JP2020055165A - 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 protective layer, a printed layer, an outer thermoplastic resin layer, a paper substrate layer and an inner thermoplastic resin layer, which are laminated in this order. The outer thermoplastic resin layer has polyethylene. The surface protective layer has a urethane (meth) acrylate that is a reactant of a polyol, an isocyanate compound and a hydroxy (meth) acrylate. At least one of the polyol, isocyanate compound or hydroxy (meth) acrylate 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 PLA, and energy consumption at the time of manufacturing the PLA and equivalence at the time of replacing 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 including a paper base layer, it is desired to reduce the amount of fossil fuel used by using raw materials derived from biomass.

  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 including a paper base material layer having an increased biomass degree.

  The present invention is a packaging material in which at least a surface protective layer, a printing layer, an outer thermoplastic resin layer, a paper base layer, and an inner thermoplastic resin layer are sequentially laminated, and the outer thermoplastic resin layer is made of polyethylene. Wherein the surface protective layer comprises a urethane (meth) acrylate which is a reaction product of a polyol, an isocyanate compound and a hydroxy (meth) acrylate, and at least one of the polyol, the isocyanate compound or the hydroxy (meth) acrylate is used. A packaging material containing a biomass-derived component.

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

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

  In the packaging material according to the present invention, a barrier layer may be further provided between the paper base layer and the inner thermoplastic resin layer.

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

  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 sectional drawing which shows an example of the packaging material of this invention. It is sectional drawing which shows an example of the packaging material of this invention. It is sectional drawing which shows an example of the packaging material of this invention. It is sectional drawing which shows an example of the packaging material of this invention. It is sectional drawing which shows an example of the packaging material of this invention. It is sectional drawing which shows an example of the packaging material of this invention. It is sectional drawing which shows an example of the packaging material of this invention. It is sectional drawing which shows an example of the packaging material of this invention. It is sectional drawing which shows an example of the packaging material of this invention. It is sectional drawing which shows an example of the packaging material of this invention. It is sectional drawing which shows an example of the packaging material of this invention. It is a figure showing an example of the liquid paper container provided with the packaging material of the present invention. It is a figure which shows the layer constitution of the packaging material of Examples 1A-1H. It is a figure which shows the layer constitution of the packaging material of Example 1I-1P. It is a figure which shows the layer constitution of the packaging material of Examples 1A-19.

  The laminate constituting the packaging material according to the present invention includes at least a surface protective layer, a printing layer, an outer thermoplastic resin layer, a paper base layer, and an inner thermoplastic resin 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.

  FIG. 1 is a sectional view showing an example of the packaging material 20 of the present invention. The packaging material 20 includes a surface protection layer 11, a printing layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, and an inner thermoplastic resin layer 15 in this order. The surface protective 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 sectional view showing another example of the packaging material 20 of the present invention. The packaging material 20 includes a surface protective layer 11, a printing layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, a barrier resin layer 21, an intermediate thermoplastic resin layer 22, and an inner thermoplastic resin. And a layer 15 in this order. The surface protective 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 of the present invention. The packaging material 20 includes a surface protective layer 11, a printing layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, a polyolefin resin layer 23, an intermediate thermoplastic resin layer 22, and a barrier resin layer 21. And an intermediate thermoplastic resin layer 24 and an inner thermoplastic resin layer 15 in this order. The surface protective 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 of the present invention. The packaging material 20 includes a surface protection layer 11, a printing layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, and a plastic film. A layer 28, an anchor coat layer 29, and an inner thermoplastic resin layer 15 are provided in this order. The surface protective 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 of the present invention. The packaging material 20 includes a surface protection layer 11, a printing layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, and a plastic film. A layer 28, an anchor coat layer 29, an adhesive resin layer 30, and an inner thermoplastic resin layer 15 are provided in this order. The surface protective 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 sectional view showing another example of the packaging material 20 of the present invention. The packaging material 20 includes a surface protection layer 11, a printing layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, and a plastic film. A layer 28, an adhesive layer 31, and an inner thermoplastic resin layer 15 are provided in this order. The surface protective 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 of the present invention. The packaging material 20 includes a surface protective layer 11, a printing layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, and an inner thermoplastic resin layer 15. Prepare in this order. The surface protective 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 of the present invention. The packaging material 20 includes a surface protective layer 11, a print layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive resin layer 30, A plastic resin layer 15 is provided in this order. The surface protective 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 cross-sectional view showing another example of the packaging material 20 of the present invention. The packaging material 20 includes a surface protective layer 11, a printing layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, and an inner heat layer. A plastic resin layer 15 is provided in this order. The surface protective 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 of the present invention. The packaging material 20 includes a surface protection layer 11, a printing layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a plastic film layer 28, an adhesive layer 27, and a barrier. A layer 26, an intermediate thermoplastic resin layer 22, and an inner thermoplastic resin layer 15 are provided in this order. The surface protective 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 showing another example of the packaging material 20 of the present invention. The packaging material 20 includes a surface protective layer 11, a print layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, a polyolefin resin layer 23, an adhesive resin layer 25, a barrier layer 26, an intermediate heat A plastic resin layer 22 and an inner thermoplastic resin layer 15 are provided in this order. The surface protective 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.

  In addition, it is also possible to appropriately combine a plurality of layer configurations of the packaging material 20 shown in FIGS. 1 to 11 described above.

  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.

  The printing layer 12 is formed by UV offset 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 UV offset 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 urethane (meth) acrylate which is a reaction product of a polyol, an isocyanate compound, and hydroxy (meth) acrylate. At least one of the polyol, the isocyanate compound and the hydroxy (meth) acrylate may or may not contain a biomass-derived component. In the following description, urethane (meth) acrylate containing a biomass-derived component is also referred to as biourethane (meth) acrylate.

  Urethane (meth) acrylate is obtained, for example, by reacting a polyol and an isocyanate with hydroxy (meth) acrylate. In the biourethane (meth) acrylate, a plant-derived polyol can be used as the polyol, a plant-derived isocyanate can be used as the isocyanate, or a plant-derived polyol can be used for both the polyol and the isocyanate.

  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. Hereinafter, each polyol will be described.

<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-pentamethylenediisocyanate or a salt thereof is carbamate first to generate pentamethylenedicarbamate (PDC) and then thermally decomposed to convert 1,5-pentamethylenediisocyanate. 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>
Next, the isocyanate compound will be described. As the isocyanate compound containing a biomass-derived component, the polyfunctional isocyanate derived from biomass described for the polyether polyol can be used.

<Hydroxy (meth) acrylate>
Next, the hydroxy (meth) acrylate will be described. Examples of the hydroxy (meth) acrylate include (meth) acryloyl groups such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. Hydroxy (meth) acrylates such as glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, sorbitol penta (meth) acrylate, etc. Hydroxy (meth) acrylate having two or more (meth) acryloyl groups is exemplified. These may be used alone or in combination of two or more.

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 0.5 μm or more and 5 μm or less, and still more preferably 0.7 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” is, for example, a value obtained by measuring the content of carbon derived from biomass by measuring radioactive carbon (C14).

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

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

(Surface protection layer)
The surface protection layer 11 is a layer that protects the printing layer 12. The surface protection layer 11 may be provided so as to be in contact with the printing layer 12. The surface protective layer 11 is formed by applying a paint containing a solid content and a solvent. As the solid content of the paint, the same material as the binder resin of the print layer 12 can be used. Therefore, the configuration of the surface protective layer 11 is the same as the configuration of the print layer 12 except that the surface protective layer 11 does not include a coloring agent.

  The surface protective layer 11 contains urethane (meth) acrylate which is a reaction product of a polyol, an isocyanate compound, and hydroxy (meth) acrylate, and at least one of the polyol, the isocyanate compound, and the hydroxy (meth) acrylate contains a biomass-derived component. . As the polyol, the isocyanate compound and the hydroxy (meth) acrylate, the polyol, the isocyanate compound and the hydroxy (meth) acrylate described in the printing layer 12 can be used.

The surface protective layer 11 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 surface protective layer 11 after drying is preferably from 0.1 g / m ^{2 to} 10 g / m ² , more preferably from 1 g / m ^{2 to} 5 g / m ² , and still more preferably from 1 g / m ^{2 to} 3 g / m ^2. m ² or less. The surface protective layer 11 has a thickness of preferably 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, and still more preferably 1 μm or more and 3 μm or less.

(Inner thermoplastic resin layer)
The inner thermoplastic resin layer 15 can be formed using a conventionally known thermoplastic resin. The inner thermoplastic resin layer 15 is located inside the packaging material 20. When the packaging material 20 includes the inner thermoplastic resin layer, 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. When the inner thermoplastic resin layer 15 is formed of a material that does not contain a biomass-derived component, the inner thermoplastic resin layer 15 can be formed using a conventionally known thermoplastic resin 15 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 include two or more biomass polyolefins having different biomass degrees, and the biomass degree of the entire polyolefin 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 polyolefin resin layer containing the biomass polyolefin can be increased, and it 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 polyolefin resin layer containing the biomass polyolefin can be increased, and it can be suitably used as an inner layer of a packaged product.

  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 polyolefin 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 a multilayer. When the biomass polyolefin as described above is used for the inner thermoplastic resin layer, the inner thermoplastic resin layer may include 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.

(Outer thermoplastic resin layer)
The outer thermoplastic resin layer 13 is a layer containing polyethylene. The outer thermoplastic resin layer 13 is located between the printing layer 12 and the paper base layer 14. When the packaging material 20 includes the outer thermoplastic resin layer 13, the paper base layer can be provided with waterproofness and can have improved sealing properties.

  Examples of the polyethylene of the outer thermoplastic resin layer 13 include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene. The outer thermoplastic resin layer 13 is formed of, for example, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer in addition to the above-mentioned polyethylene. A copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, an ionomer resin, a polyester resin, a polyvinyl chloride resin, a polystyrene resin, and nylon may be included.

  The outer thermoplastic resin layer 13 may include a material derived from biomass, or may include a material derived from fossil fuel. When the outer 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, like the inner thermoplastic resin layer 15.

  Outer thermoplastic resin layer 13 preferably has a thickness of 10 μm or more and 30 μm or less, more preferably 10 μm or more and 20 μm or less.

(Intermediate thermoplastic resin layer)
The intermediate thermoplastic resin layer can be formed using a conventionally known thermoplastic resin. Since the packaging material 20 includes the intermediate thermoplastic resin layer, it is possible to impart adhesion between the respective layers.

  As the 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 Polymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin, polyester resin, polyvinyl chloride resin, polystyrene resin, nylon And the like, and low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and ethylene-methacrylic acid copolymer are preferable.

  The 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 2 μm or more and 10 μm or less, more preferably 3 μm or more and 8 μm or less.

(Barrier resin layer)
The barrier resin layer 21 is a layer that imparts or improves gas barrier properties for preventing transmission of oxygen gas, water vapor, and the like, and light blocking properties for preventing transmission of visible light, ultraviolet light, and the like. 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 may contain additives 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 gas barrier resin layer is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 7 μm or less.

(Polyolefin resin layer)
The polyolefin resin layer 23 is a layer for increasing the adhesiveness between the paper base material layer 14 and other layers. Examples of the polyolefin of the polyolefin resin layer 23 include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, and propylene-ethylene copolymer. The polyolefin resin layer 23 is preferably a polyethylene resin layer from the viewpoint of adhesion to the paper base material layer 14.

  The polyolefin resin layer 23 preferably has a thickness of 10 μm or more and 30 μm or less, more preferably 12 μm or more and 25 μm or less, and still more preferably 15 μm or more and 22 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 16 μm or less, more preferably 9 μm or more and 12 μm or less.

(Anchor coat layer)
The anchor coat layer 29 is a layer for improving the adhesion between the plastic film layer 28 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.

(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, a resin in a molten state is extruded onto the paper base material layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13. Subsequently, the resin in a molten state is extruded on the surface of the paper base material layer 14 opposite to the surface on which the outer thermoplastic resin layer 13 is formed by the melt extrusion lamination method to form the inner thermoplastic resin layer 15. Subsequently, the above-described ink composition is applied on the outer thermoplastic resin layer 13 by offset printing, and the ink composition on the outer thermoplastic resin layer 13 is irradiated with ultraviolet rays to print on the outer thermoplastic resin layer 13. The layer 12 is formed. Subsequently, the above-described paint containing a solid content and a solvent is applied on the print layer 12, and the paint on the print layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the print layer 12. Thereby, a packaging material 20 including the surface protective layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, and the inner thermoplastic resin layer 15 can be obtained. As a method of applying the paint, an offset method or the like can be used.

  After forming the inner thermoplastic resin layer 15 on the paper base layer 14, the outer thermoplastic resin layer 13, the printing layer 12 and the surface protective 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 above-mentioned paper base material layer 14 is prepared. Subsequently, a resin in a molten state is extruded onto the paper base material layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13. Subsequently, the molten resin is extruded on the surface of the paper base layer 14 opposite to the surface on which the thermoplastic resin layer 13 is formed by a melt extrusion lamination method, and the barrier resin layer 21 and the intermediate thermoplastic resin are extruded. The layer 22 and the inner thermoplastic resin layer 15 are formed. Subsequently, the above-described ink composition is applied on the outer thermoplastic resin layer 13 by offset printing, and the ink composition on the outer thermoplastic resin layer 13 is irradiated with ultraviolet rays to print on the outer thermoplastic resin layer 13. The layer 12 is formed. Subsequently, the above-described paint containing a solid content and a solvent is applied on the print layer 12, and the paint on the print layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the print layer 12. Thereby, the packaging material 20 including the surface protective layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the barrier resin layer 21, the intermediate thermoplastic resin layer 22, and the inner thermoplastic resin layer 15 is formed. Obtainable.

  After forming the barrier resin layer 21, the intermediate thermoplastic resin layer 22 and the inner thermoplastic resin layer 15 on the paper base layer 14, the outer thermoplastic resin layer 13 and the print layer 12 are formed on the paper base layer 14. And a surface protection layer 11 may be formed.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 3 will be described. First, the above-mentioned paper base material layer 14 is prepared. Subsequently, a resin in a molten state is extruded onto the paper base material layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13. Subsequently, by a melt extrusion lamination method, the resin in a molten state is extruded onto a surface of the paper base layer 14 opposite to the surface on which the thermoplastic resin layer 13 is formed, and the polyolefin resin layer 23 and the intermediate thermoplastic resin are extruded. The layer 22, the barrier resin layer 21, the intermediate thermoplastic resin layer 24, and the inner thermoplastic resin layer 15 are formed. Subsequently, the above-described ink composition is applied on the outer thermoplastic resin layer 13 by offset printing, and the ink composition on the outer thermoplastic resin layer 13 is irradiated with ultraviolet rays to print on the outer thermoplastic resin layer 13. The layer 12 is formed. Subsequently, the above-described paint containing a solid content and a solvent is applied on the print layer 12, and the paint on the print layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the print layer 12. Thereby, the surface protection layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the polyolefin 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.

  After forming the polyolefin resin layer 23, the intermediate thermoplastic resin layer 22, the barrier resin layer 21, the intermediate thermoplastic resin layer 24, and the inner thermoplastic resin layer 15 on the paper base layer 14, the paper base layer 14 The outer thermoplastic resin layer 13, the printing layer 12, and the surface protection layer 11 may be formed thereon.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 4 will be described. First, the above-mentioned paper base material layer 14 is prepared. Subsequently, a resin in a molten state is extruded onto the paper base material layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13. 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 on which the outer thermoplastic resin layer 13 is formed and the barrier layer 26 on 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. Subsequently, the above-described ink composition is applied on the outer thermoplastic resin layer 13 by offset printing, and the ink composition on the outer thermoplastic resin layer 13 is irradiated with ultraviolet rays to print on the outer thermoplastic resin layer 13. The layer 12 is formed. Subsequently, the above-described paint containing a solid content and a solvent is applied on the print layer 12, and the paint on the print layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the print layer 12. Thereby, the surface protective layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27, the plastic film layer 28, the anchor coat layer 29 and the inner side A packaging material 20 including the 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 outer thermoplastic resin layer 13 and the printing layer 12 are formed on the paper base layer 14. And a surface protection layer 11 may be formed.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 5 will be described. First, the above-mentioned paper base material layer 14 is prepared. Subsequently, a resin in a molten state is extruded onto the paper base material layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13. 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 on which the outer thermoplastic resin layer 13 is formed and the barrier layer 26 on 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. Subsequently, the above-described ink composition is applied on the outer thermoplastic resin layer 13 by offset printing, and the ink composition on the outer thermoplastic resin layer 13 is irradiated with ultraviolet rays to print on the outer thermoplastic resin layer 13. The layer 12 is formed. Subsequently, the above-described paint containing a solid content and a solvent is applied on the print layer 12, and the paint on the print layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the print layer 12. Thereby, the surface protective layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27, the plastic film layer 28, the anchor coat layer 29, The packaging material 20 including the 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 outer thermoplastic resin layer 13 and the printing layer 12 are formed on the paper base layer 14. And a surface protection layer 11 may be formed.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 6 will be described. First, the above-mentioned paper base material layer 14 is prepared. Subsequently, a resin in a molten state is extruded onto the paper base material layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13. 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 on which the outer thermoplastic resin layer 13 is formed and the barrier layer 26 on which the plastic film layer 28 is bonded are laminated via the adhesive resin layer 25 by a sand lamination method. Subsequently, the plastic film layer 28 and the film constituting the inner thermoplastic resin layer 15 are laminated via the adhesive layer 31 by a dry lamination method. Subsequently, the above-described ink composition is applied on the outer thermoplastic resin layer 13 by offset printing, and the ink composition on the outer thermoplastic resin layer 13 is irradiated with ultraviolet rays to print on the outer thermoplastic resin layer 13. The layer 12 is formed. Subsequently, the above-described paint containing a solid content and a solvent is applied on the print layer 12, and the paint on the print layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the print layer 12. Thereby, the surface protective layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27, the plastic film layer 28, the adhesive layer 31, and the inner side A packaging material 20 including the 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 outer thermoplastic resin layer 13 and the printing layer 12 are formed on the paper base layer 14. And a surface protection layer 11 may be formed.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 7 will be described. First, the above-mentioned paper base material layer 14 is prepared. Subsequently, a resin in a molten state is extruded onto the paper base material layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13. Subsequently, the paper base layer 14 on which the outer thermoplastic resin layer 13 is formed 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. Subsequently, the above-described ink composition is applied on the outer thermoplastic resin layer 13 by offset printing, and the ink composition on the outer thermoplastic resin layer 13 is irradiated with ultraviolet rays to print on the outer thermoplastic resin layer 13. The layer 12 is formed. Subsequently, the above-described paint containing a solid content and a solvent is applied on the print layer 12, and the paint on the print layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the print layer 12. Thereby, a packaging material 20 including the surface protective layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, and the inner thermoplastic resin layer 15 can be obtained. .

  After laminating the paper base layer 14 and the film constituting the barrier layer 26 via the adhesive resin layer 25, the outer thermoplastic resin layer 13, the print layer 12 and the surface protection layer 11 are formed on the paper base layer 14. May be formed.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 8 will be described. First, the above-mentioned paper base material layer 14 is prepared. Subsequently, a resin in a molten state is extruded onto the paper base material layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13. Subsequently, the paper base layer 14 on which the outer thermoplastic resin layer 13 is formed 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. Subsequently, the above-described ink composition is applied on the outer thermoplastic resin layer 13 by offset printing, and the ink composition on the outer thermoplastic resin layer 13 is irradiated with ultraviolet rays to print on the outer thermoplastic resin layer 13. The layer 12 is formed. Subsequently, the above-described paint containing a solid content and a solvent is applied on the print layer 12, and the paint on the print layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the print layer 12. Thereby, the packaging material 20 including the surface protection layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive resin layer 30, and the inner thermoplastic resin layer 15 is provided. Can be obtained.

  After laminating the paper base layer 14 and the film constituting the barrier layer 26 via the adhesive resin layer 25, the outer thermoplastic resin layer 13, the print layer 12 and the surface protection layer 11 are formed on the paper base layer 14. May be formed.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 9 will be described. First, the above-mentioned paper base material layer 14 is prepared. Subsequently, a resin in a molten state is extruded onto the paper base material layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13. Subsequently, the paper base layer 14 on which the outer thermoplastic resin layer 13 is formed 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 layer 27 by a dry lamination method. Subsequently, the above-described ink composition is applied on the outer thermoplastic resin layer 13 by offset printing, and the ink composition on the outer thermoplastic resin layer 13 is irradiated with ultraviolet rays to print on the outer thermoplastic resin layer 13. The layer 12 is formed. Subsequently, the above-described paint containing a solid content and a solvent is applied on the print layer 12, and the paint on the print layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the print layer 12. Thereby, the packaging material 20 including the surface protective layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27, and the inner thermoplastic resin layer 15 Can be obtained.

  After laminating the paper base layer 14 and the film constituting the barrier layer 26 via the adhesive resin layer 25, the outer thermoplastic resin layer 13, the print layer 12 and the surface protection layer 11 are formed on the paper base layer 14. May be formed.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 10 will be described. First, the above-mentioned paper base material layer 14 is prepared. Subsequently, a resin in a molten state is extruded onto the paper base material layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13. Subsequently, a film constituting the plastic film layer 28 and a film constituting the barrier layer 26 are separately laminated via an adhesive layer 27 by a dry lamination method. Subsequently, the paper base layer 14 on which the outer thermoplastic resin layer 13 is formed and the plastic film layer 28 on which the barrier layer 26 is bonded are laminated via the adhesive resin layer 25 by a sand lamination method. Subsequently, the intermediate thermoplastic resin layer 22 and the inner thermoplastic resin layer 15 are formed on the barrier layer 26 by a melt extrusion lamination method. Subsequently, the above-described ink composition is applied on the outer thermoplastic resin layer 13 by offset printing, and the ink composition on the outer thermoplastic resin layer 13 is irradiated with ultraviolet rays to print on the outer thermoplastic resin layer 13. The layer 12 is formed. Subsequently, the above-described paint containing a solid content and a solvent is applied on the print layer 12, and the paint on the print layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the print layer 12. Thereby, the surface protective layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the plastic film layer 28, the adhesive layer 27, the barrier layer 26, and the intermediate thermoplastic resin layer 22 And the packaging material 20 provided with the inner thermoplastic resin layer 15 can be obtained.

  After laminating the paper base layer 14 and the plastic film layer 28 to which the barrier layer 26 is bonded via the adhesive resin layer 25, the outer thermoplastic resin layer 13 and the printing layer 12 are formed on the paper base layer 14. And a surface protection layer 11 may be formed.

  An example of a method for manufacturing the packaging material 20 shown in FIG. 11 will be described. First, the above-mentioned paper base material layer 14 is prepared. Subsequently, a resin in a molten state is extruded onto the paper base material layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13. Subsequently, a resin in a molten state is extruded on a surface of the paper base layer 14 opposite to the surface on which the thermoplastic resin layer 13 is formed by a melt extrusion lamination method to form a polyolefin resin layer 23. Subsequently, the polyolefin resin layer 23 and the film constituting the barrier layer 26 are laminated via the adhesive resin layer 25 by a sand lamination method. Subsequently, the intermediate thermoplastic resin layer 22 and the inner thermoplastic resin layer 15 are formed on the barrier layer 26 by a melt extrusion lamination method. Subsequently, the above-described ink composition is applied on the outer thermoplastic resin layer 13 by offset printing, and the ink composition on the outer thermoplastic resin layer 13 is irradiated with ultraviolet rays to print on the outer thermoplastic resin layer 13. The layer 12 is formed. Subsequently, the above-described paint containing a solid content and a solvent is applied on the print layer 12, and the paint on the print layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the print layer 12. Thereby, the surface protection layer 11, the printing layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the polyolefin resin layer 23, the adhesive resin layer 25, the barrier layer 26, the intermediate thermoplastic resin layer 22, and the inner thermoplastic resin A packaging material 20 comprising the layer 15 can be obtained.

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

<Packaging products>
An example of a packaged product formed by using the packaging material 20 will be described. FIG. 12 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. 12, the liquid paper container 40 has a square tubular body 41 including side surfaces, a square plate-shaped bottom 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 surface protective layer 11 containing a biomass-derived component, the amount of fossil fuel used can be reduced as compared with the conventional case. 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]
A liquid container base paper having a basis weight of 320 g / m ² was prepared as the paper base layer 14. Subsequently, the outer thermoplastic resin layer 13 was formed on the paper base layer 14 by a melt extrusion lamination method. As the outer thermoplastic resin layer 13, polyethylene derived from fossil fuel was used. The thickness of the outer thermoplastic resin layer 13 was 17 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 28 μm.

  Subsequently, the printed layer 12 was formed on the outer thermoplastic resin layer 13. 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 a binder resin, urethane (meth) acrylate, which is a reaction product of a fossil fuel-derived polyester polyol, a fossil fuel-derived isocyanate compound, and a fossil fuel-derived hydroxy (meth) acrylate, was used. As the polyester polyol derived from a fossil fuel, 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 used. Subsequently, an ink composition is applied on the outer thermoplastic resin layer 13 in a predetermined pattern by offset printing, and the ink composition on the outer thermoplastic resin layer 13 is irradiated with ultraviolet rays to form an ink on the outer thermoplastic resin layer 13. The printing layer 12 was formed on the substrate. The thickness of the printing layer 12 was 1 μm.

  Subsequently, the surface protection layer 11 was formed on the printing layer 12. In the step of forming the surface protective layer 11, first, a paint containing a binder resin and a solvent was prepared. As the binder resin, biourethane (meth) acrylate, which is a reaction product of a polyester polyol containing a biomass-derived component, an isocyanate compound derived from a fossil fuel, and a hydroxy (meth) acrylate derived from a fossil fuel, was used. Subsequently, a paint was applied to the entire area of the print layer 12 by an offset method, and the paint on the print layer 12 was irradiated with ultraviolet rays to form the surface protective layer 11. The thickness of the surface protective layer 11 was 1 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.
Bio table / mark / external heat 17 / paper / internal heat (2) 28
“/” 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.
"Bio table" means a surface protective layer derived from biomass. "Mark" means a printed layer. "External heat" means external heat from fossil fuels. "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, using the packaging material 20, a liquid paper container 40 shown in FIG. The liquid paper container 40 can contain milk or juice, for example.

[Example 1B]
Except for using a reaction product of a polyfunctional alcohol derived from a fossil fuel and a polyfunctional carboxylic acid containing a biomass-derived component as the polyester polyol of the binder resin of the surface protective layer 11, in the same manner as in Example 1A, A packaging material 20 was produced.

[Example 1C]
As a binder resin for the surface protective layer 11, bio-urethane (meth) acrylate, which is a reaction product of a fossil fuel-derived polyester polyol, an isocyanate compound containing a biomass-derived component, and a fossil fuel-derived hydroxy (meth) acrylate, was used. Except for this, the packaging material 20 was produced in the same manner as in Example 1A.

FIG. 13A shows the layer structure of the packaging material 20 of Examples 1A to 1C. In the column of “biomass-derived component in surface protective layer” in FIG. 13A, the description “binder resin” means that the binder resin used in the surface protective layer contains a biomass-derived component.
In the column of "Biomass-derived component in binder resin of surface protective layer", the description "polyol" means that the polyol used in the binder resin of the surface protective layer contains a biomass-derived component. Further, the description “isocyanate compound” means that the isocyanate compound used in the binder resin of the surface protective layer contains a biomass-derived component.
Further, in the column of "Type of polyol for surface protective layer", the description "ester type" means that the polyol used in the binder resin of the surface protective layer is a polyester polyol.
In the column of “Biomass-derived component in polyol of surface protective layer”, description of “polyfunctional alcohol” means that at least polyfunctional alcohol of polyester polyol among components used in polyol of binder resin of surface protective layer is used. It means that it is derived from biomass. Similarly, the description “polyfunctional carboxylic acid” means that among the components used in the polyol of the binder resin of the surface protective layer, at least the polyfunctional carboxylic acid of the polyester polyol is derived from biomass. The description "-" means that the polyol of the binder resin of the surface protective layer contains no biomass-derived component.

  In Examples 1A to 1C, in the binder resin of the surface protective layer, one of the three constituent elements of the polyfunctional alcohol or polyfunctional carboxylic acid used in the polyester polyol or the isocyanate compound is a biomass-derived component. An example is given, but is not limited to this. For example, two of the three components may include a biomass-derived component, and all three components may include a biomass-derived component.

[Example 1D]
A packaging material 20 was produced in the same manner as in Example 1A, except that polyether polyol was used as the polyol for the binder resin of the surface protective layer 11. 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.

[Example 1E]
Except for using a reaction product of a polyfunctional alcohol derived from fossil fuel and a polyfunctional isocyanate containing a biomass-derived component as the polyether polyol of the binder resin of the surface protective layer 11, in the same manner as in Example 1D, A packaging material 20 was produced.

[Example 1F]
As a binder resin of the surface protective layer 11, bio urethane (meth) acrylate which is a reaction product of a fossil fuel-derived polyether polyol, an isocyanate compound containing a biomass-derived component, and a fossil fuel-derived hydroxy (meth) acrylate is used. A packaging material 20 was produced in the same manner as in Example 1D, except that the packaging material 20 was used.

  FIG. 13A shows the layer configuration of the packaging material 20 of Examples 1D to 1F. In the column of "Type of polyol for surface protective layer" in FIG. 13A, the description "ether type" means that the polyol used in the binder resin of the surface protective layer is a polyether polyol. In the column of `` Biomass-derived component in polyol of surface protective layer '', the description of `` polyfunctional isocyanate '' means that at least the polyfunctional isocyanate among components used in the polyol of the binder resin of the surface protective layer is derived from biomass. It means there is.

  In Examples 1D to 1F, in the binder resin of the surface protective layer, one of the three constituent components of polyfunctional alcohol or polyfunctional isocyanate used in the polyether polyol or the isocyanate compound is a biomass-derived component. An example is given, but is not limited to this. For example, two of the three components may include a biomass-derived component, and all three components may include a biomass-derived component.

[Example 1G]
A packaging material 20 was prepared in the same manner as in Example 1A, except that polycarbonate polyol was used as the polyol of the binder resin of the surface protective layer 11. Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate derived from a fossil fuel was used as the polycarbonate polyol.

[Example 1H]
As a binder resin for the surface protective layer 11, biourethane (meth) acrylate, which is a reaction product of a fossil fuel-derived polycarbonate polyol, an isocyanate compound containing a biomass-derived component, and a fossil fuel-derived hydroxy (meth) acrylate, was used. Except for this, the packaging material 20 was produced in the same manner as in Example 1G.

  FIG. 13A shows the layer configuration of the packaging material 20 of Examples 1G and 1H. In the column of “Type of polyol for surface protective layer” in FIG. 13A, “carbonate-based” means that the polyol used in the binder resin for the surface protective layer is a polycarbonate polyol.

  In Examples 1G and 1H, in the binder resin of the surface protective layer, an example is shown in which one of the two components, that is, the polyfunctional alcohol used for the polycarbonate polyol or the isocyanate compound is a biomass-derived component. However, it is not limited to this. For example, both of the two components may include a biomass-derived component.

[Example 1I]
A packaging material 20 was produced in the same manner as in Example 1A, except that a material containing a biomass-derived component was used as the printing layer 12. Specifically, bio-urethane (meth), which is a reaction product of a polyester polyol containing a biomass-derived component, an isocyanate compound derived from a fossil fuel, and a hydroxy (meth) acrylate derived from a fossil fuel, as a binder resin of the printing layer 12. Acrylate was used. As the polyester polyol containing a biomass-derived component, a polyester polyol which is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid derived from a fossil fuel was used.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Bio table / Bio stamp / External heat 17 / Paper / Internal heat (2) 28
“Biomark” means a printed layer derived from biomass.

[Example 1J]
Packaging was performed in the same manner as in Example 1I, 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.

[Example 1K]
Bio-urethane (meth) acrylate, which is a reaction product of a fossil fuel-derived polyester polyol, an isocyanate compound containing a biomass-derived component, and a fossil fuel-derived hydroxy (meth) acrylate, is used as the binder resin of the print layer 12. Except for the above, a packaging material 20 was produced in the same manner as in Example 1I.

FIG. 13B shows the layer structure of the packaging material 20 of Examples 1I to 1K. In the column of “biomass-derived component in print layer” in FIG. 13B, the description “binder resin” means that the binder resin used in the print layer contains a biomass-derived component.
In the column of "Biomass-derived component in binder resin of printing layer", the description "polyol" means that the polyol used in the binder resin of the printing layer contains a biomass-derived component. Further, the description “isocyanate compound” means that the isocyanate compound used in the binder resin of the printing layer contains a biomass-derived component.
Further, in the column of "type of polyol for printing layer", description of "ester type" means that the polyol used in the binder resin of the printing layer is a polyester polyol.
Further, in the column of “biomass-derived components in the polyol of the printing layer”, the description “polyfunctional alcohol” means that among the components used in the polyol of the binder resin of the printing layer, at least the polyfunctional alcohol of the polyester polyol is derived from biomass. Means that Similarly, the description “polyfunctional carboxylic acid” means that among the components used in the polyol of the binder resin of the printing layer, at least the polyfunctional carboxylic acid of the polyester polyol is derived from biomass. The description "-" means that the polyol of the binder resin of the printing layer does not contain a biomass-derived component.

  In Examples 1I to 1K, in the binder resin of the printing layer, one of the three constituent elements of the polyfunctional alcohol or polyfunctional carboxylic acid used in the polyester polyol or the isocyanate compound is a biomass-derived component. Although an example is shown, the present invention is not limited to this. For example, two of the three components may include a biomass-derived component, and all three components may include a biomass-derived component.

[Example 1L]
A packaging material 20 was prepared in the same manner as in Example 1I, except that polyether polyol 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.

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

[Example 1N]
Bio urethane (meth) acrylate, which is a reaction product of fossil fuel-derived polyether polyol, an isocyanate compound containing a biomass-derived component, and fossil fuel-derived hydroxy (meth) acrylate, was used as the binder resin of the print layer 12. Except for this, the packaging material 20 was produced in the same manner as in Example 1L.

  FIG. 13B shows the layer configuration and the like of the packaging material 20 of Examples 1L to 1N. In the column of “type of polyol for printing layer” in FIG. 13B, the description “ether type” means that the polyol used in the binder resin of the printing layer is a polyether polyol. In the column of "biomass-derived component in polyol of printing layer", description of "polyfunctional isocyanate" means that at least polyfunctional isocyanate among components used in polyol of binder resin of printing layer is derived from biomass. Means

  In Examples 1L to 1N, in the binder resin of the printing layer, one of the three constituent elements of the polyfunctional alcohol or polyfunctional isocyanate used in the polyether polyol or the isocyanate compound is a biomass-derived component. Although an example is shown, the present invention is not limited to this. For example, two of the three components may include a biomass-derived component, and all three components may include a biomass-derived component.

[Example 10]
A packaging material 20 was prepared in the same manner as in Example 1I, except that polycarbonate polyol was used as the polyol for the binder resin of the print layer 12. Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate derived from a fossil fuel was used as the polycarbonate polyol.

[Example 1P]
Bio urethane (meth) acrylate, which is a reaction product of a fossil fuel-derived polycarbonate polyol, an isocyanate compound containing a biomass-derived component, and a fossil fuel-derived hydroxy (meth) acrylate as the binder resin of the printing layer 12 Except for the above, a packaging material 20 was produced in the same manner as in Example 10.

  FIG. 13B shows the layer configuration of the packaging material 20 of Examples 10 and 1P collectively. In the column of “type of polyol for printing layer” in FIG. 13B, the description “carbonate-based” means that the polyol used in the binder resin of the printing layer is a polycarbonate polyol.

  In Examples 1O and 1P, in the binder resin of the printing layer, an example is shown in which one of the two components, that is, the polyfunctional alcohol used for the polycarbonate polyol or the isocyanate compound is a biomass-derived component. However, it is not limited to this. For example, both of the two components may include a biomass-derived component.

[Example 1Q]
A packaging material 20 was prepared in the same manner as in Example 1A, except that polyethylene containing a biomass-derived component was used as the polyethylene of the outer thermoplastic resin layer 13 and the inner thermoplastic resin layer 15.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Bio table / mark / External heat 17 / Paper / Internal heat (2) 28
“External heat from bio” means an outer thermoplastic resin layer containing a biomass-derived component. "Heat in bio (2)" means an inner thermoplastic resin layer derived from biomass formed by a melt extrusion lamination method.

  Note that the same variation as in the case of the embodiments 1B to 1P can be adopted also in the above-described embodiment 1Q. For example, in addition to the surface protective layer shown in Example 1A, the surface protective layer shown in Examples 1B to 1H may be used as the surface protective layer containing the biomass-derived component. Further, as the printing layer, a printing layer containing a biomass-derived component as shown in Examples 1I to 1P may be used.

[Example 2]
In the same manner as in Example 1A, a paper base layer 14 was prepared, and an outer thermoplastic resin layer 13 was formed on the paper base layer 14. The thickness of the outer thermoplastic resin layer 13 was 20 μm. 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. Subsequently, the print layer 12 and the surface protection layer 11 were formed on the outer thermoplastic resin layer 13 in the same manner as in Example 1A. 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.
Bio table / Mark / External heat 20 / Paper / EVOH5 / Medium heat 5 / Internal heat (2) 20
“EVOH” means a barrier resin layer using EVOH. "Medium heat" means an intermediate thermoplastic resin layer.

  Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, fruit juice or tea.

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

[Example 3]
A packaging material 20 was prepared in the same manner as in Example 2, 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.
Bio table / mark / external heat 20 / paper / MXD6 5 / medium heat 5 / internal heat (2) 20
“MXD6” means a barrier resin layer using polymetaxylylene adipamide.

  Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, fruit juice or tea.

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

[Example 4]
A packaging material 20 was prepared in the same manner as in Example 2 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.
Bio table / Mark / External heat 20 / Paper / 6NY5 / Medium heat 5 / Internal heat (2) 20
“6NY” means a barrier resin layer using nylon 6.

  Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, fruit juice or tea.

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

[Example 5]
In the same manner as in Example 1A, a paper base layer 14 was prepared, and an outer thermoplastic resin layer 13 was formed on the paper base layer 14. The thickness of the outer thermoplastic resin layer 13 was 20 μm. Subsequently, a polyolefin resin layer 23, an intermediate thermoplastic resin layer 22, a barrier resin layer 21, an intermediate thermoplastic resin layer 24, and an inner thermoplastic resin layer 15 were formed on the paper base material layer 14 by a melt extrusion lamination method. As the polyolefin resin layer 23, polyethylene derived from fossil fuel was used. The thickness of the polyolefin resin layer 23 was 20 μm. As the intermediate thermoplastic resin layer 22, polyethylene derived from fossil fuel was used. The thickness of the intermediate thermoplastic resin layer 22 was 5 μm. 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. Subsequently, the print layer 12 and the surface protection layer 11 were formed on the outer thermoplastic resin layer 13 in the same manner as in Example 1A. 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.
Bio table / mark / outside heat 20 / paper / PE20 / medium heat 5 / EVOH5 / medium heat 5 / inner heat (2) 20
“PE” means a polyolefin resin layer using polyethylene.

  Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, fruit juice or tea.

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

[Example 6]
A packaging material 20 was prepared in the same manner as in Example 5, 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.
Bio Table / Mark / External Heat 20 / Paper / PE20 / Medium Heat 5 / MXD6 5 / Medium Heat 5 / Internal Heat (2) 20

  Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, fruit juice or tea.

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

[Example 7]
A packaging material 20 was prepared in the same manner as in Example 5, 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.
Bio table / Mark / External heat 20 / Paper / PE20 / Medium heat 5 / 6NY5 / Medium heat 5 / Internal heat (2) 20

  Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, fruit juice or tea.

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

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

  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 on which the outer thermoplastic resin layer 13 was formed 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 50 μm.

  Subsequently, the print layer 12 and the surface protection layer 11 were formed on the outer thermoplastic resin layer 13 in the same manner as in Example 1A. 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.
Bio table / mark / outside heat 20 / paper / adhesive resin 20 / AL foil 7 / contact / PET12 / AC / internal heat (2) 50
"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, using the packaging material 20, a 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 1B to 1P can be adopted. For example, in addition to the surface protective layer shown in Example 1A, the surface protective layer shown in Examples 1B to 1H may be used as the surface protective layer containing the biomass-derived component. Further, as the printing layer, a printing layer containing a biomass-derived component as shown in Examples 1I to 1P may be used.

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

  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 on which the outer thermoplastic resin layer 13 was formed 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.

  Subsequently, the print layer 12 and the surface protection layer 11 were formed on the outer thermoplastic resin layer 13 in the same manner as in Example 1A. 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.
Bio table / mark / outside heat 20 / 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, using the packaging material 20, a 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 1B to 1P can be adopted. For example, in addition to the surface protective layer shown in Example 1A, the surface protective layer shown in Examples 1B to 1H may be used as the surface protective layer containing the biomass-derived component. Further, as the printing layer, a printing layer containing a biomass-derived component as shown in Examples 1I to 1P may be used.

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

  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 on which the outer thermoplastic resin layer 13 was formed 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 plastic film layer 28 and the inner thermoplastic resin layer 15 were bonded together via an adhesive layer 31 by a dry lamination method. As the inner thermoplastic resin layer 15, a polyethylene film (thickness: 60 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 print layer 12 and the surface protection layer 11 were formed on the outer thermoplastic resin layer 13 in the same manner as in Example 1A. 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.
Bio table / mark / external heat 20 / paper / adhesive resin 20 / AL foil 7 / contact / PET12 / contact / internal heat (1) 60

  Subsequently, using the packaging material 20, a 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 1B to 1P can be adopted. For example, in addition to the surface protective layer shown in Example 1A, the surface protective layer shown in Examples 1B to 1H may be used as the surface protective layer containing the biomass-derived component. Further, as the printing layer, a printing layer containing a biomass-derived component as shown in Examples 1I to 1P may be used.

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

  Subsequently, the paper base layer 14 on which the outer thermoplastic resin layer was formed and the barrier layer 26 were bonded to each other via a bonding 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 20 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 40 μm.

  Subsequently, the print layer 12 and the surface protection layer 11 were formed on the outer thermoplastic resin layer 13 in the same manner as in Example 1A. 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.
Bio table / mark / external heat 20 / paper / adhesive resin 20 / AL foil 7 / internal heat (2) 40

  Subsequently, using the packaging material 20, a 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 1B to 1P can be adopted. For example, in addition to the surface protective layer shown in Example 1A, the surface protective layer shown in Examples 1B to 1H may be used as the surface protective layer containing the biomass-derived component. Further, as the printing layer, a printing layer containing a biomass-derived component as shown in Examples 1I to 1P may be used.

[Example 12]
A packaging material 20 was prepared in the same manner as in Example 11, 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.
Bio table / mark / external heat 20 / paper / adhesive resin 20 / VM-PET12 / internal heat (2) 40
“VM-PET” means a vapor deposited film.

  Subsequently, using the packaging material 20, a 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 1B to 1P can be adopted. For example, in addition to the surface protective layer shown in Example 1A, the surface protective layer shown in Examples 1B to 1H may be used as the surface protective layer containing the biomass-derived component. Further, as the printing layer, a printing layer containing a biomass-derived component as shown in Examples 1I to 1P may be used.

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

  Subsequently, the paper base material layer 14 on which the outer thermoplastic resin layer 13 was formed and the barrier layer 26 were adhered 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 20 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.

  Subsequently, the print layer 12 and the surface protection layer 11 were formed on the outer thermoplastic resin layer 13 in the same manner as in Example 1A. 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.
Bio table / mark / external heat 20 / paper / adhesive resin 20 / AL foil 7 / adhesive resin 20 / internal heat (1) 40

  Subsequently, using the packaging material 20, a 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 1B to 1P can be adopted. For example, in addition to the surface protective layer shown in Example 1A, the surface protective layer shown in Examples 1B to 1H may be used as the surface protective layer containing the biomass-derived component. Further, as the printing layer, a printing layer containing a biomass-derived component as shown in Examples 1I to 1P may be used.

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

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

Subsequently, using the packaging material 20, a 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 1B to 1P can be adopted. For example, in addition to the surface protective layer shown in Example 1A, the surface protective layer shown in Examples 1B to 1H may be used as the surface protective layer containing the biomass-derived component. Further, as the printing layer, a printing layer containing a biomass-derived component as shown in Examples 1I to 1P may be used.

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

  Subsequently, the paper base material layer 14 on which the outer thermoplastic resin layer 13 was formed and the barrier layer 26 were adhered 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 20 μm.

  Subsequently, the barrier layer 26 and the inner thermoplastic resin layer 15 were bonded to each other with a dry lamination method via an adhesive layer 27. As the inner thermoplastic resin layer 15, a polyethylene film (thickness: 60 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 print layer 12 and the surface protection layer 11 were formed on the outer thermoplastic resin layer 13 in the same manner as in Example 1A. Thus, a packaging material 20 having a layer configuration shown in FIG. 9 was produced.

The layer configuration of the packaging material 20 of this embodiment is expressed as follows.
Bio table / mark / external heat 20 / paper / adhesive resin 20 / AL foil 7 / contact / internal heat (1) 60

  Subsequently, using the packaging material 20, a 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 1B to 1P can be adopted. For example, in addition to the surface protective layer shown in Example 1A, the surface protective layer shown in Examples 1B to 1H may be used as the surface protective layer containing the biomass-derived component. Further, as the printing layer, a printing layer containing a biomass-derived component as shown in Examples 1I to 1P may be used.

[Example 16]
A packaging material 20 was prepared in the same manner as in Example 15 except that a vapor-deposited film (thickness: 12 μm) in which an aluminum-deposited 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.
Bio table / mark / external heat 20 / paper / adhesive resin 20 / VM-PET12 / contact / internal heat (1) 60

  Subsequently, using the packaging material 20, a 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 1B to 1P can be adopted. For example, in addition to the surface protective layer shown in Example 1A, the surface protective layer shown in Examples 1B to 1H may be used as the surface protective layer containing the biomass-derived component. Further, as the printing layer, a printing layer containing a biomass-derived component as shown in Examples 1I to 1P may be used.

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

  Subsequently, the film forming the plastic film layer 28 and the film forming the barrier layer 26 were bonded to each other 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 on which the outer thermoplastic resin layer 13 was formed and the plastic film layer 28 bonded to the barrier layer 26 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 intermediate thermoplastic resin layer 22 and the inner thermoplastic resin layer 15 were formed on the barrier layer 26 by a melt extrusion lamination method. As the intermediate thermoplastic resin layer 22, polyethylene derived from fossil fuel was used. The thickness of the intermediate thermoplastic resin layer 22 was 20 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 40 μm.

  Subsequently, the print layer 12 and the surface protection layer 11 were formed on the outer thermoplastic resin layer 13 in the same manner as in Example 1A. 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.
Bio table / mark / external heat 20 / paper / adhesive resin 20 / PET12 / contact / AL foil 7 / medium heat 20 / internal heat (2) 40

  Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, a detergent or a chemical product.

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

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

  Subsequently, a polyolefin resin layer 23 was formed on the paper base material layer 14 by a melt extrusion lamination method. As the polyolefin resin layer 23, polyethylene derived from fossil fuel was used. The thickness of the polyolefin resin layer 23 was 20 μm.

  Subsequently, the polyolefin resin layer 23 and the barrier layer 26 were bonded 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 5 μm.

  Subsequently, the intermediate thermoplastic resin layer 22 and the inner thermoplastic resin layer 15 were formed on the barrier layer 26 by a melt extrusion lamination method. 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 30 μm.

  Subsequently, the print layer 12 and the surface protection layer 11 were formed on the outer thermoplastic resin layer 13 in the same manner as in Example 1A. 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.
Bio Table / Mark / External Heat 20 / Paper / PE20 / Adhesive Resin 5 / AL Foil 7 / Medium Heat 5 / Internal Heat (2) 30

  Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, a milk drink or a soft drink.

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

[Example 19]
A packaging material 20 was prepared in the same manner as in Example 18 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.
Bio table / Mark / External heat 20 / Paper / PE20 / Adhesive resin 5 / VM-PET12 / Medium heat 5 / Internal heat (2) 30

  Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. The liquid paper container 40 can contain, for example, a milk drink or a soft drink.

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

  FIG. 14 collectively shows examples of the layer configuration of the packaging material 20 and the types of the packaging containers in Examples 1A and 1Q to 19.

DESCRIPTION OF SYMBOLS 11 Surface protective layer 12 Printing layer 13 Outer thermoplastic resin layer 14 Paper base layer 15 Inner thermoplastic resin layer 20 Packaging material 21 Barrier resin layer 22 Intermediate thermoplastic resin layer 23 Polyolefin resin layer 24 Intermediate thermoplastic resin layer 25 Adhesion Resin layer 26 Barrier layer 27 Adhesive layer 28 Plastic film layer 29 Anchor coat layer 30 Adhesive resin layer 31 Adhesive layer 40 Liquid paper container 41 Body portion 42 Bottom portion 43 Upper portion 44 Inclined plate 45 Folding portion 46 Paste

Claims (6)

At least, a surface protective layer, a printing layer, an outer thermoplastic resin layer, a paper base material layer, a packaging material in which an inner thermoplastic resin layer is sequentially laminated,
The outer thermoplastic resin layer contains polyethylene,
The surface protective layer contains urethane (meth) acrylate, which is a reaction product of a polyol, an isocyanate compound, and hydroxy (meth) acrylate,
A packaging material, wherein at least one of the polyol, the isocyanate compound, or the hydroxy (meth) acrylate contains a biomass-derived component.   The packaging material according to claim 1, wherein the polyol includes a biomass-derived component.   The packaging material according to claim 1, wherein the isocyanate compound contains a biomass-derived component.   The packaging material according to any one of claims 1 to 3, further comprising a barrier layer between the paper base material layer and the inner thermoplastic resin layer.   The packaging material according to claim 4, wherein the barrier layer is a metal foil or a vapor-deposited film.   A packaged product comprising the packaging material according to any one of claims 1 to 5.