JP7238313B2 - Packaging materials and packaging products - Google Patents

Description

The present invention relates to packaging materials containing biomass-derived components and packaged products comprising the packaging materials.

BACKGROUND ART Conventionally, various packaging materials have been developed and proposed as packaging materials for constituting packaging products for filling and packaging various articles such as food and drink, pharmaceuticals, chemicals, cosmetics, sanitary goods, daily necessities, and the like. The packaging material is composed of a laminate including at least a substrate layer and a printed layer for forming a printed pattern.

In recent years, along with the increasing demand for building a recycling-oriented society, the use of biomass has attracted attention in the field of laminates that make up packaging materials, as well as in the field of energy. there is Biomass is an organic compound that is photosynthesised from carbon dioxide and water, and is a so-called carbon-neutral renewable energy that is regenerated into carbon dioxide and water by using it. In recent years, biomass plastics using biomass as raw materials have been rapidly put to practical use, and attempts have been made to produce various resins from biomass raw materials.

As a biomass-derived resin, polylactic acid (PLA), which is produced through lactic acid fermentation, began commercial production first, but its performance as a plastic, including its biodegradability, has fallen behind that of today's general-purpose plastics. Since it is very different from the standard, it has not been widely used due to limitations in product applications and product manufacturing methods. In addition, PLA is subjected to Life Cycle Assessment (LCA) evaluation, and discussions are being made on energy consumption during PLA production and equivalence when replacing general-purpose plastics.

Here, as general-purpose plastics, various types such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, and polyester are used. In particular, polyethylene is molded into films, sheets, bottles, etc., and is used in various applications such as packaging materials, and is widely used around the world. Therefore, the use of conventional fossil fuel-derived polyethylene imposes a large environmental load. Therefore, it is desired to reduce the consumption of fossil fuels by using biomass-derived raw materials for the production of polyethylene. For example, until now, research has been conducted to produce ethylene and butylene, which are raw materials for polyolefin resin, from renewable natural raw materials (see Patent Document 1). In the field of flexible packaging such as pouches, it has been proposed to apply such biomass-derived raw materials to packaging materials (see Patent Document 2).

Japanese Patent Publication No. 2011-506628 JP 2018-51788 A

Also in the field of packaging materials including paper base layers, it is desirable to use biomass-derived raw materials to reduce the amount of fossil fuels used.

The present invention has been made in consideration of such points, and an object of the present invention is to provide a packaging material including a paper base layer with an increased degree of biomass.

The present invention provides a packaging material in which at least a surface protective layer, a printed layer, an outer thermoplastic resin layer, a paper substrate layer, and an inner thermoplastic resin layer are laminated in this order, wherein the outer thermoplastic resin layer comprises polyethylene. The printed layer contains a colorant and a urethane (meth)acrylate that is a reaction product of a polyol, an isocyanate compound, and a hydroxy (meth)acrylate, and the polyol, the isocyanate compound, or the hydroxy (meth)acrylate is a packaging material containing a biomass-derived component.

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

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

In the packaging material according to the present invention, the surface protective layer may contain urethane (meth)acrylate which is a reaction product of polyol, isocyanate compound and hydroxy (meth)acrylate.

In the packaging material according to the present invention, at least one of the polyol, the isocyanate compound and the hydroxy(meth)acrylate of the surface protective layer may contain a biomass-derived component.

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

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

The present invention is a packaged product comprising a packaging material as described above.

According to the present invention, the biomass content of a packaging material containing a paper base layer can be increased.

1 is a cross-sectional view showing an example of the packaging material of the present invention; FIG. 1 is a cross-sectional view showing an example of the packaging material of the present invention; FIG. 1 is a cross-sectional view showing an example of the packaging material of the present invention; FIG. 1 is a cross-sectional view showing an example of the packaging material of the present invention; FIG. 1 is a cross-sectional view showing an example of the packaging material of the present invention; FIG. 1 is a cross-sectional view showing an example of the packaging material of the present invention; FIG. 1 is a cross-sectional view showing an example of the packaging material of the present invention; FIG. 1 is a cross-sectional view showing an example of the packaging material of the present invention; FIG. 1 is a cross-sectional view showing an example of the packaging material of the present invention; FIG. 1 is a cross-sectional view showing an example of the packaging material of the present invention; FIG. 1 is a cross-sectional view showing an example of the packaging material of the present invention; FIG. 1 is a diagram showing an example of a paper container for liquid provided with the packaging material of the present invention; FIG. FIG. 2 shows the layer structure of the packaging materials of Examples 1A-1H. FIG. 2 shows the layer structure of the packaging materials of Examples 1I-1P. FIG. 3 shows the layer structure of the packaging materials of Examples 1A-19.

The laminate constituting the packaging material according to the present invention comprises at least a surface protective layer, a printed layer, an outer thermoplastic resin layer, a paper base layer and an inner thermoplastic resin layer laminated in order from the outer surface side to the inner surface side. The inner surface is the surface of a packaged product formed from the packaging material that faces the contents contained in the packaged product. Further, 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 "provided in this order" and "layered 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. If the degree of biomass is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

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

FIG. 2 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 printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, a barrier resin layer 21, an intermediate thermoplastic resin layer 22, and an inner thermoplastic resin layer. layer 15 in this order. The surface protective layer 11 constitutes the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes the inner surface 20x of the packaging material 20. As shown in FIG.

FIG. 3 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 printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, a polyolefin resin layer 23, an intermediate thermoplastic resin layer 22, and a barrier resin layer 21. , an intermediate thermoplastic resin layer 24 and an inner thermoplastic resin layer 15 in this order. The surface protective layer 11 constitutes the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes the inner surface 20x of the packaging material 20. As shown in FIG.

FIG. 4 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 printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, and 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 constitutes the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes the inner surface 20x of the packaging material 20. As shown in FIG.

FIG. 5 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 printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, and 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 constitutes the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes the inner surface 20x of the packaging material 20. As shown in FIG.

FIG. 6 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 printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, and 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 constitutes the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes the inner surface 20x of the packaging material 20. As shown in FIG.

FIG. 7 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 printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, and an inner thermoplastic resin layer 15. Prepare in this order. The surface protective layer 11 constitutes the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes the inner surface 20x of the packaging material 20. As shown in FIG.

FIG. 8 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 printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive resin layer 30, and an inner thermal layer. A plastic resin layer 15 is provided in this order. The surface protective layer 11 constitutes the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes the inner surface 20x of the packaging material 20. As shown in FIG.

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 printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a barrier layer 26, an adhesive layer 27, and an inner thermal layer. A plastic resin layer 15 is provided in this order. The surface protective layer 11 constitutes the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes the inner surface 20x of the packaging material 20. As shown in FIG.

FIG. 10 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 printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, an adhesive resin layer 25, a plastic film layer 28, an adhesive layer 27, and a barrier layer. 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 constitutes the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes the inner surface 20x of the packaging material 20. As shown in FIG.

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 printed layer 12, an outer thermoplastic resin layer 13, a paper base layer 14, a polyolefin resin layer 23, an adhesive resin layer 25, a barrier layer 26, and an intermediate heat layer. A plastic resin layer 22 and an inner thermoplastic resin layer 15 are provided in this order. The surface protective layer 11 constitutes the outer surface 20y of the packaging material 20, and the inner thermoplastic resin layer 15 constitutes the inner surface 20x of the packaging material 20. As shown in FIG.

It should be noted that 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.

Each layer constituting the packaging material 20 will be described below.

(Paper base layer)
The paper base 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. As the paper base layer 14, white paperboard in general can be used, but ivory paper, milk carton base paper, cup base paper, etc. using natural pulp are particularly preferable from the viewpoint of safety.

The paperboard may use neutral rosin, alkyl ketene dimer, alkenyl succinic anhydride as a sizing agent, and cationic polyacrylamide, cationic starch, etc. as a fixing agent. Moreover, it is also possible to make paper in a neutral range of pH 6 or more and pH 9 or less using aluminum sulfate. In addition to the above sizing agents as necessary, fixing agents, various fillers for papermaking, retention improvers, dry strength enhancers, wet strength enhancers, binders, dispersants, flocculants, plasticizers Agents and adhesives may be contained as appropriate.

(Print layer)
The printed layer 12 is a layer formed by printing for decoration, display of contents, display of best-before date, display of manufacturer, seller, etc., and addition of aesthetics. The print layer 12 includes a pattern layer that forms any desired pattern such as pictures, photographs, letters, numbers, figures, symbols, and patterns. The printed layer may further include a ground color layer formed by printing so as to make the pattern of the pattern layer stand out.

The print layer 12 is formed by UV offset printing. The print layer 12 contains a coloring agent and a binder resin. The ink composition for forming the printing layer 12 contains a solvent suitable for UV offset printing in addition to the colorant and binder resin.

[Coloring agent]
The coloring agent is not particularly limited, and conventionally known pigments and dyes can be used.

[Binder resin]
The binder resin contains a biomass-derived component. For example, the binder resin contains a urethane (meth)acrylate that 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 contains 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)acrylates are obtained, for example, by reacting polyols and isocyanates with hydroxy (meth)acrylates. In biourethane (meth)acrylate, a plant-derived polyol can be used as the polyol, a plant-derived isocyanate can be used as the isocyanate, or both the polyol and the isocyanate can be plant-derived.

The polyol may be a polyester polyol that is a reaction product of a polyfunctional alcohol and a polyfunctional carboxylic acid, a polyether polyol that is a reaction product of a polyfunctional alcohol and a polyfunctional isocyanate, or a reaction product of a polyfunctional alcohol and a carbonate. Certain polycarbonate polyols can be used. Each polyol will be described below.

<Polyester polyol>
When the polyester polyol contains a biomass-derived component, at least one of the polyfunctional alcohol and the polyfunctional carboxylic acid contains the biomass-derived component. Examples of polyester polyols containing biomass-derived components include the following.
・Reaction product of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Reaction product of fossil fuel-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Biomass-derived polyfunctional alcohol and fossil fuel-derived reactant with polyfunctional carboxylic acid

As polyfunctional alcohols derived from biomass, aliphatic polyfunctional alcohols obtained from plant materials such as corn, sugar cane, cassava, and sago palm can be used. Examples of biomass-derived aliphatic polyfunctional alcohols include polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), and butylene obtained from plant materials by the following methods. There are 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-hydroxypropylaldehyde (HPA) by a fermentation process in which the plant material is degraded to yield glucose. Compared with polypropylene glycol produced by the EO production method, polypropylene glycol produced by a bio-method such as the fermentation method yields useful by-products such as lactic acid from the standpoint of safety, and the production cost can be kept low. It is also preferred that it is possible.
Biomass-derived butylene glycol can be produced by producing succinic acid obtained by producing and fermenting glycol from a plant raw material, and then hydrogenating the succinic acid.
Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

As polyfunctional alcohols derived from fossil fuels, compounds having 2 or more, preferably 2 to 8 hydroxyl groups in one molecule can be used. Specifically, polyfunctional alcohols derived from fossil fuels are not particularly limited and conventionally known substances 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 polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, and the like can be used. These may be used alone or in combination of two or more.

Biomass-derived polyfunctional carboxylic acids include reproducible plant-derived oils such as soybean oil, linseed oil, tung oil, coconut oil, palm oil, and castor oil, and the recycling of waste edible oils, etc. Aliphatic polyfunctional carboxylic acids obtained from plant sources such as oils can be used. Examples of biomass-derived aliphatic polyfunctional carboxylic acids include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acid. For example, sebacic acid is produced with heptyl alcohol as a by-product by alkaline thermal decomposition of ricinoleic acid obtained from castor oil. In the present invention, it is particularly preferable to use biomass-derived succinic acid or biomass-derived sebacic acid. These may be used alone or in combination of two or more.

Aliphatic polyfunctional carboxylic acids and aromatic polyfunctional carboxylic acids can be used as polyfunctional carboxylic acids derived from fossil fuels. Aliphatic polyfunctional carboxylic acids derived from fossil fuels are not particularly limited and conventionally known substances can be used. For example, adipic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride acid, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, dimer acid, ester compounds thereof, and the like. In addition, the aromatic polyfunctional carboxylic acid derived from fossil fuels is not particularly limited and conventionally known substances can be used. Examples include isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid, their ester compounds, and the like can be used. 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 the biomass-derived component. Examples of polyether polyols containing biomass-derived components include the following.
・Reaction products of biomass-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates ・Reaction products of fossil fuel-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates ・Biomass-derived polyfunctional alcohols and fossil fuel-derived polyfunctional Reactants with functional isocyanates

As the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol described in the 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. What is obtained can be used. The biomass-derived polyfunctional isocyanate is, for example, a biomass-derived diisocyanate. Biomass-derived diisocyanates include dimer acid diisocyanate (DDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like. A plant-derived diisocyanate can also 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 methyl-esterifying the carboxyl group of lysine and then converting the amino group into an isocyanate group. Also, 1,5-pentamethylene diisocyanate can be obtained by decarboxylating the carboxyl group of lysine and then converting the amino group to an isocyanate group.

Other methods for synthesizing 1,5-pentamethylene diisocyanate include phosgenation and carbamate methods. More specifically, the phosgenation method includes a method of directly reacting 1,5-pentamethylenediamine or a salt thereof with phosgene, or a method of suspending hydrochloride of pentamethylenediamine in an inert solvent and reacting it with phosgene. 1,5-pentamethylene diisocyanate is synthesized by the method. In the carbamate-forming method, first, 1,5-pentamethylenediamine or a salt thereof is carbamated to form pentamethylenedicarbamate (PDC), which is then thermally decomposed to produce 1,5-pentamethylenediisocyanate. Synthesis. Polyisocyanates that are preferably used in the present invention include 1,5-pentamethylene diisocyanate-based polyisocyanates (trade name: STABIO (registered trademark)) manufactured by Mitsui Chemicals, Inc.

The polyfunctional isocyanate derived from fossil fuels is not particularly limited, and conventionally known substances can be used. 1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanatodiphenyl ether, 4,4′-methylenebis(phenylene isocyanate) (MDI), Aromatic diisocyanates such as dulylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4′-diisocyanate dibenzyl, and the like. In addition, 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-methylenebis(cyclohexyl isocyanate) ), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, hydrogenated XDI and other alicyclic diisocyanates. 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 fossil fuel-derived carbonate can be used as the polycarbonate polyol. Carbonates include, for example, 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 biomass-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol described in the above polyester polyol can be used.

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

<Hydroxy (meth)acrylate>
Next, hydroxy (meth) acrylate will be explained. Hydroxy (meth) acrylates 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; glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, sorbitol penta (meth) acrylate, etc. ( Hydroxy(meth)acrylates having two or more meth)acryloyl groups, and the like. Each of these may be used alone, or two or more of them may be used in combination.

The print layer 12 preferably has a biomass degree of 5% or more, more preferably 5% or more and 50% or less, and still more preferably 10% or more and 50% or less. If the degree of biomass is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced. The weight of the printed layer 12 after drying is preferably 0.1 g/m ² or more and 10 g/m ² or less, more preferably 1 g/m ² or more and 5 g/m ² or less, still more preferably 1 g/m 2 or ^more and 3 g/m 2 or more. ² or less. The print layer 12 preferably has a thickness of 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. A plurality of print layers 12 having such weight and thickness may be provided.

The “biomass degree” is, for example, a value obtained by measuring the content of biomass-derived carbon by radiocarbon (C14) measurement.

When the value obtained by measuring the content of biomass-derived carbon by radioactive carbon (C14) measurement is indicated as the "biomass degree", the "biomass degree" can be obtained as follows. That is, since carbon dioxide in the atmosphere contains a certain proportion of C14 (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. is known to be It is also known that fossil fuels contain almost no C14. Therefore, by measuring the ratio of C14 contained in the total carbon atoms in the polyester, the ratio of biomass-derived carbon can be calculated. When the content of C14 in the printed layer 12 is defined as P _C14 , the biomass-derived carbon content P _bio can be obtained as follows.
P _bio (%) = P _C14 /105.5 x 100

Also, the “biomass degree” may be the weight ratio of biomass-derived components. Hereinafter, unless otherwise specified, the “biomass degree” indicates the weight ratio of biomass-derived components.

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

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

The surface protective layer 11 preferably has a biomass degree of 5% or more, more preferably 5% or more and 50% or less, still more preferably 10% or more and 50% or less. If the degree of biomass is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced. The weight of the surface protective layer 11 after drying is preferably 0.1 g/m ² or more and 10 g/m ² or less, more preferably 1 g/m ² or more and 5 g/m ² or less, still more preferably 1 g/m 2 or more and 3 g/m ² or more. ^m2 or less. The surface protective layer 11 preferably has a thickness of 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, 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 layer 15 is located inside the packaging material 20 . By providing the inner thermoplastic resin layer, the packaging material 20 can be provided with heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties.

The inner thermoplastic resin layer 15 may or may not contain a biomass-derived component. When forming the inner thermoplastic resin layer 15 from 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 biomass-derived components, the inner thermoplastic resin layer 15 can be formed using a conventionally known fossil fuel-derived thermoplastic resin 15.

Biomass polyolefins are polymers of monomers containing olefins such as ethylene derived from biomass. Since biomass-derived olefins are used as raw material monomers, the polymerized polyolefins are biomass-derived. Note that the polyolefin raw material monomer does not have to contain 100% by mass of biomass-derived olefin.

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

Biomass-derived fermented ethanol refers to ethanol produced by contacting a culture solution containing a carbon source obtained from a plant material with a microorganism that produces ethanol or a product derived from a crushed product thereof, and then refining the ethanol. Conventionally known methods such as distillation, membrane separation, and extraction can be applied to purify ethanol from the culture medium. For example, a method of adding benzene, cyclohexane or the like to cause azeotropy, or removing water by membrane separation or the like can be mentioned.

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

Although the number of carbon atoms of the α-olefin is not particularly limited, those having 3 to 20 carbon atoms can usually be used, 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 alkyl groups as a branched structure, so that it can be made more flexible than a simple straight-chain polyolefin.

As the biomass polyolefin, polyethylene or a copolymer of ethylene and α-olefin may be used alone, or two or more of them may be mixed and used. In particular, the biomass polyolefin is preferably polyethylene. This is because the use of ethylene, which is a biomass-derived raw material, theoretically enables production from 100% biomass-derived components.

The biomass polyolefin may contain two or more biomass polyolefins with different biomass degrees, and the biomass degree of the polyolefin resin layer as a whole may be within the range described later.

The biomass polyolefin is preferably 0.91 g/cm ³ or more and 0.93 g/cm 3 or less, more preferably 0.912 g/cm ^{3 or} more and 0.928 g/cm ³ or less, still more preferably 0.915 g/cm 3 or more and 0.928 g/cm ³ or more. It has a density of 0.925 g/cm ³ or less. The density of biomass polyolefin is a value measured according to the method specified in A method of JIS K7112-1980 after annealing according to JIS K6760-1995. If the biomass polyolefin has a density of 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 packaging products. Also, if 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 enhanced, and it can be suitably used as the inner layer of packaging products.

The biomass polyolefin has a melt flow of 0.1 g/10 minutes or more and 10 g/10 minutes or less, preferably 0.2 g/10 minutes or more and 9 g/10 minutes or less, more preferably 1 g/10 minutes or more and 8.5 g/10 minutes or less. rate (MFR). The melt flow rate is a value measured by method A under conditions of a temperature of 190° C. and a load of 21.18 N in the method specified in JIS K7210-1995. If the MFR of the biomass polyolefin is 0.1 g/10 minutes or more, the extrusion load during molding can be reduced. Moreover, if 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.

Examples of biomass polyolefins that are preferably used include low-density polyethylene derived from biomass manufactured by Braskem (trade name: SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree of 95%), Braskem biomass-derived low-density polyethylene (trade name: SPB681, density: 0.922 g/cm ³ , MFR: 3.8 g/10 min, biomass degree 95%), Braskem biomass-derived linear low-density polyethylene (trade name: SLL118, density: 0.916 g/cm ³ , MFR: 1.0 g/10 min, biomass degree 87%);

Examples of the above fossil fuel-derived thermoplastic resins include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, Ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers, ionomers and the like can be mentioned.

The inner thermoplastic resin layer 15 preferably has a biomass degree of 5% or more, more preferably 10% or more and 95% or less. If the degree of biomass is within 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 multiple layers. When biomass polyolefin as described above is used for the inner thermoplastic resin layer, the inner thermoplastic resin layer may have three layers, an inner layer, an intermediate layer and an outer layer. In that case, the intermediate layer may be a layer made of biomass polyolefin or a layer made of a mixture of biomass polyolefin and conventionally known fossil fuel-derived polyolefin, and the inner and outer layers may be made of conventionally known fossil fuel-derived polyolefin. preferable.

The inner thermoplastic resin layer 15 preferably has a thickness of 10 μm to 300 μm, more preferably 20 μm to 200 μm, even more preferably 30 μm to 150 μm.

(Outer thermoplastic resin layer)
The outer thermoplastic resin layer 13 is a layer containing polyethylene. An outer thermoplastic layer 13 is located between the printing layer 12 and the paper base layer 14 . By including the outer thermoplastic resin layer 13 in the packaging material 20, it is possible to impart waterproofness to the paper substrate layer and improve sealing performance.

Examples of polyethylene for the outer thermoplastic resin layer 13 include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene. Further, the outer thermoplastic resin layer 13 may be made of polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, in addition to the polyethylene described above. Copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers, ionomer resins, polyester resins, polyvinyl chloride resins, polystyrene resins, nylons, and the like.

The outer thermoplastic resin layer 13 may contain a biomass-derived material or a fossil fuel-derived material. When the outer thermoplastic resin layer contains a biomass-derived material, it may contain biomass polyolefin, which is a polymer of biomass-derived ethylene-containing monomers, similarly to the inner thermoplastic resin layer 15 .

The 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. By providing the intermediate thermoplastic resin layer, the packaging material 20 can provide adhesion between the respective layers.

Examples of the thermoplastic resin layer include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer. 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 etc., and low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and ethylene-methacrylic acid copolymer are preferred.

The intermediate thermoplastic resin layer may contain biomass-derived material or may contain 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 biomass-derived ethylene-containing monomers, similarly to the inner thermoplastic resin layer.

The intermediate thermoplastic resin layer preferably has a thickness of 2 μm to 10 μm, more preferably 3 μm to 8 μm.

(Barrier resin layer)
The barrier resin layer 21 is a layer that imparts or improves a gas barrier property that prevents permeation of oxygen gas and water vapor, and a light shielding property that prevents permeation of visible light and ultraviolet rays. The barrier resin layer 21 contains at least one barrier resin, such as ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol, polyacrylonitrile, nylon 6, nylon 6,6 and polymetaxylylene adipamide. Examples include polyamides such as (MXD6), polyesters, polyurethanes, and (meth)acrylic resins, and among these, EVOH is preferred from the viewpoint of gas barrier properties that prevent permeation of oxygen gas, water vapor, and the like.

The barrier resin layer can contain additives within a range that does not impair the properties of the present invention. Examples of additives include cross-linking agents, antioxidants, anti-blocking agents, slip agents, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, compatibilizers and pigments. be done.

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 enhancing adhesion between the paper base 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 layer 14 .

The polyolefin resin layer 23 preferably has a thickness of 10 μm to 30 μm, more preferably 12 μm to 25 μm, even more preferably 15 μm to 22 μm.

(barrier layer)
The barrier layer 26 is a layer that imparts or improves a gas barrier property that prevents permeation of oxygen gas and water vapor, and a light shielding property that prevents permeation of visible light, ultraviolet light, and the like. The barrier layer is preferably a metal foil or a deposited film.

[Metal foil]
A metal foil is a member obtained by rolling a metal. A conventionally known metal foil can be used as the metal foil. Aluminum foil is preferable from the viewpoint of gas barrier properties that prevent permeation of oxygen gas and water vapor, and light shielding properties that prevent permeation of visible light, ultraviolet rays, and the like.

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

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 substrate may contain a biomass-derived component or may not contain 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 biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. In addition to the biomass polyester, the base material may further contain a fossil fuel-derived polyester having a 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, more preferably 15% or more and 25% or less. If the degree of biomass in the base material is 5% or more, the amount of polyester derived from fossil fuels can be reduced compared to conventional methods, and the environmental load can be reduced.

Biomass-derived ethylene glycol is produced from biomass-derived ethanol (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained by a method in which biomass ethanol is converted into ethylene glycol via ethylene oxide by a conventionally known method. Also, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol can be preferably used.

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

Further, as the aliphatic dicarboxylic acid, specifically, oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, etc., usually having 2 to 40 carbon atoms. chain or alicyclic dicarboxylic acids. In addition, as derivatives of aliphatic dicarboxylic acids, lower alkyl esters such as methyl esters, ethyl esters, propyl esters and butyl esters of the above aliphatic dicarboxylic acids and cyclic acid anhydrides of the above aliphatic dicarboxylic acids such as succinic anhydride are used. mentioned. Among these, adipic acid, succinic acid, dimer acid, or mixtures thereof are preferred, and those containing succinic acid as a main component are particularly preferred. More preferred derivatives of aliphatic dicarboxylic acids are methyl esters of adipic acid and succinic acid, or mixtures thereof. These dicarboxylic acids may be used alone or in combination of two or more.

The biomass polyester may be a copolymerized polyester obtained by adding a copolymerized component as a third component in addition to the above diol component and dicarboxylic acid component. Specific examples of copolymer components include bifunctional oxycarboxylic acids, trifunctional or higher polyhydric alcohols for forming a crosslinked structure, trifunctional or higher polycarboxylic acids and/or their anhydrides, and 3 At least one polyfunctional compound selected from the group consisting of functional or higher oxycarboxylic acids is included. Among these copolymerization components, a bifunctional and/or trifunctional or higher oxycarboxylic acid is particularly preferably used because a copolyester having a high degree of polymerization tends to be easily produced. Among them, the use of a tri- or higher functional oxycarboxylic acid is most preferable because a polyester with a high degree of polymerization can be easily produced with a very small amount without using a chain extender to be described later.

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

A resin composition of biomass polyester or a resin composition containing biomass polyester and fossil fuel-derived polyester can be used to form a substrate, for example, by forming a film by a T-die method. Specifically, after drying the above resin composition, it is supplied to a melt extruder heated to a temperature above the melting point Tm of the resin composition to Tm + 70 ° C. to melt the resin composition, for example. The base material can be formed by extruding a sheet from a die such as a T-die and rapidly cooling and solidifying the extruded sheet with a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on 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 made of a material that does not contain biomass-derived components, examples of the plastic film constituting the substrate include polyester films such as polyethylene terephthalate film and polybutylene terephthalate film, polyolefin films such as polyethylene film and polypropylene film, Alternatively, a plastic film such as a polypropylene/ethylene-vinyl alcohol copolymer co-extruded co-stretched film or a composite film obtained by laminating two or more of these films can be used.

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

(Plastic film layer)
Various plastic films may be used as the plastic film layer 28 in the present invention. For example, any of stretched polyethylene terephthalate film, stretched nylon film, stretched polypropylene film, nylon 6/meta-xylylenediamine nylon 6 co-extruded co-stretched film or polypropylene/ethylene-vinyl alcohol copolymer co-extruded co-stretched film, or A composite film obtained by laminating two or more of these films may be used. The plastic film may be coated with polyvinyl alcohol or the like.

The plastic film layer 28 preferably has a thickness of 9 μm to 16 μm, more preferably 9 μm to 12 μm.

(Anchor coat layer)
The anchor coat layer 29 is a layer for enhancing adhesion between the plastic film layer 28 and the inner thermoplastic resin layer 15 . As a material for forming the anchor coat layer 29, polyethyleneimine 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 adhered. The adhesive resin layer can be formed by a conventionally known method such as a melt extrusion lamination method or a sand lamination method. Thermoplastic resins that can be used for the adhesive resin layer include polyethylene-based resins, polypropylene-based resins, or cyclic polyolefin-based resins, or copolymer resins, modified resins, or mixtures (including alloys) containing these resins as main components. ) can be used. Polyolefin resins include, for example, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), metallocene catalyst Ethylene-α-olefin copolymer, ethylene-polypropylene random or block copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-α-olefin copolymer polymerized using Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-maleic acid copolymer, ionomer resin, adhesion between layers In order to improve the above, it is possible to use an acid-modified polyolefin resin obtained by modifying the above polyolefin resin with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, or itaconic acid. can. Further, a resin obtained by graft polymerization or copolymerization of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or an ester monomer can be used as the polyolefin resin. These materials can be used singly or in combination of two or more. Cyclic polyolefins such as ethylene-propylene copolymers, polymethylpentene, polybutene, and polynorbonene can be used as cyclic polyolefin resins. These resins can be used singly or in combination. As the polyethylene-based resin described above, the biomass content can be further improved by using the above-described biomass-derived ethylene as a monomer unit.

When the adhesive resin layer is laminated 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. The anchor coating agent includes any resin having a heat resistance temperature of 135° C. or higher, such as an anchor coating agent made of vinyl-modified resin, epoxy resin, urethane resin, polyester resin, polyethyleneimine, etc. Especially, 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. In addition, a silane coupling agent may be used together as an additive, and nitrocellulose may be used together to improve heat resistance.

The anchor coat layer after drying 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)
An adhesive layer is a layer provided when adhering arbitrary two layers. The adhesive layer may contain a biomass-derived component. In the adhesive layer containing the biomass-derived component, at least either the polyol or the isocyanate compound contains the biomass-derived component.

As the isocyanate compound containing a biomass-derived component in the adhesive layer, the same isocyanate compound containing a biomass-derived component as in the print layer 12 can be used. Moreover, in the adhesive layer, as the polyol containing the biomass-derived component, the same polyol as that for 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. Composition is also acceptable.

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

The weight of the adhesive layer 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 6 g/m ² or less, still more preferably 2 g/m 2 or ^more and 5 g/m 2 or more. ² or less.

The adhesive layer preferably has a thickness of 0.1 μm to 10 μm, more preferably 1 μm to 6 μm, even more preferably 2 μm to 5 μm.

(Manufacturing method of packaging material)
Next, an example of a method for manufacturing a laminate that constitutes 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 paper base layer 14 described above is prepared. Subsequently, a molten resin is extruded onto the paper substrate layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13 . Subsequently, by a melt extrusion lamination method, a molten resin is extruded onto the surface of the paper base layer 14 opposite to the surface on which the outer thermoplastic resin layer 13 is formed to form the inner thermoplastic resin layer 15. Subsequently, the ink composition described above is applied onto 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. A layer 12 is formed. Subsequently, the above paint containing solids and solvent is applied onto the printed layer 12, and the paint on the printed layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the printed layer 12. Thus, the packaging material 20 comprising the surface protective layer 11, the printed 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.

The outer thermoplastic resin layer 13, the printed layer 12 and the surface protection layer 11 may be formed on the paper base layer 14 after the inner thermoplastic resin layer 15 is formed on the paper base layer 14.

An example of a method for manufacturing the packaging material 20 shown in FIG. 2 will be described. First, the paper base layer 14 described above is prepared. Subsequently, a molten resin is extruded onto the paper substrate layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13 . Subsequently, by a melt extrusion lamination method, a resin in a molten state is extruded onto the surface of the paper substrate layer 14 opposite to the surface on which the outer thermoplastic resin layer 13 is formed, to form a barrier resin layer 21 and an intermediate thermoplastic resin. Layer 22 and inner thermoplastic layer 15 are formed. Subsequently, the ink composition described above is applied onto 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. A layer 12 is formed. Subsequently, the above paint containing solids and solvent is applied onto the printed layer 12, and the paint on the printed layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the printed layer 12. As a result, the packaging material 20 comprising the surface protective layer 11, the printed 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 produced. Obtainable.

After the barrier resin layer 21, the intermediate thermoplastic resin layer 22 and the inner thermoplastic resin layer 15 are formed on the paper base layer 14, the outer thermoplastic resin layer 13 and the printing layer 12 are formed on the paper base layer 14. and a surface protective 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 paper base layer 14 described above is prepared. Subsequently, a molten resin is extruded onto the paper substrate layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13 . Subsequently, by a melt extrusion lamination method, a molten resin is extruded onto the surface opposite to the surface of the paper substrate layer 14 on which the outer thermoplastic resin layer 13 is formed, and the polyolefin resin layer 23 and the intermediate thermoplastic resin are formed. A layer 22, a barrier resin layer 21, an intermediate thermoplastic resin layer 24 and an inner thermoplastic resin layer 15 are formed. Subsequently, the ink composition described above is applied onto 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. A layer 12 is formed. Subsequently, the above paint containing solids and solvent is applied onto the printed layer 12, and the paint on the printed layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the printed layer 12. Thereby, the surface protective layer 11, the printed 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 and A packaging material 20 with an inner thermoplastic layer 15 can be obtained.

After 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 are formed on the paper base layer 14, the paper base layer 14 is formed. An outer thermoplastic resin layer 13, a printed layer 12 and a surface protective layer 11 may be formed thereon.

An example of the manufacturing method of the packaging material 20 shown in FIG. 4 will be described. First, the paper base layer 14 described above is prepared. Subsequently, a molten resin is extruded onto the paper substrate layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13 . Subsequently, a film forming the barrier layer 26 and a film forming 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 the two films to be laminated. Subsequently, the applied adhesive composition is dried to volatilize the solvent. The two films are then laminated via the dried adhesive composition. Subsequently, the two laminated films are aged in an environment of, for example, 20° C. or higher for 24 hours or longer in a wound state.

Subsequently, the paper base layer 14 having the outer thermoplastic resin layer 13 formed thereon and the barrier layer 26 having the plastic film layer 28 bonded thereto are laminated via the adhesive resin layer 25 by sand lamination.

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 onto one film.

Subsequently, an anchor coat layer 29 is formed by applying an anchor coat agent on the plastic film layer 28 and drying it. Subsequently, the inner thermoplastic resin layer 15 is formed on the anchor coat layer 29 by melt extrusion lamination. Subsequently, the ink composition described above is applied onto 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. A layer 12 is formed. Subsequently, the above paint containing solids and solvent is applied onto the printed layer 12, and the paint on the printed layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the printed layer 12. As a result, the surface protective layer 11, the printed layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27, the plastic film layer 28, the anchor coat layer 29 and the inner A packaging material 20 comprising a thermoplastic layer 15 can be obtained.

After laminating the paper substrate 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 substrate layer 14. and a surface protective layer 11 may be formed.

An example of the manufacturing method of the packaging material 20 shown in FIG. 5 will be described. First, the paper base layer 14 described above is prepared. Subsequently, a molten resin is extruded onto the paper substrate layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13 . Subsequently, a film forming the barrier layer 26 and a film forming the plastic film layer 28 are separately laminated via the adhesive layer 27 by a dry lamination method. Subsequently, the paper base layer 14 having the outer thermoplastic resin layer 13 formed thereon and the barrier layer 26 having the plastic film layer 28 bonded thereto are laminated via the adhesive resin layer 25 by sand lamination. Subsequently, an anchor coat layer 29 is formed by applying an anchor coat agent on the plastic film layer 28 and drying it. 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 ink composition described above is applied onto 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. A layer 12 is formed. Subsequently, the above paint containing solids and solvent is applied onto the printed layer 12, and the paint on the printed layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the printed layer 12. As a result, the surface protective layer 11, the printed layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27, the plastic film layer 28, the anchor coat layer 29, the adhesive A packaging material 20 comprising a resin layer 30 and an inner thermoplastic layer 15 can be obtained.

After laminating the paper substrate 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 substrate layer 14. and a surface protective 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 paper base layer 14 described above is prepared. Subsequently, a molten resin is extruded onto the paper substrate layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13 . Subsequently, a film forming the barrier layer 26 and a film forming the plastic film layer 28 are separately laminated via the adhesive layer 27 by a dry lamination method. Subsequently, the paper base layer 14 having the outer thermoplastic resin layer 13 formed thereon and the barrier layer 26 having the plastic film layer 28 bonded thereto are laminated via the adhesive resin layer 25 by sand lamination. Subsequently, the plastic film layer 28 and the film forming the inner thermoplastic resin layer 15 are laminated via the adhesive layer 31 by a dry lamination method. Subsequently, the ink composition described above is applied onto 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. A layer 12 is formed. Subsequently, the above paint containing solids and solvent is applied onto the printed layer 12, and the paint on the printed layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the printed layer 12. As a result, the surface protective layer 11, the printed layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27, the plastic film layer 28, the adhesive layer 31 and the inner A packaging material 20 comprising a thermoplastic layer 15 can be obtained.

After laminating the paper substrate 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 substrate layer 14. and a surface protective layer 11 may be formed.

An example of the manufacturing method of the packaging material 20 shown in FIG. 7 will be described. First, the paper base layer 14 described above is prepared. Subsequently, a molten resin is extruded onto the paper substrate layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13 . Subsequently, the paper base layer 14 having the outer thermoplastic resin layer 13 formed thereon and the film forming 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 melt extrusion lamination. Subsequently, the ink composition described above is applied onto 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. A layer 12 is formed. Subsequently, the above paint containing solids and solvent is applied onto the printed layer 12, and the paint on the printed layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the printed layer 12. Thus, the packaging material 20 comprising the surface protective layer 11, the printed layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26 and the inner thermoplastic resin layer 15 can be obtained. .

After laminating the paper substrate layer 14 and the film constituting the barrier layer 26 with the adhesive resin layer 25 interposed therebetween, the outer thermoplastic resin layer 13, the printed layer 12 and the surface protective layer 11 are formed on the paper substrate layer 14. may be formed.

An example of the manufacturing method of the packaging material 20 shown in FIG. 8 will be described. First, the paper base layer 14 described above is prepared. Subsequently, a molten resin is extruded onto the paper substrate 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 forming 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 ink composition described above is applied onto 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. A layer 12 is formed. Subsequently, the above paint containing solids and solvent is applied onto the printed layer 12, and the paint on the printed layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the printed layer 12. As a result, the packaging material 20 comprising the surface protective layer 11, the printed layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive resin layer 30 and the inner thermoplastic resin layer 15 can be obtained.

After laminating the paper substrate layer 14 and the film constituting the barrier layer 26 with the adhesive resin layer 25 interposed therebetween, the outer thermoplastic resin layer 13, the printed layer 12 and the surface protective layer 11 are formed on the paper substrate layer 14. may be formed.

An example of the manufacturing method of the packaging material 20 shown in FIG. 9 will be described. First, the paper base layer 14 described above is prepared. Subsequently, a molten resin is extruded onto the paper substrate layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13 . Subsequently, the paper base layer 14 having the outer thermoplastic resin layer 13 formed thereon and the film forming 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 ink composition described above is applied onto 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. A layer 12 is formed. Subsequently, the above paint containing solids and solvent is applied onto the printed layer 12, and the paint on the printed layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the printed layer 12. Thus, the packaging material 20 comprising the surface protective layer 11, the printed layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the barrier layer 26, the adhesive layer 27 and the inner thermoplastic resin layer 15 can be obtained.

After laminating the paper substrate layer 14 and the film constituting the barrier layer 26 with the adhesive resin layer 25 interposed therebetween, the outer thermoplastic resin layer 13, the printed layer 12 and the surface protective layer 11 are formed on the paper substrate 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 paper base layer 14 described above is prepared. Subsequently, a molten resin is extruded onto the paper substrate 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 the adhesive layer 27 by a dry lamination method. Subsequently, the paper substrate layer 14 having the outer thermoplastic resin layer 13 formed thereon and the plastic film layer 28 having the barrier layer 26 bonded thereto 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 melt extrusion lamination. Subsequently, the ink composition described above is applied onto 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. A layer 12 is formed. Subsequently, the above paint containing solids and solvent is applied onto the printed layer 12, and the paint on the printed layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the printed layer 12. As a result, the surface protective layer 11, the printed layer 12, the outer thermoplastic resin layer 13, the paper base layer 14, the adhesive resin layer 25, the plastic film layer 28, the adhesive layer 27, the barrier layer 26, and the intermediate thermoplastic resin layer 22 are formed. and a packaging material 20 comprising an inner thermoplastic layer 15 can be obtained.

After laminating the paper substrate 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 substrate layer 14. and a surface protective layer 11 may be formed.

An example of the manufacturing method of the packaging material 20 shown in FIG. 11 will be described. First, the paper base layer 14 described above is prepared. Subsequently, a molten resin is extruded onto the paper substrate layer 14 by a melt extrusion lamination method to form the outer thermoplastic resin layer 13 . Subsequently, by melt extrusion lamination, a polyolefin resin layer 23 is formed by extruding molten resin onto the surface of the paper base layer 14 opposite to the surface on which the outer thermoplastic resin layer 13 is formed. Subsequently, the polyolefin resin layer 23 and the film forming 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 melt extrusion lamination. Subsequently, the ink composition described above is applied onto 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. A layer 12 is formed. Subsequently, the above paint containing solids and solvent is applied onto the printed layer 12, and the paint on the printed layer 12 is irradiated with ultraviolet rays to form the surface protective layer 11 on the printed layer 12. Thereby, the surface protective layer 11, the printed 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 layer 15 can be obtained.

After forming the polyolefin resin layer 23 on the paper base layer 14 , the outer thermoplastic resin layer 13 , the print layer 12 and the surface protective layer 11 may be formed on the paper base layer 14 .

<Packaging products>
An example of a packaged product formed by using packaging material 20 will now be described. FIG. 12 shows a liquid paper container 40, which is an example of a packaging product. Paper containers for liquids have excellent barrier properties, so they can be used for alcoholic beverages such as sake, shochu and wine, dairy drinks such as milk, foods such as 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 Gobel top container. there is The upper portion 43 has a pair of opposing inclined plates 44 and a pair of folding portions 45 positioned between the pair of inclined plates 44 and folded between the inclined plates 44 . Also, the pair of inclined plates 44 are adhered to each other by glue margins 46 provided at their upper ends. Alternatively, one of the pair of inclined plates 44 may be fitted with a spout and the spout may be sealed with a cap. A flat-top container may also be formed.

By configuring a packaged product using the packaging material 20 having the printed layer 12 containing the biomass-derived component, it is possible to reduce the amount of fossil fuel used compared to the past. This can reduce the environmental load.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the description of the Examples below as long as it does not exceed the gist thereof.

[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 substrate layer 14 by melt extrusion lamination. Fossil fuel-derived polyethylene was used as the outer thermoplastic resin layer 13 . The thickness of the outer thermoplastic resin layer 13 was 17 μm.

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

Subsequently, the printed layer 12 was formed on the outer thermoplastic resin layer 13 . In the step of forming the printed layer 12, first, an ink composition containing a colorant, 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, a fossil fuel-derived isocyanate compound, and a fossil fuel-derived hydroxy (meth)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 fossil fuel was used. Subsequently, an ink composition is applied in a predetermined pattern 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 obtain a pattern on the outer thermoplastic resin layer 13. A printed layer 12 was formed on the substrate. The thickness of the printed layer 12 was 1 μm.

Subsequently, a surface protective layer 11 was formed on the printed layer 12 . In the step of forming the surface protective layer 11, first, a paint containing a binder resin and a solvent was prepared. 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 binder resin. Subsequently, the paint was applied to the entire printed layer 12 by an offset method, and the paint on the printed 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 structure shown in FIG. 1 was produced.

The layer structure of the packaging material 20 of this embodiment is expressed as follows.
Table/Biomark/External heat 17/Paper/Internal heat (2) 28
"/" represents the boundary between layers. The layer on the left end is the layer forming the outer surface of the packaging material, and the layer on the right end is the layer forming the inner surface of the packaging material.
"Front" means a surface protective layer. "Biomark" means a printed layer derived from biomass. "External heat" means external heat derived from fossil fuels. "Paper" means a paper base layer. "Inner heat (2)" means an inner thermoplastic resin layer derived from fossil fuel formed by a melt extrusion lamination process. The number means the layer thickness (unit: μm).

Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. 12 was produced. The liquid paper container 40 can contain, for example, milk or juice.

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

[Example 1C]
Biourethane (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 printing layer 12. A packaging material 20 was produced in the same manner as in Example 1A, except for the above.

FIG. 13A collectively shows the layer structure of the packaging materials 20 of Examples 1A to 1C. In the column of "biomass-derived component in printed layer" in Fig. 13A, the description "binder resin" means that the binder resin used in the printed layer contains a biomass-derived component.
In the column of "biomass-derived component in the binder resin of the printing layer", the description "polyol" means that the polyol used in the binder resin of the printing layer contains the biomass-derived component. Moreover, the description "isocyanate compound" means that the isocyanate compound used in the binder resin of the printing layer contains a biomass-derived component.
In the column of "type of polyol for printing layer", the description "ester-based" means that the polyol used in the binder resin for the printing layer is polyester polyol.
In addition, in the column of "biomass-derived component in the polyol of the printing layer", the description "polyfunctional alcohol" means that at least the polyfunctional alcohol of the polyester polyol among the components used in the polyol of the binder resin of the printing layer is biomass-derived means that Similarly, the description "polyfunctional carboxylic acid" means that at least the polyfunctional carboxylic acid of the polyester polyol among the components used in the polyol of the binder resin of the printing layer is derived from biomass. Moreover, the description of "-" means that the polyol of the binder resin of the printing layer does not contain a biomass-derived component.

In Examples 1A to 1C, in the binder resin of the printing layer, one of the three constituents 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, it is not limited to this. For example, two of the three components may contain biomass-derived components, or all three components may contain biomass-derived components.

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

[Example 1F]
Biourethane (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, was used as the binder resin for the printed layer 12. A packaging material 20 was produced in the same manner as in Example 1D, except for the above.

FIG. 13A collectively shows the layer structure of the packaging materials 20 of Examples 1D to 1F. In the column of "type of polyol for printing layer" in FIG. 13A, the description "ether-based" means that the polyol used in the binder resin of the printing layer is polyether polyol. In addition, in the column of "biomass-derived component in the polyol of the printing layer", the description "polyfunctional isocyanate" means that at least the polyfunctional isocyanate among the components used in the polyol of the binder resin of the printing layer is derived from biomass. means

In Examples 1D to 1F, in the binder resin of the printing layer, one of the three constituents of polyfunctional alcohol, polyfunctional isocyanate, or isocyanate compound used in polyether polyol is a biomass-derived component. Although an example is shown, it is not limited to this. For example, two of the three components may contain biomass-derived components, or all three components may contain biomass-derived components.

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

[Example 1H]
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, is used as the binder resin of the printing layer 12. A packaging material 20 was produced in the same manner as in Example 1G, except for the above.

FIG. 13A collectively shows the layer structures of the packaging materials 20 of Examples 1G and 1H. In the column of "polyol type of printing layer" in FIG. 13A, the description "carbonate-based" means that the polyol used in the binder resin of the printing layer is polycarbonate polyol.

In Examples 1G and 1H, in the binder resin of the printing layer, one of the two constituent elements of the polyfunctional alcohol used in the polycarbonate polyol or the isocyanate compound was a biomass-derived component. , but not limited to these. For example, either of the two components may contain biomass-derived components.

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

The layer structure of the packaging material 20 of this embodiment is expressed as follows.
Bio table / bio mark / external heat 17 / paper / internal heat (2) 28
"Biosurface" means a surface protective layer derived from biomass.

[Example 1J]
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 surface protective layer 11. A packaging material 20 was produced.

[Example 1K]
Biourethane (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 as the binder resin of the surface protective layer 11. A packaging material 20 was produced in the same manner as in Example 1I, except for the above.

FIG. 13B collectively shows the layer structure and the like of the packaging materials 20 of Examples 1I to 1K. In the column of "biomass-derived component in surface protective layer" in Fig. 13B, 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. Moreover, the description "isocyanate compound" means that the isocyanate compound used in the binder resin of the surface protective layer contains a biomass-derived component.
In the column of "type of polyol for surface protective layer", the description "ester-based" means that the polyol used in the binder resin for the surface protective layer is polyester polyol.
In addition, in the column of "biomass-derived component in the polyol of the surface protective layer", the description "polyfunctional alcohol" means that at least the polyfunctional alcohol of the polyester polyol among the components used in the polyol of the binder resin of the surface protective layer is It means that it is derived from biomass. Similarly, the description "polyfunctional carboxylic acid" means that at least the polyfunctional carboxylic acid of the polyester polyol among the components used in the polyol of the binder resin of the surface protective layer is derived from biomass. Moreover, the description of "-" means that the polyol of the binder resin of the surface protective layer does not contain a biomass-derived component.

In Examples 1I to 1K, in the binder resin of the surface protective layer, one of the three constituents of the polyfunctional alcohol or polyfunctional carboxylic acid used in the polyester polyol, or the isocyanate compound was a biomass-derived component. Although a certain example was shown, it is not restricted to this. For example, two of the three components may contain biomass-derived components, or all three components may contain biomass-derived components.

[Example 1L]
A packaging material 20 was produced in the same manner as in Example 1I, 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 1M]
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 surface protective layer 11. A packaging material 20 was produced.

[Example 1N]
As the binder resin for the surface protective layer 11, biourethane (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 1L, except that

FIG. 13B collectively shows the layer structure of the packaging materials 20 of Examples 1L to 1N. In the column of "polyol type of surface protective layer" in FIG. 13B, the description "ether-based" means that the polyol used in the binder resin of the surface protective layer is polyether polyol. In addition, in the column of "biomass-derived component in the polyol of the surface protective layer", the description "polyfunctional isocyanate" means that at least the polyfunctional isocyanate among the components used in the polyol of the binder resin of the surface protective layer is biomass-derived. It means that there is

In Examples 1L to 1N, in the binder resin of the surface protective layer, one of the three components of the polyfunctional alcohol, polyfunctional isocyanate, or isocyanate compound used in the polyether polyol was a biomass-derived component. Although a certain example was shown, it is not restricted to this. For example, two of the three components may contain biomass-derived components, or all three components may contain biomass-derived components.

[Example 1O]
A packaging material 20 was produced in the same manner as in Example 1I, except that a polycarbonate 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 fossil fuel-derived carbonate was used as the polycarbonate polyol.

[Example 1P]
As the 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. A packaging material 20 was produced in the same manner as in Example 1O, except for the above.

FIG. 13B collectively shows the layer structures of the packaging materials 20 of Examples 1O and 1P. In the column of "polyol type of surface protective layer" in FIG. 13B, the description "carbonate-based" means that the polyol used in the binder resin of the surface protective layer is polycarbonate polyol.

In Examples 1O and 1P, in the binder resin of the surface protective layer, one of the two constituent elements of the polyfunctional alcohol used in the polycarbonate polyol or the isocyanate compound is a biomass-derived component. However, it is not limited to this. For example, either of the two components may contain biomass-derived components.

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

The layer structure of the packaging material 20 of this embodiment is expressed as follows.
Table/Bio Seal/Bio External Heat 17/Paper/Bio Internal Heat (2) 28
"Bio-exotherm" means an outer thermoplastic layer containing biomass-derived components. "Bio-internal heat (2)" means a biomass-derived inner thermoplastic resin layer formed by a melt-extrusion lamination method.

It should be noted that variations similar to those of Examples 1B to 1P can also be employed in Example 1Q described above. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

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

The layer structure of the packaging material 20 of this embodiment is expressed as follows.
Front/Biomark/External heat 20/Paper/EVOH5/Medium heat 5/Internal heat (2) 20
"EVOH" means a barrier resin layer using EVOH. "Medium heat" means the middle thermoplastic layer.

Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. 12 was produced. The liquid paper container 40 can contain, for example, fruit juice or tea.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

[Example 3]
A packaging material 20 was produced 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 structure of the packaging material 20 of this embodiment is expressed as follows.
Table/Biomark/External heat 20/Paper/MXD6 5/Medium heat 5/Internal heat (2) 20
"MXD6" means a barrier resin layer using poly-meta-xylylene adipamide.

Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. 12 was produced. The liquid paper container 40 can contain, for example, fruit juice or tea.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

[Example 4]
A packaging material 20 was produced 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 structure of the packaging material 20 of this embodiment is expressed as follows.
Front/Biomark/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. 12 was produced. The liquid paper container 40 can contain, for example, fruit juice or tea.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

[Example 5]
A paper substrate layer 14 was prepared in the same manner as in Example 1A, and an outer thermoplastic resin layer 13 was formed on the paper substrate layer 14 . The thickness of the outer thermoplastic resin layer 13 was 20 μm. 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 substrate layer 14 by melt extrusion lamination. Polyethylene derived from fossil fuel was used as the polyolefin resin layer 23 . The thickness of the polyolefin resin layer 23 was 20 μm. Fossil fuel-derived polyethylene was used as the intermediate thermoplastic resin layer 22 . The thickness of the intermediate thermoplastic resin layer 22 was 5 μm. EVOH was used as the barrier resin layer 21 . The thickness of the barrier resin layer 21 was 5 μm. Fossil fuel-derived polyethylene was used as the intermediate thermoplastic resin layer 24 . The thickness of the intermediate thermoplastic resin layer 24 was 5 μm. Fossil fuel-derived polyethylene was used as the inner thermoplastic resin layer 15 . The thickness of the inner thermoplastic resin layer 15 was 20 μm. Subsequently, the printed layer 12 and the surface protective 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 structure shown in FIG. 3 was produced.

The layer structure of the packaging material 20 of this embodiment is expressed as follows.
Front/Biomark/External heat 20/Paper/PE20/Medium heat 5/EVOH5/Medium heat 5/Internal 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. 12 was produced. The liquid paper container 40 can contain, for example, fruit juice or tea.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

[Example 6]
A packaging material 20 was produced 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 structure of the packaging material 20 of this embodiment is expressed as follows.
Table / biomark / 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. 12 was produced. The liquid paper container 40 can contain, for example, fruit juice or tea.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

[Example 7]
A packaging material 20 was produced 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 structure of the packaging material 20 of this embodiment is expressed as follows.
Front/Biomark/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. 12 was produced. The liquid paper container 40 can contain, for example, fruit juice or tea.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

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

Subsequently, the film forming the barrier layer 26 and the film forming the plastic film layer 28 were laminated together with the adhesive layer 27 interposed therebetween 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 polyethylene terephthalate derived from fossil fuel was used. In the dry lamination method, a polyester polyol, which is a reaction product of a fossil fuel-derived polyfunctional alcohol and a fossil fuel-derived polyfunctional carboxylic acid, was prepared as a main agent. In addition, an isocyanate compound derived from fossil fuel was prepared as a curing agent.

Subsequently, the paper base layer 14 having the outer thermoplastic resin layer 13 formed thereon and the barrier layer 26 bonded to the plastic film layer 28 were bonded together via the adhesive resin layer 25 by a sand lamination method. Polyethylene derived from fossil fuel was used as the adhesive resin layer 25 . 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 an inner thermoplastic resin layer 15 was formed on the anchor coat layer 29 by melt extrusion lamination. Fossil fuel-derived polyethylene was used as the inner thermoplastic resin layer 15 . The thickness of the inner thermoplastic resin layer 15 was 50 μm.

Subsequently, the printed layer 12 and the surface protective 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 structure shown in FIG. 4 was produced.

The layer structure of the packaging material 20 of this embodiment is expressed as follows.
Front/Biomark/External heat 20/Paper/Adhesive resin 20/AL foil 7/Contact/PET12/AC/Internal heat (2) 50
"AL foil" means aluminum foil. "Contact" means an adhesive layer. "PET" means PET film containing polyethylene terephthalate. "AC" means anchor coat layer.

Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. 12 was produced. The liquid paper container 40 can contain alcoholic beverages and soft drinks, for example.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

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

Subsequently, the film forming the barrier layer 26 and the film forming the plastic film layer 28 were laminated together with the adhesive layer 27 interposed therebetween 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 polyethylene terephthalate derived from fossil fuel was used. In the dry lamination method, a polyester polyol, which is a reaction product of a fossil fuel-derived polyfunctional alcohol and a fossil fuel-derived polyfunctional carboxylic acid, was prepared as a main agent. In addition, an isocyanate compound derived from fossil fuel was prepared as a curing agent.

Subsequently, the paper base layer 14 having the outer thermoplastic resin layer 13 formed thereon and the barrier layer 26 bonded to the plastic film layer 28 were bonded together via the adhesive resin layer 25 by a sand lamination method. Polyethylene derived from fossil fuel was used as the adhesive resin layer 25 . The thickness of the adhesive resin layer 25 was 20 μm.

Subsequently, an anchor coat layer 29 was formed on this plastic film layer 28 . Subsequently, the anchor coat layer 29 and the inner thermoplastic resin layer 15 were bonded together with the adhesive resin layer 30 interposed therebetween by a sand lamination method. As the inner thermoplastic resin layer 15, a polyethylene film (40 μm thick) derived from fossil fuel was used. Polyethylene derived from fossil fuel was used as the adhesive resin layer 30 . The thickness of the adhesive resin layer 30 was 20 μm.

Subsequently, the printed layer 12 and the surface protective 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 structure shown in FIG. 5 was produced.

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

Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. 12 was produced. The liquid paper container 40 can contain alcoholic beverages and soft drinks, for example.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

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

Subsequently, the film forming the barrier layer 26 and the film forming the plastic film layer 28 were bonded together with the adhesive layer 27 interposed therebetween 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 polyethylene terephthalate derived from fossil fuel was used. In the dry lamination method, a polyester polyol, which is a reaction product of a fossil fuel-derived polyfunctional alcohol and a fossil fuel-derived polyfunctional carboxylic acid, was prepared as a main agent. In addition, an isocyanate compound derived from fossil fuel was prepared as a curing agent.

Subsequently, the paper base layer 14 having the outer thermoplastic resin layer 13 formed thereon and the barrier layer 26 bonded to the plastic film layer 28 were bonded together via the adhesive resin layer 25 by a sand lamination method. Polyethylene derived from fossil fuel was used as the adhesive resin layer 25 . 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 with the adhesive layer 31 interposed therebetween 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 fossil fuel-derived polyfunctional alcohol and a fossil fuel-derived polyfunctional carboxylic acid, was prepared as a main agent. In addition, an isocyanate compound derived from fossil fuel was prepared as a curing agent.

Subsequently, the printed layer 12 and the surface protective 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 structure shown in FIG. 6 was produced.

The layer structure of the packaging material 20 of this embodiment is expressed as follows.
Front/Biomark/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. 12 was produced. The liquid paper container 40 can contain alcoholic beverages and soft drinks, for example.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

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

Subsequently, the paper base layer 14 having the outer thermoplastic resin layer formed thereon and the barrier layer 26 were laminated together with the adhesive resin layer 25 interposed therebetween by a sand lamination method. As the barrier layer 26, an aluminum foil (thickness 7 μm) was used. Polyethylene derived from fossil fuel was used as the adhesive resin layer 25 . 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 melt extrusion lamination. Fossil fuel-derived polyethylene was used as the inner thermoplastic resin layer 15 . The thickness of the inner thermoplastic resin layer 15 was 40 μm.

Subsequently, the printed layer 12 and the surface protective 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 structure shown in FIG. 7 was produced.

The layer structure of the packaging material 20 of this embodiment is expressed as follows.
Front/Biomark/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. 12 was produced. The liquid paper container 40 can contain alcoholic beverages and soft drinks, for example.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such 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-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 structure of the packaging material 20 of this embodiment is expressed as follows.
Front/Biomark/External heat 20/Paper/Adhesive resin 20/VM-PET12/Internal heat (2) 40
"VM-PET" means vapor deposited film.

Subsequently, using the packaging material 20, a liquid paper container 40 shown in FIG. 12 was produced. The liquid paper container 40 can contain alcoholic beverages and soft drinks, for example.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

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

Subsequently, the paper base layer 14 having the outer thermoplastic resin layer 13 formed thereon and the barrier layer 26 were laminated together with the adhesive resin layer 25 interposed therebetween by a sand lamination method. As the barrier layer 26, an aluminum foil (thickness 7 μm) was used. Polyethylene derived from fossil fuel was used as the adhesive resin layer 25 . 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 together with the adhesive resin layer 30 interposed therebetween by a sand lamination method. As the inner thermoplastic resin layer 15, a polyethylene film (40 μm thick) derived from fossil fuel was used. Polyethylene derived from fossil fuel was used as the adhesive resin layer 30 . The thickness of the adhesive resin layer 30 was 20 μm.

Subsequently, the printed layer 12 and the surface protective 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 structure shown in FIG. 8 was produced.

The layer structure of the packaging material 20 of this embodiment is expressed as follows.
Table/Biomark/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. 12 was produced. The liquid paper container 40 can contain alcoholic beverages and soft drinks, for example.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such 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 structure of the packaging material 20 of this embodiment is expressed as follows.
Table/Biomark/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. 12 was produced. The liquid paper container 40 can contain alcoholic beverages and soft drinks, for example.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

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

Subsequently, the paper base layer 14 having the outer thermoplastic resin layer 13 formed thereon and the barrier layer 26 were laminated together with the adhesive resin layer 25 interposed therebetween by a sand lamination method. As the barrier layer 26, an aluminum foil (thickness 7 μm) was used. Polyethylene derived from fossil fuel was used as the adhesive resin layer 25 . 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 together with the adhesive layer 27 interposed therebetween 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 fossil fuel-derived polyfunctional alcohol and a fossil fuel-derived polyfunctional carboxylic acid, was prepared as a main agent. In addition, an isocyanate compound derived from fossil fuel was prepared as a curing agent.

Subsequently, the printed layer 12 and the surface protective 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 structure shown in FIG. 9 was produced.

The layer structure of the packaging material 20 of this embodiment is expressed as follows.
Front/Biomark/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. 12 was produced. The liquid paper container 40 can contain alcoholic beverages and soft drinks, for example.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such 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 vapor-deposited film was formed on a polyethylene terephthalate film was used as the barrier layer 26 .

The layer structure of the packaging material 20 of this embodiment is expressed as follows.
Front/Biomark/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. 12 was produced. The liquid paper container 40 can contain alcoholic beverages and soft drinks, for example.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

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

Subsequently, the film constituting the plastic film layer 28 and the film constituting the barrier layer 26 were laminated together with the adhesive layer 27 interposed therebetween 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 polyethylene terephthalate derived from fossil fuel was used. In the dry lamination method, a polyester polyol, which is a reaction product of a fossil fuel-derived polyfunctional alcohol and a fossil fuel-derived polyfunctional carboxylic acid, was prepared as a main agent. In addition, an isocyanate compound derived from fossil fuel was prepared as a curing agent.

Subsequently, the paper base layer 14 having the outer thermoplastic resin layer 13 formed thereon and the plastic film layer 28 bonded to the barrier layer 26 were bonded together via the adhesive resin layer 25 by a sand lamination method. Polyethylene derived from fossil fuel was used as the adhesive resin layer 25 . 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 melt extrusion lamination. Fossil fuel-derived polyethylene was used as the intermediate thermoplastic resin layer 22 . The thickness of the intermediate thermoplastic resin layer 22 was 20 μm. Fossil fuel-derived polyethylene was used as the inner thermoplastic resin layer 15 . The thickness of the inner thermoplastic resin layer 15 was 40 μm.

Subsequently, the printed layer 12 and the surface protective 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 structure shown in FIG. 10 was produced.

The layer structure of the packaging material 20 of this embodiment is expressed as follows.
Table/Biomark/External Heat 20/Paper/Adhesive Resin 20/PET 12/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. 12 was produced. Liquid paper container 40 can contain, for example, detergents and chemical products.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

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

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

Subsequently, the polyolefin resin layer 23 and the barrier layer 26 were bonded together with the adhesive resin layer 25 interposed therebetween by a sand lamination method. As the barrier layer 26, an aluminum foil (thickness 7 μm) was used. Polyethylene derived from fossil fuel was used as the adhesive resin layer 25 . 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 melt extrusion lamination. Fossil fuel-derived polyethylene was used as the intermediate thermoplastic resin layer 22 . The thickness of the intermediate thermoplastic resin layer 22 was 5 μm. Fossil fuel-derived polyethylene was used as the inner thermoplastic resin layer 15 . The thickness of the inner thermoplastic resin layer 15 was 30 μm.

Subsequently, the printed layer 12 and the surface protective 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 structure shown in FIG. 11 was produced.

The layer structure of the packaging material 20 of this embodiment is expressed as follows.
Front/Biomark/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. 12 was produced. The liquid paper container 40 can contain, for example, a milk drink or a soft drink.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such 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-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 structure of the packaging material 20 of this embodiment is expressed as follows.
Front/Biomark/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. 12 was produced. The liquid paper container 40 can contain, for example, a milk drink or a soft drink.

Note that variations similar to those of Examples 1B to 1P can also be employed in this example. For example, as the printing layer containing a biomass-derived component, the printing layers shown in Examples 1B to 1H may be used in addition to the printing layer shown in Example 1A. As the surface protective layer, a surface protective layer containing a biomass-derived component, such as shown in Examples 1I to 1P, may be used.

FIG. 14 summarizes examples of layer configurations and types of packaging containers of the packaging materials 20 of Examples 1A, 1Q-19.

11 Surface protective layer 12 Printed layer 13 Outer thermoplastic resin layer 14 Paper substrate 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 Paper container for liquid 41 Body 42 Bottom 43 Top 44 Inclined plate 45 Folding portion 46 Margin

Claims (8)

A packaging material in which at least a surface protective layer, a printed layer, an outer thermoplastic resin layer, a paper base layer, and an inner thermoplastic resin layer are laminated in this order,
The outer thermoplastic resin layer and the paper base layer are in contact,
the outer thermoplastic resin layer comprises polyethylene;
The printed layer contains a colorant and a urethane (meth)acrylate that is a reaction product of a polyol, an isocyanate compound, and a hydroxy (meth)acrylate,
At least one of the polyol or the isocyanate compound contains a biomass-derived component,
The packaging material , wherein the surface protective layer does not contain a coloring agent . 2. The packaging material of claim 1, wherein said polyol comprises a biomass-derived component. The packaging material according to claim 1 or 2, wherein the isocyanate compound contains a biomass-derived component. The packaging material according to any one of claims 1 to 3, wherein the surface protective layer contains urethane (meth)acrylate which is a reaction product of polyol, isocyanate compound and hydroxy (meth)acrylate. The packaging material according to claim 4, wherein at least one of the polyol and the isocyanate compound of the surface protective layer contains a biomass-derived component. 6. The packaging material according to any one of claims 1 to 5, further comprising a barrier layer between said paper base layer and said inner thermoplastic resin layer. 7. The packaging material according to claim 6, wherein said barrier layer is a metal foil or vapor deposited film. A packaged product comprising a packaging material according to any one of claims 1-7.

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