JP2023153889A - Packaging material and packaging product - Google Patents

Abstract

To provide a packaging material with an enhanced degree of biomass.SOLUTION: The packaging material includes at least a substrate layer, a printed layer, an adhesive resin layer, an intermediate layer, and a sealant layer. The adhesive resin layer is in contact with the intermediate layer. The printed layer contains a colorant and a cured product of a polyol and an isocyanate compound, and at least one of the polyol and the isocyanate compound contains a biomass-derived component.SELECTED DRAWING: Figure 1

Description

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

Conventionally, various packaging materials have been developed and proposed as packaging materials for constructing packaging products for filling and packaging various items such as food and drink, pharmaceuticals, chemicals, cosmetics, sanitary products, daily necessities, etc. The packaging material is composed of a laminate in which at least a base layer containing stretched plastic or the like and a sealant layer for welding the packaging materials together are laminated. Usually, the laminate further includes a printing layer for forming a printed pattern and an adhesive resin layer for bonding each layer of the laminate.

In recent years, with increasing calls for building a recycling-oriented society, there is a desire to move away from fossil fuels in the field of laminates that make up packaging materials, just as in the energy field, and the use of biomass is attracting attention. There is. Biomass is an organic compound that is photosynthesized from carbon dioxide and water, and by using it, it becomes carbon dioxide and water again, so it is a so-called carbon-neutral renewable energy. In recent years, the practical use of biomass plastics made from these biomass raw materials is rapidly progressing, and attempts are also being made to produce various resins from biomass raw materials.

Commercial production of biomass-derived resins began first with polylactic acid (PLA), which is produced through lactic acid fermentation, but its performance as a plastic, including its biodegradability, is superior to that of today's general-purpose plastics. Because it is very different from the conventional method, there are limits to product applications and product manufacturing methods, and it has not become widely used. In addition, life cycle assessment (LCA) evaluations are being conducted on PLA, and discussions are taking place regarding the energy consumption during PLA production and the equivalency when replacing general-purpose plastics.

Here, various types of general-purpose plastics are used, such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, and polyester. In particular, polyethylene is formed into films, sheets, bottles, etc., and is used for various purposes such as packaging materials, and is used in large quantities around the world. Therefore, using conventional polyethylene derived from fossil fuels has a large environmental impact. Therefore, it is desired to reduce the amount of fossil fuel used by using biomass-derived raw materials in the production of polyethylene. For example, to date, research has been conducted on producing ethylene and butylene, which are raw materials for polyolefin resins, from renewable natural raw materials (see Patent Document 1).

Furthermore, polyester has excellent mechanical properties, chemical stability, heat resistance, transparency, etc., and is inexpensive, so it is widely used in various industrial applications. Polyester is obtained by polycondensing diol units and dicarboxylic acid units. For example, polyethylene terephthalate (hereinafter sometimes abbreviated as PET) is obtained by esterifying ethylene glycol and terephthalic acid as raw materials. After that, it is produced by polycondensation reaction. These raw materials are produced from petroleum, which is a fossil resource; for example, ethylene glycol is industrially produced from ethylene, and terephthalic acid is industrially produced from xylene.

Recently, attempts have been made to produce polyester from biomass raw materials. For example, products using biomass-derived ethylene glycol as a monomer component have been put into practical use. It has been proposed to apply polyester resin containing such biomass-derived raw materials to packaging materials (see Patent Document 2).

Special Publication No. 2011-506628 JP2012-96410A

In conventional packaging materials, the printed layer of the laminate is formed from fossil fuel-derived materials, which causes a decrease in the biomass content of the entire packaging material. Therefore, in a packaging material composed of a laminate including a base layer, a printed layer, an adhesive resin layer, and a sealant layer, there is a need to further increase the biomass content of the entire packaging material.

The present invention has been made in consideration of these points, and an object of the present invention is to provide a packaging material with an increased biomass content.

The present invention is a packaging material including at least a base layer, a printed layer, an adhesive resin layer, an intermediate layer, and a sealant layer, wherein the adhesive resin layer is in contact with the intermediate layer, and the printed layer is colored. and a cured product of a polyol and an isocyanate compound, at least either the polyol or the isocyanate compound contains a biomass-derived component, and the polyol of the printing layer is a cured product of a polyfunctional alcohol and a polyfunctional carboxylic acid. The reactant is a polyester polyol, one of the polyfunctional alcohol and the polyfunctional carboxylic acid of the printing layer contains a biomass-derived component and the other is derived from fossil fuel, and the base layer is a first polyester polyol containing polypropylene. The packaging material includes a base film, the intermediate layer has a vapor deposition layer, and the sealant layer includes biomass-derived low-density polyethylene.

In the packaging material according to the present invention, the intermediate layer may have a second base film containing polyester as a main component.

In the packaging material according to the present invention, the second base film may include a biomass polyester having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

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

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

According to the present invention, the biomass content of packaging materials can be increased.

FIG. 1 is a schematic cross-sectional view showing an example of a packaging material according to the present invention. FIG. 1 is a schematic cross-sectional view showing an example of a packaging material according to the present invention. FIG. 1 is a schematic cross-sectional view showing an example of a packaging material according to the present invention. FIG. 1 is a schematic cross-sectional view showing an example of a packaging material according to the present invention. FIG. 1 is a schematic cross-sectional view showing an example of a packaging material according to the present invention. FIG. 1 is a schematic cross-sectional view showing an example of a packaging material according to the present invention. FIG. 1 is a schematic front view showing an example of a packaged product according to the present invention. FIG. 1 is a schematic front view showing an example of a packaged product according to the present invention. FIG. 1 is a schematic front view showing an example of a packaged product according to the present invention. FIG. 1 is a schematic front view showing an example of a packaged product according to the present invention. FIG. 3 is a diagram showing the layer structure of the packaging materials of Examples 1A to 1N. FIG. 3 is a diagram showing the layer structure of packaging materials of Examples 2A to 2J. FIG. 3 is a diagram showing the layer structure of packaging materials of Examples 3A to 3J. FIG. 4 is a diagram showing the layer structure of packaging materials of Examples 4A to 4G. FIG. 3 is a diagram showing the layer structure of packaging materials of Examples 5A to 5C. FIG. 3 is a diagram showing examples of types of packaging containers of Examples 1A to 1N, 2A to 2J, 3A to 3J, 4A to 4G, and 5A to 5C.

<Packaging materials>
The laminate constituting the packaging material according to the present invention includes at least a base layer, a printed layer, an adhesive resin layer, an intermediate layer, and a sealant layer. The adhesive resin layer is in contact with the intermediate layer. For example, the first adhesive resin layer, which will be described later, is in contact with the intermediate layer from the base layer side. Further, a second adhesive resin layer, which will be described later, is in contact with the intermediate layer from the sealant layer side. In the present invention, by forming at least the printing layer from a material containing a biomass-derived component, the amount of fossil fuel used can be reduced compared to the conventional method, and the environmental load can be reduced. In this application, the term "in contact with the intermediate layer" includes the case where a layer other than the base film and metal foil, such as a printed layer, is present between the intermediate layer and the adhesive resin layer.

In the present invention, the degree of biomass described below in the entire laminate constituting the packaging material is preferably 3% or more, more preferably 5% or more and 60% or less, and even more preferably 10% or more and 60% or less. . If the biomass degree is within the above range, the amount of fossil fuel used can be reduced and the environmental load can be reduced.

The laminate constituting the packaging material preferably has a thickness of 10 μm or more and 500 μm or less, more preferably 20 μm or more and 300 μm or less, and even more preferably 30 μm or more and 200 μm or less.

In addition to the above-mentioned layers, the packaging material according to the present invention may further include at least one other layer such as a barrier layer such as a metal foil, a vapor deposited layer, a gas barrier coating film, or a resin layer. When having two or more other layers, they may have the same composition or different compositions.

The laminate constituting the packaging material according to the present invention will be explained with reference to the drawings. Examples of schematic cross-sectional views of a packaging material 10 according to the present invention are shown in FIGS. 1 to 6. In FIGS. 1 to 6, the reference numeral 10y represents the outer surface of the packaging material 10, and the reference numeral 10x represents the inner surface of the packaging material 10. The inner surface 10x is a surface located on the side of the contents accommodated in the packaging product, such as a bag formed from the packaging material 10. Further, the outer surface 10y is a surface located on the opposite side of the inner surface 10x. In the present application, the term "order" in descriptions such as "provided in this order" and "layered in this order" indicates the order in the direction from the outer surface 10y side to the inner surface 10x side, unless otherwise specified.

The packaging material 10 shown in FIG. 1 includes a base layer 20, a printing layer 50, a first anchor coat layer 28, a first adhesive resin layer 26, an intermediate layer 30, a second anchor coat layer 46, and sealant layer 40 in this order. The base layer 20 includes a first base film 22 . Intermediate layer 30 includes metal foil 34 .

The packaging material 10 shown in FIG. 2 includes a base layer 20, a first anchor coat layer 28, a first adhesive resin layer 26, a printing layer 50, an intermediate layer 30, a second anchor coat layer 46, and sealant layer 40 in this order. The base layer 20 includes a first base film 22 . Intermediate layer 30 includes a second base film 32.

The packaging material 10 shown in FIG. 3 includes a base layer 20, a printing layer 50, a first anchor coat layer 28, a first adhesive resin layer 26, an intermediate layer 30, a second anchor coat layer 46, A second adhesive resin layer 44 and a sealant layer 40 are provided in this order. The base layer 20 includes a first base film 22 . The intermediate layer 30 includes a second base film 32 and a vapor deposition layer 60 in this order. Sealant layer 40 includes a sealant film 42.

The packaging material 10 shown in FIG. 4 is obtained by changing the order of the second base film 32 of the intermediate layer 30 and the vapor deposition layer 60 of the packaging material 10 of FIG. 3. Specifically, the packaging material 10 in FIG. 4 includes a base layer 20, a printing layer 50, a first anchor coat layer 28, a first adhesive resin layer 26, an intermediate layer 30, and a second anchor coat layer. 46, a second adhesive resin layer 44, and a sealant layer 40 in this order. The base layer 20 includes a first base film 22 . The intermediate layer 30 includes a vapor deposition layer 60 and a second base film 32 in this order. Sealant layer 40 includes a sealant film 42.

The packaging material 10 shown in FIG. 5 is obtained by replacing the second base film 32 and the vapor deposition layer 60 of the intermediate layer 30 of the packaging material 10 of FIGS. 3 and 4 with a metal foil 34. Specifically, the packaging material 10 in FIG. 5 includes a base layer 20, a printing layer 50, a first anchor coat layer 28, a first adhesive resin layer 26, an intermediate layer 30, and a second anchor coat layer. 46, a second adhesive resin layer 44, and a sealant layer 40 in this order. The base layer 20 includes a first base film 22 . Intermediate layer 30 includes metal foil 34 . Sealant layer 40 includes a sealant film 42.

The packaging material 10 shown in FIG. 6 is different from the packaging material 10 shown in FIG. 5 in the structure of the sealant layer 40. Specifically, the packaging material 10 in FIG. 6 includes a base layer 20, a printing layer 50, a first anchor coat layer 28, a first adhesive resin layer 26, an intermediate layer 30, and a second anchor coat layer. 46, a second adhesive resin layer 44, and a sealant layer 40 in this order. The base layer 20 includes a first base film 22 . Intermediate layer 30 includes metal foil 34 .

Note that it is also possible to appropriately combine the plurality of layer configurations of the packaging material 10 shown in FIGS. 1 to 6 described above.

Each layer constituting the packaging material 10 will be explained below.

(First base film)
The first base film 22 of the base layer 20 is a plastic film. The first base film 22 may or may not contain biomass-derived components.

When the first base film 22 contains a biomass-derived component, the first base film 22 can be formed using the following biomass polyester.

Biomass polyester uses 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 layer may further include a fossil fuel-derived polyester having fossil fuel-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. It is sufficient if the following biomass degree can be achieved for the base material layer as a whole. In the present invention, since the base material layer contains biomass polyester, the amount of fossil fuel-derived polyester can be reduced compared to the conventional method, and the environmental load can be reduced.

In the present invention, the "biomass degree" may be expressed as a value obtained by measuring the content of biomass-derived carbon by radiocarbon (C14) measurement, or may be expressed as a weight ratio of biomass-derived components.

When the value of the content of carbon derived from biomass measured by radiocarbon (C14) measurement is expressed as the "degree of biomass", the "degree of biomass" can be determined as follows. In other words, since carbon dioxide in the atmosphere contains C14 at a certain rate (105.5 pMC), the C14 content in plants that grow by taking in atmospheric carbon dioxide, such as corn, is also around 105.5 pMC. It is known that It is also known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 contained in all carbon atoms in polyester, the proportion of carbon derived from biomass can be calculated. In the present invention, the biomass-derived carbon content P _bio can be determined as follows, where the C14 content in the polyester is P _C14 .
P _bio (%) = P _C14 /105.5×100

Taking polyethylene terephthalate, a typical polyester, as an example, polyethylene terephthalate is a product obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1:1. When only biomass-derived carbon is used as the polyethylene terephthalate, the biomass-derived carbon content P _bio in polyethylene terephthalate is 20%. On the other hand, the content of biomass-derived carbon in fossil fuel-derived polyethylene terephthalate produced using fossil fuel-derived ethylene glycol and fossil fuel-derived dicarboxylic acid is 0%; The biomass degree will be 0%.

Furthermore, when expressing the "degree of biomass" by the weight ratio of biomass-derived components, the "degree of biomass" can be determined as follows. For example, taking polyethylene terephthalate as an example, as mentioned above, polyethylene terephthalate is a product obtained by polymerizing ethylene glycol containing two carbon atoms and terephthalic acid containing eight carbon atoms in a molar ratio of 1:1. When only biomass-derived glycol is used, the weight ratio of biomass-derived components in polyester is about 30%, so the biomass degree is about 30%. In addition, the weight ratio of biomass-derived components in fossil fuel-derived polyester produced using fossil fuel-derived ethylene glycol and fossil fuel-derived dicarboxylic acid is 0%, and the biomass content of fossil fuel-derived polyester is 0%. It becomes 0%. Hereinafter, unless otherwise specified, "biomass degree" refers to the weight ratio of biomass-derived components.

When the first base film 22 contains a biomass-derived component, the degree of biomass in the first base film 22 is 5% or more, preferably 10% or more and 30% or less, and more preferably 15% or more and 25% or more. % or less. If the degree of biomass in the first base film 22 is 5% or more, the amount of fossil fuel-derived polyester can be reduced compared to the conventional method, and the environmental load can be reduced.

Biomass-derived ethylene glycol is made from ethanol produced from biomass (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene glycol via ethylene oxide using a conventionally known method. Moreover, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol Corporation can be suitably used.

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

Examples of aliphatic dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid, which usually have 2 to 40 carbon atoms. chain or alicyclic dicarboxylic acids. Further, as derivatives of aliphatic dicarboxylic acids, lower alkyl esters such as methyl ester, ethyl ester, propyl ester, and butyl ester of the above aliphatic dicarboxylic acids, and cyclic acid anhydrides of the above aliphatic dicarboxylic acids such as succinic anhydride may be used. Can be 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. As the aliphatic dicarboxylic acid derivative, methyl esters of adipic acid and succinic acid, or mixtures thereof are more preferred. These dicarboxylic acids can be used alone or in combination of two or more.

The biomass polyester may be a copolymerized polyester in which a copolymerized component is added as a third component in addition to the diol component and dicarboxylic acid component described above. Specific examples of copolymerization components include bifunctional oxycarboxylic acids, trifunctional or more polyhydric alcohols, trifunctional or more polycarboxylic acids and/or their anhydrides, and trifunctional or more functional polyhydric alcohols to form a crosslinked structure. At least one type of polyfunctional compound selected from the group consisting of oxycarboxylic acids having higher than functional functions is mentioned. Among these copolymerization components, bifunctional and/or trifunctional or higher functional oxycarboxylic acids are particularly preferably used because copolymerized polyesters with a high degree of polymerization tend to be easily produced. Among these, the use of trifunctional or higher functional oxycarboxylic acids is most preferable because polyester with a high degree of polymerization can be easily produced in a very small amount without using a chain extender described later.

The biomass polyester can be obtained by a conventionally known method of polycondensing the diol units and dicarboxylic acid units described above. Specifically, after performing the esterification reaction and/or transesterification reaction between the above-mentioned dicarboxylic acid component and diol component, a general method of melt polymerization in which a polycondensation reaction is performed under reduced pressure, and an organic solvent It can be produced by a known solution heating dehydration condensation method using. The amount of diol used when producing biomass polyester is substantially equimolar to 100 moles of dicarboxylic acid or its derivative, but generally it is used in 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 of the possibility of distillation.

The first base film 22 can be formed by forming a film using a T-die method using a resin composition of biomass polyester or a resin composition containing biomass polyester and fossil fuel-derived polyester. Specifically, after drying the above-mentioned 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 first base film 22 can be formed by extruding it into a sheet from a die such as a T-die, and rapidly cooling and solidifying the extruded sheet using 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, etc. can be used depending on the purpose.

When the first base film 22 is formed of a material that does not contain biomass-derived components, the first base film 22 may be, for example, a polyester film such as a polyethylene terephthalate film or a polybutylene terephthalate film, or a polyolefin such as a polyethylene film or a polypropylene film. film, a polyamide film such as a nylon film, a nylon 6/metaxylylene diamine nylon 6 co-extruded co-stretched film, a polypropylene/ethylene-vinyl alcohol copolymer co-extruded co-stretched film, or a lamination of two or more of these films. Plastic films such as composite films can be used. Note that the plastic film may be coated with polyvinyl alcohol or the like.

The first base film 22 may be a stretched plastic film stretched in a predetermined direction. In this case, the first base film 22 may be a uniaxially stretched film stretched in one predetermined direction, or a biaxially stretched film stretched in two predetermined directions. A stretched plastic film is obtained, for example, by heating a plastic film extruded onto a cooling drum using roll heating, infrared heating, or the like, and stretching the film in the longitudinal direction. This stretching is preferably carried out using the difference in circumferential speed between two or more rolls. Longitudinal stretching is usually performed at a temperature range of 50°C or higher and 100°C or lower. Further, the longitudinal stretching ratio is preferably 2.5 times or more and 4.2 times or less, although it depends on the required characteristics of the film application. If the stretching ratio is less than 2.5 times, the thickness of the film becomes uneven and it is difficult to obtain a good film.

The longitudinally stretched film is then sequentially subjected to transverse stretching, heat setting, and heat relaxation to become a biaxially stretched film. The transverse stretching is usually performed at a temperature range of 50°C or higher and 100°C or lower. The transverse stretching ratio is preferably 2.5 times or more and 5.0 times or less, although it depends on the required characteristics of this use. If it is less than 2.5 times, the thickness of the film becomes uneven and it is difficult to obtain a good film, and if it exceeds 5.0 times, breakage is likely to occur during film formation.

The breaking strength of the first base film 22 is, for example, 5 kg/mm ² or more and 40 kg/mm 2 or less in the MD direction, 5 kg/mm ^{2 or} more and 35 kg/mm ² or less in the TD direction, and the breaking elongation is, for example, 50% or more and 350% or less in the MD direction, and 50% or more and 300% or less in the TD direction. Further, the shrinkage rate when left in a temperature environment of 150° C. for 30 minutes is, for example, 0.1% or more and 5% or less.

When the first base film 22 is a biomass polyester film or a polyester film, the thickness of the first base film 22 is preferably 6 μm or more and 20 μm or less, more preferably 12 μm or more and 16 μm or less.
When the first base film 22 is a polyamide film, the thickness of the first base film 22 is preferably 10 μm or more and 30 μm or less, more preferably 15 μm or more and 25 μm or less.
When the first base film 22 is a polypropylene film, the thickness of the first base film 22 is preferably 15 μm or more and 50 μm or less, more preferably 20 μm or more and 30 μm or less.
When the first base film 22 is a biomass polyethylene film or a polyethylene film, the thickness of the first base film 22 is preferably 10 μm or more and 80 μm or less, more preferably 30 μm or more and 60 μm or less.

The first base film 22 may be a single layer film or a co-pressed film of two or more layers.

(Second base film)
The second base film 32 of the intermediate layer 30 is a plastic film similar to the first base film 22. The second base film 32, like the first base film 22, may contain biomass-derived components or may not contain biomass-derived components.

As the plastic film of the second base film 32, biomass polyester or polyester film can be particularly preferably used among the plastic films listed as examples of the first base film 22.

(metal foil)
The metal foil 34 of the intermediate layer 30 is a member obtained by rolling metal. As the metal foil 34, a conventionally known metal foil can be used. Aluminum foil is preferable from the viewpoint of gas barrier properties that block the transmission of oxygen gas, water vapor, etc., and light shielding properties that block the transmission of visible light, ultraviolet rays, etc.

(vapor deposited layer)
The deposited layer 60 is a deposited film made of an inorganic substance and/or an inorganic oxide. The deposited film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and its composition and formation method are not particularly limited. The packaging material 10 may have two or more vapor deposited layers 60. When there are two or more vapor deposited layers 60, they may have the same composition or different compositions.

The vapor deposition layer 60 includes, for example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium. A vapor deposited film of an inorganic substance or an inorganic oxide such as (Ti), lead (Pb), zirconium (Zr), or yttrium (Y) can be used.

Vapor deposited films of inorganic oxides such as silicon oxide and aluminum oxide have transparency. When the vapor deposition layer 60 is located closer to the outer surface 10y than the printing layer 50, a vapor deposition film of a transparent inorganic oxide is used as the vapor deposition layer 60.

Inorganic oxides are expressed as, for example, MO _x such as SiO _x , _AlO expressed. The value range of X is 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1 for magnesium (Mg), 0 to 1 for calcium (Ca), Potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1, 5, titanium (Ti) can take a value in the range of 0 to 2, lead (Pb) can take a value in the range of 0 to 1, zirconium (Zr) can take a value in the range of 0 to 2, and yttrium (Y) can take a value in the range of 0 to 1.5. In the above, when X=0, it is a completely inorganic substance (pure substance) and is not transparent, and the upper limit of the range of X is a completely oxidized value. Silicon (Si) and aluminum (Al) are preferably used as the vapor deposition layer 60 of the packaging material 10, with silicon (Si) having a concentration of 1.0 to 2.0 and aluminum (Al) having a concentration of 0.5 to 1. Values in the range of .5 can be used.

The thickness of the vapor-deposited film of the inorganic substance or inorganic oxide described above varies depending on the type of inorganic substance or inorganic oxide used, but is, for example, within the range of 50 Å or more and 2000 Å or less, preferably 100 Å or more and 1000 Å or less. It is preferable to select and form it arbitrarily. More specifically, in the case of a vapor deposited film of aluminum, the film thickness is desirably 50 Å or more and 600 Å or less, more preferably 100 Å or more and 450 Å or less, and in the case of a vapor deposited film of aluminum oxide or silicon oxide, The film thickness is desirably 50 Å or more and 500 Å or less, more preferably 100 Å or more and 300 Å or less.

The vapor deposition layer 60 can be formed on the first base film 22, the second base film 32, etc. using the following formation method. As a method for forming the vapor deposition layer 60, for example, a physical vapor deposition method (PVD method) such as a vacuum evaporation method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, a thermal Examples include chemical vapor deposition methods (Chemical Vapor Deposition methods, CVD methods) such as chemical vapor deposition methods and photochemical vapor deposition methods.

(Gas barrier coating film)
The gas barrier coating film is a film provided on the vapor deposition layer 60 if necessary. The gas barrier coating film functions as a layer that suppresses permeation of oxygen gas, water vapor, and the like. The gas barrier coating film has a general formula R ¹ _n M(OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents an integer of 0 or more, m represents an integer of 1 or more, and n+m represents the valence of M.) and a polyvinyl alcohol system as described above. It is obtained by a gas barrier composition containing a resin and/or an ethylene/vinyl alcohol copolymer, and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent.

As the alkoxide represented by the above general formula R ¹ _n M(OR ² ) _m , at least one of a partial hydrolyzate of an alkoxide and a condensate of hydrolysis of an alkoxide can be used. In addition, the partial hydrolyzate of the alkoxide described above does not necessarily have to have all the alkoxy groups hydrolyzed, and may be one in which one or more alkoxy groups have been hydrolyzed, or a mixture thereof. As the condensate of alkoxide hydrolysis, a dimer or more of partially hydrolyzed alkoxide, specifically a dimer to hexamer, is used.

In the alkoxide represented by the above general formula R ¹ _n M(OR ² ) _m , silicon, zirconium, titanium, aluminum, and the like can be used as the metal atom represented by M. In this embodiment, preferable metals include silicon, titanium, and the like. Furthermore, in the present invention, alkoxides can be used alone or in combination of two or more alkoxides of different metal atoms in the same solution.

Further, in the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, an i Examples include alkyl groups such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group, and others. Further, in the alkoxide represented by the above general formula R ¹ _n M(OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, an i -propyl group, n-butyl group, sec-butyl group, and others. Note that these alkyl groups in the same molecule may be the same or different.

When preparing the above gas barrier composition, for example, a silane coupling agent or the like may be added. As the silane coupling agent, known organoalkoxysilanes containing organic reactive groups can be used. In this embodiment, an organoalkoxysilane having an epoxy group is particularly preferably used, and specifically, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or , β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like can be used. The above silane coupling agents may be used alone or in combination of two or more.

(Printing layer)
The printing layer 50 is a layer formed by printing for decoration, display of contents, display of expiration date, display of manufacturer, seller, etc., and for imparting aesthetic appearance. The printing layer 50 includes, for example, a pattern layer that forms any desired pattern such as a picture, a photograph, a character, a number, a figure, a symbol, a pattern, or the like. The printing layer may further include a ground color layer formed by printing to make the pattern of the pattern layer stand out. The printing layer 50 includes a colorant and a cured product of a polyol and an isocyanate compound. The printed layer 50 contains biomass-derived components. Specifically, the printing layer 50 can be formed using a cured product in which at least one of a polyol as a main ingredient and an isocyanate compound as a curing agent contains a biomass-derived component. As the polyol, a polyester polyol that is a reaction product of a polyfunctional alcohol and a polyfunctional carboxylic acid, or a polyether polyol that is a reaction product of a polyfunctional alcohol and a polyfunctional isocyanate can be used.

[Polyester polyol]
When the polyester polyol contains a biomass-derived component, at least one of the polyfunctional alcohol and the polyfunctional carboxylic acid contains the biomass-derived component. The following examples can be given as polyester polyols containing biomass-derived components.
・Reactant of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Reactant of fossil fuel-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Biomass-derived polyfunctional alcohol and fossil fuel-derived polyfunctional alcohol reaction product with polyfunctional carboxylic acid

As the biomass-derived polyfunctional alcohol, aliphatic polyfunctional alcohols obtained from plant materials such as corn, sugarcane, 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, which are obtained from plant materials by the following methods. Examples include glycol (BG) and hexamethylene glycol, any of which can be used. These may be used alone or in combination.

Biomass-derived polypropylene glycol is produced by converting glycerol into 3-hydroxypropyl aldehyde (HPA) using a fermentation method in which glucose is obtained by decomposing plant materials. Compared to polypropylene glycol produced using the EO method, polypropylene glycol produced using biomethods such as the fermentation method described above is safer and produces useful by-products such as lactic acid, and can also be produced at lower production costs. It is also preferable that it is possible.
Butylene glycol derived from biomass can be produced by producing succinic acid obtained by producing glycol from plant materials and fermenting it, and then hydrogenating this.
Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

As the fossil fuel-derived polyfunctional alcohol, a compound having two or more hydroxyl groups, preferably 2 to 8 hydroxyl groups in one molecule can be used. Specifically, the polyfunctional alcohol derived from fossil fuels is not particularly limited, and conventionally known ones can be used, such as polypropylene glycol (PPG), neopentyl glycol (NPG), and ethylene glycol (EG). , diethylene glycol (DEG), butylene glycol (BG), hexamethylene glycol, as well as triethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, 1,9-nonanediol, 3-methyl -1,5-pentanediol, polyether polyol, polycarbonate polyol, polyolefin polyol, acrylic polyol, etc. can be used. These may be used alone or in combination of two or more.

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, as well as recycled waste cooking oils based on these oils. Aliphatic polyfunctional carboxylic acids obtained from plant materials 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 by alkaline thermal decomposition of ricinoleic acid obtained from castor oil, with heptyl alcohol as a by-product. 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.

As the polyfunctional carboxylic acid derived from fossil fuels, aliphatic polyfunctional carboxylic acids and aromatic polyfunctional carboxylic acids can be used. The aliphatic polyfunctional carboxylic acid derived from fossil fuels is not particularly limited and conventionally known ones can be used, such as adipic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride. Examples include acids, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, dimer acid, and ester compounds thereof. Furthermore, the aromatic polyfunctional carboxylic acid derived from fossil fuels is not particularly limited and conventionally known ones can be used, such as isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid, and ester compounds thereof, etc. 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. The following examples can be given as polyether polyols containing biomass-derived components.
・Reactant of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional isocyanate ・Reactant of fossil fuel-derived polyfunctional alcohol and biomass-derived polyfunctional isocyanate ・Reactant of biomass-derived polyfunctional alcohol and fossil fuel-derived polyfunctional isocyanate Reactant with functional isocyanate

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 explained in the above-mentioned polyester polyol can be used.

Biomass-derived polyfunctional isocyanates are produced by converting plant-derived divalent carboxylic acids into acid amides, reducing them to terminal amino groups, and then reacting with phosgene to convert the amino groups into isocyanate groups. What is obtained can be used. The biomass-derived polyfunctional isocyanate is, for example, a biomass-derived diisocyanate. Examples of biomass-derived diisocyanates include dimer acid diisocyanate (DDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like. Furthermore, a plant-derived diisocyanate can also be obtained by using a plant-derived amino acid as a raw material and converting its amino group into an isocyanate group. For example, lysine diisocyanate (LDI) is obtained by methyl esterifying the carboxyl group of lysine and then converting the amino group into an isocyanate group. Furthermore, 1,5-pentamethylene diisocyanate can be obtained by decarboxylating the carboxyl group of lysine and then converting the amino group into an isocyanate group.

Other methods for synthesizing 1,5-pentamethylene diisocyanate include a phosgenation method and a carbamate method. More specifically, the phosgenation method includes a method in which 1,5-pentamethylenediamine or a salt thereof is directly reacted with phosgene, and a method in which the hydrochloride of pentamethylenediamine is suspended in an inert solvent and reacted with phosgene. This method synthesizes 1,5-pentamethylene diisocyanate. In addition, in the carbamate method, 1,5-pentamethylene diisocyanate is first produced by carbamateing 1,5-pentamethylene diamine or its salt to produce pentamethylene dicarbamate (PDC), and then thermally decomposing it to produce 1,5-pentamethylene diisocyanate. It is something that is synthesized. In the present invention, the polyisocyanate preferably used includes 1,5-pentamethylene diisocyanate-based polyisocyanate (trade name: Stabio (registered trademark)) manufactured by Mitsui Chemicals, Inc.

The polyfunctional isocyanate derived from fossil fuels is not particularly limited and conventionally known ones can be used, such as toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl- 1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4'-methylenebis(phenylene isocyanate) (MDI), Aromatic diisocyanates such as jurylene diisocyanate, toridine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and dibenzyl 4,4'-diisocyanate are mentioned. Also, aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate, 4,4-methylene bis(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.

[Colorant]
The colorant is not particularly limited, and conventionally known pigments and dyes can be used.

When the printed layer 50 contains a biomass-derived component, the printed layer 50 has a biomass degree of preferably 5% or more, more preferably 5% or more and 50% or less, and even more preferably 10% or more and 50% or less. If the biomass degree is within the above range, the amount of fossil fuel used can be reduced and the environmental load can be reduced.

The weight of the printed layer 50 after drying is preferably 0.1 g/m ² or more and 10 g/m ² or less, more preferably 1 g/m ² or more and 5 g/m ² or less, and even more preferably 1 g/m 2 ^or more and 3 g/m 2 or less. ² or less.

The printed layer 50 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, and even more preferably 1 μm or more and 3 μm or less.

[Adhesive resin layer]
The adhesive resin layer is a layer provided when adhering two arbitrary layers, and can be provided, for example, between a base layer and an intermediate layer or between an intermediate layer and a sealant layer.

The adhesive resin layers such as the first adhesive resin layer 26 and the second adhesive resin layer 44 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 resins, polypropylene resins, cyclic polyolefin resins, copolymer resins, modified resins, and mixtures (including alloys) containing these resins as main components. ) can be used. Examples of polyolefin resins include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), and metallocene catalysts. Ethylene-α-olefin copolymer polymerized using ethylene-α-olefin copolymer, ethylene-polypropylene random or block copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-α-olefin copolymer Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-maleic acid copolymer, ionomer resin, and interlayer adhesion In order to improve this, it is possible to use acid-modified polyolefin resins in which the above-mentioned polyolefin resins are modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. can. Further, a resin obtained by graft polymerizing or copolymerizing an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or an ester monomer to the polyolefin resin can be used. These materials can be used alone or in combination of two or more. As the cyclic polyolefin resin, for example, cyclic polyolefins such as ethylene-propylene copolymer, polymethylpentene, polybutene, and polynorbornene can be used. These resins can be used alone or in combination. In addition, as the above-mentioned polyethylene resin, the degree of biomass can be further improved by using one using the above-mentioned biomass-derived ethylene as a monomer unit.

When laminating adhesive resin layers by the melt extrusion lamination method, the first anchor coat layer 28 and the second anchor coat are formed by applying an anchor coating agent to the surface of the layer to be laminated and drying it. An anchor coat layer, such as layer 46, may also be provided. Examples of the anchor coating agent include anchor coating agents made of any resin having a heat resistance temperature of 135°C or higher, such as vinyl modified resin, epoxy resin, urethane resin, polyester resin, polyethyleneimine, etc. An anchor coating agent that is a cured product of a polyacrylic or polymethacrylic resin (polyol) having two or more hydroxyl groups and an isocyanate compound as a curing agent can be preferably used. Further, a silane coupling agent may be used together as an additive, and nitrified cotton may be used together in order 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.

(Sealant layer)
The sealant layer 40 constitutes the inner surface 10x of the packaging material 10. The sealant layer 40 may contain a biomass-derived component, or may not contain a biomass-derived component. When forming the sealant layer 40 using a material containing a biomass-derived component, the sealant layer 40 can be formed using the following biomass polyolefin. Furthermore, when forming the sealant layer 40 using a material that does not contain biomass-derived components, the sealant layer 40 can be formed using a conventionally known fossil fuel-derived thermoplastic resin.

Biomass polyolefin is a polymer of monomers containing olefins such as ethylene derived from biomass. Since biomass-derived olefin is used as the raw material monomer, the polymerized polyolefin is biomass-derived. Note that the raw material monomer for the polyolefin 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 fermented ethanol derived from biomass obtained from plant materials. The plant raw material is not particularly limited, and conventionally known plants can be used. For example, corn, sugar cane, beets and manioc may be mentioned.

Fermented ethanol derived from biomass refers to ethanol produced by contacting a culture solution containing a carbon source obtained from a plant material with a product derived from an ethanol-producing microorganism or its crushed product, and then purified. Conventionally known methods such as distillation, membrane separation, and extraction can be applied to purify ethanol from the culture solution. For example, methods include adding benzene, cyclohexane, etc. and azeotropically distilling the mixture, or removing water by membrane separation or the like.

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.

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

As the biomass polyolefin, polyethylene or a copolymer of ethylene and α-olefin may be used alone, or two or more types may be used as a mixture. In particular, the biomass polyolefin is preferably polyethylene. This is because by using ethylene, which is a biomass-derived raw material, it is theoretically possible to manufacture with 100% biomass-derived components.

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

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, and even more preferably 0.915 g/cm 3 or more and 0.928 g/cm ³ or less. It has a density of .925 g/cm ³ or less. The density of the biomass polyolefin is a value measured according to the method specified in Method A of JIS K7112-1980 after performing annealing as described in JIS K6760-1995. If the density of the biomass polyolefin is 0.91 g/cm ³ or more, the rigidity of the polyolefin resin layer containing the biomass polyolefin can be increased, and it can be suitably used as an inner layer of a packaged product. Further, 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 improved, and it can be suitably used as an inner layer of a packaged product.

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, and 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.

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

Examples of the 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, Examples include ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, and ionomer.

The sealant layer 40 preferably has a biomass degree of 5% or more, more preferably 5% or more and 60% or less, and still more preferably 10% or more and 60% or less. If the biomass degree is within the above range, the amount of fossil fuel used can be reduced and the environmental load can be reduced.

The sealant layer 40 may be a single layer or a multilayer. When using a biomass polyolefin as described above for the sealant layer, the sealant layer may include three layers: an inner layer, an intermediate layer, and an outer layer. In that case, it is preferable that the intermediate layer is made of biomass polyolefin or biomass polyolefin and conventionally known fossil fuel-derived polyolefin, and the inner layer and the outer layer are made of conventionally known fossil fuel-derived polyolefin.

The sealant layer 40 preferably has a thickness of 10 μm or more and 300 μm or less, more preferably 20 μm or more and 200 μm or less, and still more preferably 30 μm or more and 150 μm or less.

The packaging material 10 may further include a thermoplastic resin layer as another layer. As the thermoplastic resin layer, the same material as the sealant layer can be used.

<Method for manufacturing packaging materials>
Next, an example of a method for manufacturing a laminate that constitutes the packaging material 10 will be described.

The method for manufacturing the laminate constituting the packaging material 10 according to the present invention is not particularly limited, and can be manufactured using conventionally known methods such as dry lamination, melt extrusion lamination, and sand lamination. In the present invention, it is preferable to laminate other layers via the melt-extruded polyethylene resin layer using a sand lamination method. Further, the polyethylene resin layer may be laminated on other layers by a melt extrusion lamination method.

The packaging material 10 is provided with surface functions such as chemical functions, electrical functions, magnetic functions, mechanical functions, friction/wear/lubrication functions, optical functions, thermal functions, and biocompatibility. , it is also possible to perform secondary processing. Examples of secondary processing include embossing, painting, adhesion, printing, metallization (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.). Moreover, a molded product can also be manufactured by subjecting the packaging material according to the present invention to lamination processing (dry lamination or extrusion lamination), bag making processing, and other post-processing processing.

<Packaged products>
Examples of packaging products formed using the packaging material 10 include packaging bags, lids, sheet molded products, label materials, and the like.

The packaging product including the packaging material 10 is, for example, a liquid liquid such as medicine, food/drinks, fruit juice, juice, drinking water, alcohol, cooked food, seafood paste, frozen food, meat products, boiled food, rice cake, pot soup, etc. It can be suitably used as packaging for various food and beverage products such as soups, dried soups, and seasonings, cosmetics such as liquid detergents, shampoos, rinses, and conditioners, sanitary products, daily necessities, and chemical products. Specific examples of foods and drinks include coffee, coffee beans, coffee powder, ice cream, gummies, prepared foods, pasta sauce, curry, jelly, bacon, chocolate, chocolate paste, and the like. Specific examples of daily necessities include absorbent cotton, masks, bath salts, and powdered milk.

A packaging bag for a packaging product is made by folding the packaging material 10 in half or by preparing two packaging materials 10 and placing the sealant layer 40 of the front packaging material 10 and the sealant layer 40 of the back packaging material 10 facing each other. Then, the peripheral edges are stacked, for example, side seal type, two side seal type, three side seal type, four side seal type, envelope pasting seal type, gasho pasting seal type (pillow seal type), pleated seal type, Various types of packaging bags can be manufactured by heat sealing using a heat sealing method such as a flat bottom seal type or a square bottom seal type. Furthermore, a gusset-type packaging bag can also be manufactured by heat-sealing the folded packaging material 10 inserted between the front packaging material 10 and the back packaging material 10. Note that not all of the packaging materials 10 constituting the packaging bag may be the packaging materials 10 according to the present invention. That is, it is sufficient that at least a part of the printed layer of the packaging material 10 constituting the packaging bag contains the biomass-derived component, and that the printed layer of the other part of the packaging material 10 constituting the packaging bag contains the fossil fuel-derived component. It may be a packaging material containing.

As the heat sealing method, for example, known methods such as bar sealing, rotating roll sealing, belt sealing, impulse sealing, high frequency sealing, and ultrasonic sealing can be used.

FIG. 7 is a diagram showing an example of a packaging bag 70 including the packaging material 10. The bag 70 includes a front film 74 constituting the front surface and a back film 75 constituting the back surface.

The inner surfaces of the front film 74 and the back film 75 are joined to each other by a seal portion. In a front view of the packaging bag 70 such as in FIG. 7, the seal portion is hatched. As shown in FIG. 7, the seal portion has an outer edge seal portion extending along the outer edge of the packaging bag 70. As shown in FIG. The outer edge seal portion includes a lower seal portion 72 a that extends to the lower portion 72 and a pair of side seal portions 73 a that extends along a pair of side portions 73 . In addition, in the packaging bag 70 in a state before it is filled with contents (a state in which it is not filled with contents), as shown in FIG. 7, the upper part 71 of the bag 70 is an opening 71b. After the contents are stored in the packaging bag 70, the inner surface of the front film 74 and the inner surface of the back film 75 are joined at the upper part 71, thereby forming an upper seal portion and sealing the packaging bag 70. In this way, the packaging bag 70 shown in FIG. 7 is a four-sided sealed pouch formed by joining the front film 74 and the back film 75 on four sides along the outer edges.

Note that the terms "front film" and "back film" mentioned above are just divisions of each film according to the positional relationship, and the method of providing the packaging material 10 when manufacturing the packaging bag 70 is the same as the above-mentioned method. It is not limited by terminology. For example, the packaging bag 70 may be manufactured using one packaging material 10 in which a front film 74 and a back film 75 are connected, and the total number of the front film 74 and the back film 75 is one. It may also be manufactured using two packaging materials 10.

At least one of the front film 74 and the back film 75 is constituted by the packaging material 10 having a printed layer containing a biomass-derived component. As a result, the amount of fossil fuel used can be reduced compared to conventional methods, and the environmental impact can be reduced.

FIG. 8 is a diagram showing another example of the packaging bag 70 including the packaging material 10. The packaging bag 70 is a pillow pouch that is joined at an upper part 71, a lower part 72, and a palm part.

The seal portion is arranged between an upper seal portion 71a that extends to the upper portion 71, a lower seal portion 72a that extends to the lower portion 72, and a pair of side portions 73, for example, approximately in the middle of the pair of side portions 73, and is arranged from the upper portion 71 to the lower portion 72. It has a clasped palms seal portion 77 extending toward the front. The palms-up seal portion 77 is also referred to as a back seal portion.

Further, as shown in FIG. 8, the packaging bag 70 includes a packaging material folded between a front film 74 and a back film 75, extends from an upper part 71 to a lower part 72, and has a pair of side gusset parts facing each other. It also has 78. As shown in FIG. 8, the packaging material between the front film 74 and the back film 75 is folded back so that the folded part 78a is located on the inside.

Alternatively, the packaging bag 70 may be a small packaging bag, also called a stick pouch, that does not include a pair of side gusset parts 78, as shown in FIG.

FIG. 10 is a diagram showing an example of a lidded container 90 including the packaging material 10. The lidded container 90 includes a container body 92 manufactured by sheet forming such as drawing, and a lid portion 94 joined to the container body 92.

In the example shown in FIG. 10, for example, the container body 92 is produced by drawing and forming the packaging material 10 having a printed layer containing a biomass-derived component. As a result, the amount of fossil fuel used can be reduced compared to conventional methods, and the environmental impact can be reduced.

Moreover, in the example shown in FIG. 10, the lid part 94 may be formed of the packaging material 10 having a printed layer containing a biomass-derived component. As a result, the amount of fossil fuel used can be reduced compared to conventional methods, and the environmental impact can be reduced.

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

[Example 1A]
As the first base film 22 of the base layer 20, a biaxially stretched fossil fuel-derived PET film (thickness: 12 μm) was prepared. Subsequently, a printing layer 50 was formed on the inner surface of the PET film using an ink containing a biomass-derived component. In the step of forming the printing layer 50, first, 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 prepared as a main ingredient. In addition, a fossil fuel-derived isocyanate compound was prepared as a curing agent. Subsequently, a colorant was added to a cured product of a polyester polyol containing a biomass-derived component and a fossil fuel-derived isocyanate compound to obtain an ink. Subsequently, ink was applied in a predetermined pattern to the inner surface of the PET film to form a printed layer 50.

Furthermore, aluminum foil was prepared as the metal foil 34 of the intermediate layer 30. The thickness of the aluminum foil can be 7 μm or 9 μm, but here it was 7 μm. Subsequently, polyethylene 1 is extruded as the first adhesive resin layer 26 onto the printed layer 50 provided on the first base film 22 at a resin temperature of 290° C. via an anchor coating agent using a sand lamination method. , a metal foil 34 was laminated on the first adhesive resin layer 26. As polyethylene 1, fossil fuel-derived low density polyethylene (density: 0.924 g/cm ³ , MFR: 2.0 g/10 min, biomass degree: 0%) was used. The thickness of the polyethylene 1 can be selected within the range of 10 μm or more and 30 μm or less, but here it was set to 15 μm. Next, on the side of the metal foil 34 on which the first adhesive resin layer 26 is not laminated, the above-mentioned polyethylene 1 is applied as a sealant layer 40 using a melt-extrusion lamination method using a resin at 290° C. via an anchor coating agent. A packaging material 10 was obtained by extruding at a warm temperature and laminating a sealant layer. The thickness of the polyethylene 1 can be selected within the range of 20 μm or more and 40 μm or less, but here it was set to 30 μm.

The layer structure of the packaging material 10 of this example is expressed as follows.
PET12/Mark/Anchor/Glued PE(1)15/Al foil 7/Anchor/Extruded PE(1)30
"/" represents the boundary between layers. The leftmost layer is the layer that constitutes the outer surface of the packaging material 10, and the rightmost layer is the layer that constitutes the inner surface of the packaging material 10.
"PET" means biaxially oriented polyethylene terephthalate film derived from fossil fuels. "Mark" means a printed layer derived from biomass. "Anchor" means an anchor coat layer. "Contact PE (1)" means an adhesive resin layer containing the above-mentioned polyethylene 1. "Al foil" means aluminum foil. "Extruded PE(1)" means polyethylene 1 described above. The numbers refer to the layer thickness (in μm).

Subsequently, a four-sided sealed packaging bag 70 shown in FIG. 7 was produced using the packaging material 10.

[Example 1B]
Packaging was carried out in the same manner as in Example 1A, except that a reaction product of a fossil fuel-derived polyfunctional alcohol and a polyfunctional carboxylic acid containing a biomass-derived component was used as the polyester polyol, which is the main ingredient of the printing layer 50. Material 10 was produced.

[Example 1C]
As the polyester polyol, which is the main ingredient of the printing layer 50, a reaction product of a fossil fuel-derived polyfunctional alcohol and a fossil fuel-derived polyfunctional carboxylic acid is used, and as the isocyanate compound, which is the curing agent of the printing layer 50, a biomass-derived component is used. Packaging material 10 was produced in the same manner as in Example 1A, except that the isocyanate compound containing was used.

The layer structure of the packaging material 10 of Examples 1A to 1C is summarized in FIG. 11. In the column of "Printing layer type" in FIG. 11, the description "ester-based" means that the main ingredient used in the printing layer is polyester polyol.
In addition, in the column of "Biomass-derived components in the printing layer," the statement "polyfunctional alcohol" indicates that at least the polyfunctional alcohol of the main ingredient among the ingredients of the main ingredient and curing agent used in the printing layer is derived from biomass. means. Similarly, the description "polyfunctional carboxylic acid" means that at least the polyfunctional carboxylic acid of the main ingredient among the main ingredient and curing agent components used in the printing layer is derived from biomass. Similarly, the term "isocyanate compound" means that at least the isocyanate compound of the curing agent among the main agent and curing agent components used in the printing layer is derived from biomass.

In Examples 1A to 1C, in the printing layer, one of the three components, the polyfunctional alcohol or polyfunctional carboxylic acid used in the polyester polyol as the main ingredient, or the isocyanate compound used in the curing agent, was made from biomass. Although an example of a derived component is shown, the present invention 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 10 was produced in the same manner as in Example 1A except that polyether polyol was used as the main ingredient of the printing layer 50. Specifically, as the main polyether polyol, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate derived from fossil fuel was used.

[Example 1E]
Packaging was carried out in the same manner as in Example 1D, except that a reaction product of a fossil fuel-derived polyfunctional alcohol and a polyfunctional isocyanate containing a biomass-derived component was used as the polyether polyol, which is the main ingredient of the printing layer 50. Material 10 was produced.

[Example 1F]
As the polyether polyol, which is the main ingredient of the printing layer 50, a reaction product of a fossil fuel-derived polyfunctional alcohol and a fossil fuel-derived polyfunctional isocyanate is used, and as the isocyanate compound, which is the curing agent of the printing layer 50, a biomass-derived component is used. Packaging material 10 was produced in the same manner as in Example 1D, except that the isocyanate compound containing was used.

The layer structure of the packaging material 10 of Examples 1D to 1F is summarized in FIG. 11. In the column of "printing layer type" in FIG. 11, the description "ether-based" means that the main ingredient used in the printing layer is polyether polyol. In addition, in the column of "Biomass-derived components in the printing layer," the statement "polyfunctional isocyanate" indicates that at least the polyfunctional isocyanate of the main ingredient among the main ingredient and curing agent components used in the printing layer is derived from biomass. means.

In Examples 1D to 1F, in the printing layer, one of the three components, the polyfunctional alcohol or polyfunctional isocyanate used in the main polyether polyol, or the isocyanate compound used in the curing agent, was made from biomass. Although an example of a derived component is shown, the present invention 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]
Packaging material 10 was produced in the same manner as in Example 1A, except that ethylene-methacrylic acid copolymer (EMAA) was used as sealant layer 40.

The layer structure of the packaging material 10 of this example is expressed as follows.
PET12/Mark/Anchor/Glued PE(1)15/Al foil 7/Anchor/Extruded EMAA30
"Extruded EMAA" means ethylene-methacrylic acid copolymer (EMAA).

[Example 1H]
A packaging material 10 was produced in the same manner as in Example 1A, except that a biomass-derived biaxially stretched PET film was used as the first base film 22 of the base layer 20.

The layer structure of the packaging material 10 of this example is expressed as follows.
Bio PET12/Mark/Anchor/Glued PE(1)15/Al foil 7/Anchor/Extruded PE(1)30
"Bio-PET" means a biaxially oriented polyethylene terephthalate film derived from biomass.

[Example 1I]
A packaging material 10 was produced in the same manner as in Example 1A, except that polyethylene 2, which will be described below, was used as the first adhesive resin layer 26.

In this case, 50 parts by mass of fossil fuel-derived low-density polyethylene (density: 0.924 g/cm3, MFR: 2.0 g/10 min, biomass degree: 0%) and biomass-derived low-density polyethylene (manufactured by Braskem, A tree composition (polyethylene 2) was obtained by melt-kneading 50 parts by mass of SPB681 (trade name: SPB681, density: 0.922 g/cm ³ , MFR: 3.8 g/10 min, biomass degree 95%). Next, the obtained resin composition was extruded through an anchor coating agent at a resin temperature of 290° C., and the metal foil 34 was laminated on the first adhesive resin layer 26.

The layer structure of the packaging material 10 of this example is expressed as follows.
PET12/Mark/Anchor/Glued PE(2)15/Al foil 7/Anchor/Extruded PE(1)30
"Contact PE (2)" means an adhesive resin layer containing the above-mentioned polyethylene 2.

[Example 1J]
A packaging material 10 was produced in the same manner as in Example 1A, except that the above-mentioned polyethylene 2 was used as the sealant layer 40.

The layer structure of the packaging material 10 of this example is expressed as follows.
PET12/Mark/Anchor/Glued PE(1)15/Al foil 7/Anchor/Extruded PE(2)30
"Extruded PE(2)" means polyethylene 2 described above.

[Example 1K]
Example 1A except that a biomass-derived biaxially stretched PET film was used as the first base film 22 of the base layer 20, and the above-mentioned polyethylene 2 was used as the first adhesive resin layer 26. Packaging material 10 was produced in the same manner.

The layer structure of the packaging material 10 of this example is expressed as follows.
Bio PET12/Mark/Anchor/Glued PE(2)15/Al foil 7/Anchor/Extruded PE(1)30

[Example 1L]
The same procedure as in Example 1A was carried out, except that a biomass-derived biaxially stretched PET film was used as the first base film 22 of the base layer 20, and the above-mentioned polyethylene 2 was used as the sealant layer 40. A packaging material 10 was produced.

The layer structure of the packaging material 10 of this example is expressed as follows.
Bio PET12/Mark/Anchor/Glued PE(1)15/Al foil 7/Anchor/Extruded PE(2)30

[Example 1M]
A packaging material 10 was produced in the same manner as in Example 1A, except that the above-mentioned polyethylene 2 was used as the first adhesive resin layer 26 and the above-mentioned polyethylene 2 was used as the sealant layer 40.

The layer structure of the packaging material 10 of this example is expressed as follows.
PET12/Mark/Anchor/Glued PE(2)15/Al foil 7/Anchor/Extruded PE(2)30

[Example 1N]
As the first base material film 22 of the base material layer 20, a biomass-derived biaxially stretched PET film is used, as the first adhesive resin layer 26, the above-mentioned polyethylene 2 is used, and as the sealant layer 40, the above-mentioned polyethylene 2 is used. Packaging material 10 was produced in the same manner as in Example 1A except that the following was used.

The layer structure of the packaging material 10 of this example is expressed as follows.
Bio PET12/Mark/Anchor/Glued PE(2)15/Al foil 7/Anchor/Extruded PE(2)30

Note that in Examples 1H to 1N, the sealant layer shown in Example 1G may be used as the sealant layer.

Furthermore, in Examples 1G to 1N, the printing layers shown in Examples 1B to 1F may be used as the printing layer in addition to the printing layer shown in Example 1A.

FIG. 11 shows a summary of the layer configurations of the packaging materials 10 of Examples 1A to 1N.

[Example 2A]
As the first base film 22 of the base layer 20, a biaxially stretched fossil fuel-derived PET film (thickness: 12 μm) was prepared.

Furthermore, as the second base film 32 of the intermediate layer 30, a biaxially stretched fossil fuel-derived PET film (thickness: 12 μm) was prepared. Subsequently, a printing layer 50 was formed on the outer surface of the PET film using an ink containing a biomass-derived component. The printed layer 50, like the printed layer 50 of Example 1A, has a cured product of a polyester polyol containing a polyfunctional alcohol containing a biomass-derived component and a fossil fuel-derived isocyanate compound. Subsequently, the above-mentioned polyethylene 1 (thickness: 15 μm) is extruded as the first adhesive resin layer 26 onto the first base film 22 using an anchor coating agent at a resin temperature of 290° C. using a sand lamination method. , the second base film 32 on which the printed layer 50 was formed was laminated on the first adhesive resin layer 26. Subsequently, the above-mentioned polyethylene 1 (thickness: 35 μm) is anchor-coated as a sealant layer 40 on the surface of the second base film 32 on which the first adhesive resin layer 26 is not laminated by a melt extrusion lamination method. The packaging material 10 was obtained by extrusion through a resin at a resin temperature of 290° C., and a sealant layer 40 was laminated thereon.

The layer structure of the packaging material 10 of this example is expressed as follows.
PET12/Anchor/Contact PE(1)15/Mark/PET12/Anchor/Extruded PE(1)35

Subsequently, using the packaging material 10, a lid portion 94 of a lidded container 90 shown in FIG. 10 was produced.

[Example 2B]
A packaging material 10 was produced in the same manner as in Example 2A, except that polyether polyol was used as the main ingredient of the printing layer 50. Specifically, as the main polyether polyol, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate derived from fossil fuel was used.

[Example 2C]
A packaging material 10 was produced in the same manner as in Example 2A, except that a biaxially stretched PET film containing a biomass-derived component was used as the second base film 32 of the intermediate layer 30.

The layer structure of the packaging material 10 of this example is expressed as follows.
PET12/Anchor/Contact PE(1)15/Mark/Bio PET12/Anchor/Extruded PE(1)35

[Example 2D]
A biaxially stretched PET film containing a biomass-derived component is used as the first base film 22 of the base layer 20, and a biaxially stretched PET film containing a biomass-derived component is used as the second base film 32. Packaging material 10 was produced in the same manner as in Example 2A except for the following.

The layer structure of the packaging material 10 of this example is expressed as follows.
Bio PET12/Anchor/Contact PE(1)15/Mark/Bio PET12/Anchor/Extruded PE(1)35

[Example 2E]
Same as in Example 2A, except that a biaxially stretched PET film containing a biomass-derived component was used as the second base film 32 of the intermediate layer 30, and the above-mentioned polyethylene 2 was used as the sealant layer 40. A packaging material 10 was produced.

The layer structure of the packaging material 10 of this example is expressed as follows.
PET12/Anchor/Contact PE(1)15/Mark/Bio PET12/Anchor/Extruded PE(2)35

[Example 2F]
The procedure was the same as in Example 2A, except that the above-mentioned polyethylene 2 was used as the first adhesive resin layer 26, and a biaxially stretched PET film containing a biomass-derived component was used as the second base film 32. A packaging material 10 was produced.

The layer structure of the packaging material 10 of this example is expressed as follows.
PET12/Anchor/Contact PE(2)15/Mark/Bio PET12/Anchor/Extruded PE(1)35

[Example 2G]
As the first base film 22 of the base layer 20, a biaxially stretched PET film containing a biomass-derived component is used, as the first adhesive resin layer 26, the above-mentioned polyethylene 2 is used, and as the second base film 32. A packaging material 10 was produced in the same manner as in Example 2A, except that a biaxially stretched PET film containing a biomass-derived component was used.

The layer structure of the packaging material 10 of this example is expressed as follows.
Bio PET12/Anchor/Contact PE(2)15/Mark/Bio PET12/Anchor/Extruded PE(1)35

[Example 2H]
A biaxially stretched PET film containing a biomass-derived component is used as the first base film 22 of the base layer 20, and a biaxially stretched PET film containing a biomass-derived component is used as the second base film 32. A packaging material 10 was produced in the same manner as in Example 2A, except that the above-mentioned polyethylene 2 was used as the sealant layer 40.

The layer structure of the packaging material 10 of this example is expressed as follows.
Bio PET12/Anchor/Contact PE(1)15/Mark/Bio PET12/Anchor/Extruded PE(2)35

[Example 2I]
The above-mentioned polyethylene 2 was used as the first adhesive resin layer 26, the biaxially stretched PET film containing a biomass-derived component was used as the second base film 32, and the above-mentioned polyethylene 2 was used as the sealant layer 40. Except for the above, packaging material 10 was produced in the same manner as in Example 2A.

The layer structure of the packaging material 10 of this example is expressed as follows.
PET12/Anchor/Contact PE(2)15/Mark/Bio PET12/Anchor/Extruded PE(2)35

[Example 2J]
As the first base film 22 of the base layer 20, a biaxially stretched PET film containing a biomass-derived component is used, as the first adhesive resin layer 26, the above-mentioned polyethylene 2 is used, and as the second base film 32. A packaging material 10 was produced in the same manner as in Example 2A, except that a biaxially stretched PET film containing a biomass-derived component was used and the above-mentioned polyethylene 2 was used as the sealant layer 40.

The layer structure of the packaging material 10 of this example is expressed as follows.
Bio PET12/Anchor/Contact PE(2)15/Mark/Bio PET12/Anchor/Extruded PE(2)35

Furthermore, in Examples 2C to 2J, the printing layers shown in Examples 1B to 1F may be used in addition to the printing layer shown in Example 1A.

FIG. 12 shows a summary of the layer configurations of the packaging materials 10 of Examples 2A to 2J.

[Example 3A]
As the first base film 22 of the base layer 20, a biaxially stretched polypropylene film derived from fossil fuel was prepared. Although the thickness of the polypropylene film can be selected within the range of 18 μm or more and 40 μm or less, it was set to 18 μm here. Subsequently, a printing layer 50 was formed on the inner surface of the polypropylene film using an ink containing a biomass-derived component. The printed layer 50, like the printed layer 50 of Example 1A, has a cured product of a polyester polyol containing a polyfunctional alcohol containing a biomass-derived component and a fossil fuel-derived isocyanate compound.

Further, as the second base film 32 of the intermediate layer 30, a biaxially stretched PET film derived from fossil fuel and provided with a metal vapor deposition layer 60 was prepared. The thickness of the PET film provided with the metal vapor deposition layer 60 can be 9 μm or 12 μm, but here it was 12 μm. Subsequently, the above-mentioned polyethylene 1 is applied as the first adhesive resin layer 26 onto the printed layer 50 formed on the first base film 22 using an anchor coating agent at a resin temperature of 290°C. The second base film 32 on which the vapor deposited layer 60 was formed was laminated on the first adhesive resin layer 26 . The thickness of the polyethylene 1 can be selected within the range of 5 μm or more and 20 μm or less, but here it was set to 10 μm.

Furthermore, as the sealant film 42 of the sealant layer 40, an unstretched polypropylene film derived from fossil fuels was prepared. Although the thickness of the polypropylene film can be selected within the range of 18 μm or more and 30 μm or less, it was set to 18 μm here. Subsequently, the above-mentioned polyethylene 1 and a polypropylene film as the sealant film 42 are applied to the surface of the second base film 32 on which the first adhesive resin layer 26 is not laminated using a melt coextrusion lamination method. The second adhesive resin layer 44 and the sealant film 42 are extruded through an anchor coating agent at a resin temperature of 320° C. on the second base film 32 in this order from the second base film 32 side. The packaging material 10 was obtained by laminating the layers. The thickness of the polyethylene 1 used as the second adhesive resin layer 44 can be selected within the range of 5 μm or more and 20 μm or less, but here it was set to 10 μm.

The layer structure of the packaging material 10 of this example is expressed as follows.
OPP18/Mark/Anchor/Connected PE(1)10/VMPET12/Anchor/Connected PE(1)10/CPP18
"OPP" means fossil fuel derived biaxially oriented polypropylene film. "VMPET" means a fossil fuel-derived biaxially oriented PET film provided with a vapor deposited layer of metal. "CPP" means unstretched polypropylene film derived from fossil fuels.

Subsequently, a pillow pouch-type packaging bag 70 shown in FIG. 8 was produced using the packaging material 10.

[Example 3B]
A packaging material 10 was produced in the same manner as in Example 3A, except that polyether polyol was used as the main ingredient of the printing layer 50. Specifically, as the main polyether polyol, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate derived from fossil fuel was used.

[Example 3C]
A packaging material 10 was produced in the same manner as in Example 3A, except that ethylene-methacrylic acid copolymer (EMAA) was used as the first adhesive resin layer 26.

The layer structure of the packaging material 10 of this example is expressed as follows.
OPP18/mark/anchor/connection (EMAA)10/VMPET12/anchor/connection PE(1)10/CPP18
"EMAA" means an adhesive resin layer containing ethylene-methacrylic acid copolymer (EMAA).

[Example 3D]
A packaging material 10 was produced in the same manner as in Example 3A, except that ethylene-methacrylic acid copolymer (EMAA) was used as the second adhesive resin layer 44.

The layer structure of the packaging material 10 of this example is expressed as follows.
OPP18/mark/anchor/connection PE(1)10/VMPET12/anchor/connection(EMAA)10/CPP18

[Example 3E]
Same as in Example 3A except that ethylene-methacrylic acid copolymer (EMAA) was used as the first adhesive resin layer 26 and ethylene-methacrylic acid copolymer (EMAA) was used as the second adhesive resin layer 44. Packaging material 10 was produced in the same manner.

The layer structure of the packaging material 10 of this example is expressed as follows.
OPP18/mark/anchor/connection (EMAA)10/VMPET12/anchor/connection (EMAA)10/CPP18

[Example 3F]
A packaging material 10 was produced in the same manner as in Example 3A, except that a biaxially stretched PET film containing a biomass-derived component was used as the second base film 32 of the intermediate layer 30.

The layer structure of the packaging material 10 of this example is expressed as follows.
OPP18/Mark/Anchor/Connected PE(1)10/VM Bio PET12/Anchor/Connected PE(1)10/CPP18
"VM BioPET" means a biomass-derived biaxially oriented PET film provided with a vapor-deposited layer of metal.

[Example 3G]
A packaging material 10 was produced in the same manner as in Example 3A, except that the above-mentioned polyethylene 2 was used as the second adhesive resin layer 44.

The layer structure of the packaging material 10 of this example is expressed as follows.
OPP18/Mark/Anchor/Connected PE(1)10/VMPET12/Anchor/Connected PE(2)10/CPP18

[Example 3H]
Example 3A except that a biaxially stretched PET film containing a biomass-derived component was used as the second base film 32 of the intermediate layer 30, and the above-mentioned polyethylene 2 was used as the second adhesive resin layer 44. Packaging material 10 was produced in the same manner.

The layer structure of the packaging material 10 of this example is expressed as follows.
OPP18/Mark/Anchor/Connected PE(1)10/VM Bio PET12/Anchor/Connected PE(2)10/CPP18

[Example 3I]
A packaging material 10 was produced in the same manner as in Example 3A, except that the above-mentioned polyethylene 2 was used as the first adhesive resin layer 26 and the above-mentioned polyethylene 2 was used as the second adhesive resin layer 44.

The layer structure of the packaging material 10 of this example is expressed as follows.
OPP18/Mark/Anchor/Connected PE(2)10/VMPET12/Anchor/Connected PE(2)10/CPP18

[Example 3J]
The above-mentioned polyethylene 2 is used as the first adhesive resin layer 26, the biaxially stretched PET film containing a biomass-derived component is used as the second base film 32, and the above-mentioned polyethylene 2 is used as the second adhesive resin layer 44. Packaging material 10 was produced in the same manner as in Example 3A, except that it was used.

The layer structure of the packaging material 10 of this example is expressed as follows.
OPP18/Mark/Anchor/Connected PE(2)10/VM Bio PET12/Anchor/Connected PE(2)10/CPP18

Note that variations similar to those of Examples 1B to 1N and Examples 2B to 2J may be adopted in this example as well. For example, in addition to the printing layer shown in Example 1A, the printing layers shown in Examples 1B to 1F may be used as the printing layer.

FIG. 13 shows a summary of the layer configurations of the packaging materials 10 of Examples 3A to 3J.

[Example 4A]
In the same manner as in Examples 3A to 3J, the first base film 22, the printed layer 50, the first anchor coat layer 28, the first adhesive resin layer 26, the metal foil 34, the second anchor coat layer 46, the second A packaging material 10 was produced in which an adhesive resin layer 44 and a sealant film 42 were laminated in this order. As the first base film 22, a biaxially stretched PET film (thickness: 12 μm) derived from fossil fuels was used. As the metal foil 34, aluminum foil was used. The thickness of the aluminum foil can be 6 μm, 7 μm, or 9 μm, but here it was 6 μm. Further, as the sealant film 42, a polyethylene film 1 produced as described below was used. First, 90 parts by mass of fossil fuel-derived linear low-density polyethylene (density: 0.918 g/cm ³ , MFR: 3.8 g/10 min, biomass degree: 0%) and fossil fuel-derived low-density polyethylene ( Density: 0.924 g/cm ³ , MFR: 2.0 g/10 min, biomass degree: 0%) and 10 parts by mass were melt-kneaded to obtain a resin composition. Next, the obtained resin composition was formed into a film using a top-blown air-cooled inflation coextrusion film-forming machine to obtain a single-layer polyethylene film 1 (biomass content: 0%) for the sealant layer. Although the thickness of the polyethylene film 1 can be selected within the range of 20 μm or more and 70 μm or less, it was set to 30 μm here. As the first adhesive resin layer 26 and the second adhesive resin layer 44, the above-mentioned polyethylene 1 was used. The thickness of the polyethylene 1 used for the first adhesive resin layer 26 can be selected within the range of 10 μm or more and 30 μm or less, but here it was set to 13 μm. Further, the thickness of the polyethylene 1 used for the second adhesive resin layer 44 can be selected within the range of 20 μm or more and 40 μm or less, but here it was set to 13 μm. As the printing layer 50, the same one as in Example 3A was used.

Subsequently, a small packaging bag 70, also called a stick pouch, shown in FIG. 9 was produced using the packaging material 10.

The layer structure of the packaging material 10 of this example is expressed as follows.
PET12/mark/anchor/bonded PE(1)13/Al foil 6/anchor/bonded PE(1)13/PE(1)30
"PE(1)" means the above-mentioned polyethylene film 1.

[Example 4B]
Packaging material 10 was produced in the same manner as in Example 4A, except that polyether polyol was used as the main ingredient of printing layer 50. Specifically, as the main polyether polyol, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate derived from fossil fuel was used.

[Example 4C]
Packaging material 10 was produced in the same manner as in Example 4A, except that polyethylene film 2 produced as described below was used as sealant film 42 of sealant layer 40.
A method for producing polyethylene film 2 will be explained. First, 60 parts by mass of fossil fuel-derived linear low-density polyethylene (density: 0.918 g/cm3, MFR: 3.8 g/10 min, biomass degree: 0%) and fossil fuel-derived low-density polyethylene (density : 0.924 g/cm3, MFR: 2.0 g/10 min, biomass degree: 0%) 20 parts by mass, and biomass-derived linear low-density polyethylene (LLDPE, manufactured by Braskem, product name: SLL118, density: 0.916 g/cm3, MFR: 1.0 g/10 min, biomass degree 87%) and 20 parts by mass were melt-kneaded to obtain a resin composition. Next, the obtained resin composition was formed into a film using a top-blown air-cooled inflation coextrusion film-forming machine to obtain a single-layer polyethylene film 2 (biomass content: 16%) for the sealant layer. The thickness of the polyethylene film 2 was 30 μm as in the case of the polyethylene film 1 of Example 4A.

The layer structure of the packaging material 10 of this example is expressed as follows.
PET12/mark/anchor/bonded PE(1)13/Al foil 6/anchor/bonded PE(1)13/PE(2)30
"PE(2)" means the above-mentioned polyethylene film 2.

[Example 4D]
Example 4A except that a biomass-derived biaxially stretched PET film was used as the first base film 22 of the base layer 20, and the above-mentioned polyethylene 2 was used as the second adhesive resin layer 44. Packaging material 10 was produced in the same manner.

The layer structure of the packaging material 10 of this example is expressed as follows.
Bio PET12/mark/anchor/bonded PE(1)13/Al foil 6/anchor/bonded PE(2)13/PE(1)30

[Example 4E]
As the first base film 22 of the base material layer 20, a biomass-derived biaxially stretched PET film is used, as the second adhesive resin layer 44, the above-mentioned polyethylene 2 is used, and as the sealant film 42 of the sealant layer 40, Packaging material 10 was produced in the same manner as in Example 4A, except that the above-mentioned polyethylene film 2 was used.

The layer structure of the packaging material 10 of this example is expressed as follows.
Bio PET12/Mark/Anchor/Glued PE(1)13/Al foil 6/Anchor/Glued PE(2)13/PE(2)30

[Example 4F]
As the first base material film 22 of the base material layer 20, a biomass-derived biaxially stretched PET film is used, as the first adhesive resin layer 26, the above-mentioned polyethylene 2 is used, and as the second adhesive resin layer 44, the above-mentioned polyethylene 2 is used. Packaging material 10 was produced in the same manner as in Example 4A, except that polyethylene 2 was used.

The layer structure of the packaging material 10 of this example is expressed as follows.
Bio PET12/mark/anchor/bonded PE(2)13/Al foil 6/anchor/bonded PE(2)13/PE(1)30

[Example 4G]
As the first base material film 22 of the base material layer 20, a biomass-derived biaxially stretched PET film is used, as the first adhesive resin layer 26, the above-mentioned polyethylene 2 is used, and as the second adhesive resin layer 44, the above-mentioned polyethylene 2 is used. A packaging material 10 was produced in the same manner as in Example 4A, except that the polyethylene film 2 described above was used as the sealant film 42 of the sealant layer 40.

The layer structure of the packaging material 10 of this example is expressed as follows.
Bio PET12/mark/anchor/bonded PE(2)13/Al foil 6/anchor/bonded PE(2)13/PE(2)30

Note that variations similar to those of Examples 1B to 1N, Examples 2B to 2J, and Examples 3B to 3J may also be adopted in this example. For example, in addition to the printing layer shown in Example 1A, the printing layers shown in Examples 1B to 1F may be used as the printing layer.

FIG. 14 shows examples of layer configurations of the packaging materials 10 of Examples 4A to 4G.

[Example 5A]
In the same manner as in Examples 1A to 1N, the first base film 22, the printing layer 50, the first anchor coat layer 28, the first adhesive resin layer 26, the metal foil 34, the second anchor coat layer 46, and the sealant layer were prepared. A packaging material 10 in which 40 layers were laminated in order was produced. As the first base film 22, a biaxially stretched nylon film (thickness: 15 μm) derived from fossil fuels was used. As the metal foil 34, aluminum foil was used. The thickness of the aluminum foil can be 6 μm, 7 μm, or 9 μm, but here it was 6 μm. As the printing layer 50, the first adhesive resin layer 26, and the sealant layer 40, the same ones as in Example 1A were used. The thickness of the polyethylene 1 used for the first adhesive resin layer 26 can be selected within the range of 10 μm or more and 30 μm or less, but here it was set to 15 μm. The thickness of the polyethylene 1 used for the sealant layer 40 can be selected within the range of 20 μm or more and 50 μm or less, but here it was set to 40 μm.

Subsequently, a four-sided sealed packaging bag 70 shown in FIG. 7 was produced using the packaging material 10.

The layer structure of the packaging material 10 of this example is expressed as follows.
ONY15/Mark/Anchor/Glued PE(1)15/Al foil 6/Anchor/Extruded PE(1)40
"ONY" means biaxially oriented nylon film derived from fossil fuels.

[Example 5B]
A packaging material 10 was produced in the same manner as in Example 5A, except that polyether polyol was used as the main ingredient of the printing layer 50. Specifically, as the main polyether polyol, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate derived from fossil fuel was used.

[Example 5C]
Packaging material 10 was produced in the same manner as in Example 5A, except that ethylene-methacrylic acid copolymer (EMAA) was used as sealant layer 40.

The layer structure of the packaging material 10 of this example is expressed as follows.
ONY15/mark/anchor/contact PE(1)15/Al foil 6/anchor/extrusion EMAA40

Note that variations similar to those of Examples 1B to 1N, Examples 2B to 2J, and Examples 3B to 3J may also be adopted in this example. For example, in addition to the printing layer shown in Example 1A, the printing layers shown in Examples 1B to 1F may be used as the printing layer.

FIG. 15 shows examples of layer configurations of the packaging materials 10 of Examples 5A to 5C.

Further, FIG. 16 collectively shows examples of the types of packaging containers of Examples 1A to 1N, 2A to 2J, 3A to 3J, 4A to 4G, and 5A to 5C.

(Other aspects)
Another aspect of the present invention is a packaging material including at least a base layer, a printed layer, an adhesive resin layer, an intermediate layer, and a sealant layer, wherein the adhesive resin layer is in contact with the intermediate layer, and the printed The layer is a packaging material that includes a colorant and a cured product of a polyol and an isocyanate compound, and at least either the polyol or the isocyanate compound includes a biomass-derived component.

In the packaging material according to another aspect of the present invention, the polyol of the printing layer may be a polyester polyol of a reaction product of a polyfunctional alcohol and a polyfunctional carboxylic acid.

In the packaging material according to another aspect of the present invention, at least either the polyfunctional alcohol or the polyfunctional carboxylic acid of the printing layer may contain a biomass-derived component.

In the packaging material according to another aspect of the present invention, the polyol of the printing layer may be a polyether polyol, which is a reaction product of a polyfunctional alcohol and a polyfunctional isocyanate.

In the packaging material according to another aspect of the present invention, at least either the polyfunctional alcohol or the polyfunctional isocyanate of the printing layer may contain a biomass-derived component.

In the packaging material according to another aspect of the present invention, the isocyanate compound of the printing layer may contain a biomass-derived component.

In a packaging material according to another aspect of the invention, the base layer may have a first base film comprising polyester, polyamide or polyolefin.

In the packaging material according to another aspect of the present invention, the first base film may include a biomass polyester having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

In the packaging material according to another aspect of the present invention, the intermediate layer may include at least one of a second base film containing polyester as a main component or a metal foil.

In the packaging material according to another aspect of the present invention, the intermediate layer has the second base film, and the second base film has biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid. It may contain a biomass polyester having dicarboxylic acid units.

In a packaging material according to another aspect of the invention, the sealant layer may include a polyolefin, which is a polymer of monomers containing olefins.

In a packaging material according to another aspect of the present invention, the sealant layer may include a biomass polyolefin, which is a polymer of monomers containing biomass-derived ethylene.

Another aspect of the invention is a packaging product comprising the packaging material described above.

Another aspect of the present invention is a packaging material including at least a base layer, a printed layer, an adhesive resin layer, an intermediate layer, and a sealant layer, wherein the adhesive resin layer is in contact with the intermediate layer, and the printed The layer includes a colorant and a cured product of a polyol and an isocyanate compound, at least either the polyol or the isocyanate compound includes a biomass-derived component, and the polyol of the printed layer includes a polyfunctional alcohol and a polyfunctional The polyester polyol is a reaction product with a carboxylic acid, one of the polyfunctional alcohol and the polyfunctional carboxylic acid of the printing layer contains a biomass-derived component, and the other is derived from a fossil fuel, and the base layer is made of polypropylene. It is a packaging material having a first base film comprising: the intermediate layer having a vapor-deposited layer.

In the packaging material according to another aspect of the present invention, the intermediate layer may have a second base film containing polyester as a main component.

In the packaging material according to another aspect of the present invention, the second base film may include a biomass polyester having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

In the packaging material according to another aspect of the present invention, the isocyanate compound of the printing layer may contain a biomass-derived component.

In a packaging material according to another aspect of the invention, the sealant layer may include a polyolefin, which is a polymer of monomers containing olefins.

In a packaging material according to another aspect of the invention, the sealant layer may include a biomass polyolefin.

Another aspect of the invention is a packaging product comprising the packaging material described above.

10 Packaging material 20 Base material layer 22 First base film 24 Print layer 26 First adhesive resin layer 28 First anchor coat layer 30 Intermediate layer 32 Second base film 34 Metal foil 40 Sealant layer 42 Sealant film 44 Second adhesive Resin layer 46 Second anchor coat layer 50 Print layer 60 Vapor deposition layer

Claims (5)

A packaging material comprising at least a base layer, a printed layer, an adhesive resin layer, an intermediate layer, and a sealant layer,
The adhesive resin layer is in contact with the intermediate layer,
The printing layer includes a colorant and a cured product of a polyol and an isocyanate compound, and at least either the polyol or the isocyanate compound includes a biomass-derived component,
The polyol of the printing layer is a polyester polyol of a reaction product of a polyfunctional alcohol and a polyfunctional carboxylic acid,
One of the polyfunctional alcohol and the polyfunctional carboxylic acid of the printing layer contains a biomass-derived component, and the other is derived from fossil fuel,
The base layer has a first base film containing polypropylene,
The intermediate layer has a vapor deposited layer,
The sealant layer is a packaging material containing biomass-derived low-density polyethylene. The packaging material according to claim 1, wherein the intermediate layer has a second base film containing polyester as a main component. The packaging material according to claim 2, wherein the second base film includes a biomass polyester having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. The packaging material according to any one of claims 1 to 3, wherein the isocyanate compound of the printing layer contains a biomass-derived component. A packaging product comprising the packaging material according to any one of claims 1 to 4.

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