JP7194344B2 - 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 widely used around the world. Therefore, the use of conventional fossil fuel-derived polyethylene imposes a large environmental load. Therefore, it is desired to reduce the consumption of fossil fuels by using biomass-derived raw materials for the production of polyethylene. For example, until now, research has been conducted to produce ethylene and butylene, which are raw materials for polyolefin resin, from renewable natural raw materials (see Patent Document 1).

In addition, 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 and a sealant layer, wherein the printed layer comprises a coloring agent and a cured product of a polyol and an isocyanate compound, and the polyol Alternatively, the packaging material, wherein at least one of the isocyanate compounds contains a biomass-derived component.

In the packaging material according to 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 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 the present invention, the polyol of the printed layer may be a polyether polyol which is a reactant of a polyfunctional alcohol and a polyfunctional isocyanate.

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

In the packaging material according to the invention, the substrate layer may have a substrate film comprising polyester, polyamide or polyolefin.

In the packaging material according to the present invention, the 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 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, which is a polymer of biomass-derived ethylene-containing monomers.

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. 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-1J. FIG. 4 shows the layer structure of the packaging materials of Examples 2A-2E. FIG. 4 shows the layer structure of the packaging materials of Examples 3A-3G. FIG. 4 shows the layer structure of the packaging materials of Examples 4A-4B. Figures 1A-1J, 2A-2E, 3A-3G and 4A-4B show examples of types of packaging containers;

<Packaging material>
A laminate constituting the packaging material according to the present invention includes at least a substrate layer, a printed layer, an adhesive resin layer and a sealant layer. 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 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 4, 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, an anchor coat layer 28, an adhesive resin layer 26, and a sealant layer 40 in this order. The base layer 20 includes a base film 22 . Sealant layer 40 includes a sealant film 42 .

The packaging material 10 shown in FIG. 2 differs from the packaging material 10 shown in FIG. 1 in the configuration of the sealant layer 40 . Specifically, the packaging material 10 of FIG. 2 includes a substrate layer 20, a printed layer 50, an anchor coat layer 28, an adhesive resin layer 26, and a sealant layer 40 in this order. The base layer 20 includes a base film 22 .

The packaging material 10 shown in FIG. 3 differs from the packaging material 10 shown in FIG. 1 in the configuration of the base material layer 20 . Specifically, the packaging material 10 of FIG. 3 includes a substrate layer 20, a printed layer 50, an anchor coat layer 28, an adhesive resin layer 26, and a sealant layer 40 in this order. The base layer 20 includes a base film 22 and a barrier layer 60 in this order. Sealant layer 40 includes a sealant film 42 .

The packaging material 10 shown in FIG. 4 differs from the packaging material 10 shown in FIG. 2 in the configuration of the base material layer 20 . Specifically, the packaging material 10 of FIG. 4 includes a substrate layer 20, a printed layer 50, an anchor coat layer 28, an adhesive resin layer 26, and a sealant layer 40 in this order. The base layer 20 includes a base film 22 and a barrier layer 60 in this order.

The packaging material 10 shown in FIGS. 3 and 4 includes the barrier layer 60, but the barrier layer may be a single layer structure such as a metal foil or vapor deposition layer, and a gas barrier layer may be formed on the vapor deposition layer. It may be a laminated structure in which a flexible coating film is formed.

It should be noted that it is also possible to appropriately combine a plurality of layer configurations of the packaging material 10 shown in FIGS. 1 to 4 described above.

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

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

When the base film 22 contains a biomass-derived component, the 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 _{Pbio can be determined as follows, where Pc14} is the content of _C14 in the polyester.
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 biomass-derived carbon is used as P, the biomass-derived carbon content P _bio 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 base film 22 contains a biomass-derived component, the degree of biomass in the base film 22 is 5% or more, preferably 10% or more and 30% or less, and more preferably 15% or more and 25% or less. . If the biomass degree in the base 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. 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.

Using a resin composition of biomass polyester or a resin composition containing biomass polyester and fossil fuel-derived polyester, the substrate film 22 can be formed by, for example, forming a film by a T-die method. Specifically, after drying the above resin composition, it is supplied to a melt extruder heated to a temperature above the melting point Tm of the resin composition to Tm + 70 ° C. to melt the resin composition, for example. The substrate film 22 can be formed by extruding the material into 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 base film 22 is formed of a material that does not contain biomass-derived components, examples of the base film 22 include polyester films such as polyethylene terephthalate film and polybutylene terephthalate, polyolefin films such as polyethylene film and polypropylene film, and nylon films. Polyamide films such as nylon 6 / meta-xylylenediamine nylon 6 co-extruded co-stretched films, or polypropylene / ethylene-vinyl alcohol copolymer co-extruded co-stretched films, or composite films in which two or more of these films are laminated A plastic film can be used. The plastic film may be coated with polyvinyl alcohol or the like.

The base film 22 may be a stretched plastic film stretched in a predetermined direction. In this case, the 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 circumferential 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 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. For example, it is 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 base film 22 is a biomass polyester film or a polyester film, the thickness of the 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 base film 22 is a polyamide film, the thickness of the 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 base film 22 is a polypropylene film, the thickness of the 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 base film 22 is a biomass polyethylene film or a polyethylene film, the thickness of the 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 base film 22 may be a single-layer film or a co-extruded film of two or more layers.

(barrier layer)
Layers other than those described above, such as a barrier layer, may be provided between the substrate layer and the printed layer and/or between the adhesive layer and the sealant layer. As the barrier layer, a metal foil or an inorganic or inorganic oxide deposited layer can be suitably used.

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

Vapor deposition layers include, 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 vapor-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 is positioned closer to the outer surface 10y than the printed layer 50, a vapor deposition film of a transparent inorganic oxide is used as the vapor deposition layer.

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. Silicon (Si) and aluminum (Al) are preferably used as the vapor deposition layer of the packaging material 10. Silicon (Si) is 1.0 to 2.0, and aluminum (Al) is 0.5 to 1.0. A range of values of 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 can be formed on the substrate film 22 or the like using the following forming method. Examples of methods for forming the vapor deposition layer include physical vapor deposition methods such as vacuum deposition, sputtering, and ion plating (Physical Vapor Deposition, PVD), plasma chemical vapor deposition, thermochemical 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 vapor deposition layer 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 for imparting 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 polyfunctional alcohols derived from biomass, 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.

An adhesive resin layer such as the adhesive resin layer 26 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, ethylene-polypropylene random or block copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-α-olefin copolymer polymerized using Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-maleic acid copolymer, ionomer resin, adhesion between layers In order to improve the above, it is possible to use an acid-modified polyolefin resin obtained by modifying the above polyolefin resin with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, or itaconic acid. can. Further, a resin obtained by graft polymerization or copolymerization of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or an ester monomer can be used as the polyolefin resin. These materials can be used singly or in combination of two or more. Cyclic polyolefins such as ethylene-propylene copolymers, polymethylpentene, polybutene, and polynorbonene can be used as cyclic polyolefin resins. These resins can be used singly or in combination. As the polyethylene-based resin described above, the biomass content can be further improved by using the above-described biomass-derived ethylene as a monomer unit.

When the adhesive resin layer is laminated by the melt extrusion lamination method, an anchor coat layer 28 formed by applying an anchor coat agent and drying it may be provided on the surface of the layer to be laminated. The anchor coating agent includes any resin having a heat resistance temperature of 135° C. or higher, such as an anchor coating agent made of vinyl-modified resin, epoxy resin, urethane resin, polyester resin, polyethyleneimine, etc. Especially, An anchor coating agent which is a cured product of a polyacrylic or polymethacrylic resin (polyol) having two or more hydroxyl groups and an isocyanate compound as a curing agent can be preferably used. In addition, a silane coupling agent may be used together as an additive, and nitrocellulose may be used together to improve heat resistance.

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

(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. 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 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 it can be manufactured using a conventionally known method such as a dry lamination method, a melt extrusion lamination method, a sand lamination method, or the like. 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 packaging products formed by using the packaging material 10 include packaging bags, lid materials, 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, simmered dishes, 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. In addition, as illustrated in the examples described later, the packaged product provided with the packaging material 10 configured to have heat resistance is used for containing contents that are subjected to heat sterilization treatment such as retort treatment and boiling treatment. can be used. Note that the retort treatment is a process of heating the packaged product under pressure using steam or heated hot water after filling the packaged product with contents and sealing the packaged product. The temperature of the retort treatment is, for example, 120° C. or higher. Boiling treatment is a process in which the contents are filled into a packaged product, the packaged product is sealed, and then the packaged product is boiled in hot water under atmospheric pressure. The boiling treatment temperature is, for example, 90° C. or higher and 100° C. or lower.

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 edge is 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-sticking seal type, a palm-sticking seal type (pillow seal type), a pleated seal type, Various forms 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. Note 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. 5 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. 5, the sealing portion is hatched. As shown in FIG. 5, the seal portion is arranged between an upper seal portion 71a extending over an upper portion 71, a lower seal portion 72a extending over a lower portion 72, and a pair of side portions 73, for example, approximately midway between the pair of side portions 73. and a joint seal portion 77 extending from the upper portion 71 toward the lower portion 72 . The palm-to-palm seal portion 77 is a portion also referred to as a back seal portion. Thus, the packaging bag 70 shown in FIG. 5 is a pillow pouch that is joined at the upper portion 71, the lower portion 72, and the palm-to-palm portion.

Also, as shown in FIG. 5, the packaging bag 70 includes 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. 5, the packaging material between the surface film 74 and the back film 75 is folded so that the folded portion 78a is positioned inside. Such a packaging bag 70 may be used as a drawstring bag in which the upper portion of the packaging bag 70 is tied with a band or the like.

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. 6 is a diagram showing another example of the packaging bag 70 including the packaging material 10. As shown in FIG. A packaging bag 70 shown in FIG. 6 is a four-sided seal pouch formed by joining a surface film 74 and a back film 75 along the outer edges at four sides.

As shown in FIG. 6 , 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. 6, in the packaging bag 70 before being filled with the contents (the state in which the contents are not filled), the upper part 71 of the bag 70 is an opening 71b. 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.

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 base film 22 of the base layer 20, a biaxially oriented nylon film (thickness: 15 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 .

As the sealant film 42 of the sealant layer 40, the polyethylene film 1 produced as follows was used. First, fossil fuel-derived linear low-density polyethylene (density: 0.918 g / cm3, MFR: 3.8 g / 10 minutes, biomass degree: 0%) 90 parts by mass, fossil fuel-derived low-density polyethylene (density : 0.924 g/cm3, MFR: 2.0 g/10 min, biomass content: 0%) and 10 parts by mass were melt-kneaded to obtain a resin composition. Then, 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 (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. Subsequently, on the printed layer 50 provided on the base film 22, using the sand lamination method, polyethylene 1 as the adhesive resin layer 26 was extruded at a resin temperature of 290° C. through an anchor coating agent, and the sealant film 42 was formed. was laminated on the adhesive resin layer 26 to obtain the packaging material 10. 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 20 μm here.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
ONY15/Mark/Anchor/Contact PE(1)20/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 .
"ONY" means biaxially oriented nylon 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. "PE(1)" means the polyethylene film 1 described above. The number means the layer thickness (unit: μm).

Subsequently, using the packaging material 10, a pillow pouch type packaging bag 70 shown in FIG. 5 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. 7 collectively shows the layer structure of the packaging materials 10 of Examples 1A to 1C. In the column of "printing layer type" in FIG. 7, 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. 7 collectively shows the layer structure of the packaging materials 10 of Examples 1D to 1F. In the column of "printing layer type" in FIG. 7, 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]
As the base film 22 of the base layer 20, nylon in which an inorganic oxide vapor deposition layer and a gas barrier coating film located on the vapor deposition layer are provided on the surface of a fossil fuel-derived biaxially stretched nylon film. Packaging material 10 was produced in the same manner as in Example 1A, except that a film was used.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Barrier ONY15/Mark/Anchor/Contact PE(1)20/PE(1)30
"Barrier ONY15" means a nylon film obtained by providing a biaxially stretched nylon film derived from fossil fuel with an inorganic oxide deposition layer and a gas barrier coating.

[Example 1H]
Packaging material 10 was produced in the same manner as in Example 1A, except that polyethylene 2 described below was used as 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 resulting resin composition was extruded through an anchor coating agent at a resin temperature of 290° C. to laminate the sealant film 42 on the adhesive resin layer 26 .

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
ONY15/Mark/Anchor/Contact PE(2)20/PE(1)30
"Contact PE (2)" means an adhesive resin layer containing polyethylene 2 described above.

[Example 1I]
Packaging material 10 was produced in the same manner as in Example 1A, except that polyethylene film 2 produced as described below was used as sealant film 42 of 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 1A.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
ONY15/Mark/Anchor/Contact PE(1)20/PE(2)30
"PE(2)" means the polyethylene film 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 adhesive resin layer 26 and the above polyethylene film 2 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.
ONY15/Mark/Anchor/Contact PE(2)20/PE(2)30

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

Further, in Examples 1G to 1J, 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.

[Example 2A]
As the base film 22 of the base 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 15 μm or more and 40 μm or less, it was set to 30 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.

Subsequently, the above-mentioned polyethylene 1 as the adhesive resin layer 26 and the above-mentioned polyethylene 1 as the sealant layer 40 are laminated on the printed layer 50 provided on the base film 22 using a melt coextrusion lamination method. , extruded at a resin temperature of 290 ° C. through an anchor coating agent, and laminated on the base film 22 in order from the base film 22 side, the adhesive resin layer 26 and the sealant layer 40 in this order to form a packaging material. Got 10. The thickness of the polyethylene 1 as the adhesive resin layer 26 and the sealant layer 40 can be selected within the range of 10 μm or more and 30 μm or less, and was set to 15 μm here.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
OPP30/Mark/Anchor/Wetted PE(1)15/Extruded PE(1)15
"OPP" means biaxially oriented polypropylene film derived from fossil fuels. "Extruded PE(1)" means Polyethylene 1 as described above.

Subsequently, using the packaging material 10, a four-sided seal type packaging bag 70 shown in FIG. 6 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]
As the base film 22 of the base layer 20, polypropylene obtained by providing an inorganic oxide vapor deposition layer and a gas barrier coating film positioned on the vapor deposition layer on the surface of a biaxially oriented polypropylene film derived from fossil fuel. Packaging material 10 was produced in the same manner as in Example 1A, except that a film was used.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Barrier OPP30/Mark/Anchor/Contact PE(1)15/Extrusion PE(1)15
"Barrier OPP" means a polypropylene film obtained by providing a biaxially stretched polypropylene film derived from fossil fuels with an inorganic oxide vapor deposition layer and a gas barrier coating.

[Example 2D]
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.
OPP30/mark/anchor/contact PE(1)15/extrusion PE(2)15
"Extruded PE(2)" means polyethylene 2 as described above.

[Example 2E]
The packaging material 10 was produced in the same manner as in Example 2A except that the above polyethylene 2 was used as the adhesive resin layer 26 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.
OPP30/Mark/Anchor/Wetted PE(2)15/Extruded PE(2)15

In Examples 2D to 2E, the substrate layer shown in Example 2C may be used as the substrate layer.

Further, in Examples 2C to 2E, 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. 8 summarizes the layer configurations of the packaging materials 10 of Examples 2A-2E.

[Example 3A]
A packaging material 10 in which the base film 22, the printed layer 50, the anchor coat layer 28, the adhesive resin layer 26 and the sealant layer 40 are laminated in this order was produced in the same manner as in Examples 2A to 2G. As the base film 22, a biaxially stretched PET film (thickness: 12 μm) derived from fossil fuel was used. As the adhesive resin layer 26, polyethylene 1 described above was used. The thickness of the polyethylene 1 used for the adhesive resin layer 26 can be selected within the range of 10 μm or more and 30 μm or less, and is set to 20 μm here. As the sealant layer 40, the polyethylene 1 described above was used. The thickness of the polyethylene 1 used for the sealant layer 40 can be selected within the range of 20 μm or more and 30 μm or less, and was set to 20 μm here. As the printing layer 50, the same one as in Example 2A was used.

Subsequently, using the packaging material 10, a four-sided seal type packaging bag 70 shown in FIG. 6 was produced.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
PET12/Mark/Anchor/Contact PE(1)20/Extrusion PE(1)20
"PET" means biaxially oriented polyethylene terephthalate film derived from fossil fuels.

[Example 3B]
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 3C]
As the base film 22 of the base layer 20, PET in which an inorganic oxide vapor deposition layer and a gas barrier coating film positioned on the vapor deposition layer are provided on the surface of a fossil fuel-derived biaxially stretched PET film. Packaging material 10 was produced in the same manner as in Example 1A, except that a film was used.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Barrier PET12/Mark/Anchor/Contact PE(1)20/Extrusion PE(1)20
“Barrier PET” means a polyethylene terephthalate film obtained by providing a biaxially stretched polyethylene terephthalate film derived from fossil fuels with an inorganic oxide deposition layer and a gas barrier coating.

[Example 3D]
A packaging material 10 was produced in the same manner as in Example 3A, except that a biomass-derived biaxially stretched PET film was used as the 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)20/Extrusion PE(1)20
"Bio-PET" means biomass-derived biaxially oriented polyethylene terephthalate film.

[Example 3E]
In the same manner as in Example 4A, except that a biomass-derived biaxially stretched PET film was used as the base film 22 of the base layer 20, and the above polyethylene 2 was used as the adhesive resin layer 26. , 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(2)20/Extrusion PE(1)20

[Example 3F]
In the same manner as in Example 4A, except that a biomass-derived biaxially stretched PET film was used as the base film 22 of the base layer 20, and the above polyethylene 2 was used as the sealant layer 40. A packaging material 10 was produced.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Bio PET12/Mark/Anchor/Contact PE(1)20/Extrusion PE(2)20

[Example 3G]
A biomass-derived biaxially stretched PET film is used as the base film 22 of the base layer 20, the above polyethylene 2 is used as the 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 4A, except for the above.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
Bio PET12/Mark/Anchor/Contact PE(2)20/Extrusion PE(2)20

Note that variations similar to those of Examples 1B to 1J and Examples 2B to 2E 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. 9 collectively shows examples of layer structures of the packaging materials 10 of Examples 3A to 3G.

[Example 4A]
A packaging material 10 in which the substrate film 22, the printed layer 50, the anchor coat layer 28, the adhesive resin layer 26 and the sealant film 42 are laminated in this order was produced in the same manner as in Examples 1A to 1J. As the base film 22, a biaxially oriented polypropylene film derived from fossil fuel was used. Although the thickness of the polypropylene film can be selected within the range of 15 μm or more and 40 μm or less, it was set to 20 μm here. As the sealant film 42 of the sealant layer 40, an unstretched polypropylene film derived from fossil fuel was used. Although the thickness of the polypropylene film can be selected within the range of 20 μm or more and 50 μm or less, it was set to 25 μm here. As the printed layer 50 and the adhesive resin layer 26, the same ones as in Example 1A were used. The thickness of the polyethylene 1 used for the 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.

Subsequently, using the packaging material 10, a pillow pouch type packaging bag 70 shown in FIG. 5 was produced.

The layer structure of the packaging material 10 of this embodiment is expressed as follows.
OPP20/Mark/Anchor/Contact PE(1)15/CPP25
"CPP" means unoriented polypropylene film derived from fossil fuels.

[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.

Note that variations similar to those of Examples 1B to 1J and Examples 2B to 2E 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. 10 collectively shows layer configuration examples of the packaging materials 10 of Examples 4A to 4B.

FIG. 11 also collectively shows examples of types of packaging containers for Examples 1A-1J, 2A-2E, 3A-3G and 4A-4B.

10 packaging material 20 base layer 22 base film 24 printed layer 26 adhesive resin layer 28 anchor coat layer 40 sealant layer 42 sealant film 50 printed layer 60 barrier layer

Claims (5)

A packaging material comprising at least a substrate layer, a printed layer, an anchor coat layer, an adhesive resin layer and a sealant layer in this order,
The base material layer contains polypropylene,
The sealant layer comprises polypropylene,
The thickness of the sealant layer is 10 μm or more and 25 μm or less,
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,
A packaging material, wherein one of the polyfunctional alcohol and the polyfunctional carboxylic acid of the printed layer contains a biomass-derived component, and the other is derived from a fossil fuel. 2. The packaging material of Claim 1, wherein the isocyanate compound of the printed layer comprises a biomass-derived component. 3. The packaging material according to claim 1, wherein the sealant layer comprises polyolefin, which is a polymer of olefin-containing monomers. 4. The packaging material of claim 3, wherein the sealant layer comprises a biomass polyolefin that is a polymer of biomass-derived ethylene-containing monomers. A packaged product comprising a packaging material according to any one of claims 1-4.

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