, the number of hydroxyl groups contained in one glucose unit (formula weight = 172) constituting the cellulose skeleton as a starting material is three, and thus one to three hydroxyl groups are used. Nitrate esterification (hydrogen replaced by nitro groups (non-biomass material, formula weight = 46)). Then, assuming that the original cellulose skeleton is composed of 100% by weight of the biomass material and the average number of substituted nitro groups per glucose unit is n, the ratio of the biomass material to the entire nitrocellulose molecule ( % By weight) is (172-n)
It can be calculated by × 100 / (172−n + 46n).
The ratio of the biomass material to the entire nitrocellulose molecule is about 78.8% by weight and 2 nitro groups per glucose unit constituting the cellulose skeleton, when substituted with one nitro group on average. Is about 64.9% by weight, and about 55.0% by weight when substituted with three nitro groups (calculated by the above formula).

  Hereinafter, unless otherwise specified, the “degree of biomass” indicates a weight ratio of a biomass-derived component.

(Surface resin layer)
The surface resin layer 11 can be formed using a conventionally known thermoplastic resin. The surface resin layer 11 is located outside the packaging material 20. When the packaging material 20 includes the surface resin layer 11, water resistance, heat sealability, and other physical properties can be imparted.

  Examples of the material used for the surface resin layer 11 include polyethylene such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene or high-density polyethylene, polypropylene, propylene-ethylene copolymer, and ethylene-vinyl acetate copolymer. Polyester such as coalesce, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin, polyethylene terephthalate Examples of the resin include a resin, a polyvinyl chloride resin, a polystyrene resin, and nylon. Low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and ethylene-methacrylic acid copolymer are preferable.

  The surface resin layer 11 may include a material derived from biomass, or may include a material derived from fossil fuel. When the surface resin layer contains a biomass-derived material, the surface resin layer may contain a biomass polyolefin that is a polymer containing a component derived from biomass and a polymer of a monomer containing ethylene. For example, the surface resin layer 11 may include polyethylene containing a biomass-derived component. When the surface resin layer 11 contains a material derived from biomass, the surface resin layer 11 preferably has a biomass degree of 5% or more, more preferably 10% or more and 95% or less. When the biomass degree is in the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

  Surface resin layer 11 preferably has a thickness of 10 μm or more and 30 μm or less, more preferably 20 μm or more and 25 μm or less.

(Inner thermoplastic resin layer)
The inner thermoplastic resin layer 15 can be formed using a conventionally known thermoplastic resin. The thermoplastic resin used for forming the inner thermoplastic resin layer 15 is, for example, a polyolefin such as polyethylene. The inner thermoplastic resin layer 15 is located inside the packaging material 20. When the packaging material 20 includes the inner thermoplastic resin layer 15, heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, piercing resistance, and other physical properties can be imparted.

  The inner thermoplastic resin layer 15 may include a biomass-derived component or may not include a biomass-derived component. When the inner thermoplastic resin layer 15 is formed of a material containing a biomass-derived component, the inner thermoplastic resin layer 15 can be formed using the following biomass polyolefin. In the case where the inner thermoplastic resin layer 15 is formed of a material containing no biomass-derived component, the inner thermoplastic resin layer 15 can be formed using a conventionally known thermoplastic resin derived from fossil fuel.

  Biomass polyolefin is a polymer of a monomer containing an olefin such as ethylene derived from biomass. Since an olefin derived from biomass is used as a monomer as a raw material, a polyolefin polymerized is derived from biomass. In addition, the raw material monomer of polyolefin does not need to contain 100 mass% of olefins derived from biomass.

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

  The biomass-derived fermented ethanol refers to purified ethanol produced by contacting a culture solution containing a carbon source obtained from a plant material with a microorganism-producing ethanol-produced product or a product derived from a crushed product thereof. For purification of ethanol from the culture solution, conventionally known methods such as distillation, membrane separation, and extraction can be applied. For example, a method of adding benzene, cyclohexane or the like and causing azeotropic distillation, or removing water by membrane separation or the like can be mentioned.

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

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

  As the biomass polyolefin, polyethylene or a copolymer of ethylene and an α-olefin may be used alone or in combination of two or more. In particular, the biomass polyolefin is preferably polyethylene. This is because by using ethylene, which is a biomass-derived raw material, it is theoretically possible to produce a biomass-derived component.

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

Biomass polyolefin, preferably 0.91 g / cm ³ or more 0.93 g / cm ³ or less, more preferably 0.912 g / cm ³ or more 0.928 g / cm ³ or less, more preferably 0.915 g / cm ³ or more 0 It has a density of 0.925 g / cm ³ or less. The density of the biomass polyolefin is a value measured according to the method specified in Method A of JIS K7112-1980 after performing annealing described in JIS K6760-1995. When the density of the biomass polyolefin is 0.91 g / cm ³ or more, the rigidity of the inner thermoplastic resin layer containing the biomass polyolefin can be increased, and the biomass polyolefin can be suitably used as an inner layer of a packaged product. In addition, when the density of the biomass polyolefin is 0.93 g / cm ³ or less, the transparency and mechanical strength of the inner thermoplastic resin layer containing the biomass polyolefin can be increased, and the biomass polyolefin can be suitably used as an inner layer of a packaged product. it can.

  The biomass polyolefin has a melt flow of from 0.1 g / 10 min to 10 g / 10 min, preferably from 0.2 g / 10 min to 9 g / 10 min, more preferably from 1 g / 10 min to 8.5 g / 10 min. It has a rate (MFR). The melt flow rate is a value measured by the method A at a temperature of 190 ° C. and a load of 21.18 N in a 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. When the MFR of the biomass polyolefin is 10 g / 10 minutes or less, the mechanical strength of the inner thermoplastic resin layer containing the biomass polyolefin can be increased.

Suitable biomass polyolefins include biomass-derived low-density polyethylene (trade name: SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree 95%) manufactured by Braskem. Biomass-derived low-density polyethylene manufactured by Braskem (trade name: SPB681, density: 0.922 g / cm ³ , MFR: 3.8 g / 10 minutes, biomass degree 95%), biomass-derived linear chain manufactured by Braskem Low-density polyethylene (trade name: SLL118, density: 0.916 g / cm ³ , MFR: 1.0 g / 10 minutes, biomass degree 87%) and the like.

  As the thermoplastic resin derived from the fossil fuel, for example, low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, Examples include an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, and an ionomer.

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

  The inner thermoplastic resin layer 15 may be a single layer, or may be, for example, a multilayer as shown in FIG. When the inner thermoplastic resin layer 15 is a multilayer, a part of the layers may be configured as a layer made of biomass polyolefin, and the other layers may be configured as a layer made of polyolefin derived from fossil fuel. For example, the first layer 151 in FIG. 12 may be a layer containing biomass polyolefin, and the second layer 152 may be a layer made of polyolefin derived from fossil fuel. Alternatively, the first layer 151 in FIG. 12 may be a layer made of polyolefin derived from fossil fuel, and the second layer 152 may be a layer containing biomass polyolefin. Although not shown, the inner thermoplastic resin layer 15 may include three layers: an inner layer, an intermediate layer, and an outer layer. In this case, the intermediate layer may be a layer made of biomass polyolefin, or a layer made of a mixture of biomass polyolefin and a conventionally known polyolefin derived from a fossil fuel, and the inner layer and the outer layer may be a conventionally known polyolefin derived from a fossil fuel. preferable.

  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 still more preferably 30 μm or more and 150 μm or less.

(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 impart adhesion between respective layers, pinhole resistance, and other physical properties.

  As the intermediate thermoplastic resin layer, for example, 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 can be mentioned, and low density polyethylene, linear low density polyethylene, medium density polyethylene, and ethylene-methacrylic acid copolymer are preferable.

  The intermediate thermoplastic resin layer may include a biomass-derived material or a fossil fuel-derived material. When the intermediate thermoplastic resin layer contains a biomass-derived material, it may contain biomass polyolefin, which is a polymer of a monomer containing ethylene derived from biomass, similarly to the inner thermoplastic resin layer.

  The intermediate thermoplastic resin layer preferably has a thickness of 10 μm or more and 50 μm or less, more preferably 20 μm or more and 25 μm or less.

(Barrier resin layer)
The barrier resin layer 21 contains at least one kind of barrier resin, for example, ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyacrylonitrile, nylon 6, nylon 6,6, and polymethaxylylene adipamide. Examples thereof include polyamides such as (MXD6), polyesters, polyurethanes, and (meth) acrylic resins. Among them, EVOH is preferable from the viewpoint of gas barrier properties that prevent permeation of oxygen gas and water vapor.

  The barrier resin layer 21 may contain an additive as long as the properties of the present invention are not impaired. Examples of the additives include a cross-linking agent, an antioxidant, an anti-blocking agent, a slip agent, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a compatibilizer, and a pigment. Can be

  The thickness of the barrier resin layer 21 is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 7 μm or less.

(The thermoplastic resin layer on the inner side of the paper base layer)
The paper substrate layer inner surface side thermoplastic resin layer 23 is a layer that imparts adhesion, low odor, and other physical properties between the paper substrate layer 14 and other layers. The inner surface side thermoplastic resin layer 23 of the paper base material layer can be formed using a conventionally known thermoplastic resin. The thermoplastic resin used for forming the inner surface side thermoplastic resin layer 23 of the paper base layer is, for example, polyolefin. When a polyolefin is used for forming the paper substrate layer inner surface side thermoplastic resin layer 23, examples of the polyolefin include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, and propylene-ethylene. And copolymers. The thermoplastic resin layer 23 on the inner surface side of the paper base layer is preferably a polyethylene resin layer from the viewpoint of adhesion to the paper base layer 14.

  The thermoplastic resin layer 23 on the inner surface side of the paper base layer preferably has a thickness of 25 μm or more and 80 μm or less, more preferably 30 μm or more and 40 μm or less.

(Barrier layer)
The barrier layer 26 is a layer that imparts or improves gas barrier properties for preventing transmission of oxygen gas and water vapor and the like, and light shielding properties for preventing transmission of visible light and ultraviolet light. The barrier layer is preferably a metal foil or a vapor-deposited film.

(Metal foil)
The metal foil is a member obtained by rolling metal. A conventionally known metal foil can be used as the metal foil. Aluminum foil is preferred from the viewpoint of gas barrier properties that prevent transmission of oxygen gas and water vapor and the like, and light shielding properties that prevent transmission of visible light and ultraviolet light.

(Evaporated film)
The deposition film includes a base material and a deposition film deposited on the base material. The deposited film is located on the outer surface side of the base material.

  The substrate is a plastic film. Various plastics such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, and polyester can be used as the material of the plastic film. The base material may include a biomass-derived component or may not include a biomass-derived component.

  When the substrate contains a biomass-derived component, the substrate can be formed using the following biomass polyester or biomass polyethylene.

  The biomass polyester has ethylene glycol derived from biomass as a diol unit and dicarboxylic acid derived from a fossil fuel as a dicarboxylic acid unit. The base material may further include, in addition to the biomass polyester, a fossil fuel-derived polyester having fossil fuel-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

  When the substrate contains a biomass-derived component, the degree of biomass in the substrate is 5% or more, preferably 10% or more and 30% or less, and more preferably 15% or more and 25% or less. If the biomass degree in the base material is 5% or more, the amount of polyester derived from fossil fuel can be reduced and the environmental load can be reduced as compared with the conventional case.

  Ethylene glycol derived from biomass is derived from ethanol produced from biomass (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method, for example, by producing ethylene glycol via ethylene oxide. Further, commercially available biomass ethylene glycol may be used. For example, biomass ethylene glycol commercially available from Indiaglycol Co., Ltd. can be suitably used.

  As the dicarboxylic acid unit of the biomass polyester, a dicarboxylic acid derived from a fossil fuel is used. As the dicarboxylic acid, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation. Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the derivative of the aromatic dicarboxylic acid include lower alkyl esters of the aromatic dicarboxylic acid, specifically, methyl ester, ethyl ester, propyl ester and butyl. Esters and the like. Of these, terephthalic acid is preferred, and dimethyl terephthalate is preferred as the derivative of the aromatic dicarboxylic acid.

  As the aliphatic dicarboxylic acid, specifically, oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecane diacid, dimer acid, cyclohexanedicarboxylic acid, and the like, usually have 2 to 40 carbon atoms. And a linear or alicyclic dicarboxylic acid. Further, as the derivative of the aliphatic dicarboxylic acid, a lower alkyl ester such as a methyl ester, an ethyl ester, a propyl ester and a butyl ester of the aliphatic dicarboxylic acid or a cyclic acid anhydride of the aliphatic dicarboxylic acid such as succinic anhydride is mentioned. No. Among these, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable, and those containing succinic acid as a main component are particularly preferable. As the derivative of the aliphatic dicarboxylic acid, a methyl ester of adipic acid and succinic acid, or a mixture thereof is more preferable. These dicarboxylic acids can be used alone or in combination of two or more.

  The biomass polyester may be a copolymer polyester obtained by adding a copolymer component as a third component in addition to the diol component and the dicarboxylic acid component. Specific examples of the copolymer component include a bifunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol for forming a crosslinked structure, a trifunctional or higher polycarboxylic acid and / or an anhydride thereof, and a trifunctional carboxylic acid. At least one kind of polyfunctional compound selected from the group consisting of functional or higher oxycarboxylic acids is exemplified. Among these copolymer components, copolymerized polyesters having a high degree of polymerization tend to be easily produced, and therefore oxycarboxylic acids having a bifunctionality and / or a trifunctionality or more are particularly preferably used. Among them, the use of tri- or higher functional oxycarboxylic acids is most preferable because a polyester having a high degree of polymerization can be easily produced in a very small amount without using a chain extender described later.

  The biomass polyester can be obtained by a conventionally known method of polycondensing the above-mentioned diol unit and dicarboxylic acid unit. Specifically, a general method of melt polymerization, such as performing an esterification reaction and / or a transesterification reaction between the dicarboxylic acid component and the diol component and then performing a polycondensation reaction under reduced pressure, or an organic solvent Can be produced by a known solution heat dehydration condensation method using The amount of the diol used for producing the biomass polyester is substantially equimolar to 100 mol of the dicarboxylic acid or a derivative thereof, but generally, the esterification and / or the transesterification reaction and / or the condensation polymerization reaction. It is preferable to use an amount of 0.1 mol% or more and 20 mol% or less in excess because there is a distillate inside.

  A substrate can be formed by using a resin composition of a biomass polyester or a resin composition containing a biomass polyester and a polyester derived from fossil fuel, for example, by forming a film by a T-die method. Specifically, after drying the above-described resin composition, the resin composition is supplied to a melt extruder heated to a temperature of not less than the melting point Tm of the resin composition to a temperature of Tm + 70 ° C. to melt the resin composition. A substrate can be formed by extruding a sheet from a die such as a T-die, and rapidly solidifying the extruded sheet by a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder or the like can be used according to the purpose.

  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.

  When the substrate is formed of a material containing no biomass-derived component, as a plastic film constituting the substrate, 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, Alternatively, a plastic film such as a polypropylene / ethylene-vinyl alcohol copolymer co-extrusion co-stretched film or a composite film in which two or more of these films are laminated can be used.

  As the deposition film, for example, a deposition film of a metal such as aluminum (Al) and lead (Pb) can be used.

(Plastic film layer)
In the present invention, various plastic films may be used as the plastic film layer 28. For example, any of a stretched polyethylene terephthalate film, a stretched nylon film, a stretched polypropylene film, a nylon 6 / meta-xylylenediamine nylon 6 co-pressed co-stretched film or a polypropylene / ethylene-vinyl alcohol copolymer co-pressed co-stretched film, or the like, or A composite film in which two or more of these films are laminated may be used. Incidentally, the plastic film may be coated with polyvinyl alcohol or the like.

  The plastic film layer 28 has a thickness of preferably 9 μm or more and 25 μm or less, more preferably 12 μm or more and 16 μm or less.

(Polyethylene film layer)
In the present invention, various polyethylene films may be used as the polyethylene film layer 32. The material of the polyethylene film layer 32 is, for example, polyethylene such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene. The polyethylene film layer may include a biomass-derived material or a fossil fuel-derived material.

  The polyethylene film layer 32 has a thickness of preferably 25 μm or more and 80 μm or less, more preferably 30 μm or more and 40 μm or less.

(Anchor coat layer)
The anchor coat layer 29 is a layer for improving the adhesion between the plastic film layer 28 or the polyethylene film layer 32 and the inner thermoplastic resin layer 15. As a material constituting the anchor coat layer 29, polyethylene imine or the like can be used. The anchor coat layer 29 can be formed by applying a paint containing these materials and a solvent to the plastic film layer 28 or the polyethylene film layer 32.

(Adhesive resin layer)
The adhesive resin layer is a layer provided when any two layers are bonded. The adhesive resin layer can be formed by a conventionally known method, for example, a melt extrusion lamination method or a sand lamination method. Examples of the thermoplastic resin that can be used for the adhesive resin layer include a polyethylene resin, a polypropylene resin, a cyclic polyolefin resin, or a copolymer resin, a modified resin, or a mixture (including alloys) containing these resins as a main component. ) Can be used. Examples of the polyolefin resin include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear (linear) low-density polyethylene (LLDPE), polypropylene (PP), and metallocene catalyst. Ethylene-α-olefin copolymer, ethylene-polypropylene random or block copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene / maleic acid copolymer, ionomer resin, and interlayer adhesion To improve the above-mentioned polyolefin resin , It can be used acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and an acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as itaconic acid. Further, a resin obtained by graft-polymerizing or copolymerizing an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or an ester monomer with the polyolefin resin 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, and polynorbonene can be used. These resins can be used alone or in combination of two or more. In addition, as the above-mentioned polyethylene resin, a resin using the above-mentioned ethylene derived from biomass as a monomer unit can be used to further improve the degree of biomass.

  When laminating the adhesive resin layer by the melt extrusion lamination method, an anchor coat layer formed by applying an anchor coat agent and drying it may be provided on the surface of the layer to be laminated. Examples of the anchor coating agent include any resin having a heat-resistant temperature of 135 ° C. or higher, such as a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, and a polyethylene imine. An anchor coating agent which is a cured product of a polyacrylic or polymethacrylic resin (polyol) having two or more hydroxyl groups and an isocyanate compound as a curing agent can be preferably used. Further, a silane coupling agent may be used as an additive thereto, and nitrified cotton may be used in combination to increase heat resistance.

  The dried anchor coat layer has a thickness of 0.1 μm or more and 1 μm or less, preferably 0.3 μm or more and 0.5 μm or less. The adhesive resin layer after drying has a thickness of 1 μm or more and 10 μm or less, preferably 2 μm or more and 5 μm or less. The adhesive resin layer preferably has a thickness of 5 μm or more and 50 μm or less, preferably 10 μm or more and 30 μm or less.

(Adhesive layer)
The adhesive layer is a layer provided when two arbitrary layers are bonded. The adhesive layer may include a biomass-derived component. In the adhesive layer containing the biomass-derived component, at least one of the polyol and the isocyanate compound contains the biomass-derived component.

  In the adhesive layer, as the isocyanate compound containing a biomass-derived component, the same isocyanate compound containing a biomass-derived component as in the above-described printing layer 12 can be used. In addition, in the adhesive layer, as the polyol containing the biomass-derived component, the same polyol as that of the print layer 12 can be used. 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 may have different compositions. The composition may be used.

  The adhesive layer has a biomass degree of preferably 5% or more, more preferably 5% or more and 50% or less, and still more preferably 30% or more and 50% or less. When the biomass degree is in the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

The weight of the adhesive layer after drying is preferably from 0.1 g / m ^{2 to} 10 g / m ² , more preferably from 1 g / m ^{2 to} 6 g / m ² , and still more preferably from 2 g / m ^{2 to} 5 g / m ^{2. 2} or less.

  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 still more preferably 2 μm or more and 5 μm or less.

(Production method of packaging material)
Next, an example of a method for manufacturing a laminate constituting the packaging material 20 will be described.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 1 will be described. First, the above-mentioned paper base material layer 14 is prepared. Subsequently, the ink composition described above is printed on the paper base layer 14 by gravure printing to form the print layer 12 on the paper base layer 14. Subsequently, the resin in a molten state is extruded onto the print layer 12 by a melt extrusion lamination method, and the surface resin layer 11 is formed on the print layer 12. Subsequently, the resin in a molten state is extruded on the surface opposite to the surface on which the printing layer 12 and the surface resin layer 11 of the paper base material layer 14 are formed by the melt extrusion lamination method to form the inner thermoplastic resin layer 15. I do. Thereby, a packaging material 20 including the surface resin layer 11, the printing layer 12, the paper base layer 14, and the inner thermoplastic resin layer 15 can be obtained.

  After the inner thermoplastic resin layer 15 is formed on the paper base layer 14, the print layer 12 and the surface resin layer 11 may be formed on the paper base layer 14.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 2 will be described. First, the paper base material layer 14 on which the above-described printing layer 12 and surface resin layer 11 are formed is prepared. Subsequently, the molten resin is extruded on the surface of the paper base layer 14 opposite to the surface on which the printed layer 12 and the surface resin layer 11 are formed by a melt extrusion laminating method, and the barrier resin layer 21 and the intermediate heat The plastic resin layer 22 and the inner thermoplastic resin layer 15 are formed. Thereby, a packaging material 20 including the surface resin layer 11, the printing layer 12, the paper base layer 14, the barrier resin layer 21, the intermediate thermoplastic resin layer 22, and the inner thermoplastic resin layer 15 can be obtained.

  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 print layer 12 and the surface resin layer 11 are formed on the paper base layer 14. May be.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 3 will be described. First, the paper base material layer 14 on which the above-described printing layer 12 and surface resin layer 11 are formed is prepared. Subsequently, a resin in a molten state is extruded by a melt extrusion lamination method onto a surface of the paper base layer 14 opposite to the surface on which the printing layer 12 and the surface resin layer 11 are formed, and the inside of the paper base layer is thermoplastic. The 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 are formed. Thereby, the surface resin layer 11, the print layer 12, the paper base layer 14, the paper base layer inner side thermoplastic resin layer 23, the intermediate thermoplastic resin layer 22, the barrier resin layer 21, the intermediate thermoplastic resin layer 24, A packaging material 20 including the inner thermoplastic resin layer 15 can be obtained.

  Note that, on the paper base layer 14, a paper base layer inner surface side thermoplastic 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. Thereafter, the printing layer 12 and the surface resin layer 11 may be formed on the paper base layer 14.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 4 will be described. First, the paper base material layer 14 on which the above-described printing layer 12 and surface resin layer 11 are formed is prepared. Subsequently, a film constituting the barrier layer 26 and a film constituting the plastic film layer 28 are separately laminated via the adhesive layer 27 by a dry lamination method.

  In the dry lamination method, first, an adhesive composition is applied to one of two films to be laminated. Subsequently, the applied adhesive composition is dried to evaporate the solvent. Thereafter, the two films are laminated via the dried adhesive composition. Subsequently, aging is performed for at least 24 hours in an environment of, for example, 20 ° C. or more while the two laminated films are wound up.

  Subsequently, the paper base layer 14 and the barrier layer 26 to which the plastic film layer 28 is bonded are laminated via the adhesive resin layer 25 by a sand lamination method.

  In the sand lamination method, first, the adhesive resin layer 25 is formed on one of the two films to be laminated, and the molten resin is extruded. Subsequently, the other film is laminated on the resin extruded into one film.

  Subsequently, an anchor coat agent is applied on the plastic film layer 28 and dried to form an anchor coat layer 29. Subsequently, the inner thermoplastic resin layer 15 is formed on the anchor coat layer 29 by a melt extrusion lamination method. Thereby, the surface resin layer 11, the printing layer 12, 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, and the inner thermoplastic resin layer 15 are provided. The packaging material 20 can be obtained.

  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, the print layer 12 and the surface resin layer 11 are formed on the paper base layer 14. May be.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 5 will be described. First, the paper base material layer 14 on which the above-described printing layer 12 and surface resin layer 11 are formed is prepared. Subsequently, a film constituting the barrier layer 26 and a film constituting the plastic film layer 28 are separately laminated via the adhesive layer 27 by a dry lamination method. Subsequently, the paper base layer 14 and the barrier layer 26 to which the plastic film layer 28 is bonded are laminated via the adhesive resin layer 25 by a sand lamination method. Subsequently, an anchor coat agent is applied on the plastic film layer 28 and dried to form an anchor coat layer 29. Subsequently, the anchor coat layer 29 and the film constituting the inner thermoplastic resin layer 15 are laminated via the adhesive resin layer 30 by a sand lamination method. Thereby, the surface resin layer 11, the print layer 12, 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 A packaging material 20 including the resin layer 15 can be obtained.

  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, the print layer 12 and the surface resin layer 11 are formed on the paper base layer 14. May be.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 6 will be described. First, the paper base material layer 14 on which the above-described printing layer 12 and surface resin layer 11 are formed is prepared. Subsequently, a film constituting the barrier layer 26 and a film constituting the plastic film layer 28 are separately laminated via an adhesive layer 27 by a dry lamination method, and the plastic film layer 28 and the polyethylene film layer 32 are laminated. The layers are laminated via the adhesive layer 31. Subsequently, the paper base layer 14 and the barrier layer 26 to which the plastic film layer 28 is bonded are laminated via an adhesive resin layer 25 by a sand lamination method. Subsequently, the anchor coat layer 29 is formed on the polyethylene film layer 32 by applying and drying an anchor coat agent. Subsequently, the inner thermoplastic resin layer 15 is formed on the anchor coat layer 29 by a melt extrusion lamination method. Thereby, the surface resin layer 11, the printing layer 12, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27, the plastic film layer 28, the adhesive layer 31, the polyethylene film layer 32, the anchor coat layer Thus, the packaging material 20 including the thermoplastic resin 29 and the inner thermoplastic resin layer 15 can be obtained.

  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, the print layer 12 and the surface resin layer 11 are formed on the paper base layer 14. May be. Further, a step of laminating the film constituting the barrier layer 26 and the film constituting the plastic film layer 28 via the adhesive layer 27, and the step of laminating the plastic film layer 28 and the polyethylene film layer 32 via the adhesive layer 31 The step of laminating may be performed in two steps. For example, first, a film constituting the barrier layer 26 and a film constituting the plastic film layer 28 are laminated via the adhesive layer 27, and then the plastic film layer 28 and the polyethylene film layer 32 are laminated via the adhesive layer 31. They may be stacked.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 7 will be described. First, the paper base material layer 14 on which the above-described printing layer 12 and surface resin layer 11 are formed is prepared. Subsequently, a film constituting the barrier layer 26 and a film constituting the plastic film layer 28 are separately laminated via an adhesive layer 27 by a dry lamination method, and the plastic film layer 28 and the polyethylene film layer 32 are laminated. Are laminated with an adhesive layer 31 interposed therebetween. Subsequently, the paper base layer 14 and the barrier layer 26 to which the plastic film layer 28 is bonded are laminated via an adhesive resin layer 25 by a sand lamination method. Subsequently, the anchor coat layer 29 is formed on the polyethylene film layer 32 by applying and drying an anchor coat agent. Subsequently, the anchor coat layer 29 and the film constituting the inner thermoplastic resin layer 15 are laminated via the adhesive resin layer 30 by a sand lamination method. Thereby, the surface resin layer 11, the printing layer 12, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27, the plastic film layer 28, the adhesive layer 31, the polyethylene film layer 32, the anchor coat layer 29, a packaging material 20 including the adhesive resin layer 30 and the inner thermoplastic resin layer 15 can be obtained.

  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, the print layer 12 and the surface resin layer 11 are formed on the paper base layer 14. May be. Further, a step of laminating the film constituting the barrier layer 26 and the film constituting the plastic film layer 28 via the adhesive layer 27, and the step of laminating the plastic film layer 28 and the polyethylene film layer 32 via the adhesive layer 31 The step of laminating may be performed in two steps. For example, first, a film constituting the barrier layer 26 and a film constituting the plastic film layer 28 are laminated via the adhesive layer 27, and then the plastic film layer 28 and the polyethylene film layer 32 are laminated via the adhesive layer 31. They may be stacked.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 8 will be described. First, the paper base material layer 14 on which the above-described printing layer 12 and surface resin layer 11 are formed is prepared. Subsequently, the paper base layer 14 and the film constituting the barrier layer 26 are laminated via the adhesive resin layer 25 by a sand lamination method. Subsequently, the inner thermoplastic resin layer 15 is formed on the barrier layer 26 by a melt extrusion lamination method. Thereby, the packaging material 20 including the surface resin layer 11, the printing layer 12, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, and the inner thermoplastic resin layer 15 can be obtained.

  After the paper base layer 14 and the film constituting the barrier layer 26 are laminated via the adhesive resin layer 25, the print layer 12 and the surface resin layer 11 may be formed on the paper base layer 14.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 9 will be described. First, the paper base material layer 14 on which the above-described printing layer 12 and surface resin layer 11 are formed is prepared. Subsequently, the paper base layer 14 and the film constituting the barrier layer 26 are laminated via the adhesive resin layer 25 by a sand lamination method. Subsequently, the barrier layer 26 and the film constituting the inner thermoplastic resin layer 15 are laminated via the adhesive resin layer 30 by a sand lamination method. Thereby, the packaging material 20 including the surface resin layer 11, the printing layer 12, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive resin layer 30, and the inner thermoplastic resin layer 15 can be obtained.

  After the paper base layer 14 and the film constituting the barrier layer 26 are laminated via the adhesive resin layer 25, the print layer 12 and the surface resin layer 11 may be formed on the paper base layer 14.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 10 will be described. First, the paper base material layer 14 on which the above-described printing layer 12 and surface resin layer 11 are formed is prepared. Subsequently, the barrier layer 26 and the polyethylene film layer 32 are laminated via the adhesive layer 27 by a dry lamination method. Subsequently, the paper base layer 14 and the film constituting the barrier layer 26 are laminated via the adhesive resin layer 25 by a sand lamination method. Subsequently, the anchor coat layer 29 is formed on the polyethylene film layer 32 by applying and drying an anchor coat agent. Subsequently, the inner thermoplastic resin layer 15 is formed on the anchor coat layer 29 by a melt extrusion lamination method. Thereby, the surface resin layer 11, the printing layer 12, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27, the polyethylene film layer 32, the anchor coat layer 29, and the inner thermoplastic resin layer 15 are provided. The packaging material 20 can be obtained.

  After laminating the paper base layer 14 and the barrier layer 26 to which the polyethylene film layer 32 is bonded via the adhesive resin layer 25, the print layer 12 and the surface resin layer 11 are formed on the paper base layer 14. May be.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 11 will be described. First, the paper base material layer 14 on which the above-described printing layer 12 and surface resin layer 11 are formed is prepared. Subsequently, the barrier layer 26 and the polyethylene film layer 32 are laminated via the adhesive layer 27 by a dry lamination method. Subsequently, the paper base layer 14 and the film constituting the barrier layer 26 are laminated via the adhesive resin layer 25 by a sand lamination method. Subsequently, the anchor coat layer 29 is formed on the polyethylene film layer 32 by applying and drying an anchor coat agent. Subsequently, the anchor coat layer 29 and the film constituting the inner thermoplastic resin layer 15 are laminated via the adhesive resin layer 30 by a sand lamination method. Thereby, the surface resin layer 11, the printing layer 12, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27, the polyethylene film layer 32, the anchor coat layer 29, the adhesive resin layer 30, and the inner thermoplastic resin A packaging material 20 including the resin layer 15 can be obtained.

  After laminating the paper base layer 14 and the barrier layer 26 to which the polyethylene film layer 32 is bonded via the adhesive resin layer 25, the print layer 12 and the surface resin layer 11 are formed on the paper base layer 14. May be.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 12 will be described. First, the paper base material layer 14 on which the above-described printing layer 12 and surface resin layer 11 are formed is prepared. Subsequently, the resin in a molten state is extruded on the surface of the paper base layer 14 opposite to the surface on which the printing layer 12 and the surface resin layer 11 are formed by the melt extrusion lamination method, and the first layer 151 and the second layer 151 are formed. The inner thermoplastic resin layer 15 having a two-layer structure including the layer 152 is formed. Thereby, a packaging material 20 including the surface resin layer 11, the printing layer 12, the paper base layer 14, and the inner thermoplastic resin layer 15 can be obtained.

<Packaging products>
An example of a packaged product formed by using the packaging material 20 will be described. FIG. 13 is a diagram illustrating a liquid paper container 40 which is an example of a packaged product. Liquid paper containers have excellent barrier properties, and are used for alcohol such as sake, shochu, and wine, milk drinks such as milk, soft drinks such as orange juice and tea, and chemical products such as car wax, shampoo and detergent. It can be suitably used as a wrapping paper container for liquids in general.

  As shown in FIG. 13, the liquid paper container 40 has a square tubular body 41 including side surfaces, a square plate-shaped bottom portion 42, and an upper portion 43, and is a so-called Gebel-top type container. I have. The upper portion 43 has a pair of inclined plates 44 facing each other, and a pair of folded portions 45 located between the pair of inclined plates 44 and folded between the inclined plates 44. Further, the pair of inclined plates 44 are bonded to each other by a margin 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. Further, a flat top type container may be formed.

  By configuring a packaged product using the packaging material 20 including the printed layer 12 containing a biomass-derived component, the amount of fossil fuel used can be reduced as compared with the related art. Thereby, environmental load can be reduced.

Second Embodiment Next, a second embodiment of the present invention will be described. In the second embodiment, the same portions as those in the above-described first embodiment are denoted by the same reference numerals, and detailed description is omitted. Further, when it is clear that the operation and effect obtained in the first embodiment can also be obtained in this embodiment, the description thereof may be omitted.

  The layer configuration of the packaging material according to the second embodiment is the same as the layer configuration of the packaging material according to the first embodiment shown in FIG. That is, the packaging material 20 according to the second embodiment includes the surface resin layer 11, the printing layer 12, the paper base layer 14, and the inner thermoplastic resin layer 15 in this order. The surface resin layer 11 forms the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 forms the inner surface 20x of the packaging material 20.

  Hereinafter, each layer constituting the packaging material 20 according to the second embodiment will be described.

(Surface resin layer, paper substrate layer, inner thermoplastic resin layer)
As the surface resin layer 11, the paper base layer 14, and the inner thermoplastic resin layer 15, the surface resin layer 11, the paper base layer 14, and the inner thermoplastic resin layer 15 described in the first embodiment may be used. it can.

(Print layer)
The binder resin of the print layer 12 may further include a polyamide resin in addition to the nitrocellulose and the cured product of the polyol and the isocyanate compound described in the first embodiment. In this case, the polyamide resin is preferably derived from biomass. Polyamide resin is a resin obtained by reacting an acid component with an amine component. The acid component is mainly a polymerized fatty acid, and may further contain a part of aliphatic, alicyclic and aromatic dicarboxylic acids or aliphatic monocarboxylic acids. The amine component is mainly an aliphatic amine, an alicyclic amine, an aromatic / aliphatic or aromatic polyamine alone or as a mixture, and may further contain a part of primary and secondary monoamines. The polyamide resin is preferably produced under the condition that biomass is used for at least 50% or more of the acid component or the amine component or both components.

  A polymerized fatty acid as a raw material of a polyamide resin using a biomass material as a synthetic material is obtained by polymerizing an unsaturated fatty acid or an ester thereof derived from a dry or semi-dry oil such as a vegetable oil or an animal oil. This unsaturated fatty acid mainly has 8 to 24 carbon atoms. The polymerized fatty acid includes a monobasic fatty acid, a dimerized polymerized fatty acid (also referred to as a dimer fatty acid or a dimer acid), a trimerized polymerized fatty acid, or the like by a polymerization reaction. The composition is preferably 0 to 10% by mass of a basic acid, 60 to 99% by mass of a dibasic acid having 36 carbon atoms, and 30% by mass or less of a tribasic acid or more having 54 carbon atoms.

  As the polycarboxylic acid compound of the acid component, the above-mentioned polymerized fatty acids may be used alone, but furthermore, succinic acid, adipic acid, azelaic acid, aliphatic dicarboxylic acids such as maleic acid, and alicyclics such as cyclohexanedicarboxylic acid. Aromatic dicarboxylic acids such as aromatic dicarboxylic acids, isophthalic acid and terephthalic acid may be used in combination. Examples of the monocarboxylic acid include acetic acid, propionic acid, stearic acid, oleic acid, and linoleic acid.

  Among the above-mentioned acid components, biomass material is a polymerized fatty acid, stearic acid, oleic acid, or linoleic acid, which is obtained as a saponified product of the above animal and plant fats and oils. In addition, acetic acid and propionic acid produced by the fermentation method can be used as an acid component, which makes it possible to save petroleum resources and suppress the generation of excess carbon dioxide, and it can be used industrially sufficiently. Biomass material.

  Examples of the polyamine compound of the amine component include aliphatic polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, and diethylenetriamine, and aromatic compounds such as xylylenediamine, diaminophenylmethane, phenylenediamine, triaminobenzene, triaminophenol, and tetraaminobenzene. Group polyamines and the like. Furthermore, mono- and di-alkylamines such as butylamine, octylamine and diethylamine, and monoamines such as mono- and di-alkanolamines such as monoethanolamine, monopropanolamine, diethanolamine and dipropanolamine may be used in combination. Good. The hydrocarbon group portion of the amine component is derived from a petroleum-derived component.

  The weight average molecular weight of the polyamide resin using the biomass material as a synthetic material is preferably about 3,000 to 100,000, and more preferably about 5,000 to 50,000. When the weight average molecular weight of the polyamide resin is lower than 3,000, the resin film becomes brittle, and the friction resistance and the like are reduced as it is. When it exceeds 100,000, the ink viscosity becomes too high and the ink viscosity is good as it is. It becomes difficult to obtain printability.

  The content ratio of the nitrocellulose resin and the polyamide resin derived from biomass is preferably from 1 / 0.4 to 1 / 9.5, and more preferably from 1 / 0.5 to 1/9. If the content ratio of the biomass-derived polyamide resin is smaller than 0.4 with respect to nitrocellulose resin 1, the water resistance is poor. When the content ratio of the polyamide resin derived from biomass is larger than 9.5 with respect to nitrocellulose resin 1, heat resistance is inferior. In the case where a packaged product including the packaging material 20 is used for an application requiring heat resistance, the printed layer 12 may not include a polyamide resin.

  When the "biomass degree" is represented by the weight ratio of the biomass-derived component for the polyamide resin, the "biomass degree" can be determined as follows. Examples of the acid component for synthesizing the polyamide resin include 19 mol of a dimer of linoleic acid derived from vegetable oil (a mixture of compounds having several types of acyclic and cyclic structures, molecular weight 558 to 560) and stearic acid (molecular weight 284). ) 1 mole, and as the amine component, there are 19 moles of petroleum-derived ethylenediamine (molecular weight 60) and 1 mole of butylamine (molecular weight 60). When these are reacted, if the reaction proceeds ideally, 19 molecules of linoleic acid dimer and ethylenediamine (total of 38 carboxyl groups and 38 total of amino groups) and 1 molecule of stearic acid and butylamine One mole of a dehydration condensation product of (one carboxyl group and one amino group) (= polyamide resin molecule, molecular weight 11384-11422) and 39 moles of water are produced. In the polyamide resin molecule, 19 sites (formulas 524 to 526) consisting of atomic groups excluding the amount (OH × 2) lost by the dehydration reaction from the linoleic acid dimer, There is one site (formula 267) consisting of atomic groups excluding the amount (OH × 1) lost by the dehydration reaction. Therefore, the ratio (% by weight) of the biomass material in the polyamide resin molecule is (524 × 19 + 267) × 100/11384 to (526 × 19 + 267) × 100/11422 ≒ 89.8%.

(Production method of packaging material)
The method for manufacturing the packaging material 20 according to the second embodiment is, for example, the same as the method for manufacturing the packaging material 20 shown in FIG. 1 in the first embodiment.

<Packaging products>
An example of a packaged product formed by using the packaging material 20 according to the second embodiment will be described. FIG. 14 is an example of a packaged product 50 formed by using the packaging material 20 according to the second embodiment. The packaged product 50 is a general paper container such as an outer box for sweets, a paper box for bottles, and an outer box for medicines.

  By configuring the packaged product 50 using the packaging material 20 including the printed layer 12 containing the biomass-derived component, it is possible to reduce the amount of fossil fuel used compared to the related art. Thereby, environmental load can be reduced.

  Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the description of the following examples unless it exceeds the gist.

[Example 1A]
Ivory paper having a basis weight of 260 g / m ² was prepared as the paper base layer 14. Subsequently, the printing layer 12 was formed on the paper base layer 14. In the step of forming the print layer 12, first, an ink composition containing a colorant, a binder resin, and a solvent was prepared. As the binder resin, a resin containing nitrocellulose derived from biomass and a cured product of a polyester polyol derived from a fossil fuel and an isocyanate compound derived from a fossil fuel were used. Subsequently, the ink composition was applied on the paper base material layer 14 in a predetermined pattern by gravure printing to form the print layer 12. The thickness of the printing layer 12 was 2 μm.

  Subsequently, a resin in a molten state was extruded onto the print layer 12 by a melt extrusion lamination method to form the surface resin layer 11. As the surface resin layer 11, polyethylene derived from fossil fuel was used. The thickness of the surface resin layer 11 was 20 μm.

  Subsequently, an inner thermoplastic resin layer 15 was formed on the paper base layer 14 by a melt extrusion lamination method. 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. Thus, the packaging material 20 having the layer configuration shown in FIG. 1 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / Biomark / Paper / Internal heat (2) 20
“/” Represents a boundary between layers. The leftmost layer is a layer constituting the outer surface of the packaging material, and the rightmost layer is a layer constituting the inner surface of the packaging material.
“Table” means a surface resin layer derived from a fossil fuel formed by a melt extrusion lamination method. “Biomark” means a printed layer derived from biomass. "Paper" means a paper substrate layer. “Internal heat (2)” means an inner thermoplastic resin layer derived from a fossil fuel formed by a melt extrusion lamination method. The number means the thickness of the layer (unit: μm).

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can accommodate, for example, milk drinks, soft drinks, and the like.

[Example 1B]
A packaging material 20 was prepared in the same manner as in Example 1A, except that a fossil fuel-derived polyether polyol was used as the polyol of the binder resin of the printing layer 12.

[Example 1C]
A packaging material 20 was produced in the same manner as in Example 1A, except that a fossil fuel-derived polycarbonate polyol was used as the polyol of the binder resin of the print layer 12.

FIG. 15 collectively shows the layer configuration and the like of the packaging material 20 of Examples 1A to 1C. In the column of “polyol type” in FIG. 15, the description “ester type” means that the polyol is a polyester polyol. Further, the description “ether type” means that the polyol is a polyether polyol. Further, the description "carbonate-based" means that the polyol is a polycarbonate polyol.
Further, in the column of "biomass-derived component in cured product of polyol and isocyanate compound", the description "-" means that the cured product of polyol and isocyanate compound does not contain biomass-derived component. Further, in the column of "biomass-derived component in polyol", the description "-" means that the polyol does not contain a biomass-derived component.

[Example 1D]
Example 1A of Example 1A, except that as the binder resin of the printing layer 12, a resin containing nitrocellulose derived from fossil fuel and a cured product of a polyester polyol containing a biomass derived component and an isocyanate compound derived from fossil fuel was used. As in the case, the packaging material 20 was produced. As a polyester polyol containing a biomass-derived component, specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid derived from a fossil fuel was used.

[Example 1E]
Packaging was performed in the same manner as in Example 1D, except that a reaction product of a polyfunctional alcohol derived from a fossil fuel and a polyfunctional carboxylic acid containing a biomass-derived component was used as the polyester polyol of the binder resin of the print layer 12. Material 20 was produced.

  FIG. 15 shows the layer configuration of the packaging material 20 of Examples 1D and 1E. In the column of "biomass-derived component in polyol" in FIG. 15, the description "polyfunctional alcohol" means that among the components used for the polyol, at least the polyfunctional alcohol of the polyester polyol is derived from biomass. Similarly, the description “polyfunctional carboxylic acid” means that among the components used for the polyol, at least the polyfunctional carboxylic acid of the polyester polyol is derived from biomass.

  In Examples 1D and 1E, one of the two components, that is, the polyfunctional alcohol or the polyfunctional carboxylic acid used for the polyol is a biomass-derived component, but the present invention is not limited to this. There is no. For example, either of the two components may include a biomass-derived component.

[Example 1F]
A packaging material 20 was produced in the same manner as in Example 1D, except that a polyether polyol containing a biomass-derived component was used as the polyol of the binder resin of the printing layer 12. Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate derived from a fossil fuel was used as the polyether polyol containing a biomass-derived component.

[Example 1G]
Packaging was performed in the same manner as in Example 1F, except that a reaction product of a polyfunctional alcohol derived from fossil fuel and a polyfunctional isocyanate containing a biomass-derived component was used as the polyether polyol as the binder resin of the printing layer 12. Material 20 was produced.

  FIG. 15 shows the layer structure of the packaging material 20 of Examples 1F and 1G. In the column of “biomass-derived component in polyol” in FIG. 15, the description “polyfunctional isocyanate” means that at least the polyfunctional isocyanate among the components used in the polyol is derived from biomass.

  In Examples 1F and 1G, one of the two components, ie, the polyfunctional alcohol or the polyfunctional isocyanate used for the polyol, is an example in which the component is a biomass-derived component. However, the present invention is not limited to this. Absent. For example, either of the two components may include a biomass-derived component.

[Example 1H]
A packaging material 20 was prepared in the same manner as in Example 1D, except that a polycarbonate polyol containing a biomass-derived component was used as the polyol of the binder resin of the print layer 12. Specifically, as a polycarbonate polyol containing a biomass-derived component, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate derived from a fossil fuel was used. FIG. 15 shows the layer configuration of the packaging material 20 of Example 1H.

[Example 1I]
Example 1D of Example 1D, except that as the binder resin of the printing layer 12, a resin containing nitrocellulose derived from fossil fuel and a cured product of a polyester polyol derived from fossil fuel and an isocyanate compound containing a biomass-derived component was used. As in the case, the packaging material 20 was produced.

[Example 1J]
A packaging material 20 was produced in the same manner as in Example 1I, except that a fossil fuel-derived polyether polyol was used as the polyol for the binder resin of the print layer 12.

[Example 1K]
A packaging material 20 was produced in the same manner as in Example 1I, except that a fossil fuel-derived polycarbonate polyol was used as the polyol of the binder resin of the print layer 12.

  FIG. 15 shows the layer structure of the packaging material 20 of Examples 1I to 1K. In Examples 1D to 1K, in a cured product of a polyol and an isocyanate compound, an example is shown in which one of the two components, a polyol or an isocyanate compound, is a biomass-derived component, but is not limited thereto. Never. For example, both of the two components may include a biomass-derived component.

  Further, in Examples 1A to 1K, an example is shown in which one of the two constituents of the printed layer, a cured product of nitrocellulose or a polyol and an isocyanate compound, is a biomass-derived component. It will not be done. For example, both of the two components may include a biomass-derived component.

[Example 1L]
A packaging material 20 was produced in the same manner as in Example 1A, except that a polyethylene containing a biomass-derived component was used as the polyethylene of the surface resin layer 11.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Bio table / Bio stamp / Paper / Internal heat (2) 20
"Bio table" means a surface resin layer derived from biomass formed by a melt extrusion lamination method.

[Example 1M]
A packaging material 20 was produced in the same manner as in Example 1L, except that a polyethylene-containing component was used as the polyethylene of the inner thermoplastic resin layer 15.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Bio table / Bio stamp / Paper / Bio internal heat (2) 20
"Heat in bio (2)" means an inner thermoplastic resin layer derived from biomass formed by a melt extrusion lamination method.

  FIG. 15 shows the layer structure of the packaging materials 20 of Examples 1L and 1M. Note that the same variations as those in the embodiments 1A to 1K can be adopted in the above-described embodiments 1L and 1M. For example, as the printing layer containing the biomass-derived component, the printing layer shown in Examples 1B to 1K may be used in addition to the printing layer shown in Example 1A.

[Example 1N]
A packaging material 20 was produced in the same manner as in Example 1A, except that the two-layer inner thermoplastic resin layer 15 including the first layer 151 and the second layer 152 shown in FIG. 12 was formed by co-extrusion. did. As the first layer 151, a 10 μm-thick polyethylene layer containing a biomass-derived component was used. As the second layer 152, a 10 μm-thick polyethylene layer derived from fossil fuel was used.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Bio table / Bio stamp / Paper / Internal heat (2) 10 / Bio internal heat (2) 10

[Example 10]
As in Example 1N, except that a 10 μm thick polyethylene layer derived from fossil fuel was used as the first layer 151 and a 10 μm thick polyethylene layer containing a biomass-derived component was used as the second layer 152. Thus, a packaging material 20 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Bio table / Bio stamp / Paper / Bio internal heat (2) 10 / Internal heat (2) 10

  FIG. 15 shows the layer structure of the packaging material 20 of Examples 1N and 10 collectively. Note that the same variations as those of the embodiments 1A to 1K can be adopted in the above-described embodiments 1N and 10 as well. For example, as the printing layer containing the biomass-derived component, the printing layer shown in Examples 1B to 1K may be used in addition to the printing layer shown in Example 1A.

[Example 1P]
A packaging material 20 was produced in the same manner as in Example 1A, except that a layer (thickness: 20 μm) of fossil fuel-derived polyethylene terephthalate formed by a melt extrusion lamination method was used as the surface resin layer 11.

[Example 1Q]
A packaging material 20 was prepared in the same manner as in Example 1A, except that a layer of fossil fuel-derived polypropylene (thickness: 20 μm) formed by a melt extrusion lamination method was used as the surface resin layer 11.

  FIG. 16 shows the layer configuration of the packaging material 20 of Examples 1P and 1Q together with the layer configuration of the packaging material 20 of Examples 1A and 1L. Note that the same variations as those in the embodiments 1A to 1K can be adopted in the above-described embodiments 1P and 1Q. For example, as the printing layer containing the biomass-derived component, the printing layer shown in Examples 1B to 1K may be used in addition to the printing layer shown in Example 1A.

[Example 2A]
A milk carton base paper having a basis weight of 150 g / m ² was prepared as the paper base layer 14. Subsequently, the printing layer 12 and the surface resin layer 11 were formed on the paper base layer 14 in the same manner as in Example 1A. Subsequently, a barrier resin layer 21, an intermediate thermoplastic resin layer 22, and an inner thermoplastic resin layer 15 were formed on the paper base layer 14 by a melt extrusion lamination method. EVOH was used for the barrier resin layer 21. The thickness of the barrier resin layer 21 was 5 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 inner thermoplastic resin layer 15, polyethylene derived from fossil fuel was used. The thickness of the inner thermoplastic resin layer 15 was 20 μm. Thus, the packaging material 20 having the layer configuration shown in FIG. 2 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / Biomark / 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.

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, a milk drink or a soft drink.

[Example 2B]
A packaging material 20 was prepared 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.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / Biomark / Paper / MXD6 5 / Medium heat 5 / Internal heat (2) 20
“MXD6” means a barrier resin layer using polymetaxylylene adipamide.

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, a milk drink or a soft drink.

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

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / Biomark / Paper / 6NY5 / Medium heat 5 / Internal heat (2) 20
“6NY” means a barrier resin layer using nylon 6.

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, a milk drink or a soft drink.

  Note that, in the above-described embodiments 2A to 2C, the same variations as in the case of the embodiments 1A to 1K can be adopted. For example, as the printing layer containing the biomass-derived component, the printing layer shown in Examples 1B to 1K may be used in addition to the printing layer shown in Example 1A. Further, as the surface resin layer, a surface resin layer as shown in Examples 1L, 1P and 1Q may be used.

[Example 3A]
In the same manner as in Example 2A, the paper base layer 14 was prepared, and the print layer 12 and the surface resin layer 11 were formed on the paper base layer 14. Subsequently, the thermoplastic resin layer 23, the intermediate thermoplastic resin layer 22, the barrier resin layer 21, the intermediate thermoplastic resin layer 24, and the inner thermoplastic The resin layer 15 was formed. As the thermoplastic resin layer 23 on the inner surface side of the paper base material layer, polyethylene derived from fossil fuel was used. The thickness of the thermoplastic resin layer 23 on the inner surface side of the paper base material layer 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. EVOH was used for the barrier resin layer 21. 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. Thus, a packaging material 20 having the layer configuration shown in FIG. 3 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / Biomark / Paper / PE5 / Medium heat 5 / EVOH5 / Medium heat 5 / Internal heat (2) 20
“PE” means a thermoplastic resin layer on the inner surface side of a paper base material layer using polyethylene.

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, a milk drink or a soft drink.

[Example 3B]
A packaging material 20 was prepared in the same manner as in Example 3A, except that polymeta-xylylene adipamide was used as the barrier resin layer 21. The thickness of the barrier resin layer 21 was 5 μm.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / Biomark / Paper / PE5 / Medium heat 5 / MXD6 5 / Medium heat 5 / Internal heat (2) 20

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, a milk drink or a soft drink.

[Example 3C]
A packaging material 20 was prepared in the same manner as in Example 3A, except that nylon 6 was used as the barrier resin layer 21. The thickness of the barrier resin layer 21 was 5 μm.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / Biomark / Paper / PE5 / Medium heat 5 / 6NY5 / Medium heat 5 / Inner heat (2) 20

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, a milk drink or a soft drink.

  Note that the same variations as those in the embodiments 1A to 1K can be adopted in the above-described embodiments 3A to 3C. For example, as the printing layer containing the biomass-derived component, the printing layer shown in Examples 1B to 1K may be used in addition to the printing layer shown in Example 1A. Further, as the surface resin layer, a surface resin layer as shown in Examples 1L, 1P and 1Q may be used.

[Example 4]
In the same manner as in Example 2A, the paper base layer 14 was prepared, and the print layer 12 and the surface resin layer 11 were formed on the paper base layer 14.

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

  Subsequently, the paper base layer 14 and the barrier layer 26 bonded to the plastic film layer 28 were bonded via the adhesive resin layer 25 by a sand lamination method. As the adhesive resin layer 25, polyethylene derived from fossil fuel was used. The thickness of the adhesive resin layer 25 was 20 μm.

  Subsequently, an anchor coat layer 29 was formed on the plastic film layer 28, and the inner thermoplastic resin layer 15 was formed on the anchor coat layer 29 by a melt extrusion lamination method. 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. Thus, a packaging material 20 having the layer configuration shown in FIG. 4 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / Biomark / Paper / Adhesive resin 20 / AL foil 7 / Contact / PET12 / AC / Internal heat (2) 20
"AL foil" means aluminum foil. "Contact" means the adhesive layer. "PET" means a PET film containing polyethylene terephthalate. “AC” means an anchor coat layer.

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, alcoholic beverages and soft drinks.

  In this embodiment, the same variations as those in the embodiments 1A to 1K can be adopted. For example, as the printing layer containing the biomass-derived component, the printing layer shown in Examples 1B to 1K may be used in addition to the printing layer shown in Example 1A. Further, as the surface resin layer, a surface resin layer as shown in Examples 1L, 1P and 1Q may be used.

[Example 5]
In the same manner as in Example 2A, the paper base layer 14 was prepared, and the print layer 12 and the surface resin layer 11 were formed on the paper base layer 14.

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

  Subsequently, the paper base layer 14 and the barrier layer 26 bonded to the plastic film layer 28 were bonded via the adhesive resin layer 25 by a sand lamination method. As the adhesive resin layer 25, polyethylene derived from fossil fuel was used. The thickness of the adhesive resin layer 25 was 20 μm.

  Subsequently, an anchor coat layer 29 was formed on the plastic film layer 28. Subsequently, the anchor coat layer 29 and the inner thermoplastic resin layer 15 were bonded via the adhesive resin layer 30 by a sand lamination method. As the inner thermoplastic resin layer 15, a polyethylene film (40 μm in thickness) derived from fossil fuel was used. As the adhesive resin layer 30, polyethylene derived from fossil fuel was used. The thickness of the adhesive resin layer 30 was 20 μm. Thus, the packaging material 20 having the layer configuration shown in FIG. 5 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / bioprint / paper / adhesive resin 20 / AL foil 7 / contact / PET12 / AC / adhesive resin 20 / internal heat (1) 40
“Inner heat (1)” means an inner thermoplastic resin film derived from fossil fuel.

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, alcoholic beverages and soft drinks.

  In this embodiment, the same variations as those in the embodiments 1A to 1K can be adopted. For example, as the printing layer containing the biomass-derived component, the printing layer shown in Examples 1B to 1K may be used in addition to the printing layer shown in Example 1A. Further, as the surface resin layer, a surface resin layer as shown in Examples 1L, 1P and 1Q may be used.

[Example 6]
In the same manner as in Example 2A, the paper base layer 14 was prepared, and the print layer 12 and the surface resin layer 11 were formed on the paper base layer 14.

  Subsequently, the film forming the barrier layer 26 and the film forming the plastic film layer 28 are bonded to each other via the adhesive layer 27 by a dry lamination method, and the plastic film layer 28 and the polyethylene film layer 32 are bonded to each other. The layers were bonded via the agent layer 31. As the barrier layer 26, an aluminum foil (thickness: 7 μm) was used. As the plastic film layer 28, a PET film (thickness: 12 μm) containing fossil fuel-derived polyethylene terephthalate was used. As the polyethylene film layer 32, a polyethylene film (thickness: 30 μm) derived from fossil fuel was used. In the dry lamination method, a polyester polyol, which is a reaction product of a polyfunctional alcohol derived from a fossil fuel and a polyfunctional carboxylic acid derived from a fossil fuel, was prepared as a main agent. Further, an isocyanate compound derived from a fossil fuel was prepared as a curing agent.

  Subsequently, the paper base layer 14 and the barrier layer 26 bonded to the plastic film layer 28 were bonded via the adhesive resin layer 25 by a sand lamination method. As the adhesive resin layer 25, polyethylene derived from fossil fuel was used. The thickness of the adhesive resin layer 25 was 20 μm.

  Subsequently, the anchor coat layer 29 was formed on the polyethylene film layer 32, and the inner thermoplastic resin layer 15 was formed on the anchor coat layer 29 by melt extrusion lamination. As the inner thermoplastic resin layer 15, polyethylene derived from fossil fuel was used. The thickness of the inner thermoplastic resin layer 15 was 15 μm. Thus, the packaging material 20 having the layer configuration shown in FIG. 6 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / bioprint / paper / adhesive resin 20 / AL foil 7 / contact / PET12 / contact / PEF30 / AC / internal heat (2) 15
"PEF" means polyethylene film layer.

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can store alcoholic beverages such as wine, for example.

  In this embodiment, the same variations as those in the embodiments 1A to 1K can be adopted. For example, as the printing layer containing the biomass-derived component, the printing layer shown in Examples 1B to 1K may be used in addition to the printing layer shown in Example 1A. Further, as the surface resin layer, a surface resin layer as shown in Examples 1L, 1P and 1Q may be used.

[Example 7]
In the same manner as in Example 2A, the paper base layer 14 was prepared, and the print layer 12 and the surface resin layer 11 were formed on the paper base layer 14.

  Subsequently, the film forming the barrier layer 26 and the film forming the plastic film layer 28 are bonded to each other via the adhesive layer 27 by a dry lamination method, and the plastic film layer 28 and the polyethylene film layer 32 are bonded to each other. The layers were bonded via the agent layer 31. As the barrier layer 26, an aluminum foil (thickness: 7 μm) was used. As the plastic film layer 28, a PET film (thickness: 12 μm) containing fossil fuel-derived polyethylene terephthalate was used. As the polyethylene film layer 32, a polyethylene film (thickness: 30 μm) derived from fossil fuel was used. In the dry lamination method, a polyester polyol, which is a reaction product of a polyfunctional alcohol derived from a fossil fuel and a polyfunctional carboxylic acid derived from a fossil fuel, was prepared as a main agent. Further, an isocyanate compound derived from a fossil fuel was prepared as a curing agent.

  Subsequently, the paper base layer 14 and the barrier layer 26 bonded to the plastic film layer 28 were bonded via the adhesive resin layer 25 by a sand lamination method. As the adhesive resin layer 25, polyethylene derived from fossil fuel was used. The thickness of the adhesive resin layer 25 was 20 μm.

  Subsequently, an anchor coat layer 29 was formed on the polyethylene film layer 32. Subsequently, the anchor coat layer 29 and the inner thermoplastic resin layer 15 were bonded via the adhesive resin layer 30 by a sand lamination method. As the inner thermoplastic resin layer 15, a polyethylene film (thickness: 30 μm) derived from fossil fuel was used. As the adhesive resin layer 30, polyethylene derived from fossil fuel was used. The thickness of the adhesive resin layer 30 was 15 μm. Thus, a packaging material 20 having the layer configuration shown in FIG. 7 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / bioprint / paper / adhesive resin 20 / AL foil 7 / contact / PET12 / contact / PEF30 / AC / adhesive resin 15 / internal heat (1) 30

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can store alcoholic beverages such as wine, for example.

  In this embodiment, the same variations as those in the embodiments 1A to 1K can be adopted. For example, as the printing layer containing the biomass-derived component, the printing layer shown in Examples 1B to 1K may be used in addition to the printing layer shown in Example 1A. Further, as the surface resin layer, a surface resin layer as shown in Examples 1L, 1P and 1Q may be used.

[Example 8A]
In the same manner as in Example 2A, the paper base layer 14 was prepared, and the print layer 12 and the surface resin layer 11 were formed on the paper base layer 14.

  Subsequently, the paper base layer 14 and the barrier layer 26 were bonded to each other via the adhesive resin layer 25 by a sand lamination method. As the barrier layer 26, an aluminum foil (thickness: 7 μm) was used. As the adhesive resin layer 25, polyethylene derived from fossil fuel was used. The thickness of the adhesive resin layer 25 was 30 μm.

  Subsequently, the inner thermoplastic resin layer 15 was formed on the barrier layer 26 by a melt extrusion lamination method. 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. Thus, a packaging material 20 having the layer configuration shown in FIG. 7 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / Biomark / Paper / Adhesive resin 30 / AL foil 7 / Internal heat (2) 20

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, alcoholic beverages and soft drinks.

[Example 8B]
A packaging material 20 was prepared in the same manner as in Example 8A, except that a vapor deposition film (thickness: 12 μm) in which an aluminum vapor deposition film was formed on a polyethylene terephthalate film was used as the barrier layer 26.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / Biomark / Paper / Adhesive resin 30 / VM-PET12 / Internal heat (2) 20
“VM-PET” means a vapor deposited film.

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, alcoholic beverages and soft drinks.

  Note that the same variations as those in the embodiments 1A to 1K can be adopted in the above-described embodiments 8A and 8B. For example, as the printing layer containing the biomass-derived component, the printing layer shown in Examples 1B to 1K may be used in addition to the printing layer shown in Example 1A. Further, as the surface resin layer, a surface resin layer as shown in Examples 1L, 1P and 1Q may be used.

[Example 9A]
In the same manner as in Example 2A, the paper base layer 14 was prepared, and the print layer 12 and the surface resin layer 11 were formed on the paper base layer 14.

  Subsequently, the paper base layer 14 and the barrier layer 26 were bonded to each other via the adhesive resin layer 25 by a sand lamination method. As the barrier layer 26, an aluminum foil (thickness: 7 μm) was used. As the adhesive resin layer 25, polyethylene derived from fossil fuel was used. The thickness of the adhesive resin layer 25 was 30 μm.

  Subsequently, the barrier layer 26 and the inner thermoplastic resin layer 15 were bonded to each other via the adhesive resin layer 30 by a sand lamination method. As the inner thermoplastic resin layer 15, a polyethylene film (40 μm in thickness) derived from fossil fuel was used. As the adhesive resin layer 30, polyethylene derived from fossil fuel was used. The thickness of the adhesive resin layer 30 was 20 μm. Thus, the packaging material 20 having the layer configuration shown in FIG. 8 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / Biomark / Paper / Adhesive resin 30 / AL foil 7 / Adhesive resin 20 / Internal heat (1) 40

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, alcoholic beverages and soft drinks.

[Example 9B]
A packaging material 20 was prepared in the same manner as in Example 9A, except that a vapor deposition film (thickness: 12 μm) in which an aluminum vapor deposition film was formed on a polyethylene terephthalate film was used as the barrier layer 26.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / Biomark / Intermediate resin 30 / Paper / Adhesive resin 20 / VM-PET12 / Adhesive resin 20 / Internal heat (1) 40

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, alcoholic beverages and soft drinks.

  Note that, in the above-described embodiments 9A and 9B, the same variations as in the case of the embodiments 1A to 1K can be adopted. For example, as the printing layer containing the biomass-derived component, the printing layer shown in Examples 1B to 1K may be used in addition to the printing layer shown in Example 1A. Further, as the surface resin layer, a surface resin layer as shown in Examples 1L, 1P and 1Q may be used.

[Example 10A]
In the same manner as in Example 2A, the paper base layer 14 was prepared, and the print layer 12 and the surface resin layer 11 were formed on the paper base layer 14.

  Subsequently, the barrier layer 26 and the polyethylene film layer 32 were bonded together via the adhesive layer 27 by a dry lamination method. As the barrier layer 26, an aluminum foil (thickness: 7 μm) was used. As the polyethylene film layer 32, a polyethylene film (thickness: 30 μm) derived from fossil fuel was used. In the dry lamination method, a polyester polyol, which is a reaction product of a polyfunctional alcohol derived from a fossil fuel and a polyfunctional carboxylic acid derived from a fossil fuel, was prepared as a main agent. Further, an isocyanate compound derived from a fossil fuel was prepared as a curing agent.

  Subsequently, the paper base layer 14 and the barrier layer 26 bonded to the polyethylene film layer 32 were bonded via the adhesive resin layer 25 by a sand lamination method. As the adhesive resin layer 25, polyethylene derived from fossil fuel was used. The thickness of the adhesive resin layer 25 was 30 μm.

  Subsequently, the anchor coat layer 29 was formed on the polyethylene film layer 32, and the inner thermoplastic resin layer 15 was formed on the anchor coat layer 29 by melt extrusion lamination. As the inner thermoplastic resin layer 15, polyethylene derived from fossil fuel was used. The thickness of the inner thermoplastic resin layer 15 was 15 μm. Thus, the packaging material 20 having the layer configuration shown in FIG. 10 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / bioprint / paper / adhesive resin 30 / AL foil 7 / contact / PEF30 / AC / internal heat (2) 15

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can store alcoholic beverages such as wine, for example.

[Example 10B]
A packaging material 20 was prepared in the same manner as in Example 10A, except that a vapor deposition film (thickness: 12 μm) in which an aluminum vapor deposition film was formed on a polyethylene terephthalate film was used as the barrier layer 26.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / bioprint / paper / adhesive resin 30 / VM-PET12 / contact / PEF30 / AC / internal heat (2) 15

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can store alcoholic beverages such as wine, for example.

  Note that the same variations as those in the embodiments 1A to 1K can be adopted in the above-described embodiments 10A and 10B. For example, as the printing layer containing the biomass-derived component, the printing layer shown in Examples 1B to 1K may be used in addition to the printing layer shown in Example 1A. Further, as the surface resin layer, a surface resin layer as shown in Examples 1L, 1P and 1Q may be used.

[Example 11A]
In the same manner as in Example 2A, the paper base layer 14 was prepared, and the print layer 12 and the surface resin layer 11 were formed on the paper base layer 14.

  Subsequently, the barrier layer 26 and the polyethylene film layer 32 were bonded together via the adhesive layer 27 by a dry lamination method. As the barrier layer 26, an aluminum foil (thickness: 7 μm) was used. As the polyethylene film layer 32, a polyethylene film (thickness: 30 μm) derived from fossil fuel was used. In the dry lamination method, a polyester polyol, which is a reaction product of a polyfunctional alcohol derived from a fossil fuel and a polyfunctional carboxylic acid derived from a fossil fuel, was prepared as a main agent. Further, an isocyanate compound derived from a fossil fuel was prepared as a curing agent.

  Subsequently, the paper base layer 14 and the barrier layer 26 bonded to the polyethylene film layer 32 were bonded via the adhesive resin layer 25 by a sand lamination method. As the adhesive resin layer 25, polyethylene derived from fossil fuel was used. The thickness of the adhesive resin layer 25 was 30 μm.

  Subsequently, an anchor coat layer 29 was formed on the polyethylene film layer 32. Subsequently, the anchor coat layer 29 and the inner thermoplastic resin layer 15 were bonded via the adhesive resin layer 30 by a sand lamination method. As the inner thermoplastic resin layer 15, a polyethylene film (thickness: 30 μm) derived from fossil fuel was used. As the adhesive resin layer 30, polyethylene derived from fossil fuel was used. The thickness of the adhesive resin layer 30 was 15 μm. Thus, the packaging material 20 having the layer configuration shown in FIG. 11 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / bioprint / paper / adhesive resin 30 / AL foil 7 / contact / PEF30 / AC / adhesive resin 15 / internal heat (1) 30

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can store alcoholic beverages such as wine, for example.

[Example 11B]
A packaging material 20 was prepared in the same manner as in Example 10A, except that a vapor deposition film (thickness: 12 μm) in which an aluminum vapor deposition film was formed on a polyethylene terephthalate film was used as the barrier layer 26.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / bioprint / paper / adhesive resin 30 / VM-PET12 / contact / PEF30 / AC / adhesive resin 15 / internal heat (1) 30

  Subsequently, the liquid paper container 40 shown in FIG. The liquid paper container 40 can store alcoholic beverages such as wine, for example.

  It should be noted that the same variations as those in the embodiments 1A to 1K can be adopted in the above-described embodiments 11A and 11B. For example, as the printing layer containing the biomass-derived component, the printing layer shown in Examples 1B to 1K may be used in addition to the printing layer shown in Example 1A. Further, as the surface resin layer, a surface resin layer as shown in Examples 1L, 1P and 1Q may be used.

[Example 12]
Ivory paper having a basis weight of 260 g / m ² was prepared as the paper base layer 14. Subsequently, the printing layer 12 was formed on the paper base layer 14. In the step of forming the print layer 12, first, an ink composition containing a colorant, a binder resin, and a solvent was prepared. As the binder resin, a resin containing nitrocellulose derived from biomass and a cured product of a polyester polyol derived from a fossil fuel and an isocyanate compound derived from a fossil fuel were used. Subsequently, the ink composition was applied on the paper base material layer 14 in a predetermined pattern by gravure printing to form the print layer 12. The thickness of the printing layer 12 was 2 μm.

  Subsequently, a resin in a molten state was extruded onto the print layer 12 by a melt extrusion lamination method to form the surface resin layer 11. As the surface resin layer 11, polyethylene derived from fossil fuel was used. The thickness of the surface resin layer 11 was 20 μm.

  Subsequently, an inner thermoplastic resin layer 15 was formed on the paper base layer 14 by a melt extrusion lamination method. 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. Thus, the packaging material 20 having the layer configuration shown in FIG. 1 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Table / Biomark / Paper / Internal heat (2) 20

  Then, the paper container 50 shown in FIG. 14 was produced using the packaging material 20. The paper container 50 can be used, for example, as an outer box for confectionery, an outer box for medicines, or the like.

  In this embodiment, the same variations as those in the embodiments 1A to 1Q can be adopted. For example, as the print layer containing the biomass-derived component, the print layers described in Examples 1B to 1K may be used. Further, as the surface resin layer, a surface resin layer as shown in Examples 1L, 1P and 1Q may be used.

  FIG. 17 collectively shows examples of the layer configuration of the packaging material 20 and the types of the packaging containers in Examples 1A and 2A to 12.

Reference Signs List 11 surface resin layer 12 print layer 14 paper base layer 15 inner thermoplastic resin layer 151 first layer 152 second layer 20 packaging material 21 barrier resin layer 22 intermediate thermoplastic resin layer 23 paper base layer inner thermoplastic resin Layer 24 Intermediate 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 32 Polyethylene film layer 40 Liquid paper container 41 Body 42 Bottom 43 Top 44 Inclined plate 45 Folding portion 46 Glue margin 50 Packaging product

Claims (7)

At least, a packaging material in which a surface resin layer, a printing layer, and a paper base layer are sequentially laminated,
The surface resin layer includes polyethylene, polyethylene terephthalate, or polypropylene,
The printing layer includes a coloring agent, nitrocellulose, a cured product of a polyol and an isocyanate compound,
A packaging material, wherein at least one of the nitrocellulose, the polyol or the isocyanate compound contains a biomass-derived component.   The packaging material according to claim 1, wherein the nitrocellulose includes a biomass-derived component.   The packaging material according to claim 1, wherein at least one of the polyol and the isocyanate compound contains a biomass-derived component.   The packaging material according to any one of claims 1 to 3, wherein the printing layer further includes a polyamide resin.   The packaging material according to claim 4, wherein the polyamide resin contains a biomass-derived component.   The packaging material according to any one of claims 1 to 5, wherein the surface resin layer includes polyethylene containing a biomass-derived component.   A packaged product comprising the packaging material according to any one of claims 1 to 6.