JP7322982B2 - Packaging materials and packaging products - Google Patents

Description

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

BACKGROUND ART Conventionally, various packaging materials have been developed and proposed as packaging materials for constituting packaging products for filling and packaging various articles such as food and drink, pharmaceuticals, chemicals, cosmetics, sanitary goods, daily necessities, and the like. The packaging material is composed of a laminate obtained by laminating at least a substrate layer containing a stretched plastic or the like and a sealant layer for welding the packaging materials together. 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, along with the increasing demand for building a recycling-oriented society, the use of biomass has attracted attention in the field of laminates that make up packaging materials, as well as in the field of energy. there is Biomass is an organic compound that is photosynthesised from carbon dioxide and water, and is a so-called carbon-neutral renewable energy that is regenerated into carbon dioxide and water by using it. In recent years, biomass plastics using biomass as raw materials have been rapidly put to practical use, and attempts have been made to produce various resins from biomass raw materials.

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

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

Moreover, polyesters are widely used in various industrial applications because they are excellent in mechanical properties, chemical stability, heat resistance, transparency, etc., and are inexpensive. Polyester is obtained by polycondensation of 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. It is produced by a polycondensation reaction after 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.

Attempts have recently been made to produce polyester from biomass raw materials. For example, ethylene glycol, which is a monomer component, has been put into practical use using biomass-derived ethylene glycol. It has been proposed to apply polyester resins containing such biomass-derived raw materials to packaging materials (see Patent Document 2).

Japanese Patent Publication No. 2011-506628 JP 2012-96410 A

In conventional packaging materials, the printed layer of the laminate is formed of a fossil fuel-derived material, which has been a cause of lowering the biomass content of the entire packaging material. Therefore, in a packaging material composed of a laminate including a substrate layer, a printing layer, an adhesive resin layer, and a sealant layer, it is desired to further increase the biomass content of the entire packaging material.

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

The present invention provides a packaging material comprising at least a substrate 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, wherein at least one of the polyol and the isocyanate compound contains a biomass-derived component, and the polyol of the printing layer is a mixture 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, the other is derived from a fossil fuel, and the base layer comprises polypropylene. A packaging material having a substrate film and the intermediate layer having a vapor deposition layer.

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 contain a biomass polyester having a biomass-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

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

In the packaging material according to the present invention, the sealant layer may contain polyolefin, which is a polymer of olefin-containing monomers.

In the packaging material according to the present invention, the sealant layer may contain biomass polyolefin.

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

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

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows an example of the packaging material by this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows an example of the packaging material by this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows an example of the packaging material by this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows an example of the packaging material by this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows an example of the packaging material by this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows an example of the packaging material by this invention. It is a model front view which shows an example of the packaging product by this invention. It is a model front view which shows an example of the packaging product by this invention. It is a model front view which shows an example of the packaging product by this invention. It is a model front view which shows an example of the packaging product by this invention. FIG. 2 shows the layer structure of the packaging materials of Examples 1A-1N. FIG. 4 shows the layer structure of the packaging materials of Examples 2A-2J. FIG. 3 shows the layer structure of the packaging materials of Examples 3A-3J. FIG. 4 shows the layer structure of the packaging materials of Examples 4A-4G. FIG. 5 shows the layer structure of the packaging materials of Examples 5A-5C. Figures 1A-1N, 2A-2J, 3A-3J, 4A-4G and 5A-5C show examples of types of packaging containers;

<Packaging material>
A laminate constituting a packaging material according to the present invention 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. For example, a first adhesive resin layer, which will be described later, is in contact with the intermediate layer from the substrate layer side. 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 printed layer from a material containing a biomass-derived component, it is possible to reduce the amount of fossil fuels used and reduce the environmental load compared to conventional methods. In the present application, "in contact with the intermediate layer" is a concept including the case where a layer other than the base film and the metal foil, such as a printed layer, is present between the intermediate layer and the adhesive resin layer.

In the present invention, the biomass degree 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 still more preferably 10% or more and 60% or less. . If the degree of biomass is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

The 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, still more preferably 30 μm or more and 200 μm or less.

In addition to the above layers, the packaging material of the present invention may further have at least one barrier layer such as a metal foil, a vapor deposition layer, or a gas barrier coating film, or another layer such as a resin layer. When two or more other layers are provided, they may have the same composition or may have different compositions.

A laminate constituting the packaging material according to the present invention will be described with reference to the drawings. Examples of schematic cross-sectional views of packaging material 10 according to the present invention are shown in FIGS. 1 to 6, reference numeral 10y represents the outer surface of the packaging material 10 and reference numeral 10x represents the inner surface of the packaging material 10. In FIGS. The inner surface 10x is a surface of a packaged product such as a bag formed from the packaging material 10, which faces the contents contained in the packaged product. 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 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 substrate layer 20, a printed 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 sealant layer 40 is provided 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 substrate layer 20, a first anchor coat layer 28, a first adhesive resin layer 26, a printed layer 50, an intermediate layer 30, a second anchor coat layer 46, A sealant layer 40 is provided 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 substrate layer 20, a printed 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 deposited 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 and the deposition layer 60 of the intermediate layer 30 of the packaging material 10 shown in FIG. Specifically, the packaging material 10 in FIG. 4 includes a substrate layer 20, a printed 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 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 vapor deposition layer 60 of the intermediate layer 30 of the packaging material 10 shown in FIGS. Specifically, the packaging material 10 of FIG. 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 differs from the packaging material 10 shown in FIG. 5 in the configuration of the sealant layer 40 . Specifically, the packaging material 10 shown in FIG. 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 .

In addition, it is also possible to appropriately combine a 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 described below.

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

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

The biomass polyester has biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. In addition to the biomass polyester, the base material layer may further contain a fossil fuel-derived polyester having a fossil fuel-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. It suffices if the base material layer as a whole can achieve the following biomass degree. In the present invention, since the substrate layer contains biomass polyester, the amount of fossil fuel-derived polyester can be reduced compared with the conventional method, and the environmental load can be reduced.

In the present invention, the “biomass degree” may be indicated by a value obtained by measuring the content of biomass-derived carbon by radioactive carbon (C14) measurement, or may be indicated by a weight ratio of biomass-derived components.

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

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

Further, when the "biomass degree" is represented by the weight ratio of biomass-derived components, the "biomass degree" can be obtained as follows. Taking polyethylene terephthalate as an example, as mentioned above, polyethylene terephthalate is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms at a molar ratio of 1:1. When only biomass-derived glycol is used, the weight ratio of the biomass-derived component in the polyester is approximately 30%, and thus the degree of biomass is approximately 30%. In addition, the weight ratio of the biomass-derived component in the fossil fuel-derived polyester produced using fossil fuel-derived ethylene glycol and fossil fuel-derived dicarboxylic acid is 0%, and the biomass degree of the fossil fuel-derived polyester is 0%. Hereinafter, unless otherwise specified, the “biomass degree” indicates 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, more preferably 15% or more and 25%. % 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 case, and the environmental load can be reduced.

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

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

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

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

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

A resin composition of biomass polyester or a resin composition containing biomass polyester and fossil fuel-derived polyester can be used to form a film by, for example, a T-die method to form the first base film 22. 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 a sheet from a die such as a T-die and rapidly cooling and solidifying the extruded sheet with a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose.

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 polyethylene terephthalate film or polybutylene terephthalate, or a polyolefin film such as polyethylene film or polypropylene film. A film, a polyamide film such as a nylon film or a nylon 6/meta-xylylenediamine nylon 6 coextruded and costretched film, or a polypropylene/ethylene-vinyl alcohol copolymer coextruded and costretched film, or a laminate of two or more of these films. Plastic films such as composite films can be used. 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 by roll heating, infrared heating, or the like, and stretching it in the longitudinal direction. This stretching is preferably carried out using a difference in peripheral speed between two or more rolls. Longitudinal stretching is usually performed in 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 properties required for the film application. If the draw ratio is less than 2.5 times, the thickness unevenness of the film becomes large, making it difficult to obtain a good film.

The longitudinally stretched film is then successively subjected to transverse stretching, heat setting, and heat relaxation steps to obtain a biaxially stretched film. Lateral stretching is usually performed in a temperature range of 50°C or higher and 100°C or lower. The lateral stretching ratio is preferably 2.5 times or more and 5.0 times or less, although it depends on the properties required for the application. If it is less than 2.5 times, the thickness of the film becomes uneven, making it difficult to obtain a good film.

The film 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 and 5 kg/mm ² or more and 35 kg/mm ² or less in the TD direction. 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. Also, 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-extruded 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 . Like the first base film 22, the second base film 32 may or may not contain a biomass-derived component.

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

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

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

As the deposition layer 60, for example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), and other inorganic substances or inorganic oxide deposited films 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 positioned closer to the outer surface 10 y than the printed layer 50 , a transparent vapor deposition film of inorganic oxide is used as the vapor deposition layer 60 .

Inorganic oxides are represented by MO _X such as SiO _X and AlO _X (wherein M represents an inorganic element, and the value of X varies depending on the inorganic element). expressed. The range of values 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 range from 0 to 2, lead (Pb) from 0 to 1, zirconium (Zr) from 0 to 2, and yttrium (Y) from 0 to 1.5. In the above, when X=0, it is a completely inorganic substance (pure substance) and not transparent, and the upper limit of the range of X is the fully oxidized value. As the vapor deposition layer 60 of the packaging material 10, silicon (Si) and aluminum (Al) are preferably used. Silicon (Si) is 1.0 to 2.0, aluminum (Al) is 0.5 to 1 Values in the range of 0.5 can be used.

The film thickness of the vapor-deposited film of the inorganic substance or inorganic oxide as described above varies depending on the type of inorganic substance or inorganic oxide used. It is desirable to select and form them 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. 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 forming method. As a method for forming the deposited layer 60, for example, a physical vapor deposition method (physical vapor deposition method, PVD method) such as a vacuum deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, a thermal A chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a chemical vapor deposition method and a photochemical vapor deposition method can be used.

(Gas barrier coating film)
The gas barrier coating film is a film provided on the deposition layer 60 as required. The gas barrier coating film functions as a layer that suppresses permeation of oxygen gas and water vapor. The gas barrier coating film has the 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, 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 at least one or more alkoxides represented by the above polyvinyl alcohol-based It contains a resin and/or an ethylene-vinyl alcohol copolymer, and is obtained by polycondensation by a sol-gel method in the presence of a sol-gel catalyst, acid, water and an organic solvent.

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

In the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , the metal atom represented by M can be silicon, zirconium, titanium, aluminum, or the like. In this embodiment, preferred metals include, for example, silicon and titanium. In the present invention, alkoxides can be used either singly or as a mixture of alkoxides of two or more different metal atoms in the same solution.

Further, in the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , specific examples of the organic group represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, i -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group, and the like. Further, in the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , specific examples of the organic group represented by R ² include a methyl group, an ethyl group, an n-propyl group, i -propyl group, n-butyl group, sec-butyl group, and the like. These alkyl groups may be the same or different in the same molecule.

For example, a silane coupling agent may be added when preparing the gas barrier composition. Known organic reactive group-containing organoalkoxysilanes can be used as the silane coupling agent. In this embodiment, an organoalkoxysilane having an epoxy group is particularly preferably used. Specifically, examples include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or , β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like can be used. The above silane coupling agents may be used singly or in combination of two or more.

(Print layer)
The printed layer 50 is a layer formed by printing for decoration, display of contents, display of best-before date, display of manufacturer, seller, etc., and addition of aesthetics. The print layer 50 includes a pattern layer that forms any desired pattern such as pictures, photographs, characters, numbers, graphics, symbols, and patterns. The printed layer may further include a ground color layer formed by printing so as to make the pattern of the pattern layer stand out. The print layer 50 contains a coloring agent and a cured product of a polyol and an isocyanate compound. The print layer 50 contains a biomass-derived component. Specifically, the printed layer 50 can be formed using a cured product in which at least one of a polyol as a main agent and an isocyanate compound as a curing agent contains a biomass-derived component. As the polyol, a polyester polyol which is a reaction product of a polyfunctional alcohol and a polyfunctional carboxylic acid, or a polyether polyol which 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. Examples of polyester polyols containing biomass-derived components include the following.
・Reaction product of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Reaction product of fossil fuel-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Biomass-derived polyfunctional alcohol and fossil fuel-derived reactant with polyfunctional carboxylic acid

As biomass-derived polyfunctional alcohols, 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 obtained from plant materials by the following methods. There are glycol (BG), hexamethylene glycol, etc., and any of them can be used. These may be used alone or in combination.

Biomass-derived polypropylene glycol is produced from glycerol via 3-hydroxypropylaldehyde (HPA) by a fermentation process in which the plant material is degraded to yield glucose. Compared with polypropylene glycol produced by the EO production method, polypropylene glycol produced by a bio-method such as the fermentation method yields useful by-products such as lactic acid from the standpoint of safety, and the production cost can be kept low. It is also preferred that it is possible.
Biomass-derived butylene glycol can be produced by producing succinic acid obtained by producing and fermenting glycol from a plant raw material, and then hydrogenating the succinic acid.
Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

As polyfunctional alcohols derived from fossil fuels, compounds having 2 or more, preferably 2 to 8 hydroxyl groups in one molecule can be used. Specifically, polyfunctional alcohols derived from fossil fuels are not particularly limited and conventionally known substances can be used, for example, polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG) , diethylene glycol (DEG), butylene glycol (BG), hexamethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, 1,9-nonanediol, 3-methyl -1,5-Pentanediol, polyether polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, and the like can be used. These may be used alone or in combination of two or more.

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

Aliphatic polyfunctional carboxylic acids and aromatic polyfunctional carboxylic acids can be used as polyfunctional carboxylic acids derived from fossil fuels. Aliphatic polyfunctional carboxylic acids derived from fossil fuels are not particularly limited and conventionally known substances can be used. For example, adipic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride acid, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, dimer acid, and ester compounds thereof; In addition, the aromatic polyfunctional carboxylic acid derived from fossil fuels is not particularly limited and conventionally known substances can be used. Examples include isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid, and their ester compounds and the like can be used. These may be used alone or in combination of two or more.

[Polyether polyol]
When the polyether polyol contains a biomass-derived component, at least one of the polyfunctional alcohol and the polyfunctional isocyanate contains the biomass-derived component. Examples of polyether polyols containing biomass-derived components include the following.
・Reaction products of biomass-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates ・Reaction products of fossil fuel-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates ・Biomass-derived polyfunctional alcohols and fossil fuel-derived polyfunctional Reactants with functional isocyanates

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

As a biomass-derived polyfunctional isocyanate, a plant-derived divalent carboxylic acid is acid-amidated, converted to a terminal amino group by reduction, and further reacted with phosgene to convert the amino group to an isocyanate group. What is obtained can be used. The biomass-derived polyfunctional isocyanate is, for example, a biomass-derived diisocyanate. Biomass-derived diisocyanates include dimer acid diisocyanate (DDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like. A plant-derived diisocyanate can also be obtained by using a plant-derived amino acid as a raw material and converting the amino group into an isocyanate group. For example, lysine diisocyanate (LDI) is obtained by methyl-esterifying the carboxyl group of lysine and then converting the amino group into an isocyanate group. Also, 1,5-pentamethylene diisocyanate can be obtained by decarboxylating the carboxyl group of lysine and then converting the amino group to an isocyanate group.

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

The polyfunctional isocyanate derived from fossil fuels is not particularly limited, and conventionally known substances can be used. 1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanatodiphenyl ether, 4,4′-methylenebis(phenylene isocyanate) (MDI), Aromatic diisocyanates such as dulylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4′-diisocyanate dibenzyl, and the like. In addition, aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate) ), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, hydrogenated XDI and other alicyclic diisocyanates. These may be used alone or in combination of two or more.

[Coloring agent]
The coloring agent 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 preferably has a biomass degree of 5% or more, more preferably 5% or more and 50% or less, and still more preferably 10% or more and 50% or less. If the degree of biomass is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

The weight of the printed layer 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 still more preferably 1 g/m 2 or more and 3 g/m 2 or ^more . ² or less.

The print 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 still more preferably 1 μm or more and 3 μm or less.

[Adhesive resin layer]
The adhesive resin layer is a layer provided when any two layers are adhered, and can be provided, for example, between the base layer and the intermediate layer or between the intermediate layer and the sealant layer.

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

When the adhesive resin layer is laminated by the melt extrusion lamination method, 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 be provided. The anchor coating agent includes any resin having a heat resistance temperature of 135° C. or higher, such as an anchor coating agent made of vinyl-modified resin, epoxy resin, urethane resin, polyester resin, polyethyleneimine, etc. Especially, An anchor coating agent which is a cured product of a polyacrylic or polymethacrylic resin (polyol) having two or more hydroxyl groups and an isocyanate compound as a curing agent can be preferably used. In addition, a silane coupling agent may be used together as an additive, and nitrocellulose may be used together to improve heat resistance.

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

(sealant layer)
Sealant layer 40 constitutes inner surface 10 x of packaging material 10 . The sealant layer 40 may contain a biomass-derived component or may not contain a biomass-derived component. When the sealant layer 40 is formed from a material containing a biomass-derived component, the sealant layer 40 can be formed using the following biomass polyolefin. Moreover, when the sealant layer 40 is formed of 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 polyolefins are polymers of monomers containing olefins such as ethylene derived from biomass. Since biomass-derived olefins are used as raw material monomers, the polymerized polyolefins are biomass-derived. Note that the polyolefin raw material monomer does not have to contain 100% by mass of biomass-derived olefin.

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

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

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

Although the number of carbon atoms of the α-olefin is not particularly limited, those having 3 to 20 carbon atoms can usually be used, and preferably butylene, hexene, or octene. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a raw material derived from biomass. In addition, by containing such an α-olefin, the polymerized polyolefin has alkyl groups as a branched structure, so that it can be made more flexible than a simple straight-chain polyolefin.

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

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

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

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

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

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

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

The sealant layer 40 may be a single layer or multiple layers. When biomass polyolefin as described above is used for the sealant layer, the sealant layer may have three layers, an inner layer, an intermediate layer and an outer layer. In this case, it is preferable that the intermediate layer is 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 to 300 μm, more preferably 20 μm to 200 μm, even more preferably 30 μm to 150 μm.

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

<Method for manufacturing packaging material>
Next, an example of a method for manufacturing a laminate constituting 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 a melt-extruded polyethylene resin layer using a sand lamination method. Also, the polyethylene resin layer may be laminated on another layer by a melt extrusion lamination method.

The packaging material 10 is provided with a chemical function, an electrical function, a magnetic function, a mechanical function, a friction/abrasion/lubricating function, an optical function, a thermal function, and a surface function such as biocompatibility. , it is also possible to apply secondary processing. Examples of secondary processing include embossing, painting, adhesion, printing, metallizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.). Also, the packaging material according to the present invention can be subjected to lamination (dry lamination or extrusion lamination), bag making, and other post-treatments to produce a molded product.

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

Packaged products that include the packaging material 10 include, for example, medicines, food and drink, fruit juices, juices, drinking water, sake, cooked foods, fish paste products, frozen foods, meat products, boiled foods, rice cakes, and liquid soups such as hot pot soups. - It can be suitably used as packaging for various foods and drinks such as soups, dry soups and seasonings, cosmetics such as liquid detergents, shampoos, rinses and conditioners, sanitary products, daily necessities and chemical products. Specific examples of food and drink include coffee, coffee beans, coffee powder, ice cream, gummies, side dishes, pasta sauce, curry, jelly, bacon, chocolate, and chocolate paste. Specific examples of daily necessities include absorbent cotton, masks, bath agents, powdered milk, and the like.

The packaging bag for the packaged product is made by folding the packaging material 10 in two or by preparing two sheets of the packaging material 10 and placing the sealant layer 40 of the packaging material 10 on the front side and the sealant layer 40 of the packaging material 10 on the back side facing each other. Then, the peripheral edges thereof are subjected to, for example, a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope pasted seal type, a palm pasted seal type (pillow seal type), a pleated seal type, Various types of packaging bags can be manufactured by heat-sealing in a heat-sealing form such as a flat-bottom seal type or a square-bottom seal type. A gusset type packaging bag can also be manufactured by performing heat sealing in a state in which the folded packaging material 10 is inserted between the packaging material 10 on the front side and the packaging material 10 on the back side. It should be noted that not all the packaging material 10 that constitutes the packaging bag may be the packaging material 10 according to the present invention. That is, at least a part of the printed layer of the packaging material 10 constituting the packaging bag should contain the biomass-derived component, and 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, known methods such as bar sealing, rotary 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. As shown in FIG. The bag 70 includes a surface film 74 that forms the front surface and a back surface film 75 that forms the back surface.

The inner surfaces of the surface film 74 and the back surface film 75 are joined together by a sealing portion. In the front view of the packaging bag 70 such as FIG. 7, the sealing portion is hatched. As shown in FIG. 7 , the sealing portion has an outer edge sealing portion extending along the outer edge of the packaging bag 70 . The outer edge seal portion includes a lower seal portion 72 a extending over the lower portion 72 and a pair of side seal portions 73 a extending along the pair of side portions 73 . As shown in FIG. 7, the upper portion 71 of the packaging bag 70 is an opening 71b before the content is filled (the state in which the content is not filled). After the contents are contained in the packaging bag 70 , the inner surface of the surface film 74 and the inner surface of the back film 75 are joined at the upper portion 71 to form an upper sealing portion and the packaging bag 70 is sealed. Thus, the packaging bag 70 shown in FIG. 7 is a four-sided seal pouch formed by joining the surface film 74 and the back film 75 along the outer edge at four sides.

In addition, the terms "surface film" and "back surface film" described above merely refer to sections 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 that described above. It is not limited by terminology. For example, the packaging bag 70 may be manufactured using one sheet of packaging material 10 in which the surface film 74 and the back film 75 are continuously arranged. It may be manufactured using two sheets of packaging material 10 .

At least one of the surface film 74 and the back film 75 is composed of the packaging material 10 having a printed layer containing biomass-derived components. As a result, it is possible to reduce the amount of fossil fuel used compared to the conventional method, thereby reducing the environmental load.

FIG. 8 is a diagram showing another example of the packaging bag 70 including the packaging material 10. As shown in FIG. The packaging bag 70 is a pillow pouch that is joined at an upper portion 71, a lower portion 72 and palm-to-palm portions.

The seal portion is arranged between an upper seal portion 71 a extending over the upper portion 71 , a lower seal portion 72 a extending over the lower portion 72 , and a pair of side portions 73 , for example, approximately midway between the pair of side portions 73 . It has a joint seal portion 77 extending toward. The palm-to-palm seal portion 77 is also called a back seal portion.

As shown in FIG. 8, the packaging bag 70 includes a packaging material folded between a surface film 74 and a back film 75, extends from an upper portion 71 to a lower portion 72, and has a pair of side gusset portions facing each other. 78 are further provided. As shown in FIG. 8, the packaging material between the surface film 74 and the back film 75 is folded so that the folded portion 78a is positioned inside.

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

FIG. 10 is a diagram showing an example of a lidded container 90 that includes the packaging material 10. As shown in FIG. 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 made by drawing a packaging material 10 having a printed layer containing biomass-derived components. As a result, it is possible to reduce the amount of fossil fuel used compared to the conventional method, thereby reducing the environmental load.

Moreover, in the example shown in FIG. 10, the lid portion 94 may be formed of the packaging material 10 having a printed layer containing biomass-derived components. As a result, it is possible to reduce the amount of fossil fuel used compared to the conventional method, thereby reducing the environmental load.

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

[Example 1A]
As the first substrate film 22 of the substrate layer 20, a biaxially stretched PET film (thickness: 12 μm) derived from fossil fuel was prepared. Subsequently, a printed layer 50 was formed on the inner surface side of the PET film using an ink containing a biomass-derived component. In the step of forming the printed layer 50, first, a polyester polyol, which is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a fossil fuel-derived polyfunctional carboxylic acid, was prepared as a main agent. In addition, an isocyanate compound derived from fossil fuel was prepared as a curing agent. Subsequently, a coloring agent 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 on the inner surface side of the PET film to form the printed layer 50 .

Also, an aluminum foil was prepared as the metal foil 34 of the intermediate layer 30 . Although the thickness of the aluminum foil can be 7 μm or 9 μm, it was set to 7 μm here. Subsequently, on the printed layer 50 provided on the first base film 22, using a sand lamination method, polyethylene 1 as the first adhesive resin layer 26 was extruded at a resin temperature of 290° C. through an anchor coating agent. , a metal foil 34 was laminated on the first adhesive resin layer 26 . As the polyethylene 1, a 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, and is set to 15 μm here. Subsequently, on the surface of the metal foil 34 on which the first adhesive resin layer 26 is not laminated, the polyethylene 1 described above is applied as the sealant layer 40 by a melt extrusion lamination method, through an anchor coating agent. A packaging material 10 was obtained by hot extrusion and lamination of a sealant layer. Although the thickness of the polyethylene 1 can be selected within the range of 20 μm or more and 40 μm or less, it is set to 30 μm here.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
PET12/marking/anchor/contact PE(1)15/Al foil 7/anchor/extrusion PE(1)30
"/" represents the boundary between layers. The layer on the left end is the layer that forms the outer surface of the packaging material 10 , and the layer on the right end is the layer that forms 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 polyethylene 1 described above. "Al foil" means aluminum foil. "Extruded PE(1)" means Polyethylene 1 as described above. The numbers mean the layer thicknesses (unit: μm).

Subsequently, using the packaging material 10, a four-side seal type packaging bag 70 shown in FIG. 7 was produced.

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

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

FIG. 11 collectively shows the layer structure of the packaging materials 10 of Examples 1A to 1C. In the column of "printing layer type" in FIG. 11, the description "ester-based" means that the main agent used in the printing layer is polyester polyol.
In addition, in the column of "biomass-derived components in the printing layer", the description "polyfunctional alcohol" means that at least the polyfunctional alcohol of the main agent among the components of the main agent and the 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 agent among the components of the main agent and curing agent 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 components of the main agent and the curing agent used in the printed layer is derived from biomass.

In Examples 1A to 1C, in the printed layer, one of the three constituents of the polyfunctional alcohol or polyfunctional carboxylic acid used in the main polyester polyol, or the isocyanate compound used in the curing agent was biomass. Although an example of a derived component has been shown, it is not limited to this. For example, two of the three components may contain biomass-derived components, or all three components may contain biomass-derived components.

[Example 1D]
A packaging material 10 was produced in the same manner as in Example 1A, except that polyether polyol was used as the base material of the printed layer 50 . Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate derived from a fossil fuel was used as the main polyether polyol.

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

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

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

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

[Example 1G]
A packaging material 10 was produced in the same manner as in Example 1A, except that an ethylene-methacrylic acid copolymer (EMAA) was used as the sealant layer 40 .

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
PET12/Mark/Anchor/Contact PE(1)15/Al foil7/Anchor/Extrusion 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 embodiment is expressed as follows.
Bio-PET12/Mark/Anchor/Contact PE(1)15/Al foil7/Anchor/Extrusion PE(1)30
"Bio-PET" means biomass-derived biaxially oriented polyethylene terephthalate film.

[Example 1I]
A packaging material 10 was produced in the same manner as in Example 1A, except that polyethylene 2 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 / cm, MFR: 2.0 g / 10 minutes, biomass degree: 0%) and biomass-derived low-density polyethylene (manufactured by Braskem, Product name: SPB681, density: 0.922 g/cm ³ , MFR: 3.8 g/10 min, biomass content: 95%) were melt-kneaded to obtain a resin composition (polyethylene 2). Next, the obtained resin composition was extruded through an anchor coating agent at a resin temperature of 290° C. to laminate the metal foil 34 on the first adhesive resin layer 26 .

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

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

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

[Example 1K]
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, and the polyethylene 2 described above was used as the first adhesive resin layer 26. A packaging material 10 was produced in the same manner.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Bio-PET12/Mark/Anchor/Contact PE(2)15/Al foil7/Anchor/Extrusion PE(1)30

[Example 1L]
The procedure was the same 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, and the polyethylene 2 described above was used as the sealant layer 40. Then, a packaging material 10 was produced.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Bio-PET12/Mark/Anchor/Contact PE(1)15/Al foil7/Anchor/Extrusion PE(2)30

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

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
PET12/marking/anchor/bonding PE(2)15/Al foil 7/anchor/extrusion PE(2)30

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

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

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

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

FIG. 11 collectively shows the layer structure of the packaging materials 10 of Examples 1A-1N.

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

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

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
PET12/anchor/bonded PE(1)15/mark/PET12/anchor/extruded PE(1)35

Subsequently, using the packaging material 10, the lid portion 94 of the 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 base material of the printed layer 50 . Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate derived from a fossil fuel was used as the main polyether polyol.

[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 embodiment is expressed as follows.
PET12/anchor/contact PE(1)15/mark/bio PET12/anchor/extrusion 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. A packaging material 10 was made in the same manner as in Example 2A, except that

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

[Example 2E]
The 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 polyethylene 2 described above was used as the sealant layer 40. Then, a packaging material 10 was produced.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
PET12/anchor/contact PE(1)15/mark/bio PET12/anchor/extrusion PE(2)35

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

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
PET12/anchor/contact PE(2)15/mark/bio PET12/anchor/extrusion 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 polyethylene 2 described above 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 embodiment is expressed as follows.
Bio-PET12/Anchor/Wetted 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 polyethylene 2 was used as the sealant layer 40 .

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Bio-PET12/Anchor/Wet PE(1)15/Mark/Bio-PET12/Anchor/Extrusion PE(2)35

[Example 2I]
The polyethylene 2 described above 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 polyethylene 2 described above is used as the sealant layer 40. A packaging material 10 was produced in the same manner as in Example 2A, except for the above.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
PET12/anchor/contact PE(2)15/mark/bio PET12/anchor/extrusion 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 polyethylene 2 described above 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 polyethylene 2 was used as the sealant layer 40.

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

Further, in Examples 2C to 2J, the printed layer shown in Examples 1B to 1F may be used as the printed layer in addition to the printed layer shown in Example 1A.

FIG. 12 summarizes the layer configurations of the packaging materials 10 of Examples 2A-2J.

[Example 3A]
As the first substrate film 22 of the substrate layer 20, a biaxially oriented 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 printed layer 50 was formed on the inner surface side of the polypropylene film using an ink containing a biomass-derived component. The printed layer 50 has a cured product of a polyfunctional alcohol-containing polyester polyol containing a biomass-derived component and a fossil fuel-derived isocyanate compound, similarly to the printed layer 50 of Example 1A.

In addition, as the second base film 32 of the intermediate layer 30, a PET film made of biaxially stretched PET film derived from fossil fuel and provided with a metal deposition layer 60 was prepared. The thickness of the PET film provided with the vapor deposition layer 60 of metal can be 9 μm or 12 μm, and was set to 12 μm here. Subsequently, on the printed layer 50 formed on the first base film 22, using the sand lamination method, the polyethylene 1 described above was applied as the first adhesive resin layer 26 via an anchor coating agent at a resin temperature of 290°C. to laminate the second base film 32 on which the deposited layer 60 was formed 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, and was set to 10 μm here.

As the sealant film 42 of the sealant layer 40, a non-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 30 μm or less, it was set to 18 μm here. Subsequently, the above 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. , extruded at a resin temperature of 320° C. through an anchor coating agent, and on the second substrate film 32, the second adhesive resin layer 44 and the sealant film 42 are sequentially formed from the second substrate film 32 side in this order. A packaging material 10 was obtained by lamination. 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, and was set to 10 μm here.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
OPP18/mark/anchor/contact PE(1)10/VMPET12/anchor/contact PE(1)10/CPP18
"OPP" means biaxially oriented polypropylene film derived from fossil fuels. "VMPET" means biaxially oriented PET film derived from fossil fuels provided with a vapor deposited layer of metal. "CPP" means unoriented polypropylene film derived from fossil fuels.

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

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

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

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
OPP18/Mark/Anchor/Contact (EMAA)10/VMPET12/Anchor/Contact PE(1)10/CPP18
"EMAA" means an adhesive resin layer comprising ethylene-methacrylic acid copolymer (EMAA).

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

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

[Example 3E]
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, it was the same as in Example 3A. A packaging material 10 was produced in the same manner.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
OPP18 / Mark / Anchor / Contact (EMAA) 10 / VMPET12 / Anchor / Contact (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 embodiment is expressed as follows.
OPP18/Mark/Anchor/Contact PE(1)10/VM Bio PET12/Anchor/Contact PE(1)10/CPP18
"VM bio-PET" 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 polyethylene 2 was used as the second adhesive resin layer 44 .

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

[Example 3H]
In the case of 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 polyethylene 2 described above was used as the second adhesive resin layer 44. A packaging material 10 was produced in the same manner.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
OPP18/mark/anchor/contact PE(1)10/VM bio PET12/anchor/contact PE(2)10/CPP18

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

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
OPP18/mark/anchor/contact PE(2)10/VMPET12/anchor/contact PE(2)10/CPP18

[Example 3J]
The polyethylene 2 described above 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 polyethylene 2 described above is used as the second adhesive resin layer 44. A packaging material 10 was made in the same manner as in Example 3A, except that it was used.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
OPP18/mark/anchor/contact PE(2)10/VM bio PET12/anchor/contact PE(2)10/CPP18

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

FIG. 13 summarizes the layer configurations of the packaging materials 10 of Examples 3A-3J.

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

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

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
PET12/Mark/Anchor/PE(1)13/Al foil 6/Anchor/PE(1)13/PE(1)30
"PE(1)" means the polyethylene film 1 described above.

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

[Example 4C]
A packaging material 10 was produced in the same manner as in Example 4A, except that a polyethylene film 2 produced as described below was used as the sealant film 42 of the sealant layer 40 .
A method for producing the polyethylene film 2 will be described. First, fossil fuel-derived linear low-density polyethylene (density: 0.918 g / cm 3, MFR: 3.8 g / 10 min, biomass degree: 0%) 60 parts by mass, fossil fuel-derived low-density polyethylene (density : 0.924 g / cm 3, MFR: 2.0 g / 10 minutes, biomass degree: 0%) 20 parts by mass, biomass-derived linear low density polyethylene (LLDPE, manufactured by Braskem, trade name: SLL118, density: 0.916 g/cm 3 , MFR: 1.0 g/10 min, biomass content of 87%) and 20 parts by mass were melt-kneaded to obtain a resin composition. Next, the obtained resin composition was formed into a film by a top-blown air-cooled inflation co-extrusion film-forming machine to obtain a single-layer polyethylene film 2 (biomass degree: 16%) for a sealant layer. The thickness of the polyethylene film 2 was set to 30 μm as in the case of the polyethylene film 1 of Example 4A.

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

[Example 4D]
In 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 polyethylene 2 described above was used as the second adhesive resin layer 44. A packaging material 10 was produced in the same manner.

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

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

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

[Example 4F]
As the first substrate film 22 of the substrate layer 20, a biomass-derived biaxially stretched PET film is used, as the first adhesive resin layer 26, the polyethylene 2 described above is used, and as the second adhesive resin layer 44, the above-described A packaging material 10 was produced in the same manner as in Example 4A, except that polyethylene 2 of No. 2 was used.

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

[Example 4G]
As the first substrate film 22 of the substrate layer 20, a biomass-derived biaxially stretched PET film is used, as the first adhesive resin layer 26, the polyethylene 2 described above is used, and as the second adhesive resin layer 44, the above-described A packaging material 10 was produced in the same manner as in Example 4A, except that the polyethylene 2 of the sealant layer 40 was used and 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 embodiment is expressed as follows.
Bio PET12/mark/anchor/contact PE(2)13/Al foil 6/anchor/contact 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 can also be employed in this example. For example, as the printed layer, the printed layers shown in Examples 1B to 1F may be used in addition to the printed layer shown in Example 1A.

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

[Example 5A]
First base film 22, printed layer 50, first anchor coat layer 28, first adhesive resin layer 26, metal foil 34, second anchor coat layer 46 and sealant layer in the same manner as in Examples 1A to 1N A packaging material 10 in which 40 were laminated in order was produced. As the first base film 22, a biaxially stretched nylon film (thickness: 15 μm) derived from fossil fuel was used. Aluminum foil was used as the metal foil 34 . Although the thickness of the aluminum foil can be 6 μm, 7 μm or 9 μm, it was 6 μm here. As the printed 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, and was set to 15 μm here. 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, and was set to 40 μm here.

Subsequently, using the packaging material 10, a four-side seal type packaging bag 70 shown in FIG. 7 was produced.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
ONY15/Mark/Anchor/Contact PE(1)15/Al foil 6/Anchor/Extrusion 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 base material of the printed layer 50 . Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate derived from a fossil fuel was used as the main polyether polyol.

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

The layer structure of the packaging material 10 of this embodiment 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 can also be employed in this example. For example, as the printed layer, the printed layers shown in Examples 1B to 1F may be used in addition to the printed layer shown in Example 1A.

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

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

(Other aspects)
Another aspect of the present invention is a packaging material comprising at least a substrate 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 containing a colorant and a cured product of a polyol and an isocyanate compound, wherein at least either the polyol or the isocyanate compound contains a biomass-derived component.

In the packaging material according to another aspect of the present invention, the polyol of the printed layer may be a polyester polyol which is a reactant of a polyfunctional alcohol and a polyfunctional carboxylic acid.

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

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

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

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

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

In the packaging material according to another aspect of the present invention, the first base film may contain a biomass polyester having a biomass-derived ethylene glycol as a diol unit and a 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 have at least one of a second base film containing polyester as a main component and 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 contains biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid may contain a biomass polyester having a dicarboxylic acid unit.

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

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

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

10 Packaging Material 20 Base Layer 22 First Base Film 24 Printed 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 Adhesion Resin layer 46 Second anchor coat layer 50 Printed layer 60 Vapor deposition layer

Claims (7)

A packaging material comprising at least a substrate layer, a printing 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 coloring agent 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,
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 printed layer contains a biomass-derived component, and the other is made of only a fossil fuel-derived material,
The polyfunctional alcohol is polypropylene glycol or butylene glycol,
The base layer has a first base film containing polypropylene,
The packaging material, wherein the intermediate layer has a vapor deposition layer. The packaging material according to claim 1, wherein the intermediate layer has a second base film containing polyester as a main component. 3. The packaging material according to claim 2, wherein the second base film contains a biomass polyester having a biomass-derived ethylene glycol as a diol unit and a 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 printed layer contains a biomass-derived component. 5. The packaging material according to any one of claims 1 to 4, wherein the sealant layer comprises polyolefin, which is a polymer of olefin-containing monomers. 6. The packaging material of Claim 5, wherein the sealant layer comprises a biomass polyolefin. A packaged product comprising a packaging material according to any one of claims 1-6.

Images