JP2019142037A - Packaging material and packaging product - Google Patents

Abstract

To provide a packaging material with an improved degree of biomass.SOLUTION: A packaging material at least has a substrate layer, a printed layer, an adhesive resin layer, an intermediate layer and a sealant layer. The printed layer has a colorant, and a cured product of polyol and an isocyanate compound. At least one of the polyol or isocyanate compound has a biomass-derived component.SELECTED DRAWING: Figure 1

Description

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

  2. Description of the Related Art Conventionally, various packaging materials have been developed and proposed as packaging materials for configuring packaging products that are filled and packaged with various articles such as foods and drinks, pharmaceuticals, chemicals, cosmetics, hygiene products, daily necessities, and the like. The packaging material is composed of a laminate in which a base material layer containing stretched plastic and the like and a sealant layer for welding the packaging materials are laminated at least. Usually, the laminate further includes a printed layer for forming a printed pattern and an adhesive resin layer for joining the layers of the laminate.

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

  As a biomass-derived resin, commercial production of polylactic acid (PLA) produced via lactic acid fermentation has begun, but it is biodegradable, and its performance as a plastic is now a general-purpose plastic. Therefore, it has not been widely used due to its limitations in product applications and product manufacturing methods. Moreover, life cycle assessment (LCA) evaluation is performed for PLA, and discussion is made on energy consumption at the time of PLA production, equivalence at the time of replacement of general-purpose plastics, and the like.

  Here, various types such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, and polyester are used as the general-purpose plastic. In particular, polyethylene is molded into films, sheets, bottles, etc., and is used for various applications such as packaging materials, and is used in large amounts all over the world. For this reason, the use of conventional fossil fuel-derived polyethylene has a large environmental impact. Therefore, it is desired to reduce the amount of fossil fuel used by using raw materials derived from biomass for the production of polyethylene. For example, production of ethylene and butylene, which are raw materials for polyolefin resins, from renewable natural raw materials has been studied (see Patent Document 1).

  Polyesters are widely used in various industrial applications because they are excellent in mechanical properties, chemical stability, heat resistance, transparency, and the like and inexpensive. Polyester is obtained by polycondensation of a diol unit and a dicarboxylic acid unit. For example, polyethylene terephthalate (hereinafter sometimes abbreviated as PET) is obtained by esterifying ethylene glycol and terephthalic acid as raw materials. After the polycondensation reaction. These raw materials are produced from petroleum, which is a fossil resource, for example, ethylene glycol is produced industrially from ethylene and terephthalic acid is produced industrially from xylene.

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

Special table 2011-506628 gazette JP 2012-96410 A

  In the conventional packaging material, the printed layer of the laminate is formed of a fossil fuel-derived material, which is a cause of reducing the biomass degree of the entire packaging material. Therefore, in the packaging material comprised from the laminated body containing a base material layer, a printing layer, an adhesive resin layer, and a sealant layer, it is calculated | required that the biomass degree of the whole packaging material should be raised more.

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

  The present invention is a packaging material including at least a base material layer, a printing layer, an adhesive resin layer, and a sealant layer, wherein the printing layer includes a colorant and a cured product of a polyol and an isocyanate compound, and the polyol Alternatively, at least one of the isocyanate compounds is a packaging material containing a biomass-derived component.

  In the packaging material according to the present invention, the polyol of the printing layer may be a polyester polyol that is a reaction product 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 reaction product 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.

  The packaging material by this invention WHEREIN: The said base material layer may have the base film containing polyester, polyamide, or polyolefin.

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

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

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

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

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

It is a schematic cross section which shows an example of the packaging material by this invention. It is a schematic cross section which shows an example of the packaging material by this invention. It is a schematic cross section which shows an example of the packaging material by this invention. 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 figure which shows the layer structure of the packaging material of Example 1A-1J. It is a figure which shows the layer structure of the packaging material of Examples 2A-2E. It is a figure which shows the layer structure of the packaging material of Example 3A-3G. It is a figure which shows the layer structure of the packaging material of Example 4A-4B. It is a figure which shows the example of the type of the packaging container of Examples 1A-1J, 2A-2E, 3A-3G, and 4A-4B.

<Packaging materials>
The laminated body which comprises the packaging material by this invention contains a base material layer, a printing layer, an adhesive resin layer, and a sealant layer at least. In the present invention, at least the printed layer is formed of a material containing a biomass-derived component, so that the amount of fossil fuel used can be reduced compared to the conventional case, and the environmental load can be reduced.

  In the present invention, the biomass degree described below is preferably 3% or more, more preferably 5% or more and 60% or less, and further preferably 10% or more and 60% or less in the entire laminate constituting the packaging material. . If the degree of biomass is in 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 to 500 μm, more preferably 20 μm to 300 μm, and even more preferably 30 μm to 200 μm.

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

  The laminated body which comprises the packaging material by this invention is demonstrated referring drawings. Examples of schematic cross-sectional views of the packaging material 10 according to the present invention are shown in FIGS. 1-4, the code | symbol 10y represents the outer surface of the packaging material 10, and the code | symbol 10x represents the inner surface of the packaging material 10. In FIG. The inner surface 10x is a surface located on the side of the contents accommodated in the packaged product in a packaged product such as a bag formed from the packaging material 10. 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 “stacked in order” represents the order in the direction from the outer surface 10y side to the inner surface 10x side unless otherwise specified.

  The packaging material 10 shown in FIG. 1 includes a base material layer 20, a printing layer 50, an anchor coat layer 28, an adhesive resin layer 26, and a sealant layer 40 in this order. The base material layer 20 includes a base material film 22. The sealant layer 40 includes a sealant film 42.

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

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

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

  The packaging material 10 shown in FIGS. 3 and 4 includes the barrier layer 60. However, the barrier layer may have a single layer configuration such as a metal foil or a vapor deposition layer, and a gas barrier may be formed on the vapor deposition layer. The laminated structure in which the adhesive coating film was formed may be sufficient.

  In addition, it is also possible to combine suitably the several layer structure of the packaging material 10 shown in FIG. 1 thru | or FIG. 4 mentioned above.

  Hereinafter, each layer which comprises the packaging material 10 is demonstrated.

(Base film)
The substrate film 22 of the substrate 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 includes a biomass-derived component, the base film 22 can be formed using the following biomass polyester.

  Biomass polyester uses biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. In addition to biomass polyester, the base material layer may further include 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. The following biomass degree should just be implement | achieved as the whole base material layer. In the present invention, since the base material layer contains biomass polyester, it is possible to reduce the amount of polyester derived from fossil fuel and reduce the environmental load as compared with the conventional case.

  In the present invention, “biomass degree” may be indicated by a value obtained by measuring the content of biomass-derived carbon by measurement of radioactive carbon (C14), 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 measurement of radioactive carbon (C14) is shown as “biomass degree”, “biomass degree” can be obtained as follows. That is, since carbon dioxide in the atmosphere contains C14 at a constant rate (105.5 pMC), the C14 content in plants that grow by incorporating carbon dioxide in the atmosphere, for example, corn, is also about 105.5 pMC. It is known that It is also known that fossil fuel contains almost no C14. Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of C14 contained in all the carbon atoms in the polyester. In the present invention, in the case where the content of C14 in the polyester was P _C14, the content P _{bio Bio} carbon from biomass, can be obtained as follows.
P _bio (%) = P _C14 /105.5×100

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 in a molar ratio of 1: 1. When only the biomass-derived material is used, the biomass-derived carbon content P _bio in the polyethylene terephthalate is 20%. On the other hand, the content of biomass-derived carbon in fossil fuel-derived polyethylene terephthalate produced using fossil fuel-derived ethylene glycol and fossil fuel-derived dicarboxylic acid is 0%, and the fossil fuel-derived polyethylene terephthalate The degree of biomass is 0%.

  Moreover, when the “biomass degree” is expressed by the weight ratio of the biomass-derived component, the “biomass degree” can be obtained as follows. For example, taking polyethylene terephthalate as an example, polyethylene terephthalate is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1: 1 as described above. When only a biomass-derived component is used as the glycol, the weight ratio of the biomass-derived component in the polyester is about 30%, so the biomass degree is about 30%. The weight ratio of biomass-derived components 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, “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, more preferably 15% or more and 25% or less. . If the degree of biomass in the base film 22 is 5% or more, it is possible to reduce the amount of polyester derived from fossil fuels and reduce the environmental burden compared to the conventional case.

  Biomass-derived ethylene glycol uses ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method, such as a method of producing ethylene glycol via ethylene oxide. Moreover, you may use commercially available biomass ethylene glycol, for example, the biomass ethylene glycol marketed from India Glycol can be used conveniently.

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

  Specific examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid. And a chain or alicyclic dicarboxylic acid. Examples of the aliphatic dicarboxylic acid derivative include lower alkyl esters such as methyl ester, ethyl ester, propyl ester and butyl ester of aliphatic dicarboxylic acid, and cyclic acid anhydrides of aliphatic dicarboxylic acid such as succinic anhydride. Can be mentioned. Among these, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable, and succinic acid as the main component is particularly preferable. As the derivative of the aliphatic dicarboxylic acid, methyl esters of adipic acid and succinic acid, or a mixture thereof are more preferable. These dicarboxylic acids can be used alone or in combination of two or more.

  The biomass polyester may be a copolymer polyester obtained by adding a copolymer component as a third component in addition to the diol component and the dicarboxylic acid component. Specific examples of the copolymer component include a bifunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol, a trifunctional or higher polyvalent carboxylic acid and / or an anhydride thereof, and 3 Examples include at least one polyfunctional compound selected from the group consisting of functional or higher oxycarboxylic acids. Among these copolymer components, a bifunctional and / or trifunctional or higher functional oxycarboxylic acid is particularly preferably used because a copolymer polyester 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 having a high degree of polymerization can be easily produced with a very small amount without using a chain extender described later.

  Biomass polyester can be obtained by a conventionally known method in which the above-described diol unit and dicarboxylic acid unit are polycondensed. 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 a polycondensation reaction under reduced pressure, or an organic solvent It can be produced by a known solution heating dehydration condensation method using The amount of the diol used when producing the biomass polyester is substantially equimolar with respect to 100 mol of the dicarboxylic acid or derivative thereof. Generally, however, esterification and / or transesterification and / or polycondensation reactions are performed. It is preferable to use an excess amount of 0.1 mol% or more and 20 mol% or less because of the distillation in the inside.

  The base film 22 can be formed by forming a film by, for example, a T-die method using a biomass polyester resin composition or a resin composition containing biomass polyester and a fossil fuel-derived polyester. Specifically, after drying the resin composition described above, the resin composition is supplied to a melt extruder heated to a temperature of the melting point Tm or higher of the resin composition to a temperature of Tm + 70 ° C. to melt the resin composition, for example, The base film 22 can be formed by extruding into a sheet form from a die such as a T-die and quenching 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 film such as nylon 6 / metaxylylenediamine nylon 6 co-extrusion co-stretched film, polypropylene / ethylene-vinyl alcohol copolymer co-extrusion co-stretched film, or composite film 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 that is stretched in a predetermined direction. In this case, the base film 22 may be a uniaxially stretched film stretched in a predetermined direction, or may be a biaxially stretched film stretched in a predetermined two directions. The stretched plastic film is obtained, for example, by heating a plastic film extruded on a cooling drum by roll heating, infrared heating, or the like, and stretching it in the longitudinal direction. This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls. The longitudinal stretching is usually performed in a temperature range of 50 ° C. or more and 100 ° C. or less. Further, the ratio of the longitudinal stretching is preferably 2.5 times or more and 4.2 times or less, although it depends on the required characteristics of the film application. When the draw ratio is less than 2.5, the thickness unevenness of the film becomes large and it is difficult to obtain a good film.

  The longitudinally stretched film is successively subjected to the transverse stretching, heat setting, and thermal relaxation treatment steps to form a biaxially stretched film. The transverse stretching is usually performed in a temperature range of 50 ° C. or more and 100 ° C. or less. The transverse stretching ratio is preferably 2.5 times or more and 5.0 times or less, although it depends on the required characteristics of this application. If it is less than 2.5 times, the thickness unevenness of the film becomes large and it is difficult to obtain a good film, and if it exceeds 5.0 times, breakage tends to occur during film formation.

Breaking strength of the film of the base film 22 is, for example, in the MD direction 5 kg / mm ² or more 40 kg / mm ² or less, at 35 kg / mm ² or less 5 kg / mm ² or more in the TD direction, elongation at break, 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. Further, the shrinkage rate when left in a temperature environment of 150 ° C. for 30 minutes is, for example, 0.1% or more and 5% or less.

When the base film 22 is a biomass polyester film or a polyester film, the thickness of the base film 22 is preferably 6 μm to 20 μm, more preferably 12 μm to 16 μm.
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-pressed film having two or more layers.

(Barrier layer)
Layers other than those described above, such as a barrier layer, may be provided between the base material layer and the printing layer and / or between the adhesive layer and the sealant layer. As the barrier layer, a metal foil or an inorganic or inorganic oxide vapor deposition layer can be preferably used.

(Metal foil)
As the metal foil constituting the barrier layer 60, a conventionally known metal foil can be used. Aluminum foil is preferred from the viewpoints of gas barrier properties that prevent transmission of oxygen gas, water vapor, and the like, and light shielding properties that prevent transmission of visible light, ultraviolet light, and the like.

(Deposition layer)
The vapor deposition layer which comprises the barrier layer 60 is a vapor deposition film which consists of an inorganic substance and / or an inorganic oxide. A vapor deposition film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and its composition and formation method are not particularly limited. The packaging material 10 may have two or more vapor deposition layers. When it has two or more vapor deposition layers, each may have the same composition or different compositions.

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

  A vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide has transparency. When a vapor deposition layer is located in the outer surface 10y side rather than the printing layer 50, the vapor deposition film of the inorganic oxide which has transparency is used as a vapor deposition layer.

Representation of the inorganic oxide, for _example, SiO X, as such AlO _X MO _X (In the formula, M represents an inorganic element, the value of X, varies each of an inorganic element range.) In expressed. As a range of the value of X, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, 0 to 0.5 for potassium (K), 0 to 2 for tin (Sn), 0 to 0.5 for sodium (Na), 0 to 1,5 for boron (B), titanium (Ti) Can take values in the range of 0 to 2, lead (Pb) in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5. In the above, when X = 0, it is a complete inorganic simple substance (pure substance) and is not transparent, and the upper limit of the range of X is a completely oxidized value. As the vapor deposition layer of the packaging material 10, silicon (Si) and aluminum (Al) are preferably used. Silicon (Si) is 1.0 to 2.0, and aluminum (Al) is 0.5 to 1. A value in the range of 5 can be used.

  The film thickness of the inorganic or inorganic oxide vapor deposition film as described above varies depending on the type of the inorganic or inorganic oxide used, but is, for example, in the range of 50 to 2000 mm, preferably in the range of 100 to 1000 mm. It is desirable to select and form arbitrarily. More specifically, in the case of an aluminum deposited film, the film thickness is preferably 50 to 600 mm, more preferably 100 to 450 mm, and in the case of an aluminum oxide or silicon oxide deposited film, The film thickness is from 50 to 500 mm, more preferably from 100 to 300 mm.

  A vapor deposition layer can be formed in the base film 22 etc. using the following formation methods. As a method for forming a vapor deposition layer, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, a plasma chemical vapor deposition method, a thermochemistry, or the like. Examples thereof include a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a vapor phase growth method and a photochemical vapor deposition method.

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

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , at least one kind of a partial hydrolyzate of alkoxide and a condensate of hydrolysis of alkoxide can be used. Moreover, as a partial hydrolyzate of said alkoxide, all the alkoxy groups do not need to be hydrolyzed, The thing by which 1 or more was hydrolyzed, and its mixture may be sufficient. As a condensate of hydrolysis of alkoxide, a dimer or more of partially hydrolyzed alkoxide, specifically, a 2 to 6 mer is used.

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

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

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

(Print layer)
The print layer 50 is a layer formed by printing for display of decoration, display of contents, display of a best-before period, display of a manufacturer, a seller, etc., and addition of aesthetics. The print layer 50 includes, for example, a picture layer that forms a desired arbitrary picture such as a picture, a photograph, letters, numbers, figures, symbols, and patterns. The printed layer may further include a ground color layer formed by printing so as to make the pattern of the pattern layer stand out. The printing layer 50 includes a colorant and a cured product of a polyol and an isocyanate compound. The printed layer 50 includes a biomass-derived component. Specifically, the printing 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 a polyfunctional alcohol and a polyfunctional carboxylic acid contains a biomass-derived component. The following examples can be given as polyester polyols containing biomass-derived components.
・ Reactant of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・ Reaction product of polyfunctional alcohol derived from fossil fuel and multifunctional carboxylic acid derived from biomass ・ Derived from multifunctional alcohol derived from biomass and fossil fuel Reactant with polyfunctional carboxylic acid

  As the polyfunctional alcohol derived from biomass, an aliphatic polyfunctional alcohol obtained from plant materials such as corn, sugar cane, cassava, and sago palm can be used. As the aliphatic polyfunctional alcohol derived from biomass, for example, polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butylene obtained from plant raw materials by the following method. There are glycol (BG) and hexamethylene glycol, and any of them can be used. These may be used alone or in combination.

Biomass-derived polypropylene glycol is produced from glycerol via 3-hydroxypropyl aldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant raw materials. Polypropylene glycol produced by a bio-method such as the fermentation method can produce useful by-products such as lactic acid from the viewpoint of safety compared to polypropylene glycol of the EO production method, and can also keep production costs low. It is also preferable that it is possible.
Biomass-derived butylene glycol can be produced by obtaining succinic acid obtained by producing glycol from plant raw materials and fermenting it and hydrogenating it.
Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

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

  Biomass-derived polyfunctional carboxylic acids are recycled from recyclable soybean oil, linseed oil, tung oil, palm oil, palm oil, castor oil and other plant-derived oils, and waste edible oils mainly composed of them. Aliphatic polyfunctional carboxylic acids obtained from plant materials such as oil can be used. Examples of the biomass-derived aliphatic polyfunctional carboxylic acid include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acid. For example, sebacic acid is produced as a by-product of heptyl alcohol by alkaline pyrolysis 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.

  As the polyfunctional carboxylic acid derived from fossil fuel, an aliphatic polyfunctional carboxylic acid or an aromatic polyfunctional carboxylic acid can be used. The aliphatic polyfunctional carboxylic acid derived from fossil fuel is not particularly limited, and conventionally known ones can be used. For example, adipic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride Examples thereof include acid, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, and dimer acid, and ester compounds thereof. In addition, the aromatic polyfunctional carboxylic acid derived from fossil fuel is not particularly limited and conventionally known ones can be used, for example, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, phthalic anhydride, trimellitic acid, And pyromellitic acid, and ester compounds thereof 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 a polyfunctional alcohol and a polyfunctional isocyanate contains a biomass-derived component. The following examples can be given as polyether polyols containing biomass-derived components.
・ Reaction product of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional isocyanate ・ Reaction product of polyfunctional alcohol derived from fossil fuel and polyfunctional isocyanate derived from biomass ・ Multi-functional alcohol derived from biomass and many derived from fossil fuel Reactant with functional isocyanate

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

  As a polyfunctional isocyanate derived from biomass, a plant-derived divalent carboxylic acid is acidified, converted to a terminal amino group by reduction, and further reacted with phosgene to convert the amino group into an isocyanate group. What was obtained can be used. The biomass-derived polyfunctional isocyanate is, for example, a biomass-derived diisocyanate. Examples of the diisocyanate derived from biomass include dimer acid diisocyanate (DDI), octamethylene diisocyanate, decamethylene diisocyanate and the like. Moreover, plant-derived diisocyanate can also be obtained by using a plant-derived amino acid as a raw material and converting its amino group to an isocyanate group. For example, lysine diisocyanate (LDI) can be obtained by converting a carboxyl group of lysine into a methyl ester and then converting an amino group into an isocyanate group. 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 synthesis methods of 1,5-pentamethylene diisocyanate include a phosgenation method and a carbamate method. More specifically, the phosgenation method includes a method in which 1,5-pentamethylenediamine or a salt thereof is directly reacted with phosgene, or a hydrochloride salt of pentamethylenediamine is suspended in an inert solvent and reacted with phosgene. 1,5-pentamethylene diisocyanate is synthesized by the method. In the carbamation method, first, 1,5-pentamethylenediamine or a salt thereof is carbamatized to form pentamethylene dicarbamate (PDC), and then thermally decomposed to obtain 1,5-pentamethylene diisocyanate. To be synthesized. In the present invention, examples of the polyisocyanate preferably used include 1,5-pentamethylene diisocyanate polyisocyanate (trade name: STAVIO (registered trademark)) manufactured by Mitsui Chemicals.

  The polyfunctional isocyanate derived from fossil fuel is not particularly limited, and conventionally known ones can be used. For example, toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl- 1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4′-methylenebis (phenylene isocyanate) (MDI), Julylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4'-diisocyanate di Aromatic diisocyanate such as Njiru the like. In addition, aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) ), Alicyclic diisocyanates such as 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, hydrogenated XDI, and the like. These may be used alone or in combination of two or more.

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

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

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

  The printed layer 50 preferably has a thickness of 0.1 μm to 10 μm, more preferably 1 μm to 5 μm, and still more preferably 1 μm to 3 μm.

[Adhesive resin layer]
The adhesive resin layer is a layer provided when two arbitrary layers are bonded. For example, the adhesive resin layer can be provided between the base material layer and the intermediate layer or between the intermediate layer and the sealant layer.

  The adhesive resin layer such as the adhesive resin layer 26 can be formed by a conventionally known method such as a melt extrusion laminating method or a sand laminating method. Examples of the thermoplastic resin that can be used for the adhesive resin layer include a polyethylene resin, a polypropylene resin, or a cyclic polyolefin resin, or a copolymer resin, a modified resin, or a mixture (including alloy) containing these resins as a main component. ) Can be used. Examples of polyolefin resins include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear (linear) low density polyethylene (LLDPE), polypropylene (PP), and metallocene catalysts. Ethylene-α / olefin copolymer, ethylene / polypropylene random or block copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene / maleic acid copolymer, ionomer resin, and interlayer adhesion In order to improve the , It can be used acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and an acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as itaconic acid. Further, a resin obtained by graft 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 alone or in combination of two or more. As the cyclic polyolefin-based resin, for example, cyclic polyolefins such as ethylene-propylene copolymer, polymethylpentene, polybutene, and polynorbornene can be used. These resins can be used alone or in combination. In addition, as said polyethylene-type resin, what used the above ethylene derived from biomass as a monomer unit can be used, and a biomass degree can further be improved.

  When the adhesive resin layer is laminated by the melt extrusion laminating 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. Examples of the anchor coating agent include an anchor coating agent made of any resin having a heat resistant temperature of 135 ° C. or higher, such as a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, or a polyethyleneimine. An anchor coating agent that is a cured product of a polyacrylic or polymethacrylic resin (polyol) having two or more hydroxyl groups and an isocyanate compound as a curing agent can be preferably used. Moreover, a silane coupling agent may be used in combination as an additive, and nitrified cotton may be used in combination in order to improve heat resistance.

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

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

  Biomass polyolefin is a polymer of monomers containing olefins such as ethylene derived from biomass. Since a biomass-derived olefin is used as a monomer as a raw material, the polymerized polyolefin is derived from biomass. In addition, the raw material monomer of polyolefin does not need to contain 100 mass% of olefin derived from biomass.

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

  Biomass-derived fermented ethanol refers to ethanol that has been purified by bringing a microorganism or ethanol-derived product from ethanol into contact with a culture solution containing a carbon source obtained from plant raw materials. For the purification of ethanol from the culture solution, conventionally known methods such as distillation, membrane separation, and extraction can be applied. For example, a method of adding benzene, cyclohexane or the like and azeotropically or removing water by membrane separation or the like can be mentioned.

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

  The α-olefin is not particularly limited, but can usually be one having 3 to 20 carbon atoms, and is preferably butylene, hexene or octene. This is because if it is butylene, hexene or octene, it can be produced by polymerization of ethylene which is a biomass-derived raw material. In addition, by including such an α-olefin, the polymerized polyolefin has an alkyl group as a branched structure, and therefore can be more flexible than a simple linear one.

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

  The biomass polyolefin may contain two or more kinds of biomass polyolefins having different biomass degrees, and the biomass degree of the polyolefin resin layer as long as it is within the range described later.

Biomass polyolefin, preferably 0.91 g / cm ³ or more 0.93 g / cm ³ or less, more preferably 0.912 g / cm ³ or more 0.928 g / cm ³ or less, more preferably 0.915 g / cm ³ or more 0 It has a density of 925 g / cm ³ or less. The density of biomass polyolefin is a value measured according to the method prescribed | regulated to A method among JISK7112-1980 after performing annealing as described in JISK6760-1995. If the density of the biomass polyolefin is 0.91 g / cm ³ or more, the rigidity of the polyolefin resin layer containing the biomass polyolefin can be increased, and it can be suitably used as the inner layer of the packaged product. Moreover, if the density of biomass polyolefin is 0.93 g / cm < ³ > or less, the transparency and mechanical strength of the polyolefin resin layer containing biomass polyolefin can be improved, and it can be used suitably as an inner layer of a packaged product.

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

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

  Examples of the fossil fuel-derived thermoplastic resin include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, Examples thereof include an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, or an ionomer.

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

  The sealant layer 40 may be a single layer or a multilayer. When using the biomass polyolefin as described above for the sealant layer, a sealant layer including three layers of an inner layer, an intermediate layer, and an outer layer may be used. In that case, it is preferable that the intermediate layer is made of biomass polyolefin or biomass polyolefin and a 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, and still more preferably 30 μm to 150 μm.

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

<Method for manufacturing packaging material>
Next, an example of the manufacturing method of the laminated body which comprises the packaging material 10 is demonstrated.

  The manufacturing method of the laminated body which comprises the packaging material 10 by this invention is not specifically limited, It can manufacture by using conventionally well-known methods, such as a dry lamination method, a melt extrusion lamination method, and a sand lamination method. In the present invention, it is preferable to laminate another layer through a melt-extruded polyethylene resin layer using a sand laminating method. Moreover, you may laminate | stack a polyethylene resin layer on another layer by the melt-extrusion laminating method.

  For the purpose of providing the packaging material 10 with chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubrication functions, optical functions, thermal functions, surface functions such as biocompatibility, etc. Secondary processing can also be performed. Examples of secondary processing include embossing, painting, adhesion, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, Coating, etc.). In addition, the packaging material according to the present invention can be subjected to laminating (dry laminating or extrusion laminating), bag making, and other post-processing to produce a molded product.

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

  The packaging product provided with the packaging material 10 is, for example, liquids such as drugs, foods and drinks, fruit juices, juices, drinking water, liquor, cooked foods, marine products, frozen foods, meat products, boiled foods, rice cakes, pot soups, etc. -It can be suitably used as packaging for various foods and drinks such as pu, dried soup and seasonings, liquid detergents, shampoos, rinses, conditioners and other cosmetics, hygiene products, daily necessities and chemical products. Specific examples of the food and drink include coffee, coffee beans, coffee powder, ice cream, gummy, side dish, pasta sauce, curry, jelly, bacon, chocolate, and chocolate paste. Specific examples of daily necessities include absorbent cotton, a mask, a bath agent, and powdered milk. Moreover, as illustrated in the examples described later, the packaged product including the packaging material 10 configured to have heat resistance is used for containing contents subjected to heat sterilization processing such as retort processing and boil processing. Can be used. The retort process is a process of filling the packaged product with the contents and sealing the packaged product, and then heating the packaged product in a pressurized state using steam or heated hot water. The temperature of retort processing is 120 degreeC or more, for example. The boil process is a process in which the packaged product is filled with the contents and the packaged product is sealed, and then the packaged product is boiled under atmospheric pressure. The temperature of boil processing is 90 degreeC or more and 100 degrees C or less, for example.

  The packaging bag of the packaging product is obtained by folding the packaging material 10 in two or by preparing two packaging materials 10 so that the sealant layer 40 of the front side packaging material 10 and the sealant layer 40 of the back side packaging material 10 face each other. Further, the peripheral edge portion is, for example, a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, a palm-attached seal type (pillow seal type), a pleated seal type, Various types of packaging bags can be manufactured by heat sealing using a flat bottom sealing type, a square bottom sealing type or the like. In addition, a gusset-type packaging bag can be manufactured by performing heat sealing in a state where the folded packaging material 10 is inserted between the front packaging material 10 and the back packaging material 10. In addition, all of the packaging material 10 which comprises a packaging bag may not be the packaging material 10 by this invention. That is, it is sufficient that at least a part of the printing layer of the packaging material 10 constituting the packaging bag contains a biomass-derived component, and the other printing layer of the packaging material 10 constituting the packaging bag is a fossil fuel-derived component. It may be a packaging material containing.

  As a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal can be used.

  FIG. 5 is a diagram illustrating an example of a packaging bag 70 including the packaging material 10. The bag 70 includes a surface film 74 constituting the front surface and a back film 75 constituting the back surface.

  As for the surface film 74 and the back surface film 75, inner surfaces are joined by the seal part. In the front view of the packaging bag 70 shown in FIG. 5 and the like, the seal portion is hatched. As shown in FIG. 5, the seal portion is disposed between the upper seal portion 71 a extending in the upper portion 71, the lower seal portion 72 a extending in the lower portion 72, and the pair of side portions 73, for example, approximately in the middle of the pair of side portions 73. And a palm seal portion 77 extending from the upper portion 71 toward the lower portion 72. The joint seal part 77 is a part also called a back seal part. As described above, the packaging bag 70 shown in FIG. 5 is a pillow pouch joined at the upper portion 71, the lower portion 72 and the palm portion.

  Further, as shown in FIG. 5, the packaging bag 70 includes a packaging material folded between the front film 74 and the back film 75, extends from the upper part 71 to the lower part 72, and a pair of side gusset parts facing each other. 78 is further provided. As shown in FIG. 5, the packaging material between the front 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 part of the packaging bag 70 is bound by a band or the like.

  Note that the terms “surface film” and “back film” described above are only those obtained by dividing each film according to the positional relationship, and the method for providing the packaging material 10 when the packaging bag 70 is manufactured is described above. It is not limited by terms. For example, the packaging bag 70 may be manufactured using a single packaging material 10 in which a surface film 74 and a back film 75 are continuously provided, and the total of one surface film 74 and one back film 75 may be included. It may be manufactured using two packaging materials 10.

  At least one of the front film 74 and the back film 75 is constituted by the packaging material 10 having a printed layer containing a biomass-derived component. Thereby, the usage-amount of fossil fuel can be reduced compared with the past, and an environmental load can be reduced.

  FIG. 6 is a diagram illustrating another example of the packaging bag 70 including the packaging material 10. The packaging bag 70 shown in FIG. 6 is a four-sided seal pouch formed by joining a front film 74 and a back film 75 along four sides along the outer edge.

  As shown in FIG. 6, the seal portion has an outer edge seal portion that extends along the outer edge of the packaging bag 70. The outer edge seal portion includes a lower seal portion 72 a extending in the lower portion 72 and a pair of side seal portions 73 a extending along the pair of side portions 73. In addition, in the packaging bag 70 in a state before the contents are filled (a state in which the contents are not filled), as shown in FIG. 6, the upper portion 71 of the bag 70 is an opening 71b. After the contents are stored in the packaging bag 70, the inner surface of the front film 74 and the inner surface of the back film 75 are joined at the upper portion 71, whereby an upper seal portion is formed and the packaging bag 70 is sealed.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

[Example 1A]
A biaxially stretched nylon film (thickness: 15 μm) derived from fossil fuel was prepared as the substrate film 22 of the substrate layer 20. Then, the printing layer 50 was formed in the surface by the side of the inner surface of PET film using the ink containing a biomass origin component. In the step of forming the printed layer 50, first, a polyester polyol that is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid derived from a fossil fuel was prepared as a main agent. Moreover, the fossil fuel-derived isocyanate compound was prepared as a hardening | curing agent. Subsequently, a colorant was added to a cured product of a polyester polyol containing a biomass-derived component and an isocyanate compound derived from a fossil fuel to obtain an ink. Subsequently, ink was applied in a predetermined pattern on the inner surface of the PET film to form the printing layer 50.

Moreover, the polyethylene film 1 produced as follows was used as the sealant film 42 of the sealant layer 40. 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, biomass degree: 0%), and low density polyethylene derived from fossil fuel (density) : 0.924 g / cm3, MFR: 2.0 g / 10 min, biomass degree: 0%) and 10 parts by mass were melt-kneaded to obtain a resin composition. Subsequently, the obtained resin composition was formed into a film by a top blow air-cooled inflation coextrusion film forming machine to obtain a single layer polyethylene film (biomass degree: 0%) for a sealant layer. The thickness of the polyethylene film 1 can be selected within the range of 20 μm or more and 70 μm or less, but is 30 μm here. Subsequently, on the printing layer 50 provided on the base film 22, polyethylene 1 as the adhesive resin layer 26 is extruded at a resin temperature of 290 ° C. via an anchor coating agent by using a sand laminating method, and the sealant film 42. Was laminated on the adhesive resin layer 26 to obtain the packaging material 10. As polyethylene 1, low-density polyethylene derived from fossil fuel (density: 0.924 g / cm ³ , MFR: 2.0 g / 10 min, biomass degree: 0%) was used. The thickness of the polyethylene 1 can be selected within the range of 10 μm or more and 30 μm or less, but here it is 20 μm.

The layer structure of the packaging material 10 of the present embodiment is expressed as follows.
ONY15 / mark / anchor / contact PE (1) 20 / PE (1) 30
“/” Represents a boundary between layers. The leftmost layer is a layer constituting the outer surface of the packaging material 10, and the rightmost layer is a layer constituting the inner surface of the packaging material 10.
“ONY” means a biaxially stretched nylon film derived from fossil fuel. “Mark” means a biomass-derived printed layer. “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 thickness of the layer (unit: μm).

  Subsequently, a pillow pouch type packaging bag 70 shown in FIG.

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

[Example 1C]
As a polyester polyol which is the main component 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 a biomass-derived component is used as an isocyanate compound which is a curing agent of the printing layer 50. A packaging material 10 was produced in the same manner as in Example 1A, except that the isocyanate compound contained was used.

The layer structure of the packaging material 10 of Examples 1A to 1C is collectively shown in FIG. In the “printing layer type” column of FIG. 7, the description of “ester type” means that the main agent used in the printing layer is a polyester polyol.
In addition, in the column of “biomass-derived component in the printing layer”, the description “polyfunctional alcohol” means that at least the main component polyfunctional alcohol 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 the curing agent used in the printed layer is derived from biomass. Similarly, the description of “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 printing layer, one of the three constituent elements of the polyfunctional alcohol or polyfunctional carboxylic acid used in the main component polyester polyol or the isocyanate compound used in the curing agent is biomass. Although the example which is an origin component was shown, it is not restricted to this. For example, two of the three components may include a biomass-derived component, and all three components may include a biomass-derived component.

[Example 1D]
A packaging material 10 was produced in the same manner as in Example 1A except that polyether polyol was used as the main component of the printing 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 polyether polyol of the main agent.

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

[Example 1F]
As a polyether polyol which is the main component 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 a biomass-derived component is used as an isocyanate compound which is a curing agent of the printing layer 50. A packaging material 10 was produced in the same manner as in Example 1D except that the isocyanate compound contained was used.

  The layer structure of the packaging material 10 of Examples 1D to 1F is collectively shown in FIG. In the column of “type of printing layer” in FIG. 7, the description of “ether type” means that the main agent used in the printing layer is a polyether polyol. Moreover, in the column of “biomass-derived component in the printing layer”, the description “polyfunctional isocyanate” means that at least the main component polyfunctional isocyanate used in the printing layer is derived from biomass. Means.

  In Examples 1D to 1F, in the printing layer, one of the three constituent elements of the polyfunctional alcohol or polyfunctional isocyanate used in the main polyether polyol or the isocyanate compound used in the curing agent is biomass. Although the example which is an origin component was shown, it is not restricted to this. For example, two of the three components may include a biomass-derived component, and all three components may include a biomass-derived component.

[Example 1G]
As the base film 22 of the base layer 20, nylon in which a biaxially stretched nylon film derived from fossil fuel is provided with a vapor deposition layer of inorganic oxide and a gas barrier coating film positioned on the vapor deposition layer A 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 the present embodiment is expressed as follows.
Barrier ONY15 / mark / anchor / contact PE (1) 20 / PE (1) 30
“Barrier ONY15” means a nylon film in which a vapor-deposited layer of an inorganic oxide and a gas barrier coating film are provided on a biaxially stretched nylon film derived from fossil fuel.

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

In this case, low-density polyethylene derived from fossil fuel (density: 0.924 g / cm 3, MFR: 2.0 g / 10 minutes, biomass degree: 0%) 50 parts by mass, biomass-derived low-density polyethylene (manufactured by Brasschem, 50 parts by mass of trade name: SPB681, density: 0.922 g / cm ³ , MFR: 3.8 g / 10 min, biomass degree 95%) was melt-kneaded to obtain a tree composition (polyethylene 2). Next, the obtained resin composition was extruded through an anchor coating agent at a resin temperature of 290 ° C., and the sealant film 42 was laminated on the adhesive resin layer 26.

The layer structure of the packaging material 10 of the present embodiment is expressed as follows.
ONY15 / mark / anchor / contact PE (2) 20 / PE (1) 30
“Contact PE (2)” means an adhesive resin layer containing the polyethylene 2 described above.

Example 1I
A packaging material 10 was produced in the same manner as in Example 1A, except that the 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, 60 parts by mass of linear low density polyethylene derived from fossil fuel (density: 0.918 g / cm 3, MFR: 3.8 g / 10 min, biomass degree: 0%), and low density polyethylene derived from fossil fuel (density) : 0.924 g / cm3, MFR: 2.0 g / 10 min, biomass degree: 0%) 20 parts by mass, biomass-derived linear low-density polyethylene (LLDPE, manufactured by Braschem, trade name: SLL118, density: 0.916 g / cm <3>, MFR: 1.0 g / 10 min, biomass degree 87%) and 20 parts by mass were melt-kneaded to obtain a resin composition. Subsequently, the obtained resin composition was formed into a film by a top blow 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 30 μm as in the case of the polyethylene film 1 of Example 1A.

The layer structure of the packaging material 10 of the present 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-described polyethylene 2 was used as the adhesive resin layer 26 and the above-described polyethylene film 2 was used as the sealant film 42 of the sealant layer 40. .

The layer structure of the packaging material 10 of the present embodiment is expressed as follows.
ONY15 / mark / anchor / contact PE (2) 20 / PE (2) 30

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

  In Examples 1G to 1J, the print layers shown in Examples 1B to 1F may be used as the print layer in addition to the print layer shown in Example 1A.

[Example 2A]
As the base film 22 of the base layer 20, a biaxially stretched polypropylene film derived from fossil fuel was prepared. The thickness of the polypropylene film can be selected within the range of 15 μm or more and 40 μm or less, but here it is 30 μm. Then, the printing layer 50 was formed in the surface by the side of the inner surface of a polypropylene film using the ink containing a biomass origin component. Similar to the printing layer 50 of Example 1A, the printing layer 50 has a cured product of a polyester polyol containing a polyfunctional alcohol containing a biomass-derived component and an isocyanate compound derived from a fossil fuel.

  Subsequently, the above-described polyethylene 1 as the adhesive resin layer 26 and the above-described polyethylene 1 as the sealant layer 40 are formed on the printing layer 50 provided on the base film 22 using a melt coextrusion laminating method. Extrusion is performed at a resin temperature of 290 ° C. through an anchor coating agent, and an adhesive resin layer 26 and a sealant layer 40 are laminated in this order on the base film 22 from the base film 22 side. 10 was obtained. 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.

The layer structure of the packaging material 10 of the present embodiment is expressed as follows.
OPP30 / mark / anchor / contact PE (1) 15 / extruded PE (1) 15
“OPP” means a biaxially stretched polypropylene film derived from fossil fuel. “Extruded PE (1)” means the polyethylene 1 described above.

  Subsequently, a four-side sealed packaging bag 70 shown in FIG. 6 was produced using the packaging material 10.

[Example 2B]
A packaging material 10 was produced in the same manner as in Example 2A, except that polyether polyol was used as the main component of the printing 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 polyether polyol of the main agent.

[Example 2C]
As the base film 22 of the base layer 20, a polypropylene in which a vapor-deposited layer of inorganic oxide and a gas barrier coating film located on the vapor-deposited layer are provided on the surface of a biaxially stretched polypropylene film derived from fossil fuel. A 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 the present embodiment is expressed as follows.
Barrier OPP30 / Mark / Anchor / Welding PE (1) 15 / Extruded PE (1) 15
“Barrier OPP” means a polypropylene film in which a vapor-deposited layer of inorganic oxide and a gas barrier coating film are provided on a biaxially stretched polypropylene film derived from fossil fuel.

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

The layer structure of the packaging material 10 of the present embodiment is expressed as follows.
OPP30 / mark / anchor / contact PE (1) 15 / extruded PE (2) 15
“Extruded PE (2)” means the polyethylene 2 described above.

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

The layer structure of the packaging material 10 of the present embodiment is expressed as follows.
OPP30 / mark / anchor / contact PE (2) 15 / extruded PE (2) 15

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

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

  In FIG. 8, the layer structure of the packaging material 10 of Example 2A-2E is shown collectively.

[Example 3A]
In the same manner as in Examples 2A to 2G, the 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 were sequentially laminated was produced. 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, the above-described polyethylene 1 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, but here it is 20 μm. As the sealant layer 40, the above-described polyethylene 1 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, but here it is 20 μm. As the printing layer 50, the same one as in Example 2A was used.

  Subsequently, a four-side sealed packaging bag 70 shown in FIG. 6 was produced using the packaging material 10.

The layer structure of the packaging material 10 of the present embodiment is expressed as follows.
PET12 / Mark / Anchor / Welding PE (1) 20 / Extruded PE (1) 20
“PET” means a biaxially stretched polyethylene terephthalate film derived from fossil fuel.

[Example 3B]
A packaging material 10 was produced in the same manner as in Example 4A, except that polyether polyol was used as the main component of the printing 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 polyether polyol of the main agent.

[Example 3C]
As the base material film 22 of the base material layer 20, a PET film provided with an inorganic oxide vapor deposition layer and a gas barrier coating film positioned on the vapor deposition layer on the surface of a biaxially stretched PET film derived from fossil fuel. A 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 the present embodiment is expressed as follows.
Barrier PET12 / Mark / Anchor / Welding PE (1) 20 / Extruded PE (1) 20
“Barrier PET” means a polyethylene terephthalate film in which a biaxially stretched polyethylene terephthalate film derived from fossil fuel is provided with an inorganic oxide vapor deposition layer and a gas barrier coating film.

[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 substrate film 22 of the substrate layer 20.

The layer structure of the packaging material 10 of the present embodiment is expressed as follows.
Bio PET12 / Mark / Anchor / Welding PE (1) 20 / Extruded PE (1) 20
“Bio-PET” means a biaxially stretched polyethylene terephthalate film derived from biomass.

[Example 3E]
As in the case of Example 4A, except that a biaxially stretched PET film derived from biomass was used as the base film 22 of the base layer 20, and the above-described 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 the present embodiment is expressed as follows.
Bio PET12 / Mark / Anchor / Welding PE (2) 20 / Extruded PE (1) 20

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

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

[Example 3G]
A biaxially stretched PET film derived from biomass was used as the base material film 22 of the base material layer 20, the above-mentioned polyethylene 2 was used as the adhesive resin layer 26, and the above-mentioned polyethylene 2 was used as the sealant layer 40. Except for the above, a packaging material 10 was produced in the same manner as in Example 4A.

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

  In the present embodiment, variations similar to those in Embodiments 1B to 1J and Embodiments 2B to 2E can be employed. For example, the print layers shown in Examples 1B to 1F may be used as the print layer in addition to the print layer shown in Example 1A.

  In FIG. 9, the layer structural example of the packaging material 10 of Example 3A-3G is shown collectively.

[Example 4A]
In the same manner as in Examples 1A to 1J, the 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 film 42 were sequentially laminated was produced. As the base film 22, a biaxially stretched polypropylene film derived from fossil fuel was used. The thickness of the polypropylene film can be selected within the range of 15 μm or more and 40 μm or less, but here it is 20 μm. As the sealant film 42 of the sealant layer 40, an unstretched polypropylene film derived from fossil fuel was used. The thickness of the polypropylene film can be selected within a range of 20 μm or more and 50 μm or less, but is 25 μm here. As the printing 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, but here it is 15 μm.

  Subsequently, a pillow pouch type packaging bag 70 shown in FIG.

The layer structure of the packaging material 10 of the present embodiment is expressed as follows.
OPP20 / mark / anchor / contact PE (1) 15 / CPP25
“CPP” means an unstretched polypropylene film derived from fossil fuel.

[Example 4B]
A packaging material 10 was produced in the same manner as in Example 4A, except that polyether polyol was used as the main component of the printing 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 polyether polyol of the main agent.

  In the present embodiment, variations similar to those in Embodiments 1B to 1J and Embodiments 2B to 2E can be employed. For example, the print layers shown in Examples 1B to 1F may be used as the print layer in addition to the print layer shown in Example 1A.

  In FIG. 10, the layer structural example of the packaging material 10 of Example 4A-4B is shown collectively.

  Moreover, in FIG. 11, the example of the type of the packaging container of Examples 1A-1J, 2A-2E, 3A-3G, and 4A-4B is shown collectively.

DESCRIPTION OF SYMBOLS 10 Packaging material 20 Base material layer 22 Base material film 24 Print layer 26 Adhesive resin layer 28 Anchor coat layer 40 Sealant layer 42 Sealant film 50 Print layer 60 Barrier layer

Claims (11)

A packaging material including at least a base material layer, a printing layer, an adhesive resin layer, and a sealant layer,
The printed layer includes a colorant and a cured product of a polyol and an isocyanate compound, and at least one of the polyol or the isocyanate compound includes a biomass-derived component.   The packaging material according to claim 1, wherein the polyol of the printing layer is a polyester polyol that is a reaction product of a polyfunctional alcohol and a polyfunctional carboxylic acid.   The packaging material according to claim 2, wherein at least one of the polyfunctional alcohol or the polyfunctional carboxylic acid of the printing layer contains a biomass-derived component.   The packaging material according to claim 1, wherein the polyol of the printing layer is a polyether polyol which is a reaction product of a polyfunctional alcohol and a polyfunctional isocyanate.   The packaging material according to claim 4, wherein at least one of the polyfunctional alcohol or the polyfunctional isocyanate of the printing layer contains a biomass-derived component.   The packaging material as described in any one of Claims 1 thru | or 5 in which the said isocyanate compound of the said printing layer contains a biomass origin component.   The packaging material according to any one of claims 1 to 6, wherein the base material layer has a base film containing polyester, polyamide, or polyolefin.   The packaging material according to claim 7, wherein the base film includes biomass polyester having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.   The packaging material according to any one of claims 1 to 8, wherein the sealant layer contains a polyolefin which is a polymer of a monomer containing an olefin.   The packaging material according to claim 9, wherein the sealant layer includes biomass polyolefin which is a polymer of a monomer including ethylene derived from biomass.   Packaged product provided with the packaging material as described in any one of Claims 1 thru | or 10.